CN1299835A - Synthesis of high-hydroscopicity resin polymerized at room temperature - Google Patents
Synthesis of high-hydroscopicity resin polymerized at room temperature Download PDFInfo
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- CN1299835A CN1299835A CN 99126336 CN99126336A CN1299835A CN 1299835 A CN1299835 A CN 1299835A CN 99126336 CN99126336 CN 99126336 CN 99126336 A CN99126336 A CN 99126336A CN 1299835 A CN1299835 A CN 1299835A
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Abstract
The synthesis method of high water absorption resin by polymerization at room temp. saves heating process outside polymerization, reduces energy consumption and processing cost, and adopts a column-shaped polymerization unit with a certain size, adds single component initiator to make initiation, uses potassium chloride to produce salt effect to control resolution of metal ions being in bentonite, and utilizes self-body produced polymerization heat to implement acrylic acid-starch-bentonite graft copolymerization at room temp. to obtain the invented product water gel with neutrality and high water absorption.
Description
The invention belongs to the synthetic method of High hydrophilous resin.
In recent years, High hydrophilous resin enters the substantive application stage in many fields such as desert afforestation, afforestation and agriculture water conservations, the novel synthesis that reduces production costs constantly occurs, the radiation method synthesizing super absorbent resin has been realized polymerized at room temperature, the chemical method synthesizing super absorbent resin that be not subjected to the restriction of cobalt source, generally adopts, do not need external heating modes such as water-bath, air, at room temperature finish the polymerized at room temperature of polymerization whole process, do not see the report that makes a breakthrough as yet.Chinese patent 89101086.6 discloses and has been entitled as " high-absorbent material synthetic method ", this method is a raw material with wilkinite and acrylamide, ammonium persulphate or Potassium Persulphate are the oxidation component in the initiator, five water S-WATs are reduction components in the initiator, add linking agent and fully stirring again, polymerization at room temperature 20 minutes places 50～70 ℃ of polymerizations of thermostat container 1～4 hour, obtains gelatin polymer; This invention increases substantially solid content owing to add wilkinite in the acrylamide system, reduces raw materials cost; And room temperature prepolymerization 20 minutes, all polymerization time is no more than 4 hours 20 clocks, reduces energy consumption, the reduction of raw materials cost and tooling cost in 4～8 hours than common water-bath polymerization, product competitive power in industries such as farming, woods is strengthened, beyond doubt a desirable technology; But the unsatisfactory part one of this method is: because major ingredient acrylamide and wilkinite are alkalescence, hydrogel is alkalescence, and users such as farming, woods are difficult to direct use; It two is that the polymerization whole process still mainly needs outer heating, and the polymerized at room temperature ratio is little, if the polymerization whole process is polymerized at room temperature, this part second largest energy consumption that is only second to oven dry in the production whole process can be reduced to zero, and tooling cost is reduced significantly.
The synthetic method that the purpose of this invention is to provide a kind of high-hydroscopicity resin polymerized at room temperature.This method is to be no more than in the cylindrical polymerizer of 180mm at diameter, adding the single component initiator causes, Repone K produces metal ion stripping in the salt effect control wilkinite, utilize and self produce heat of polymerization, finish vinylformic acid-starch-wilkinite graft copolymerization whole process under the room temperature, it is neutral that the goods hydrogel is, and the agricultural user is directly available, and water absorbent rate can satisfy agricultural user needs.
The present invention obtains wilkinite in acidic medium by the salt effect that acidity, wilkinite add-on, Repone K in the conciliation system produce, the stripping quantity that metal ion is suitable, controlled polymerization speed and cross-linking density thus, reach not implode or cross-linking density is excessive, can cause smoothly again and good polymeric purpose, guarantee that finally the water absorbent rate minimum value reaches the acceptable degree of user.Realize that another measure of above-mentioned target is only to add oxidation component in the initiator, no longer add that controlled polymerization speed is slowly at the uniform velocity polymerization such as reduction components such as S-WATs; The assist measure of controlled polymerization speed of the present invention and cross-linking density is to regulate cylindrical polymerizer physical dimension, the heat of polymerization that material self is produced does not does not promptly all scatter and disappear, also not too much and overheated because of accumulating, formation is beneficial to acquisition thermal equilibrium temperature higher relatively and relatively stable water absorbent rate and distributes.
