CN1912006A - Humic acid base superstrength water retaining agent and its preparation method - Google Patents
Humic acid base superstrength water retaining agent and its preparation method Download PDFInfo
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- CN1912006A CN1912006A CN 200510090362 CN200510090362A CN1912006A CN 1912006 A CN1912006 A CN 1912006A CN 200510090362 CN200510090362 CN 200510090362 CN 200510090362 A CN200510090362 A CN 200510090362A CN 1912006 A CN1912006 A CN 1912006A
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- 239000004021 humic acid Substances 0.000 title claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 66
- 229920002472 Starch Polymers 0.000 claims abstract description 24
- 239000008107 starch Substances 0.000 claims abstract description 24
- 235000019698 starch Nutrition 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003245 coal Substances 0.000 claims abstract description 22
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 42
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 20
- 235000019394 potassium persulphate Nutrition 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000002250 absorbent Substances 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- 230000002745 absorbent Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000499 gel Substances 0.000 claims description 9
- 239000000017 hydrogel Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000004159 Potassium persulphate Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 239000002585 base Substances 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000002689 soil Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000050 nutritive effect Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
Landscapes
- Fertilizers (AREA)
Abstract
The present invention is humic acid based super powerful water retaining agent and its preparation process, and the water retaining agent consists of coal humic acid, acrylic acid, industrial starch, cross-linking agent, sodium hydroxide solution and potassium persulfate. The preparation process includes extracting humic acid from coal material, reacting humic acid with sodium hydroxide to form humate as the base material for the water retaining agent, grafting copolymerizing with hydrophilic monomer and starch in water at 60 deg.c to form ropy gel product; cooling to room temperature, chipping, drying, crushing and sieving to obtain granular black humic acid based super powerful water retaining agent. The water retaining agent has high hydroscopicity, nourishing function, high degradability and low cost.
Description
Technical field
This invention relates to a kind of water-holding agent and preparation method thereof, and particularly a kind of humic acid base superstrength water retaining agent and preparation method thereof is applicable to the agroforestry field, can be used for keeping crop seedling from drought, increasing both production and income, improves the soil, checks winds and fixes drifting sand, soil conservation etc., also can dress seed.
Background technology
Water-holding agent is a kind of functional high molecule material with high-strength absorbing performance and high-strength water retention capacity.Because super absorbent resin has many excellent water absorbing properties, is widely used in various fields such as farming, woods, gardening, medicine, medical treatment, physiological hygiene, oil, chemical, daily necessities, environment protection, beauty and make-up, building materials, biochemical technology and food.Common water-holding agent is to be raw material with hydrophilic monomer or polymer, and synthetic or modification generates.But common water-holding agent exists effectiveness single in the agroforestry Application for Field, can only bring into play " water conservation " effect, do not have " protecting fertile getting fat " effect, and salt resistance ability and rate of water absorption is lower; After common water-holding agent and other nutritive ingredient are mixed, influence its water absorbent rate, nutritive ingredient also runs off easily.And the production cost height, be unsuitable for big area use in soil.
The patent of invention content
The objective of the invention is in order to solve above existing problem, with the higher coal of humic acids content is that raw material extracts humic acids, with humic acids and highly basic reaction, form the matrix of humate solution as synthetic water-holding agent, and with hydrophilic monomer and starch graft copolymer, synthetic humic acid base superstrength water retaining agent.This water-holding agent has good water absorbing properties, trophicity and readily degradable, and product cost is lower.
Humic acids has good coordination, crab is closed and the chemical reaction ability, but humic acids is a non-water soluble substance, is difficult to form homogeneous system with other hydroaropic substance, can not form the multipolymer of structure homogeneous with the hydrophilic monomer polymerization.The present invention is by being dissolved in basic solution with coal humic acid, form water-soluble phytate, and form homogeneous system, by solution polymerization process synthetic coal humic acid base superstrength water retaining agent with other copolymerization components, humic acids is fixed in the macromolecular structure, brings into play the multiple biological activity of its inherent.
The present invention realizes in the following manner:
Coal humic acid is dissolved in highly basic such as NaOH or the KOH solution, forms humate solution.Add in the deionized water starch and gelatinization, make starch-containing hydrogel.The two mixes, add certain density acrylic acid solution and minor N again, N '-methylene-bisacrylamide solution, constantly stir, drip potassium persulfate solution then, the above-mentioned container that fills reaction mixture is placed water-bath, keep 60 ℃ of reactions of bath temperature to stop when forming viscous gel shape product, take out product, be cooled to room temperature, be cut into small pieces and put into the baking oven drying, pulverize with pulverizer, by certain grade screening, promptly obtain the humic acid base superstrength water retaining agent of the black particle shape of different-grain diameter.According to the service requirements of water-holding agent, can adjust the starch add-on; Also can simplify technological process and select not add starch ingredients.
