CN1317307C - Method for preparing high water adsorbing resin by sun light radiation polymerization - Google Patents
Method for preparing high water adsorbing resin by sun light radiation polymerization Download PDFInfo
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- CN1317307C CN1317307C CNB2005100116634A CN200510011663A CN1317307C CN 1317307 C CN1317307 C CN 1317307C CN B2005100116634 A CNB2005100116634 A CN B2005100116634A CN 200510011663 A CN200510011663 A CN 200510011663A CN 1317307 C CN1317307 C CN 1317307C
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- acrylate
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- water absorption
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- 229920005989 resin Polymers 0.000 title claims abstract description 55
- 239000011347 resin Substances 0.000 title claims abstract description 55
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 230000005855 radiation Effects 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 239000000654 additive Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- 238000010521 absorption reaction Methods 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000002250 absorbent Substances 0.000 claims description 28
- 230000002745 absorbent Effects 0.000 claims description 25
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 229920002472 Starch Polymers 0.000 claims description 11
- 239000008107 starch Substances 0.000 claims description 10
- 235000019698 starch Nutrition 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 229940048053 acrylate Drugs 0.000 claims description 9
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 claims description 8
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 8
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 claims description 8
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 8
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 7
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 7
- 229920002101 Chitin Polymers 0.000 claims description 7
- 229920001661 Chitosan Polymers 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 229940047670 sodium acrylate Drugs 0.000 claims description 7
- -1 6-methoxybenzoyl Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 4
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 claims description 4
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 4
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 claims description 4
- 244000028419 Styrax benzoin Species 0.000 claims description 4
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 4
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 4
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 claims description 4
- 229960002130 benzoin Drugs 0.000 claims description 4
- 235000019382 gum benzoic Nutrition 0.000 claims description 4
- DIVXVZXROTWKIH-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylpropan-1-one Chemical compound C=1C=CC=CC=1C(O)(C)C(=O)C1=CC=CC=C1 DIVXVZXROTWKIH-UHFFFAOYSA-N 0.000 claims description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
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- 239000002699 waste material Substances 0.000 abstract description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract 2
- 230000000977 initiatory effect Effects 0.000 abstract 2
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000004971 Cross linker Substances 0.000 description 12
- 239000000499 gel Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- USNWAMPROKAEIT-UHFFFAOYSA-N [Na].C(C=C)(=O)O Chemical compound [Na].C(C=C)(=O)O USNWAMPROKAEIT-UHFFFAOYSA-N 0.000 description 3
- 239000011358 absorbing material Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
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- 239000004584 polyacrylic acid Substances 0.000 description 2
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- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
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- 210000004369 blood Anatomy 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
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- 229920005862 polyol Polymers 0.000 description 1
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- HPKNNSJBWTXMHS-UHFFFAOYSA-N potassium;prop-2-enoic acid Chemical compound [K].OC(=O)C=C HPKNNSJBWTXMHS-UHFFFAOYSA-N 0.000 description 1
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- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920000247 superabsorbent polymer Polymers 0.000 description 1
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Landscapes
- Polymerisation Methods In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a method for preparing water absorption resin by sunlight radiation polymerization, which belongs to the preparation field of macromolecule materials. Raw materials such as polymerization monomer, a sunlight initiation agent, a crosslinking agent, and an additive agent with the modified resin performance are added in according to a certain mass ratio, and are uniformly mixed so that a pre-polymer solution is obtained; the pre-polymer solution is positioned and irradiated under sunlight and is exposed for 1 to 120 minutes so that transparent polymer gel is obtained; the gel is cut and is dried so that high water absorption resin is obtained. The polymerization monomer, the sunlight initiation agent, the crosslinking agent, and the additive agent with the modified resin performance are different from previous raw materials and are adopted in the present invention, and the present invention uses sunlight, is carried out at a normal temperature, has the advantages of simple process, easy control and high production efficiency, is continuously produced, has no three-waste pollution, and is a green chemical synthetic method with low cost, high efficiency and no pollution. The synthetic high water absorption resin has more than hundreds to thousands of times of water absorption rate, and is used for the field of agriculture, forestry, medical treatment sanitary, building materials, packaging, etc.
Description
Technical Field
A method for preparing high water absorption resin by sunlight radiation polymerization belongs to the field of high polymer material preparation.