Synthesis step of the present invention is as follows: prepare six kinds of components respectively, component 1 is to add wilkinite in (weight percent, as follows) 1.42～1.57% aqueous sodium hydroxide solutions, is mixed with the soup compound that contains wilkinite 15.48～17.84%; Component 2 is mixed with starch-containing 34.38～38.05% starch salt brine solution for to stir into starch in 4.76～7.84% potassium chloride solutions; Component 3 is to make 15～18.29% aqueous sodium hydroxide solutions and 45.24～54.76% acrylic acid aqueous solution generation neutralization reactions, and the vinylformic acid that is neutralized accounts for and adds vinylformic acid 32.87～44.53%; Component 4 is a pure acrylic acid solution; Component 5 is 0.74～0.99% ammonium persulfate aqueous solution; Component 6 is NN '-methylene-bisacrylamide aqueous solution of 0.45～0.99%, under agitation each component is added the batch mixing reactor according to 1～6 order, component 1～6 accounts for total amount weight percent composition and is: 35.91～41.15%, 9.28～9.53%, 36.52～41.69%, 3.57～5.37%, 4.37～6%, 1.46～3.29%; Diameter 80～180mm packs into behind each component mixing, in the cylindrical polymerizer of high 1000mm, be placed in 18～33 ℃ the room temperature environment, slow voluntarily polymerization 16～24 hours, polymerization finishes, and obtains High hydrophilous resin through granulation, oven dry, pulverizing again, water absorbent rate is 361～728 times, it is neutral that hydrogel is, and measures water absorbent rate with the nickel screen method, and calculation formula is: weight before water absorbent rate=[suction back weight-blank weight]/suction; Check the hydrogel acid-basicity with the PH test paper.
This method is compared with the chemical method service water phase-polymerization of common employing, owing to save 4～8 hours production stage of polymerization in 40～80 ℃ of constant temperature water baths, thereby, must not drop into water bath, recirculated water, corresponding temperature controlling instruments etc., this has just saved the expense that corresponding device input, management, energy consumption, artificial, material loss etc. cause, the reduction of polymerization cost not only cuts down finished cost, and has also simplified processing step.In addition, this method has solved and added the difficult problem that wilkinite is difficult to carry out aqueous polymerization in acidic medium, and it is neutral that hydrogel is, and the agricultural user can directly use; Compare with normally used vinylformic acid-starch grafting type high water absorption resin,, improve solid content, also reduce raw materials cost relatively, improve salt tolerance owing to add wilkinite.
Embodiment provided by the invention is as follows:
Embodiment 1:
The 11Kg wilkinite is stirred in 1.42% aqueous sodium hydroxide solution, make and contain wilkinite 15.48% component 1; Starch added obtain starch-containing 37.99% component 2 in 7.84% potassium chloride solution; With among 18.08% the aqueous sodium hydroxide solution 25.88Kg and 49.92% acrylic acid aqueous solution, the vinylformic acid that is neutralized accounts for and adds vinylformic acid 39.87%, obtains component 3; Get pure acrylic acid solution 7.4Kg and obtain component 4; Component 5 is 0.99% ammonium persulfate aqueous solution; Component 6 is 0.99%NN '-methylene-bisacrylamide solution; Under agitation each component is added the batch mixing reactor according to 1～6 order, component 1～6 accounts for total amount weight percent composition and is: 41.02%, 9.5%, 39.38%, 4.27%, 4.37%, 1.46%; The diameter 110mm that packs into behind each component mixing in the cylindrical polymerizer of high 1000mm, is placed in 25 ℃ the room temperature environment, slow voluntarily polymerization 21 hours, polymerization finishes, and obtains High hydrophilous resin through granulation, oven dry, pulverizing again, water absorbent rate is 610 times, checks that with the PH test paper hydrogel is neutral.
