CN109705830A - One type magnetism delays swollen volume expansion grain and preparation method thereof - Google Patents
One type magnetism delays swollen volume expansion grain and preparation method thereof Download PDFInfo
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- CN109705830A CN109705830A CN201910064192.5A CN201910064192A CN109705830A CN 109705830 A CN109705830 A CN 109705830A CN 201910064192 A CN201910064192 A CN 201910064192A CN 109705830 A CN109705830 A CN 109705830A
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- 230000005389 magnetism Effects 0.000 title claims abstract description 44
- 230000001934 delay Effects 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 18
- 239000000178 monomer Substances 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 84
- 229910052757 nitrogen Inorganic materials 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000002994 raw material Substances 0.000 claims description 24
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 23
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 22
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 22
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 22
- 238000007664 blowing Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000004090 dissolution Methods 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000000084 colloidal system Substances 0.000 claims description 18
- 229920002472 Starch Polymers 0.000 claims description 16
- 239000003431 cross linking reagent Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 239000008107 starch Substances 0.000 claims description 16
- 235000019698 starch Nutrition 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 12
- 235000019394 potassium persulphate Nutrition 0.000 claims description 12
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 12
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 12
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 9
- -1 acrylyl Chemical group 0.000 claims description 8
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 229920002907 Guar gum Polymers 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000000665 guar gum Substances 0.000 claims description 4
- 229960002154 guar gum Drugs 0.000 claims description 4
- 235000010417 guar gum Nutrition 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- XQCSYTYZEGIYFL-UHFFFAOYSA-M [Cl-].[NH4+].C(C=C)(=O)O[N+](C)(C)C.[Cl-] Chemical compound [Cl-].[NH4+].C(C=C)(=O)O[N+](C)(C)C.[Cl-] XQCSYTYZEGIYFL-UHFFFAOYSA-M 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims 1
- 238000004220 aggregation Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 235000013339 cereals Nutrition 0.000 description 83
- 239000006166 lysate Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 7
- CQIOFKRONDXZJC-UHFFFAOYSA-N n-methylideneprop-2-enamide Chemical compound C=CC(=O)N=C CQIOFKRONDXZJC-UHFFFAOYSA-N 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 235000013312 flour Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical group CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 description 1
- BFOCLBAICAUQTA-UHFFFAOYSA-N 2-methylpropane;prop-2-enamide Chemical compound CC(C)C.NC(=O)C=C BFOCLBAICAUQTA-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention discloses a type magnetism to delay swollen volume expansion grain, the N-type volume expansion grain of S type volume expansion grain 25~75wt% and 25~75wt% including 25~75wt%.Class magnetism of the invention delays swollen volume expansion grain and contains S type and N-type monomer, and the heat and salinity tolerance performance of two class monomers is better than common volume expansion grain, still can achieve under the conditions of high temperature and high salinity and delays performance that is swollen and attracting aggregation.
Description
Technical field
The present invention relates to oil field profile control agent fields, and in particular to be that a type magnetism delays swollen volume expansion grain and its preparation side
Method.
Background technique
It has a large amount of water in the recovery process of petroleum to generate, the stratum of heterogeneity is to displacements such as polymer flooding, water drives
The sweep efficiency of liquid influences increasingly serious, it is desirable to reach higher oil recovery factor, only pass through improved, more efficient deep
The technology of profile control effectively improves the heterogeneity of oil reservoir, to improve the sweep efficiency of profile control solution, to can just significantly improve note
Enter water in the oil recovery factor in water filling stage.Water flood field development late stage fracture reservoir forms the inefficient circulation of injection water,
Water is caused excessively to produce and oil production rapid decrease.By changing the flow direction of water stream channel, moisture content is reduced, output water pair is reduced
The influence of environment.Water blockoff, tune are taken for the various oil, well of fluid-channeling channel type (extra-high permeability, crack, macropore) oil reservoir
The technology of cuing open can greatly improve oil recovery factor.Therefore, it is a kind of robust techniques that crosslinking polymer, which opposes and improves recovery ratio,
One of.
