CN1616506A - Process for preparing carboxymethyl chitosan grafted polyacrylic acid high water absorptive resin - Google Patents
Process for preparing carboxymethyl chitosan grafted polyacrylic acid high water absorptive resin Download PDFInfo
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- CN1616506A CN1616506A CN 200410080501 CN200410080501A CN1616506A CN 1616506 A CN1616506 A CN 1616506A CN 200410080501 CN200410080501 CN 200410080501 CN 200410080501 A CN200410080501 A CN 200410080501A CN 1616506 A CN1616506 A CN 1616506A
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- chitosan
- absorbent resin
- super absorbent
- product
- carboxymethyl chitosan
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000011347 resin Substances 0.000 title claims abstract description 34
- 229920005989 resin Polymers 0.000 title claims abstract description 34
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 30
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 title claims abstract description 9
- 229920002125 Sokalan® Polymers 0.000 title claims abstract description 6
- 239000004584 polyacrylic acid Substances 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012153 distilled water Substances 0.000 claims abstract description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 230000000977 initiatory effect Effects 0.000 claims abstract 2
- 230000002745 absorbent Effects 0.000 claims description 28
- 239000002250 absorbent Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 12
- 229920000578 graft copolymer Polymers 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000009775 high-speed stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims 1
- 235000019395 ammonium persulphate Nutrition 0.000 claims 1
- 210000003298 dental enamel Anatomy 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 238000000247 postprecipitation Methods 0.000 claims 1
- 230000003252 repetitive effect Effects 0.000 claims 1
- 238000005201 scrubbing Methods 0.000 claims 1
- 229910001220 stainless steel Inorganic materials 0.000 claims 1
- 239000010935 stainless steel Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 2
- 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 abstract 1
- -1 N, N'-methylene Chemical group 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 239000012567 medical material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 239000000178 monomer Substances 0.000 description 14
- 239000002504 physiological saline solution Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004744 fabric Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 229920002101 Chitin Polymers 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000002906 microbiologic effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000023597 hemostasis Effects 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides the preparation process of carboxymethyl chitosan grafted high water absorption polyacrylic acid resin. After carboxymethyl chitosan is dissolved in distilled water and under the initiation of persulfate initiator, sodium or potassium hydroxide neutralized acrylic acid is grafting copolymerized on its molecular chain, cross-linking agent N, N'-methylene biacrylamide is added for cross-linking, the product is ethanol deposited after finishing reaction, washed and dried to prepare the carboxymethyl chitosan grafted high water absorption polyacrylic acid resin. The preparation process is simple, and the product has high water absorption capacity, fast water absorbing rate and stable performance, and may find its wide application in medical material, physiological sanitary material and other fields.
Description
Technical field:
The present invention relates to the preparation method of the macromolecule modified super absorbent resin of a kind of new type natural, is exactly the method that cm-chitosan and acrylic graft copolymer prepare super absorbent resin specifically.The invention belongs to the synthetic field of macromolecular material.
Technical background:
High hydrophilous resin is the new functional macromolecule material that the class that grows up the sixties in 20th century contains the strong hydrophilicity group.Because it has good suction, water retention property, has all obtained widespread use at health care, daily life, petroleum industry and other numerous areas.Recent two decades comes, and each state is all in the research work of carrying out this respect energetically.China also begins to carry out the research work of super absorbent resin the eighties in 20th century, and has obtained very big progress in this respect.
The kind of super absorbent resin mainly contains polyacrylate series, starch-acrylate series, carboxymethyl cellulose-acrylate series, vinyl acetate between to for plastic analog copolymer, maleic anhydride analog copolymer and polyvinyl alcohol series etc.Adopt the natural macromolecular material such as starch, Mierocrystalline cellulose, chitin and the chitosan etc. that are rich in hydroxyl, amino isoreactivity functional group on the molecular chain two big advantages to be arranged for the feedstock production super absorbent resin: the one, this class material source enriches, and can constantly regenerate, cost is low; The 2nd, this class material non-toxic, good biocompatibility, and also waste easily degraded by microbiological degradation, and environmental pollution is little, meets the psychology of people's back to nature.Therefore, the research of this respect and production enjoy attention.
