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
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- acrylate
- methyl
- hydroxy
- phenyl
- additive
- Prior art date
- 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.)
- Expired - Fee Related
Links
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
Prepare the method for super absorbent resin with sun light radiation polymerization, belong to macromolecule material preparation area.
Background technology
Super absorbent resin is the crosslinked high molecular polymer of a kind of low density as special functional high molecule material.It can absorb the water that is equivalent to own wt hundred times even thousands of times, and has high-moisture-retention.It is different from general natural water-absorbing material, as sponge, silica gel, cotton or toilet paper etc., has only very little water-absorbent and water-retentivity.The high-hydroscopicity of super absorbent resin and water-retentivity make it can substitute these natural materialss fully, are widely applied to industry fields such as soil improvement, desert afforestation, afforestation, health care, food and building materials and packing in recent years.
With vinylformic acid and acrylate is a series of super absorbent resins of main raw material institute synthetic, has that absorption speed is fast, water regain is high, good water-retaining property, is easy to synthesize, is difficult for going mouldy and characteristics such as low production cost.Traditional polymerization process comprises mass polymerization, and solution polymerization process and inverse suspension polymerization etc. owing to use thermolysis type initiator, all belong to the method for thermopolymerization.
Super absorbent resin is born in the sixties in this century as a kind of functional high molecule material.Be 1966 the earliest, the USDA north G.F.Fanta of institute etc. has carried out the research of starch-grafted vinyl cyanide, has from then on begun the research of water-absorbing polymer.SANYO GS change into company in 1978 in selling starch and vinylformic acid synthetic super absorbent resin in the world first.After this, the Grain Processing Co. of the U.S., General Mill Chemical Co., the day shallow lake chemical company of Japan proposes a large amount of evolutionary approach to starch-grafted vinyl cyanide system super absorbent resin again.Enter the eighties, U.S. AmericanColloid Co., Dow Chemical Com., Nalco Chemical Co., National Starch Co., GrainProcessing Co., German BASF, Japanese Kao Co., catalyst chemical industrial company and Sanyo change into industry etc. super absorbent resin have been carried out a large amount of research and development.At present, what maintain the leading position in this field is the Japan and the U.S., and product innovation and achievement in research are very abundant.
The patent aspect:
WO 2003043671 A1 are with Acrylic Acid Monomer, with N, and N '-methylene-bisacrylamide is that linking agent and sorbitanic etc. have synthesized super absorbent resin;
It is that the water-absorbing resin of main raw material is as sanitary product with the polyacrylic acid that WO 2003092757 A1, WO 2001056625 A2 and US 2002035353 A1 have prepared;
The high water absorbency polymer that WO 2003076711 A1 have prepared acrylic acid series comes modified building thing topcoating;
WO 2003045453 A1 are that principal monomer prepares medical water absorbent polymer with vinylformic acid;
JP 2002080305 A2 have developed the agricultural water-absorption particle of acrylic acid series;
TW 399062 B have prepared the water absorbent polymer of the Racemic glycidol ether copolymer of unsaturated carboxylic acid and ethoxylation polyol;
FR 2818560 A1 have prepared vinylformic acid, sodium acrylate and 2-methyl-2-sulfonic group acrylamide copolymer water-absorbing material;
WO 2001000259 A1 have prepared netted water absorbent polymer and fiber;
DE 10016041 A1 have prepared and have mixed with Al
2(SO
4)
3The high salt solution material of inhaling of surface-crosslinked polyacrylic acid;
WO 2001047569 A1 have prepared and have contained acrylic acid multi-usage water absorbent polymer.
More than these patented technologies all be with the synthetic method for preparing water-absorbing material of thermopolymerization.
Sun light radiation polymerization is a kind of method of radio polymerization.Radio polymerization is that monomer molecule borrows radiating capacity to cause to activate into free radical or ion and the chain reaction polymerization carried out, and the available energy has daylight, UV-light, gamma-rays and electron beam etc., and wherein daylight is the energy most economical and cleaning.With the technology of the super absorbent resin of the method acrylic acid synthesizing-acrylate copolymerization system of sun light radiation polymerization, do not see any patent or other reported in literature as yet.
