CN1286870C - Process for preparing novel carboxymethl chitosan modified high water absorptive resin - Google Patents
Process for preparing novel carboxymethl chitosan modified high water absorptive resin Download PDFInfo
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- CN1286870C CN1286870C CN 200410080502 CN200410080502A CN1286870C CN 1286870 C CN1286870 C CN 1286870C CN 200410080502 CN200410080502 CN 200410080502 CN 200410080502 A CN200410080502 A CN 200410080502A CN 1286870 C CN1286870 C CN 1286870C
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Abstract
The present invention provides a preparation method of novel carboxymethyl chitosan modified high water absorbent resin. After carboxymethyl chitosan is dissolved in distilled water, a mixture of acrylate and N-vinyl pyrrolidone is copolymerized in the way of graft on a molecule chain of the carboxymethyl chitosan under the initiation of initiators of azodiisobutyronitrile, or H2O2/NH3. H2O, etc., and a crosslinking agent N, N'-methylene biacrylamide is added and crosslinked for preparing high water absorbent resin. The preparation method has the advantages of simple process, high water absorption rate of a product, high water absorption speed, good salt tolerance and stable performance. The product can be widely applied to the fields of medical materials, physiological hygiene materials, etc.
Description
Technical field:
The present invention relates to the preparation method of a class natural macromolecule modification super absorbent resin, is exactly the method that cm-chitosan and acrylate and the graft copolymerization of N-vinyl pyrrolidone prepare super absorbent resin specifically.The invention belongs to the synthetic field of macromolecular material.
Technical background:
Super absorbent resin is a class new functional macromolecule material of developing in recent years, and it contains strong hydrophilic radical, and has little crosslinked reticulated structure, can absorb the moisture of own wt hundreds of even thousands of times, and the water retention property excellence.Because the good performance of super absorbent resin has obtained widespread use in medical material, physiological hygiene articles for use, agricultural and gardening, desertification control, civil construction and filed of daily-use chemical industry.The great attention that the research and development and the preparation of super absorbent resin has been subjected to various countries.From USDA north institute in 1961 makes starch and acrylonitrile graft copolymer super absorbent resin with ceric ammonium nitrate as initiator since, the GrainProcessing company that the U.S. is successively arranged, Hercules company and NationalStarch company, the sumitomo chemical company of Japan, flower Wang Shi alkali company, catalyst chemical company and Sanyo chemical company have all developed successfully various types of super absorbent resins in succession.China begins to carry out the research of super absorbent resin in early 1980s, nineteen eighty-two Chinese Academy of Sciences's chemistry institute people such as yellow beautiful jade synthesize at first with silicon-dioxide at home be carrier poly--γ-mercapto propyl-siloxane is an initiator, water-retaining capacity is 400 times a sodium polyacrylate super absorbent resin, and patent and the bibliographical information about super absorbent resin increases gradually afterwards.China classified the application of super absorbent resin as great sci-tech popularization's project and agriculturally used the end of the nineties, used it for transplanting nursery stock as Jilin Province, and provinces such as Xinjiang, Henan and Gansu improve the soil with it etc.
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.Unsaturated ethylene thiazolinyl monomers such as chitosan and vinylformic acid, methacrylic acid, acrylamide, methyl methacrylate are carried out the existing a large amount of research of grafting, copolymerization and modification.Also can make super absorbent resin with carrying out to a certain degree crosslinked after chitosan and the vinyl monomer-grafted polymerization.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, carry out adding behind the graft copolymerization that free radical causes linking agent with it by acrylate and N-vinyl pyrrolidone and carry out crosslinkedly obtaining little crosslinked cancellated novel high polymer material that has, and make poly-(acrylate-N-vinyl pyrrolidone) super absorbent resin of carboxymethyl chitosan grafted branch by product being carried out a series of purge process.
Traditional superabsorbent polyacrylate potential resistance to electrolyte contamination poor-performing, when having metal ion to exist in the solution that is adsorbed, water-retaining capacity reduces greatly.Owing to the contained ionogen situation of the liquid complexity that needs in the practical application to absorb, the potential resistance to electrolyte contamination performance that therefore improves resin becomes the important topic that needs to be resolved hurrily.In the present invention, adopt the N-vinylpyrrolidone monomer and the acrylate copolymerization of nonionic, its adding can reduce the influence of ion shielding effect to the resin absorbent, improves the salt resistant character of resin; Because the Polyvinylpyrolidone (PVP) segment has good water-solubility, hypotoxicity and biocompatibility, its introducing can further improve the biological activity of resin, further make resin satisfy the application demand of medical material and physiological hygiene material, in addition, the Polyvinylpyrolidone (PVP) segment also is easy to carry out chemical modification, can improve the functional of resin.