Currently used volume expansion grain and hydroexpanding body are relatively more, they meet water and expand, and reach maximum swollen in 24 hours
Swollen multiple has direct pass using deep-well transfer drive, the particle size and water plugging effect of volume expansion grain still, is unfavorable near wellbore formation
System, has the water-absorption particle of as low as nanometer in the market, also there is the bulky grain greatly to millimeter.Each partial size has to answer corresponding water blockoff hole
Hole dia, only stifled hole diameter in need quite just can be effective with product diameter used.Due to the limitation recognized stratum
Property, and to increase many chance components between stifled and not stifled in the crushing performance unevenness of particle moving process, increase
Delayed expansion, crush resistance, elasticity and the crushing resistance of grain are the projects of particle blocking agent.
Summary of the invention
In view of the above shortcomings, the purpose of the present invention is to provide a kind of solutions to delay expansion, solves crush resistance, together
When have both the volume expansion grain of certain elasticity and crushing resistance.This is a kind of product mixed by two kinds of polymer, in polymer
It is middle to introduce a large amount of hydrophobic monomer, nonionic and add required inorganic matter, polymer ions intensity is reduced, to prolong
Slow water swelling time；The monomer to attract each other is divided into S class and N class, changes the different content of S and N class monomer, preparation is different
Volume expansion grain, and control required partial size, in the synthesis process, the swollen particle of diplobiont is prepared respectively, S type volume expansion grain,
The monomer of S containing different proportion；N-type volume expansion grain, the monomer of N containing different proportion；When product inject stratum when under the effect of external force,
Grain can also be bound together again after being broken, and with the movement of particle, according to the size of stratum Hole diameter, particle can
Freely to separate (when thering is external pressure and space to limit), while shape together can be freely combined again in large space and without external pressure when
At aggregation shape.Both contain the volume expansion grain of S type monomer and the synthesis of N-type monomer, after water suction in certain particle size range, they
Between attraction they can be flocked together again completely, formed dough.Under external force, they can divide again
It opens, attracting each other between this phenomenon and magnet is much like with repulsion, therefore is named as class magnetism and delays swollen volume expansion grain.
Technical solution of the present invention is summarized as follows:
One type magnetism delays swollen volume expansion grain, wherein S 25~75wt% of type volume expansion grain and 25 including 25~75wt%
The N-type volume expansion grain of~75wt%.
Preferably, the class magnetism delays swollen volume expansion grain, wherein the S type volume expansion grain includes 10~15wt%
Acrylamide monomer, 3~5wt%S type function monomer, 5~10wt% 2-Hydroxy ethyl acrylate, 5~10wt% metering system
Sour methyl esters, 5~10wt% nonionic, 3~10wt% inorganic matter, 0.1~0.5wt% crosslinking agent, 20~55wt% go from
Sub- water.
Preferably, the class magnetism delays swollen volume expansion grain, wherein the N-type volume expansion grain includes 10~15wt%
Acrylamide monomer, 3~5wt%N type function monomer, 5~10wt% 2-Hydroxy ethyl acrylate, 5~10wt% metering system
Sour methyl esters, 5~10wt% nonionic, 3~10wt% inorganic matter, 0.1~0.5wt% crosslinking agent, 20~55wt% go from
Sub- water.
Preferably, the class magnetism delays swollen volume expansion grain, wherein the S type function monomer is selected from sodium acrylate, 2-
One of acrylamide-2-methyl propane sulfonic sodium, n-vinyl pyrrolidone, sodium styrene sulfonate, maleimide are more
Kind.
Preferably, the class magnetism delays swollen volume expansion grain, wherein the N-type function monomer is selected from methacryl
One of oxy-ethyl-trimethyl salmiac, dimethyl diallyl ammonium chloride, acryloyloxytrimethylammonium ammonium chloride are a variety of.
Preferably, the class magnetism delays swollen volume expansion grain, wherein the nonionic is selected from guar gum, starch
One of or combinations thereof.
Preferably, the class magnetism delays swollen volume expansion grain, wherein the inorganic matter is selected from active carbon, carbon fiber, cunning
One of mountain flour or combinations thereof.