Summary of the invention
Purpose of the present invention: utilize daylight as source of radiation, the direct acrylic acid synthesizing-acrylate of light polymerization method is that the series copolymer super absorbent resin of principal monomer is a kind of brand-new technology.Have the area at sunshine all can carry out with solar radiation method synthesizing high-hydroscopicity resin any, and especially suitable for the west area of China, the region, there is wide, and physical features is higher, and sunshine is very sufficient, and the while west area is drought and water shortage again.Solar radiation method synthesizing high-hydroscopicity resin technology both can make full use of western sufficient sunlight, can solve the insufficient problem of water resources aspect the agroforestry development again, killed two birds with one stone and benefited the nation and the people, thereby have the meaning of very big research and development.
The invention provides a kind of method for preparing super absorbent resin with sun light radiation polymerization.
A kind ofly prepare the method for super absorbent resin with sun light radiation polymerization, the preparation process of this method is:
(1) the configuration pre-gathering solutions mixes reaction raw materials according to following mass ratio, obtains pre-gathering solutions:
Polymerization single polymerization monomer 50～99wt%; Day light trigger 0.001～10wt%;
Linking agent 0.001～25wt%; Additive (0.01～50wt%);
The mass percent sum of described reaction raw materials is 100%;
Described polymerization single polymerization monomer is any mixture in vinylformic acid and the following three kinds of acrylate: potassium acrylate, sodium acrylate or ammonium acrylate, its ratio are that mass ratio (20: 1) is to (1: 100);
Light trigger was A in described day:
The 1-65wt% benzoin dimethylether
1-55wt% Alpha-hydroxy cyclohexyl-phenyl ketone
1-45wt% two (2, the 6-methoxybenzoyl)-2,4,4-tri-methyl-amyl phosphorus oxide
1-55wt% 2-methyl isophthalic acid-[4-(methyl thio-phenyl)-2-morpholino acetone]
The 1-25wt% Alpha-hydroxy, α-phenyl Propiophenone
1-55wt% 1-hydroxy cyclohexyl phenylketone
1-65wt% 2-hydroxy-2-methyl-1-phenyl-acetone
Or B:
The 1-75wt% benzoin dimethylether
1-55wt% Alpha-hydroxy cyclohexyl-phenyl ketone
1-45wt% two (2, the 6-methoxybenzoyl)-2,4,4-tri-methyl-amyl phosphorus oxide
1-55wt% two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxide
1-25wt% is right-(β-hydroxy ethoxy) phenyl-2-hydroxy-2-methyl acetone
1-35wt% 2-hydroxy-2-methyl-1-phenyl-acetone
1-65wt% 1-hydroxy cyclohexyl phenylketone
Any one or two kinds of among both;
(2) pre-gathering solutions with step (1) gained places under the solar radiation, exposes 1～120 minute, obtains water white polymer gel;
(3) with gel cutting, the oven dry of step (2) gained, promptly obtain super absorbent resin.
Described linking agent is N, N '-methylene-bisacrylamide, Hydroxyethyl acrylate, vinylformic acid-2-hydroxypropyl acrylate, glycerol, diethylene glycol diacrylate, three polyethyleneglycol diacrylates, any one or more in four polyethyleneglycol diacrylates.
Described additive comprises monomeric additive and polymeric additive or their mixture, and its purpose is for improving resin property.
Described monomeric additive comprises MALEIC ANHYDRIDE, acrylamide, N hydroxymethyl acrylamide, acrylate, methacrylic acid, methyl methacrylate, p styrene sulfonic acid, any one or more in the p styrene sulfonic acid salt.
Described polymeric additive comprises starch, Mierocrystalline cellulose, polyvinyl alcohol, polyacrylamide, chitin, in the chitosan any one or more.
Described additive also can be above-mentioned monomeric additive and above-mentioned polymeric additive mixture.