Feature of the present invention is that the prescription that is used for synthetic this water-holding agent contains:
Coal humic acid (HA) is 0.05: 1~0.35: 1 with the weight ratio of vinylformic acid (AA),
The weight ratio of industrial starch and vinylformic acid (AA) is 0~0.45: 1,
Linking agent (MBA) is 0.01: 1~0.001: 1 with vinylformic acid (AA) mol ratio,
NaOH solution and vinylformic acid (AA) mol ratio is 0.20: 1~0.50: 1,
Potassium Persulphate (KPS) is 0.007: 1~0.01: 1 with vinylformic acid (AA) mol ratio,
Described linking agent is N, N '-methylene-bisacrylamide (MBA).
Preparation method of the present invention is:
Coal humic acid is dissolved in highly basic such as NaOH or the KOH solution, forms humate solution; Add in the deionized water starch and gelatinization, make starch-containing hydrogel; The two is mixed, add degree of neutralization in proportion and be 75%-80% acrylic acid solution and N, N '-methylene-bisacrylamide solution also stirs; Drip potassium persulfate solution, keep 60 ℃ of reactions of bath temperature to forming viscous gel shape product; Take out product, be cooled to room temperature, be cut into small pieces and put into the baking oven drying, pulverize,, promptly obtain the humic acid base superstrength water retaining agent of the black particle shape of different-grain diameter by certain grade screening with pulverizer.
Wherein starch needs to make the hydrogel that starch content is 30%-35% 80 ℃ of following gelatinizations.The weight concentration of NaOH solution is 2~5%.N, N '-methylene-bisacrylamide (MBA) solution weight concentration is 0.5%~2.0%, and to be 1.0%~4.0%. vinylformic acid (AA) be neutralized to degree of neutralization with the NaOH solution of weight concentration 20%~30% to Potassium Persulphate (KPS) aqueous solution weight concentration is 75%-80%.
Coal humic acid can extract in the following manner:
Get weathered coal and put into container, adding deionized water, NaOH (or KOH) stir, at room temperature extracting 2h.Reactant in the container is filtered by B, and the filtrate that obtains is Sodium salts humic acids (or potassium humate) solution.Add a certain amount of hydrochloric acid soln in the filtrate, make the humic acids acid out, precipitation.Filtrate is left standstill, and suction filtration leaches thing 70 ℃~80 ℃ oven dry down, promptly gets coal humic acid.
Concrete enforcement: put into container as getting 60~120g weathered coal, adding 400~800ml deionized water, 5~10gNaOH (or KOH) stir, at room temperature extracting 2h.Reactant in the container is filtered by B, and the filtrate that obtains is Sodium salts humic acids (or potassium humate) solution.A certain amount of concentration of adding is 36%~38% hydrochloric acid soln in the filtrate, and the add-on of hydrochloric acid soln becomes neutrality to exceed with filtrate, makes the humic acids acid out, precipitation.Filtrate is left standstill, and suction filtration leaches thing 70 ℃~80 ℃ oven dry down, promptly gets coal humic acid.
Wherein, humic acids content is 50%~70% in the used coal.
Humic acid base superstrength water retaining agent is made up of three kinds of active principles, and wherein the humic acids in the copolymer structure can provide plant-growth required lasting nutrient, reaches the nutrition slow-release effect; Natural polymer starch in the copolymer structure makes humic acid base superstrength water retaining agent not only have good water-absorbent, and can improve the biodegradability of humic acid base superstrength water retaining agent, helps protecting Soil structure; Vinylformic acid in the copolymer structure can produce strongly hydrophilic polyacrylic acid side chain, improves the water absorbing properties of humic acid base superstrength water retaining agent.Humic acids and starch can reduce product cost to a certain extent.