Preferably, the class magnetism delays swollen volume expansion grain, wherein the crosslinking agent is selected from N, N methylene acryloyl
One of amine, divinylbenzene or combinations thereof.
One type magnetism delays the preparation method of swollen volume expansion grain, wherein the following steps are included:
A) preparation of the S type volume expansion grain
(1) raw material is weighed by weight, deionized water is added in the first dissolution kettle, and sequentially add acrylamide, S type
Function monomer, 2-Hydroxy ethyl acrylate, methyl methacrylate, nonionic, inorganic matter and crosslinking agent stirring and dissolving,
Obtain the first mixed liquor；
(2) the first mixed liquor pH value is adjusted to 5.5~6.5, controlled at 25~27 DEG C, is then added into reaction kettle
In, sequentially add under nitrogen protection the catalyst V50 of 0.1~1.0wt%, the potassium peroxydisulfate of 0.3~1.0wt% and 0.5~
The sodium hydrogensulfite of 1.5wt%, until system becomes viscous, it is mixed to obtain second for stopping nitrogen blowing for the inflated with nitrogen mixing into reaction kettle
Close liquid；
(3) the second mixed liquor is kept the temperature 5 hours at 85~95 DEG C and obtains the first colloid, by the first granulating from colloid, drying, powder
It is broken to obtain S type volume expansion grain；
B) preparation of the N-type volume expansion grain
(I) raw material is weighed by weight, deionized water is added in the second dissolution kettle, and sequentially add acrylamide, N-type
Function monomer, 2-Hydroxy ethyl acrylate, methyl methacrylate, nonionic, inorganic matter and crosslinking agent stirring and dissolving,
Obtain third mixed liquor；
(II) third mixed liquor pH value is adjusted to 5.5~6.5, controlled at 20~25 DEG C, is then added into reaction
In kettle, the catalyst V50 of 0.5~1.5wt%, the potassium peroxydisulfate and 0.5 of 0.5~1.0wt% are sequentially added under nitrogen protection
The sodium hydrogensulfite of~1.5wt%, and inflated with nitrogen mixing stops nitrogen blowing, obtains the until system becomes viscous into reaction kettle
Four mixed liquors；
(III) the 4th mixed liquor is kept the temperature 5 hours at 85-95 DEG C and obtains the second colloid, by the second granulating from colloid, drying, powder
It is broken to obtain N-type volume expansion grain；
C) the class magnetism delays the preparation of swollen volume expansion grain
N-type volume expansion grain obtained in S type volume expansion grain obtained in step a), step b) is mixed in the ratio and is stirred
It mixes 20 minutes, obtains the class magnetism and delay swollen volume expansion grain.
Preferably, the class magnetism delays the preparation method of swollen volume expansion grain, wherein the N-type volume expansion grain and S type
Volume expansion grain partial size is 60~150 mesh.
The beneficial effects of the present invention are:
(1) class magnetism of the invention delays swollen volume expansion grain and contains S type and N-type monomer, the heat and salinity tolerance performance of two class monomers
Better than common volume expansion grain, it still can achieve under the conditions of high temperature and high salinity and delay performance that is swollen and attracting aggregation.
(2) class magnetism of the invention is delayed swollen volume expansion grain and is prepared using aqueous solution chlorination reduction catalysts polymerization, is dropping
While the ionic strength of low product and nonionic is introduced, so that polymer, which has, significantly delays swollen performance, and enough
Flexibility, can satisfy the profile control demand on deep-well stratum；By introducing inorganic matter, the resistance to compression energy of product is greatly enhanced
Power.
(3) after N/S type absorbs water respectively, dispersed at them, but if they form state of aggregation after the two is mixed, this
Illustrate binding force attractive between N-type and S type, that is, flocking together, this state of aggregation under external force, can be with
It is stabilized, when binding force is more than a critical value, they can scatter again.
Specific embodiment
The present invention will be further described in detail below with reference to the embodiments, to enable those skilled in the art referring to specification
Text can be implemented accordingly.