Background
The high water absorption resin is a low-density cross-linked high molecular polymer as a special functional high molecular material. It can absorb water several hundred times or even thousands times its own weight and has high water retentivity. It is different from common natural water-absorbing materials, such as sponge, silica gel, cotton or toilet paper, and has only small water absorption and water retention. The super absorbent resin has high water absorption and water retention property, so that the super absorbent resin can completely replace the natural materials and is widely applied to the fields of soil improvement, desert greening, afforestation, medical treatment and public health, food, building materials, packaging and other industries in recent years.
A series of high water-absorbing resins synthesized by using acrylic acid and acrylate as main raw materials have the characteristics of high water absorption speed, high water absorption, good water retention, easiness in synthesis, difficulty in mildew, low production cost and the like. Conventional polymerization methods include bulk polymerization, solution polymerization, reverse suspension polymerization, and the like, and are thermal polymerization methods due to the use of a thermal decomposition type initiator.
Superabsorbent resins are produced in the sixties of this century as a functional polymer material. The study of starch grafted acrylonitrile was first conducted in 1966 by northern institute of agriculture, U.S. department of agriculture, g.f. fanta et al, and the study of water-absorbent polymers was started from this time. The sanyo chemical company of japan sells a super absorbent resin synthesized from starch and acrylic acid for the first time in 1978 in the world. Thereafter, the following Japanese Rika Chemical company, in General Mill Chemical Co., U.S. in the field of gain Processing Co., has proposed a number of improvements in the manufacture of superabsorbent resins by grafting acrylonitrile to starch. In the 80 s, a great deal of research and development has been conducted on super absorbent resins, such as American colloid Co., Dow Chemical Comm., Nalco Chemical Co., National Starch Co., GrainProcessing Co., German BASF, Japanese Kao Co., catalytic Chemical industries, and Sanyo Chemical industries. At present, the leading position in this field is japan and the united states, and new products and research results are abundant.
In the patent aspect:
WO 2003043671A 1 synthesizes super absorbent resin by using acrylic acid monomer, N' -methylene bisacrylamide as a cross-linking agent, sorbitan and the like;
WO 2003092757A 1, WO 2001056625A 2 and US 2002035353A 1 prepare water-absorbent resins which take polyacrylic acid as a main raw material and are used as sanitary articles;
WO 2003076711A 1 prepares acrylic superabsorbent polymers to modify building surface coatings;
WO 2003045453A 1 uses acrylic acid as a main monomer to prepare a medical water-absorbing polymer;
JP 2002080305 a2 developed acrylic agricultural water-absorbing granules;
TW 399062B prepared a water-absorbing polymer of a glycidyl ether copolymer of an unsaturated carboxylic acid and an ethoxylated polyol;
FR 2818560A 1 prepares a water-absorbing material of acrylic acid, sodium acrylate and 2-methyl-2-sulfonic acrylamide terpolymer;
WO 2001000259 a1 produced reticulated water-absorbing polymers and fibers;
DE 10016041A 1 describes the preparation of Al-doped2(SO4)3The surface-crosslinked polyacrylic acid superabsorbent material of (1);
WO 2001047569A 1 produces multipurpose water-absorbing polymers containing acrylic acid.
The above patent technologies are all methods for preparing water-absorbing materials by thermal polymerization synthesis.
Solar radiation polymerization is a method of radiation polymerization. Radiation polymerization is the chain polymerization of monomer molecules initiated by radiation energy to form free radicals or ions, and available energy sources include sunlight, ultraviolet light, gamma rays, electron beams and the like, wherein sunlight is the most economical and clean energy source. The technology for synthesizing the super absorbent resin of the acrylic acid-acrylate copolymerization system by using a solar radiation polymerization method has not been reported in any patent or other documents.
Disclosure of Invention
The purpose of the invention is as follows: the direct synthesis of serial copolymer super absorbent resin with acrylic acid-acrylate as main monomer by utilizing sunlight as radiation source and photopolymerization process is one new technology. The synthesis of high water absorption resin by solar radiation method can be carried out in any area with sunshine, and is especially suitable for western area of China, where the area is wide, the terrain is high, the sunshine is sufficient, and the western area is dry and lack of water. The technology for synthesizing the high water-absorbent resin by the solar radiation method can not only fully utilize the sufficient sunlight in the west, but also solve the problem of insufficient water resources in the aspect of agriculture and forestry development, achieves two purposes at one stroke, benefits the nation and the people, and has great research and development significance.
The invention provides a method for preparing super absorbent resin by sunlight radiation polymerization.