Embodiment
Embodiment 1:
1.1,10g coal humic acid (HA) is dissolved in the 200mL weight concentration is in 4% the NaOH solution, makes sodium humate solution, it is standby to get supernatant liquor;
1.2, will 21g starch add in the 39g deionized water and and make hydrogel 80 ℃ of following gelatinizations;
1.3,50g vinylformic acid is neutralized to degree of neutralization with the NaOH solution of weight concentration 20% is 75%;
1.4, above-mentioned three components are added in the container successively, add 18g concentration again and be 0.8% N,N methylene bis acrylamide (MBA), stir;
1.5, be that 4% Potassium Persulphate (KPS) aqueous solution slowly adds wherein with 36g concentration, keeping bath temperature is 60 ℃, reaction stops when forming the viscous gel product, takes out product, is cooled to room temperature, be cut into the 5-10mm fritter put into 80 ℃ in baking oven down dry 24 hours to constant weight, pulverize with pulverizer,, promptly obtain the humic acid base superstrength water retaining agent of the black particle shape of different-grain diameter by certain grade screening, its water absorbent rate is 400~480g/g, generally can reach 450g/g.
Example 2:
2.1, the 16g coal humic acid is dissolved in the 200mL weight concentration is in 5% the KOH solution, makes sodium humate solution, it is standby to get supernatant liquor;
2.2, will 10g starch add in the 20g deionized water and and make hydrogel 80 ℃ of following gelatinizations;
2.3,50g vinylformic acid is neutralized to degree of neutralization with 20% NaOH solution is 80%;
2.4, above-mentioned three components are added in the container successively, add the 10g weight concentration again and be 1.0% N, N '-methylene-bisacrylamide stirs;
2.5, be that 4% persulfate aqueous solution slowly adds wherein with 50g concentration, keeping bath temperature is 60 ℃, reaction stops when forming the viscous gel product, takes out product, is cooled to room temperature, be cut into the 5-10mm fritter put into 80 ℃ in baking oven down dry 24 hours to constant weight, pulverize with pulverizer,, promptly obtain the humic acid base superstrength water retaining agent of the black particle shape of different-grain diameter by certain grade screening, its water absorbent rate is 300~400g/g, generally can reach 350g/g.
Example 3:
3.1, the 10g coal humic acid is dissolved in the 300mL weight concentration is in 4% NaOH (or KOH) solution;
3.2,60g vinylformic acid is neutralized to degree of neutralization with the NaOH solution of weight concentration 20% is 75%;
3.3, above-mentioned two components are added in the container, add the 13g weight concentration again and be 1.0% N, N '-methylene-bisacrylamide stirs;
3.4, be that 4% persulfate aqueous solution slowly adds wherein with the 40g weight concentration, keeping bath temperature is 60 ℃, question response stops when forming the viscous gel product, take out product, be cooled to room temperature, be cut into the 5-10mm fritter put into 80 ℃ in baking oven down dry 24 hours to constant weight, pulverize with pulverizer, by certain grade screening, promptly obtain the humic acid base superstrength water retaining agent of the black particle shape of different-grain diameter, its water absorbent rate generally can reach 470g/g for its water absorbent rate is 400~500g/g.
Claims (7)
1, a kind of humic acid base superstrength water retaining agent is characterized in that the prescription that is used for synthetic this water-holding agent contains:
Coal humic acid (HA) is 0.05: 1~0.35: 1 with the weight ratio of vinylformic acid (AA),
The weight ratio of industrial starch and vinylformic acid (AA) is 0~0.45: 1,
Linking agent (MBA) is 0.01: 1~0.001: 1 with vinylformic acid (AA) mol ratio,
NaOH solution and vinylformic acid (AA) mol ratio is 0.20: 1~0.50: 1,
Potassium Persulphate (KPS) is 0.007: 1~0.01: 1 with vinylformic acid (AA) mol ratio.
2,, it is characterized in that described linking agent is N, N methylene-bisacrylamide (MBA) according to claims 1 described humic acid base superstrength water retaining agent.
3, a kind of humic acid base superstrength water retaining agent preparation method is characterized in that:
3.1 coal humic acid is dissolved in highly basic such as NaOH or the KOH solution, forms humate solution;
3.2 add in the deionized water starch and gelatinization, make starch-containing hydrogel;
3.3 the two is mixed, add degree of neutralization and be 75%-80% acrylic acid solution and N, N '-methylene-bisacrylamide solution also constantly stirs;
3.4 the dropping potassium persulfate solution keeps 60 ℃ of reactions of bath temperature to forming viscous gel shape product;
3.5 the taking-up product is cooled to room temperature, is cut into small pieces to put into the baking oven drying, pulverizes with pulverizer, by certain grade screening, promptly obtains the humic acid base superstrength water retaining agent of the black particle shape of different-grain diameter.