The invention discloses a type magnetism to delay swollen volume expansion grain, and the S type volume expansion grain 25 including 25~75wt%~
The N-type volume expansion grain of 75wt% and 25~75wt%.
As the another embodiment of this case, wherein S type volume expansion grain include 10~15wt% acrylamide monomer, 3~
5wt%S type function monomer, 5~10wt% 2-Hydroxy ethyl acrylate, 5~10wt% methyl methacrylate, 5~10wt%
Nonionic, 3~10wt% inorganic matter, 0.1~0.5wt% crosslinking agent, 20~55wt% deionized water.
As the another embodiment of this case, wherein N-type volume expansion grain include 10~15wt% acrylamide monomer, 3~
5wt%N type function monomer, 5~10wt% 2-Hydroxy ethyl acrylate, 5~10wt% methyl methacrylate, 5~10wt%
Nonionic, 3~10wt% inorganic matter, 0.1~0.5wt% crosslinking agent, 20~55wt% deionized water.
As the another embodiment of this case, wherein S type function monomer is selected from sodium acrylate, 2- acrylamide -2- methyl-prop sulphur
One of sour sodium, n-vinyl pyrrolidone, sodium styrene sulfonate, maleimide are a variety of.
As the another embodiment of this case, wherein N-type function monomer be selected from MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride,
One of dimethyl diallyl ammonium chloride, acryloyloxytrimethylammonium ammonium chloride are a variety of.
As the another embodiment of this case, wherein nonionic is selected from one of guar gum, starch or combinations thereof.It is logical
Addition nonionic is crossed, so that polymer, which has, significantly delays swollen performance and enough flexibilities, with can satisfy deep-well
The profile control demand of layer, the preferred nonionic of this case are guar gum, in starch.
As the another embodiment of this case, wherein inorganic matter is selected from one of active carbon, carbon fiber, talcum powder or a variety of.
As the another embodiment of this case, wherein crosslinking agent is selected from N, and one in N methylene acrylamide, divinylbenzene
Kind or combinations thereof.
One type magnetism delays the preparation method of swollen volume expansion grain, wherein the following steps are included:
A) preparation of S type volume expansion grain
(1) by weight raw material is weighed, deionized water is added in the first dissolution kettle, and sequentially add acrylamide, S type
Function monomer, 2-Hydroxy ethyl acrylate, methyl methacrylate, nonionic, inorganic matter and crosslinking agent stirring and dissolving,
Obtain the first mixed liquor；
(2) the first mixed liquor pH value is adjusted to 5.5~6.5, controlled at 25~27 DEG C, is then added into reaction kettle
In, sequentially add under nitrogen protection the catalyst V50 of 0.1~1.0wt%, the potassium peroxydisulfate of 0.3~1.0wt% and 0.5~
The sodium hydrogensulfite of 1.5wt%, until system becomes viscous, it is mixed to obtain second for stopping nitrogen blowing for the inflated with nitrogen mixing into reaction kettle
Close liquid；
(3) the second mixed liquor is kept the temperature 5 hours at 85~95 DEG C and obtains the first colloid, by the first granulating from colloid, drying, powder
It is broken to obtain S type volume expansion grain；
B) preparation of N-type volume expansion grain
(I) by weight raw material is weighed, deionized water is added in the second dissolution kettle, and sequentially add acrylamide, N-type
Function monomer, 2-Hydroxy ethyl acrylate, methyl methacrylate, nonionic, inorganic matter and crosslinking agent stirring and dissolving,
Obtain third mixed liquor；
(II) third mixed liquor pH value is adjusted to 5.5~6.5, controlled at 20~25 DEG C, is then added into reaction
In kettle, the catalyst V50 of 0.5~1.5wt%, the potassium peroxydisulfate and 0.5 of 0.5~1.0wt% are sequentially added under nitrogen protection
The sodium hydrogensulfite of~1.5wt%, and inflated with nitrogen mixing stops nitrogen blowing, obtains the until system becomes viscous into reaction kettle
Four mixed liquors；
(III) the 4th mixed liquor is kept the temperature 5 hours at 85-95 DEG C and obtains the second colloid, by the second granulating from colloid, drying, powder
It is broken to obtain N-type volume expansion grain；
C) class magnetism delays the preparation of swollen volume expansion grain
N-type volume expansion grain obtained in S type volume expansion grain obtained in step a), step b) is mixed in the ratio and is stirred
It mixes 20 minutes, obtains the class magnetism and delay swollen volume expansion grain.
