DE2939114A1 - METHOD FOR CHANGING THE PROPERTIES OF AQUEOUS LIQUIDS BY MEANS OF POLYMERISATS, ESPECIALLY WHILE DRILLING LIQUIDS - Google Patents

Description

Process for changing the properties of aqueous Liquids raitIeis polymers, especially with

Drilling fluids

The invention relates to a method for changing the properties of an aqueous fluid, in particular fluids which are used in the production and operation of boreholes, and means for carrying through them; such treatment procedures. In the erf i nduiigsgcirißen method i nsbesondere the Flu jd flow or liquid flow and the surface properties of POZ ¹ OrUi) transmitting particulate formations, and in particular underground formations that are ei IHiLT borehole durehteuft, modified, Gemäli the invention can also the Viscosity can be increased or (] ■>:; gelling of w ^: is: ri j: cn I ¹ '] iissjgkei th, in particular of acids, which; are; evv ^ jdi; for the handling of such earth formations . can be changed the Bolrmdlung of Erd rorni.-itionen nii t the erfi ndinigsgemäßen Zusnir ruMiset / UUG <.ii HTTiegliclit a w <'.'; rn <, li modifying the transit

η 3 η in ü / (ι η / .;

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permeability and surface properties of the formation, so that the flow of aqueous fluids, especially water and saline solutions of the formation through a part of the formation can be prevented or reduced, so that the water-oil ratio or the WOR value of fluid flowing through this formation or fluid recovered from this formation is reduced and in In some cases the production of hydrocarbons can be increased. In the treatment method according to the invention branched, organic polymers with a broad molecular weight range are used. The branches the polymers are preferably hydrophilic and the polymer contains binding groups, e.g. ionic, binding groups which attract or repel a substrate, a particulate formation, from suspended Solids, other polymers or segments, carrier liquid or a fluid to be treated or serve a liquid to be treated.

Various working methods have been used to create earth formations, and particularly subterranean ones, from one To treat oil well-drilled formations which produce both water and oil or hydrocarbons. The production of water or saline solution reduces the value of a well, since water is normally undesirable and requires costly and laborious methods of elimination. In a similar way it is Penetration of aqueous fluids into earth formations is often undesirable, especially during drilling, the completion or the revision phases of an oil well, in which this is done in certain formations filtrate entering the wellbore could damage the formation. In the treatment of underground formations for this and

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other purposes are for stimulation, e.g. one Acid treatment or a practice, for a completion, e.g. a cementing, a pack with Pebbles and perforating, for drilling, for reworking, for injection treatment, respectively Potting, gels often used for agility control and water control. Furthermore are Various systems are available to increase the viscosity of aqueous liquids such as acidic liquids. However, previously known procedures and means have disadvantages, e.g. that they are only temporarily successful cause them to be unstable or have other disadvantages.

Various of the numerous methods used to date to reduce the flow of aqueous liquids into or out of such formations are described in the following U.S. patents: 3,393,912, 3,868,999, 3,830,302, 3,826,311, 3,820,603, and 3,779,316. U.S. Patent 3,393,912 discloses a method for Reduction of water production from oil wells described, with a viscous oil being injected into the well containing a coupling agent in the form of phenolic resins or furan resins. In the US PS 3 868 999 is a method for reducing water permeability of a formation in comparison to the 01-permeability described, wherein in the formation a Liquid sludge is injected, which is a hydrocarbon solvent, colloidal silica, water and a contains polymeric material. In US Pat. No. 3,830,302 there is a method of reducing the water-to-oil ratio a production well described, wherein a formation with a combination of an aqueous, organic polyelectrolyte such as a polyacrylamide and a cationic, surfactant is treated. In the

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U.S. Patent 3,826,311 is the use of a particular copolymer of (3-acrylamido-3-methyl) butyltrimethylammonium chloride and acrylamide with a molecular weight of at least 100,000 to reduce water pumping finger-shaped veins in a water flooding process using emulsions of a water-soluble, anionic Vinyl addition polymer and a water-soluble, cationic polymer described.

In addition to the above-mentioned publications, methods for use are also found in numerous publications, Production and use of polymers for the treatment of earth formations described, for example in the the following patents and publications:

1. Can. Patent No. 731.212

2. Can. Patent No. 864,433 to Kaufman

3. U.S. RE 29,595 to Adams et al

4. U.S. 1,877,504 to Grebe et al

5. U.S. 2,138,763 to Graves

6. U.S. 2,222,208 to Ulrich

7. U.S. 2,223,930 to Griessbach et al

8. U.S. 2,223,933 tons of Garrison

9. U.S. 2,265,759 to Lawton et al

10. U.S. 2,272,489 to Ulrich

11. U.S. 2,296,225 to Ulrich

12. U.S. 2,296,226 to Ulrich

13. U.S. 2,331,594 to Blair

14. U.S. 2,345,713 to Moore et al

15. U.S. 2,382,185 to Ulrich

16. U.S. 2,570,895 to Wilson

17. U.S. 2,663,689 to Kingston et al

18. U.S. 2,677,679 to Barney

19. U.S. 2,731,414 to Binder et al

20. U.S. 2,745,815 tons of rope

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21. U.S. 22nd U.S. 23 U.S. 24. U.S. 25th U.S. 26th U.S. 27 U.S. 28. U.S. 29 U.S. 30th U.S. 31. U.S. 32. U.S. 33. U.S. 34. U.S. 35. U.S. 36. U.S. 37. U.S. 38. U.S. 39. U.S. 40. U.S.

2,758,970

2,761,843 to Brown 2,771,138 to Beeson 2,772,179 to Kalinowski et al

2,801,984 to Morgan et al

2,801,985 to Roth 2,823,191 2,924,861

2,827,964 to Sandiford et al 2,842,338 to Davis et al 2,842,492 to by Engelhardt et al 2,852,467 to Hollyday 2,864,448 to Bond et al

2,908,641 to Boyle 2,940,729 to Rakowitz 2,940,889 to Justice 2,985,609 to Plitt 3,002,960 to Kolodny 3,020,953 to Zerweck et al 3,023,760 to Dever et al

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41. U.S. 3,025,237 tons of Roper

42. U.S. 3,028,351 tons of chippings

43. U.S. 3,039,529 to McKennon

44. U.S. 3,042,641 to West et al

45. U.S. 3,050,493 to Wagner et al

46. U.S. 3,051,751 to Levis et al

47. U.S. 3,053,765 tons of Sparks

48. U.S. 3,057,798 tons of Knox

49. U.S. 3 /) 70,158 to Roper et al

50. U.S. 3,087,543 to Arendt

51. U.S. 3,102,548 to Smith et al

52. U.S. 3,108,069 to Monroe et al

53. U.S. 3,116,791 to Sandiford et al

54. U.S. 3,179,171 to Beale

55. U.S. 3,210,310 to Holbert et al

56. U.S. 3,254,719 tons of root

57. U.S. 3,283,812 to Ahearn et al

58. U.S. 3,284,393 to Vanderhoff et al

59. U.S. 3,305,016 to Lindblom et al

60. U.S. 3,308,885 tons of Sandiford

61. U.S. 3,317,442 to Clarke

62. U.S. 3,334,689 to McLaughlin

63. U.S. 3,349,032 tons of war

64. U.S. 3,367,418 to Routson

65. U.S. 3,370,647 to Wolgemuth

66. U.S. 3,370,650 tons of Watanabe

67. U.S. 3,376,924 to Felsenthal et al

68. U.S. 3,380,529 to Hendrickson

69. U.S. 3,382,924 to Veley et al

70. U.S. 3,399,725 to Pye

71. U.S. 3,415,673 to clock

72. U.S. 3,418,239 tons of Copper

73. U.S. 3,419,072 to Maley et al

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74. U.S 75. U.S 76. U.S 77. U.S 78. U.S 79. U.S 80. U.S 81. U.S 82. U.S 83. U.S 84. U.S 85. U.S 86. U.S 87. U.S 88 U.S 89 U.S 90 U.S 91. · U.S 92. U.S 93. U.S 94. U.S 95. U.S 96 U.S 97. U.S 98 U.S 99 U.S 100. U.S 101. U.S 102. U.S 103. U.S 104. U.S 105. U.S 106. U.S 107. U.S 108. U.S 109. U.S 110. U.S

US 3,422,890 to Darley 3,434,971 to Atkins 3,451,480 to Zeh et al 3,483,121 to Jordan 3,483,923 to Darley 3,491,049 to Gibson et al 3,494,965 to Jones et al 3,500,929 to Eilers et al 3,510,342 to Denunig et al 3,516,944 to Litt et al 3,537,525

3,545,130 to Strother et al 3,562,226 to Gayley et al 3,565,941 to Dick et al 3,567,659 to Nagy 3,572,416 to Kinney et al 3,578,781 to Abrams et al 3,603,399 tons. Reed 3,609,191 to Wade 3,624,019 to Anderson et al 3,625,684 to Poot et al 3,635,835 tons of Perterson 3,640,741 tons of Estes 3,660,431 tons of Hatch et al 3,666,810 tons of Hoke 3,734,873 to Anderson et al. 3,738,437 to Scheuerman 3,741,307 to Sandiford et al 3,744,566 tons Tamas et al 3,779,316 tons Bott 3,729,914 tons Nimerick 3,781,203 to Clark et al 3,791,446 to Täte 3,820,603 to Knight et al 3,822,749 tons Thigpen 3,826,3Ll to Szabo et al 3,827,495 tons Reed

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111. U.S. 3,827,500 tons of reed

112. U.S. 3,830,302 to Dreher et al

113. U.S. 3,833,718 to Reed et al

39114

114. U, .S 115. U. .S 116. U. .S 117. U. .S 118. U. .S 119. U. S. 120 U. S. 121. U. S. 122. U. S. 123. U. S, 124. U. S. 125. U. S, 126. U. S, 127. U. S. 128. U. S. 129. U. S. 130 U. S. 131. U. S. 132. U. S. 133. U. S. 134. U. S. 135. U. S.

3,842,911 to Knox et al 136. U.S. 4,094,795 to DeMartino et 3,845,824 to Tinsley 137. U.S. 4,094,831 tons of sand stream 3,868,328 tons of Boothe et al

3,868,999 to Christopher et al 3,888,312 to Tiner et al 3,893,510 to Elphingstone 3,768,566 to Ely et al 3,898,165 to Ely et al 3,909,423 to Hessert et al 3,922,173 to Misak

3,939,912 to Sparlin et al. 3,974,220 to Heib et al 3,994,344 to Friedman 4,021,355 to Holtmyer et al 4,033,415 to Holtmyer et al 4,029,747 to Merkl 4,058,491 to Steckler 4,069,365 to Rembaum 4,073,763 to Tai 4,079,027 to Phillips et al 4,079,059 to Dybas et al, 3,878, 895 to Wieland

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ARTICLES AND BOOKS

Barkman, J.H .; Abrams, A .; Darley, H.C.H .; & Hill, H.J .; "An Oil Coating Process to Stabilize Clays in Fresh Water Flooding Operation," SPE-4786, SPE of AIME Symposium on Formation Damage Control, New Orleans, La., Feb. 7-8, 1974. Coppel, Claude F .; Jennings, Harley X .; & Reed, M.G .; "Field Results From Wells Treated With Hydroxy-Aluminum," JOURNAL OF PETROLEUM TECHNOLOGY (Sept. 1973) pp. 1108-1112.

Dow Chemical Company, "PEI Polymers ... Infinite Modifications, Practical Versality," Copyrighted 1974. Graham, John W .; Monoghan, PH; & Osoba, JS; "Influence of Propping Sand Wettability of Productivity of Hydraulically Fractured Oil Wells," PETROLEUM TRANSACTIONS, AIME, Vol. 216 (1959).

Hower, Wayne F .; "Influence of Clays on the Production of Hydrocarbons," SPE-4785, SPE of AIME Symposium on Formation Damage Control, New Orleans, La., Feb. 7-8, 1974. Hower, Wayne F .; "Adsorption of Surfactants on Montmorillonite," CLAYS AND CLAY MINERALS, Pergamon Press (1970) Vol. 18, pp. 97-105.

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7. Hoover, M.F., & Butler, G.B .; "Recent Advances in Ion-Containing Polymers, "J. POLYMER SCI, Symposium No. 45, 1-37 (1974).

8. Jackson, Kern C; TEXTBOOK OF LITHOLOGY, McGraw-Hill Book Company (1970) (Library of Congress Catalog Card No. 72-958LO) pp. 95-103.

9. Theng, B.K.G .; THE CHEMISTRY OF CLAY-ORGANIC REACTIONS, John Wiley & Son (1974) (Library of Congress Catalog Card No. 74-12524) pp. 1-16.

10. Veley, CD .; "How Hydrolyzable Metal Ions Stabilize Clays To Prevent Permeability Reduction, "SPE-2188, 43rd Annual Fall Meeting of SPE of AIME, Houston, Texas (Sept. 29-Oct. 2, 1968).

11. Milchem Incorporated, "Milchem's SHALE-TROL Sticky Shale Can't Stop You Anymore, "DF-5-75-1M.

12. Chemergy Corporation, "Maintain Maximum Production

With PermaFIX and PermaFLO Treatments for CLAY / FINE and SAND CONTROL. "

13. ENCYCLOPEDIA POLYMER SCIENCE AND TECHNOLOGY, Suppl. 1, "Alkylenimine Polymers," Interscience Publ., N.Y., Copyrighted 1976, pp25-52.

14. Roberts, John D. & Caserio, Marjorie, C, BASIC PRINCIPLES OF ORGANIC CHEMISTRY, pub. W.A. Benjamin Inc., N.Y., 1965.

15. Mettzer, Yale L .; WATER SOLUBLE RESINS AND POLYMERS, Noyes Data Corp., Park Ridge, N.J., 1976

16. Whistler, Roy L .; INDUSTRIAL GUMS, Academic Press, N.Y., 1973.

17. Hoover, Fred M .; "Cationic Quaternary Polyelectrolytes— A Literature Review, "J. MACROMOL. SCI-CHEM.,. A4 (6), October, 1970, pp 1327-1418.

18. Robinson and Stokes, "Electrolyte Solutions," Butterworth Scientific Publications, 1959.

19. ___ ^ "Enhanced Oil and Gas Recovery & Improved Drilling Methods, "4th Annual DOE Sumposium, Vol. IA (Oil) of Proceedings, Aug. 29-31, 1978; pp B-1/1-B-1/25; Tulsa, OkIa; Published by The Petroleum Publishing Co., Box 1260, Tulsa, OK 74104.

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In addition to these references, a presently pending US patent application by Homer C. McLaughlin and Jimmie D. Weaver, S.N. 901,664, filed on Jan. May 1978, the use of various polymers to stabilize clays in earth formations, in particular an underground formation. The reference to the aforementioned publications is made in order to include an ins to be able to omit individual detailed explanations of this.

The invention relates to a method for changing the properties of aqueous or organic liquids or combinations thereof. The term "aqueous liquids" means any liquids which contain at least a small amount of water. Such liquids can also contain other ingredients or Components such as hydrocarbons, e.g. Alcohols, ethers and other miscible or partially miscible solvents, Acids, water-soluble or water-dispersible salts, easily gasifiable components such as COp and Np or Contain solids such as sand, Portland cement or sealants or other plastics or polymers such as resins. Such materials can include substances that can be hardened to form a rigid or semi-rigid solid, likewise substances that cannot be hardened. The liquid can also be particulate matter such as Contain sand, clay or acid-soluble particles such as carbonate. The fluid properties are main the viscosity and the resulting apparent viscosity of the liquid in various media. This change the fluid properties is beneficial for making more viscous and gelled fluids and for treating various substrates to change the properties of the substrate such as its surface-active properties Properties or the interaction between a treated substrate and different liquids

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or fluids. The agents provided according to the invention for changing the liquid properties or for treating various substrates can be formulated in such a way that the combination of the desired properties of the agent or the composition is achieved ,

e.g. with regard to solubility, affinity or repellency properties for different liquids or fluids and / or solids, stability to or degradation by components such as oxygen, acids and water at various Temperatures or with regard to the viscosity properties, which with time, temperature, concentration etc. vary. Such means and procedures can be used in particular in the thickening of various Liquids such as aqueous liquids and acids for the treatment of earth formations and in particular of one Well-drilled formations are applied such as those used for the production of water, oil, gas, steam and others Serving fabrics. The agents use a certain type of polymer as an essential component. This type of polymer is a branched, organic polymer with a backbone chain or backbone chain with an average value of at least one branched chain per backbone chain or backbone chain, this branched chain being one Average value of at least two polymer units having in length. In the branched polymer, up to 98 per 100 framework polymer units can have one or have multiple branches. The branched polymer can have one or more branched chains on each Have polymer unit in the backbone chain, if the conditions of the polymerization or of the grafting, the polymer units, economic or technical reasons and the like enable this. The term “polymer unit” used here means that part of a polymer chain to understand which of a monomer differ

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originates, irrespective of whether in the backbone chain, the branched chain or in both and irrespective of whether directly from one Monomers or from a partially polymerized product derived from or for the formation of a polymer precursor, an oligomer or a polymer chain implemented.

A preferred class of polymers within the broad class of branched polymers according to the invention are branched, water-soluble polymers. The branched polymers can polymer units, Contain segments or sections in various arrangements which are oleophilic, oleophobic, hydrophilic, hydrophobic are, or combinations thereof. A preferred class of branched polymers contains large sections, Concentrations or proportions of hydrophilic units or segments. The »branched polymer according to the invention generally contains combinations of hydrocarbon radicals and hetero groups. The one in the description the term "hydrocarbon radicals" as used in the present invention which is generally represented by R means radicals which are hydrogen and carbon contain and can further contain heteroatoms or hetero groups, but predominantly generally hydrogen and carbon in terms of number of atoms. For example, the hydrocarbon residue can include:

₂ ^ -O *, -KCH ₂ JN *, - (CH ₂ ) -, - (CH ₃ ), - (CH ₂ -CH ₂ ) -, - (CH ₂ -CH ₂ -O) -, - (CH ₂ -CH ₂ -NH) -, -HCH ₂ ) -N- (CH ₂ H-, - (CH ₂ -CHOH-CH ₂ ) -, and - (CH ₂ -CH) -.

CH ₂ OH

Another preferred class of branched polymers according to the invention are polymers which contain ionic groups contain. These ionic groups can be cationic, anionic, amphoteric, neutral or ionically balanced be or have combinations thereof. The Ionic

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Groups are usually heteroatoms or hetero groups or contain these, whereby these are oxygen, nitrogen, Sulfur, phosphorus, metals such as alkali metals, alkaline earth metals, metals of groups IV, V and VII of the periodic table, Combinations thereof and combinations thereof with carbon and / or hydrogen can be. Ionic Groups can be divided into aromatic groups, heterocyclic groups, unsaturated bonds, carboxyl, carbonyl, Keto, amide, imide, sulfo, hydroxyl groups and the like be included or present together with it.

The invention can therefore be viewed quite generally as the use of certain types of branched polymers and it is based on the surprising plague, that certain, branched polymers have unexpected stability and performance. For example can be used in treating an earth formation or in changing the properties of an aqueous fluid using a water-dispersible polymer improves the treatment or modification be that one of these particular branched polymers with a molecular weight of about 900-50 million with an average value of at least one branched chain per backbone chain is used, the branched chain has an average value of at least two polymer units in length. That branched Polymer can optionally be ionic or contain ionic and / or non-ionic segments, which depends on the desired, special effect and the desired, special application. That branched Polymer can be made by any of several methods or variations thereof and it can be built to have the particular, desired combination of segments and

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the desired properties in terms of the following still contains given teachings. In the same way, the branched polymer according to any of the numerous methods or variations thereof can be employed or employed.

According to one embodiment of the invention, branched, ionic polymers are used for treating particulate or fibrous formations, especially used by earth particles, to improve the fluid flow properties and / or to change the surface properties of the particles or the earth formation. The inventively used, branched polymers can be used to increase the viscosity or gel structure of numerous aqueous To change liquids and to change the surface properties, the liquid flow, the properties regarding To change the attraction / repulsion of numerous formations. Same mechanism or different Mechanisms can produce the changes in different applications. The formations can be made loose or solidified particles or fibers. The formation can also consist of suspended particles, fibers or crowds exist. A formation can be a solid, impermeable mass that is used to form a porous, permeable formation has been etched or leached, which then a porous, permeable formation is produced by compacting particles or fibers. Compacted formations can be loose or by natural or artificial binders such as resins, inorganic cements, including silicate cement and portland cement types. As used herein, particulate matter and particulate matter Formations "includes any of the aforementioned types of particles, formations, or structures. The one herein

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As used term "liquid flow property or surface properties" means the pure response of the particles or the formation to the flow or the flow resistance relative to a particular fluid or a particular liquid and with regard to the attraction, the repulsion or the relative inertness of the particles or the formation to one or several fluids or liquids or materials which are suspended in the fluids or liquids. The particles can be suspended in a liquid or either loose or tightly packed into a mass. In this embodiment of the invention, a particular method involves treating particles packed into a formation to reduce the permeability of the formation to the flow of water or an aqueous fluid. The method comprises merely placing or contacting a liquid phase adjacent the formation containing an effective amount of a polymerizate to treat at least a portion of the adjacent formation. The treated zone should preferably have a minimum thickness of about 2.5 cm. Of course, in applications to change the properties of aqueous fluids such as to modify the fluid loss of a treatment or in drilling fluids, the penetration of the aqueous fluid and the branched polymer should be minimal or a fraction of 2.54 cm. The polymer is preferably a branched, organic polymer with a molecular weight of about 900-50,000,000 with a backbone chain or skeleton chain with reactive sites on wel chen a branched chain can be bound or has been bound, the branched chains to the backbone chain or skeleton chain in a concentration of

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0.1-99 % of the reactive places are bound. The branched, organic polymer also has a hydrophilic component in a concentration sufficient to produce the desired hydrophilic-hydrophobic balance within the formation and to change the hydrophilic properties in the formation. This liquid phase flows or is pumped or injected into the formation and the polymerizate is allowed to contact the formation. For this purpose, the preferred classes of polymers have binding groups, for example ionic groups for binding or holding to the formation. For example, if the formation is generally anionic in nature, a preferred polymer would be a cationic polymer so that the cationic groups can adhere to or bond to the anionic sites in the formation. The polymers with a higher molecular weight and polymers with high concentrations of ionic groups also tend to make the treatment more permanent and to have improved performance or effectiveness.

According to a further embodiment of the invention, another class of polymers can be prepared which have some hydrophobic and / or oleophilic sections or branches or are all of these, so that these polymers Can be bound to formations or can be suspended within fluids in the formation to form a surface effect on the particles or formation, thereby increasing the flow of organic liquids or hydrocarbon liquids is inhibited and the Permeability of the formation to aqueous fluids is increased or there is a tendency to hydrocarbon to gel fluids or fluids on an organic basis. The term "hydrocarbon fluids" as used herein includes both oil, gas and mixtures thereof.

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an embodiment for changing the permeability of the formation is the change in the WOR value, i.e. the Water to oil ratio. The WQR used here includes the ratio of aqueous liquid to hydrocarbons including oil, gas or mixtures thereof. The production of different polymer classes to achieve the desired modification, to produce the desired kick-off or suspension properties and to produce the desired level of viscosity increase, gelling, or preference for organic or aqueous liquids can be carried out according to the description given below.

For example, a preferred class of cationic polymers which are hydrophilic and highly hydrophilic Having branch chains, used for treatment or for binding to a formation with anionic sites will. This binding is long-lasting or practically permanent, since the effect is not by washing the formation With acids, bases, organic or aqueous fluids or allowing such substances to flow, this is easily canceled can be. These polymers are also advantageous for stabilizing clay. The hydrophilic portion or section the polymer hydrates in the presence of water, saline or most aqueous liquids, this is believed to induce a pseudo-structure in the aqueous liquid, which appears to be an increase the viscosity results. In other words, the benefit is the resistance to flow or to increase the pressure required to produce a given flow of aqueous liquid. It will assumed that the hydrophilic portion partially dehydrated, shrunk, or a smoother flow channel in the presence of hydrocarbons or other organic

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Fluids "forms so that the permeability to organic fluids is increased or the permeability to hydrocarbons is practically not changed. Certain preferred polymers according to the invention have such an effectiveness that they a change of at least 10 % in the relative permeability to an aqueous liquid most loose or solidified, particulate formations, both in packings and in cores. This hydrophilic property of the branched polymer also results in an aqueous gelling agent with unexpectedly high efficiency and high stability, even with aqueous and especially acidic liquids. The effectiveness in gelling an aqueous liquid is indicated by a significant increase in viscosity such as at least a 10% increase compared to similar, straight-chain polymers.

In addition, have certain preferred classes of polymers long-term stability, which means that this effect continues even after 1000 pore volumes of one normally noxious liquid or fluid has passed through the treated formation. These Stability is influenced by the nature of the polymer and the particulate formation to be treated. For example a cationic polymer is preferred in silica-containing or anionic formations, and in cationic formations or neutral formations such as limestone or dolomite, an anionic or amphoteric polymer is preferred. With formations and / or particles which do not have a distinct ionic character or where the ionic character is weak, the stability or longevity can often be improved by increasing the molecular weight of the polymer, for example by networking, and / or the length and the number of branched chains can be increased.

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Another preferred class of polymers is essentially neutral, nonionic or amphoteric Nature, so that they are preferably only weakly suspended on most guest formations and / or pests, e.g. particulate pesticides is adsorbed. In addition, this polymer can be mixed with either aqueous or organic fluids solvate and / or swell, depending on the exact hydrophilic-hydrophobic nature of the polymer is dependent in order to generate the desired flow resistance. These polymers can be used for acid treatment, for breaking open, when packing pebbles or sand, for skimming off flowing into a formation Pluids or liquids, for diverting liquids or pluids, when drilling, when completing boreholes, be used in cementation, flooding or tertiary extraction, or a combination thereof. The polymers are particularly advantageous for mobility control such as, for example, polymer flooding or other methods of improving recovery.

Specific uses of the preferred classes of branched polymers include:

(1) The reduction of the WOR value, i.e. the water-to-oil ratio for drill holes,

(2) the reduction of water flow,

(3) increasing the flow or production of hydrocarbons including oil, gas or mixtures thereof, either individually or in the presence of an aqueous one Liquid,

sealing or diverting a flow of aqueous fluid in or into portions of a formation in,

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(5) increasing the viscosity and / or controlling the fluid loss of pluids or liquids that are involved in a borehole, for example in carrier or treatment fluids, in fluids for packing pebbles, drilling fluids, reworking or completion fluids,

(6) redirecting the flow of borehole or formation fluids, e.g. to alter mobility or descent Injection profile or to control liquid injection,

(7) the reduction or increase of the flow resistance of aqueous liquids, organic fluids, mixtures thereof or a component thereof in a formation,

(8) increasing the viscosity of aqueous liquids or organic fluids and especially liquids, which occur in or occur in certain types of formations,

(9) the rejection of certain fluids, salts, solids, or materials in a formation or structure or of materials suspended in a liquid,

(10) the gelling of aqueous liquids, especially acidic liquids,

(11) as carrier liquids for particulate solids, e.g. when packing pebbles, when breaking up, when Acid treatment or a combination thereof,

(12) when stabilizing sound,

(13) as a flocculant for suspended particles,

(14-) for the treatment of surfaces, so that these are aqueous or attract or repel organic liquids or fluids or ionic materials,

(15) as an acid extender or acid retarder,

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(16) for fluid loss control and / or as a viscosity modifier when breaking open and / or acidifying,

(17) to prevent or break down certain emulsions, in particular of water and hydrocarbon emulsions, which are often found in formations,

(18) to form an aqueous cementation gel all around Lines such as pipelines, boreholes, tunnels, mine shafts, sewers, taverns for hydrocarbon storage,

(19) Agent acting as a surfactant or binder between pesticides and fluids, as one or several fluid phases, for example to increase the adhesion of resins or solidifying materials in certain cases Surfaces or as one or more solid phases, for example between those suspended in a fluid Solids and a formation, and

(20) in the treatment of uncoated or only weakly coated silicon dioxide surfaces with a resin solidification of solids, e.g. in packings of pebbles, particles of the formation and the like, to the obtained To make solidification more resistant to damage by water.

In general, therefore, a preferred use according to the invention comprises one or more processes and polymer compositions for changing the surface properties and / or the fluid flow properties of a substrate or a formation, this formation being brought into contact with a highly branched, organic polymer, which has an attracting portion and a modifying portion. The attractive section of the polymer generally has ionic groups that provide the desired ionic bond or repulsion in the formation

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result. The modifying section of this polymer has the desired hydrophile-hydrophobic balance, vuQ the desired surface properties of the formation to obtain and / or to generate the desired interaction with fluids such as gelling and to achieve the permeability to increase or decrease certain liquids or fluids.

Preferred polymers can according to the main properties the formation to be treated or the application, the type of attraction or adsorption mechanism of the polymer, the type of the modifying polymer segment, the polymer solubility or the suspension properties as well as the functions which the polymer can fulfill, according to the information in the following Table.

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Properties of branched polymers

Polymer formation

Puncture

'Attractive section

Ionic nature

Strength of adsorption

Modifying section i_

hydrophilic / ionic solubility hydrophobic natural properties

of the polymer type

main
ionic
nature

strong

hydrophilic

ionic aqueous liquids or liquids and / ionic or polar

Solvent

arnrrrisph or moderately amphoteric

hydrophilic

cationically strong

hydrophobic

ionic or non-ionic

non-ionic

aqueous liquids and / or polar solvents

organic solvent sandstone

anionic

limestone

cationic

Sandstone

anionic

Reduced water permeability, increased oil flow or increasing the viscosity of aqueous liquid

Decrease in water permeability, increase the flow of oil or increase dea? Viscosity of the aqueous liquid

Increasing the water permeability or increasing the viscosity did of organic fluid

anionic moderate hydrophobic not- organic Kalk- kat & or Hgffh increase in VJasser- or Ionic solvent stone rhirrhiBRerigrlrA-ih cAern amphoteric Increasing the Vis viscosity of organ shem fluid

Continuation of the table

Polymer formation function

Attractive section Modifying section

Ionic strength of the main hydrophilic / ionic solubility type Adsorption hydrophobic natural properties borrowed

the polymeric sates nature

non-weakly hydrophilic non-aqueous fluent sand increase the

ionic or ionic liquids and / or stone viscosity

none or polar or watery

Solvent lime liquid

stone or diversion

the current

_c> . of watery

_ω liquid.