A method for preparing high water absorption resin by sunlight radiation polymerization comprises the following preparation steps:
(1) preparing a prepolymerization solution, and uniformly mixing the reaction raw materials according to the following mass ratio to obtain the prepolymerization solution:
50-99 wt% of a polymerized monomer; 0.001-10 wt% of a solar initiator;
0.001-25 wt% of a crosslinking agent; an additive (0.01-50 wt%);
the sum of the mass percentages of the reaction raw materials is 100%;
the polymerized monomer is a mixture of acrylic acid and any one of the following three acrylates: potassium acrylate, sodium acrylate or ammonium acrylate in a mass ratio of (20: 1) to (1: 100);
the solar initiator is A:
1-65 wt% benzoin dimethyl ether
1-55 wt.% of alpha-hydroxycyclohexyl phenyl ketone
1-45 wt% bis (2, 6-methoxybenzoyl) -2, 4, 4-trimethylpentylphosphine oxide
1-55 wt% 2-methyl-1- [4- (methylthiophenyl) -2-morpholinoacetone ]
1-25 wt.% of alpha-hydroxy, alpha-phenylpropiophenone
1-55 wt.% of 1-hydroxycyclohexyl benzophenone
1-65 wt.% 2-hydroxy-2-methyl-1-phenylpropanone
Or B:
1-75 wt% benzoin dimethyl ether
1-55 wt.% of alpha-hydroxycyclohexyl phenyl ketone
1-45 wt% bis (2, 6-methoxybenzoyl) -2, 4, 4-trimethylpentylphosphine oxide
1-55 wt.% of bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide
1-25 wt.% of p- (. beta. -hydroxyethoxy) phenyl-2-hydroxy-2-methyl acetone
1-35 wt.% 2-hydroxy-2-methyl-1-phenylpropanone
1-65 wt.% of 1-hydroxycyclohexyl benzophenone
Either or both of them;
(2) placing the pre-polymerization solution obtained in the step (1) under solar radiation, and exposing for 1-120 minutes to obtain colorless and transparent polymer gel;
(3) and (3) cutting and drying the gel obtained in the step (2) to obtain the super absorbent resin.
The cross-linking agent is any one or more of N, N' -methylene bisacrylamide, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycerol, diethylene glycol diacrylate, triethylene glycol diacrylate and tetraethylene glycol diacrylate.
The additives include monomeric and polymeric additives or mixtures thereof, with the aim of improving the resin properties.
The monomer additive comprises any one or more of maleic anhydride, acrylamide, N-hydroxymethyl acrylamide, acrylate, methacrylic acid, methyl methacrylate, p-styrene sulfonic acid and p-styrene sulfonate.
The polymer additive comprises any one or more of starch, cellulose, polyvinyl alcohol, polyacrylamide, chitin and chitosan.
The additive may also be a mixture of the above-mentioned monomer additives and the above-mentioned polymer additives.
The invention synthesizes various high water absorption resin products of acrylic acid-acrylate copolymer by one step directly from monomers through sunshine. The method has simple process, easy control and high production efficiency, can realize continuous production, basically has no energy consumption, and can be carried out at normal temperature; the method has the characteristics of high polymerization speed, high efficiency, normal-temperature reaction and the like, and greatly simplifies the polymerization process; sunlight exists in nature, so that the energy consumption of the polymerization method is zero, and energy is saved to the greatest extent; the polymerization method takes water as a solvent, has no three-waste pollution, is a green chemical synthesis method with low cost, high efficiency and no pollution, and opens up a new way for industrially producing the super absorbent resin. The water absorbing capacity of the synthesized super absorbent resin product can exceed 1000 times of the self weight, and the water absorbing capacity of the synthesized super absorbent resin product can exceed 100 times of the self weight, has strong absorbing capacity for blood and urine, and simultaneously has strong water and liquid retaining capacity under certain pressure. The product can be widely used in many fields such as soil modification, wind prevention and sand fixation, afforestation, medical and sanitary products, building materials and the like.
Drawings
FIG. 1 is a schematic diagram of a polymerization reaction route for preparing a super absorbent resin by a sunlight polymerization method.
Detailed Description
FIG. 1 is a schematic diagram of a polymerization route for preparing a super absorbent resin by a sunlight polymerization method.
Wherein,the acrylate is: any one of potassium acrylate, sodium acrylate or ammonium acrylate; addingThe agent is
One or more of the monomeric or polymeric additives or a mixture of monomeric and polymeric additives.