As the another embodiment of this case, wherein N-type volume expansion grain and S type volume expansion grain partial size are 60~150 mesh.
Specific embodiment is listed below:
Embodiment 1:
The synthesis of S type volume expansion grain: raw material is weighed by weight, wherein raw material proportioning are as follows: acrylamide monomer 10wt%,
Sodium styrene sulfonate 3wt%, 2-Hydroxy ethyl acrylate 10wt%, methyl methacrylate 10wt%, starch 10wt% are sliding
Mountain flour 10wt%, N, N methylene acrylamide 0.5wt%, deionized water 46.5wt%.At room temperature, to equipped with agitating device
Dissolution kettle in the deionized water measured in formula is added, be successively slowly added to acrylamide, sodium styrene sulfonate, third under stiring
Olefin(e) acid -2- hydroxy methacrylate, methyl methacrylate, starch, talcum powder and N, N methylene acrylamide stirring sufficiently dissolution；It adjusts
Whole lysate pH value is to 5.5；Lysate temperature is adjusted to 25 DEG C；Lysate is fully transferred in reaction kettle, into reaction kettle
Nitrogen blowing 15 minutes in liquid；Catalyst V50 (1.0wt%), potassium peroxydisulfate are sequentially added under the protection of nitrogen
(1.0wt%), sodium hydrogensulfite (1.5wt%)；Catalyst continues nitrogen blowing mixing after adding until system becomes viscous stopping and blows
Nitrogen, and reactor is closed, it is keeping the temperature under confined conditions after being warming up to 85 DEG C, then keep the temperature 5 hours；By what is polymerize
Colloid is granulated, is dried, is ground into the finished product of 150 mesh particles, that is, has obtained S type volume expansion grain.
The synthesis of N-type volume expansion grain: raw material is weighed by weight, wherein raw material proportioning are as follows: acrylamide monomer 10wt%,
N-type function monomer dimethyl diallyl ammonium chloride 5wt%, 2-Hydroxy ethyl acrylate 10wt%, methyl methacrylate
10wt%, starch 10wt%, carbon fiber 10wt%, crosslinking agent 0.5wt%, deionized water 44.5wt%, at room temperature, to being equipped with
The deionized water measured in formula is added in the dissolution kettle of agitating device, is successively slowly added to acrylamide, dimethyl under stiring
Diallyl ammonium chloride, 2-Hydroxy ethyl acrylate, methyl methacrylate, starch, carbon fiber and N, N methylene acryloyl
Amine stirring sufficiently dissolution；Lysate pH value is adjusted to 5.5；Lysate temperature is adjusted to 20 DEG C；Lysate is fully transferred to instead
It answers in kettle, nitrogen blowing 15 minutes in liquid into reaction kettle；Sequentially added under the protection of nitrogen catalyst V50 (1.5wt%),
Potassium peroxydisulfate (1.0wt%), sodium hydrogensulfite (1.5wt%)；Catalyst continues nitrogen blowing mixing after adding until system becomes sticky
Thick stopping nitrogen blowing, and reactor is closed, it is keeping the temperature under confined conditions after being warming up to 85 DEG C, then keep the temperature 5 hours；It will
The colloid having polymerize is granulated, is dried, is ground into the finished product of 150 mesh particles.N-type volume expansion grain is obtained.