Summary of the invention:
The objective of the invention is to realize by the following method:
Cm-chitosan and acrylate and the graft copolymerization of N-vinyl pyrrolidone prepare super absorbent resin: after in distilled water cm-chitosan fully being dissolved, hierarchy of control temperature (to being reflected in 60～100 ℃ of scopes that Diisopropyl azodicarboxylate causes, adopts H at 40～100 ℃
2O
2/ NH
3H
2What O caused is reflected in 40～80 ℃ of scopes), under nitrogen protection, add the Diisopropyl azodicarboxylate of monomer 1～9wt% or the H of monomer 2.5～11wt%
2O
2/ NH
3H
2O initiator (the 30%H of 1/3 volume
2O
2Dense NH with 2/3 volume
3H
2O), react after 30 minutes add with the cm-chitosan mass ratio be 5～14: 1 mixture (vinylformic acid account for monomer total mass 50～90%) with sodium hydroxide or complete neutral vinylformic acid of potassium hydroxide and N-vinyl pyrrolidone, and the linking agent N of adding monomer 0.02～3wt%, N '-methylene-bisacrylamide, Total Water is 5～40: 1 with the monomer mass ratio in the hierarchy of control, continues to react stopped reaction after 3～10 hours under aforementioned temperature.It is by 2500 rev/mins high-speed stirring precipitation to be smashed behind 8～45: 1 ethanol sedimentation that product is used with the monomer mass ratio, and under high-speed stirring, use washing with alcohol repeatedly, behind the suction filtration filter cake is dispersed in to soak in the ethanol/water mixing solutions and is further purified, once more behind the suction filtration with filter cake vacuum-drying and pulverize and obtain poly-(acrylate-N-vinyl pyrrolidone) super absorbent resin of carboxymethyl chitosan grafted branch.This product water absorbent rate can reach 720～1330 gram/grams, inhales the physiological saline multiplying power and can reach 90～180 gram/grams, and the suction of 15～35 minutes resins can be near saturated.
The measuring method of the saturated water absorbent rate of super absorbent resin in distilled water (physiological saline): accurately take by weighing 0.100 gram, 100～120 height of eye water-absorbing 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; Because the cheap vinylformic acid of a large amount of employings is the graft copolymerization monomer, product cost is low; Compare with other commercially available super absorbent resin, the water absorbent rate of product is higher, the very fast and good salt tolerance of rate of water absorption.
Embodiment:
Below in conjunction with embodiment patent of the present invention is elaborated:
Embodiment 1:
After in distilled water, 1.5 parts of cm-chitosan fully being dissolved; hierarchy of control temperature is at 80 ℃; the Diisopropyl azodicarboxylate that under nitrogen protection, adds monomer 2.5wt%; react after 30 minutes that to add with the cm-chitosan mass ratio be 10: 1 unsaturated ethylene thiazolinyl monomer mixture; be 70% wherein with the acrylic acid massfraction of sodium hydroxide neutral; the massfraction of N-vinyl pyrrolidone is 30%; the linking agent N that adds monomer 2wt% simultaneously; N '-methylene-bisacrylamide; Total Water is 15: 1 with the monomer mass ratio in the hierarchy of control; stopped reaction after reacting 5 hours under 80 ℃; it is by high-speed stirring precipitation to be smashed behind 18: 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 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 1312 gram/grams, inhales the physiological saline multiplying power and can reach 176 gram/grams, and all resins suction in 26 minutes can be near saturated.
Embodiment 2:
The reaction process of present embodiment is with example 1, but adopts in the potassium hydroxide and Acrylic Acid Monomer.The product for preparing under this condition is inhaled the distilled water multiplying power can reach 1268 gram/grams, inhales the physiological saline multiplying power and can reach 167 gram/grams, and the resin suction can be near saturated about 23 minutes.
Embodiment 3:
The reaction process of present embodiment is with example 1, but omits the step of soaking with the ethanol/water mixing solutions.It is 1172 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 151 gram/grams, and the resin suction can be near saturated about 30 minutes.
Embodiment 4:
The reaction process of present embodiment is protected reaction system but omit with nitrogen with example 1.It is 980 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 132 gram/grams, and the resin suction can be near saturated about 25 minutes.