The present invention is from the super absorbent resin product of monomer through the multiple vinylformic acid of direct one-step synthesis at sunshine-acrylate multipolymer.This method technology is controlled and the production efficiency height simply, easily, can realize continuous production, does not have energy consumption substantially, can carry out at normal temperatures; Have that polymerization velocity is fast, efficient is high and but normal temperature such as reacts at characteristics, greatly simplified polymerization technique; Itself is present in nature daylight, thereby the energy consumption of this polymerization process is zero, has saved the energy most possibly; As solvent, three-waste free pollution is a kind of low cost, high-level efficiency and pollution-free green chemical synthesis process, for the industrial production super absorbent resin is opened up new approach to this polymerization process with water.Synthetic super absorbent resin product, water-retaining capacity can surpass 1000 times of deadweight, inhales salt solution 0.9%NaCl solution) ability surpasses 100 times of deadweight, and blood and urine are also had very strong receptivity, possesses the ability that very strong water conservation under certain pressure is protected liquid simultaneously.This product can be widely used in the soil modification, checks winds and fixes drifting sand, plants trees, medical treatment and many fields such as sanitary product and material of construction.
Description of drawings
Fig. 1 is equipped with the polyreaction path synoptic diagram of super absorbent resin with day photopolymerization reaction legal system.
Embodiment
The polyreaction path synoptic diagram that is equipped with super absorbent resin as shown in Figure 1 with day photopolymerization reaction legal system.
Wherein,
Acrylate is: potassium acrylate, sodium acrylate or ammonium acrylate any; Additive is
The mixture of one or more in described monomeric additive or the polymeric additive or monomeric additive and polymeric additive.
Synthesizing of embodiment 1 vinylformic acid-potassium acrylate series super absorbent resin
Get 10g Acrylic Acid Monomer and 10g potassium acrylate monomer, add monomeric additive 1g (MALEIC ANHYDRIDE 0.1g, acrylamide 0.2g, N hydroxymethyl acrylamide 0.1g, acrylate 0.1g, methacrylic acid 0.1g, methyl methacrylate 0.15g, p styrene sulfonic acid 0.15g and styrene sulfonate 0.1g), add polymeric additive 2g (starch 0.5g, Mierocrystalline cellulose 0.3g, polyvinyl alcohol 0.5g, polyacrylamide 0.3g, chitin 0.2g and chitosan 0.2g), add 0.15g daylight initiator A, add 0.1g linking agent N, N '-methylene-bisacrylamide mixes pre-gathering solutions standby;
Pre-gathering solutions is placed under the solar radiation, and the time shutter is 1 minute, obtains water white polymer gel;
With gel cutting, oven dry, obtain super absorbent resin, productive rate is greater than 98%.
Synthesizing of embodiment 2 Acrylic Acid Sodium Acrylate series super absorbent resin
Get 10g Acrylic Acid Monomer and 10g sodium acrylate monomers, add monomeric additive 1g (MALEIC ANHYDRIDE 0.1g, acrylamide 0.2g, N hydroxymethyl acrylamide 0.1g, acrylate 0.1g, methacrylic acid 0.1g, methyl methacrylate 0.15g, p styrene sulfonic acid 0.15g and styrene sulfonate 0.1g), add polymeric additive 2g (starch 0.5g, Mierocrystalline cellulose 0.3g, polyvinyl alcohol 0.5g, polyacrylamide 0.3g, chitin 0.2g and chitosan 0.2g), add 0.15g daylight initiator A, add 0.1g linking agent N, N '-methylene-bisacrylamide mixes pre-gathering solutions standby;
Pre-gathering solutions is placed under the solar radiation, and the time shutter is 30 minutes, obtains water white polymer gel;
With gel cutting, oven dry, obtain super absorbent resin, productive rate is greater than 98%.
