CN1464007A - Temperature-resistant salt-resistant water-absorbent resin - Google Patents
Temperature-resistant salt-resistant water-absorbent resin Download PDFInfo
- Publication number
- CN1464007A CN1464007A CN 02121292 CN02121292A CN1464007A CN 1464007 A CN1464007 A CN 1464007A CN 02121292 CN02121292 CN 02121292 CN 02121292 A CN02121292 A CN 02121292A CN 1464007 A CN1464007 A CN 1464007A
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- Prior art keywords
- water
- resistant
- total amount
- salt
- temperature
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011347 resin Substances 0.000 title claims abstract description 20
- 229920005989 resin Polymers 0.000 title claims abstract description 20
- 150000003839 salts Chemical class 0.000 title claims description 13
- 239000002250 absorbent Substances 0.000 title abstract description 3
- 239000000178 monomer Substances 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000002091 cationic group Chemical group 0.000 claims abstract description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920001897 terpolymer Polymers 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000012764 mineral filler Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- PVVUWCYTDNBWJC-UHFFFAOYSA-N n-benzyl-n-methyldodecan-1-amine;hydrochloride Chemical compound [Cl-].CCCCCCCCCCCC[NH+](C)CC1=CC=CC=C1 PVVUWCYTDNBWJC-UHFFFAOYSA-N 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 230000002829 reductive effect Effects 0.000 abstract description 4
- 239000011256 inorganic filler Substances 0.000 abstract description 3
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 3
- 239000011358 absorbing material Substances 0.000 abstract description 2
- 230000033558 biomineral tissue development Effects 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 150000001408 amides Chemical class 0.000 description 7
- 229920000297 Rayon Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- -1 dimethyl diallyl ammonia chlorides Chemical class 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 1
- USNWAMPROKAEIT-UHFFFAOYSA-N [Na].C(C=C)(=O)O Chemical compound [Na].C(C=C)(=O)O USNWAMPROKAEIT-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 206010025482 malaise Diseases 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- HPKNNSJBWTXMHS-UHFFFAOYSA-N potassium;prop-2-enoic acid Chemical compound [K].OC(=O)C=C HPKNNSJBWTXMHS-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A temperature-resistant salt-tolerant water-absorbent resin comprises an acrylic acid, acrylamide and a cationic monomer terpolymer, wherein an inorganic filler with a layered structure is added into the acrylic acid, the acrylamide is 10-70% of the total amount of monomers, the inorganic filler with the layered structure is 10-150% of the total amount of the monomers, the cationic monomer is 5-15% of the total amount of the monomers, and the resin can keep expansibility for a long time without shrinkage or structural damage under the conditions of 70-150 ℃ and a mineralization degree of 5000-100000 PPm. When used as a water plugging profile control agent, the agent is safe to use, free of pollution and toxicity, long in validity period and remarkable in economic benefit. The water-absorbing material provided by the invention is a novel composite material, and is mainly used for water-absorbing expansion occasions with harsh conditions on temperature and salinity, such as large-pore water-plugging profile control of high-temperature and high-salinity oil reservoirs and water plugging in buildings. Meanwhile, if the water-retaining agent is used in sanitary towels and baby diapers and in the water-retaining process of agriculture and forestry, the production cost can be greatly reduced.
Description
Relate to the field:
The invention belongs to macromolecule material preparation area, specifically, is a kind of heat-resistant salt-resistant type water-absorbing resin.
Background technology:
In the existing related background art, aqua-solution method is produced high-absorbent material and is mainly contained following a few class:
1) pure acrylic acid homopolymerization cross-linking system, as: EP349241, EP347241, US4921904;
2) acrylic acid adds the graft copolymerization cross-linking system of starch or cellulose family, as: CN1258686A, CN1258686A;
3) acrylic acid and third rare acid amides copolymerization cross-linking system, as: CN125082A.US4525527；
4) acrylic acid adds the homopolymerization of a small amount of activation kaolin, as: CN1080642A;
5) third rare acid amides adds a certain amount of wilkinite homopolymerization, aqueous solution radiation method, CN85102156.
First three class synthetic water-absorbing resin suction multiple height in the above-mentioned system, speed are fast, but the salt tolerant heat resistance is poor, and the cost height is unwell to agricultural, gardening, heavy dose of purposes occasions such as oil field oil recovery.And 4,5 classes make the composite performance of water-absorbing resin increase owing to added activation kaolin and wilkinite, and especially thermotolerance increases.But also need this resin to have adsorptivity if be used for Water in Water Shutoff in Oil Field, in order to avoid not anti-secular water washes away and lost efficacy to the stratum.What the present invention proposed is, adds certain cationic monomer terpolymer in acrylic acid, third rare acid amides and mineral filler system, and this filler has laminate structure, can be adsorbed in the crosslinking polymerization network chain, makes water-absorbing resin have composite performance.Mainly be that heat-resistant salt-resistant improves greatly, production cost reduces; Simultaneously, owing to added cationic monomer in the polymerization system, make this water-absorbing resin have to showing the adsorptivity of electronegativity rock stratum, to such an extent as to it is long heavy dose of to be used for the water blockoff transfer drive engineering and the validity period of macropore, large fracture under the high temperature and high salt condition of oil field fully.