Adopt and to contain the crosslinked preparation super absorbent resin that carries out to a certain degree after the natural macromolecular material starch that enriches hydroxyl and Mierocrystalline cellulose and the monomer-grafted polymerization of hydrophilic unsaturated ethylene thiazolinyl on the molecular chain big quantity research has been arranged.United States Patent (USP) (USP3,935,099; 3,997,484; 3,985,616; 3,981,100; 4,405,387; 4,155,888), Japanese Patent (day special public clear 58-19,333), Chinese patent (CN 1,172, and 124; 1,075,488; 1,058,972; GK 85,100, and 849; 85,104,864; 85,103,771) all have a large amount of reports.This class lower cost for material, the water absorbent rate height of product has obtained widespread use in a plurality of fields.But this class material also exists easy going mouldy, and is easily lost shortcomings such as water-absorbing-retaining performance by microbiological degradation.
Contain modifiable groups such as a large amount of hydroxyls, amino on the natural macromolecular material chitosan molecule chain, be easy to obtain various functional high-polymers, enlarge its range of application by modification.To chitosan carry out the existing a large amount of research of grafting, copolymerization and modification (Chen Yu, Lu Ming, Tan Huimin etc. the grafting, copolymerization and modification of chitin and chitosan, polymer circular, 2004 (2): 54～62).Also can make super absorbent resin with carrying out to a certain degree crosslinked after chitosan and the monomer-grafted polymerization of unsaturated ethylene thiazolinyl.Because excellent properties such as chitosan has good pain relieving, hemostasis, promotion wound healing, reduces scar, antibacterial, excellent biological compatibility and biodegradability, with this class material is that the feedstock production super absorbent resin may be given its water absorbing and retaining properties and performances such as biological activity, biodegradability simultaneously, is expected to obtain widespread use in biomedical materials field.But the research of this respect report is few at present, and this mainly is because the solubility property of chitosan is limited, and preparation process is comparatively complicated.Cm-chitosan is a kind of important soluble derivative of chitosan, and it also has good biological activity and biodegradability, but is that the feedstock production super absorbent resin yet there are no report with it.
The objective of the invention is to novel water-solubility chitosan derivative-cm-chitosan is carried out modification, by carrying out the graft copolymerization that free radical causes with Acrylic Acid Monomer with the two keys of insatiable hunger, add linking agent N simultaneously, N '-methylene-bisacrylamide carries out crosslinked little crosslinked cancellated product that obtains having, by product being carried out last handling processes such as purifying and drying, obtain novel carboxymethyl chitosan grafted branch polyacrylic acid high water absorptive resin.
Summary of the invention:
The objective of the invention is to realize by the following method:
The preparation of carboxymethyl chitosan grafted branch polyacrylic super absorbent resin: after in distilled water, cm-chitosan fully being dissolved; hierarchy of control temperature is at 40～80 ℃; (also can without nitrogen protection) adds the persulfate initiator of monomer 0.5～3.3wt% under nitrogen protection; react after 30 minutes add with the cm-chitosan mass ratio be that 5～10: 1 employing sodium hydroxide or potassium hydroxide neutral degree of neutralization are 20～70% Acrylic Acid Monomer; and the linking agent N of adding monomer 0.01～2.3wt%; N '-methylene-bisacrylamide; Total Water is 6～30: 1 with the monomer mass ratio in the hierarchy of control, stopped reaction after 30～80 ℃ continuation is reacted 2～10 hours down.It is to smash precipitation by 2500 rev/mins high-speed stirring behind 8～35: 1 the ethanol sedimentation that product is used with the monomer mass ratio, and under high-speed stirring, use washing with alcohol repeatedly, again filter cake is dispersed in volume ratio behind the suction filtration and is to soak in 4: 1 the ethanol/water mixing solutions and be further purified in 24 hours, again with the filter cake vacuum-drying behind the suction filtration and pulverize and obtain final product.This product is inhaled the distilled water multiplying power can reach 680～1200 gram/grams, inhales the physiological saline multiplying power and can reach 75～125 gram/grams, and product was inhaled distilled water at 20～30 minutes can be near saturated.