Synthesizing of embodiment 3 vinylformic acid-ammonium acrylate series super absorbent resin
Get 10g Acrylic Acid Monomer and 10g ammonium acrylate monomer, add monomeric additive 1g (MALEIC ANHYDRIDE 0.1g, acrylamide 0.2g, N hydroxymethyl acrylamide 0.1g, acrylate 0.1g, methacrylic acid 0.1g, methyl methacrylate 0.15g, p styrene sulfonic acid 0.15g and styrene sulfonate 0.1g), add polymeric additive 2g (starch 0.5g, Mierocrystalline cellulose 0.3g, polyvinyl alcohol 0.5g, polyacrylamide 0.3g, chitin 0.2g and chitosan 0.2g), add 0.15g daylight initiator A, add 0.1g linking agent N, N '-methylene-bisacrylamide mixes pre-gathering solutions standby; Pre-gathering solutions is placed under the solar radiation, and the time shutter is 120 minutes, obtains water white polymer gel; With gel cutting, oven dry, obtain super absorbent resin, productive rate is greater than 98%.
Synthesizing of embodiment 4 Acrylic Acid Sodium Acrylate series super absorbent resin
Get 10g Acrylic Acid Monomer and 9.8g sodium acrylate monomers, add monomeric additive 0.03g (MALEIC ANHYDRIDE 0.003g, acrylamide 0.003g, N hydroxymethyl acrylamide 0.003g, acrylate 0.003g, methacrylic acid 0.003g, methyl methacrylate 0.003g, p styrene sulfonic acid 0.006g and styrene sulfonate 0.006g), add polymeric additive 0.02g (starch 0.5g, Mierocrystalline cellulose 0.3g, polyvinyl alcohol 0.5g, polyacrylamide 0.3g, chitin 0.2g and chitosan 0.2g), add 0.1g day photoinitiator b, add 0.05g linking agent N, N '-methylene-bisacrylamide mixes pre-gathering solutions standby;
Pre-gathering solutions is placed under the solar radiation, and the time shutter is 60 minutes, obtains water white polymer gel;
With gel cutting, oven dry, obtain super absorbent resin, productive rate is greater than 98%.
Synthesizing of embodiment 5 Acrylic Acid Sodium Acrylate series super absorbent resin
Get 10g Acrylic Acid Monomer and 10g sodium acrylate monomers, add monomeric additive 2g (MALEIC ANHYDRIDE 0.08g, acrylamide 0.08g, N hydroxymethyl acrylamide 1.5g, acrylate 0.08g, methacrylic acid 0.08g, methyl methacrylate 0.08g, p styrene sulfonic acid 0.08g and styrene sulfonate 0.02g), add polymeric additive 12g (starch 10g, Mierocrystalline cellulose 0.4g, polyvinyl alcohol 0.4g, polyacrylamide 0.4g, chitin 0.4g and chitosan 0.4g), add 1g day photoinitiator b, add 5g linking agent Hydroxyethyl acrylate, pre-gathering solutions is mixed standby.
Pre-gathering solutions is placed under the solar radiation, and the time shutter is 90 minutes, obtains water white polymer gel;
With gel cutting, oven dry, obtain super absorbent resin, productive rate is greater than 98%.
Embodiment 6: be similar to embodiment 1, with linking agent N, N '-methylene-bisacrylamide changes the 0.5g Hydroxyethyl acrylate into, obtains super absorbent resin, and productive rate is greater than 98%.
Embodiment 7: be similar to embodiment 1, with linking agent N, N '-methylene-bisacrylamide changes 0.5g vinylformic acid-2-hydroxypropyl acrylate into, and productive rate is greater than 98%.
Embodiment 8: be similar to embodiment 1, with linking agent N, N '-methylene-bisacrylamide changes the 1.5g glycerol into, and productive rate is greater than 98%.
Embodiment 9: be similar to embodiment 1, with linking agent N, N '-methylene-bisacrylamide changes the 0.5g diethylene glycol diacrylate into, obtains super absorbent resin, and productive rate is greater than 98%.
Embodiment 10: be similar to embodiment 1, with linking agent N, N '-methylene-bisacrylamide changes 1g three polyethyleneglycol diacrylates into, obtains super absorbent resin, and productive rate is greater than 98%.
