JPH05505847A - Polyurethane prepolymer compositions for use with reduced water and prepolymer mixing ratios - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Polyurethane prepolymer compositions used with reduced water and prepolymer mixing ratios product field of invention The present invention provides a polyurethane resin useful as a grout for sealing water-containing structures and as a soil stabilizing composition. The present invention relates to rethane prepolymer compositions.

Various polyurethane prepo as grouts for soil consolidation applications and structure sealing. Remer compositions have been used for a long time. Speech Rice National Patent No. 3.985.688 describes a sewage backer (P) that pushes sewage through cables. foam polyurethane that is typically press-fitted into a sewer line using a Tang grout is listed. This sewage backer stops at each joint. Seal and expand to form a seal on the opposite side of the joint. Gura By injecting the joint into the center of this backer, the joint is sealed and the glass is injected. After curing of the joint, this backer shrinks and moves to the next joint. Usually Huo Mug grout is difficult to handle with this type of backer. Because pre During the reaction of the polymer with water, this foam exhibits a volumetric expansion of more than about 100%. It is from. This excessive expansion causes excessive backflow of the foam into the backer. As a result, this backer becomes fixed in the sewer line.

Other ports, such as those described in Asao et al., U.S. Pat. No. 3,719,050, The urethane prepolymer composition is a gel and during the reaction of the prepolymer with water Does not exhibit volumetric expansion of more than about 50%. The problem with this Asao composition is that the desired To provide a good gel, this prepolymer should be added to 1 part of prepolymer. 8 or 9 parts of water. Such reactants Due to the proportion of The key point.

Other compositions used as sewage sealing compositions are acrylamide-based. Ru. This composition is usually a liquid mixed with water in a 1:1 ratio and is used at the leak site and its surrounding area. By pressurizing it into the surrounding soil, it forms a hardened gel and prevents leakage. water and Acrylamide or acrylate type seal that is mixed in a ratio of 1.1 and then press-fitted and cured. Many sewage sealing devices are designed in the United States and other countries to use sealant compositions. has been done.

Summary of the invention Surprisingly, compatible water-miscible organic solvents or relatively low solids content of hydrophilic polyurethane prepolymers in mixed solvents. The solution reacts with water in a volume ratio of approximately 1:1 to It has been found that it produces an excellent gel useful for stabilization purposes. This group The composition consists of a water-miscible organic solvent or mixed solvent and water having a terminal incyanate group. Contains soluble polyurethane prepolymer. These polyurethane prepolymers (1) at least two terminal active hydrogen groups, ranging from about 3.000 to 20.000; The number average molecular weight of reacted with a polyether compound randomly having a small amount of let The high alkylene oxide units contain 3 or more carbon atoms and are preferred. or propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, selected from the group consisting of carbon oxides and mixtures thereof. This polyether (2) the required amount of an organic compound having at least two terminal isocyanations; from about 5:1 to about 1.05:1 by reacting with a polyisocyanate compound. ．． An NCO:OH ratio of 0 is provided. The composition of the present invention has an organic solvent content of about 10% or more. and has a solids content of about 50% less than the prepolymer.

During the curing process, the compositions of the invention exhibit a volumetric expansion of less than 50%, preferably In some cases, the volumetric expansion is less than 30%. Dimensions sealed by low volumetric expansion This is desirable because it provides mechanical adhesion of the grout to the yoint.

drawing Using the composition of the invention to seal seams in concrete sewers 1 shows an example of a preferred known device for carrying out the method of the invention.

Figure 1 shows a three-part bunker at the joint of a sewer line (shown in cross section). FIG.

Figure 2 shows the joint separated by expanding both ends of the packer in Figure 1. , the annular cavity formed at the joint part is filled with gel. FIG.

Figure 3 shows that the gel is press-fitted from the cavity into the joint by fully expanding it. FIG. 2 is a top view showing the packer of FIG. 1 in a closed state;

Figure 4 shows a two-part packer at the joint of a sewer line (shown in cross section). FIG.

Figure 5 shows how the joint can be opened by expanding both ends of the two-part backer of Figure 4. Separate and connect between the expansion packer surface and the inner surface of the sewage line at the joint part. FIG. 3 is a top view showing a state in which an annular cavity is formed.