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According to a preferred embodiment, the invention relates to a simple one step ^ single phase or single agent treatment process to modify the surface properties, the wettability or the fluid flow properties an earth formation, in particular a subterranean formation through which a borehole has drilled such as an oil or gas production well. The treatment can also be carried out so that the branched polymer is grafted or formed in situ. This treatment is essentially permanent and highly stable to Acids, oxygen and temperatures up to at least 93 »3 Ms 177 ° G. For some preferred polymers even higher temperatures are permissible. Furthermore, the treatment is in the presence of most electrolyte solutions very stable such as salt solutions or sols, which normally affect other polymers, e.g. polyacrylamides and derivatives, which were previously used for such treatments. These acrylamide polymers have a tendency to in desorb or degrade the formation. In this treatment procedure is a certain class of branched, organic polymers with a molecular weight in the range of about 900- 50,000,000 in a liquid carrier medium, preferably an aqueous, liquid phase brought into contact with or applied to the formation. The polymer carrier liquid can also be a Emulsion, aqueous solution of inorganic salts, a hydrocarbon fluid, a polar solvent such as polar and / or oxygenated hydrocarbons or mixtures be of this. The polymer has certain ionic and hydrophilic properties. Depending on the desired Surface properties or wetting characteristics of the treated earth formation or particulate Formation, the polymer can be nonionic, amphoteric, neutral, anionic, cationic or a combination of these Have properties. For treating most sandy

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A cationic polymer is preferred for rock formations and, in particular, of underground, oil-supplying formations. For some formations, for example formations with a high concentration of carbonates, an anionic polymer or an amphoteric polymer is preferred. If weak or reversible adsorption is preferred, nonionic polymers can be used, for example for polymer flooding or in tertiary flooding to change the mobility ratio of fluid phases in the formation. The ionic polymer preferably has a calculated ion concentration of about 5 ^× 10 to 1 χ 10 or preferably 5 × 10 to 1 χ " ^-3 ion sites per gram atomic weight.

The ion concentration of certain preferred polymers is calculated so that the number of charges in the form of ionically charged atoms, residues or groups including both the backbone chain, the pendant groups and the branched chains are added and then these Charge number by Graimn atomic weight or molecular weight the repeating polymer unit or the representative Section of the polymer is divided. This gives the number of charges per representative unit weight of the Polymer. For example, polyethylene amine has a nitrogen on each repeating polymer unit, e.g.

■ 4 —NA ₂ ~ - ° ^H 2 - ° ^H 2 ~ "^ ~»

one positively charged nitrogen atom or cation per repeating Unit and a molecular weight of 44, this gives a charge density of 1/44 or about 2.3 x 10 ". This The calculation does not include the counterion (A "). For polymers such as polyalkylamines, the ion charge or the degree of ionization can be determined by adjusting the pH, using the solvent

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tel or salts in the solvent varied or changed will. For purposes of calculating the ion concentration, all atoms, residues or groups that normally can receive charges under certain conditions of use, as charge carriers for the calculation "considered unless settings for ionizing some groups would deionize or interfere with others would.

In another example for calculating the charge density for a branched copolymer of units A, B and C, like a polymer of the following formula results in:

CALCULATION OF GRAM ATOMIC WEIGHT OR MOLECULAR

Polymer unit

A B C

WEIGHT

Molecular weight Number of units weight in the polymer

58
5263

1000 114 000 Average 1000 58 000 Gram atom 10 ? 2 630 weight or 224 630 Average Molecular weight

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CALCULATION OF THE NUMBER OF CHARGES PER UNIT

Polymerizat- charges number of one-number of units per single-hex charge unit

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A 2 1,000 2,000

B 0 1000 0

C 1 10 10

2,010 total average number of loads

Average charge concentration = 2010 charges / 224 weight = 8.9 x 10 ~ * charges per gram atomic weight

A preferred type of branched polymer has an essentially linear backbone chain or an essentially linear backbone with reactive sites on which branched chains can be bound. This essentially linear skeleton can be a homopolymer or a copolymer with the reactive sites in the skeleton chain or the pendant groups. The term "essentially linear" as used herein encompasses polymers with pendant groups which are no more than about two polymer units in length. The monomeric units of this backbone chain can be aliphatic or aromatic, or contain hetero groups or combinations thereof. As used herein, the term "homopolymer" means a polymer made using monomers having a concentration of at least about 98 % of one type of monomer, and the term "copolymer" includes polymers made using more than one type of monomer in concentrations of at least about 1%, ie in substantial proportions.

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The term "copolymer" includes copolymers and terpolymers etc., which have 2-8 types of monomers in different concentrations, or homopolymers, in which some monomeric units or polymeric units have been derivatized, for example hydrolyzed acrylamide. Both homopolymers and copolymers or sections thereof can be used in a single-stage, regular or statistical polymerization of monomers, oligomers, polymers or mixtures thereof or by multi-stage polymerization of monomers, oligomers, prepolymers or mixtures thereof. That branched Polymer can be randomly polymerized sections, regular polymerized sections, block polymerized sections or combinations thereof. The branched polymer or sections thereof can according to any or prepared by any number of conventional batch or continuous polymerization processes or it can be polymerized in situ, for example in an earth formation where it is to be deposited or applied will. The effectiveness of the branched polymer for a specific application, its structure and Its viscosity, the degree of branching, the length of the polymer chains are compared to the polymerization conditions and the tight limits of controlling factors such as temperature, diluents or solvents, the Sensitive to pressure, pH, electrolyte type and concentration, agitation and other normal variables. Each branched chain can be essentially linear or branched in itself or the following still specified, have the desired degree of branching. The stability of the branched polymer is a function of the polymer links and the environment to which they are exposed. The polymer should be exposed to high levels Temperatures, acids, oxidizing influences, hydrolysis and shear must be stable. For WOR applications is a high stability he wishes. For other uses such as gelling

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of acids, the polymer need not be as stable over long periods of time. Preferred backbone bonds include the bonds C-C, C-N-C, C-O-C and combinations thereof. The stability the ties of the branched chain and the attached chain Groups is also critical and there should be high stability for most applications. To change the Fluid flow properties in formations include certain preferred branched polymers, polyamine and polyether linkages in the chains. It is assumed that branching also increases the backbone stability of certain polymers such as those containing ester linkages. Certain, preferred polymers with C-C bonds, ester bonds and polyether branches surprisingly remained effective at temperatures above about 177 ° C. this results in a preferred polymer with high stability. In the carbon-to-carbon bond, the are ionic Groups and the hydrophilic or water-solubilizing groups in the pendant groups or branch chains. At least one should be used for adequate water solubility ionic or hydrophilic group are present on each about five or six carbon atoms. This means that the ratio of carbon! heteroatom or the group ratio less than should be about 7: 1. The type of ionic or hydrophilic Groups and the type of carbon or hydrocarbon groups present affect solubility and the ratio of carbon atoms to hydrophilic groups. A preferred class of polymers are water-soluble polymers, but not all polymers have to be water-soluble depending on their application or function. As used herein, "water solubility" means a solubility of at least five parts per million (tpm), preferably about 1% by weight, in an aqueous liquid. For polymers which are to be ionically bound to a charged formation or structure to be treated, must the polymer in a * liquid or a fluid at least

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at least dispersible and at least partially in the presence a solvent such as water, a polar solvent, or mixtures thereof can be ionized. The usage of hydrocarbon liquids, substituted or polar hydrocarbons such as oxygenated hydrocarbons can be beneficial. These hydrocarbon solvents include alcohols (methanol, ethanol, isopropanol), Glycol ethers and ethylene glycol and the like. Readily gasifiable carrier liquids which are advantageous include without limitation carbon dioxide, ammonia, nitrogen, hydrocarbons or substituted hydrocarbons with low molecular weight. These materials can also be used as an easily gasifiable component of a liquid System or as the main component of a fog or foam carrier. These liquids or fluids can be used as solvents, carrier fluids, pre-wash solutions, Post-rinse solutions or combinations thereof are used, to bring the polymer in place or to suspend it. The degree of branching, the networking, that Molecular weight and steric configuration must be also taken into account together with the chemical components, e.g. hydrophilic groups and the ionic nature are related to solubility, attraction, repulsion, suspending, adsorption and other properties to determine what the degree of binding or adherence to the formation or suspension in a fluid continue to determine the fluid properties including the adsorption, hydration and resistance or increase of fluid flow for either aqueous or organic fluids or liquids. For some applications it can be advantageous to use a polymer or parts thereof to have available which solids, the surrounding formation and / or other polymer chains repel, suspend-

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ren or disperse. A polymer with a high molecular weight xond a high concentration of hydrocarbon groups has a tendency to form a fluid of high viscosity and poor solubility in an aqueous liquid. Such a polymer could also be soluble or dispersible in organic fluids. A high Concentration of hydrophilic groups has the tendency to increase the water solubility, the hydration or of solvation. It is believed that at a given molecular weight a highly branched, hydrophilic Polymer has a tendency to trap or influence more water than a more linear, hydrophilic one Polymerizate, and it would hydrate or swell more effectively to increase the viscosity of an aqueous liquid, in which it was dissolved or with which it came into contact during attachment to a formation or structure. This means that random, branched polymers would or would have a larger hydrodynamic volume would associate with more water and would be more effective at reducing the flow of an aqueous liquid. However, a polymer with longer, hydrophilic branches would be more effective for gelling aqueous liquids or to lower the WOR value as a polymer with shorter branches, especially in the case of highly permeable formations or formations with larger pores.

For polymers with high solubility in aqueous liquids or those with high ion concentrations, it is advantageous to if heteroatoms or hetero groups such as nitrogen, oxygen, phosphorus or sulfur atoms, carboxyl, carbonyl, Carbinol, cyano, ether, acetal, carboxyamide, alkylidene, alkylene groups or substituted aromatic groups in the branched polymer are present. The aforementioned first eleven atoms or groups are preferred. Heterogroups and branched Chains should be according to the desired stability

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to be selected. They can also be arranged so that the stability of the polymer for some applications is lowered, for example by hydrolysis, attack by acid or oxygen or by thermal decomposition.

In a process for the production of the branched polymer, the backbone chain must contain reactive sites, those with a corresponding, reactive place in the monomer or in the branched chain that are bound should be able to react. The branching can also be achieved by homopolymerization, in which the monomer with other monomers, oligomers or polymers for statistical formation of branches or a branched polymer as in the case of certain alkylene imines, (e.g. an aziride to form PEI), in which the alkylene groups preferably contain about 2-3 carbon atoms, reacted. In another method, the branched chain can be attached to a monomer unit, and then one type or mixture of monomers is polymerized to form the backbone chain, branched chain, or both. The branching can also be brought about by the fact that a branched polymer chain with a linear one Backbone chain, a weakly branched backbone chain or a backbone chain having pending groups implemented or is grafted onto it. The branched chain can by corresponding, reactive places on the linear Backbone chain or the assumed pendant chain or a pendant group of the branched chain. After the branched chain or monomers for the branched chain have been bound, the reactive Place can be regarded as no longer responsive. As with the backbone chain, the branched chain or the pending groups - but without limitation - heteroatoms or hetero groups such as oxygen, nitrogen, phosphorus or Halogen atoms, hydroxyl, carbinol, acetal, hydroxy, alkoxy, alkepoxy, carboxyl, ester, keto, cationic

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Salt, amide, amine, imide, imine, other nitrogen groups, similar sulfur groups, unsaturated and cyclic carbon-to-carbon or have carbon-to-heteroatom bonds. The term "hetero" or "hetero group" used here includes metals such as alkali metals (group IA), alkaline earth metals (group IIA) and metals of groups III, IV, V and VIII of the periodic table such as lithium, sodium, potassium, copper, rubidium, silver, cesium, magnesium, calcium, zinc, Strontium, cadmium, barium, aluminum, titanium, zirconium, cerium, molybdenum, lead, vanadium, arsenic, antimony, bismuth, Chromium, tungsten, manganese, iron, cobalt, nickel and combinations thereof. The branched polymer can also by converting or polymerizing one or more monomers to reactive sites in or on the backbone chain with the formation of branches at different locations of the backbone polymer and / or on different ones branched chains of random length can be produced.

In one method, the reactive sites can be in the polymer backbone, the branched chain, or the monomer be any atom, any residue or any group which is associated with a corresponding, reactive Group in the backbone chain, the branched chain or the monomers react to form the branched chain to tie to the backbone chain. During the formation, branching or grafting of the polymer, at least one must be reactive There can be space in the backbone chain to tie a branched chain, however, one or more reactive sites must be present in the branched chain, provided that the networking is not a significant problem. The reactive site or sites can be viewed as a means of branching. That Branching agent can also be a complete mono-

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mer or polymeric unit with one or more reactive Be places which with the formation of the branched polymer according to the invention or a part thereof reacts or polymerizes. Especially for in-situ grafting or polymerization becomes the branching agent as a monomer, oligomer or polymer and not just viewed as a reactive site or group, such as epichlorohydrin, bound to the branching or crosslinking polymer. A little networking can be tolerated, and in special cases such as low ionic attraction, high porosity of the formation and high temperature of the environment is extensive networking along with branching for stability and performance, in particular for reducing the WOR value, for cementing, for diverting currents, etc. advantageous. That However, the polymer obtained should still be soluble in water.

The reactive sites can be selected from one or more of the following chemical groups to react with a appropriate, reactive place can be selected: (1) alcohol, (2) aldehyde or ketone, (3) alkene, (4-) alkyl halide, (5) alkyne, (6) amine, (7) an acid or an acid equivalent including an ester, anhydride or of an acyl halide, (8) amide, (9) epoxide, (10) acetal or ketal, (11) nitrile, (12) sulfides and similar or equivalents, reactive groups.

It should be noted that the effectiveness of branched polymers to reduce the water flow and / or to change the properties of an aqueous liquid appears to encompass several molecular variables. Special Characteristics can be built into the branched polymers in order to satisfy the various applications.

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genes, for example the extent of branching, the length of the chains, the ionic nature of the backbone and the branching, the molecular weight of the backbone and branches and the degree of crosslinking.

To bind the polymer to particulate solids, it is generally preferred if the predominant ionic charge reacted on the surfaces of a substrate or solid with a branched polymer which has opposite ion charges in the backbone structure, however, the feasibility is on does not limit this mechanism. Branched polymers with a higher molecular weight also have the Tendency to adhere to surfaces which have the same predominant surface charge as the polymer. Some degree of crosslinking of the branched polymers also appears to increase this molecular weight and to give this improved property. The mechanism or mechanisms involved in coating occur on this surface have not yet been fully elucidated.

Greater efficiency in reducing water permeability becomes with a higher degree of branching and with the higher molecular weight of hydrophilic branches and backbone structures related. A certain Crosslinking can be beneficial because of the molecular structure is enlarged. However, there must still be enough open-ended branches in order to reduce the water pumping and / or bring about mobility.

To bind to predominantly anionic sandstone formations (silica deformations), certain, preferred, polymeric Structures have sufficient cationic places (+) - places in order to strongly attract the polymer

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the sandstone surfaces or other particulate pests (with anionic surface properties). These strongly cationic polymers stabilize also clays and fine parts within a surface or an underground structure, while they are the desired ones Properties (as previously described) in the formation or in the particulate pesticides result. These polymers stabilize sensitive formations such as clay-containing formations, so that these against swelling, dispersion, erosion, or other damage from fluids such as hydrocarbon fluids (especially gas), aqueous liquids or other fluids of the formation are less sensitive, whereby these result in migration, clogging or other types of damage with a reduction in permeability could. These polymers also increase the stability of a resin-hardened or consolidated formation. These polymers can also change the surface properties of particles such as sand, silicon dioxide powder, Increase asbestos and the like.

In another case, it is advantageous to mix predominantly cationic, particulate solids, which are composed of calcareous components, with cationic (+) surfaces, e.g. CaCO ₅ , CaMg (COz) ₂ (dolomite), FeCO ₅ (siderite, etc. ) are treated with polymers which have a sufficient amount of anionic (-) - sites in order to obtain a strong attraction of the polymer to the solids. Limestone formations are representatives of the calcareous structures described above.

Formations often contain particulate solids of varying or mixed compositions and ionic surface properties. The formations can be treated separately with two or more types of polymer be, for example a treatment can be a

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cationic (+) polymer structure to promote attraction on the anionic (-) surfaces (sand, clay, silicon dioxide, etc.). Simultaneous or subsequent treatment Polymerizate contained with an anionic places can be applied to a strong attraction to the cationic To bring about surfaces. The example above describes a method for treating a formation with different ionic surfaces. Branched polymers with different ionic groups or mixtures of different ionic properties can also be used in a formation with a predominantly ionic character. Alternatively, an inventive Polymer contains anionic, cationic or other types of ionic groups, sections or segments, so that formations mixed with. Compositions or under different formations of varying nature with one Type of polymer material that can be treated in one or more application stages. However, the invention encompasses also other working methods and modifications that reflect the basic concept.

For some applications it is advantageous if the polymer molecules have little or no chemical crosslinking are characterized by polymeric segments. Some networking can be beneficial in other cases. The polymers must have sufficient hydrophilic properties to allow a certain degree of thickening of aqueous liquids bring about. In general it was given at a Family of branched polymers observed that polymers with higher viscosity are more effective than those are of the same family with lower viscosity at the same concentration.

For certain, preferred polymers, the backbone or framework, if definable, can be linear, branched, irregular

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moderately shaped or in any other configuration and can be composed of a homopolymer or copolymer structure. It must be sufficiently responsive There should be places on the framework or the backbone to chemically bond the desired polymeric chains. Side chains can also be represented by a homopolymer structure or copolymer structure, and they can have a linear, branched, irregularly shaped, or other configuration. The branched chain can also be bound to pending groups of a polymeric backbone or skeleton. The polymeric structure obtained must have the required ionic charges, the required flexibility and the required balance, to facilitate the strong and long lasting ionic bond between it and the particulate solids. she should provide sufficient hydrophilic (water-attracting) segments of sufficient ionic nature to produce a significant to bring about effective resistance to the flow of aqueous liquids through porous media, while this creates little or no resistance to the flow of hydrocarbons will. The polymeric material can also have long lasting surface properties on the particulate solids bring about, for example, the promotion or increase of oil flow by increasing the oil permeability. Polymer structures should have the following additional properties: The ionic property of the polymer can be of one or more types, e.g. a polymeric molecule can only have cationic properties possess, while another polymeric structure is non-ionic, may have cationic, anionic, neutral, amphoteric segments or combinations thereof. An influence on the interior or ion interaction within the polymer or between Iblymerisaten can cause problems with different Create types of ionic segments.

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For a preferred class of highly branched, water-soluble, cationic polymers, the backbone or Framework the cationic groups or radicals and the branched chains can contain additional groups, amphoteric groups, contain non-ionic groups and / or a neutral group. For substantially linear backbone chains, the molecular weight of the backbone should be in the range of about 1000-5 Be 000 000.

The polymer unit of the branched chains can be one or be several of the polymer units given for the polymer backbone chain. As previously indicated, the branched Chains contain the same polymer units for randomly polymerized homo- or copolymers. For randomly polymerized backbone chains, branched chains, or both, the polymer chain can be arbitrary be selected so that even the branched chains still have branches. For graft polymerizations or for the separate binding of the branched chain to the backbone chain, the branched chain can also have multiple branches have, which are bound by one or more reactive sites. The branched chains can further comprise different random polymer units, which consist of one type of repeating Unit or one or more different repeating units can be constructed. Branched chains can also on the polymer backbone in graft polymerized in a separate polymerization stage be. More than one type or length of branched chain can be grafted onto the backbone chain. The branched The chain can also be another homo- or copolymer chain be, which has a responsive place that is in a corresponding, responsive place binds in the backbone polymer chain. The molecular weight range these branched chains can be about 100-5,000,000 or preferably about 300-1,000,000 for water

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soluble polymers to reduce the WOR value or for aqueous liquids be gelling polymers.

The polymer chain can have hydrophilic or hydrophobic groups, oleophilic or oleophobic groups, hetero groups and / or contain ionic groups including amphoteric, nonionic, cationic, neutralized or anionic groups. Either the polymer backbone or the branched one Chain or both can include ionic groups. The number or concentration of each of these groups, theirs Arrangement and the surrounding medium, solvent or fluid determine the overall properties and the effect of the branched, organic polymer. The branched polymers according to the invention can be prepared by conventional methods be prepared as described in the aforementioned publications. The backbone chain, the branched one Chain or both can be regular homopolymers, random copolymers of two or more monomers, Block copolymers, segmented, random copolymers or combinations thereof.

The branched polymers according to the invention can have a molecular weight in the range from about 900-50,000,000. The molecular weight is generally not critical, except for a minimum value for each family of polymers depending on the application and the other polymer properties such as the degree of branching, the ionic nature, the degree of crosslinking as well as the desired effectiveness and stability. The higher the molecular weight, around the more effective the polymer is in general for increasing the viscosity or reducing the permeability versus fluid flow. Polymers with a molecular weight close to the lower, critical limit for a given application may be effective for a short period of time, but are generally less stable against

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via harmful fluid flow or adverse conditions. A higher degree of branching and / or networking makes the lower molecular weight polymers are generally more effective for most applications. Preferred Classes of branched polymers have an average molecular weight of about 100,000-5,000,000 for most Applications, higher viscosities in aqueous liquids are with molecular weights up to about 10,000,000-15,000 achieved. Polymers with molecular weights of about 10,000-2,000,000 are effective for various purposes, and they are easier to handle than high molecular weight polymers. For certain applications where high viscosity or high effectiveness are not critical, or for less permeable formations, polymers can be used lower molecular weight such as 1,000-9,000,000 can be used. Some polymers can still be used for one easier handling and / or used for greater effectiveness and branched or networked in situ.

The backbone polymers can have a molecular weight of about 800 to nearly 50,000,000, preferably about 1,000-5,000 for a reduction of the WOR value, as well as of about 10,000-10,000,000 for use as a viscosity enhancer for aqueous liquids or as a fluid loss regulator. These backbone polymers can be used to produce branched Polymers with a molecular weight of about 9,000-9,000,000, about 100,000-20,000,000 or even higher than 50,000,000 depending on the number and size of the bound, branched chain and the extent of crosslinking, if available, can be used.

The branched chains can have molecular weights up to about 1 million or even higher, if generally the Chain is highly hydrophilic and is itself highly branched. A class of preferred, branching polymers before Binding to the backbone has molecular weights of about

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300-50,000. For greater effectiveness in terms of the WQR value, a higher molecular weight and a higher one Degree of branching "preferred, even up to a molecular weight of about 100,000 or even about 1,000,000.

With more soluble, more highly branched or compact polymers are polymers with a higher molecular weight preferred as they are generally more effective and can be handled in an acceptable manner. The networking either during preparation or in situ can actually increase the molecular weight of the branched polymer. This crosslinking can take place during the batchwise or continuous preparation of the branched polymer or in situ occur when the branched polymer is applied to a formation. The degree of crosslinking limits the extent of the Water solubility or water dispersibility, as the polymer becomes less soluble or dispersible with increasing crosslinking and forms a stiffer gel structure. the Gel structure is great for some uses such as plugging or sealing formations or cementing or Filling with pebbles of voids or zones of high permeability around pipes such as boreholes, taverns, Tunnels, pipelines and the like are advantageous. The limiting factor regarding the molecular weight of the backbone polymer, the branching chain polymer and / or the branched organic polymer obtained is the maximum fluid viscosity that will be used in the manufacture, mixing, and placing-in-place of the Components and / or the polymer obtained can still be handled.

The branched chains of the polymer can be any polymeric group which has the desired hydrophilic-hydrophobic properties as well as having a reactive group associated with the reactive places

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enters into a connection on the backbone chain. The responsive The group is preferably at one end or near one end of the branched chain, but it can also be any are in the chain or in a pendent group. For a preferred class of polymers used to reduce the flow of water through earth formations or to reduce the production of water in an oil well are used, the branched chain and the entire polymer should be hydrophilic, the branched chain of about Has 2-50,000 repeating polymer units. These branched chains can themselves be practically linear or branched be. In some cases, multifunctional or difunctional, branched polymers can be used, which have terminal reactive groups, if a reactive group for prevention or reduction the networking can be masked or inactivated. A certain degree of networking, for example of about 5% »can can be tolerated and is even advantageous for certain applications. Several preferred groups of branched polymer chains are polyalkyleneimines and polyalkylene oxides in which the alkylene radicals have about 1-3 carbon atoms contain. Examples of other monomeric units used to form the branched polymer chains are: acrylamide, acrylate, vinyl alcohol, vinyl ether, hexoses, allyl alcohols, allylamines, substituted derivatives thereof such as sulfonated acrylamide, also copolymers and combinations thereof. In general, monomers, Polymers and polymer units which can be used for the backbone chain, for the branched one Chain can be used.

For one type of preferred, hydrophilic, branched polymer, which are used as viscosity agents, to lower the WOR value or to lower the flow of aqueous Liquids in or within a formation are advantageous

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are, the predominant ionic groups are preferably cationic groups in or near the backbone chain. The preferred, repeating units of the polymer branch are -Sr- CH ₂ -CH ₂ —0 -} - »

- OH ₀ —CH ₀ - or combinations or substituents here-

C. C.

from. These preferred polymer units can be used as

in which R has the definition given here and X represents a hetero group such as nitrogen, oxygen or sulfur with at least two bonds. The aforementioned R group is the C ₂ -alkyl radical ethylene. X can also be another R radical, absent, or within the R group. These chains are preferably monofunctional or more reactive at one end so that they can be capped or terminated at one end by a relatively non-reactive group and at the other end by a branching agent. These ^ -RX ^ radicals can be acrylate, acrylamide, vinyl alcohol, methyl vinyl ether, a C ^ -C ^ -alkyl, aryl, combinations thereof or combinations thereof with hetero groups, in particular through one of the aforementioned heteroatoms such as a C ^ -Cg -alkyl radical with stapler groups be. Examples of preferred, terminal groups are alkoxy groups, for example -OCH ₃₅ , -OCHp-CH ;, and aroxy groups, for example

Commercially available monomers, equivalents or polymers containing them (either homopolymers or Copolymers ^ those for the branched polymers (either in the backbone, the branching or in both Proportions) according to the invention can be used are acrylic acid, acrylic ester, methacrylic acid, methacrylate ester, Maleic anhydride, itaconic acid, 2-acrylamido-2-methylpropane sulfonic acid, Acrylonitrile, sodium vinyl sulfonate, sodium styrene sulfonate, diraethylaminoethyl methacrylate, allyl sulfonate, Vinyl acetate, methacryloyloxyätliyltrimethylammoniummethosul-

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fat, alkenes, vinylacetamide, vinyl ethers, vinyl phosphonates, Vinyl phosphates, vinyl phosphines, diethylaminoethyl acrylate, ^ -Methacryloyloxy ^ -hydroxypropyl-trimethylanunonium chloride, 4-vinylpyridine, 2-vinylpyridine, N-methyl ^ -methyl ^ -vinylpyridiniximmethosulf ate, 1,1-dimethyl -1- (2-hydroxypropyl) -

aminomethacrylamide, dimethyldiallylammoniurachloride, diallylamine, Triallylamine, methyldiallylamine, diallylammonium salts, beta-Acryloyloxyäthyldimethylsulfoniummethosulfat, ethylene oxide, Propylene oxide, Ν, Ν-disubstituted methacrylamides, N-substituted methacrylamides, methacrylamide, Ν, Ν-disubstituted Acrylamides, N-substituted acrylamides, N-vinylpyrrolidone, acrylamide, diacetone acrylamide, ethyleneimine, Propyleneimine, ethylene chloride, reacted with ammonia, 1-vinyl-2,3-dimethylimidazolinium methyl sulfate, N-vinylimidazole, glycidyl alcohol, epichlorohydrin, glycidyl methacrylate, vinyl carbonate, Allyl glycidyl ethers, isoprene and chloroprene.

Conventional methods of polymerization, for grafting or for branching and for handling can be used to prepare and apply the polymers according to the invention, reference being made to the teachings of the publications cited here. Typical polymers, polymerization procedures and methods of use are described in the following US patents and other patents: RE 29 595 by Adams et al., 2,223,933, 2,331,594-, 2,345,713, 3,500,929, 3,822 74- 9 and 4- 058 491, which are hereby incorporated by reference. A preferred method for formulating a cationic, branched polymer according to the invention is the solvent method using an aqueous medium which contains a high concentration of electrolyte such as an alkali metal halide, preferably sodium chloride or potassium chloride. In this preferred method, the reaction conditions should, _t is time and stirring are controlled so that the branched polymer of the desired MoIe-

030015/0842

29391U

kular weight and the desired structure without a no permissible mechanical shear of the polymer chain or disturbance of the reaction is formed. For higher values of the With stirring, the reaction time should be extended in order to form the desired polymer size and structure. That Molecular weight, structure and effectiveness of the branched polymer obtained for a particular Application are against the reaction conditions and the conditions to which the polymer is exposed, including the pH value, the temperature, the pressure, the time, the contaminants, the solvents or diluents, electrolyte, concentration, agitation and other typical variables. Typical working methods are described in more detail under the following manufacturing methods. The aforementioned References also describe various solvent and aqueous emulsion procedures and organic phase that can be applied.