The measuring method of super absorbent resin saturated water absorbent rate in distilled water (physiological saline): accurately take by weighing 0.100 gram, 100～120 purpose High hydrophilous resins, place the nylon cloth bag, and put it into and fill distilled water (pH=7.0, temperature is 25 ℃) or the beaker of the physiological saline of 0.9wt% in, make the at room temperature abundant swelling of resin remove the moisture on cloth bag surface after 12 hours, the quality of weighing suction back resin.Water absorbent rate Q calculates by following formula:
Q in the formula: water absorbent rate, gram/gram; m
1The quality of super absorbent resin before the-suction, gram; m
2The quality of-suction back super absorbent resin, gram.
Rate of water absorption measuring method: accurately take by weighing 0.100 gram, 100～120 purpose High hydrophilous resins, place the nylon cloth bag, and put it into and fill distilled water (pH=7.0, temperature is 25 ℃) beaker in, certain hour takes out cloth bag at interval, removes its surperficial moisture, the quality of weighing suction back resin, water absorbent rate according to (1) formula calculating resin obtains the relation between time and the resin water absorbent rate.
Advantage of the present invention:
Simple and the processing condition of the synthesis step process of this super absorbent resin are easy to control; Owing to the recyclable utilization of adopting in the purge process of ethanol, reduced the burden of sewage disposal; Adopting cheap vinylformic acid is the graft copolymerization monomer, and product cost is low; Compare with other commercially available super absorbent resin, the water absorbent rate of product is higher, and rate of water absorption is very fast.
Embodiment:
Below in conjunction with embodiment patent of the present invention is elaborated:
Embodiment 1:
After in distilled water, cm-chitosan fully being dissolved; hierarchy of control temperature is at 55 ℃; the ammonium persulfate initiator that under nitrogen protection, adds monomer 2wt%; react after 30 minutes add with the cm-chitosan mass ratio be that 8.6: 1 the sodium hydroxide neutral degree of neutralization that passes through is 30% Acrylic Acid Monomer and the linking agent N of monomer 0.6wt%; N '-methylene-bisacrylamide; Total Water is 9: 1 with the monomer mass ratio in the hierarchy of control; stopped reaction after reacting 6 hours under 55 ℃; it is by 2500 rev/mins high-speed stirring precipitation to be smashed behind 12: 1 the ethanol sedimentation that product is used with the monomer mass ratio; and under this stirring velocity, use washing with alcohol repeatedly; again filter cake is dispersed in volume ratio and is to soak in 4: 1 the ethanol/water mixing solutions and be further purified in 24 hours, behind the suction filtration with filter cake vacuum-drying and pulverize and obtain final product.This product is inhaled the distilled water multiplying power can reach 1160 gram/grams, inhales the physiological saline multiplying power and can reach 123 gram/grams, and product was inhaled distilled water in 22 minutes can be near saturated.
Embodiment 2:
The reaction process of present embodiment is initiator with example 1 but adopt Potassium Persulphate.The product for preparing under this condition is inhaled the distilled water multiplying power can reach 1025 gram/grams, inhales the physiological saline multiplying power and can reach 112 gram/grams, and product was inhaled distilled water in 25 minutes can be near saturated.
Embodiment 3:
The reaction process of present embodiment is with example 1, but omits the step of soaking with the ethanol/water mixing solutions, and it is 872 gram/grams that the product for preparing under this condition is inhaled the distilled water multiplying power, and suction physiological saline multiplying power can reach 93 gram/grams.
Embodiment 4:
The reaction process of present embodiment is with example 2, but omits the step of soaking with the ethanol/water mixing solutions, and it is 780 gram/grams that the product for preparing under this condition is inhaled the distilled water multiplying power, and suction physiological saline multiplying power can reach 91 gram/grams.