Embodiment 11: be similar to embodiment 1, with linking agent N, N '-methylene-bisacrylamide changes 0.5g four polyethyleneglycol diacrylates into, obtains super absorbent resin, and productive rate is greater than 98%.
Embodiment 12: be similar to embodiment 1, change the daylight initiator A into 0.25g day photoinitiator b, obtain super absorbent resin, productive rate is greater than 98%;
Embodiment 13: be similar to embodiment 12, with linking agent N, N '-methylene-bisacrylamide changes the 0.5g Hydroxyethyl acrylate into, obtains super absorbent resin, and productive rate is greater than 98%.
Embodiment 14: be similar to embodiment 12, with linking agent N, N '-methylene-bisacrylamide changes 0.5g and becomes vinylformic acid-2-hydroxypropyl acrylate, obtains super absorbent resin, and productive rate is greater than 98%.
Embodiment 15: be similar to embodiment 12, with linking agent N, N '-methylene-bisacrylamide changes the 1.5g glycerol into, obtains super absorbent resin, and productive rate is greater than 98%
Embodiment 16: be similar to embodiment 12, with linking agent N, N '-methylene-bisacrylamide changes the 0.5g diethylene glycol diacrylate into, obtains super absorbent resin, and productive rate is greater than 98%.
Embodiment 17: be similar to embodiment 12, with linking agent N, N '-methylene-bisacrylamide changes 1g three polyethyleneglycol diacrylates into, obtains super absorbent resin, and productive rate is greater than 98%.
Embodiment 18: be similar to embodiment 12, with linking agent N, N '-methylene-bisacrylamide changes 0.5g four polyethyleneglycol diacrylates into, obtains super absorbent resin, and productive rate is greater than 98%.
Claims (1)
1, a kind ofly prepare the method for super absorbent resin, it is characterized in that the preparation process of this method is with sun light radiation polymerization:
(1) the configuration pre-gathering solutions mixes reaction raw materials according to following mass ratio, obtains pre-gathering solutions:
Polymerization single polymerization monomer 50～99wt%, day light trigger 0.001～10wt%,
Linking agent 0.001～25wt%, additive 0.01～50wt%;
The mass percent sum of described reaction raw materials is 100%;
Described polymerization single polymerization monomer is any mixture in vinylformic acid and the following three kinds of acrylate: potassium acrylate, sodium acrylate or ammonium acrylate, its ratio are that mass ratio (20: 1) is to (1: 100);
Light trigger was A in described day:
The 1-65wt% benzoin dimethylether
1-55wt% Alpha-hydroxy cyclohexyl-phenyl ketone
1-45wt% two (2, the 6-methoxybenzoyl)-2,4,4-tri-methyl-amyl phosphorus oxide
1-55wt% 2-methyl isophthalic acid-[4-(methyl thio-phenyl)-2-morpholino acetone]
The 1-25wt% Alpha-hydroxy, α-phenyl Propiophenone
1-55wt% 1-hydroxy cyclohexyl phenylketone
1-65wt% 2-hydroxy-2-methyl-1-phenyl-acetone
Or B:
The 1-75wt% benzoin dimethylether
1-55wt% Alpha-hydroxy cyclohexyl-phenyl ketone
1-45wt% two (2, the 6-methoxybenzoyl)-2,4,4-tri-methyl-amyl phosphorus oxide
1-55wt% two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxide
1-25wt% is right-(β-hydroxy ethoxy) phenyl-2-hydroxy-2-methyl acetone
1-35wt% 2-hydroxy-2-methyl-1-phenyl-acetone
1-65wt% 1-hydroxy cyclohexyl phenylketone
Any one or two kinds of among both;
Described linking agent is N, N '-methylene-bisacrylamide, Hydroxyethyl acrylate, vinylformic acid-2-hydroxypropyl acrylate, glycerol, diethylene glycol diacrylate, three polyethyleneglycol diacrylates, any one or more in four polyethyleneglycol diacrylates;
Described additive is monomeric additive or polymeric additive or their mixture; Described monomeric additive comprises MALEIC ANHYDRIDE, acrylamide, N hydroxymethyl acrylamide, acrylate, methacrylic acid, methyl methacrylate, p styrene sulfonic acid, any one or more in the p styrene sulfonic acid salt; Described polymeric additive comprises starch, Mierocrystalline cellulose, polyvinyl alcohol, polyacrylamide, chitin, in the chitosan any one or more;
(2) pre-gathering solutions with step (1) gained places under the solar radiation, exposes 1～120 minute, obtains water white polymer gel;