The polymers used in accordance with the invention can be used with most particulate solids or formations either by spraying, pouring or adding the polymer directly to the formation or particles can be applied. The polymer can be in a suitable liquid phase or a suitable liquid Medium adjacent to the formation to be treated in place and the liquid phase can in the formation can be allowed to enter, pressed in, injected or pumped, so that the polymer the formation or the desired portion of the formation to change the wettability or surface properties the formation contacted or treated as required. Particulate material, e.g. Sand, silica powder and asbestos can also be added to the polymer or to a liquid containing the polymer

030015/0842

29391U

fluid can be added or suspended therein. For an oil well this can be achieved in a simple manner that an aqueous, organic or mixed liquid phase containing the polymer is brought adjacent to the formation to be treated and the liquid phase containing the polymer is brought into the formation by displacement or by injection is introduced. The carrier fluid or the carrier liquid can be any gas, liquid or solids or mixtures thereof such as foams, emulsions or slurries. The treatment of a subterranean formation by an oil well can be achieved by using one or more liquid spacer fluids, pre-wash fluids or post-wash fluids such as a dilute saline solution, preferably an ammonium halide and / or an aqueous alkali metal halide solution, in the formation for pretreatment or cleaning of the formation and then the liquid phase containing the polymer in a concentration of up to 10 % and preferably from 0.005 to 1.0% is injected in the calculated amount to form the desired portion of the formation with the liquid phase and the highly branched, ionic polymer to bring in contact. In some cases, a pre-rinse solution containing a diluent such as a surfactant, a nonionic polymer, or an ionic linear polymer that is adsorbed on the formation can be used to displace the branched treatment polymer away from the wellbore or To enable formation surface. This pre-flush actually uses up ion sites in the formation and enables the branched polymer to pass through this zone with minimal treatment by the branched polymer. This diluent treated zone would normally have a high permeability to water. The Ver-

030015/0842

-136- 29391U

The branched polymer would then form the adjacent formation zone treat. This would create a zone of high permeability to water between that treated with branched polymer Zone and the oil well. This would actually be the effective radius or diameter of the branched Increase polymer treated area around the borehole. The polymer can be in a liquid phase, which is a aqueous phase, an organic phase or a substituted hydrocarbon phase such as an alcohol, ester, ether, Ketone, aldehyde, amide phase or an emulsion or a mixture of two or more of these liquid phases with water or another organic liquid. A foam carrier can also be used. the Carrier or other fluid phases can be acidic, basic or be neutral. Acids or acidic carrier fluids can also be used.

If appropriate, the polymer can also be used as a carrier in an aqueous acid or an aqueous salt solution. A preferred acid carrier can be up to 37 ° / ° acid such as a mineral acid, organic acid or mixtures thereof such as hydrochloric acid, hydrofluoric acid, acetic acid, fumaric acid and the like. Other preferred acid concentrations are: up to about 28 % and 15-28% for fracturing acid treatment, 3-5% for fracturing acid treatment with a sealant such as sand, and 0-5 % when used in WOR control treatments. acidic carrier should have a pH adjusted to below 7 or 6.5 with a suitable mineral or organic acid or an equivalent thereof such as hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, hydroxyacetic acid, amidosulfonic acid, citric acid, fumaric acid, oxalic acid or sodium dihydrogen phosphate. Possess value. Acid Generating Compounds, Equivalents

030015/0842

or precursor compounds can also be used, for example ammonium bifluoride, acetic anhydride and Methyl formate. For higher concentrations of certain polymers, the high viscosity and the pump pressure become a problem. The carrier liquid or the carrier fluid can be one or more acids, diluents, Solvent or other liquid phases contain as a carrier fluid or be injected in sequence with the carrier. if the branched polymer is mixed with an acid or an acidic liquid, the mixture for one or multiple functions such as breaking, acid treatment, acid breaking or removing unwanted items Material such as crusts, carbonates, rust and other clogging materials from boreholes, pipelines, a formation or process equipment can be used. In some cases, the branched polymer could be designed so that the cleaned surfaces are treated like a particulate formation. This treatment with Branched polymer can also serve to prevent the deposition or formation of certain harmful materials such as paraffin, crusts, carbonates, rust and the like. Some branched polymers can also serve to lengthen the acids or to inhibit, in other words, the polymer extends the for a given Concentration of the acid required time to react with a given amount of substrate. this makes possible a deeper injection of an acid containing the polymer into a formation before the acid is depleted and allows for reaction with material deeper in the formation. The carrier liquid can either a water-in-oil emulsion or an oil-in-water emulsion and the carrier fluid may optionally contain ingredients such as particulate material used in breaking up, surfactants compatible with the polymer, inhibitors and diversion agents. The poly

030015/0842

merisate can be mixed with other polymers or additives, so that at the same time more than a treatment is carried out. Because "certain preferred polymer treatments are essentially permanent and are stable to saline and most acids, these polymer phases can come out of the borehole displaced or within the treated formation using additional carrier fluid, Acids, aqueous or organic phases are shifted. In addition, the treatment can be in a or in several treatment phases with different spacing fluids or liquids or other types of treatment fluids or liquids carried out between the liquid phase containing the polymer will.

For use in borehole fluids such as drilling, at finishing, testing, cementing, or in cementing compositions is a preferred vehicle an aqueous liquid. This liquid preferably has a basic pH value or a pH value greater than about 6.5 or 7, and preferably above about or 12. The pH of most portland cement compositions is above about 12. In these liquids, the branched polymer can be used to treat formations in contact with the fluid or to treat the fluid itself, i.e. to reduce it the loss of fluid, to increase the viscosity of the fluid and to gel the fluid.

Polymer units, which for the branched polymers can be used according to the invention, can generally be of any type of polymer unit, which are bonded to other polymer units of the same type or of a different type in order to obtain a

030016/0842

* 29391U

to form branched, water-soluble polymer. The polymer units can preferably be produced or derived from one or more classes, these comprising: (1) vinyl monomers or diene monomers which form a chain with a carbon-to-carbon bond which can contain a double bond, (2) Diallyl monomers, which can form a cyclic or heterocyclic section in the polymer chain, (3) monomers of the imine or amine type, which produce nitrogen atoms in the polymer chain, (4-) monomers of the amide type, which contain nylon units and polymer units of the protein type, (5) Saccharide monomer units, polymers and derivatives thereof which include starches, guar resins, xanthan gum, cellulose and derivatives thereof, (6) ethers and sulfides which include oxygen and sulfur in the polymer chain, (7) carbonates which include the carbonate group in the polymer chain either in a linear chain or in a pendant group, and (8) urethanes containing the Include urethane linkage in the polymer chain either in a linear chain or in a pendant group. These polymer units can be present as a predominant class or combined in a regular or randomly distributed arrangement, in block combinations or in other various combinations. In the case of polymer units which are less soluble than desired in a particular fluid, other polymer units, substituents, certain branched chains or combinations thereof can be used in order to achieve the desired solubility and the overall polymer properties which are required for the intended purpose. However, the polymers according to the invention include those in which a significant proportion, at least about 0.1% and preferably 1 % of the branched polymer units are defined by the classes given above or at least one of the formulas mentioned above. The aforementioned polymer

030015/0842

29391U

units can be represented by one or more of the following structural formulas reproduced or explained,

Class I: Vinyl or diene polymer units can be defined as:

ι "

CR ₉ -J] -R fll

12th

^ l 3

16

.7

n.

where mean:

^R 4 » ^R 7»

^R 8 » ^R 10» ^R 13 »

_{1 2} 7 8 » ^R 10» ^R 13 » ^R 14 ^{and R} 16 independently of one another a hydrogen atom, an alkyl, alkenyl, alkynyl, aryl, acyl, cyclic carbon-hydrogen, heterocyclic hydrocarbon, hydroxyl, Carboxyl, carbonyl radical or the radicals
-OH ₁₉ , -NR ₁₉ R ₂₀₁ -SR ₂₃ , -SR ₁₉ R ₂₀ , X _A , or combinations thereof, which can also contain oxygen, sulfur, nitrogen or phosphorus, in which

X _{A is} -Cl, -Br or -NO ₂ ,

R ₅ , Rc, R ₆ , Rg, R ₁₁ , R ₁₂ , R ₁ ^, R ₁₇ and R _1Q independently of one another a nonexistent radical or alkyl, alkenyl, alkynyl, aryl, acyl, carbonyl, Carboxyl, aromatic hydrocarbon, cyclic hydrocarbon, heterocyclic hydrocarbon radical or combinations thereof, which can also contain oxygen, sulfur, nitrogen or phosphorus,

R ₁ O, R ₂₀ , R ₂₁ and R ₂₂ independently of one another a nonexistent radical or a hydrogen atom or an alkyl, alkenyl, alkynyl, aryl, acyl, cyclic hydrocarbon, heterocyclic hydrocarbon radical or combinations thereof, which also May contain oxygen, sulfur, nitrogen or phosphorus,

030015/0842

R ₂ , independently of one another, is a hydrogen atom in each position, an alkyl, alkenyl, alkynyl, aryl, acyl, cyclic hydrocarbon, heterocyclic hydrocarbon radical or the radicals M ⁺¹ , M ⁺² , M ⁺⁵ , M ⁺ \ ⁺ NR _y . ₍ ^ 20 ^R 2 "\ ^R 22 ^or combinations thereof, which can also contain oxygen, sulfur, nitrogen or phosphorus,

R ₂ ^ independently in each position an alkyl, alkenyl, alkynyl, aromatic hydrocarbon radical or combinations thereof, which also contain oxygen, sulfur,

May contain nitrogen or phosphorus, in which the radical R ₂ *. has two or more atoms bonded together with nitrogen to form a ring, M independently of one another in each position an ammonium radical or substituted ammonium radical, a metal ion or a mixture thereof, G ₁ , Gp and G, independently of one another, a non-existent radical, a hydrogen atom or the radicals -SO ₃ R ₂₃ ,

OO -OSO ₃ R ₂₃ , -PO ₃ R ₂₃ ^ R ₂₃ , -OR ₂₃ , -0-CR ₁₉ , -C-OR ₂₃ ,

or combinations thereof,

U ₁ , n ₂ and n, independently of one another, integers of

about O - 5OO 000, where n ₁ + n ₂ + n ₃ > 3,

each hydrocarbon radical independently of one another from 0 to 10 carbon atoms and optionally from 0 to 4 hetero groups of oxygen, sulfur, nitrogen or phosphorus, and

wherein the radicals attached to each atom and the structural formula thereof balance the bonds of that atom.

030015/0842

29391H

In the description, any unspecified bond or radical may be a hydrogen atom, a double bond, a cyclic bond, or, where permissible, one or the other structures described herein. The radicals or groups which have a numerical designation marked with a prime, eg R. «,, R ₂₀ I etc., are independently defined as the same radicals with the basic number not provided with a prime. With regard to this information, the person skilled in the art knows the radicals, bonds and structures which are suitable or possible for any combination to form a stable polymer configuration. For example, the structural formula of each polymer unit, each radical or each group can have internal atoms or radicals, internal bonds, more than one bond or different bond types in order to balance the bonds of adjacent units, radicals or groups. As used herein, the term "stability" means only that the structure and / or combination is possible or is a definition, and not that the structure has the capability of evidence or isolation. As used herein, substituted ammonium groups are defined as groups """NR.qR ^ R ^ R ^. The term" M "used refers to a cation and" A "refers to an anion whose charge is from can vary approximately 1-4.

030015/0842

29391H

Class II; Diallyl polymer units can be defined as:

where mean:

** 25 »^ 26» ^ 28 »^ 29 '^ 31 ^utl ^ ^ 32 ^utla ^ ⁿ ä ⁿ SiS of each other the same meaning as R ^;

Rp ₇ , RxQ and R "independently of one another an alkyl, alkenyl, alkynyl, aromatic hydrocarbon radical or combinations thereof, which can also contain oxygen, nitrogen, sulfur or phosphorus, each of these radicals R having two or more atoms bonded together with the has shown G group to form a ring,

, G ₁ - and

where R-4Q, Rpn ^utu * have defined,

independently of one another the residues

i 9 ^R 20 »

Sl ^e i ^cne importance as before

n ^, tir and n ^ independently of one another are integers of about 0-500,000, where η ^ + η ^ + η ^ > 3, and

the other suitable Class I conditions also applying to the Class II polymer units.

030015/0842

29391U

Class III: polymer units of the imine or amine type can be defined as:

34 j R

f35

37

36

n.

^R 39

40

Ml

R., I 43

n,

where mean:

jT) ^R 38 » ^R 41» ^R 42 ^{and R} 45 ^{independent of} one another

the same definition as

' ^R

from each other

35 * 36 '39' 40 '43
a hydrogen atom or an alkyl, alkenyl, alkynyl, aryl, acyl, carboxyl, carbonyl, cyclic hydrocarbon, heterocyclic hydrocarbon radical or the radicals -ORp 1, -NR ₁₀ R ₂₅ , -SR ₂₅ , -SR ₁ QR ₂₅ ⁺ , X * or combinations thereof, which can also contain oxygen, nitrogen, sulfur or phosphorus,

where R ^ q and Rp have the meaning given above,

Qn, ng and nq are independently integers of about 0-500,000, where n ^ + no + nQ ^ 3, and

the other suitable conditions for class I also applying to the polymer units of class III.

030015/0842

Class IV: Amide-type polymer units can be defined as:

NR ₄₁ -C- ^R 47

10

50

52 '53

54

12th

where mean:

^ / l6 »^ 4-7» ^ 4Q * ^ 5O * ^ S2 ^{un <} ^ ^ 53 ^una ^ ⁿ ängig each other the same meaning as R ^ with the exception for -OR ₁₉ , -M ₁₉ R ₂₀ , -SR ₁₉ , -SR ₁₉ R ₂₀ ⁺ and X _A , where they can also be radicals that are not present independently of one another,

R ^ jQ, R ^ ₁ and Rr /, independently of one another, have the same meaning as R ,, but provided that not all three radicals R can be non-existent radicals,

n ₁₀ , n ^ and n _{12 are} independently integers from about 0-500,000, where n ₁₀ + n ₁₁ + n _i2 £ 3, and

wherein the other suitable conditions for class I also apply to the polymer units of class IV.

030015/0842

Class V: Saccharic! And saccharide derivative units can be defined as:

* 13

where mean:

R ₅₆ , R ₅₇ ,

R ₆₁ * ^R 62

_{5 58} , R ₅₉ , R ₆₀ IR ₆₁ * ^R 62 ^ ^R 63 ^ dependent

from each other a hydrogen atom or an alkyl, alkenyl, Alinyl, aryl, acyl, carboxyl, carbonyl, cyclic hydrocarbon, heterocyclic hydrocarbon radical

or the remnants of M

+1

₊ 2 _{M +} 3

, a pentose unit, η, or combinations

a hexose unit, the remainder -OR ^ q of which, which may also contain oxygen, nitrogen, sulfur or phosphorus,

M has the meaning given above,

η ^ .χ, n ^ and nr are independently integers from about 0-500,000, where n. -z + n ^^ + n ^ c- £ 3, and

wherein the other suitable conditions for Class I apply to the Class V polymer units.

As previously indicated, conventional chemical terminology is used so that the carbon atoms are at the interface of the lines of the six-membered rings except where the oxygen atom (O) is indicated are shown. No specific stereochemistry or stereostructure should be determined by the structural formulas given. This means, that the structural formulas shown include all applicable variations and equivalents.

0300 1 5/0842

29391U

Class VI ; Ether and sulfide polymer units can be defined as:

I ^l 64 ~ f ~ " ^X B"

^k 66

16

f68

^R 67 y ^x c

^R 69

17th

72

where mean:

^ 64 »^ 67 ^{un <} ^ ^ 70 ^una ^ ^{> n} änsi6 each other the same meaning as R ,,

^ 6S ¹ ^ 66 »^ 68» ^ 69 »^ 71 ^{un (} ^ ^ 72 ^una ^ ⁿ ängig each other the same meaning as R, - with the exception of a hydroxyl radical,

Xg, X _Q and Xjj independently of one another are oxygen or sulfur,

n ^ jg, n ^ r; and n ^ o are independently integers from about 0-500,000, where ^tl i6 ^{+ n} i7 ^{+ n} 'i8 ~ ^, and

wherein the other suitable conditions for Class I apply to the polymer units of Class VI.

030015/0842

29391U

Class VII; Carbonate polymer units can be defined as:

-C-O

-R ₇₁ -OCO

20th

O = C-O- -

O I R.

C-O-

21st

where mean:

and

R ^
Meaning like

independently the same

ⁿ ° 1 / ^"n 20 ^{and n} 21 ^una khängig are integers from about 0 to 500,000, where n ^ + n ^ g ^ np + Q> 3, and

wherein the other suitable conditions for Class I apply to the polymer units of Class VII.

As previously shown, the unbonded bonds the polymer unit of type np, with another, be connected similar polymer unit, or each bond can be independently of one another with another Type of residue or polymer unit to be connected.

030015/0842

29391H

Class VIII: urethane or urea polymer units can be defined as:

22nd

O = C-NH-R ₀₁ -UX

where mean:

^R 76 » ^R 77» ^R 78 » ^R 79» ^R 80 ^{and R} 81 ^{independently} SiS have the same meaning as R ,,

• Xc, X ₆ , X ₇ and Xq independently of one another the groupings:

-0-, = HH ₁₉ , = HI ₁₉ or -S-,

ripp and up, independently of one another, integers from about 0-500,000, where ^ P ^ i - ^ " ⁵ ^ ^{un (} ^

wherein the other suitable conditions for Class I and Class VII are based on the Class VIII polymer units hold true.

The hydrogen atom bound to the nitrogen atoms can with another residue such as a ketone, isocyanate, acid halide, Epoxy and the like are reacted for further branching or crosslinking of the branched polymer.

030015/0842

29391H

Examples of polymer units within A.

f ^H 3

I. NH

CH ₂ f »2

C ₂ H ₅ C ₂ H ₅

n.

C = O

Lh

N (CH

HO-CH CH

CH CH

2 X,

OCH.

f ^H 3

-c-c

H C = O O

HO-

- "2

:H

n.

where are:

, R ₂ , R ₇ , R ₈ , R ₁₃ ,

= Hydrogen,

R ₄ , R ₁₀ and

-CH ₃ ;

R ₃ , R ₆ , R ₉ , R ₁₂ , R ₁₅ and R ₁₈ = nonexistent radical R ₅ = nonexistent radical R ₁₁ and R ₇ = carbonyl radical

G ₁ = - -C-NR ₁₉ R ₂₀ with = H and R,

^l 20

with

R ₁ = no presence of the remainder, R ₃₀ = H and R

= 20-700 and

21st

wherein

N ⁺ (C ₂ H ₅ J ₂ CH ₂ CH (OH) I

-OH.

23

R ₂₃ = • <CH ₂ f ₂ - ^ N (CH ₃ J ₂ CH ₂ CH (OH) CH ₂

wherein X ₂ = 20-700 and η _χ = 10-5,000; n ₂ = 0-20 n ₃ = 0-20, but n ^ and n, not both, can have the value zero.

030015/0842

-29391U

ff

-C-C-

kl

CH.

where are:

^R 3 ' ^R 5' ^R 6 '
dene leftovers,
₄ ,

~ ^0CH

^R 9 '

, R ₂ , R ₄ , R ₇ ,

-C- - (OCH ₂ CH

-CH-.C = O

n.

H H

r;

15 ' ^R 17

and ^R 18

3 H,

n.

not available

OR- nit R- = carbonyl radical (-C-);

₂ CH ₂ ^ OCH ₃ with; X ₃ S 10-1,000; n ₂ ^ ³ IO-LOOO; and n 20-700; and, = "2-1,000.

030015/0642

-CH ₂ CH

_Y ⁿ i

where are:

- 152 -29391U

CH ₂ CH

CH, = 0

-CH ₂ Y n ₂

, R ₂ , R ₄ , R ₇ , R ₈ , R ₁₀ , R ₁₃ , and

CH ₂ CH

= H,

R ₃ , R ₆ , R _g , R ₁₂ , R ₁₅ , solid,

, G ₁ , R ₁₁ and R ₃ = nonexistent

O-

G _{2 =} N

-CH CHOHCH (OCH CH ^ OCH ,;

/ ί Δ X ₄ y

η ,, n ~,

0-500 with

is not zero, X ₄ = 20-700.

- 10-600, however

030015/0842

Examples of class II polymer units are:

where are:

>' ^R 26' ^R 26 '

31 '"32

= H,

G ₄ and G ₅

CH-CH (OH) CH with x_ and χ = 0-3,000; n ₄ = 10-5,000; n _{5 and} n ₆ = 0-2,500, but where n _{c are} not both zero, / n ₄ + n ₅ + n ₆ = 10-10,000.

and

030016 / 08A2

Examples of polymer units within class III are:

H
N-CH ₂ CH ₂

n.

where are: R , r

N-CH ₂ CH ₂

'2

^C 8 ^

R ₄₂ = nonexistent residues,

35 ^l 37

R ₃₉ and R ₄₃ = H-,

R ₄₁ and R ₄₅ = -CH ₂ CH ₂ - (ethylene);

R ₃₆ = - (CH ₂ CH ₂ -N

with. x. 10-200;

with

10-200;

_2222x3

- (CH CH ₉ -N ⁺ * with x _Q = 10-200; and 9 others

n _n , _no and _no each independent -of a / = 10-1500 / 0 y '

030015/0842

2939ΊΗ

CH _n

--N-CH ₂ CH (OH) CH ₂ -

ⁿ 7

CH.

-N-CH-CH (OH) CH ₉

I ^{2 2}

Γ ²

CH (OH)

CH ₉ - (OCH ₉ CH - * - OCH ζ δ i X ₁₀

CH,

I * CH, 0H

³ II

(CH ₂ -Ch-CH- 2 j X ₁₁ J 2

O = Q

NH ₂ C = O

NH

2y

where are:

₃₄ , R ₃₈ ipd R ₄₂ s non-existent residues,

ν R ₃₄ ,

35 '

· ^R

44

-CH ₃ ;

R ₄₀ = -CH ₂ CH (OH) CH ₂ - (OCH ₂ CH ₂ ^ -OCh ₃ with X ₁₀ ~ 10-700; R ₃₇ and R ₄₁ β -CH ₂ CH (OH) CH ₂ -;

: ₂ -CH-CH ₂ -

R ₄₅ =

CH ₂ CH ₂ -C -NH ₂

X ₁₁ = 20-20,000; ^and

n _{? /} n- tnd n _g = '^ 0-500, but where n _Q and n ^ are not both zero.

030015/0842

29391U

A preferred group of polymer units or monomer units comprises the alkyl group of alkyleneimines in which the alkyl or alkylene group contains about 2-4 carbon atoms, for example polyethyleneimine. This type of polymer can be prepared by homopolymerization or copolymerization to give either virtually linear or randomly branched polymers. Each type of polymer can be grafted with branched chains using the same or a different alkyleneimine or alkylimine monomer or polyalkyleneimine polymers. Other types of branching monomers or polymers can also be bound to the backbone polymer chain, for example oxygen-containing monomers or polymers, for example -fO-R ·) - or -4N-R ^ -, in which R is an alkyl, aryl, alkenyl, cycloalkyl radical or combinations thereof, wherein each hydrocarbon radical is 1-10 carbon atoms arranged in a structure on v / e and wherein the combination or ratio is such that the desired hydrophilic-hydrophobic properties are produced. The randomly branched polyalkylimine can be used as a branched polymer as such, or it can be further branched or substituted. For these and most preferred polymers and applications, the degree of branching should be in the range of about 1-99 % and preferably 10-35 % , in other words, 1 to 99 of every 100 potential branching sites should have a bound, branched chain. For the polyalkylimine this would also mean that the nitrogen atom to which each branch was attached would be quaternized or protonated, as shown below for PEI:

H CH ₀ CH ₀ -N

N '+ + I H

N
C.

H ₀ CH ₀ -NH ₀ 2 2.2

030015/0842

29391U

Preferred molecular weight ranges for this class of polymers are about 800-50,000,000 and preferably about 1000-1,000,000 for the WOR control, for viscosity agents and for the mobility control of aqueous ones Liquids.

Examples of polymer units within Class IV

H
I.

Π p

CH ₂ -CH (OH) CH ₂ - (O-CH ₂ CH ₂ ) - _x OCH ₃

12th

10

HHO O

JIM Il

- -N- {CH ₂ > ₆ NC-CH ₂ -N-CH ₂ -C

CH ₂ CH (OH) CH ₂ - (O-CH ₂ CH ₂ ) - ^ - OCH ₃

13 _

11

HO

where are:, ^

^R 47 ' ^R 50 and ^R 53 ⁼ nonexistent residues,

^R 46 ' ^R 49 ^{and R} 52 ^{= H}

-CH ₂ CH ₂ -N-CH ₂ CH ₂ -

CH ₃ CH (OH) CH ₂ - (OCH ₂ CH ₂ ^ - OCH ₃

with X ₁₂ ^{= 20} ~ ⁷⁰⁰ »
R _1,. = - (CH _o > _c NH-C-CH _o -N-CH.c

OL ZO Zi Z

with R “.

= 0-700;

Γ 9

L ^{2 6}

CH CH (OH) CH ₉ - (OCH CH ) OCH

n ₁₀ and n i = 0-1500; n, ₂ = 10-3000, however

not both are zero.

030015 / 08A2

29391U

B.

NH-CH-C A

10

-NH-CH-CI CH _n

CH.,

CHCONH _n

Il

-NH-CH-C-

CH

where are:

, R ₁ -Q and Rcx = nonexistent radicals, R _/ jQ = -OH-, where A is any of the naturally present

coming amino acids is present alpha substituents, these occur in the polymeric polyamides commonly known as proteins. One that goes into detail Explanations of the chemical nature of the alpha substituents and the structures of the polymeric proteins can be found in Books of biochemistry.

R ₅₁

CH ₂ -CHCH ₂ CHCONH ₂ f ^

with

= 10-50-000;

R ₅₄ = - (CH ₂ ^ ₄ NH-CH ₂ CH (OH) CH ₂ - (OCH ₂ CH ₂ ^ -CCH ₃ with X ₁₅ = 10-50-000; and

n ₁₀ = 10-3000; η _χι and η _χ2 «= 0-1500, although not both are zero at the same time.

and·

030015/0842

29391U

Examples of polymer units within class V.

are:
A.

where are:

OCH ₂ CH (OH) CH ₂ - (OCH ₂ CH ₂ > -OCH ₃

GO ₂ Well

R ₅₆ and R ₅₉ =

n ^ ₅ = O or absent, R ₅₅ = -CH ₂ CH ₂ (OCH ₂ CH ₂ ^ Oh UDdR ₆₀ -CH ^ (OCH ^^ Ofl with

16 Π

and X ₁₇ = independent. one another 0-100, R _{57 =} -CH ₂ CO ₂ Na;

R ₁ -O = -CH_CH (0H) CH _- (OCH "CH_i OCH- with X _1Q = 10-700; and

JO Δ Δ ί C X. η J ίο

η ₁₃ = 5-5000 and

1-1000.

030015/0842

B. \ -

* 13

wherein R ₅₆ * R ₅₈ / R ₅₉ /

R ₅₅ =

29391U

, CHCONH-, ί H

2 ⁷ X.

A polysubstituted hexose unit with xg = about 0-1000; R ₅₇ = -CH ₂ CH (OH) CH ₂ - (OCH ₂ CH ₂ ^ OCh ₃ with X ₂₀ S! 0-700;

^R 60 ^ ^R 63 -

^{H 1} ^

^X 22 "^ ⁵⁰⁰⁰ ' ^and

030015 / 08Λ2

! Examples of polymer sateinheiten are within the class VI:

CH ₂ -C-CH ₂

-O

CH ₉ OfCH ₀ CH-O) - \ ^X24

_Y ⁿ 16

-CH ₂ -CH-O-

17th

-CH ₂ CH ₂ -

18th

wherein: R ₅₅ , R ₆₆ , R ₆₉ , R ₆₇ uri. R ₇₀ = -CH ₂ -; R ₆₈

with ^X 24

= about 0-3000,

however, X ₂₅ and X _{24 are} not both zero , Xg, x _c and X _0. = -O-; and

n ₁₆ = 1-5000; n _1? = 0-5000; and n ₁₈ = 0-5000;

NH ₂
C = O

CH ₂ OfCH ₂ CH ^ _x -H CH ₂ C-CH ₂ -O-

CH ^ CKCH ₉ CH ₉ O) (CH CH-O) H

* ^X 26 ^ l ^X 27

-CH ₂ -CH-O-

17th

16

18th

wherein: R ₆₅ , R
R ₆₇ and

R ₇₁ and R ₇₃ = H,

- (CH ₂ ) -; = -CH ₃ ;

CH ₀ OfCH ₀ CHCONH-I ^{2 2 2}

R _{C / f} = -CH ₀ -C-64 2 ι

with X ₂₅ = 0-5000 and

CH ₉ OfCH CH O> - (CH ₉ CHOh-H

26th

Cn,

^X 27

X ₉₆ and X ₉₇ = 0-3000, but where x ^ Xg, x _{c and x D} = -ο-; and η, ^ = 1-5000; η, _n and n _1Q = 0-5000.

XO X / Xo

^ and X ^ _1n not 6

/ all are zero,

030015 / 08A2

29391H

A preferred class of polymer units from a or more of the aforementioned classes is that in which the branched-chain polymer polymer unit s of the following formulas:

and combinations thereof, in which R _Q2, independently of one another, has the same meaning as R ^ in each position and Rg, independently in each position, has the same meaning as Ry. Has. Within this class, a preferred group of polymers consists of substances in which the radicals R _{Q2 are} predominantly Cg-rO ^ -alkylidene radicals, such as ethylene, propylene and / or butylene radicals. These branching chains should preferably have a molecular weight of up to about 50, for example about 800-30,000. These branched chains can contain an average value of about 2-25,000 or even up to 50,000 polymer units. The branched chains of any polymer can be essentially uniform or they can be mixtures with different chain lengths and / or configurations. Certain polyethylene imine polymers, as described here, can be used to stabilize clays or to change WOR values. For other purposes of use, these polymers, and in particular those with lower molecular weights and regions, should have additional branching or crosslinking. Certain other preferred polymers of these classes are useful in cements, aqueous liquids with a pH of less than about 10, and especially in acidic media with a pH of less than about 6.5 or even 3.0.