Embodiment 5:
After in distilled water 1.5 parts of cm-chitosan fully being dissolved, hierarchy of control temperature adds the H of monomer 3wt% at 65 ℃ under nitrogen protection
2O
2/ NH
3H
2O initiator (the 30%H of 1/3 volume
2O
2Dense NH with 2/3 volume
3H
2O) be initiator, react after 30 minutes that to add with the cm-chitosan mass ratio be 10: 1 unsaturated ethylene thiazolinyl monomer mixture, be 70% wherein with the acrylic acid massfraction of sodium hydroxide neutral, the massfraction of N-vinyl pyrrolidone is 30%, the linking agent N that adds monomer 2.2wt% simultaneously, N '-methylene-bisacrylamide, Total Water is 15: 1 with the monomer mass ratio in the hierarchy of control.Stopped reaction after reacting 5 hours under 60 ℃, it is by high-speed stirring precipitation to be smashed behind 18: 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 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 835 gram/grams, inhales the physiological saline multiplying power and can reach 122 gram/grams, and the resin suction can be near saturated about 27 minutes.
Embodiment 6:
The reaction process of present embodiment is with example 5, but adopts in the potassium hydroxide and Acrylic Acid Monomer.The product for preparing under this condition is inhaled the distilled water multiplying power can reach 812 gram/grams, inhales the physiological saline multiplying power and can reach 115 gram/grams, and the resin suction can be near saturated about 31 minutes.
Embodiment 7:
The reaction process of present embodiment is with example 5, but omits the step of soaking with the ethanol/water mixing solutions.It is 760 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 96 gram/grams, and the resin suction can be near saturated about 34 minutes.
Claims (5)
1, the preparation method of carboxymethyl chitosan modified high water absorption resin.After being characterized in cm-chitosan dissolved in distilled water, at Diisopropyl azodicarboxylate or H
2O
2/ NH
3H
2Under the initiation of O initiator, make mixture graft copolymerization on the molecular chain of cm-chitosan of acrylate and N-vinyl pyrrolidone, and adding linking agent N, N '-methylene-bisacrylamide carries out crosslinked, 40～100 ℃ the reaction 3～10 hours after stopped reaction, use the ethanol sedimentation product, and the product process of post precipitation is washed purifying final vacuum drying, obtain super absorbent resin.
2, the H that passes through as claimed in claim 1
2O
2/ NH
3H
2The preparation method of the carboxymethyl chitosan modified high water absorption resin that the O initiator causes, the proportioning that is characterized in initiator are 30% H of 1/3 volume
2O
2NH with 2/3 volume
3H
2O.
3, the preparation method of carboxymethyl chitosan modified high water absorption resin as claimed in claim 1, being reflected in 60～100 ℃ of scopes of being characterized in that Diisopropyl azodicarboxylate causes carried out, and adopts H
2O
2/ NH
3H
2Being reflected in 40～80 ℃ of scopes that O causes carried out, and adopts nitrogen that system is protected in the reaction process.
4, the preparation method of carboxymethyl chitosan modified high water absorption resin as claimed in claim 1, the washing purification step that is characterized in precipitated product is by high-speed stirring the product of post precipitation to be smashed and repetitive scrubbing, soaks with the ethanol/water mixing solutions to be further purified again.
5, the preparation method of carboxymethyl chitosan modified high water absorption resin as claimed in claim 1 is characterized in that this polyreaction carries out in the polymerization reactor of stainless steel or enamel lining.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410080502 CN1286870C (en) | 2004-09-30 | 2004-09-30 | Process for preparing novel carboxymethl chitosan modified high water absorptive resin |
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|---|---|---|---|
| CN 200410080502 CN1286870C (en) | 2004-09-30 | 2004-09-30 | Process for preparing novel carboxymethl chitosan modified high water absorptive resin |
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| CN1616507A CN1616507A (en) | 2005-05-18 |
| CN1286870C true CN1286870C (en) | 2006-11-29 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977269B (en) * | 2012-11-12 | 2014-10-29 | 中山大学 | Chitosan acrylate graft latex and cotton fiber processing solution containing chitosan acrylate graft latex |
| CN103027925B (en) * | 2013-01-09 | 2014-06-04 | 中国人民解放军第二军医大学 | Polymer with hemostatic and bactericidal activity |
| 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 |
| 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 |
| CN114106367B (en) * | 2021-12-27 | 2023-10-20 | 浙江工业大学 | Biomass full-degradation high-antibacterial high-hydroscopicity resin and preparation method thereof |
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