(3) with gel cutting, the oven dry of step (2) gained, promptly obtain super absorbent resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100116634A CN1317307C (en) | 2005-04-29 | 2005-04-29 | Method for preparing high water adsorbing resin by sun light radiation polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100116634A CN1317307C (en) | 2005-04-29 | 2005-04-29 | Method for preparing high water adsorbing resin by sun light radiation polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1693313A CN1693313A (en) | 2005-11-09 |
| CN1317307C true CN1317307C (en) | 2007-05-23 |
Family
ID=35352457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100116634A Expired - Fee Related CN1317307C (en) | 2005-04-29 | 2005-04-29 | Method for preparing high water adsorbing resin by sun light radiation polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1317307C (en) |
Families Citing this family (5)
| 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 |
| WO2008090961A1 (en) * | 2007-01-24 | 2008-07-31 | Nippon Shokubai Co., Ltd. | 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 |
-
2005
- 2005-04-29 CN CNB2005100116634A patent/CN1317307C/en not_active Expired - Fee Related
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1693313A (en) | 2005-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1241961C (en) | Process for preparing high water absorption resin | |
| CN105924686B (en) | A kind of bio-based polymers aeroge oil absorption material and preparation method thereof | |
| CN1317307C (en) | Method for preparing high water adsorbing resin by sun light radiation polymerization | |
| CN1140540C (en) | Polyacrylate superabsorbent post-polymerization neutralized with solid non-hydroxyl neutralizing agent | |
| CN102336861A (en) | Polyacrylate super absorbent resin and preparation method thereof | |
| CN101501131A (en) | Particulate water absorbing agent and production method thereof | |
| CN101045776A (en) | Method for synthesizing high water absorption resin by glutinous wheat starch | |
| CN1033280A (en) | The method for preparing absorbable polymer | |
| CN101050147A (en) | Water retaining slow-release / controled fertilizer, and preparation method | |
| CN106590310A (en) | Uvioresistant paint with self-repairing function and preparation method and application thereof | |
| CN104448660B (en) | Superabsorbent resin as well as preparation method and applications thereof | |
| CN102702538B (en) | Preparation method for wood flour mixing with hydrogel | |
| CN101076555A (en) | Superabsorbent polymer particles with improved surface cross-linking and improved hydrophilicity and method of making them using vacuum uv radiation | |
| CN105294957A (en) | Method for preparing high-aldehyde content polymer microspheres on basis of lignin | |
| CN1008099B (en) | Process for preparation of thermoplastic mass | |
| CN101117422A (en) | Method for preparing alta-mud composite highly-absorbent resin by optical polymerization process | |
| CN109456451A (en) | A kind of corn stover base super moisture absorbing resin and preparation method thereof | |
| CN1320002C (en) | High water absorptive resin for sanitary material | |
| CN114213568B (en) | Light conversion microsphere, preparation method and application | |
| CN100404612C (en) | Preparation method of swelled vermiculite/ polyacrylic acid potassium- acrylamide high water absorption composite material | |
| CN105754050A (en) | Humic acid-based composite water-absorbent resin and preparation method thereof | |
| CN101993517A (en) | Method for preparing humic acid-based compound superabsorbent resin through ultraviolet light initiation | |
| CN1142208C (en) | Process for preparing high-water-absorption flexible material by ultraviolet surface graft method | |
| CN100424103C (en) | Weather resistant water-retaining agent and its prepn | |
| CN105031706B (en) | A kind of preparation method of polyvinyl alcohol medical sponge |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070523 Termination date: 20130429 |