Embodiment 5:
The reaction process of present embodiment is with example 1, but adopts in the potassium hydroxide and Acrylic Acid Monomer, and the product for preparing under this condition is inhaled the distilled water multiplying power can reach 1078 gram/grams, and suction physiological saline multiplying power can reach 118 gram/grams.
Embodiment 6:
The reaction process of present embodiment is with example 2, but adopts in the potassium hydroxide and Acrylic Acid Monomer, and the product for preparing under this condition is inhaled the distilled water multiplying power can reach 970 gram/grams, and suction physiological saline multiplying power can reach 106 gram/grams.
Embodiment 7:
The reaction process of present embodiment is protected reaction system but omit with nitrogen with example 1, and it is 962 gram/grams that the product for preparing under this condition is inhaled the distilled water multiplying power, inhales the physiological saline multiplying power and can reach 102 gram/grams.
Claims (5)
1, the cm-chitosan mentioned of the present invention and the acrylic graft copolymer method for preparing super absorbent resin, its preparation process is after cm-chitosan is dissolved in distilled water, under the initiation of initiator, make graft copolymerization on its molecular chain by sodium hydroxide or potassium hydroxide neutral vinylformic acid, and the adding linking agent carries out crosslinked, after finishing, reaction, after washing, drying, makes carboxymethyl chitosan grafted branch polyacrylic acid novel super absorbent resin with the product ethanol sedimentation.
2, as claimed in claim 1ly prepare the method for super absorbent resin, be characterized in that adopting ammonium persulphate or Potassium Persulphate in polymerization process is initiator by cm-chitosan and acrylic graft copolymer.
3, as claimed in claim 1ly prepare the method for super absorbent resin by cm-chitosan and acrylic graft copolymer, be characterized in adding N in polymerization system, N '-methylene-bisacrylamide is a linking agent.
4, the method for preparing super absorbent resin by cm-chitosan and acrylic graft copolymer as claimed in claim 1, be characterized in its washing, drying process, promptly the product of post precipitation is smashed and repetitive scrubbing, be further purified with the immersion of ethanol/water mixing solutions again by high-speed stirring.
5, as claimed in claim 1ly prepare the method for super absorbent resin, be characterized in that this polyreaction can carry out in the polymerization reactor of general stainless steel or enamel lining by cm-chitosan and acrylic graft copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410080501 CN1616506A (en) | 2004-09-30 | 2004-09-30 | Process for preparing carboxymethyl chitosan grafted polyacrylic acid high water absorptive resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410080501 CN1616506A (en) | 2004-09-30 | 2004-09-30 | Process for preparing carboxymethyl chitosan grafted polyacrylic acid high water absorptive resin |
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| Publication Number | Publication Date |
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| CN1616506A true CN1616506A (en) | 2005-05-18 |
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| CN 200410080501 Pending CN1616506A (en) | 2004-09-30 | 2004-09-30 | Process for preparing carboxymethyl chitosan grafted polyacrylic acid high water absorptive resin |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225123B (en) * | 2007-12-07 | 2010-10-13 | 北京化工大学 | Water-soluble chitosan derivatives as well as preparation method and uses thereof |
| CN102382207A (en) * | 2011-09-08 | 2012-03-21 | 江苏天竹化工科技有限公司 | Natural biomaterial acrylate derivative and preparation method thereof |