4, according to claims 3 described humic acid base superstrength water retaining agent preparation methods, it is characterized in that:
4.1 described starch needs to make the starch hydrogel that starch content is 30%-35% 80 ℃ of following gelatinizations;
4.2 described highly basic such as NaOH or KOH strength of solution are 2%~5%;
4.3 described N, N '-methylene-bisacrylamide (MBA) strength of solution is 0.5%~2.0%;
4.4 described Potassium Persulphate (KPS) concentration of aqueous solution is 1.0%~4.0%;
4.5 it is 75%-80% that described vinylformic acid (AA) is neutralized to degree of neutralization with 20%~30% NaOH solution.
5, according to claims 3 or 4 described humic acid base superstrength water retaining agent preparation methods, it is characterized in that:
5.1, the 10g coal humic acid is dissolved in 300mL concentration is in 2% NaOH (or KOH) solution;
5.2,60g vinylformic acid is neutralized to degree of neutralization with 20% NaOH solution is 75%;
5.3, above-mentioned two components are added in the container, add 10g concentration again and be 1.0% N, N '-methylene-bisacrylamide stirs;
5.4, be that 1% persulfate aqueous solution slowly adds in the container with 40g concentration, container is put into the water-bath that keeps 60 ℃, question response stops when forming the viscous gel product, take out product, be cooled to room temperature, be cut into 5~10mm fritter put into 80 ℃ in baking oven down dry 24 hours to constant weight, pulverize with pulverizer, by certain grade screening, promptly obtain the humic acid base superstrength water retaining agent of the black particle shape of different-grain diameter, its water absorbent rate can reach 470g/g.
6, according to claims 3 or 4 described humic acid base superstrength water retaining agent preparation methods, it is characterized in that:
6.1,10g coal humic acid (HA) is dissolved in 200mL concentration is in 4% the NaOH solution, makes sodium humate solution, it is standby to get supernatant liquor;
6.2, will 21g starch add in the 39g deionized water and and make hydrogel 80 ℃ of following gelatinizations;
6.3,50g vinylformic acid is neutralized to degree of neutralization with 20% NaOH solution is 75%;
6.4, above-mentioned three components are added in the container successively, add 18g concentration again and be 0.8% N,N methylene bis acrylamide (MBA), stir;
6.5, be that 4% Potassium Persulphate (KPS) aqueous solution slowly adds wherein with 36g concentration, keeping bath temperature is 60 ℃, reaction stops when forming the viscous gel product, take out product, be cooled to room temperature, be cut into 5~10mm fritter put into 80 ℃ in baking oven down dry 24 hours to constant weight, pulverize with pulverizer, by certain grade screening, promptly obtain the humic acid base superstrength water retaining agent of the black particle shape of different-grain diameter, its water absorbent rate can reach 470g/g.
7, according to claims 3 or 4 described humic acid base superstrength water retaining agent preparation methods, it is characterized in that:
7.1, the 16g coal humic acid is dissolved in 200mL concentration is in 4% the KOH solution, makes sodium humate solution, it is standby to get supernatant liquor;
7.2, will 10g starch add in the 20g deionized water and and make hydrogel 80 ℃ of following gelatinizations;
7.3,50g vinylformic acid is neutralized to degree of neutralization with 20% NaOH solution is 80%;
7.4, above-mentioned three components are added in the container successively, add 13g concentration again and be 1.0% N, N '-methylene-bisacrylamide stirs;
7.5, be that 1% persulfate aqueous solution slowly adds wherein with 50g concentration, keeping bath temperature is 60 ℃, reaction stops when forming the viscous gel product, take out product, be cooled to room temperature, be cut into the 5-10mm fritter put into 80 ℃ in baking oven down dry 24 hours to constant weight, pulverize with pulverizer, by certain grade screening, promptly obtain the humic acid base superstrength water retaining agent of the black particle shape of different-grain diameter, its water absorbent rate is 396g/g.
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CN101914209A (en) * | 2010-08-13 | 2010-12-15 | 中国矿业大学(北京) | Method for grafting humic acid into high water absorption resin and high water absorption resin obtained by same |
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CN101914209A (en) * | 2010-08-13 | 2010-12-15 | 中国矿业大学(北京) | Method for grafting humic acid into high water absorption resin and high water absorption resin obtained by same |
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