030015/0842

These branched chains can be attached to different types of Be bound backbone polymers. The backbone chain and the branched chain can both be essentially the same Type of polymer units or combinations of Have polymer units. The branched polymer can have a backbone polymer chain and polymer units of the branched chain, which are substantially different from one another and are each essential different properties such as hydrophilic-hydrophobic properties, ionic character or solubility in different Have pluids or liquids. For example, the backbone chain can be strongly ionic, e.g., either anionic, cationic, amphoteric or a mixture thereof, and the branched chain can be essentially nonionic, while still being highly hydrophilic or solvatable is in the presence of aqueous liquids. The ionic groups can be in linear backbone chains, in pendent Groups of the backbone chain or both. Another preferred polymer can be a stronger one have hydrophilic backbone chain, and the ionic groups can be in the branched chains. At a This section of the backbone chains and / or the branched chains can accordingly be another preferred polymer the descriptions given above. The overall properties of the branched polymer can do this make it strongly or only slightly soluble in water. The same can be said of other fluids such as organic fluids or substituted organic fluids including polar solvents such as alcohols (C-i-C / io) »organic Acids, sulfonated hydrocarbons, oxygenated Soluble hydrocarbons or polyol hydrocarbons be. ·

Another preferred class of polymers from the aforementioned classes are those substances which are more as one type of polymer unit. This poly-

030015/0842

Merisates can be substances as previously defined by a single formula from the eight classes mentioned above or a combination of two or more formulas from different classes. This class of polymers includes those in which at least one type of polymer unit is made from alkyl acrylate, aryl acrylate, alkyl acrylamide, arylacrylamide, alkyl azirides, arylazirides, alkoxide, alkyl epoxide, the reaction product of ammonia or alkylamine reacted with alkyl dihalide, an alkyl diepoxide or combinations thereof or combinations of these polymer units exhibit. The carbon residues in these units can contain 1-10 carbon atoms. In certain units such as acrylate and acrylamide, the hydrocarbon has 0 carbon atoms and is therefore absent. More than one hydrocarbyl substituent can be present in other units, and the substituent can be present in one of several positions in each unit. A particularly preferred and surprisingly stable and efficient polymer for gelling aqueous liquids, especially acidic, aqueous liquids, and also for reducing the WOR value, comprises polymers and copolymers which have substantial amounts of methacrylate units in the backbone chain. These polymers with alkylidene oxide branches are practically permanent and stable at high temperatures, even in high pressure steam. These polymers are also effective in controlling fluid loss from aqueous liquids such as cement slurries, treatment fluids, breaking fluids and acidifying fluids, stabilizing clays in the presence of aqueous liquids, and reducing friction loss when pumping various liquids or fluids. The term "stability" used here relates to the use of the polymers to increase the viscosity of aqueous liquids

030015/0842

_ ₁₆₅ - 29391U

possibilities, in particular for gelling acids for breaking and / or acid treatment and means that the mixture of polymer / Pluid the greater part of its viscosity for two hours at about 60 O ⁰ G in 5% hydrochloric acid without significant loss of viscosity or Formation of a precipitate maintains.

Further examples of polymer units within one or more of the aforementioned classes are:

030015/0842

= - O - 166 - I.
C. 2 NH

CH.

NH,

29391U

CH -, - N -CH.
I.
CH,

"CH

CH ₃ CH ₃

-CH

I.

p-o

CH

ζ -N ⁺ -CH

CH,

-CH:

SO ₃ H

CH

C = O

f «2
CH ₂

CH ₃ -N ⁺ -CH ₃
CH ₃

CH fc

:H

N ^ -CH ₃ CH ₃

CH ₂ -C

C = O

CH,

η

_nd -CH ₂ -C

P'3

C = O 0

CH-,

CH ₃ CH ₃

030015/0842

- 16? -

Some of these formulas can be written in more general terms like this:

Γ 84 CH-

or

wherein

f.,

C.

C = O

X-

I • c

^R 86 ^R 87

C = O ^X 6 ^R 95

* 96

^C 7 ^R 98

^l 99 '

, R ₉₅ ,

independently of one another have the same meaning as,

^ 9 »Rg5» £ 96 » ^R 97> ¹ ^ s ^and ^ 9 ^{independently of} one another have the same meaning as R ^, and Xt-, Xg and X ₇ independently of one another have the same meaning as G ^.

030015/0042

Several preferred polymer units comprise the alkyl acrylates and acrylamides and substituted alkyl acrylates and acrylamides and can be more generalized by the following Formula to be defined:

100

CH ₂ - C-

C = O O

^R 101

and

^v 102

-CH ₂ -CC

103

'104

where are:

■ ^ 100 ^un ^ ^ß 102 ^e ^ " ⁿ hydrogen atom, ^e i ^Q alkyl radical, aryl radical, hetero groups or combinations thereof, each hydrocarbon radical having about 1 to 6 carbon atoms,

^ 101 ' ^R 103 ^{and R} 104 ^e ^ ⁿ ^ ^aster "t ^{ojE> f} atom, an isoalkyl radical or n-alkyl radical, aryl radical, hetero groups or combinations thereof, each hydrocarbon radical being selected independently of one another and having about 1 to 6 carbon atoms .

Preferred branch chains or reagents R for these polymer units include the leftovers

^or

where R ^ qc and R ^ _{06 are} an alkylene radical with etv / a 1-10 carbon atoms per hydrocarbon radical and η is an integer bi3 of about 50,000 and preferably up to about 2000.

030015/0842

A particularly preferred class of polymers for modification the properties of aqueous liquids such as the reduction of the WOR value, for the gelling of aqueous liquids, for fluid loss control and for increasing the primary production are those which are alkyl acrylate backbone units and contain ethylene oxide branches as defined by the following formula:

C = O

CH ₀

CH

CH.

L ³

OH

CH

wherein χ is about 10 to 60,000, and preferably 10 to 15,000 y is about 1 to 90,000 and preferably 1 to 5,000 and ζ is about 2 to 25,000 and preferably 2 to 10,000 and A "is connected to the quaternary nitrogen atom Means anion.

These preferred polymer units can also
other substituents, especially on the carbon
and have nitrogen atoms. The polyethylene oxide chain, 40CH ₂ GH ₂ > _z , can also be replaced by hydrogen, Ifydroxyl-,
C ₁ -C ₆ -oxyalkyl, Og-Og-oxyaryl, oxy (2 ~ hydroxy-3-chloropropane) or oxy-0-2,3-oxopropane) radicals and also terminated by the methoxy group shown at the end be.

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29391U

A particularly preferred class of polymers for modification the properties of aqueous liquids such as the reduction of the WOR value, for the gelling of aqueous liquids Liquids and for promoting primary production are those which contain 2-hydroxypropyl-IT, N-dialkylaiiiin-backbone units and acrylamide branches and / or polyalkoxide branches reacted with epichlorohydrin, as shown by the following formulas is shown:

CH

OH I

N-CH ₂ CH-CH ₂ -

CH.

N -CH ₀ CH-CH ^ I ^{2 2}

f-2

CHOH

(OCH ₂ CH ₂ ^ -OCH ₃

where are:

ν = »about 0-60,000 and preferably 0-2,000, w β about 2-10,000 and preferably 2-1,000, χ = »about 10-60,000 and preferably 10-10,000, y = about 0-60,000 and preferably 0-2,000, ζ = »about 3-100,000 and preferably 3-30,000, and A "is an anion linked to the quaternary nitrogen atom.

These preferred polymer units can also other substituents, especially on the carbon and nitrogen atoms.

030015/0842

The polyalkyloxide chain (OR) can also be replaced by hydrogen, hydroxyl, O ₁ -C ₆ -AIlCyI-, 0 ₆ -0 ₁₀ -aryl, oxy- (2-hydroxy-3-chloropropane) - or oxy- (2, 3 -oxopropane) residues as well as the methoxy residue shown at the end.

A "particularly" preferred class of modification polymers the properties of aqueous fluids such as the reduction of the WOR value, for the gelling of aqueous fluids Liquids and promoting oil production are those which have methylenepiperidinium backbone units and contain epichlorohydrin have reacted polyalkoxide branches as shown by the following formulas:

"CH.

CH

CH ₃ XIH

where are:

χ = about 10-50,000 and preferably 10-3,000, y = about 1-10,000 and preferably 2-1,000, and ζ = about 2-10,000 and preferably 2-1,000.

These preferred polymer units can also other substituents, especially on the carbon and nitrogen atoms.

The polyalkyloxide chain, (0R) _z , can furthermore be replaced by hydrogen, hydroxyl, O ₁ -G ₆ alkyl, G ₆ -C ₁₀ aryl, oxy (2-hydroxy-3-chloropropane) or oxy ( 2,3-oxopropane) residues as well as by the methoxy group shown at the end.

030015/0842

29391U

A particularly preferred class of polymers for modification the properties of aqueous fluids like the Reduction of the WOR value, for the gelling of aqueous Fluids and those used to promote primary production are those which have alkyl ether and butanedicarboxylate backbone units and reacted as branching chains with epichlorohydrin Have polyalkoxide units and / or polyalkoxide units as shown by the following formulas is:

OCH ₃

CH ₂ -CH-

, -CH.

C = O C = O

Jo 'ο

(CH ₂ CH _;

-CH ₂ -CH-

! _l
CO ₂ CO ₂

where are:

u = about 10-60,000 and preferably 10-10,000, ν = 0-10,000 and preferably 0-2,000, w = 2-10 000 and preferably 2- 1000, χ = about 10-60 000 and preferably 10-10 000, y = 0-10,000 and preferably 0-2,000, and ζ = about 2-10,000 and preferably 2-,000.

These preferred polymer units can also other substituents, especially on the carbon and have nitrogen atoms.

The polyalkyloxide chain, (OR) ₁ , can furthermore be replaced by hydrogen, hydroxyl, C ^ iO ^ -alkyl, Cg-C ₁₀ -aryl, oxy- (2-hydroxy-3-chloropropane) - or oxy- (2 , 3-oxopropane) residues as well as by the methoxy group shown at the end.

030015/0842

29391H

The production of branched polymers is explained in more detail below with the aid of production methods.

Manufacturing method A

Production of a branched polymer with polyacrylamide branches

1. In one provided with a cooler, a stirring device, a gas inlet pipe and a temperature measuring device 250 ml three-necked flasks were distilled 50 ml Uasser and 30 g of a commercially available polymer, made from epichlorohydrin and dimethylamine.

2. The flask was purged with nitrogen gas, during which time 0.4 g of isopropyl alcohol and 20 g of acrylamide monomer (in the form of a 40% strength aqueous solution) were added. The reaction mixture was heated to 64 ⁰ C.

3. 0.27 g of an azobisisobutyronitrile initiator for the free radical polymerization were added and the temperature was kept at 85.degree. C. for 3 hours. The product consisted of a pale yellow to amber colored liquid having a viscosity cP 2000-8000, measured with a Brookfield spindle no. 3 at 12 rpm, 25 ⁰ C

Method of manufacture B

Production of a backbone polymer and subsequent grafting of chains onto the polymer

1. In one with a cooler, a stirring device, a gas inlet pipe and a temperature measuring device as well 5OO ml provided with a heating mantle and a dropping funnel Three-necked flasks were 160 g of dimethyldiallylamine monomer (as a 40% strength aqueous solution) and 40 g of diallylamine monomer given. The pH of the reaction mixture was adjusted to approximately 4.0.

030015 / 08A2

29391U

2. The flask was purged with nitrogen gas, during which time the contents were heated ^{to 70 ° G.}

3. 10 g of ammonium persulfate catalyst was dissolved in 100 g of water and added to the dropping funnel. The catalyst was added in 5 equal portions every 30 minutes while maintaining the temperature at 70 ° C. The Realctionsgemisch was then held for a further 2 hours at 80 ⁰ G. The reaction mixture was cooled and the nitrogen purge was stopped. The reaction product was a viscous, yellow liquid.

4 ·. A portion of the product from stage 3 was removed; it corresponded to 1.76 g of active gopoly (dimethyldiallyldiallyl) ammonium chloride. To this, 2.6 g of active MPEO-epichlorohydrin adduct product, prepared as described under the following preparation method G, were added. This mixture was diluted with water to a concentration of about 4 % active polymer.

5. The pH was adjusted to about 9.5 with 50% sodium hydroxide solution set. Salt can be added to reduce viscosity.

6. The polymer mixture was placed in a sealed container and placed in a water bath at 60 ° G for Used for 2 hours to allow the reaction to proceed. This can be stirred to make it pumpable to maintain, however, the agitation can increase the amount of time required to obtain a product with a given viscosity influence.

7. The branched or grafted copolymer was diluted to a concentration of about 2% with water or saline solutions and the liquid was poured into a

030015/0842

-175- 29391H

Niche, e.g. a high-speed Hamilton Beach mixer, Sheared to constant viscosity.

8. The viscosity was determined and the product obtained was used to test effectiveness as a WOR alteration product or as an acid gelling agent as under the The following working methods E to 0 are used.

Manufacturing method G

Manufacture of a branching agent or a polymeric branch chain

1. It was a methoxypolyethylene glycol or oxide, im hereinafter referred to as MPEG or KPEO, as they are commercially available, for example the product with the trade name CARBOWAX ^ MPEG 5000 in an amount of 0.04 mol or 200 g, in one having a condenser, a stirrer, a gas inlet pipe and a temperature measuring device equipped 500 ml three-necked flask entered.

2. The flask was purged with nitrogen gas while the Glycol was melted using a 65-75 ° C water bath.

3. The water bath was removed and 0.12 mol

= 11.1 g of epichlorohydrin added and for 15 min mixed in with stirring.

4. Boron trifluoride etherate was added and the temperature was kept between 65-75 ° C by cooling or heating as required.

030015/0842

-176- 29391U

5. The MIEO-epichlorohydrin reaction product, i.e. the MEEG- or MEEO adduct, was stirred for 1 hour.

6. Excess epichlorohydrin was removed on a rotary evaporator removed, and the branching adduct or branching agent was added with an equal amount of Water diluted.

Manufacturing method D

Production of a branched copolymer from a commercially available copoly (methyl vinyl ether / maleic anhydride) backbone polymer

1. In a 250 ml three-necked flask equipped with a stirrer, a stirring device, a heating mantle and a temperature measuring device, 90 ml v / water, 7-3 g of a mixed oxide polyglycol with high molecular weight and 1.4 g of nonylphenol as a surface-active agent were added. The reaction device was heated ^{to 50 ° C.}

2. To the stirred, heated contents of the reaction flask 1.3 g of commercially available methyl vinyl ether / Maleic anhydride polymer added, and the reaction mixture was heated for 4 hours. This turned out to be an off-white liquid with a viscosity

of 5800 cP at 25 ° C, measured with a Brookfield spindle ITr. 3 at 12 rpm.

030015/0842

Production method E

Production of a branched copolymer from a commercially available polydimethylaminoethyl methacrylate (PDMAEM)

1. The amount of cationic backbone polymer given in Table XII below was placed in a container, the specified amount of water was added and the mixture was stirred until the polymer had dissolved. Then the specified Amount of branching chain adduct polymer added and stirred for 3 minutes.

2. The pH was adjusted to about 9.5 with 50% sodium hydroxide solution added. Salt can be added to reduce viscosity.

3. The closed container was placed in a water bath at 60 ^° C. for 2 hours in order to allow the reaction to proceed. In order to keep the mixture pumpable, stirring can be carried out, but the stirring can affect the time taken to achieve a given molecular weight or viscosity.

4 ·. The liquid of the branched or grafted copolymer was diluted with 15 ml of water and the liquid was sheared in a mixer, for example in a high-speed Hamilton-Beach mixer, to a constant viscosity.

5. Viscosity was determined in cps using a Fann Model 35 Viscometer at 300 Upra with a standard spindle and sleeve.

6. To investigate the performance of the polymer for gelling aqueous acid, the necessary Amount of concentrated acid, see the following table-

030015 / 08A2

len XII, XIII, XIV, XV and XVI, to the concentrated, aqueous polymer mixture added. Then, if necessary, to the desired concentration of acid and polymer diluted with stirring. The viscosity of the mixture was determined with the Fann viscometer as before determined, e.g. at a 1.5% concentration of active polymer solids in 5% hydrochloric acid.

Production method F

Production of a modified-branched polymer (PEI)

1. It was the desired amount of a commercially available, branched Polyäthyleniminpolymerisates with a molecular weight of about 40,000 to 100,000 added to water to give a 6% concentration to obtain active polymer of PEI.

2. It has an extending agent or a branching agent as indicated in Table XIX (6% concentration) was added and stirred under heating at pH> 60.0 at 9-10 ⁰ O until the occurrence of gelation.

3. The viscous gel was diluted to the desired acid concentration with hydrochloric acid.

4. Apparent viscosity was measured on a Fann Viscometer, Model 55A, Spring # 1, standard spindle and sleeve certainly.

030015/0842

-179- 29391U

Working method G

Determination of the performance of a branched Polymer to reduce the flow of an aqueous liquid

1. A small amount of glass wool was placed on the bottom of a 100 ml burette.

2. There were 50 ml of deionized water in the closed Poured in burette.

3. There were 5> 0 g of a sand with a grain size of 2.38-1.68 mm on the bottom of the burette, then 25 g of sand with a grain size of 0.84-0.42 mm. Then were another 5> 0 6 sand with a grain size of 2.38-1.68 mm

on top of the sand filled with a grain size of 0.84-0.42 mm.

4. The burette was gently tapped to remove a pack length of sand with a grain size of 0.84-0.42 mm 8-9 cm.

5. The excess deionized water would drain to the top of the packing with a particle size of 2.38-1.68 mm and the height of the meniscus in the burette was determined and recorded as the "zero level".

6. There were 25 ml of deionized water taking into the burette Use a syringe or pipette to fill it and determine the length of time required to pass through the pack and required to reach the zero level was. This is the "beginning time". -

7. A solution of the branched polymer having 1000 ppm polymer solids in deionized water was obtained and adjusted to a pH below about 5.0 with an acid such as hydrochloric acid.

0300 15/0842

29391U

8. 100 ml of this branched polymer treatment solution was introduced and through the burette to the fill level let flow.

9. The treatment was continued with 75 ml of deionized water .

10. Step 6 was repeated, the value obtained is this
"End Times".

11. The start time was divided by the end time and multiplied by 100 to get the value in % of the start flow rate.

Production method H

Production of a branched polymer
in situ

Part of a backbone polymer such as polyethyleneimine with a molecular weight of ~ 40,000 - 100,000 g / mol (g / m) in an aqueous liquid with an equal active weight of IiFEO-epichlorohydrin adduct (about 5000 g / m) prepared according to the information and the preparation method C, combined and with water to a total polymer concentration diluted by about 5000 tpm. The pH was adjusted to above about 7-8. These Solution was then injected into either the test core or the formation to be treated.

Procedure I should be used when treating a test core, and when treating a formation Operation N may be used with the exception that after the treatment stage is complete, the system will run for one is left static for a period of time determined by the temperature, e.g. 24 hours at 71i1 ° G. After this curing time has elapsed the test medium is returned to production and the changes in flow rates are determined.

030015/0842

- 29391H

Working method I

Method for determining the effectiveness of branched polymer for reduction; the Flow of an aqueous liquid through a clay packing of sand

A dry mix of sand was made by mixing 88 parts of a sand with a grain size of about 0.21-0.088 mm with 10 parts of fine silica flour (particle size less than about 0.074 mm) and 2 parts of a smectic clay. 100 g of this mixture was placed in a test chamber lined with polytetrafluoroethylene polymer with an internal diameter of 2.38 cm or in a Hassler sleeve test chamber with an internal diameter of 2.38 cm. Approximately 25 ml of a 6.7 gauge saline solution was pumped through the sand pack and the test chamber was locked either overnight or for 2 hours at 80 ° C to ensure complete hydration of the clays. Then a 6.7% strength sodium chloride salt solution was conveyed through the sand pack until equilibrium conditions were reached, ie no change in the differential pressure (ΔΡ.) And flow rate (Q ₁ ) occurred any more. A solution of the chemical to be tested was then injected through the sand pack in the opposite direction. The production was then continued until equilibrium conditions were again present and the flow rate (Q _f ) and the differential pressure (ΔP _f ) were noted. The percentage retention (% K.) Of the initial permeability was then obtained by the following equation:

(AP.) Κ * χ 100

^{x 10} ° ^or

where mean: Q. = initial flow rate,

Q ~ = end flow councils,

= Initial pressure drop across the Kamiaer and = Ultimate pressure drop or differential pressure.

% Reduction = 100 - % K. .

030015/0842

- 29391U

Working method J Determination of the relative oil permeability in one Sand packing

After determining the percentage retention of the initial saline solution permeability (% K.) According to procedure I, kerosene (2.7 cP) was pumped through the sand pack. The flow rate and differential pressure were determined. The percentage the oil permeability compared to the initial saline permeability was calculated as follows:

(Q _of ) (AP _Bi ) (2.7)% KoiB = ^{x 10} °

Working method K

Determination; the effectiveness of a branched polymer to reduce the flow of aqueous liquid through

a core

A Berea sandstone core or limestone core with an outer 2.38 cm in diameter and 10 cm in length was placed in a Hassler sleeve test chamber with an inner diameter of 2.38 cm mounted. About 25 ml of 6.7% saline solution became conveyed through the core and the test chamber was closed either overnight or for 2 hours at 80 ° 0, to ensure complete hydration of the clays. A 6.7% saline solution was then passed through the core to Achievement of equilibrium conditions promoted, i.e. no changes in pressure and flow rate. A solution the chemical to be tested was then injected through the core in the opposite direction. Then the promotion continued until equilibrium conditions were regained and the flow rate and the Differential pressure determined. The percentage of the initial permeability was then obtained from the following equation:

030015/0842

(Q ₁ O (A p ₁ )

where are: Q. = initial flow rate and Q- = final flow rate.

Working method L Determination of the relative oil permeability

in a core

After determining the percentage retention of the initial saline solution permeability (% K.) According to method K, kerosene (2.7 cP) was pumped through the core. The flow rate and the differential pressure were determined. Of the Percentage of initial saline solution permeability to that of oil was calculated as follows:

(Q ₀ Jf) (ΔΡ _Β1 ) (2.7)

^{01 ΰχ} -τ χ 100

Working method M Typical WOR working method

A typical WOR procedure is designed for 151 liters of polymer mixture per 30.5 cm of perforations. This is done by diluting a concentrated solution of a branched, ionic polymer concentrate by about 10: 1 to 70: 1 with water, e.g. water from the formation, salt solution or 2% potassium chloride solution, and then adding hydrochloric acid (about 32 %) to adjust the pH value reached to about 3-6. After the pressure test of the pipeline and the setting of the injection rate, the solution of the branched polymer is pumped in an amount of about 318 liters per minute and then water is pumped. This procedure is repeated in the following steps until the entire solution of the branched polymer is injected into the borehole. After pumping in the last stage, water is pumped in as a final rinse.

030015/0842

- 29391U

Working method N

A recommended way of working is to use around 13 »6 kg of one branched, ionic polymer in a concentrate solution (calculated as pesticides) per 30.5 cm section, diluted around 15: 1 - 50: 1. The treatment volume depends on the porosity and the desired radial penetration in the formation. Table XXII gives the recommended Volumes.

If the entire water-bearing section is not known, it is recommended that a penetration of approximately 3.05 to 9.14 m is applied over the entire conveying section in order to determine the treatment volume. If the entire, water-producing Section is known or a good estimate is available, a penetration of 9 »14 · to 15» 24 m is approx recommended in this section. It can be estimated for this calculation that the entire treatment liquid in enters the water-producing zone. A more dilute solution can be used for greater radial penetration.

The mixed water can be any compatible saline solution. Additives, e.g. corrosion inhibitors, bactericides, surface-active Means etc. , must be examined for their tolerance.

The polymer should be mixed with the carrier liquid can be added. 2 to 4 times circulating the tank with a piston pump or a turbine or a mixer tape type should give sufficient mixing. The pH should be adjusted to 3-5 with hydrochloric acid or another acid.

030015/0842

An initial injection rate and an initial injection pressure should be determined using water or another available aqueous liquid. The rate should be as high as possible while maintaining, however, a pressure below the fracture pressure or break-up pressure will. It may be necessary to reduce the injection rate in order to get below the maximum allowable pressure stay. The treatment solution with the branched, ionic Polymer should be made using an aqueous liquid, a gas or a hydrocarbon such as V / water, Nitrogen or oil are displaced further. The borehole can then be operated again for production immediately.

Treatment sequence

1. A test well with a known history of production is selected.

2. Proposed carrier fluids such as water, crude oil etc. and the information on the well production are evaluated.

3. The solution of the branched polymer is mixed.

4. It will take the injection rate and the injection pressure Use of an available liquid is determined.

5. The treatment solution of the branched polymer is through the pipeline, the annular gap or through both pumped, maintaining a pressure below the formation fracture pressure.

6. The branched ionic polymer solution is introduced into the formation using an available fluid v / ie an aqueous liquid, a gas, a hydrocarbon or a mixture thereof.

7. The well is switched to production.

015/0842

Working method 0 Example or working method for a method for reducing the WOR value (water-gas ratio)

A dry sand pack with a length of 65 cm × 0.72 cm in diameter was produced from a mixture of 80 parts of sand with a grain size of 0.21-0.088 mm, 15 parts of silicon dioxide flour and 5 parts of a smectite. The equilibrium flow rate of gas (methane) through the dry pack was 3900 ml / min with a Different! al pressure of 34.5 bar. After saturating the sand pack with 6.7 % ± ger NaCl solution, a maximum flow rate of 1020 ml / min methane at 34.5 bar differential pressure was achieved. This sand packing was then grafted with 100 ml of a solution of 1000 ppm of a water-soluble, ionic, branched polymer (PDMAEM, molar weight = 800,000-1,000,000, with polyethylene oxide branching (molar weight = 5000) at a weight ratio of the backbone: Branches = 1: 1) treated. The flow of water was reduced by more than 90% , while the gas flow was 170 % of the initial value. About 1000 liters of methane were required to restore equilibrium flow conditions.

030015/0842

Table I.

Change in flow and viscosity properties due to polyethyleneimine polymers with change in branching and molecular weight

Polymerizat Mol.-Gew.- Viscosity, Active- Test- Reduction % K _oiB

Range cP, Brook- concentration at temp, the water-

5% aqueous solution (? O)
.. Solution; __________

PSI 12 1 200 3.1 1.0 27 da 0.0 ND ²

(Dow Chemical Co)

PSI 600 40 000-60 000 28 0.5 27 yes 75.4 84.8

(Dow Chemical Co ^

S PSI 600 40 000-60 000 28 0.1 27 yes 73.5 100.5

ο (DowChemical Co.)

PSI 1000 50 000-100 000 1200 0.05 27 yes 91.6 90.0

cn (powChemical Co.)

ο PSI 1000 50 000-100 000 1200 .1.33 27 yes 87.7 93.0

whether (Dow Chemical Co.)

f: psi 1000 50 000-100 ooo 1200 1.0 27 yes 85.6 75.7

(DowChemical Co.)

PSI 1000 50 000-100 000 1200 1.0 60 yes 80.5 99.2

(DowCbanicalCo.)

PSI 1000 50 000-100 000 1200 0.1 27 yes 83.6 90.0

(Dow Chemical Co.)

PSI 1000 50 000-100 000 1200 0.1 27 yes 81.2 ⁵ 93, L. ^

(Dow Chemical Co.) co

PSI 1000 50 000-100 000 1200 0.1 82 yes 98 ⁴ '140 ⁴ 5 ^

(Dow Chemical Co.) ^

Polymin P 50,000-55,000 7 0.5 60

(BASI ¹ )

there 0.0
16.0
75.4 there 73.5 there 91.6 there 87.7 there 85.6 there 80.5 there 83.6 there 81.2 there 98 ⁴ no 66 ⁴ '

Continued from Table I.

, 7

ND '

no 42, 7

EPOKm P-1000 60 000-80 000 9 0.1 27 no (Japan Catalytic
Chemical Co .;

EPONIN P-1000 108.000 ^ 0.05 27

(Japan Catalytic Chemical Co.) Polymer grafted with methoxy polyethylene oxide branches (8th)

1 - All flow tests were performed on clay-containing sand packs (88: 10: 2 parts by weight of Oklahoma No. 1 sand, fine silica flour £ ~ = <0.074 mm and bentonite), unless otherwise stated.

2 - ND = not determined.

3 - Test sand consisted of a mixture of 2:10:88 parts by weight bentonite, CaCO ^ particles

with a grain size of 0.21 - 0.088 mm, fine silicon dioxide powder and sand Oklahoma No. with a grain size of 0.21 - 0.088 mm.

4 - Flow tests conducted using a Berea core.

Viscosity of a 2.0% aqueous solution.

All tests involved flowing fluids at a stabilized rate, but that persisted extended flow over this point up to 10,000 pore volumes on the same tests. *

The core was different from the core used to test PEI 1000, the difference At its core there may be some change or variation in test results condition.

8 - Polymer grafted using production methods such as C and E with a weight ratio of backbone polymer to branching polymer of 1: 1.

9 - / ^ ₀ -JjJ, determined according to the working methods J or L.

The data show that branched high molecular weight PEI polymers are susceptible to change the permeability to aqueous itLuiden are effective, with which PSI with low Molecular weight is not as effective and / or long lasting.

00 CO

5 -

6 -

7 -

ro CO CO CD

Table II

Comparison of the change in flow properties in sands using linear polyacrylamide and branched polyethyleneimine polymers

Reduction of water permeability (%)

Polymer Test-
temp.
( ⁰ C) Focus on
active polymer
sat in treatment
solution (%) Polyacrylamide
(Calgon WC-500) 24 0.05 PSI * 1000
(Dow Chemical Co.) 24 0.05 co
O PSI 1000
(Dow Chemical Co.) 60 0.5 cn PEI 1000
(Dow Chemical Co.) 82 0.5 O
OO 1 - Testand passed from 85 : 15 parts by weight of sand

2?