EXAMPLE 1 Synthesis of acrylic acid-potassium acrylate-series super absorbent resin
Taking 10g of acrylic acid monomer and 10g of potassium acrylate monomer, adding 1g of monomer additive (0.1 g of maleic anhydride, 0.2g of acrylamide, 0.1g of N-hydroxymethyl acrylamide, 0.1g of acrylate, 0.1g of methacrylic acid, 0.15g of methyl methacrylate, 0.15g of p-styrenesulfonic acid and 0.1g of styrene sulfonate), adding 2g of polymer additive (0.5 g of starch, 0.3g of cellulose, 0.5g of polyvinyl alcohol, 0.3g of polyacrylamide, 0.2g of chitin and 0.2g of chitosan), adding 0.15g of daylight initiator A, adding 0.1g of cross-linking agent N, N' -methylene bisacrylamide, and uniformly mixing the pre-polymerization solution for later use;
placing the pre-polymerization solution under the irradiation of sunlight for 1 minute to obtain colorless and transparent polymer gel;
cutting and drying the gel to obtain the super absorbent resin with the yield of more than 98 percent.
EXAMPLE 2 Synthesis of acrylic acid-sodium acrylate-series super absorbent resin
Taking 10g of acrylic acid monomer and 10g of sodium acrylate monomer, adding 1g of monomer additive (0.1 g of maleic anhydride, 0.2g of acrylamide, 0.1g of N-hydroxymethyl acrylamide, 0.1g of acrylate, 0.1g of methacrylic acid, 0.15g of methyl methacrylate, 0.15g of p-styrene sulfonic acid and 0.1g of styrene sulfonate), adding 2g of polymer additive (0.5 g of starch, 0.3g of cellulose, 0.5g of polyvinyl alcohol, 0.3g of polyacrylamide, 0.2g of chitin and 0.2g of chitosan), adding 0.15g of daylight initiator A, adding 0.1g of cross-linking agent N, N' -methylene bisacrylamide, and uniformly mixing the pre-polymerization solution for later use;
placing the pre-polymerization solution under the irradiation of sunlight, wherein the exposure time is 30 minutes, and obtaining colorless and transparent polymer gel;
cutting and drying the gel to obtain the super absorbent resin with the yield of more than 98 percent.
EXAMPLE 3 Synthesis of acrylic acid-ammonium acrylate-series super absorbent resin
Taking 10g of acrylic acid monomer and 10g of ammonium acrylate monomer, adding 1g of monomer additive (0.1 g of maleic anhydride, 0.2g of acrylamide, 0.1g of N-hydroxymethyl acrylamide, 0.1g of acrylate, 0.1g of methacrylic acid, 0.15g of methyl methacrylate, 0.15g of p-styrene sulfonic acid and 0.1g of styrene sulfonate), adding 2g of polymer additive (0.5 g of starch, 0.3g of cellulose, 0.5g of polyvinyl alcohol, 0.3g of polyacrylamide, 0.2g of chitin and 0.2g of chitosan), adding 0.15g of daylight initiator A, adding 0.1g of cross-linking agent N, N' -methylene bisacrylamide, and uniformly mixing the pre-polymerization solution for later use; placing the pre-polymerization solution under the irradiation of sunlight, wherein the exposure time is 120 minutes, and obtaining colorless and transparent polymer gel; cutting and drying the gel to obtain the super absorbent resin with the yield of more than 98 percent.
EXAMPLE 4 Synthesis of acrylic acid-sodium acrylate-series super absorbent resin
Taking 10g of acrylic acid monomer and 9.8g of sodium acrylate monomer, adding 0.03g of monomer additive (0.003 g of maleic anhydride, 0.003g of acrylamide, 0.003g of N-hydroxymethyl acrylamide, 0.003g of acrylate, 0.003g of methacrylic acid, 0.003g of methyl methacrylate, 0.006g of styrene sulfonic acid and 0.006g of styrene sulfonate), adding 0.02g of polymer additive (0.5 g of starch, 0.3g of cellulose, 0.5g of polyvinyl alcohol, 0.3g of polyacrylamide, 0.2g of chitin and 0.2g of chitosan), adding 0.1g of daylight initiator B, adding 0.05g of cross-linking agent N, N' -methylene bisacrylamide, and uniformly mixing the prepolymerization solution for later use;
placing the pre-polymerization solution under the irradiation of sunlight, wherein the exposure time is 60 minutes, and obtaining colorless and transparent polymer gel;
cutting and drying the gel to obtain the super absorbent resin with the yield of more than 98 percent.