Class magnetism delays swollen volume expansion grain synthesis: by weight raw material is weighed, wherein raw material proportioning is S type volume expansion grain
50%, N-type volume expansion grain 50% delays swollen volume expansion grain in being mixed 20 minutes in feed bin to get to class magnetism, and number is
TT990。
Embodiment 2:
The synthesis of S type volume expansion grain: raw material is weighed by weight, wherein raw material proportioning are as follows: acrylamide monomer 10wt%,
Sodium styrene sulfonate 3wt%, 2-Hydroxy ethyl acrylate 10wt%, methyl methacrylate 10wt%, starch 10wt% are sliding
Mountain flour 10wt%, divinylbenzene 0.5wt%, deionized water 46.5wt%.At room temperature, to the dissolution kettle that agitating device is housed
It is middle that the deionized water measured in formula is added, it is successively slowly added to acrylamide, sodium styrene sulfonate, acrylic acid -2- under stiring
Hydroxy methacrylate, methyl methacrylate, starch, talcum powder and divinylbenzene stirring sufficiently dissolution；Adjust lysate pH value extremely
6；Lysate temperature is adjusted to 26 DEG C；Lysate is fully transferred in reaction kettle, into reaction kettle, nitrogen blowing 15 is divided in liquid
Clock；Catalyst V50 (1.0wt%), potassium peroxydisulfate (1.0wt%), sodium hydrogensulfite are sequentially added under the protection of nitrogen
(1.5wt%)；Catalyst continues nitrogen blowing mixing after adding until system becomes viscous stopping nitrogen blowing, and reactor is closed,
It is keeping the temperature under confined conditions after being warming up to 90 DEG C, then is keeping the temperature 5 hours；The colloid having polymerize is granulated, is dried, powder
It is broken into the finished product of 150 mesh particles.S type volume expansion grain is obtained.
The synthesis of N-type volume expansion grain: raw material is weighed by weight, wherein raw material proportioning are as follows: acrylamide monomer 10wt%,
Dimethyl diallyl ammonium chloride 5wt%, 2-Hydroxy ethyl acrylate 10wt%, methyl methacrylate 10wt%, starch
10wt%, carbon fiber 10wt%, divinylbenzene 0.5wt%, deionized water 44.5wt%, at room temperature, to equipped with stirring dress
The deionized water measured in formula is added in the dissolution kettle set, is successively slowly added to acrylamide, two allyl of dimethyl under stiring
Ammonium chloride, 2-Hydroxy ethyl acrylate 10wt%, methyl methacrylate, starch, carbon fiber and divinylbenzene stirring are filled
Divide dissolution；Lysate pH value is adjusted to 6；Lysate temperature is adjusted to 22 DEG C；Lysate is fully transferred in reaction kettle, to anti-
Answer in kettle nitrogen blowing 15 minutes in liquid；Catalyst V50 (1.5wt%), potassium peroxydisulfate are sequentially added under the protection of nitrogen
(1.0wt%), sodium hydrogensulfite (1.5wt%)；Catalyst continues nitrogen blowing mixing after adding until system becomes viscous stopping and blows
Nitrogen, and reactor is closed, it is keeping the temperature under confined conditions after being warming up to 90 DEG C, then keep the temperature 5 hours；By what is polymerize
Colloid is granulated, is dried, is ground into the finished product of 150 mesh particles.N-type volume expansion grain is obtained.
Class magnetism delays swollen volume expansion grain synthesis: by weight raw material is weighed, wherein raw material proportioning is S type volume expansion grain
25%, N-type volume expansion grain 75% delays swollen volume expansion grain in being mixed 20 minutes in feed bin to get to class magnetism, and number is
TT991。
Embodiment 3:
The synthesis of S type volume expansion grain: raw material is weighed by weight, wherein raw material proportioning are as follows: acrylamide monomer 10wt%,
Sodium styrene sulfonate 3wt%, 2-Hydroxy ethyl acrylate 10wt%, methyl methacrylate 10wt%, starch 10wt% are sliding
Mountain flour 10wt%, N, N methylene acrylamide 0.3wt%, divinylbenzene 0.2wt%, deionized water 46.5wt%.In room temperature
Under, the deionized water measured in formula is added into the dissolution kettle equipped with agitating device, is successively slowly added to acryloyl under stiring
Amine, sodium styrene sulfonate, 2-Hydroxy ethyl acrylate, methyl methacrylate, starch, talcum powder, N, N methylene acryloyl
Amine and divinylbenzene stir sufficiently dissolution；Lysate pH value is adjusted to 5.5-6.5；Lysate temperature is adjusted to 27 DEG C；It will be molten
Solution liquid is fully transferred in reaction kettle, nitrogen blowing 15 minutes in liquid into reaction kettle；It sequentially adds and urges under the protection of nitrogen
Agent V50 (1.0wt%), potassium peroxydisulfate (1.0wt%), sodium hydrogensulfite (1.5wt%)；Catalyst continues nitrogen blowing after adding
Mixing becomes viscous stopping nitrogen blowing up to system, and reactor is closed, is keeping the temperature under confined conditions after being warming up to 95 DEG C,
5 hours are kept the temperature again；The colloid having polymerize is granulated to, is dried, is ground into the finished product of 150 mesh particles.S type body is obtained
Swollen particle.