Figure 6 shows the packer in Figure 4 with the cavity explained in Figure 5 filled with gel. FIG.

Figure 7 shows that the gel material was allowed to flow into the joint area and the surrounding soil before shrinking. Figure 5 is a top view of the packer of Figure 4 in a state;

The explanation will be given from FIG. 1 along with the attached drawings. In Figure 1, the number 10 indicates the general Indicates sewer line. This sewage line is prone to water intrusion into the sewage line. It has a component 11. A packer 12 is installed in this sewage line 10.

Although this can be inflated with air, it is shown in the folded state in Figure 1. It has a stretchable diaphragm portion 13.14.16. Packer diaphragm part The air to inflate the parts is introduced by hoses 17, 18 and 19, respectively The hoses are arranged on each of the three packer diaphragm sections. The printer of the present invention The repolymer mixture is introduced into the packer through hose 20 and is Water or latex contained in sufficient water is introduced through hose 21. all All hoses are tied together by a band 15. Packer 12 is taken by Packer. attached cables 22a and 22b, which are For example, it is coupled to an external packer moving device such as a winch.

In FIG. 2, outer diaphragm portions 13 and 14 of packer 12 are inflated; The joint 11 is separated and a circular or annular cavity 23 is formed in the joint part. is formed. The sealing composition of the present invention is placed in the cavity 23 together with water in a determined amount. is injected into. In this case, measures such as colliding two individual spray streams may be used. The use of stages ensures mixing and reaction in a short time.

After a short period of time (e.g. 30 seconds) after injection, the gel 24 forms in the cavity 23. The reaction is started by expanding the central part 16 as shown in FIG. press fit into the joint 11. After about 5 to 2000 seconds, the gel 24 reaches its maximum viscosity. , and a gel body sealing the joint 11 is formed. packer 12 is deflated is moved to the next joint by cables 22a and 22b, where it is The above operation is repeated.

In FIG. 4, the sewage packer 26 is an inflatable diaphragm section shown in a collapsed condition. having minutes 27 and 28. Inflatable diaphragms 27 and 28 are air hoses 31 into the packer 26 to expand it. Prepoly of the present invention The polymer mixture is introduced by hose 30 and the water required for reaction of the prepolymer is , or latex with sufficient water and sufficient water added as needed. The filler is introduced through hose 29. Packer 26 is attached to the packer. The cables 22a and 22b are is connected to a packer moving means such as a winch.

In FIG. 5, inflating the inflatable portions 27 and 28 of the packer 26 The joint 11 is separated from the wall of the packer and the inner wall of the sewer line. A circular or annular cavity 33 is formed in the yoint portion. controlled amount The sealing composition of the present invention contains water or latex and an optionally added filler. is injected into the cavity 33 together with the color material. These ingredients are separate packers - introduced as a pressure controlled flow through orifices 34 and 35; One ori The prepolymer is introduced through the fissure, and the water or latex and the necessary Filler components added as needed are introduced. The reaction occurs when this fluid is mixed. A reaction occurs and a gel-forming sealing composition is formed.

As shown in FIG. 6, the formation of the shell 24 begins within the cavity 33 and It is injected into the soil, and a small amount gets mixed into the surrounding soil.

In FIG. 7, inflatable portions 27 and 28 are shown in a deflated state. of this contraction Later, the packer 26 is moved to the next joint by cables 22a and 22b. and the above operation is repeated.

Description of preferred embodiments of the invention The prepolymer composition of the present invention forms a gel by reacting with water in a ratio of about 1.1. Form. This gel has a concentration of about 50%, preferably about 30% or less during gel formation. Defined as a urethane hydrogel matrix that exhibits rotational expansion. degree of expansion A predetermined volume of reactants is placed in a beaker and, after gelation, at least 1 Assessed by raising for 5 minutes and then quickly measuring the water displacement volume of the gel. Ru.