Summary of the invention
The object of the present invention is to provide a kind of at water-absorbing resin, particularly tertiary oil production in oil field that can life-time service below 150 ℃ a kind of heat-resistant salt-resistant type water-absorbing resin with the water blockoff transfer drive engineering of macropore, large fracture under the high temperature and high salt.
The present invention is achieved in that
The present invention includes the mineral filler that adding has laminate structure in acrylic acid, acrylamide and the cationic monomer terpolymer, acrylamide is 10～70% of a monomer total amount, the mineral filler of laminate structure is 10～150% of a monomer total amount, and cationic monomer is 5～15% of a monomer total amount.
Described alkali is yellow soda ash, sodium hydroxide, sodium bicarbonate, salt of wormwood, potassium hydroxide etc.
Mineral filler can be activation kaolin, wilkinite, atlapulgite.
Cationic monomer is dimethyl diallyl ammonia chloride, diethyl diallyl ammonia chloride, trimethylammonium allyl group chlorination amine, dodecyl methyl benzyl ammonia chloride.
The resulting water-absorbing resin of the present invention can keep swelling property and shrink-proof or structure deteriorate for a long time under 70 ℃～150 ℃, the situation of 5000～100000PPm salinity.When the water blockoff adjusting driving agnet, safe in utilization, pollution-free, toxicological harmless, validity period is long and distinct economic arranged.Water-absorbing material provided by the present invention is a kind of novel composite material, is mainly used in the water-swelling occasion that temperature and salinity is had severe condition, as leak stopping water in the macropore water blockoff transfer drive of high temperature and high salt oil deposit and the building.Simultaneously, if be used in sanitary towel and baby's diaper and the agroforestry water conservation process, can reduce production costs greatly.
Concrete enforcement
Water-absorbing resin involved in the present invention, employing be that acrylic acid, third rare acid amides and cationic monomer crosslinking copolymerization form.Owing to added cationic monomer in the system, made this water-absorbing resin have to showing the adsorptivity of electronegativity rock stratum; In this system, the mineral filler that is added has laminate structure simultaneously, makes the water-absorbing resin of being invented by this patent have high gel-strength and thermotolerance.
Embodiment 1:
In the acrylic acid solution of 120 grams 11%, add 5.32 gram sodium hydroxide and neutralize, make the acrylic acid sodium solution, add 39 grams, third rare acid amides, 3 gram dimethyl diallyl ammonia chlorides then, stir, add the kaolin of 50 grams again, after stirring, charge into nitrogen, after 10 minutes, add linking agent, oxygenant, reductive agent and FB auxiliary agent, stop to charge into nitrogen after charging into nitrogen number minute again, after half an hour to 4 hour, solution is thickened to blob of viscose gradually, and reaction is promptly finished.Blob of viscose is formed certain particle with the tablets press granulation, and oven dry is pulverized can become product.
Embodiment 2:
In the acrylic acid solution of 50 grams 10%, add 2 gram potassium hydroxide, make the acrylic acid potassium solution, and then add 9 grams, third rare acid amides, 2 gram diethyl diallyl ammonia chlorides, stir, add the bentonite inorganic filler of 20 grams again, after stirring, charge into nitrogen, after 20 minutes, add linking agent, oxygenant, reductive agent and FB auxiliary agent, stop to charge into nitrogen after charging into nitrogen number minute again, after half an hour, solution is thickening gradually, after 4 hours, solution is the blob of viscose shape, and reaction is promptly finished.With blob of viscose tablets press granulation, oven dry crushes and screens and promptly becomes product.
Embodiment 3:
In the acrylic acid solution of 225 grams 10%, add 3465 gram yellow soda ash, make the acrylic acid salts solution, add 80ml (40%) third rare acid amides, 3 gram dimethyl diallyl ammonia chlorides then, after stirring, add the atlapulgite of 50 grams again, after stirring, charge into nitrogen, after 30 minutes, add linking agent, oxygenant, reductive agent and FB auxiliary agent, stop to charge into nitrogen after charging into nitrogen number minute again, solution thickening gradually after half an hour, after 4 hours, solution is the blob of viscose shape, and reaction is promptly finished.With blob of viscose tablets press granulation, oven dry crushes and screens and can become product.
Claims (4)
1. heat-resistant salt-resistant type water-absorbing resin, it is characterized in that: comprise the mineral filler that adding has laminate structure in acrylic acid, acrylamide and the cationic monomer terpolymer, acrylamide is 10～70% of a monomer total amount, the mineral filler of laminate structure is 10～150% of a monomer total amount, and cationic monomer is 5～15% of a monomer total amount.
2. a kind of heat-resistant salt-resistant type water-absorbing resin according to claim 1, it is characterized in that: described alkali is yellow soda ash, sodium hydroxide, sodium bicarbonate, salt of wormwood, potassium hydroxide etc.