94.4 104

98.1 123

70.2 MD ³

2 - linear polyacrylamide resulted in a significant reduction in water permeability,

but its effectiveness decreases very quickly, see Table XIII).

3 - MD a not "determined.

4-20% anionic polyacrylamide. 5 - Determined according to J.

The values show that a branched PEI polymer to reduce the permeability K> to an aqueous liquid and to increase the permeability to oil cd is efficient compared to a polyacrylamide polymer. <-O

Table III

Reduction of water permeability after treatment with PSI-1000 "with different permeable sand packs

Sand Oklahoma Mr. 1 permeability permeability reduction of the + fine silicon of sand after treatment with water permeable dioxide powder (Darcy) (Darcy) fluid (Parts by weight)

1: 0 11.9 8.80 26.0

S 9.75: 0.25 9.60 6.60 31.0

9.25: 0.75 1.04 0.035 96.5

JJ 9: 1 0.246 0.030 87.5 Cd

^ 8: 2 0.197 0.003 98.5 °

S 7: 3 0.090 0.004 95.5

• ο 1 - These tests were carried out in a sleeve consolidation apparatus made of polytetrafluoroethylene

polymer carried out at room temperature. Both the initial permeability and the final permeability was also obtained from stabilized flow rates. the Treatments were carried out with 75 ml of 0.5% ΡΞΙ-1000 with the pH adjusted to 4.

These values show the relative effectiveness of a particular polymer in the

Use in loose sand packs of different permeability. The performance i> o

ability of other, branched, polymeric structures according to the invention ^

vary with the properties of the polymer and the formation. The polymeric molecules ^co

Molecules can vary in molecular weight, the extent of polymer branching, the length of the poly- —χ

several chains etc. vary to reflect different effects and sizes of effectiveness in *** Depending on the matrix to be treated.

29391H

Table IV

Influence of a branched polymer on the change in the water permeability of a clay-containing sand pack which is subjected to a steam flow.

Working methods
step

3
4th

Step description Pack 1 Pack 2 Pack 3

% Initial water permeability at 21.1 ⁰ O

Treatment volume of a branched polymer (1000 tpm) at 21.1 ⁰ G (ml)

% Initial water permeability after treatment at 21.1 ⁰ O

Funded volume

100

600

of steam at 177 ^υ 0 (ml)

% Initial water permeability after treatment with steam flow

Delivered volume of steam at 260 ° C (ml)

° / o at the initial water permeability at 21.1 ⁰ O after treatment with steam of 260 0

Applied volume of 15% oil to clean the sand pack (ml)

% of the initial water permeability after the acid treatment

700

2400

200

100

800

200

3.9

100

500

0 ,8th 0 , 3 4000 2000 9 , 7 16 A. 2400 900 1 1 ,1

200

1.6

Each of these three sand packs consisted of 88: 10: 2 parts by weight of sand with a grain size of 0.21-0.088 mm, silicon dioxide steel or smectite. The results of this investigation show that this branched, water-soluble polymer

030015/0842

_ ₁₉ 2- 29391U

(a branched methacrylate copolymer with mol. ^ v 1 000 000) in reducing water permeability in environments with dynamic steam from 177 to 260 ° C was effective. The values also show that deposited, branched polymers resist being washed out are resistant to acidic liquids. These fluids are often used to stimulate fluid production the formation applied to hydrocarbon producing formations.

030015/0842

Table V

Change of the flow and viscosity properties as a function of the characteristics of the Verzw e temperate Polymeri sa tes

% K _± , using 0.05%

NaGl

Molecular
weight of
MPEO - Viscosity of the
Polymer 1.5% in
5%
HGl 0 0 /, Ar,
C. / O 1Π
fresh
water 71
59
24
28 5000
2000
750
350 161
121
81
78

3.1 6.0 38 44

* Change in the flow properties in a Berea core. K. = initial salt solution permeability of the core.

** MPEO - methoxy polyethylene glycol or methoxy polyethylene oxide (Commercial product from Union Garbide with the designation Garbowax),

A commercial PDMAEM product with a molecular weight of 600-000-800,000 formed the backbone. The viscosity of the aqueous solution of the backbone ^{polymer was approximately 20 el 1 at 25 °} C. and 2% polymer solids. All grafted polymers had a weight ratio of 1: 1 of the HPEO to the backbone polymer. There was less branching with MPEO with a molecular weight of 5000 than with grafts of an MPEO with a molecular weight of 350. The branched or grafted polymers were prepared according to the preparation methods G and E. The values in Table V show that as the branched chain decreases, the number of branches increases and the % K value. increases from 3.1 to 44. Therefore, the K ^ value becomes significant by little

030015/0842

long branch chains and even influenced by a larger number of short branch chains. The data also show that fewer branching chains with higher molecular weight for this particular polymer family to increase the viscosity of
aqueous liquids and aqueous, acidic liquids are more effective.

030015/0842

Table VI

Properties of the immersion of aqueous liquid and the reduction of the water permeability of FCMAEM branched with mehoxpolyethylene oxide -working of the simultaneous injection ¹

Water permeability (Darcy) test sand before after No. Treatment treatment

0.762

0.016

Reduction of water permeability due to the treatment (%)

97.9

0.481

0.053

0.011

0.028

0.007

0.004

94.2

86.8

64.6

Test-

composition (parts by weight)

88: 10: 2

Sand Oklahoma No. 1,

fine silicon dicocid flour and Bentonite

88.9: 11.1

Sand Oklahoma # 1

and fine SiIi ziumdicDcid flour

Berea core, horizontal permeability

Berea core, vertical permeability

Relative outflow volume that passes through each sand (ml)

173.9

188.6

47.7 35.2

CD CO CO

- Using a conventional multiple device, the fluid injection was carried out simultaneously on all of the test sands different permeabilities carried out. The injection pressure was the same for all test sands. the Treatment fluids were therefore allowed to enter each test sample in inverse proportion to the resistance encountered with each sample. Treatment with the polymer solution gave a more uniform one Injection profile of liquids in the test samples with change in permeability. It should be noted that the permeability of the test sand 1 is 40 times that of the test sand 4. While After the polymer treatment, only 4 times the amount of liquid flowed through the test sand 1 M compared to the test sand The values show a significant reduction in the permeability to aqueous liquid flow for all four samples indicating that the branched polymer is effective in controlling aqueous fluid loss.

TARFT.T.E VII

Properties of the branched polymer. Their influence on the reduction of the water permeability

Backbone polymer: PDMAEM

Molecular weight about 1,000,000, reacted with branching polymer: methoxypolyethylene oxide (MPBO) Molecular weight: 5000

Weight ratio s
Backbone polymer:
Branching polymer Concentration of
Polymer in
the treatment
solution (%) Reducing the salt
solution permeable
speed (%) 0: 1 0.05 0-5 1:10 0.05 55 1: 5 0.05 76 1: 2.5 0.05 94 1: 1 0.05 96.9 1: 0.5 0.05 92 1: 0.25 0.05 99.4 1: 0.25 0.01 92 1: 0.12 0.05 89 1: 0.03 0.05 99 1: 0.015 0.05 71 1: 0.08 0.05 11 1: 0.004 0.05 13th 1: 1 not implemented ⁺ 0.05 5 1-0 0.05 0.0

The backbone polymer (PDMAEM) (only mixed with the MPEO polymer (not reacted with it).

All tests were carried out at 66 C using Berea cores. An 8% NaCl solution was used to introduce the polymer solution used.

030015/0842

The values in Table VII show that some branching is required and that with certain polymers a small amount or degree of branching produces a significant effect. If the number of As branching increases, the effectiveness is increased up to a certain, optimal point. This shows that each Polymer family a critical range of the ratio of backbone polymer to the number of branched Has chains. The values in the first row, the penultimate row and the last row of the three columns of the table apply to a non-branched polymer or a polymer mixture and they show that the non-branched one Polymer does not have an unexpected effect on the permeability of the aqueous liquid, which with the family the branched polymers is achieved.

030015/0842

TABLE VIII

Changes in the flow properties in Bedford limestone due to branched polymers

Polymer Conc entrat ion
in the treatment
solution Test-
temp. discount of
Water through
nonchalance (%) Polyethylene imine 0.5 60 74 ⁺ PEI-1000 (Dow Chemical Co.) PDMAEM 0.01 66 94 (Mol.wt. = 1,000,000 with grafted Polyethylene oxide branch supply (mol.wt. = 15,000) Weight ratio Backbone branching = 1: 1

PEI-1000 was apparently washed off the sandstone core, i.e. this is not an equilibrium value or stabilized value.

The graft polymer can also have a certain degree of crosslinking.

The values show that at least two different, cationic Polymers with high molecular weight branches and high molecular weight, branched polymers in reducing the permeability for aqueous liquids are effective.

030015/0842

T ARRT .T F IX

Influence of some branched polymers in calcium carbonate packings of 0.21-0.074 im Grain size

Treatment polymer

A and C combines A then C.

concentration
(Tpn)
in saline discount of
Water through
nonchalance (%) 1000 42 1000 23 1000 25th 500 Tpn each 74 1000 tpn each 72

A is a copolymer with the same molar ratio of maleic anhydride and methyl vinyl ether (~ 500,000 g / m), grafted with an equal weight of methoxy polyethylene glycol (/ v- 5000 g / m); B is a copolymer with the same Molecular ratio of maleic anhydride and methyl vinyl ether (A * 5000 g / m), grafted with an equal weight of polyethylene oxide (/ V 5000 g / m); C is a polymer of dimethylaminoethyl methacrylate («v 800,000 g / m), grafted

with an equal weight of methoxypolyethylene glycol-epichlorohydrin adduct (/ v 5000 g / m).

030015/0842

- 200 TABLE X

Changes in flow properties due to branched and non-branched polymers

No.

Polymer

Pore volume Reduction of injecting water Salt solution permeable through test sand (%)

CH ₁
1.3

OH Cl

-N-CH ₂ -CH-CH ₂ - _CH ₃

η = 300 10

0.0

Poly (dimethyl-2-hydroxypropyl antiionium chloride).

CH ₃ α

- -N ⁺ -CH ₂ -CH-CH ₂ CH ₃ OH

ft ^cl

"-CH ₂ -CH-CH ₂ J--

0 _, 100

43

p ₂

HC-CONH

χ = 300 y = 30 ζ = 1000

Graft copolymer of the first polymer with polyacrylamide branches.

4-N ⁺
CH

-CH ₂ -CH = CH-CH ₂ -

0.0

η = 100

Poly (diniethyl-2-butcnyl-aiiiTK) nium chloride)

030015/0842

- 2O1 -

Continuation of Table X

29391U

-CH CH-CH ₂ -

Cl

CH ₃ CH ₃

η = 200

Poly (dimethyldiallylanmonium chloride)

0.0

5.

CH.

-CH ₂ -C

H ₃ Cl

_ η

10

0.0

η = 3000
Poly (dimethylaminoethylnifthacrylate) salt with an anion such as A.

6. H-CH ₂ -CH ₂ -O-

10

0-5

η = 100

Poly (ethylene oxide)

030015/0842

Table X continued

29391U

--CH ₂ -C Ö

H ₃ CN-CH ₃

₃ CN

CH ₂ -C

C = O I

CH Cl

H ₁ CN ⁺ -CH-3 1

HIGH

10,000

2 y

CH

-H

CH-

x = 3000 y = 30 ζ = 100

A graft copolymer of polymer no. 5, grafted with Methoxy polyethylene glycol-epichlorohydrin adduct.

C = O

40

C = O ^J

I-

NH_

Na ⁺

χ = 50,000 y = 15,000

Partially hydrolyzed polyacrylamide or Co (polyacrylamide-sodium acrylate) .

The values in the table show that the branched polymers for Reduction of the permeability for a flow of aqueous liquid are effective, while this is not the case with linear polymers.

030015/0842

TABLE XI

Water wetting properties of aqueous solutions of various polymers and surface-active agents " ¹ "

Chemical contact angle (degrees)

Zero sample from deionized water 36

Polyethyleneimine polymer 31.8

(PEI-1000 (Dow Chemical CoJ)

PDMAEM x 22.2

branches with MPEO adduct

Diallyl dimethyl ammonium chloride- 35.6

polymer (Calgon TRO-522)

Branched and crosslinked polyamine- 39.0

polymer (MW = 20,000-25,000)
(Nalco-607)

Condensation polymer of 44.5

Dimethylamine and epichlorohydrin
(MG = 5000) (Nalco-108)

Anionic, aromatic petroleum sulfate 16.5

(water-wetting)

Mixture of cationic, interfacial 134.0

quaternary amine active agents

(oil wetting)

All test solutions were at pH = 4 with 1% polymer solids or a 1% concentration of active ingredients.

The fourth of this table shows that the branched, cationic polymers are water-wetting and have some surface-active properties. The contact angles were measured using a clean microscope slide of glass measured immersed in diesel oil with the polymer or surfactant dissolved in deionized water.

For the treatment of aqueous liquid with specific, branched The surface tension of polymers is reduced, which also normally results in a lower interfacial tension between aqueous and organic liquids or hydrocarbon liquids.

030015/0842

~ ^2O4 ~ 29391U

Table XII

Influence of a branched polymer on the relative oil permeability

Test level

Test 1
(untreated) Test 2
(treated with polymer) 911 906 0 2 911 38 8th 164

Initial water permeability (md) polymer treatment (PV)

Vote permeability after treatment (md)

oil permeability (md) ^c

a - extracted crude oil, extracted water and the nuclear material used was from the Ranger Formation, Wilmington Field, California, USA

b - A concentration of 1000 Tpn was used.

c - These oil permeabilities were when the water saturation was irreducible stormed.

The core samples were stabilized to the flow with pumped water, then treated with the pore volume (PV) of polymer, and the permeability was measured with pumped water and crude oil.

The values show that the treatment with branched polymer increases the permeability for aqueous liquid decreased and the permeability for oil flow increased.

030015/0842

TABLE XIII

Change in the flow properties of different polymers. Effectiveness against prolonged flow

Polymer

Test solids

Initial permeability
of test solids (Wed.)

Polyethyleneimine (Dow PEI-12) (MG = 1200)

Polyethyleneimine (Dow PEI-1000) (MW = 50,000-100

Polyacrylamide (Calgon WC-500) 20% anionic

Polyacrylamide (Dow J-217) (MW = 1,800,000 13% anionic 5.8 fundamental viscosity number

PDMAEM

(MG = 600,000-800,000) Branched with MPEO adduct (MG 5000)

Backbone and branch polymer converted in a weight ratio of 1: 1.75

Bedford

limestone

Berea sandstone

Berea-

Sandstone

100

42.5

450

88

95.5

Polymer in treatment solution

0.5

0.5

0.05

0.3

0.01

Pore volumes of injected by treated solids Saline solution

45 80

120

1000 2000 3000 4000

120 270 380 570

30th

60 200 270 270

190

1270 2108 3427

5949 11580 13499

Reduction of permeability ⁰

60 33

65 65 60 58

51 38 29 22

66 56

15 11 11

88

88

87

86 K ₅

85 cd

83 OJ

88 CD

Continuation of Table XIII

PDMAEM Bedford- 13.8 0.1 200 75

(MG = 600,000-800,000 limestone 400 75

Branched with polyethylene glycol 600 75

(Union Carbide Carbowax 2OM- 800 75

MG: 15,000) 1000 75

Rickgrat and branching poly- '

ο merisat implemented in a ge q

ω weight ratio of 1: 1 ^

ο '

cn a - Test solids # 1 consisted of 88: 10: 2 parts by weight Oklahoma # 1 sand, silica _flour or bentonite, respectively. Test # 2 solids consisted of 85:15 parts by weight Oklahoma # 1 sand or silica flour.
• whether - A small amount of crosslinking may be present in the finished polymer along with the branching. A certain

hydrophilic crosslinking in specific areas of application can be advantageous, c - permeability to saline solution.

The values show that the resistance to washing out or the stability with the polymer structure

varied, and that the branched polymers with high molecular weight were very stable or after the post-CD

CJ spools with more than 10,000 pore volumes of aqueous liquid have not been washed out. <Φ

Table XIV

29391U

Relative amounts of backbone and branching

polymer

Weight ratio
cationic poly
merisat: Mdukt Solution of the cationic
Polymer (10%
Polymer solids)
(G) water
case) MPEO-Mdukt
(50% poly
merisatfest
fabrics) (g) 1.5O: O 30th 45 0 1.25: O; 25 25th 49 1 1.00: 0.50 20th 53 2 0.75: 0.75 15th 57 3 0.50: 1.00 10 61 4th 0.25: 1.25 5 65 5 0: 1.50 0 69 6th

030015/0842

29391H

r Apparent viscosity (cP) at 25 ° C 5% HCl 8th table XV water (2% active polymer) (1.5% active polymer 25th 27 32 Viscosity properties of PDMAEM grafted with MPEO adduct 82 28 Weight ratio 73 ⁺ 7th 78 ⁺ 3 25th 1 1.5: 0 14th 1.25: 0.25 3 1.00: 0.5 0.75: 0.75 0.5: 1.0 0.25: 1.25 0: 1.5

frothy

A commercially available PDMAEM with a molecular weight of about 600,000-800,000. MPBO 350 is a methoxy polyethylene glycol or oxide with a molecular weight of about 350 (commercially available product from Union Carbide under the trade name "CARBOWAX" 1

The values show that branching for a stable polymer leads to Gelation of aqueous liquids and aqueous, acidic liquids is required. The values also show that the number of Branching affects the efficiency or effectiveness of the branched polymer for gelling aqueous liquids.

030015/0842

- 2O9 -

TABLE XVI

Viscosity of PDMAEM grafted with MPBO adduct

Weight ratio Apparent viscosity (cP) at 25 ° C PDMAEM: MPEO 75O ⁺ * water
(2% active
Polymer) 5% HCl
(1.5% ac
ves polymer) 1.5: 0 17th 7th 1.25: 0.25 39 28 1.0: 0.5 52 ⁺ 26th 0.75: 0.75 81 24 0.5: 1.0 7th 5 0.25: 1.25 3 1 0: 1.50 1 1 frothy

ΜΡΕΌ 750 is a methoxy polyethylene glycol or oxide with a molecular weight of around 750 (Union Carbide product called CARnOWAX)

The values show the same effects as in Table XV plus the effect
of higher molecular weight or longer branch chains.

030015/0842

Table XVII

Viscosity of PDMAEM grafted with MPEO adduct

Weight ratio apparent viscosity (cP)

PDMAEM: MPEO 200O ⁺ *

water
(2% active 5% HCl (1.5% active
Polymer) after 24 h
at 6OC Polymer) at the start 11 13th 7th 4th 37 20th 50 105 45 142 200 114 152 198 ⁺ 127 80 121 59 44 75 20th 8th 7th 3 1 3 1

1.5: 0
1.43: 0.07 1.36: 0.14 1.25: 0.25 1.00: 0.50 0.75: 0.75 0.50: 1.00 0.25: 1.25 0 : 1.5O

frothy
⁺⁺ MPBO - molecular weight about 2000.

The values show the same effects as in Tables XV and XVI for higher molecular branching chains. The values also show that the branched polymer in acid at high temperatures for longer periods of time is stable.

030015/0842

TABLE XVIII water
(2% active
Polymer) 5% HCl (1.5% active »Polymer) viscosity from PDMAEM, grafted ι Ä
15th at the beginning after 24 h at 60 ° C Weight ratio 26th 6th 8th PDMAEMrMPEO 500O ⁺ with MPEO adduct 6O 14th 15th 1.5: 0 Apparent viscosity (cP) 120 39 15th 1.43: 0.07 141 49 52 1.36: 0.14 161 68 56 1.25: 0.02.5 124 71 77 1.0: 0.5 98 46 - 0.75: 0.75 32 23 27 0.60: 0.90 7th 7th 9 0.5; 1.0 3 3 21st 0.25: 1.25 8th 1 1 0.14: 1.36 4th - 0: 1.5 0.7510.7S ¹⁺

MPEO 5000 is a polymer with a molecular weight of about 5000 (product of Union Carbide with the name CARBOWAX).

For the mixture of PDMAEM no epichlorohydrin with the Polyäthylenoxidpolymerisat was reacted for the preparation of an adduct, but the pH was adjusted to about 9.5, and heating the polymer solution for two hours at 60 ⁰ C in accordance with the production method E.

The values show the same effects as Table XVII.

030015 / 08A2

29391U

Table XIX

Viscosity properties of modified, branched polymers (polyethyleneimine)

Branched Polymer Modifying Apparent Viscosity

(CP) at 25 ° C) (4 % active ingredients)

Mean (cP) at 25 ⁰ C)

Polyäthylenimin i ^a Ethylen-Propylen- 114

oxide copolymer,
reacted with epichlorohydrin ^c

Polyethyleneimine II ^b "79

Polyethyleneimine I polyethylene glycol

250, implemented with
Epichlorohydrin ^d 46

"none 5

Polyethyleneimine II none 3

Product with the trade name Chemicat P-14 5 from Alcolac

Incorp.

Product with the trade name EPOMIN P-1000 from Japan

Catalytic

Product with the trade name Nalco PS 2OO7M Product with the trade name Nalco R69M

030015/0842

" ²¹³ " 29391U

Table XX

Influence of branched, cationic polymers on the reaction time of 5% HCl with limestone ^a

Acid solution 5% HCl

5% HCL gelled with modified PEI ^b

Contact time (min)
with limestone lag behind
ending% HCl 0 5 5 2.6 10 2.3 0 5 5 3.4 10 3.25 30th 3.0 45 2.8

Bedford Limestone

Polyethyleneimine, modified with ethylene-propylene oxide copolymer-epichlorohydrin adduct (4% active solution) (the poly ^: ethyleneimine was a product with the trade name EPOMIN P-1000). The modification was carried out according to the method of preparation F.

030015/0842

- 214 TABLE XXI 29391U

Viscosity and stability of various polymers

in water and acid

Polymer

Apparent viscosity (cP)

water

(2% active polymer)

Polyvinyl alcohol 42

VINOL 1540 (Air Products & Chemicals, Inc.)

Poly ^ -acrylamido - ^ - methyl- 55 " ¹ propylsulfonate)

AMPS (Lubrizol Company)

Polyvinyl pyrrolidone 3 5

PVP (GAF Corporation)

Acrylate copolymer (30 I) 135 and acrylamide (70%)

Copolymer of AMPS (20%) 115 and acrylamide (8O%)

Copolymer of acrylamide (70%) 120 and Ν, Ν, Ν-trimethylaminoethyl methacrylate

Copolymer of acrylamide (70%) 78 and Ν, Ν-dimethylaminoethyl methacrylate

5% HCl (1.5% active polymer

beginning after 24 h at 6O ⁰ C 35

35

22nd

37

62

10

28

12th

frothy
Polymer precipitated.

The values show the effectiveness and stability of various, linear Polymers in aqueous and aqueous, acidic liquids for extended times at high temperatures.

0015/0842

Radial penetration into a formation against porosity

29391H

porosity

Radial treatment distance (m)

Treatment volume per interval (Ft.) (bbl / ft)

10 3.05 5.6 10 6.10 22nd 10 9.14 50 10 12.19 90 10 15.24 140 20th 3.05 11.8 20th 6.10 44.7 20th 7.62 70 20th 9.14 101 20th 12.19 179 20th 15.24 280 30th 3.05 16.8 30th 6.10 67 30th 9.14 151 30th 12.19 269 30th 15.24 420

030015/0842

Table XXIIi OQQQ 1 1 /

Development treatment of a borehole Δ Ό O 3 I IH

This development production well was located on a water flood project and had been closed due to excessive water production. Production was resumed in order to reach the initial production levels. Monitoring of the ingress of liquid was carried out before and after the WOR-PoI ^ r isate treatment. This borehole was packed with pebbles and had a production distance of about 256 m. Treatment with 30 traimels of concentrated polymer solution of a cationic polymer with nonionic branches, diluted 1:40 with injection water, resulted in an increase in the injection pressure of about 107.5 bar. This solution was moved further with 350 barrels (55.9 m ³ ) of injection water.

Production rate

All in all water oil calculated FOP * pressure Productivity 9.8 Time (BPD) (BPD) (BPD) water (ft) waste index 9.6 (Days) 4310 - 55 (BPD) 1500 (PSI) (BPD / PSI) 9.8 Beginning 5200 5145 55 1725 9.4 0 4183 4094 89 5145 - 46 113 9.3 1 3995 3929 66 - 954 - - - 2 5004 4937 67 495 704 365 11.0 7.9 6th 4867 4782 85 484 704 469 10.7 - 7th 4823 4721 102 469 - 469 10.4 8.7 8th 4821 4717 104 - 649 - - - 9 4817 4723 94 442 624 491 —— 10 4815 4711 104 433 649 502 11 4814 4695 119 441 604 491 12th 4794 4677 117 424 604 510 13th 4628 4520 108 422 - 510 15th 4227 4118 109 - 549 - 16 4701 4587 114 356 - 533 17th 4732 4596 136 - 524 - 18th 4713 4567 146 389 - 543 19th 4684 4542 142 - - 20th -

030015/0842

Continuation from Table XXIII 29391 14

21 4660 4519 141 - - - -

22 4663 4520 143 - - - -

23 4616 4481 135 -

24 4624 4474 150 362 464 568

25 4625 4479 146 - - - -

26 4593 4439 154 - - - -

27 4578 4437 141 - 764 * - -

28 4704 4534 170 - ~

29 4676 4491 185 - -

30 collapse in the lower part of the borehole turning on the pump -

31 5065 5026 39 - 1500 140 36.2

32 5419 5314 105 - - - -

33 5092 4965 127 _____ _

34 5193 5106 87 - - - -

35 5160 4864 296

36 4493 4460 33 - - - -

37 5112 4780 332 - 565 527

38 5032 4755 277 _____ __

39 5131 4735 396 - 565 -

40 4355 4099 346 - 565 - -

41 5063 4700 363 - - - -

42 5027 4686 341-515 547

43 4970 4673 297 - - -

45 4979 4677 302 - - ~

46 4985 4641 344 _____ _

48 4964 4579 385 - 405 - -

49 4811 4606 205 _____ _

50 4487 4417 70 - - Liquid inlet

51 4850 4608 242 - .515 - -

52 4807 - 193 - - - -

53 4892 - 363 - -

54 4783 4537 246 - 405 - ~

55 4790 4530 - 260 - 430 - -

56 4782 4536 246 - 405 - -

57 4737 4460 277 - - - -

O30015 / 08A2

29391H

Continuation from Table XXII

58 4730 4508 222 - 310 59 4738 4588 . 250 - - 60 4707 4481 266 515 65 4958 4411 547 - - 66 4732 4411 321 - - 67 4717 4378 339 - - 68 - - - - 310 90 4800 355 - 400

Height of the liquid in (ft) above the pump

030015/0842

- 219 Table XXIV

Development drilling treatment

This development treatment well was on a water flood project. It was packed with pebbles and had a pure delivery fluid of 174 m. Several test monitors and fluid ingress monitors were carried out before and after the WDR polymer treatment. The initial oil production rate varied. The WDR polymer treatment consisted of 24 Tramieln concentrated polymer solution of a cationic polymer with nonionic branches, diluted 1:48 with Injection water for an additional displacement with 191.5 m of injection water.

Remarks

Production rate Total water
(BPD) (BPD) - Oil-water-oil-gas
(BPD) ratio (irrif) pressure Time
(Days) 2057 2006 40-73 50-27 - FOP
(ft) tSeqinn 2075 2084 69 29 16 480 0 2176 1599 92 - - 482 1 1689 1393 90 ~ - - 2 1466 * 1266 73 - 21 - 3 1325 1190 59 - 147 4th 1252 - 62 ~ - - 5 - 1119 - - - 6th 1174 1106 55 ~ 146 7th 1147 - 4] _ __ - 8th - - - - - - 9 - 1669 = - - 447 10 1718 1404 49 - 11 1481 1266 77 - 12th 1326 - 60 - - - 13th - 1157 - - 359 15th 1214 1146 57 - - 294 16 1186 1108 40 - - —— 17th 1165 57 - - - 18th 2 <? 4

the total choke pressure was 24/64

switched on = 20.7 bar

The choke was exhaled

The pump fell off.

Pump cycle

030016/08 ^ 2

" ²² °" 29391H

Continuation of Table XXIV

19 1144 1100 44 -

20 1129 1066 53

21 1106 1052 54 - - -

22 1094 1041 53

25 1057 1011 46 - - 214

26 1054 1008 46 - -

27 1045 993 52 -

28 1031 - 34 - ~ 274

30 1016-52

31 - __ __ __ __ 274

32 1015 980 35

33 1013 962 31 - - -

34 1014 973 41 - -

34 Ran tool introduced for monitoring fluid ingress,

this turned out to be not well stabilized.

36 732 704 28 - - 674

36 1180 1107 73 - - _

37 1125 1076 49 ~ -

38 1117 1070 47 - _ ~ -

39 1119 1064 55 - - 274

40 Pan tool introduced for fluid ingress monitoring. 40 am 900 880 20 - - -

40 pn 900 860 40

40 San monitoring of the fluid entry.

42 1167 1119 48 -

43 1148 1110 38 - -

44 1138 1083 55 21

45 - - - - - 214 60 1020 - 52 19 - 280

030015/0842

29391H

Table XXV Development well treatment

This borehole was an old streaming borehole with a static one Bottom temperature (ΒΗΕΤΓ) of around 104 ° C with perforations over 1.52 m at a depth of 3490 m. Four parts of heated, concentrated Polymer solution of a cationic polymer with nonionic Branches were used at a 1:30 dilution. These were additionally postponed with 47.9 m of extinguishing water.