The solids content of the compositions of the present invention is greater than about 10% by weight and about 50% solids in the organic solvent. Below repolymer. Compositions with solids content below 10% are too soft It lacks tensile strength and has long gel times for most sealing applications. Undesirable. A low solids content also means the presence of excessive water flow pressure in the area of use. This results in the problem of grout weakening. Has a solids content of more than about 50% The composition forms a foam rather than a gel when mixed with water in an approximately 1:1 ratio. Ru. Preferably, the solids content is in the range of about 20-40%. solid in this range Due to the water content, slight fluctuations in the amount of water for reaction that occur during actual use in the field can be avoided. An acceptable high strength gel is provided.

Reaction ratio of water and prepolymer composition in practical application of the composition of the present invention A ratio of 1:1 is used. This is because most of the This is because the press-fitting device can only be press-fitted at this ratio. At least 1 under normal conditions It should be understood that an indentation ratio variation of 0% is observed.

The compositions of the present invention also have lower prepolymerization than conventional polyurethane grout compositions. mer content than currently commercially available polyurethane grout compositions. It also has the advantage of exhibiting low viscosity. This low viscosity makes press-fitting easier. Better compatible with currently used grouting equipment.

Preparation of isocyanate-terminated prepolymers used in the sealing compositions of the present invention and and their reaction with water to form polyureas have been disclosed, e.g. For example, U.S. Patent Nos. 2.726.219, 2.948.691, and 3. 719.050, Canadian Patent No. 3.985, 688, and Canadian Patent No. 1.035. ．． No. 521, and “Polyurethanes: Chemistry and Technology” hanes: Chemistry and Technology) J, Sarah Saunders and Fr1sch, Part 1 , Inter-science Pub, N. Y., 1962.

The urethane prepolymer used in the present invention is an aliphatic or aromatic polyisocyanate. and the polyether polyactive hydrogen compound in a ratio of about 5:1 to about 1.05:1. It is prepared by reacting with an NCO/active hydrogen equivalent ratio.

This terminal active hydrogen group polyether polyactive hydrogen compound has ethylene glycol, Glycerin, trimethanolpropane, trimethanolethane, pentaerythri Polyols such as toll, sorbitol, sucrose, and methyl glucoside Provided by In addition, active hydrogen is ethylenediamine, ethylenetriamine and amines such as methylamine. Amine-terminated polyoxia Examples of lekylene compounds include Jeffamines' (Texas (Texas), Belair, Texaco Chemical Co. (Texas) (commercially available from Co. Chemical Co.). other Active hydrogen-containing compounds include carboxylic acids such as castor oil, tar oil, and rosin; and combinations of aldehydes and other compounds (e.g. olefins, aromatic hydrocarbons, etc.) Examples include compounds having at least two hydroxyl groups obtained by reaction.

In order to ensure water miscibility, this polyether polyactive hydrogen compound is contained in a small amount (approximately It has a polymer backbone with 50% ethylene oxide units. Generally, this The repolymer has a molecular weight of about 3.000 to 2.000, preferably 5.000 to io, oo It has a molecular weight in the range of o. Prepare the water-soluble isocyanate-terminated prepolymer described above. Commercially available polyol precursors useful for preparing are hydrophilic polyols, e.g. , “Carbowax J (CT, Danbury) ), commercially available from Union Carbide ). Poly(oxyethylene-oxypropylene) polyol or hete Hydrophilic polyester with heteric oxyethylene-oxypropylene chains Oars can also be used.

To provide better crosslinking in gel formation, more than two isoisomers per molecule Preferably, it has cyanate functionality. More preferably, this prepolymer has three polyether branches from the central triol moiety. Or like this The crosslinking is facilitated by polyfunctional end moieties at the ends of the polyether backbone or by prepolymerization. By including a crosslinking agent such as trimethylolpropane in the remer composition, will be promoted. Additionally, polyisomers with an average isocyanate functionality of more than two The use of cyanates provides good gel matrix formation.

used in the present invention and used to prepare the isocyanate-terminated prepolymers described above. Vine polyisocyanates include traditional aliphatic and aromatic polyisocyanates. Included. Preferred polyisocyanates are aromatic polyisocyanates.