The synthesis of N-type volume expansion grain: raw material is weighed by weight, wherein raw material proportioning are as follows: acrylamide monomer 10wt%,
Dimethyl diallyl ammonium chloride 5wt%, 2-Hydroxy ethyl acrylate 10wt%, methyl methacrylate 10wt%, starch
10wt%, carbon fiber 10wt%, N, N methylene acrylamide 0.3wt%, divinylbenzene 0.2wt%, deionized water
44.5wt% the deionized water measured in formula is added into the dissolution kettle equipped with agitating device, under stiring successively at room temperature
Be slowly added to acrylamide, dimethyl diallyl ammonium chloride, 2-Hydroxy ethyl acrylate, methyl methacrylate, starch,
Carbon fiber, N, N methylene acrylamide, divinylbenzene stir sufficiently dissolution；Lysate pH value is adjusted to 6.5；Adjustment dissolution
Liquid temperature is to 25 DEG C；Lysate is fully transferred in reaction kettle, nitrogen blowing 15 minutes in liquid into reaction kettle；In nitrogen
Catalyst V50 (1.5wt%), potassium peroxydisulfate (1.0wt%), sodium hydrogensulfite (1.5wt%) are sequentially added under protection；Catalyst
Continue nitrogen blowing mixing after adding until system becomes viscous stopping nitrogen blowing, and it is reactor is closed, heat preservation under confined conditions
Until after being warming up to 95 DEG C, then keep the temperature 5 hours；The colloid having polymerize is granulated, is dried, is ground into 150 mesh particles
Finished product.N-type volume expansion grain is obtained.
Class magnetism delays swollen volume expansion grain synthesis: by weight raw material is weighed, wherein raw material proportioning is S type volume expansion grain
75%, N-type volume expansion grain 25% delays swollen volume expansion grain in being mixed 20 minutes in feed bin to get to class magnetism, and number is
TT992。
The class magnetism of Example 1-3 delays swollen volume expansion grain, and it is as follows to carry out Experimental comparison's data with commercially available volume expansion grain:
Compared with prior art, class magnetism of the invention delays swollen volume expansion grain, and performance is superior to commercially available volume expansion grain.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details.
Claims (10)
1. a type magnetism delays swollen volume expansion grain, which is characterized in that 25~75wt% of S type volume expansion grain including 25~75wt%
With the N-type volume expansion grain of 25~75wt%.
2. class magnetism according to claim 1 delays swollen volume expansion grain, which is characterized in that the S type volume expansion grain includes 10
~15wt% acrylamide monomer, 3~5wt%S type function monomer, 5~10wt% 2-Hydroxy ethyl acrylate, 5~10wt%
Methyl methacrylate, 5~10wt% nonionic, 3~10wt% inorganic matter, 0.1~0.5wt% crosslinking agent, 20~
55wt% deionized water.
3. class magnetism according to claim 1 delays swollen volume expansion grain, which is characterized in that the N-type volume expansion grain includes 10
~15wt% acrylamide monomer, 3~5wt%N type function monomer, 5~10wt% 2-Hydroxy ethyl acrylate, 5~10wt%
Methyl methacrylate, 5~10wt% nonionic, 3~10wt% inorganic matter, 0.1~0.5wt% crosslinking agent, 20~
55wt% deionized water.