Production ratio

Time All in all Vvasser or vJasser-oil- pressure Notes (Days) (PPD) (BPD) (BPD) relationship (PSI 24/64 choke at the start 1425 - 28 50 525 24/64 choke 0 1425 1397 28 50 525 1 1242 1217 25th 29 - 2 1260 1234 26th 47 560 3 1284 1220 64 19th 825 3 1296 1231 65 19th 800 5 1240 1178 62 19th 800 6th 1260 1197 63 19th 800 7th 1254 1191 63 19th 800 12th 1211 1150 61 19th - 28/64 Q «oke 13th 1658 1575 83 19th 560 25/64 choke 15th 1451 1378 73 19th 642 25/64 choke 50 1400 73 18th 642

030015/0842

TABLE XXVI

Development well treatment

This hole was perforated at a depth of 3050 meters of 3.05 m and was on gas production. The treatment was carried out using 12 drums of concentrated polymer solution of a cationic polymer with nonionic branches, diluted 1:19, carried out with preheated extinguishing water and an additional shift with 47.9 m extinguishing water.

Production rate

) 1 Wa C ₅₅ ^ r-OI-

choke

Time
(Days) All in all
(BPD) water
(BPD) oil
(BPD) ^rt jasser oil at the start 642 629 13th 49 1 580 493 87 - 2 1297 1297 0 - 3 1376 1348 28 - 4th 1318 1292 26th - 16 1119 1097 22nd - 18th 1431 1403 28 - 29 1431 - - 31 15th 1431 28 50

48/64

030015/0842

Time,
(Days) oil
(BPD) water
(BPD) before the
treatment 36 1270 8th 23 1508 9 37 1514 13th 49 1288 15th 43 1291 18th 47 1447 21st 61 1470

- 223 Table XXVII

29391H

Development well treatment

Water, Oil, API, Fluid, Total Differential Ratio Gravity level fluid fluid level

35 17.6 2548 1306

20.3 2935 1531 387 20.3 3062 1561 518 20.3 3126 1337 578 20.3 3126 1334 578 20.3 3222 1494 674 20.4 3286 1531 738

030015/0842

29391U

Table XXVIII

Development well treatment

This borehole became one with eight tramples of concentrated polymer cationic polymer with nonionic branches, dissolved in 23.9 m NH.Cl water with a spacing liquid amount of 4 m and treated with an additional displacement of 27.9 m of spent saline solution.

Production data

Time
(Days) Total water
(BPD) (BPD) 1164 oil
(BPD) Itfasser-oil-
relationship GL print
(PSI) Pipe pressure
(PSI) before the 1180 16 73 - - treatment 1040 2 1066 1128 26th 40 800 150-350 1156 1266 28 40 780 120-430 4th 1282 1296 16 79 780-800 120-430 7th 1310 1279 14th 93 785 125-430 22nd 1298 26th 50 __ _

Total Injected Gas Recovered (FCF) ()

33 240

34 209

35 209
37 209

203 267 249 244

* GL = the gas delivery pressure at the surface.

03001 5/0842

- ²²⁵ ~ 29391U

Table XXIX

Effect of the injection rate through a perforation tunnel of a solution of a branched polymer

% of initial

polymer,

effectiveness ^D

Polymer
concentration
(Tpn) Injection
rate
(1 / fciin) 1600 (not
sheared) 0 16O0 3.8 1600 11.4 1600 41.6 800 (not
sheared) 0 800 3.8 800 11.4 800 41.6

100

102 1O9 102 100

103 110 113

a - The treatment solution was through a simulated perforation tunnel (tube of 9.5 mm inner diameter χ 76.2 mn) at various Rates were pumped and samples were taken. These Samples were examined and the results reported relate to the polymer treatment solution not subjected to shear treatment for the production of the water permeability of a Berea sandstone.

b -% of the initial WDR effectiveness.

The data show that the branched polymer by a rapid Pumping is not significantly affected or sheared by a perforation.

O30015 / 08U ORIGINAL INSPECTED

Claims (1)