Because prepolymers formed from them generally react faster with water It is et al. One of the most useful polyisocyanate compounds for this purpose is Lylene diisocyanate, especially 80% by weight tolylene-2,4-isocyanate and 20% by weight of tolylene-2,6-isocyanate, 2.4- and 65235 with the 2.6-isomer! Compounds can also be used. There are other vines to use. Useful polyinsyanate compounds include other isomers of tolylene diisocyanate, xamethylene-1,6-diisocyanate, diphenyl-methane-2,4-di Isocyanate, diphenyl-methane-4゜4'-diisocyanate, m- or are p-fuynylene diisocyanate and 1,5-naphthalene diisocyanate , or a mixture thereof. Also, polymethylene polyphenyl polyisocyanate Polymeric polyisocyanates such as esters are also used.

Useful commercially available polyisocyanates include Kirk α1rk) and Othmer (Oth Encyclopedia on Chemical Technology (Enc cyclopedia of Chemical Technology), 2nd edition , Volume 12, Pages 46 and 47, Interscience Publishing. ce Pub, ), 1967. Most preferably, this Socyanate has low volatility so that it does not cause harm to humans by inhalation.

The polyurethane prepolymer of the present invention is liquid or grease-like at room temperature or It is a pasty solid. They are reactive in the presence of water and exhibit a high degree of elasticity. Forms a cross-linked, water-insoluble, water-containing gelatinous solid. Prepolymer in water The reaction time for conversion to a gel in the presence of be.

The solvent used to dissolve the prepolymer is a water-miscible polar organic solvent. preferred In particular, these may be used as sealing compositions. It is volatile under ambient conditions and does not react with isocyanates. useful mixture Aqueous solvents include methyl acetate, tetrahydrofuran, dimethylformamide , ethylene glycol monoethyl ether acetate (“Cellosolve” acetate) Sold by Union Carbide under the trademark It is. ), ε-caprolactone (TONE' monomer EC as Union Commercially available from Carbide Corporation, Danbury, CT has been done. ), N-methylpyrrolidone, N-methylmorpholine and ethylene Included are glycol monomethyl ether acetate. The preferred solvent is acetate. and diethylene glycol ethyl ether acetate. The composition of these The gelation time of a product can be adjusted by adjusting the solvent or solvent mixture to adjust the pill of the composition. By changing the vine. Compositions prepared using basic solvents produce shorter gels. They tend to have a long maturation time.

Higher compression by adding additional filler materials to the sealing composition of the present invention A shrink resistant cured encapsulant composition having strength is provided. For this purpose all A number of filler compositions have been found to be particularly effective. useful files As a particle size below about 500 μm, preferably a particle size of 1 to 50 μm scratches. and has a specific gravity in the range of 0.1 to 4.0, preferably 1.0 to 3.0. Water soluble particulate filler materials are included. Filler of the cured sealing composition of the present invention The content is preferably about 60 parts by weight of filler per 100 parts by weight of the cured sealing composition. The amount is preferably 5 to 20 parts by weight per 100 parts by weight.

A preferred method of reinforcing this polyurethane gel is disclosed in U.S. Pat. No. 4,315,703. is to mix a water-based polymer latex and a prepolymer as described in . In this embodiment, the filler is used together with the water component of the gel to form the final polyurethane gel. Introduce it to the system.

Other additional components are also included in the sealants of the present invention. They also form gels It may be added to the water component when For example, it extends the life of the gel and is effective against various bacteria. Various bactericidal agents may be added to prevent corrosion by. others for various purposes Active ingredients are also added to the vine (eg, plant root erosion inhibitors, etc.). Viscosity of the composition filler so as not to adversely affect the reaction time, and the stability of the prepared gel. Care must be taken in selecting additives and other additives.

For example, tertiary amine catalyst, 2.4.6-tridimethylaminomethylphenol , 1,4-diazabicyclo(2,2,2)-octane, triethylamine, and is known as a base catalyst, such as other amines, and as a catalyst in the urethane technology field. normal sewage temperatures (typically around 10°C) by adding metal compounds that curing time is reduced. This tertiary amine typically reacts with the water used. or added to the prepolymer composition. in which case Also, the tertiary amine is used in an amount of about 0.1-1.0% by weight of the prepolymer. Small The basic catalyst used in the amount can be used without adversely affecting the physical properties of the cured foam. Accelerates curing speed.