4. class magnetism according to claim 2 delays swollen volume expansion grain, which is characterized in that the S type function monomer is selected from third
Olefin(e) acid sodium, 2- acrylamide-2-methyl propane sulfonic sodium, n-vinyl pyrrolidone, sodium styrene sulfonate, in maleimide
It is one or more.
5. class magnetism according to claim 3 delays swollen volume expansion grain, which is characterized in that the N-type function monomer is selected from first
Base acrylyl oxy-ethyl-trimethyl salmiac, dimethyl diallyl ammonium chloride, one in acryloyloxytrimethylammonium ammonium chloride
Kind is a variety of.
6. class magnetism according to claim 2 or 3 delays swollen volume expansion grain, which is characterized in that the nonionic is selected from
One of guar gum, starch or combinations thereof.
7. class magnetism according to claim 2 or 3 delays swollen volume expansion grain, which is characterized in that the inorganic matter is selected from activity
One of charcoal, carbon fiber, talcum powder are a variety of.
8. class magnetism according to claim 2 or 3 delays swollen volume expansion grain, which is characterized in that the crosslinking agent is selected from N, and N is sub-
One of Methacrylamide, divinylbenzene or combinations thereof.
9. class magnetism described in one of claim 1~8 delays the preparation method of swollen volume expansion grain, which is characterized in that including following
Step:
A) preparation of the S type volume expansion grain
(1) raw material is weighed by weight, deionized water is added in the first dissolution kettle, and sequentially add acrylamide, S type function
Monomer, 2-Hydroxy ethyl acrylate, methyl methacrylate, nonionic, inorganic matter and crosslinking agent stirring and dissolving, obtain
First mixed liquor；
(2) the first mixed liquor pH value is adjusted to 5.5~6.5, controlled at 25~27 DEG C, is then added into reaction kettle,
Sequentially add under nitrogen protection the catalyst V50 of 0.1~1.0wt%, the potassium peroxydisulfate of 0.3~1.0wt% and 0.5~
The sodium hydrogensulfite of 1.5wt%, until system becomes viscous, it is mixed to obtain second for stopping nitrogen blowing for the inflated with nitrogen mixing into reaction kettle
Close liquid；
(3) the second mixed liquor is kept the temperature 5 hours at 85~95 DEG C and obtains the first colloid, by the first granulating from colloid, drying, crushed
To S type volume expansion grain；
B) preparation of the N-type volume expansion grain
(I) raw material is weighed by weight, deionized water is added in the second dissolution kettle, and sequentially add acrylamide, N-type function
Monomer, 2-Hydroxy ethyl acrylate, methyl methacrylate, nonionic, inorganic matter and crosslinking agent stirring and dissolving, obtain
Third mixed liquor；
(II) third mixed liquor pH value is adjusted to 5.5~6.5, controlled at 20~25 DEG C, is then added into reaction kettle,
Sequentially add under nitrogen protection the catalyst V50 of 0.5~1.5wt%, the potassium peroxydisulfate of 0.5~1.0wt% and 0.5~
The sodium hydrogensulfite of 1.5wt%, and until system becomes viscous, stopping nitrogen blowing obtaining the 4th for inflated with nitrogen mixing into reaction kettle
Mixed liquor；
(III) the 4th mixed liquor is kept the temperature 5 hours at 85-95 DEG C and obtains the second colloid, by the second granulating from colloid, drying, crushed
To N-type volume expansion grain；
C) the class magnetism delays the preparation of swollen volume expansion grain
N-type volume expansion grain obtained in S type volume expansion grain obtained in step a), step b) is mixed 20 in the ratio
Minute, it obtains the class magnetism and delays swollen volume expansion grain.
10. the preparation method that class magnetism according to claim 9 delays swollen volume expansion grain, which is characterized in that the N-type body is swollen
Particle and S type volume expansion grain partial size are 60~150 mesh.
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