Embodiment 2:
All the other stir into the 9.5Kg wilkinite in 1.57% sodium hydroxide solution with embodiment 1, make to contain wilkinite 15.75% component 1; Starch added obtain starch-containing 34.38% component 2 in 4.76% Klorvess Liquid; With among 15% the aqueous sodium hydroxide solution 28Kg and 54.76% acrylic acid aqueous solution, the vinylformic acid that is neutralized accounts for and adds vinylformic acid 32.87%, component 3; Get pure acrylic acid solution 6Kg and obtain component 4; Component 5 is 0.74% ammonium persulfate solution; Component 6 is 0.45%NN '-methylene-bisacrylamide solution; Component 1～6 accounts for the total amount weight percent and forms and to be: 35.91%, 9.53%, 41.69%, 3.57%, 6%, 3.29%, and the diameter 80mm that packs in the cylindrical polymerizer of high 1000mm, is placed on 28 ℃ indoor autohemagglutination 24 hours, 728 times of its water absorbent rates.Check that with the PH test paper hydrogel is neutral.
Embodiment 3:
All the other stir into the 12Kg wilkinite in 1.43% sodium hydroxide solution with embodiment 1, make to contain wilkinite 16.65% component 1; Starch added obtain starch-containing 38.05% component 2 in 7.48% Klorvess Liquid; With among 18.29% the aqueous sodium hydroxide solution 25.7Kg and 45.24% acrylic acid aqueous solution, the vinylformic acid that is neutralized accounts for and adds vinylformic acid 44.53%, component 3; Get pure acrylic acid solution 9.5Kg and obtain component 4; Component 5 is 0.92% ammonium persulfate solution; Component 6 is 0.83%NN '-methylene-bisacrylamide solution; Component 1～6 accounts for the total amount weight percent and forms and to be: 40.77%, 9.28%, 38.3%, 5.37%, 4.57%, 1.71%, and in the diameter 150mm cylindricality of packing into the polymerizer, 33 ℃ indoor autohemagglutinations 18 hours, 504 times of its water absorbent rates.Check that with the PH test paper hydrogel is neutral.
Embodiment 4:
All the other stir into the 13Kg wilkinite in 1.45% sodium hydroxide solution with embodiment 1, make to contain wilkinite 17.84% component 1; Starch added obtain starch-containing 38.02% component 2 in 7.75% Klorvess Liquid; With among 18.22% the aqueous sodium hydroxide solution 25.68Kg and 51.28% acrylic acid aqueous solution, the vinylformic acid that is neutralized accounts for and adds vinylformic acid 42.12%, component 3; Get pure acrylic acid solution 9.5Kg and obtain component 4; Component 5 is 0.79% ammonium persulfate solution; Component 6 is 0.71%NN '-methylene-bisacrylamide solution; Component 1～6 accounts for the total amount weight percent and forms and to be: 41.15%, 9.28%, 36.52%, 5.36%, 5.69%, 1.99%, and in the diameter 180mm cylindricality of packing into the polymerizer, 18 ℃ indoor autohemagglutinations 16 hours, 361 times of its water absorbent rates.Check that with the PH test paper hydrogel is neutral.
Claims (1)
1. the synthetic method of a High hydrophilous resin is characterized in that preparing respectively six kinds of components, and component 1 adds wilkinite in (weight percent) 1.42～1.57% aqueous sodium hydroxide solutions, is mixed with the soup compound that contains wilkinite 15.48～17.84%; Component 2 is mixed with starch-containing 34.38～38.05% starch salt brine solution for to stir into starch in 4.76～7.84% potassium chloride solutions; Component 3 is to make 15～18.29% aqueous sodium hydroxide solutions and 45.24～54.76% acrylic acid aqueous solution generation neutralization reactions, and the vinylformic acid that is neutralized accounts for and adds vinylformic acid 32.87～44.53%; Component 4 is a pure acrylic acid solution; Component 5 is 0.74～0.99% ammonium persulfate aqueous solution; Component 6 is NN '-methylene-bisacrylamide aqueous solution of 0.45～0.99%, under agitation each component is added the batch mixing reactor according to 1～6 order, component 1～6 accounts for total amount weight percent composition and is: 35.91～41.15%, 9.28～9.53%, 36.52～41.69%, 3.57～5.37%, 4.37～6%, 1.46～3.29%; Diameter 80～the 180mm that packs into behind each component mixing in the cylindrical polymerizer of high 1000mm, is placed in 18～33 ℃ the room temperature environment, slowly polymerization 16～24 hours voluntarily, and polymerization finishes, and obtains High hydrophilous resin through granulation, oven dry, pulverizing again.