29391U 2 Sep 7 1979 Patent attorneys Dipl.Ing. R. Shomerua Dipl.Ing. H. Arendt Hubertusstrasse 2 3ooο Hanover 1 H 523 / Sch HALLIBURTON COMPANY PO Drawer H31
Duncan, Oklahoma 73533, USA Claims 1. Procedure for changing the properties of a aqueous liquid, characterized by the fact that this liquid is branched with a Polymer is brought into contact, which has a molecular weight of about 900 to about 50 million, a hydrophilic portion and a significant portion of at least one polymer unit of the following Structural formula contains: I ⁵ 7 ^R 10 R ₉ ί R ₁₂ ί ¹³ Ria 16 ^R 15 CR ₁₈ - 14 ^R 17 030015/0842 ORIGINAL INSPECTtD _ ₂ _ 29391U where mean: R ₁ * ^R 2 » ^R 4» ^R 7 » ^R 8» ^R 10 ' ^R 13 » ^R 14 ^{and R} 16 from each other a hydrogen atom, an alkyl, alkenyl, Alkynyl, aryl, acyl, cyclic hydrocarbon, heterocyclic hydrocarbon, hydroxyl, carboxyl, Carbonyl radical or the radicals -QR ₁₉ , -NR ₁₉ R ₂₀ , -SR ₂ 3 »" ^ I ^^ · ^X A » ^or combinations thereof, which can also contain oxygen, sulfur, nitrogen or phosphorus, in which X _{A is} -Gl, -Br or -NO ₂ , R ₃ , R ₅ , R ₆ , R ₉ , R ₁₁ , R ₁₂ , R ₁₅ , R ₁₇ and R ₁₈ independently of one another a nonexistent radical or alkyl, alkenyl, alkynyl, aryl, acyl, carbonyl , Carboxyl, aromatic hydrocarbon, cyclic hydrocarbon, heterocyclic hydrocarbon radical or combinations thereof, which can also contain oxygen, sulfur, nitrogen or phosphorus, R ₁ Q, R ₂₀ , R ₂₁ and R ₂₂ independently of one another a nonexistent radical or a hydrogen atom or an alkyl, alkenyl, alkynyl, aryl, acyl, cyclic hydrocarbon, heterocyclic hydrocarbon radical or combinations thereof, which also May contain oxygen, sulfur, nitrogen or phosphorus, R ₂ x independently of one another in each position is a hydrogen atom, an alkyl, alkenyl, alkynyl, aryl, acyl, cyclic hydrocarbon, heterocyclic hydrocarbon radical or the radicals M ⁺¹ , M ⁺² , M ⁺ ^, H ⁺ ^ ₉ ^ ^R 19 ^R 20 ^R 21 ^R 22 ^{0 (} * ^er combinations thereof, which can also contain oxygen, sulfur, nitrogen or phosphorus, R ₂ 4 independently in each position is an alkyl, alkenyl, alkynyl, aromatic hydrocarbon radical or combinations thereof, which also contain oxygen, sulfur, 030015/0842 Nitrogen or phosphorus, in which the radical Rp _{4 has} two or more atoms bonded together with nitrogen to form a ring, M independently of one another in each position is an ammonium radical or substituted ammonium radical, a metal ion or a mixture thereof, G, -, Gp and G, independently of one another, a nonexistent radical, a hydrogen atom or the radicals -SO ₃ R ₂₃ , -OSO ₃ R ₂₃ , -PO ₃ R ₂₃ IR ₂₃ , -OR ₂₃ , -0-0-R ₁₉ , -C-OR ₂₃ , 0 -C-NR ₁₉ R ₂₀ , -NR ₁₉ R ₂₀ R ₂₁₁ -NJl ₂₄ , -SR ₂₃ , -SR ₁₉ R ₂₀ or combinations thereof, n,., n ₂ and n, independently of one another whole Zah l s of about 0 - 500,000, where n ^ ng + nj £ 3, wherein each hydrocarbon radical is independent of one another 0 to 10 carbon atoms and optionally 0 to 4 hetero groups of oxygen, sulfur, nitrogen or phosphorus, and in which the radicals bonded to each atom and the structural formula thereof compensate for the bonds of this atom 2. The method according to claim 1, characterized in that a polymer is used in which one of the radicals R ₁ , R ₂ , R ₄ , R ₇ , R _Q , R ₁₀ , R ₁₃ , R ₁₄ and R _{16 is} a hydrogen atom is. 3. The method according to claim 1, characterized in that a polymer is used in which at least one of the radicals R ₁ , R ₂ , R ₄ , R ₇ , R ₈ , R ₁₀ , R ^ ₃ , R and R ₁₆ a Is a hydrocarbon residue. 030015/0842 29391U Process according to Claim 1, characterized in that a polymer is used in which at least one of the radicals R ^, R ₂ , R ^, R ₀ , R ₈ , R ^ q, R ^ 3 »and R ^ / · none Is hydrogen atom. 5. The method according to claim 1, characterized in that a polymer is used in which at least one of the radicals R ,, Rg, Rq, R ^ f ^R 15 ^{and R} -j8 is not present. 6. The method according to claim 1, characterized in that a polymer is used in which the radicals R ,, Rg, R _Q , R ^ ₂ , R ^ 5 ^and R ^ e are not present. 7. The method according to claim 1, characterized in that a polymer is used in which the radicals R ^., R ₂ , B ", R _Q , R ^, and R,. ^ Are hydrogen atoms and the radicals R ,, R _Q and R ^ c are absent. 8. The method according to claim 1, characterized in that a polymer is used in which the radicals R,., R ₂ , R ", Rg, R ,, ^ and R ^ are hydrogen atoms and the radicals R ,, Rg, Rq , R ^ ₂ , R ^ c and R ^ ₈ are absent. Process according to Claim 1, characterized in that a polymer is used in which at least one of the radicals R ^, R ^ ₀ and R ^ g is not a hydrogen atom. 10. The method according to claim 1, characterized in that a polymer is used in which the radicals R ^, Rg, R ^, R ^ ₂ , R ^^ and R ^ _{8 are} not present and at least one of the radicals R ^, R ^ ₀ and R ^ g is a radical having about 1-10 carbon atoms and optionally about 0-4 hetero groups. 030015/0842 11. The method according to claim 1, characterized in that a polymer is used in which at least one of the radicals R, -, R ^ » ^S 17» ^G 1 ' ^G 2 ^{and <i G} 3 contains at least one of the following groupings: -OH, -O-, -C-, -i-o-, -C = N, O O Il Il -CH-, -CH ₂ -CH-, -C-NH ₂ , -C-NH-, C = NC = N -CH ₂ -CH-, -CH ₂ -CH-, -S-, r ° NH ₂ ■ f0- (CH ₂ JX ₂ CH ₃ ], - (CH ₂ CH (OH) CH H, HCH ₂ ^ x cfCH ₂ > _3r 5 I. f, [CH ₃ -fCH ₂ > x N-iCH ₂ f _x CH ₃ ] +, -SE-fCH ₂ > x Of, ¹³ iy 293911 « P- (OCH ₅ CH ₂ ^ _x -, -0
2 I X ₁₅ -CH ₂ -CH- -CHo-CH- CH ₃ -C-CH ₃ and -CH ₂ -CH- -SO ₃ H wherein R is a hydrocarbon radical having 0-10 carbon atoms and optionally 0-4 hetero groups and Xy.-Xy.n are independently integers of about 0-4. 12. The method according to claim 1, characterized in that that a polymer is used in which the branched chain of the branched polymer is hydrophilic and is essentially non-ionic " 030015/0842 _ ₇ _ 29391U 13. The method according to claim 12, characterized in that a branched polymer is used, which has ionic groups Process according to Claim 1, characterized in that a branched polymer is used which has more than one type of polymer unit. 15. The method according to claim 1, characterized in that a polymer is used in which the branched chains can be more strongly solvated than the skeletal chain or backbone chain. 16. The method according to claim 1, characterized in that a branched polymer is used which has an average value of about 1 or more branched chains per backbone polymer chain up to an average value of one or more has more branched chains on 98 out of 100 polymer units in each case in the backbone chain. 17. The method according to claim 1, characterized in that a branched polymer which is a branched chain with an average value of about 2-25,000 polymer units is used owns. 18. The method according to claim 1, characterized in that the branched polymer directly with an aqueous liquid to change at least one property of this aqueous liquid Liquid is mixed. 030015/0842 29391U 19. Process according to claim 1, characterized in that the branched polymer is mixed with an aqueous liquid and the mixture has a pH of less than about 10. 20. The method according to claim 1, characterized in that the branched polymer is mixed with an aqueous liquid, and that the mixture has a pH greater than about 7. 21. The method according to claim 1, characterized in that the branched polymer is mixed with an aqueous liquid, and that the mixture has a pH of less than about 3. 22. The method according to claim 20, characterized in that that the mixture has a pH greater than about 10. 23 · The method according to claim 19, characterized in that that the mixture has a pH of less than about 7. 24. The method according to claim 19, characterized in that that the mixture is applied to a particulate formation. Process according to Claim 24, characterized in that the mixture is used in a particulate formation to change the permeability of this formation to certain liquids or fluids. 26. The method according to claim 23, characterized in that a mixture is used which contains one or more acids in the form of hydrofluoric acid, hydrochloric acid, 030015/0842 29391H Nitric acid, sulfuric acid, phosphoric acid, acetic acid, Formic acid, hydroxyacetic acid, fumaric acid, citric acid, oxalic acid, an acid-forming compound or Contains mixtures thereof » 27. The method according to claim 26, characterized in that g e k e η η - ζ ei chnet that the mixture at a particulate Formation at a pressure greater than the fracture pressure or fracture pressure of this formation is applied. 28. The method according to claim 26, characterized in that the mixture in a particulate Formation at a pressure less than the fracturing pressure of the formation is applied. 29. The method according to claim 26, characterized in that the mixture in a particulate Formation is applied to react with a portion of this formation and to remove it. 30. The method according to claim 1, characterized in that the branched polymer with an aqueous, acidic liquid containing at least one acid for extending the reaction the acid is mixed. 31 · The method according to claim 18, characterized in that the mixture for transporting of particulate! Material is used in a pipe. 32. The method according to claim 31, characterized in that the mixture for bringing in-place of particulate! Material is used in a zone adjacent to an earth formation. 030015/0842 29391U 33. The method according to claim 24 or 32, characterized in that the mixture for acid fracturing a formation is used. 34. The method according to claim 1, characterized in that that the branched polymer with an aqueous liquid to change the flow of the liquid is mixed into a permeable formation adjacent to the mixture. 35. The method according to claim 1, characterized in that that the branched polymer with an aqueous, acidic liquid to reduce the liquid loss this mixture is mixed, and that the mixture in a particulate formation for change the flow properties of the fluid in this formation is used. 36. The method according to claim 35 »characterized in that that the mixture in a subterranean, drilled by a wellbore formation at a greater pressure is applied as the fracturing pressure of this formation. 37. The method according to claim 1, characterized in that that the branched polymer is introduced into an aqueous liquid within a permeable formation is used to vary the resistance to fluid flow of portions of this permeable formation. 38. The method according to claim 37, characterized in that that the branched polymer is formed in situ in this aqueous liquid after placing in place begins. 030015/0842 39 · The method of claim 37 characterized in that the mixture is used to alter the mobility profile adjacent a wellbore used for injecting aqueous fluid into a formation _; 40. The method according to claim 37 or 38, characterized in that the mixture for sealing a Formation used to prevent fluid flow through part of it 41. The method according to claim 1, characterized in that that the branched polymer is applied to a particulate material to improve the surface properties to change this particulate material. 42. The method according to claim 41, characterized in that that the branched polymer to change the WOR value of the liquid, which by a Zone of this particulate material flows, is applied. 43. The method according to claim 41, characterized in that that the branched polymer is applied to the particulate material by the branched Polymer is mixed with a carrier liquid and the mixture is allowed to flow through the material. 44. The method according to claim 43, characterized in that that the branched polymer to change the flow of aqueous liquid within the particulate material is applied. 45. The method according to claim 44, characterized in that that a carrier liquid is used which further contains an aqueous component. 030016/0842 46. The method according to claim 43, characterized in that a carrier liquid is used which at least one organic phase, an easily gasified component, a water-soluble salt, an acid, particulate Material, an O ^ -Cg alcohol, a Ο ^ -Ο ^ ο " Contains polyol, an aqueous phase or a mixture of two or more thereof. 47. The method according to claim 41, characterized net that the branched polymer on a particulate Material is applied by placing the particulate material in a liquid with the branched Polymer is suspended. 48. The method according to claim 41, characterized in that that the branched polymer is applied in a particulate formation to parts of the formation to make them less sensitive to liquids. 49. The method according to claim 48, characterized in that that the branched polymer is applied to a particulate formation containing clay to make the formation less sensitive to liquids. 50. The method according to claim 47, characterized in that that the surface properties of the particulate material to flocculate the suspended particles to be changed. 51. The method according to claim 41, characterized in that that the branched polymer is applied to a particulate formation to reduce the flow of Improve hydrocarbon fluids through a portion of this formation. 030015/0842 29391U 52. The method according to claim 41 , characterized in that a particulate formation which has been solidified by a resin is treated with branched polymer in order to make part of this formation less sensitive to liquids. 53. A method for changing the property of an aqueous liquid, characterized in that the liquid is brought into contact with a branched polymer which has a molecular weight of about 900-50 million and a significant proportion of at least one polymer unit of the following structural formula: where mean: from each other a hydrogen atom an alkyl, alkenyl, alkynyl, Aryl, acyl, cyclic hydrocarbon, heterocyclic hydrocarbon, hydroxyl, carboxyl, Carbonyl radical or the rest / "YD MD DQ ^- D CTD" D ^ / ττ _ j _ __ 19 »~ 19 20» "" ^ 19 »~ ^b 19 20» A ' ^oCLer combinations of these, which also contain oxygen, May contain sulfur, nitrogen or phosphorus; wherein X _{A is} -Cl, -Br or -NO ₃ , ^ 27 * ^ 30 33 each other an alkyl, Alkenyl, alkynyl, aromatic hydrocarbon radical or combinations thereof which also contain oxygen, nitrogen, sulfur or phosphorus can, where of each of these radicals R two 030015/0842 or more atoms together with the G group to form of a binge are bound, G *, Gc and Gg independently represent the radicals + + V I 9 » ^R 20» R ^ q and R ₂₀ independently of one another a nonexistent radical, a hydrogen atom or an alkyl, alkenyl, alkynyl, aryl, acyl, cyclic hydrocarbon, heterocyclic hydrocarbon radical or combinations thereof, which also contain oxygen, sulfur, nitrogen or May contain phosphorus, R ₂ ^. independently in each position an alkyl, alkenyl, alkynyl, aromatic hydrocarbon radical or combinations thereof, which can furthermore contain oxygen, sulfur, nitrogen or phosphorus, where R ₂ ^. has two or more atoms bonded together with the nitrogen to form a ring, n ^ ,, nc and ng independently of one another integers from about 0 to 500,000, where n ^ + Hr + n ₆ > 3, with each hydrocarbon radical being independent of one another Has 0 to 10 carbon atoms and optionally has 0 to hetero groups of oxygen, sulfur, nitrogen or phosphorus, and wherein the radicals attached to each atom and the structural formula thereof balance the bonds of that atom. 54. The method according to claim 53, characterized in that a polymer is used in which at least one of the radicals R ₂ c, ^R P6 » ^R 28» ^R 29 » ^R; 51 ^and Ri ₂ ^ß i ^{n is} hydrogen atom, 55 · The method according to claim 53, characterized in that a polymer is used in which at least one of the radicals R ₂ ^, R ^ ₀ , R ", G ^, G ₅ and Gg are the radicals 030015 / 08A2 f, CHOH-fCH ₂ ) -x ] _{2x 2χ 2χ} or combinations thereof, in which, depending on one another, have the value 0-4. -Xg independent56. Process according to Claim 53 »characterized in that a polymer is used in which at least one of the groups: ' O O ³ includes the following best: OCH ₃ OCH OCH ₃ where X ^ -X ^ independently of one another have the value 0-3000. 030015/0842 -16- 29391U 57 · The method according to claim 53 »characterized in that a polymer is used in which at least one of the radicals Rp5» ^ 26 '^ 28 * ^ 29 »^ 31 ^and ^ ^ 32 ^e ^ ^{n is a} hydrocarbon radical. 58 · The method according to claim 53, characterized in that a polymer is used in which at least one of the groups x- ^R p7 »/ ^ 50 ^{un (} * / ^ 33 contains one of the following residues: ! 0
-, -CO-, -C = II, -CH-, -CH ₂ -CH-, -C-NH ₂ , -C-NH-, C = NC = N -CH ₂ -CH-, -S-, ^Λ * '- "-Eo- (CH ₂ ) - _X ■ fO- <CH ₂ > _x CH ₃ ], -ECH ₂ CH (OH) CH ₂ f, CH-fCH ₂ f _x H, HCE ₂ ^ _x C ■ ^ 5 I. N- 030016/0642 29391H 10 11 CH ₃ ] -fS- (CH ₂ > _Y 13th 14th 16
CH -CH ₂ -CH- -CH ₂ -CH- C C C = O HH CH ₃ -C-CH ₃ CH ₂ I SO ₃ H and -CH ₂ -CH- , = 0 SO ₃ H wherein R is a hydrocarbon radical having 0-10 carbon atoms and optionally 0-4 hetero groups and X ^ -X _{117 are} independently integers of about 0-4. 030015/0842 59 · The method according to claim 53 »characterized in that a branched polymer is used, whose branched chain is hydrophilic and essentially non-ionic. 60. The method according to claim 59 »characterized in that that a branched polymer is used which has ionic groups. 61. The method according to claim 53, characterized in that that a branched polymer is used which has more than one type of polymer unit " 62. The method according to claim 53 »characterized by · net that a polymer is used in which the branched chains are more readily solvatable than the backbone chain or backbone chain. 63. The method according to claim 53, characterized in that that a branched polymer with an average of about 1 or more branched chains per backbone polymer chain up to an average of 1 or more branched chains for every 98 out of 100 polymer units having in the scaffolding chain. 64. The method according to claim 53, characterized in that that a branched polymer is used which has a branched chain with an average value of has about 2-25,000 polymer units. 65 · The method according to claim 53, characterized in, that the branched polymer directly with an aqueous liquid to change at least one Property of this aqueous liquid is mixed. 030015/0842 66. The method according to claim 53 »characterized in that that the branched polymer is mixed with an aqueous liquid, and that the mixture has a pH value of less than about 10. 67. The method according to claim 53 »characterized in that that the branched polymer is mixed with an aqueous liquid, and that the mixture has a pH value larger than about 7 ". 68. The method according to claim 53 »characterized in that that the branched polymer is mixed with an aqueous liquid, and that the mixture has a pH value of less than about 3. 69 · The method according to claim 67, characterized in, that the mixture has a pH greater than about 10. 70. The method according to claim 66, characterized in that that the mixture has a pH of less than about 7. 71 · The method according to claim 66, characterized in that that the mixture is applied to a particulate formation. 72. The method according to claim 71 »characterized in that that the mixture in the case of a particulate formation to change the permeability of this formation certain liquids or fluids is applied. 73. The method according to claim 70, characterized in that that the mixture contains one or more acids in the form of hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, Phosphoric acid, acetic acid, formic acid, hydroxy 03001S / 0842 -20- 29391U acetic acid, fumaric acid, citric acid, oxalic acid, one
contains acid-forming compound or mixtures thereof. 74 · The method according to claim 73 »characterized in that that, in the case of a particulate formation, the mixture is at a pressure greater than the fracturing pressure this formation is applied. 75 · The method according to claim 73 »characterized in that that the mixture is in a particulate formation at a lower pressure than the breaking pressure or fracturing pressure this formation is applied. 76. The method according to claim 73 »characterized in that that, in the case of a particulate formation, the mixture is for reaction with a portion of that formation and for removal of which is applied. 77 · The method according to claim 53 »characterized in that that the branched polymer with an aqueous, acidic, at least one acid-containing liquid for Extending the reaction of the acid being mixed. 78. The method according to claim 65, characterized in that that the mixture for the transport of particulate! Material is used in a pipe. 79 · The method according to claim 78, characterized in, that the mixture for placing particulate material in place in a zone adjacent to one Earth formation is applied. 80. The method according to claim 71 or 79, characterized in that the mixture for acid breakdown one Formation is used. 030015/0842 81. The method according to claim 53 »characterized in that that the branched polymer with an aqueous liquid to change the flow of the liquid is mixed into a permeable formation adjacent to this mixture. 82. The method according to claim 53 »characterized in that that the branched polymer with an aqueous, acidic liquid to reduce the loss of liquid of the mixture is mixed, and that this mixture is applied to a particulate formation to change the flow properties of the liquid in that formation will. 83. The method according to claim 82, characterized in that that the mixture in a subterranean, drilled by a wellbore formation at a greater pressure than the fracturing pressure of this formation is applied. 84-. Method according to claim 53 »characterized in that that the branched polymer in an aqueous liquid within a permeable formation for Changes in the resistance of parts of this permeable formation to the flow of liquid introduced will. 85 · Method according to claim 84-, characterized in that that the branched polymer is formed in situ in this aqueous liquid after placing in place begins. 86. The method according to claim 84, characterized in that that the mixture for changing the mobility profile in the vicinity of a borehole that is to be injected of aqueous fluid used in a formation is applied. 030015/0842 -22- 29391U 87 · The method according to claim 84 or 85 1, characterized in that the mixture is used for sealing a formation to prevent fluid flow through a part thereof. 88. The method according to claim 53, characterized in that that the branched polymer to one-particle Material for changing the surface properties of this particulate material is applied. 89. The method according to claim 88, characterized in that that the branched polymer to change of the WOR value of through a zone of this particulate Material flowing fluid is applied, 90. The method according to claim 88, characterized in that that the branched polymer is applied to the particulate material by the particulate Polymer is mixed with a carrier liquid and the mixture is allowed to flow through the material. 91. The method according to claim 90, characterized in that that the branched polymer to change the flow of aqueous liquid within the particulate Material is applied. 92. The method according to claim 91, characterized in that that the carrier liquid also contains an aqueous component. 93. The method according to claim 90, characterized in that the carrier liquid has at least one organic phase, an easily gasified component, a water-soluble salt, an acid, particulate material, a C ₁ -C ₆ -AlkOhOl, a C ₁ -C ₁₀ - PolyOl, an aqueous phase or a mixture of two or more thereof. 030015/0842 Process according to Claim 88, characterized in that that the branched polymer is applied to a particulate material by the particulate Material is suspended in a liquid with the branched polymer. 95. The method according to claim 88, characterized in that that the branched polymer is applied in a particulate formation to parts of the formation to make less sensitive to fluids " 96 · The method according to claim 95 »characterized in that that the branched polymer is applied to a particulate formation containing clay to make the formation less sensitive to fluids 97 · Method according to claim 94 ·, characterized in that that the surface properties of the particulate material are changed to the suspended particles to flocculate. 98. The method according to claim 88, characterized in that that the branched polymer is applied to a particulate formation to reduce the flow of hydrocarbon - Improve fluids through part of this formation. 99 · The method according to claim 88, characterized in that that a particulate formation which has been solidified by a resin is treated with branched polymer to make part of this formation less sensitive to fluids. 030015/0842 100. A method for changing the properties of an aqueous liquid, characterized in that this liquid is brought into contact with a branched polymer which has a molecular weight of about 900 to about 50 million and which contains a significant proportion of at least one polymer unit of the following structural formula: n, where mean: R, ^, R ^ r ₇ , R, Q, R ^ ₁ , R ^ ₂ and R ^ independently of one another a nonexistent radical or an alkyl, alkenyl, alkynyl, acyl, aryl, carbonyl, carboxyl -, aromatic hydrocarbon, cyclic hydrocarbon, heterocyclic hydrocarbon radical, or combinations thereof, which may also contain oxygen, sulfur, nitrogen or phosphorus, ^R 35 ^'R 36' ^R 39 * ^R 4O ^"R 4-3 ^{and R} 44 ^{una 'Dll} ä ⁿ SiS represent a hydrogen atom, an alkyl, alkenyl, alkynyl, aryl, acyl, carboxyl, carbonyl, cyclic hydrocarbon, heterocyclic hydrocarbon radical or the radicals from one another -OR ₁₉ , -NR ₁₉ R ₂₀ , -SR ₂₅ , -SR ₁₉ R ₂₀ , X _A , or combinations thereof, which can also contain oxygen, sulfur, nitrogen or phosphorus, in which X _{A is} -Cl, -Br or -NO ₂ and R _{35 is} independently in each position a hydrogen atom, an alkyl, alkenyl, alkynyl, aryl, acyl, cyclic hydrocarbon, heterocyclic hydrocarbon radical or a radical 030015/0842 M ⁺¹ , M ⁺² , M ⁺⁵ , M ⁺⁴ , """BR ₁ qR ₂₀ R ₂₁ R ₂₂ or combinations thereof, which can also contain oxygen, sulfur, nitrogen or phosphorus, and Ryjn» ^R 20 » R ₂₁ and R ₂₂ independently of one another a nonexistent radical, a hydrogen atom or an alkyl, alkenyl, alkynyl, aryl, acyl, cyclic hydrocarbon, heterocyclic hydrocarbon radical or combinations thereof, which also contain oxygen, sulfur, nitrogen or phosphorus may contain, mean O ₇ , n ₈ and ng are independently integers from about 0-500,000, where n ^ + n ^ n, Jk 3, wherein each hydrocarbon radical is independent of one another From 0 to 10 carbon atoms and optionally from 0 to 4 · hetero groups of oxygen, sulfur, nitrogen or phosphorus, and , wherein the radicals bonded to each atom and the structural formula balance the bonds of this atom. 101. The method according to claim 100, characterized in that a polymer is used in which at least one of the radicals R ^, R37 "^ 5"' ^R 41' ^R 42 ^and ^ ^R 45 is a hydrocarbon radical having 1 to 10 carbon atoms. 102. The method according to claim 100, characterized in that a polymer is used in which at least one of the radicals R, ^, ^ 371 ^R 3a » ^R 41» ^R 42 and ^R 45 is not present. 103. The method according to claim 100, characterized in that a polymer is used in which at least two of the radicals R, ^, R, n, R ™, R ^ ₁ , R ^ ₂ and R ^ _{5 are} hydrocarbon radicals. 030015/0842 -26- 29391H 104. The method according to claim 100, characterized in that a polymer is used in which at least two of the radicals Rxc ^ ^R 3ß » ^R 39» ^R 40 * ^R 43 ^ ¹¹ ^ ^R 44 are hydrocarbon radicals. 105. The method according to claim 100, characterized in that a polymer is used in which at least one of the radicals R35 » ^R 36» ^R 39 » ^R 40» ^R 43 ^{and R} 44 contains one of the following groupings: / _CH phch f · ) ₁ T- CH- (CH ₂ Hp- *; -HCH ± -0 $; -HCH-Hr-N *; -HCH-f. = - Λ ^ ZA ₂ ^ X ₃ 2 X ₄ 2 X ₅ ; - (C-NH ₂ ) or ic) -; j ₂ where X ^ -J. ^ are independently integers from about 0-4. 106.Verfahren according to claim 100, characterized in that a polymer is used in which at least one of the radicals R, ^, R ₅ , -, R3 ₆ , ^R 37> ^R 3q> ^R 3g » ^R 4O» ^R 4i » ^R 42 » ^R 43» ^E 44 ^{and R} 45 contains at least one of the following groupings: Q Ο -OH, -Ο-, -C-, -C-O-, -C = N, 0 0 -pH-, -CH ₂ -CH-, -C-NH ₂ , -C-NH-, C = H C = N -CH ₂ -CH-, -CH ₂ -CH-, -S-, C = OC = O NH ₂ 0- 030015/0842 - 27 - 29391U [CH, -ECH, Hr-N-ECH 3 I XJ CH-], J. .frt \, -S-HCH frr — Oi-, 2 X ₁₃ i X ₁₄ P-EOCH
I. CH ₂ -CH- 15th Ö-C-CH. ^{Λ Λ} 16 O-ECH Hr-CH, , -CH ₂ -CH- C = O NH CH ₃ -C-CH ₃ SO ₃ H and -CH ₂ -CH- C = O \ NH R-SO _x H wherein R is a hydrocarbon radical with 0-10 carbon atoms and optionally 0-4 hetero groups and X ^ -X ^ r, independently of one another, are integers from 0-4. 030015/0842 107 · The method according to claim 100, characterized in that the mixture of branched polymer and
the aqueous liquid does not contain portland cement, acid-soluble carbonate particles or a combination thereof, 108 · The method according to claim 100, characterized in that a polymer is used in which the branched chain of the branched polymer is hydrophilic
and is substantially non-ionic. 109. The method according to claim 108, characterized in that that a branched polymer is used which has ionic groups. 110. The method according to claim 100, characterized in that a branched polymer is used which has more than one type of polymer unit. 111. The method according to claim 100, characterized in that a polymer is used in which the
branched chains are more readily solvatable than the backbone chain or backbone chain. 112. The method according to claim 100, characterized in that a branched polymer is used which
an average of about 1 or more branched chains per backbone polymer chain to an average of one or more branched chains for every 98
of 100 polymer units in the backbone chain. 113 · The method according to claim 100, characterized in that a branched polymer is used,
this is a branched chain with an average value of
has about 2-25,000 polymer units. 114. The method according to claim 100, characterized in that the branched polymer directly with a
aqueous liquid for changing at least one
Property of this aqueous liquid is mixed. 030015/0842 29391H - 29- Method according to claim 100, characterized in that that the branched polymer is mixed with an aqueous liquid and the mixture has a pH value of less than about 10. . Method according to claim 100, characterized in that that the branched polymer is mixed with an aqueous liquid, and that the mixture has a pH value greater than about 7. . Process according to Claim 100, characterized in that the branched polymer is mixed with an aqueous liquid and that the mixture has a pH of less than about 3. 118. The method according to claim H "6, characterized in that that the mixture has a pH greater than about 10 owns. 119. The method according to claim 115 »characterized in that that the mixture has a pH of less than owns about 7. 120 · Method according to claim H 5, characterized in that that the mixture is applied to a particulate formation. 121. The method according to claim 120, characterized in that that the mixture in a particulate formation to change the permeability of that formation is applied to certain liquids or fluids. 122. The method according to claim 119, characterized in that that a mixture is used which contains one or more acids in the form of hydrofluoric acid, hydrochloric acid, 030015/0842 29391U Nitric acid, sulfuric acid, phosphoric acid, acetic acid, Formic acid, hydroxyacetic acid, fumaric acid, citric acid, oxalic acid, an acid-forming compound or Contains mixtures thereof. 123 · Method according to claim 122, characterized in that g e k e η η that the mixture in a particulate formation at a pressure greater than that Breaking pressure or fracturing pressure of this formation is applied. 124 * The method according to claim 122, characterized in that the mixture in a particulate Formation at a pressure less than the fracturing pressure of the formation is applied. · The method according to claim 122, characterized in that the mixture in a particulate Formation is applied to react with a portion of this formation and to remove it. . Process according to claim 1CD, characterized in that the branched polymer with an aqueous, acidic liquid containing at least one acid for extending the reaction the acid is mixed. · The method according to claim 114, characterized in that the mixture for transport of particulate! Material is used in a pipe. · The method according to claim 127, characterized in that the mixture is put in place of particulate! Material is used in a zone adjacent to an earth formation. 030015 / 08A2 29391U 129. The method according to claim 120 or 128, characterized in that the mixture for acid fracturing a formation is used. 130. The method according to claim 100, characterized in that that the branched polymer with an aqueous liquid to change the flow of the liquid is mixed into a permeable formation adjacent to the mixture. 131 ,. Method according to claim 100, characterized in that that the branched polymer with an aqueous, acidic liquid to reduce the loss of liquid this mixture is mixed, and that the mixture in a particulate formation for change the flow properties of the fluid in this formation is used. 132. The method according to claim 131, characterized in that that the mixture in a subterranean, drilled by a wellbore formation at a greater pressure is applied as the fracturing pressure of this formation. 133. The method according to claim 100, characterized in that that the branched polymer is introduced into an aqueous liquid within a permeable formation is used to vary the resistance to fluid flow of portions of this permeable formation. 134-. Process according to Claim 133 _J, characterized in that the branched polymer is formed in situ in this aqueous liquid after the placing in place begins. 030015/0842 29391H 135 · Method according to claim 133 »marked thereby net that the mixture is used to create the mobility profile adjacent to a wellbore used to inject aqueous fluid into a formation will change. . 136. The method according to claim 133 or 13 * »characterized in that the mixture for sealing a Formation to prevent fluid flow through any part thereof is applied. 137. The method according to claim 1004, characterized in that that the branched polymer is applied to a particulate material to improve the surface properties to change this particulate material. 138. The method according to claim 137 »characterized in that that the branched polymer to change the WOR value of the liquid flowing through a zone of this particulate material is applied will. 139 The method according to Claim 137> characterized in that that the branched polymer is applied to the particulate material by the branched Polymer is mixed with a carrier liquid and the mixture is allowed to flow through the material. 140. The method according to claim 139, characterized in that that the branched polymer to change the flow of aqueous liquid within the particulate material is applied. Process according to Claim 140, characterized in that that a carrier liquid is used which further contains an aqueous component. 030015/0842 29391U 142. The method according to claim 139 »characterized in that a carrier liquid is used which contains at least one organic phase, an easily gasified component, a water-soluble salt, an acid, particulate material, a C ^ -Cg alcohol, a G ^ -O ^ q- polyol, an aqueous phase or a mixture of two or more thereof. 143. The method according to claim 137 »characterized thereby net that the branched polymer on a particulate Material is applied by placing the particulate material in a liquid with the branched Polymer is suspended. 144. The method according to claim 157, characterized in net that the branched polymer at a particulate Formation is used to make parts of the formation less sensitive to liquids. 14-5. Method according to Claim 144, characterized net that the branched polymer at a particulate Formation, which contains clay, is applied to make the formation less sensitive to liquids close. 146. The method according to claim 143, characterized in net that the surface properties of the particulate Material to flocculate the suspended particles can be changed. 147. The method according to claim 137 »characterized in that the branched polymer is applied to a particulate formation to reduce the flow of
Improve hydrocarbon fluids through a portion of this formation. 030016/0842 148 · The method according to claim 137, characterized in that a particulate formation which has been solidified by a resin is treated with branched polymer in order to make part of this formation less sensitive to liquids. 149. A method for changing the properties of an aqueous liquid, characterized in that the liquid is brought into contact with a branched polymer which has a molecular weight of about 900-50 million and a significant proportion of at least one polymer unit of the following structural formula: - Ν R ₄₈ ö- ¹ IO 52 ₅₄ - IL where mean: ^R 46 » ^R 47» ^R 49 » ^R 5O» ^R 52 ^{and R} 53 independently of one another a nonexistent radical, a hydrogen atom, an alkyl, alkenyl, alkynyl, aryl, acyl, cyclic hydrocarbon, heterocyclic hydrocarbon , Hydroxyl, carboxyl, carbonyl radical or combinations thereof, which can also contain oxygen, nitrogen, sulfur or phosphorus, ^{un (} * ^ from each other a nonexistent radical or an alkyl, alkenyl, alkynyl, Aryl, acyl, carbonyl, carboxyl, aromatic hydrocarbon, cyclic hydrocarbon, heterocyclic Hydrocarbon radical or combinations thereof, which continue to be oxygen, sulfur, nitrogen or phosphorus, but all three radicals R cannot be non-existent, 030015/0842 «29391U n ^ Q, n ^^ j and n ^ independently of one another whole numbers from about 0 to 500,000, where n ^ + n ^ + n ^ > 3, wherein each hydrocarbon radical is independent of one another Has 0 to 10 carbon atoms and optionally 0 to hetero groups of oxygen, sulfur, nitrogen or Has phosphorus, and wherein the radicals attached to each atom and the structural formula balance the bonds of that atom. 150. The method according to claim 149, characterized in that a polymer is used in which at least one of the radicals R ^ g ₁ ^R 47 » ^R 49» ^R 50 * ^R 52 ^ ⁰⁰ ^ ^R 53 is not present. I5I · The method according to claim 149, characterized in that a polymer is used in which at least one of the radicals R ^, R ₁ - ^. and R, - ^, is absent. 152. The method according to claim 149, characterized in that a polymer is used in which at least two of the radicals R ^ g, ^R & 9 » ^R 4Q» ^R 50 »^ 52 ¹ ^ ^ 53 are hydrogen atoms. 153 · The method according to claim 149, characterized in that a polymer is used in which at least three of the radicals R ^ ₆ , R ^ r ₇ , ^R 4g * ^R 50 » ^R 52 ^{and R} 53 are hydrogen atoms. 154.Verfahren according to claim 149, characterized in that a polymer is used in which at least one of the radicals R ₄₆ , R ₄₇ , R ₄₃ , R ₄₉ , R ₅₀ , R ₅₁ , Rc ₂ »Rcχ and Rc ^. contains the following polymer units: 030015/0842 29391H - (CH ₂ K, NH-CO- (CH,) ·, - (OCH ₇ CH ₀ ) -, ι ^Χ 1 ^{2 Χ} 2 ²² | - (CH ₂ ) - NH- (CH f, - (CH ₂ ) - CO-NH- (CH ₂ ) -, "(CH ₂ ) - -N- (CH ₂ K., ^Χ 3 ^ 4 ^ ^Χ 5 ^{Ζ Χ} 6 ^Χ 7 ' N *, -HCH ₂ K, NHf, - (CH 9 ^{Ζ Χ} 12 Λ CH- (CH ₀ V, - (OCH ₁ ), ^W 12 CH ₃ ] where x ^ -χ, -ο are independently integers of about O Ms 10. «The method according to claim 149, characterized in that a polymer is used in which at least one of the radicals R / ig, - ^ 4.7» * Wj »R ^ iQ, R ₁ -Q, R ₁ -,], Rcp, Rrz and R _n - /, contains at least one of the following groupings: O Q -OH, -0-, -C-, -C-O-, -C = N, 3 pp -C-NH. ,, -ö- -CH-, -CH ₂ -CH-, -C-NH ₂ , -C-NH-, C = N -CH ₂ -CH-, -CH ₂ - £ H-, -S-, ; = ο ^ι 2 , = 0 ■ fO-iCH. 03001B / 08A2 , -fCH ₂ CH (OH) ■ f NH- (CH [CH ₃ - (CH ₂ f ^ l J Z X _lo | _r2 ^ _r 8 P- (OCH CH> -CH ₂ -CH- -C-CH OP-O-fCH 2 * X il ' 0- (CH _o >, CH. 17th -CH ₂ -CH- : = o iH CH, -C- CH ₂ SO ₃ H and -CH ₀ -CH- ^d I C = OI MI I R-SO _x H where R is a hydrocarbon radical having 0-10 carbon atoms and optionally 0-4 hetero groups and X * -Xy, rp are, independently of one another, integers from 0-4. 030015/0842 29391U 156. The method of claim 149, characterized net gekennzeich that a polymer is used, in which the branched chain of the branched polymer is hydrophilic and essentially non-ionic. 157. The method according to claim 156, characterized in net that a branched polymer is used, which has ionic groups. 158. The method according to claim 149, characterized in that a branched polymer is used, which has more than one type of polymer unit. 159 · The method according to claim 149, characterized in net that a polymer is used in which the branched chains are more readily solvatable than the backbone chain or backbone chain. 160. The method according to claim 149, characterized in that a branched polymer is used, that is an average of about 1 or more branched chains per backbone polymer chain up to one Average value of one or more branched chains for every 98 of 100 polymer units in the backbone chain owns. 161. The method according to claim 149, characterized in that that a branched polymer is used, which has a branched chain with an average value of about 2-25,000 polymer units. 162. The method according to claim 149, characterized in that that the branched polymer directly with an aqueous liquid to change at least one Property of this aqueous liquid is mixed. 030015/0842 29391H 163. The method according to claim 149, characterized in that that the branched polymer is mixed with an aqueous liquid and the mixture has a pH value of less than about 10. 164. The method according to claim 149, characterized in that that the branched polymer is mixed with an aqueous liquid, and that the mixture has a pH value greater than about 7. 165. The method according to claim 149, characterized in that that the branched polymer is mixed with an aqueous liquid, and that the mixture has a pH value of less than about 3. 166. The method according to claim 164, characterized in that that the mixture has a pH greater than about 10. 167. The method according to claim 163, characterized that the mixture has a pH of less than owns about 7. 168. The method according to claim 163, characterized in that that the mixture is applied to a particulate formation. 169. The method according to claim 168, characterized in that that the mixture in a particulate formation to change the permeability of that formation is applied to certain liquids or fluids. 170. The method according to claim 167, characterized in that that a mixture is used which contains one or more acids in the form of hydrofluoric acid, hydrochloric acid, 030015/0842 -40- 29391U Nitric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, hydroxyacetic acid, fumaric acid, citric acid, Contains oxalic acid, an acid-forming compound or mixtures thereof 171 · Method according to claim 170, characterized in that g e k e η η ζ ei ch net that the mixture in a particulate formation at a pressure greater than that Breaking pressure or fracturing pressure of this formation is applied. 172. The method according to claim 170, characterized in that the mixture in a particulate Formation at a pressure less than the fracturing pressure of the formation is applied. 173 · The method according to claim 170, characterized in that the mixture in a particulate Formation is used to react with and remove any part of that formation, 174 ·. Process according to claim 14-9, characterized in that the branched polymer with an aqueous, acidic liquid containing at least one acid for extending the reaction the acid is mixed. 175 · The method according to claim 162, characterized in that the mixture for transporting of particulate! Material is used in a pipe. 176. The method according to claim 175, characterized in that the mixture for bringing-in-place of particulate! Material is used in a zone adjacent to an earth formation. 030015 / 08U 29391H 177. The method according to claim 168 or 176, characterized in that the mixture for acid fracturing a formation is used. 178. The method according to claim 149, characterized in that that the branched polymer with an aqueous liquid to change the flow of the liquid is mixed into a permeable formation adjacent to the mixture. 179 · The method according to claim I49 £ a characterized by, that the branched polymer with an aqueous, acidic liquid to reduce the loss of liquid this mixture is mixed, and that the mixture in a particulate formation for change the flow properties of the fluid in this formation is used. 180. The method according to claim 179, characterized in that that the mixture in a subterranean, drilled by a wellbore formation at a greater pressure is applied as the fracturing pressure of this formation. 181. The method according to claim "W9, characterized in that that the branched polymer is introduced into an aqueous liquid within a permeable formation is used to vary the resistance to fluid flow of portions of this permeable formation. 182. The method according to claim 181, characterized in that that the branched polymer is formed in situ in this aqueous liquid after placing in place begins. 030015/0842 29391Η -42 - 183 * Method according to claim 181, characterized in that that the mixture is used to create the mobility profile adjacent to a borehole that is to be injected of aqueous fluid used in a formation to change. 184. The method according to claim 181 or 182, characterized in that the mixture for sealing a Formation to prevent fluid flow through any part thereof is applied. 185. The method according to claim 149, characterized in that that the branched polymer is applied to a particulate material to improve the surface properties to change this particulate material. 186. The method according to claim 185, characterized in that that the branched polymer to change the WOR value of the liquid, which by a Zone of this particulate material flows, is applied. 187. The method according to claim 185, characterized in that that the branched polymer is applied to the particulate material by the branched Polymer is mixed with a carrier liquid and the mixture is allowed to flow through the material. 188. The method according to claim 187, characterized in that that the branched polymer to change the flow of aqueous liquid within the particulate material is applied. 189. The method according to claim 188, characterized in that that a carrier liquid is used which further contains an aqueous component. 030015/0842 29391U