EXAMPLE 5 Synthesis of acrylic acid-sodium acrylate-series super absorbent resin
Taking 10g of acrylic acid monomer and 10g of sodium acrylate monomer, adding 2g of monomer additive (0.08 g of maleic anhydride, 0.08g of acrylamide, 1.5g of N-hydroxymethyl acrylamide, 0.08g of acrylate, 0.08g of methacrylic acid, 0.08g of methyl methacrylate, 0.08g of p-styrene sulfonic acid and 0.02g of styrene sulfonate), adding 12g of polymer additive (10 g of starch, 0.4g of cellulose, 0.4g of polyvinyl alcohol, 0.4g of polyacrylamide, 0.4g of chitin and 0.4g of chitosan), adding 1g of daylight initiator B, adding 5g of crosslinking agent hydroxyethyl acrylate, and uniformly mixing the prepolymer solution for later use.
Placing the pre-polymerization solution under the irradiation of sunlight, wherein the exposure time is 90 minutes, and obtaining colorless and transparent polymer gel;
cutting and drying the gel to obtain the super absorbent resin with the yield of more than 98 percent.
Example 6: in analogy to example 1, the crosslinker N, N' -methylenebisacrylamide was replaced by 0.5g of hydroxyethyl acrylate to give a superabsorbent resin with a yield of more than 98%.
Example 7: in analogy to example 1, the crosslinker N, N' -methylenebisacrylamide was exchanged for 0.5g of 2-hydroxypropyl acrylate, in a yield of > 98%.
Example 8: in analogy to example 1, the crosslinker N, N' -methylenebisacrylamide was exchanged for 1.5g of glycerol with a yield of more than 98%.
Example 9: in analogy to example 1, the crosslinker N, N' -methylenebisacrylamide was replaced by 0.5g of diethylene glycol diacrylate to give a superabsorbent resin with a yield of more than 98%.
Example 10: in analogy to example 1, the crosslinker N, N' -methylenebisacrylamide was replaced by 1g of triethylene glycol diacrylate to give a superabsorbent resin with a yield of more than 98%.
Example 11: in analogy to example 1, the crosslinker N, N' -methylenebisacrylamide was replaced by 0.5g of tetraethyleneglycol diacrylate to give a superabsorbent resin with a yield of more than 98%.
Example 12: in analogy to example 1, the daylight initiator A was replaced by 0.25g of daylight initiator B to give a superabsorbent resin with a yield of more than 98%;
example 13: in analogy to example 12, the crosslinker N, N' -methylenebisacrylamide was replaced by 0.5g of hydroxyethyl acrylate to give a superabsorbent resin with a yield of more than 98%.
Example 14: in analogy to example 12, the crosslinker N, N' -methylenebisacrylamide was changed to 0.5g to 2-hydroxypropyl acrylate to give a superabsorbent resin with a yield of more than 98%.
Example 15: in analogy to example 12, the crosslinker N, N' -methylenebisacrylamide was changed to 1.5g of glycerol to give a superabsorbent resin with a yield of more than 98%
Example 16: in analogy to example 12, the crosslinker N, N' -methylenebisacrylamide was replaced by 0.5g of diethylene glycol diacrylate to give a superabsorbent resin with a yield of more than 98%.
Example 17: in analogy to example 12, the crosslinker N, N' -methylenebisacrylamide was replaced by 1g of triethylene glycol diacrylate to give a superabsorbent resin with a yield of more than 98%.
Example 18: in analogy to example 12, the crosslinker N, N' -methylenebisacrylamide was replaced by 0.5g of tetraethyleneglycol diacrylate to give a superabsorbent resin with a yield of more than 98%.