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| CN99126336A CN1122051C (en) | 1999-12-16 | 1999-12-16 | Synthesis of high-hydroscopicity resin polymerized at room temperature |
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| CN99126336A CN1122051C (en) | 1999-12-16 | 1999-12-16 | Synthesis of high-hydroscopicity resin polymerized at room temperature |
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| CN1122051C CN1122051C (en) | 2003-09-24 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322029C (en) * | 2002-06-19 | 2007-06-20 | 杨头雄 | Biological decomposability, water absorbent resin and preparation method thereof |
| CN101319031B (en) * | 2008-07-23 | 2010-10-06 | 哈尔滨工业大学 | Starch graft acrylic acid/modified verdelite high-water-absorption resin and preparing method thereof |
| CN102358773A (en) * | 2011-07-11 | 2012-02-22 | 桂林理工大学 | Preparation method for water-preserving and salt-tolerant alkaline concrete internal curing agent |
| CN102585099A (en) * | 2012-01-20 | 2012-07-18 | 天津大学 | Synthesis method of high-hygroscopicity resin containing imvite and polysaccharide at room temperature |
| CN103224592A (en) * | 2013-05-03 | 2013-07-31 | 中国地质科学院郑州矿产综合利用研究所 | Method for preparing water absorbing material by reasonably utilizing exothermic reaction process |
| CN111718554A (en) * | 2020-07-28 | 2020-09-29 | 中国科学院长春应用化学研究所 | Automobile suspension noise reduction damping liquid containing gel and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935379B (en) * | 2010-10-09 | 2011-08-10 | 内蒙古大学 | Method for synthesizing nitrogenous super absorbent resin from alkaline gelatinized potato starch through graft copolymerization |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1020617C (en) * | 1989-03-01 | 1993-05-12 | 荣庸 | Synthtic method for high water absorption material |
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1999
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322029C (en) * | 2002-06-19 | 2007-06-20 | 杨头雄 | Biological decomposability, water absorbent resin and preparation method thereof |
| CN101319031B (en) * | 2008-07-23 | 2010-10-06 | 哈尔滨工业大学 | Starch graft acrylic acid/modified verdelite high-water-absorption resin and preparing method thereof |
| CN102358773A (en) * | 2011-07-11 | 2012-02-22 | 桂林理工大学 | Preparation method for water-preserving and salt-tolerant alkaline concrete internal curing agent |
| CN102358773B (en) * | 2011-07-11 | 2012-10-10 | 桂林理工大学 | Preparation method for water-preserving and salt-tolerant alkaline concrete internal curing agent |
| CN102585099A (en) * | 2012-01-20 | 2012-07-18 | 天津大学 | Synthesis method of high-hygroscopicity resin containing imvite and polysaccharide at room temperature |
| CN103224592A (en) * | 2013-05-03 | 2013-07-31 | 中国地质科学院郑州矿产综合利用研究所 | Method for preparing water absorbing material by reasonably utilizing exothermic reaction process |
| CN103224592B (en) * | 2013-05-03 | 2015-05-20 | 中国地质科学院郑州矿产综合利用研究所 | Method for preparing water absorbing material by reasonably utilizing exothermic reaction process |
| CN111718554A (en) * | 2020-07-28 | 2020-09-29 | 中国科学院长春应用化学研究所 | Automobile suspension noise reduction damping liquid containing gel and preparation method thereof |
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| CN1122051C (en) | 2003-09-24 |
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