| CN103834037A (en) * | 2014-03-05 | 2014-06-04 | 陕西科技大学 | Preparation method of leather finishing agent for water-soluble chitosan modified acrylic resin |
| CN104497210A (en) * | 2014-11-13 | 2015-04-08 | 苏州威尔德工贸有限公司 | Super absorbent resin used for paper diaper and production method thereof |
| CN104987461A (en) * | 2015-07-31 | 2015-10-21 | 浙江金壳药业有限公司 | Chitosan derivative antibacterial superabsorbent gel and preparation method therefor |
| CN108671352A (en) * | 2018-05-21 | 2018-10-19 | 南阳市第二人民医院 | A kind of trachea cannula |
| CN108753452A (en) * | 2018-06-15 | 2018-11-06 | 黄钱英 | A kind of method of Organophosphorus Pesticide Residues in removal tea oil |
| CN109734519A (en) * | 2019-03-15 | 2019-05-10 | 招远市金虹精细化工有限公司 | A kind of nutrient solution and its application method for administering grassland desertification |
| CN111820498A (en) * | 2019-04-19 | 2020-10-27 | 天津大学 | PM2.5 mask based on electrostatic adsorption and high-molecular water-absorbent resin |
| CN112309624A (en) * | 2020-11-19 | 2021-02-02 | 安徽宏业仪表电缆有限公司 | Fire-resistant moisture-proof composite cable and preparation method thereof |
| CN113061330A (en) * | 2021-03-22 | 2021-07-02 | 华南农业大学 | Soil heavy metal removal composite material and preparation method and application thereof |
| CN115108645A (en) * | 2022-06-09 | 2022-09-27 | 南京大学环境规划设计研究院集团股份公司 | Carboxylic acid chitosan modified material with double functions of corrosion inhibition and scale inhibition and preparation method thereof |
-
2004
- 2004-09-30 CN CN 200410080501 patent/CN1616506A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225123B (en) * | 2007-12-07 | 2010-10-13 | 北京化工大学 | Water-soluble chitosan derivatives as well as preparation method and uses thereof |
| CN102382207A (en) * | 2011-09-08 | 2012-03-21 | 江苏天竹化工科技有限公司 | Natural biomaterial acrylate derivative and preparation method thereof |
| CN102382207B (en) * | 2011-09-08 | 2012-11-14 | 江苏天竹化工科技有限公司 | Natural biomaterial acrylate derivative and preparation method thereof |
| CN103834037B (en) * | 2014-03-05 | 2016-06-08 | 陕西科技大学 | The preparation method of the acrylic resin modified hide finishes of a kind of water-soluble chitosan |
| CN103834037A (en) * | 2014-03-05 | 2014-06-04 | 陕西科技大学 | Preparation method of leather finishing agent for water-soluble chitosan modified acrylic resin |
| CN104497210A (en) * | 2014-11-13 | 2015-04-08 | 苏州威尔德工贸有限公司 | Super absorbent resin used for paper diaper and production method thereof |
| CN104987461A (en) * | 2015-07-31 | 2015-10-21 | 浙江金壳药业有限公司 | Chitosan derivative antibacterial superabsorbent gel and preparation method therefor |
| CN108671352A (en) * | 2018-05-21 | 2018-10-19 | 南阳市第二人民医院 | A kind of trachea cannula |
| CN108753452A (en) * | 2018-06-15 | 2018-11-06 | 黄钱英 | A kind of method of Organophosphorus Pesticide Residues in removal tea oil |
| CN109734519A (en) * | 2019-03-15 | 2019-05-10 | 招远市金虹精细化工有限公司 | A kind of nutrient solution and its application method for administering grassland desertification |
| CN111820498A (en) * | 2019-04-19 | 2020-10-27 | 天津大学 | PM2.5 mask based on electrostatic adsorption and high-molecular water-absorbent resin |
| CN112309624A (en) * | 2020-11-19 | 2021-02-02 | 安徽宏业仪表电缆有限公司 | Fire-resistant moisture-proof composite cable and preparation method thereof |
| CN113061330A (en) * | 2021-03-22 | 2021-07-02 | 华南农业大学 | Soil heavy metal removal composite material and preparation method and application thereof |
| CN113061330B (en) * | 2021-03-22 | 2022-03-25 | 华南农业大学 | Soil heavy metal removal composite material and preparation method and application thereof |
| CN115108645A (en) * | 2022-06-09 | 2022-09-27 | 南京大学环境规划设计研究院集团股份公司 | Carboxylic acid chitosan modified material with double functions of corrosion inhibition and scale inhibition and preparation method thereof |
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