Claims (1)
1. A method for preparing high water absorption resin by sunlight radiation polymerization is characterized by comprising the following preparation steps:
(1) preparing a prepolymerization solution, and uniformly mixing the reaction raw materials according to the following mass ratio to obtain the prepolymerization solution:
50-99 wt% of polymerized monomer, 0.001-10 wt% of solar initiator,
0.001-25 wt% of cross-linking agent and 0.01-50 wt% of additive;
the sum of the mass percentages of the reaction raw materials is 100%;
the polymerized monomer is a mixture of acrylic acid and any one of the following three acrylates: potassium acrylate, sodium acrylate or ammonium acrylate in a mass ratio of (20: 1) to (1: 100);
the solar initiator is A:
1-65 wt% benzoin dimethyl ether
1-55 wt.% of alpha-hydroxycyclohexyl phenyl ketone
1-45 wt% bis (2, 6-methoxybenzoyl) -2, 4, 4-trimethylpentylphosphine oxide
1-55 wt% 2-methyl-1- [4- (methylthiophenyl) -2-morpholinoacetone ]
1-25 wt.% of alpha-hydroxy, alpha-phenylpropiophenone
1-55 wt.% of 1-hydroxycyclohexyl benzophenone
1-65 wt.% 2-hydroxy-2-methyl-1-phenylpropanone
Or B:
1-75 wt% benzoin dimethyl ether
1-55 wt.% of alpha-hydroxycyclohexyl phenyl ketone
1-45 wt% bis (2, 6-methoxybenzoyl) -2, 4, 4-trimethylpentylphosphine oxide
1-55 wt.% of bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide
1-25 wt.% of p- (. beta. -hydroxyethoxy) phenyl-2-hydroxy-2-methyl acetone
1-35 wt.% 2-hydroxy-2-methyl-1-phenylpropanone
1-65 wt.% of 1-hydroxycyclohexyl benzophenone
Either or both of them;
the cross-linking agent is any one or more of N, N' -methylene bisacrylamide, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycerol, diethylene glycol diacrylate, triethylene glycol diacrylate and tetraethylene glycol diacrylate;
the additive is a monomer additive or a polymer additive or a mixture thereof; the monomer additive comprises any one or more of maleic anhydride, acrylamide, N-hydroxymethyl acrylamide, acrylate, methacrylic acid, methyl methacrylate, p-styrene sulfonic acid and p-styrene sulfonate; the polymer additive comprises any one or more of starch, cellulose, polyvinyl alcohol, polyacrylamide, chitin and chitosan;
(2) placing the pre-polymerization solution obtained in the step (1) under solar radiation, and exposing for 1-120 minutes to obtain colorless and transparent polymer gel;
(3) and (3) cutting and drying the gel obtained in the step (2) to obtain the super absorbent resin.
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| CN1317307C true CN1317307C (en) | 2007-05-23 |
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| CN101168580B (en) * | 2006-10-27 | 2012-09-26 | 台湾塑胶工业股份有限公司 | Method for producing high water absorption resin |
| CN101589066B (en) * | 2007-01-24 | 2013-07-03 | 株式会社日本触媒 | Particulate water-absorbent polymer and process for production thereof |
| CN101709103B (en) * | 2009-10-23 | 2011-06-15 | 北京化工大学 | Method for preparing photoresponse hydrogel containing azo monomer by utilizing light sources with different wavelengths |
| CN101824124A (en) * | 2010-04-20 | 2010-09-08 | 常州杰森化工材料科技有限公司 | Preparation method of photoresponse hydrogel containing azo monomers |
| CN115160503A (en) * | 2022-08-09 | 2022-10-11 | 安徽广谱新材料有限公司 | Long-acting water-absorbing polymer resin ball and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165152A (en) * | 1997-04-22 | 1997-11-19 | 梅秀泉 | Polyacrylate type high water absorption resin |
| WO2001047569A1 (en) * | 1999-12-28 | 2001-07-05 | Kimberly-Clark Worldwide, Inc. | Superabsorbent polymers |
| JP2002080305A (en) * | 2000-09-06 | 2002-03-19 | Chisso Corp | Agrochemical particle and method for producing the same, and coated agrochemical granule |
| CN1359974A (en) * | 2001-12-29 | 2002-07-24 | 中国科学院长春应用化学研究所 | Process for preparing high-hydroscopicity composite resin for agricultural purpose |
| WO2003092757A1 (en) * | 2002-05-01 | 2003-11-13 | Basf Aktiengesellschaft | Plasticized superabsorbent polymer sheets and use thereof in hygienic articles |
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2005
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165152A (en) * | 1997-04-22 | 1997-11-19 | 梅秀泉 | Polyacrylate type high water absorption resin |
| WO2001047569A1 (en) * | 1999-12-28 | 2001-07-05 | Kimberly-Clark Worldwide, Inc. | Superabsorbent polymers |
| JP2002080305A (en) * | 2000-09-06 | 2002-03-19 | Chisso Corp | Agrochemical particle and method for producing the same, and coated agrochemical granule |
| CN1359974A (en) * | 2001-12-29 | 2002-07-24 | 中国科学院长春应用化学研究所 | Process for preparing high-hydroscopicity composite resin for agricultural purpose |
| WO2003092757A1 (en) * | 2002-05-01 | 2003-11-13 | Basf Aktiengesellschaft | Plasticized superabsorbent polymer sheets and use thereof in hygienic articles |
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