The invention is further illustrated by the following non-limiting examples.

Prepolymers ASB and C useful in preparing encapsulating compositions to practice the present invention was prepared as follows.

Prepolymer ^ Benzoyl chloride (77% final solids composition acid 0.035% by weight) at room temperature. 1 equivalent of about 5000 M, v, polyether triol (“po-blind”) under nitrogen atmosphere Commercially available from Olin Corp. (copolymer of ethylene oxide and propylene oxide).

Then, 235 equivalents of 2.4-trilenine diisonoanate and 2.6-1-lylenine Quickly add the 8020 mixture with the diisonore and mix the resulting mixture vigorously. Stirred. The mixture was heated to 80-85°C until the end point of the reaction was confirmed by titration. Maintained. This reaction mixture was then diluted with a sufficient amount of diethylene glycol ethyl ethyl ether. -tel acetate (Eastman Chemical Co., Ltd.) ``Ectasolve DE Acetate (E It is commercially available as ktasolve DE Acetate) J. From then on, D It is called E acetate. ) to give a solid content of 77%.

Prepolymer B By changing reagent grade acetone to DE acetate and increasing the solids content to 80%. The polymer was prepared in the same manner as the prepolymer described above. Additionally, blue dye (0.05% by weight) was also added.

Prepolymer C 1 equivalent of polyether triol with a molecular weight of about 5000 ("Poly G33-34J, Ethylene oxide commercially available from OLin Corp. copolymer with propylene oxide) containing a high proportion of 2.4' diphenylmethane di Based on diphenylmethane diisocyanate containing incyanate isomers Polyisocyanate prepolymer (Ilondur) XP-74 4. Mobay Chemical Corporation 2.5 eq. After addition is complete A sufficient amount of DE acetate was added to bring the solids content to about 95%.

The mixture was then heated and maintained at 80-85°C for 4 hours. Next, the DE Dilute to 30% solids by adding cetate to further dilute the reaction mixture. did. Benzoyl chloride was then added (approximately 0% of the final 30% solids composition). ．． 013% by weight). Completion of the reaction was confirmed by titration. The viscosity of the prepolymer is 1 It was 40cps.

Example 1 foam by reducing the solids (prepolymer) content of the grout. Hana (To confirm the effect of gel formation, the prepolymer^ was DE acetate diluted to various solid contents and mixed with distilled water in various volume ratios at room temperature. Made it harder.

The evaluation results are shown below.

Diluted prepolymer Mixing ratio Gelation Gel properties Swelling rate Solid content Viscosity (Water: Prepolymer) Time (%) (cps) (Parts: N) (Seconds) (%) 77 11.40 8:1 45 gel θ~577 1140 5:1 66 gel 40-5077 1140 1:1 60 form 20465 700 6:1 44 gel -603505:1 42 gel - 604503:1 40 form 60 350 1:1 65 form 11450 150 1:1 70 Foam 5740 105 tri 86 gel 1430 80 1:1 120 Gel 325 64 1:1 179 Gel 220 52 1:1 221 Gel 2 Grout with a solid content of 30% or less has a low viscosity, so it is better than high-viscosity materials. Can be easily mixed with water. This is true for packers sold commercially for sewer repair. This is advantageous when using

Example 2 Add the following additives to distilled water to demonstrate the effect of additives on gel properties: We conducted an evaluation. The water:prepolymer volume ratio was 1:1. in all cases Prepolymer A was used and diluted with DE acetate to the following solid content.

The percentages shown in the table below are by weight.

Prepolymer Aqueous component Gel time Gel properties Solid content Composition (%) (seconds) 30 Distilled water 100 Gel 3050% distilled water 92 gel 5612 of 50% 3080% distilled water 88 gel 20% 5612 3080% distilled water 69 gel 20% 5612 + 0.25% 56012550% distilled water 110 gel 5612 of 50% 2050% distilled water 135 gel 5612 of 50% 3085% distilled water 5 gel 15% 5611 30 Distilled water + 0.25% tri-75 gel ethanolamine 3050% distilled water 41 gel 50% Wifco IFW-160 30 distilled water + 2% 5611 + 66 gel 0.1% Niax A-99 D612 = Scotch-Seal 7M trademark gel Reinforcement Agent 5612, carboxylated styrene-butadiene polymer ester in water Mulsion (manufactured by 3M).

