CN1693313A - 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 PDF

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CN1693313A
CN1693313A CN 200510011663 CN200510011663A CN1693313A CN 1693313 A CN1693313 A CN 1693313A CN 200510011663 CN200510011663 CN 200510011663 CN 200510011663 A CN200510011663 A CN 200510011663A CN 1693313 A CN1693313 A CN 1693313A
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additive
acrylate
super absorbent
polymerization
absorbent resin
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CN1317307C (en
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阮维青
王晓工
黄毓礼
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Tsinghua University
Beijing University of Chemical Technology
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Tsinghua University
Beijing University of Chemical Technology
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Abstract

A process for preparing high-hydroscopicity resin by sunlight irradiated polymerizing includes such steps as proportionally mixing the raw material (polymer), sunlight trigger, cross-linking agent and improver, irradiating the solution by sunlight for 1-120 min to obtain gel, cutting and baking. Its advantages are high productivity and no environmental pollution.

Description

Method for preparing high water absorption resin by solar radiation polymerization
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:
WO2003043671A1 synthesizes super absorbent resin by using acrylic acid monomer, N' -methylene bisacrylamide as a cross-linking agent, sorbitan and the like;
WO2003092757A1, WO2001056625A2 and US2002035353A1 prepare water-absorbent resins which take polyacrylic acid as a main raw material and are used as sanitary articles;
WO2003076711A1 prepares acrylic superabsorbent polymers to modify building surface coatings;
WO2003045453A1 uses acrylic acid as a main monomer to prepare a medical water-absorbing polymer;
JP2002080305a2 developed acrylic agricultural water-absorbing granules;
TW399062B prepared a water-absorbing polymer of a glycidyl ether copolymer of an unsaturated carboxylic acid and an ethoxylated polyol;
FR2818560A1 prepares a water-absorbing material of acrylic acid, sodium acrylate and 2-methyl-2-sulfonic acrylamide terpolymer;
WO2001000259a1 produced reticulated water-absorbing polymers and fibers;
DE10016041A1 describes the preparation of Al-doped2(SO4)3The surface-crosslinked polyacrylic acid superabsorbent material of (1);
WO2001047569A1 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 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.% [ 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-morpholino acetone ], 1-25 wt.% [ alpha-hydroxy, [ alpha-phenylpropyl ketone ], 1-55 wt.% [ 1-hydroxycyclohexyl phenyl ketone ], 1-65 wt.% [ 2-hydroxy-2-methyl-1-phenyl acetone ] ] ] }
Or B: {1-75 wt.% [ benzoin bismethyl ether ], 1-55 wt.% [ alpha-hydroxycyclohexyl phenyl ketone ], 1-45 wt.% [ bis (2, 6-methoxybenzoyl) -2, 4, 4-trimethylpentylphosphine oxide ], 1-55 wt.% [ bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide ], 1-25 wt.% [ p- (. beta. -hydroxyethoxy) phenyl-2-hydroxy-2-methyl acetone ], 1-35 wt.% [ 2-hydroxy-2-methyl-1-phenyl acetone ], 1-65 wt.% [ 1-hydroxycyclohexyl phenyl ketone ] };
(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; the additive is one or more of the monomer additive or the polymer additive or a mixture of the monomer additive and the polymer additive.
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 (5)

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 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 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.% [ 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-morpholino acetone ], 1-25 wt.% [ alpha-hydroxy, [ alpha-phenylpropyl ketone ], 1-55 wt.% [ 1-hydroxycyclohexyl phenyl ketone ], 1-65 wt.% [ 2-hydroxy-2-methyl-1-phenyl acetone ] ] ] }
Or B: {1-75 wt.% [ benzoin bismethyl ether ], 1-55 wt.% [ alpha-hydroxycyclohexyl phenyl ketone ], 1-45 wt.% [ bis (2, 6-methoxybenzoyl) -2, 4, 4-trimethylpentylphosphine oxide ], 1-55 wt.% [ bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide ], 1-25 wt.% [ p- (. beta. -hydroxyethoxy) phenyl-2-hydroxy-2-methyl acetone ], 1-35 wt.% [ 2-hydroxy-2-methyl-1-phenyl acetone ], 1-65 wt.% [ 1-hydroxycyclohexyl phenyl ketone ] };
(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.
2. The method for preparing super absorbent resin by solar radiation polymerization as claimed in claim 1, wherein the cross-linking agent is any one or more of N, N' -methylenebisacrylamide, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycerol, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate.
3. The method for preparing super absorbent resin by solar radiation polymerization according to claim 1, wherein the additive is a monomer additive comprising any one or more of maleic anhydride, acrylamide, N-methylolacrylamide, acrylate, methacrylic acid, methyl methacrylate, p-styrene sulfonic acid, and p-styrene sulfonate.
4. The method for preparing super absorbent resin by solar radiation polymerization as claimed in claim 1, wherein the additive is a polymer additive comprising one or more of starch, cellulose, polyvinyl alcohol, polyacrylamide, chitin, and chitosan.
5. A method for preparing high water absorption resin by solar radiation polymerization according to claim 1, wherein the additive is a mixture of the monomer additive according to claim 5 and the polymer additive according to claim 6.
CNB2005100116634A 2005-04-29 2005-04-29 Method for preparing high water adsorbing resin by sun light radiation polymerization Expired - Fee Related CN1317307C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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
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

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1087749C (en) * 1997-04-22 2002-07-17 梅秀泉 Polyacrylate type high water absorption resin
DE60029996T2 (en) * 1999-12-28 2007-02-01 Kimberly-Clark Worldwide, Inc., Neenah SUPER ABSORBING POLYMERS
JP2002080305A (en) * 2000-09-06 2002-03-19 Chisso Corp Agrochemical particle and method for producing the same, and coated agrochemical granule
CN1160407C (en) * 2001-12-29 2004-08-04 中国科学院长春应用化学研究所 Process for preparing high-hydroscopicity composite resin for agricultural purpose
US7662460B2 (en) * 2002-05-01 2010-02-16 Basf Aktiengesellschaft Plasticized superabsorbent polymer sheets and use thereof in hygienic articles

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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