- 43 - 190 · · The method according to claim 187 ^ characterized in that a carrier liquid is used which contains at least an organic phase, an easily gasified component, a water-soluble salt, an acid, particulate material, a C ^ -Gg alcohol, a ^G. <tC * Q- polyol, an aqueous phase or a mixture of two or more of these contains 191 · The method according to claim 185, characterized in that the branched polymer is based on a particulate Material is applied by the particle blow dryer Material is suspended in a liquid with the branched polymer, 192 · Method according to Claim 185, characterized in net that the branched polymer at a particulate Formation is used to make parts of the formation less sensitive to liquids 193 · Method according to Claim 192, characterized in net that the branched polymer at a particulate Formation, which contains clay, is applied to make the formation less sensitive to liquids close· 194. The method according to claim 191, characterized in that net that the surface properties of the particulate Material to flocculate the suspended particles can be changed. The method according to claim 18 5, characterized in that the branched polymer is applied to a particulate formation to reduce the flow of
Improve hydrocarbon fluids through a portion of this formation. 030016/0842 29391U 196. The method according to claim 185, characterized in that a particulate formation, which has been solidified by a resin, is treated with branched polymer to make up part of it Make formation less sensitive to liquids. 197 Process for changing the properties of an aqueous liquid, characterized in that that this liquid is brought into contact with a branched polymer having a molecular weight of owns about 900-50 million and has a significant Contains at least one polymer unit of the following structural formula: 2 ^OR 58 '56 ^OR 63 where mean: R ₆₁ and ^v cn »-" 5Qj - "- c ^ q» "απ ''"'oil"^ ¹ " · ^Λ 6 ^ 5 independently of one another a hydrogen atom, an alkyl, alkenyl, alkynyl, aryl, acyl, Carboxyl, carbonyl, cyclic hydrocarbon, heterocyclic hydrocarbon radical, one of the radicals M, M, M ⁺ *, M, a pentose unit, a hexose unit or combinations thereof, which can also contain oxygen, sulfur, nitrogen or phosphorus, 15/0842 29391U wherein M is independently an ammonium radical, substituted ammonium radical, or a metal ion in each position or a mixture thereof, n. ,, n. ^ and n ^ c are independently integers from about 0-500,000, where η ^, + η ^ + η ^, -> 3 is wherein each hydrocarbon radical is independent of one another 0 to 10 carbon atoms and optionally 0 to 4 hetero groups of oxygen, sulfur, nitrogen or phosphorus contains and wherein the radicals attached to each atom and the structural formula balance the bonds of that atom. 198. The method according to claim 197 »characterized in that a polymer is used in which at least one of the radicals Hrr, ^ ςς» ^ «57» Reg, Ηγλ, ^R 50 » ^R 61 ' ^R 62 ^{and R} 63 has ^a branched chain Polymer units of the formula ^ RX) · Contains, in which R is a C ^ -CQ hydrocarbon radical and X is nitrogen, oxygen or sulfur. 199 · The method according to claim 197, characterized in that a polymer is used in which at least one of the radicals Rrr, ^ 50 »^« 571 Reg » ^R 59» ^R 60 » ^R 61» ^R 62 ^{and R} 63 ^{has a} branched chain which contains pentose units, hexose units, or a combination thereof. 200. The method according to claim 197 »characterized in that a polymer is used in which at least one of the radicals Rrr, Rrg, Rrn, ^R 58» ^R 59 » ^R 60» ^R 61 » ^R 62 ^{and R} 63 has ^a branched polymer chain, which polymer units of the following formulas contains: «O-CH ₂ CH ₂ >, -CH ₂ CHCH ₂ ) -, -HCH ₂ ^ _x CH- (CH ₂ > _X f, -fO-fCH ^ CH ₃ ], 030015 / 0ΘΑ2 29391U or combinations thereof, where x ^ -x * are independently integers of are around 0-4. 201. The method according to claim 197, characterized in that a polymer is used in which at least one of the radicals firr, ^ 55 »^ 57» Hrg, ^B CQ » ^R 60» ^R 61, ^R 62 ^{and R} 63 ^Gru PPi ^erun g ^{s of the} following formulas: zr, 44-OL, -fO-fCH , K, CH-] , -iC-NH-f or -fä-NH where χ ,, - χ ^, independently of each other integers of are around 0-4. 202. The method according to claim 197 »characterized in that a polymer is used in which at least one of the radicals Rrr, ^ 55» ^ 57 »Reg» R59 » ^B 50» ^ 61 * ^ 62 ^{un (} * ^ 65 ^wen iS ^s ^ ^{ens contains} a grouping of the following formulas: ^ -30016 / 0842 Ϊ p -OH, -0-, -C-, -C-O-, -C = N, 29391U -CH-, -CH ₂ -CH-, -C-NH ₂ , -C-NH-, C = N -CH ₂ -CH-, C = O NH. C = O 0- ♦ ϊ , -fCH ₂ CH Kr-CH- (CH-frr-fj, -RCH Ht-C ^Λ 3 4 si ₂ ^ H-, [CH ₃ - (CH ₂ f ^ 7 8 [CH ₁ - (CH ₉ Hr-N- (CH f ^ - CH], J £ X ₁₀ I -ί A ₁₁ J CH ₃ ], jf = J, 2 X ₁₃ Ί.5 - OP-O- (CH ₂ f 2'X 04CH, J. 16 CH. 030015/0842 29391H -CH ₂ -CH-, -CH ₂ -CH- O-C-CH-C = O NH ^S0 3 ^H and -CH ₂ -CH- C = O NH R-SO ₃ H wherein R is a hydrocarbon radical having 0-10 carbon atoms and optionally 0-4 hetero groups and X _-1 -X ^ r _{7 are} independently integers of about 0-4. 203 · The method according to claim 197 »characterized in that a polymer is used in which the branched chain of the branched polymer is hydrophilic and essentially non-ionic is. 030015/0842 29391U 204. The method according to claim 203, characterized in that a branched polymer is used which has ionic groups. 205. The method according to claim 197, characterized in that a branched polymer is used which has more than one type of polymer unit. 206. The method according to claim 197, characterized in that a polymer is used in which the branched chains are more solvatable than the backbone chain or backbone chain 207 · Process according to Claim 197, characterized in that a branched polymer is used which has an average of about 1 or more branched chains per backbone polymer chain up to an average of one or more branched chains for every 98 out of 100 polymer units owns in the backbone chain. 208. The method according to claim 197, characterized in that a branched polymer which is a branched chain with an average value of about 2-25,000 polymer units is used owns. 209. The method according to claim 197, characterized in that the branched polymer directly with an aqueous liquid to change at least one property of this aqueous liquid Liquid is mixed. 030015/0842 210. The method according to claim 197, characterized in that that the branched polymer is mixed with an aqueous liquid and the mixture has a pH value of less than about 10. 211. The method according to claim 197, characterized in that that the branched polymer is mixed with an aqueous liquid, and that the mixture has a pH value greater than about 7. 212. The method according to claim 197, characterized in that that the branched polymer is mixed with an aqueous liquid, and that the mixture has a pH value of less than about 3. 213 · Method according to claim 2H, characterized in that that the mixture has a pH greater than about 10. 214. The method according to claim 210, characterized in that that the mixture has a pH of less than owns about 7. 215. The method according to claim 210, characterized in that that the mixture is applied to a particulate formation. 216. The method according to claim 215, characterized in that the mixture in a x * particulate formation used to change the permeability of this formation to certain liquids or fluids will. 217. The method according to claim 214, characterized in that that a mixture is used which contains one or more acids in the form of hydrofluoric acid, hydrochloric acid, 030015/0842 -51- 29391U Nitric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, hydroxyacetic acid, fumaric acid, citric acid, Contains oxalic acid, an acid-forming compound or mixtures thereof. 218. The method according to claim 217, characterized in that g e k e η η - ζ e i ch η e t that the mixture at a particulate Formation at a pressure greater than the fracture pressure or fracture pressure of this formation is applied. 219. The method according to claim 217, characterized in that the mixture in a particulate Formation at a pressure less than the fracturing pressure of the formation is applied. 220. The method according to claim 217, characterized in that the mixture in a particulate Formation is applied to react with a portion of this formation and to remove it. 221. The method according to claim 197, characterized in that the branched polymer with an aqueous, acidic liquid containing at least one acid for extending the reaction the acid is mixed. 222. The method according to claim 209, characterized in that the mixture for transporting of particulate! Material is used in a pipe, 223. The method according to claim 222, characterized in that the mixture for bringing in-place of particulate! Adjacent material in a zone used to form an earth formation. 030015/0842 224. The method according to claim 215 or 223, characterized in that the mixture for acid fracturing a formation is used. 225. The method according to claim 197, characterized in that that the branched polymer with an aqueous liquid to change the flow of the liquid is mixed into a permeable formation adjacent to the mixture. 226. The method according to claim 197, characterized in that that the branched polymer with an aqueous, acidic liquid to reduce the loss of liquid this mixture is mixed, and that the mixture in a particulate formation for change the flow properties of the fluid in this formation is used. 227. The method according to claim 226, characterized in that that the mixture in a subterranean, drilled by a wellbore formation at a greater pressure is applied as the fracturing pressure of this formation. 228. The method according to claim 197 »characterized in that that the branched polymer is introduced into an aqueous liquid within a permeable formation is used to vary the resistance to fluid flow of portions of this permeable formation. 229 * Method according to claim 228, characterized in that that the branched polymer is formed in situ in this aqueous liquid after placing in place begins. 030015/0842 230. The method according to claim 228, characterized in that the mixture is used to create the mobility profile adjacent to a wellbore used to inject aqueous fluid into a formation will change. . 231. The method according to claim 228 or 229, characterized in that the mixture for sealing a Formation to prevent fluid flow through any part thereof is applied. 232. The method according to claim 197, characterized in that that the branched polymer is applied to a particulate material to improve the surface properties to change this particulate material. 233. The method according to claim 232, characterized in net that the branched polymer to change the WOR value of the liquid flowing through a zone of this particulate material is applied will. Method according to Claim 232, characterized in that net that the branched polymer on the particulate Material is applied by mixing the branched polymer with a carrier liquid and flowing the mixture through the material. 235. The method according to claim 23 ^, characterized net that the branched polymer to change the flow of aqueous liquid within the particulate material is applied. 236. The method according to claim 235, characterized in net that a carrier liquid is used, which furthermore contains an aqueous component. 030015/0842 29391U 237. The method according to claim 235, characterized in net that a carrier liquid is used, which at least one organic phase, an easily gasified component, a water-soluble salt, an acid, particulate Material, a C ^ -Gg alcohol, a C ^ -C ^ q polyol, contains an aqueous phase or a mixture of two or more thereof. 238. The method according to claim 232, characterized in that the branched polymer is based on a particle-shaped Material is applied by the particle blow dryer Material is suspended in a liquid with the branched polymer. 239. The method according to claim 232, characterized in that the branched polymer in a particulate Formation is used to make parts of the formation less sensitive to liquids. 240. The method according to claim 239, characterized in net that the branched polymer at a particulate Formation, which contains clay, is applied to make the formation less sensitive to liquids close. 241. The method according to claim 238, characterized in that net that the surface properties of the particulate Material to flocculate the suspended particles can be changed. 242. The method according to claim 232, characterized in that net that lasted branched polymer with a particulate Formation is applied to the flow of hydrocarbon fluidsu through a portion of this formation to improve. 030015/0842 29391U 243. The method according to claim 232, characterized in that a particulate formation, which has been solidified by a resin, is treated with branched polymer to make up part of it Make formation less sensitive to liquids. 244. A method for changing the properties of an aqueous liquid, characterized in that that this liquid is brought into contact with a branched polymer having a molecular weight of about 900-50 million and a significant proportion of at least one polymer unit of the following Structural formula contains: ^l 64 " 65 66 16 where mean: ^R 64 » ^R 67 ^{and R} 70 independently of one another a nonexistent radical or an alkyl, alkenyl, alkynyl, Aryl, acyl, carbonyl, carboxyl, aromatic hydrocarbon, cyclic hydrocarbon, heterocyclic hydrocarbon radical or combinations thereof, which also contain oxygen, sulfur, May contain nitrogen or phosphorus, ^R 65 * ^R 66 » ^R 68 ' ^R 69 » ^R 71 ^{and R} 72 from one 68 ' ^R 69 »
on the other a hydrogen atom, an alkyl, alkenyl, alkynyl, aryl, acyl, cyclic hydrocarbon, heterocyclic hydrocarbon, carboxyl, 030015/0842 -56- 29391H Carbonyl radical or the radical -OR _x JQ, -NR ^ -SR ^ qRp ₀ , X., or combinations thereof, which can also contain oxygen, nitrogen, sulfur or phosphorus,
wherein X _{A is} -Cl, -Br or -NO ₂ , X _ß , X _fl and XQ independently of one another oxygen or sulfur, RQ, Ep ₀ , R ₂ ^ and Rp ₂ independently of one another a nonexistent radical, a hydrogen atom, an alkyl, alkenyl, alkynyl, aryl, acyl, cyclic hydrocarbon, heterocyclic hydrocarbon radical or combinations thereof, which furthermore contain oxygen May contain sulfur, nitrogen or phosphorus, Rp, independently of one another in each position, is a hydrogen atom, an alkyl, alkenyl, alkynyl, aryl, acyl, cyclic hydrocarbon, heterocyclic hydrocarbon radical, a radical M ⁺ " ¹ , M ⁺² , M ⁺ ^, M , R ^ _Q , Rp ₀ , Rp., Rpp or combinations thereof, which can also contain oxygen, sulfur, nitrogen or phosphorus, where M is independently an ammonium radical in each position, substituted aminium radical, a metal ion or a mixture thereof, n ^ g, n ^ rp and n ^ g independently of one another whole numbers from about 0 - 500,000, where n.g + n ^ + n ^ g> 3, wherein each hydrocarbon radical is independent of one another 0 to 10 carbon atoms and optionally 0 to 4 hetero groups of oxygen, sulfur, nitrogen or phosphorus contains, and wherein the radicals attached to each atom and the structure thereof balance the bonds of that atom. 030015/0842 -57- 29391U 245. The method according to claim 244, characterized in that a polymer is used in which X ₂ , X * and X ^ are oxygen. 246. The method according to claim 244, characterized in that a polymer is used in which Xp, X, and X ^, are sulfur. 247. The method according to claim 244, characterized in that a polymer is used in which the radicals Rg / i »Rgo and R„ _{o are} not present. 248. The method according to claim 244, characterized in that a polymer is used in which the radicals R54. » R50 and Rr ₇ QC ^ -Gg-alkyl radicals ,are. 249. The method according to claim 244, characterized in that a polymer is used in which the radicals Rgc, Rgg >> 68 >> 69 >> 71 ^{and R} 72 are hydrogen atoms. 250. The method according to claim 244, characterized in that a polymer is used in which at least four of the radicals R ^ c » ^ ■ ffj ^ 68» ^ 6 Rr ₇ ,, and R ^ 2 are hydrogen atoms. 251. The method according to claim 244, characterized in that a polymer is used in which at least one of the radicals R ₆ ^ p R ₆₇ and R ₇₀ contains branched chains. 252. The method according to claim 244, characterized in that a polymer is used 030015/0842 -58- 29391H in which at least three of the radicals Rgc »^ gg» - ^ 68 '^ 6 R ™ and R _{7 are} 2 hydrogen atoms. 253. The method according to claim 244, characterized in that a polymer is used in which at least one of the radicals Rgcf ^ 55 »^ 68 * ^ and R _{7 are} 2 hydrogen atoms. 254. The method according to claim 244, characterized in that a polymer is used in which at least one of the radicals Egr, ^ gg »^ 68» ^ Rr;,. and Rrpo is Cj-Cg alkyl. 255 · The method according to claim 244, characterized in that a polymer is used in which the repeating unit of the branched chain is selected from the grouping £ R-X}, wherein R is a C ^ -Cg hydrocarbon radical and X is nitrogen, Are oxygen or sulfur. 256. The method according to claim 244, characterized in that a polymer is used in which at least one branched chain has at least one polymer unit of the following groupings contains: CH>, - (CH ₂ -CH-C-OR ₁ ) - ° ^^ ^r -CH ₂ -CH-C where R = H, CR ^ or a C ₂ -C ₆ hydrocarbon radical and R ^ j, R2, R, and R ^ independently of one another are a hydrogen atom, an alkyl, alkenyl, alkynyl, aryl, acyl , 030C1S / 0842 -59- 29391U cyclic hydrocarbon, heterocyclic hydrocarbon radical or combinations thereof, which can further contain 0, N, S or P. 257. The method according to claim 244, characterized in that a polymer is used in which at least one of the radicals Rgc, ^ gg »^ 68 * RgQ, Rr _7,. and Rr ₇ O contains at least one grouping of the following formulas: - (CH ₂ CH ₂ O *, - (CH ₂ -CH-O *, -C = O, Η0Η ₂ ) - _χ CH- (CH ₂ * _x * -CH-O *, -C = O, -KCH ₉ * I Τ ^x CH-, NHt 3 ^NM 2 or l> j wherein X ^ and X _{2 are} independently integers from about 0-4. 258. The method according to claim 244, characterized in that a polymer is used in which at least one of the radicals R ^ c, Rgg » ^R 68» RgO, R ₁₇ ^ and R _{72 has} branched chains. 259 · The method according to claim 244, characterized in that a polymer is used in which at least one of the radicals Rg /. j Rgc; » ** 66 ^l Rgr>, Rgg, ^ 59 "^ 70" ^ 71 ^{un <^} ^ 72 ^who i6 ^s t ^ens a grouping of the following formulas: 030015/0842 29391H ο ο Il H -OH, -0-, -C-, -C-O-, -C = N, 0 Il H-, -CH ₂ -CH-, -C-NH ₂ , -C-NH-, -CH ₂ -CH-, -CH ₂ -CH-, -S-, C = OC = O ι Γ NH "0- ₊ 9 «S>,« P *, -EO- (CH KrH-, , -ECH ₂ CH (OH) CH ₂ +, ■ HCH-frr- CH- (CH, * ^A 3 4 -fNH- (CH 10l r 51 ₂ ^ 8 9 ^X 12 ₉ Kr] -, 2 X ₁₃ 15th 0 Il 16 CH. _17th 030015/0842 CH ₀ -CH-, -CH ₀ -CH- - 61 - 29391Η O-C-CH, C = O NH CH ₃ -C-CH ₃ f ^H 2 SO, H and ^J -CH ₀ -CH- ² I.
C = O NH
R-SO ₃ H wherein R is a hydrocarbon radical with 0-10 carbon atoms and optionally 0-4 hetero groups and X _x JX _-1 P _{7 are,} independently of one another, integers of about 0-4. 260.Verfahren according to claim 244, characterized in that a polymer is used, in which the branched chain of the branched polymer is hydrophilic and essentially non-ionic is. 030015/0842 _ ₆₂ _ 29391U 261.Verfahren according to claim 260, characterized in that a branched polymer is used which has ionic groups. 262. The method according to claim 244, characterized in that a branched polymer is used which has more than one type of polymer unit. 263. The method according to claim 244, characterized in that a polymer is used in which the branched chains can be more strongly solvated than the skeletal chain or backbone chain. 264. The method according to claim 244, characterized in that a branched polymer is used which has an average of about 1 or more branched chains per backbone polymer chain up to an average of one or more branched chains for every 98 out of 100 polymer units owns in the backbone chain. 265. The method according to claim 244 / i, characterized in that a branched polymer which is a branched chain with an average value of about 2-25,000 polymer units is used owns. 266. The method according to claim 244, characterized in that the branched polymer directly with an aqueous liquid to change at least one property of this aqueous liquid liquid is mixed. 030015/0842 267. The method according to claim 244, characterized in that that the branched polymer is mixed with an aqueous liquid and the mixture has a pH value of less than about 10. 268. The method according to claim 244, characterized in that that the branched polymer is mixed with an aqueous liquid, and that the mixture has a pH value greater than about 7. 269 · The method according to claim 244, characterized in that that the branched polymer is mixed with an aqueous liquid, and that the mixture has a pH of less than about 3. 270 · The method according to claim 268, characterized in that that the mixture has a pH greater than about 10. 271. The method according to claim 267, characterized in that that the mixture has a pH of less than owns about 7. 272. The method according to claim 267, characterized in that that the mixture is applied to a particulate formation. 273. The method according to claim 272, characterized in that that the mixture in a particulate formation to change the permeability of that formation is applied to certain liquids or fluids. 274. The method according to claim 271, characterized in that that a mixture is used which contains one or more acids in the form of hydrofluoric acid, hydrochloric acid, 030015/0842 -64- 29391H Nitric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, hydroxyacetic acid, fumaric acid, citric acid, Contains oxalic acid, an acid-forming compound or mixtures thereof. acidic, oxalic acid, an acidic
Contains mixtures thereof. 275. The method according to claim 274, characterized in that g e k e η η that the mixture in a particulate formation at a pressure greater than that Break-up pressure or fracturing pressure of this formation is applied. 276. The method according to claim 274, characterized in that the mixture in a particulate Formation at a pressure less than the fracturing pressure of the formation is applied. 277 · The method according to claim 274, characterized in that the mixture is applied to a particulate formation for reaction with a part of this formation and for removal therefrom. 278 .. The method according to claim 244 / l, characterized in that the branched polymer with an aqueous, acidic liquid containing at least one acid for extending the reaction the acid is mixed. 279. The method according to claim 266, characterized in that the mixture is for transporting of particulate! Material is used in a pipe. 280 «Method according to claim 279, characterized in that the equipment is to be put in place of particulate! Material is used in a zone adjacent to an earth formation. 030015/0842 -65-29391H 281. The method according to claim 272 or 280, characterized in that the mixture for acid fracturing a formation is used. 282. The method according to claim 244, characterized in that that the branched polymer with an aqueous liquid to change the flow of the liquid is mixed into a permeable formation adjacent to the mixture. 283. The method according to claim 244, characterized in that that the branched polymer with an aqueous, acidic liquid to reduce the loss of liquid this mixture is mixed, and that the mixture in the case of a particulate formation for modification the flow properties of the fluid in this • formation is used. 284. The method according to claim 283, characterized in that that the mixture in a subterranean, drilled by a wellbore formation at a greater pressure is applied as the fracturing pressure of this formation. 285. The method according to claim 244, characterized in that that the branched polymer is introduced into an aqueous liquid within a permeable formation is used to vary the resistance to fluid flow of portions of this permeable formation. 286. The method according to claim 285, characterized in that that the branched polymer is formed in situ in this aqueous liquid after the placement and placement begins. 0300 15/0842 - 66-29391H 287. The method according to claim 285, characterized in that the mixture is used to create the mobility profile adjacent to a wellbore used to inject aqueous fluid into a formation will change. 288. The method according to claim 285 or 286, characterized in that the mixture for sealing a Formation to prevent fluid flow through any part thereof is applied. 289. The method according to claim 244, characterized in that that the branched polymer is applied to a particulate material to improve the surface properties to change this particulate material. 290. The method according to claim 289, characterized in that the branched polymer for changing the WOR value of the liquid flowing through a zone of this particulate material is applied will. 291 .. The method according to claim 289, characterized in that net that the branched polymer on the particulate Material is applied by mixing the branched polymer with a carrier liquid and flowing the mixture through the material. 292. The method according to claim 291, characterized in that that the branched polymer to change the flow of aqueous liquid within the particulate material is applied. 293. The method according to claim 292, characterized in that that a carrier liquid is used which further contains an aqueous component. 030015/0842 294 .. The method according to claim 291, characterized in that a carrier liquid is used which contains at least one organic phase, an easily gasified component, a water-soluble salt, an acid, particulate material, a C 1-4 alcohol, a ^g ^ ~ ^g ^ q- "
Contains polyol, an aqueous phase or a mixture of two or more thereof. 295. The method according to claim 289, characterized in net that the branched polymer on a particulate Material is applied by placing the particulate material in a liquid with the branched Polymer is suspended. 296. The method according to claim 289, characterized in net that the branched polymer at a particulate Formation is used to make parts of the formation less sensitive to liquids. 297 · Method according to claim 296 ?, characterized net that the branched polymer at a particulate Formation, which contains clay, is used to make the formation less sensitive to liquids close. 298 »Method according to claim 295, characterized in this net that the surface properties of the particulate Material to flocculate the suspended particles can be changed. 299. The method according to claim 289, characterized in that the branched polymer is applied in a particulate formation to the flow of
Improve hydrocarbon fluids through a portion of this formation. 030015/0842 29391U 300. The method according to claim 289, characterized in that a particulate formation, which has been solidified by a resin, is treated with branched polymer to make up part of it Make formation less sensitive to liquids. 301. Branched polymer with a molecular weight of about 900-50 million, characterized in that that the polymer is a water-soluble polymer with a substantial proportion of vinyl, acrylate, Methacrylate, acrylamide, methacrylamide polymer units or a combination thereof in the skeleton chain or backbone chain and that the branched chain has at least two polymer units. 302. Branched polymer according to claim 301, characterized in that the branched chain is hydrophilic is. 303. Branched polymer according to claim 301, characterized in that the branched polymer contains ionic groups. 304. Branched polymer according to claim 301, characterized in that the polymer at least a type of polymer unit derived from alkyl acrylate, Arylacrylate, alkyl acrylamide, arylacrylamide, alkylazirides, arylazirides, alkylene oxide, alkylene epoxide, Alkoxide, alkyl epoxide, alkyl halide, ammonia or one Alkylarain, reacted with alkyl dihalide, alkyl diepoxide or combinations thereof, or combinations of these polymer units in which no hydrocarbon radical is present may be present or contains 1-10 carbon atoms, owns. 030015/0842 305. Branched polymer according to claim 301, characterized in that the branched chain is practically is non-ionic. 506. Branched polymer according to claim 301, characterized in that there is more than one type of
Contains polymer unit. 307. Branched polymer according to claim 301, characterized in that the branched chain of
is derived from a monofunctional polymer. 308. Branched polymer according to claim 301, characterized in that each hydrocarbon radical may not be present or contain up to about 6 carbon atoms. 309. Branched polymer according to claim 301, characterized in that it is characterized that the branched polymer contains at least one of the following polymer units: 0 0 -OH, -0-, -C-, -C-O-, -CHN, Ο O -CH-, -CH ₂ -CH-, -C-NH ₂ , -C-NH-, C = N C-ΞΝ -CH ₂ -CH-, -CH ₂ -CH-, -S-, C = OC = O NH ₂ O- 030015/0842 29391U -HCH ₂ ^ χ-CH-f CH ₂ y [CHz- ^ CH -) - ^ - N- (CH) - J i A ₁₀ I Z a, -ES- (CH ^ l ·, -S-HCH. 8 CH], 12th - P- (OCH-CH ^) - '15 -FOP-O- (CH-H ₅ I ^{2 X} 16 0- (CH_) - _Y CH. -CH ₂ -CH- I? 0-C-CH. -CH ₂ -CH- C = O IH CH ₁ -C-CH. ³ I. SO ₃ H and -CH - CH- C = O NH R-SO ₃ H wherein R is a hydrocarbon radical with 0-10 carbon atoms and optionally 0-4 heteroatoms and groups Χ ^ .- ^ Χ ₇ are independently integers from about ¹ V 0-. 030015/0842 310. Branched, organic polymer according to claim 301, characterized in that the organic Polymer at least 0.1% polymer units of the following Formula contains: ^l 73 7 6 κ-, " 4- C = O 77 where mean: and n ₁ , independently of one another a hydrogen atom or a hydrocarbon radical that is aryl, alkyl, Alkenyl, alkynyl radicals, hetero groups or combinations thereof, each hydrocarbon the remainder contains about 1 to 10 carbon atoms, Xg and Xj ₁ independently of one another a hetero radical in the form of nitrogen, oxygen, phosphorus or sulfur, Rnr is a radical which is independently one or more hydrocarbon radicals contains the aryl, alkyl, alkenyl, alkynyl radicals, hetero groups or combinations thereof each hydrocarbon radical containing from about 1-50,000 carbon atoms, provided that the ratio of carbon atoms to hetero groups in the organic polymer is about 6: 1 or less and the organic polymer is hydrophilic, 030015/0842 29391H R ₇₇ and R ₇₈ independently of one another either do not exist or a hydrogen atom or one or more hydrocarbon radicals, which aryl, alkyl, alkenyl, alkynyl radicals, hetero groups or combinations thereof can have, each hydrocarbon radical containing about 2-50,000 carbon atoms, provided that the ratio of carbon atoms to heteroatoms in the organic polymer is about 6: 1 or less and the organic polymer is hydrophilic, although the radicals Hr ₇ ^, Rnn and Rr ₇ Q cannot all be non-existent radicals and provided that the number of residues attached to each atom balances the number of bonds on that atom. 311. Branched, water-soluble, organic, ionic polymer according to claim 301, characterized in that that it contains a substantial proportion of the following polymer units: Κι ' -C C = O ^l 80 Ro ι 82 ^l 83 or 030015/0842 -73- 29391H where mean: R ₇ q and _{Rq 1} , independently of one another, a hydrogen atom or a hydrocarbon radical, which can contain alkyl groups or hetero groups, or combinations thereof, each hydrocarbon radical having about 1-10 carbon atoms, Rg ₀ and Rgc- independently of one another one or more hydrocarbon radicals, which can contain alkyl radicals or hetero groups, or combinations thereof, each hydrocarbon radical having about 1-10 carbon atoms, ^R 81 » ^R 82» ^R 83 » ^R 86» ^R 87 ^{and R} 88 ^unal: > radicals which are not present depending on one another, a hydrogen atom or one or more hydrocarbon radicals which may not be present or which may contain alkyl radicals or hetero groups, or combinations thereof , each hydrocarbon radical containing from about 2-50,000 carbon atoms, provided that the ratio of carbon atoms to heteroatoms in the organic polymer is about 5: 1 or less and the organic polymer is hydrophilic, and provided that the number of those bonded to each atom Remnants offsets the number of bonds of this atom. 312. Branched, organic polymer according to claim 301, characterized in that the organic Polymer contains a substantial proportion of polymer units of the following formulas: 030015/0842 29391Η and wherein up to three of the radicals R on - ^ 92 ^ ater- atoms or hydrocarbon residues with 0-10 Carbon atoms and optionally 0-4 · hetero groups are, at least one of the radicals Ron »Rqo» ^ Qi ^{un <} * ^ Qp is a branched chain with a content of about 2-10,000 polymer units of the formula 0 £ CH _o } _v where X is ₇ , an integer from about 1-4, A ~ is an anion, X _x . means an integer from about 10-50,000, and X2 means an integer from about 10-3000. 313 · Branched, organic polymer according to claim 301, characterized in that the organic Polymer contains a substantial proportion of polymer units of the following formulas: 030015/0842 - • 75 - JCH _;
Η— -CH ₂ - CH- ; co- col and —-CH 29391H where mean: u an integer from about 10-60,000, ν is an integer from about 0-10 000, w is an integer from about 2-10 000, χ an integer from about 10-60,000, y is an integer from about 0-10,000, and ζ an integer from about 2-10 000, provided that ν and y do not both have the value at the same time Own zero. 314-. Branched, organic polymer according to claim 301, characterized in that the organic polymer has a substantial proportion of polymer units contains the following iOrmules: 030015/0842 -CH- OH .H- -CH- CH- CH CH-CONH CH _: f -CH. : f ² I CHOH ! L. CH ₂ (OCH ₂ CH ₂ ^ OCH ₃ where mean: χ an integer from about 10-60,000, y an integer from about 0-60,000, ζ an integer from about 3-100,000, ν an integer from about 0-60,000, and w is an integer from about 2-10 000, provided that ν and y do not both have the value zero at the same time. 030015/08 ^ 2 315 · A method of treating a particulate material using a polymerizate having a molecular weight in the range of about 900-50,000,000, characterized thereby that a branched polymer with an average value of at least one or more, branched chains per backbone chain "or framework chain having, this branched chain having an average value of at least two polymer units. 316. The method according to claim 315 »characterized thereby net that the branched polymer is a mixture of ionic polymers with different ion charges includes. 317. The method according to claim 315 »characterized in that the branched polymer is a mixture of Ionic polymers, in which one polymer is anionic and the other polymer is cationic Contains groups. 318. The method according to claim 315 »characterized in that a branched polymer is used, in which at least one of the groupings is included: O. O.
-OH, -0-, -C-, -CO-, -C = H, O O -CH-, -CH ₂ -CH-, -C-NH ₂ , -C-NH-, C = N CSN -CH ₂ -CH-, -CH ₂ -CH-, -S-, 0- 030015/0842 4ΡΨ, 29391Η -HCH-K, CH- (CH ₀ Hr-B-, -HCH Hr-C- (CH
X- i X. ^ Λ ^ ι ί. [CH ₃ - (CH ₂ ^ _x - N- (CH ₂ - ^ _x CH ₃ ], 8 9 N- (CH-Hr-CH,], 4N- (CH Hr-X ₁₁ 3 ^ X ₁ -eS- (CH ^X 13 --P- (OCH ₀ CH. ι ² - -CH ₂ -CH-0
0-C-CH. ^k 15 ^X 14th , --0P-O- (CH ₀ ) ^X 16 0- (CH) -— CH ₁
X ₁₇ 3 , -CH ₂ -CH- C = O NH CH-C-CH CH ₀ SO ₃ H _nd - CH ₂ -CH-C = O NH I R-SO ₃ H wherein R is a hydrocarbon radical having 0-10 carbon atoms and optionally 0-4 hetero groups and Xy.-Xs.rp are independently integers of about 0-4. 030015/0842 " ⁷⁹ " 29391U 319. The method according to claim 315, characterized in that a branched polymer is used which has a substantial proportion of polymer units which are not derived from an alkyl aziride or the reaction product of ammonia or an alkyl amine with an alkyl dihalide, alkyl diepoxide or combinations thereof, in which each alkyl unit may not be present or has 1-3 carbon atoms. 320. The method according to claim 315 »characterized in that the branched polymer is applied using an aqueous liquid with a pH of less than about 6.5. 321. The method according to claim 315 »characterized in that the branched polymer under Use of an aqueous liquid with a pH less than about 3 is applied. 322. The method according to claim 315 »characterized in that the branched polymer in situ is prepared by using a mixture of branching agent and at least one polymeric material for preparation the backbone polymer chain and the branched chain is used. 323. The method according to claim 322, characterized in that the branching means to a Part of the polymeric material is bound. 324. The method according to claim 322, characterized in that the polymeric material is more than contains one type of polymer unit. 030015/0842 325. The method according to claim 322, characterized in that the polymeric material is a backbone polymer and that the branched chain consists of one or more monomer units, oligomer units, Polymer units or combinations thereof will be produced. 326. The method according to claim 322, characterized in that the polymeric material is one or contains several monomers, oligomers, polymers or a combination thereof. 327. The method according to claim 315 »characterized in that the branched polymer in a carrier liquid is applied, which is an aqueous liquid, a normally liquid Hydrocarbon, a substituted, polar hydrocarbon, a foam one that is easy to gasify Component containing liquid, a particulate Material containing liquid and an acidic liquid or a mixture thereof. 328. The method according to claim 315j, characterized in that the branched polymer in a carrier fluid is applied to an earth formation. 329. The method according to claim 328, characterized in that the branched polymer in a carrier fluid is present which is applied to a subterranean formation to alter fluid flow properties this formation is applied. 330. The method according to claim 328, characterized in that the branched polymer is used to change the permeability of the formation to a flow of an aqueous liquid. 030015/0842 -81- 29391U 331. The method according to claim 328, characterized in that the branched polymer at an underground formation to reduce the permeability of the flow of aqueous fluid, to increase the permeability of the flow of hydrocarbon liquid, or for both purposes is applied. 332. The method according to claim 328, characterized in that the branched polymer at A formation is applied to the path of flow of aqueous fluid in the formation or to change within the formation. 333. The method according to claim 328, characterized in that the branched polymer in a carrier fluid at a pressure less than the hydraulic fracture gradient in the formation is used to modify the fluid flow properties of a portion of this formation. 334-. Process according to Claim 328, characterized in that the branched polymer is in a carrier fluid at a pressure greater than the hydraulic fracture gradient of that formation is used to increase the fluid flow capacity of the formation for certain fluids. 335 «Method according to claim 333 or 334, characterized in that an acidic carrier liquid is used. 030015/0842 29391U 336. The method according to claim 333 or 334 »characterized in that a carrier liquid is used which contains particulate material. 337. The method according to claim 328, characterized in that the branched polymer at the formation is applied to the fluid flow or Substantially restrict fluid flow in any portion of this formation. 338. The method according to claim 328, characterized in that the branched polymer at a subterranean formation is applied in a carrier fluid which is in a borehole during drilling, packing, refurbishing, completing, treating or cementing the borehole will. 339 · Process for changing the properties of an aqueous liquid by adding a polymer to it Liquid, characterized in that a branched polymer with a molecular weight of about 900-50,000,000 is added in which the branched chain has an average value of at least two polymer units in length. Process according to Claim 339 »characterized in that a branched polymer is used which has a substantial proportion of polymer units which are not from an alkyl aziride or the reaction product of ammonia or an alkylamine with an alkyl dihalide, alkyl di-epoxide, or a combination thereof wherein any alkyl moiety is absent or contains 1-3 carbon atoms. 030015/0842 29391H 341. The method according to claim 339, characterized in that the aqueous liquid a Has a pH of less than about 10. 342. The method according to claim 339 »characterized in that the aqueous liquid a Has a pH greater than 10. 343. The method according to claim 339, characterized in that the aqueous liquid a Has a pH of less than about 7. 344. The method according to claim 339, characterized in that a branched polymer is used whose branched chains are hydrophilic. 345. The method according to claim 339, characterized in that a polymer is used which has more than one type of polymer units. 346. The method according to claim 339, characterized in that a polymer is used which contains ionic groups. 347. The method according to claim 346, characterized in that a polymer is used whose ionic groups are anionic, cationic, nonionic, amphoteric, neutral or a combination consist of two or more such groups. 348. The method according to claim 339, characterized in that it is used to increase the viscosity an aqueous liquid is applied. 030015/0842 Method 7, ac]) .'mi / prueh 339, thereby g ο ke η τι γ, ο i levels that a Folymeri sat is used in which a substantial proportion of the polymers r.atei.nhei 1 on the; Polymers of vinyl monomers, di al 1 yl monomers ; ':, Ivii mono]; e pure, / uni üinonoinorein, aetherinonomereir. ₅ Ππΐ i'i iiü! Ütior; (re; n or a combination lii ervon abatai Verfahrc-n nncli ^ Kspruch 339, dnduj'ch £ υ] <: cn η: 'eich net, i.e. if the mixture is a C, -C ^ -A ] voliol, Uli-, or a wnr.'ier] öisl iclici-. ^r 'r _; l ;: from AviunDi un, o'nei :: 3 Hetnl] or a goiiiinc)] of this. Vei ¹ ] ', ·)'] ίΜ.Ίΐ n.'ic}) / «. ι ·: φπκ'1] 3 ^ °, ι ',, - ΜΓιΐί · » ^1. }] fj ir]. c: η η ζ c ic Ii net, d.'iss a ro],> jn (? ri i: / ti- V (, rv, (iidet is from which a who.entl i clior Λ nt part of the. V'ol virit.-ri below nhe J do of Vin.yl-inonoiiiei'eni, Di nl 1;. Ί monoireri ι ^ί , I lO ^ M '-. Onoiner ·; ■, oiil fi dinonoiiif ^ rera odei · one ] 'oml) in; d, i on of this ;'. \) \ u .- '.: mei \. .Verfnhren lificl) ^ n .'- pinjch 3 ^ 9, dndujv ;.]] f ^ e] ·: e η η ζ ei ο Ii net that an Iblymeri nut is used in which ei ti essential / mtei 1 dei ¹ 3Ό1 yjnori s file i]! I (-: i th of imine monomei'ein, / »mi nmonomerera odei · a: * liombi n-iti on derive from it. 353 · Method η ac Ii claim 3 ^ 9 »dndurcli ge L e η η ζ eic Ii net that the mixture of polymer and w ^: i :::: ri ^ qr liquid is acidic and is aijj / viandt in a Krdformnti on . 35 ^. Method nnc] i Ansjiruch 350, thereby ceke η η ζ eic Ii net that the mixture is applied in a hrdf ormati on r.iu'liöliung the passages / ^ ability of the formation. 355o Verfaln-en according to: li claim 353, thereby g e k e η η: -: c i (■ Ji - net that the mixture with a Lrd / orir.Mi i on bej one greater pressure than the liydraul i see GradiMjUn d <r J (H ¹ Jn-tion is applied. 0 3 (1 ί) 1 Π / Π W ■ '? 29391H 356. The method according to claim 3 ^ 8, characterized in that the mixture of polymer and aqueous liquid is used to treat an earth formation while drilling a borehole. Process according to claim 3 ^ 8, characterized in that the mixture of polymer and aqueous fluid for treating an earth formation traversed by a borehole to reduce Fluid loss is applied to this formation, 358. The method according to claim 3 ^, characterized in that the mixture of polymer and aqueous liquid for the treatment of an earth formation traversed by a borehole to change the Liquid flow properties adjacent to that Borehole is applied. 359. The method according to claim 34-9 »characterized in that the mixture of polymer and aqueous fluid used to treat an earth formation to stabilize clay within the formation will. 360. The method according to claim 3 ^ 8, characterized in that the branched polymer in sι tu branched and applied to an earth formation w L rd. 361. Ver'f, -ihren for branching a polymer through Attachment of a branched-chain polymer to one Part of the polymer units, whereby the branching chain includes: f) -J (Ii)] r> / OH L 2 " ^6G " 29391 H wherein: K _{1 is} a hydrocarbon residue with 1-10 carbon atoms and optionally 0-4 hetero groups, R ~ is a hydrocarbon residue with 1-6 carbon atoms and optionally 0- Λ hetero groups, R _{z is} a carbon residue with 0-10 carbon atoms and optionally Q- ¹ V ilet croup. X _{1 is} oxygen, nitrogen or sulfur, Xp comprises a halide or epoxide, and η is a fjatize number of about 2-25,000. η jdii ι ^f i / u