5601-Scotch-Seal T' Trademark Accelerator 5 601.2-(dimethylamino)-ethanol (manufactured by 3M).

5611 - Scotch-Seal 1 Trademark Gel Control Agent 5611, Polymer in Water Meramine solution (manufactured by 3M).

Witcobond? -160=Wicco Chemical Co., Ltd. (fitc) urethane in water commercially available from Chemical Corp. ion dispersion.

Niax ^-991! Bis-2-dimethylaminoethyl ether , a urethane catalyst commercially available from Union Carbide.

Example 3 To illustrate the use of a mixture of water-miscible solvents, prepolymer B was solidified with acetone. diluted to 30%. The resulting composition is easily mixed with water at a ratio of 1:1 and has a The gelation time was shown in seconds.

Example 4 To illustrate the use of other miscible solvents, prepolymer A was mixed with DE acetate. In a mixture with N-methylpyrrolidone (Tovirol J, available from GAF) It was diluted to 30% solids and evaluated as a 1:1 gel with distilled water at room temperature.

Solvent composition Diethylene glycol N-methyl viscosity gelled ethyl ether pyrrolidone Time Acetate (%) (%) (sec) 0 100 75 1g All the above compositions were easily mixed with water.

Example 5 To illustrate the use of isocyanates based on diphenylmethane diisocyanate, For this purpose, prepolymer C was converted by curing with distilled water in a 1:1 ratio. It was evaluated as an academic grout. This prepolymer mixed easily with water. in 88 seconds A tolerable vine gel was formed.

abstract Used for water-containing structures and soil stabilization when reacted with water in a 1:1 volume ratio More than 10% and 50% prepoly in organic solvents form excellent gels useful for in compatible water-miscible solvents or mixed solvents with a solids content below Hydrophilic polyurethane prepolymer in. In the curing step, the composition of the present invention exhibits an expansion rate of less than 50%, preferably less than 30%.

Submission of translation of written amendment (Article 184-7, Paragraph 1 of the Patent Act) September 30, 1992 “1ff”! 1's 1. Indication of patent application: PCT/US911023362, title of invention: Polyurethane prepolymer compositions used with reduced water and prepolymer mixing ratios product 3. Patent applicant Name: Minnesota Mining and Manufacturing Company 4. Agent Address: Twin 215, 2-1-61 Mi, Chuo Ward, Osaka City, Osaka Prefecture, year of submission of amendment Date: September 16, 1991 6, List of attached documents (1) One translation of the written amendment 1. Reaction between water-miscible organic solvent or mixed solvent and the following (i) and (ii) A water-soluble polyurethane prepolymer with terminal iso/anate groups formed by containing more than 10% but less than 50% prepolymer solids in the organic solvent. Encapsulating composition having an amount of: (i) High alkyleneoxy having ethylene oxide units and 3 or more carbon atoms and at least two terminal units randomly in a molar ratio of at least 1:1. Polymers having active hydrogen groups and having a number average molecular weight ranging from 3.000 to 20.000 - Compound: (ii) 5: Provides an NCO:active hydrogen ratio of 1 to 1.05:1. an organic polyester having a sufficient amount of at least two terminal isocyanate groups to Socyanate compounds.

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Claims (1)

[Claims] 1. Reaction between a water-miscible organic solvent or mixed solvent and the following (i) and (ii) A water-soluble polyurethane prepolymer with terminal isocyanate groups formed by containing more than 10% but less than 50% prepolymer solids in the organic solvent. Encapsulating composition having an amount of: (i) High alkyleneoxy having ethylene oxide units and 3 or more carbon atoms and at least two terminal units randomly in a molar ratio of at least 1:1. Polymers having active hydrogen groups and having a number average molecular weight ranging from 3,000 to 20,000 - compound: (ii) sufficient to provide an NCO:OH ratio of 5:1 to 1.05:1. an organic polyisocyanate having a sufficient amount of at least two terminal isocyanate groups; compound.