3. a kind of heat-resistant salt-resistant type water-absorbing resin according to claim 1 is characterized in that: mineral filler can be activation kaolin, wilkinite, atlapulgite.
4. a kind of heat-resistant salt-resistant type water-absorbing resin according to claim 1 is characterized in that: cationic monomer is dimethyl diallyl ammonia chloride, diethyl diallyl ammonia chloride, trimethylammonium allyl group chlorination amine, dodecyl methyl benzyl ammonia chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021212929A CN1181133C (en) | 2002-06-14 | 2002-06-14 | Temperature-resistant salt-resistant water-absorbent resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021212929A CN1181133C (en) | 2002-06-14 | 2002-06-14 | Temperature-resistant salt-resistant water-absorbent resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1464007A true CN1464007A (en) | 2003-12-31 |
| CN1181133C CN1181133C (en) | 2004-12-22 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021212929A Expired - Fee Related CN1181133C (en) | 2002-06-14 | 2002-06-14 | Temperature-resistant salt-resistant water-absorbent resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1181133C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250276A (en) * | 2011-05-10 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Clay-based amphoteric hydrophobic salt-resistant and high water absorbent resin and its preparation method |
| US8247488B2 (en) | 2010-10-21 | 2012-08-21 | Ripi | Modified polyacrylamide hydrogel |
| CN101808728B (en) * | 2007-09-28 | 2012-10-17 | 株式会社日本触媒 | Water absorbing agent and production method thereof |
| CN103773342A (en) * | 2013-12-12 | 2014-05-07 | 中国石油化工股份有限公司 | Large-pore composite plugging system and preparation method thereof |
| CN104212423A (en) * | 2014-08-17 | 2014-12-17 | 无棣华信石油技术服务有限公司 | Oil well compound plugging agent and preparation method thereof |
| CN104449611A (en) * | 2013-09-12 | 2015-03-25 | 陕西慷麟石油技术开发有限公司 | Fixing agent and preparation method thereof |
| CN104449637A (en) * | 2013-11-04 | 2015-03-25 | 郭保祥 | Semi-permeable membrane type profile-control and water-plugging oil-displacing agent and preparation method thereof |
| CN108048106A (en) * | 2017-12-15 | 2018-05-18 | 苏州纳贝通环境科技有限公司 | One kind efficiently goes saline and alkaline retaining soil moisture modifying agent and preparation method and application |
| CN110317590A (en) * | 2018-03-30 | 2019-10-11 | 中国石油化工股份有限公司 | It is suitble to the transfer drive system and preparation method thereof of high contents of calcium and magnesium oil reservoir |
-
2002
- 2002-06-14 CN CNB021212929A patent/CN1181133C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101808728B (en) * | 2007-09-28 | 2012-10-17 | 株式会社日本触媒 | Water absorbing agent and production method thereof |
| US8247488B2 (en) | 2010-10-21 | 2012-08-21 | Ripi | Modified polyacrylamide hydrogel |
| CN102250276A (en) * | 2011-05-10 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Clay-based amphoteric hydrophobic salt-resistant and high water absorbent resin and its preparation method |
| CN102250276B (en) * | 2011-05-10 | 2014-10-22 | 中国科学院兰州化学物理研究所 | Clay-based amphoteric hydrophobic salt-resistant and high water absorbent resin and its preparation method |
| CN104449611A (en) * | 2013-09-12 | 2015-03-25 | 陕西慷麟石油技术开发有限公司 | Fixing agent and preparation method thereof |
| CN104449611B (en) * | 2013-09-12 | 2017-10-13 | 陕西慷麟石油技术开发有限公司 | A kind of fixative and preparation method thereof |
| CN104449637A (en) * | 2013-11-04 | 2015-03-25 | 郭保祥 | Semi-permeable membrane type profile-control and water-plugging oil-displacing agent and preparation method thereof |
| CN104449637B (en) * | 2013-11-04 | 2018-09-07 | 克拉玛依国勘石油技术有限公司 | A kind of semi-transparent membranous type profile control and water plugging oil displacement agent and preparation method thereof |
| CN103773342A (en) * | 2013-12-12 | 2014-05-07 | 中国石油化工股份有限公司 | Large-pore composite plugging system and preparation method thereof |
| CN104212423A (en) * | 2014-08-17 | 2014-12-17 | 无棣华信石油技术服务有限公司 | Oil well compound plugging agent and preparation method thereof |
| CN108048106A (en) * | 2017-12-15 | 2018-05-18 | 苏州纳贝通环境科技有限公司 | One kind efficiently goes saline and alkaline retaining soil moisture modifying agent and preparation method and application |
| CN110317590A (en) * | 2018-03-30 | 2019-10-11 | 中国石油化工股份有限公司 | It is suitble to the transfer drive system and preparation method thereof of high contents of calcium and magnesium oil reservoir |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1181133C (en) | 2004-12-22 |
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