CN104558442A - Method for synthesizing chitosan cross-linked polymaleic anhydride super absorbent resin - Google Patents
Method for synthesizing chitosan cross-linked polymaleic anhydride super absorbent resin Download PDFInfo
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- CN104558442A CN104558442A CN201410818719.6A CN201410818719A CN104558442A CN 104558442 A CN104558442 A CN 104558442A CN 201410818719 A CN201410818719 A CN 201410818719A CN 104558442 A CN104558442 A CN 104558442A
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Abstract
The invention discloses a method for synthesizing chitosan cross-linked polymaleic anhydride super absorbent resin. The method is as follows: biodegradable N-maleoyl chitosan is used as a cross-linking agent, maleic anhydride (MA) and acrylic acid (AA) are used as raw materials, and ammonium persulfate and sodium bisulfite are used as initiating agents; an aqueous solution free radical polymerization reaction is performed to synthesize the biodegradable super absorbent resin; an orthogonal experiment method is used to optimize the synthesis conditions to obtain optimum synthesis conditions. The chitosan cross-linked polymaleic anhydride super absorbent resin prepared using the method provided by the invention is good in water absorption, swelling dynamic performance, water retention capability under natural conditions, repeated water absorption, pH sensitivity and biodegradability.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of synthetic method of chitosan crosslinked polymaleic anhydride High hydrophilous resin.
Background technology
Super absorbent resin (SAP) is that a kind of coming across has excellent water-absorbent and water-retentivity the sixties in 20th century and the new functional macromolecule material with micro-cross-linked three D network structure.Owing to containing a large amount of strongly hydrophilic groups in its molecule (as hydroxyl, carboxyl etc.), and there is the molecular expansion performance of polymer electrolyte, simultaneously, due to micro-cross-linked three D network structure of its uniqueness, the further expansion of molecule can be hindered, make that resin is only swelling in water not to be dissolved, it forms gelatinous material after absorbing the water being equivalent to own wt hundreds of times or thousands of times, and apply the moisture that certain pressure absorbs to it and also can not spill, jello after water suction can also be repeated again its water absorbing properties after drying, thus in industry, agricultural gardening, physiological hygiene, medicine food, civil engineering work, there is important application prospect in each field such as daily-use chemical industry.
High hydrophilous resin can be divided into cellulose family, starch based and synthesizing super absorbent resin according to synthesis material difference.
At present, have a large amount of report to the research of starch and cellulose family super absorbent resin, the advantage of this kind of High hydrophilous resin is cheap, and shortcoming is that soaking effect is bad, product easily goes mouldy, and is therefore very restricted in application aspect.Adopt hydrophilic vinyl monomer (as vinylformic acid, polyvinyl alcohol etc.) or polymers manufacturing synthesis class High hydrophilous resin, wherein, acrylic acid or the like High hydrophilous resin is modal synthesizing super absorbent resin, its raw material sources are extensive, cheap, synthesis technique is simple, and the soaking effect of product is better.
But, along with improving constantly of standard of living, the performance requriements of people to High hydrophilous resin improves constantly, and the performance of common High hydrophilous resin can not meet the requirement of people, this just needs the more high performance High hydrophilous resin of people's design and synthesis, makes it use under particular circumstances.Apparatus has nontoxic, biodegradable, to be easy to carry out chemical modification natural macromolecular material such as starch, chitosan and Mierocrystalline cellulose to be that the focus that super absorbent resin is current research is prepared in raw material and hydrophilic vinyl monomer (as vinylformic acid, polyvinyl alcohol, acrylamide etc.) graft copolymerization.Chitosan has the excellent properties such as good germ resistance, degradability and biocompatibility, in physiological hygiene material articles for use, all has broad application prospects in super absorbent resin.
Summary of the invention
in order to overcome the above problems, the invention provides a kind of synthetic method of chitosan crosslinked polymaleic anhydride High hydrophilous resin.
A synthetic method for chitosan crosslinked polymaleic anhydride High hydrophilous resin, said method comprising the steps of:
(1) chitosan of 10-100 part is got in single port flask, add 50-200 part deionized water, 1-5 part acetic acid, after stirring makes chitosan dissolve completely, dropwise add the acetone soln of 1-100 part maleic anhydride, under room temperature, continue stirring reaction 5 ~ 10 h, linking agent N-Nmaleoyl chitosan is separated out with acetone, at 40 DEG C, be fully dried to constant weight with vacuum drying oven, obtain linking agent N-Nmaleoyl chitosan;
(2) take the above-mentioned N-Nmaleoyl chitosan of 1-5 part in beaker, add deionized water, be stirred to after linking agent dissolves completely, in beaker, add the vinylformic acid of 2000-10000 part, mix, with in sodium hydroxide solution and part acrylic acid;
(3) then add maleic anhydride 100-500 part that massfraction is 20%, continue to stir and heat to make the temperature of system rise to 50 DEG C, maleic anhydride is dissolved completely, then adds ammonium persulphate, sodium bisulfite composite initiator;
(4) by after reaction solution strong stirring 30 ~ 40s, stop stirring, and under the condition of 60 DEG C, be incubated 4 h complete polyreaction;
(5) by excessive distilled water immersion 48 h of the water-absorbing resin of gained, make it fully swelling, to remove unreacted monomer and lyotrope;
(6) water-absorbing resin of gained is put into refrigerator and cooled to freeze, proceed in freeze drier after solidification completely, lyophilize 24 h, obtained dry chitosan crosslinked polymaleic anhydride High hydrophilous resin.
Further, in the ammonium persulphate added in step (3), sodium bisulfite composite initiator, the mol ratio of ammonium persulphate and sodium bisulfite is 1-10:5-20.
Further, the ammonium persulphate added in step (3), the parts by weight of sodium bisulfite composite initiator are 10-80 part.
The beneficial effect that the present invention reaches is: utilize orthogonal experiment to be optimized synthesis condition and obtain optimum synthesis condition, and the chitosan crosslinked polymaleic anhydride High hydrophilous resin that described method obtains has water retention property under good water-intake rate, Swelling Dynamics performance, natural condition, repeats water absorbing properties, pH susceptibility and biological degradability.
Embodiment
Embodiment 1
A synthetic method for chitosan crosslinked polymaleic anhydride High hydrophilous resin, said method comprising the steps of:
(1) chitosan of 10 parts is got in single port flask, add 50 parts of deionized waters, 1 part of acetic acid, after stirring makes chitosan dissolve completely, dropwise add the acetone soln of 10 parts of maleic anhydrides, under room temperature, continue stirring reaction 5 h, linking agent N-Nmaleoyl chitosan is separated out with acetone, at 40 DEG C, be fully dried to constant weight with vacuum drying oven, obtain linking agent N-Nmaleoyl chitosan;
(2) take 1 part of above-mentioned N-Nmaleoyl chitosan in beaker, add deionized water, be stirred to after linking agent dissolves completely, in beaker, add the vinylformic acid of 2000 parts, mix, with in sodium hydroxide solution and part acrylic acid;
(3) maleic anhydride 100 parts that massfraction is 20% is then added, continue to stir and heat to make the temperature of system rise to 50 DEG C, maleic anhydride is dissolved completely, add ammonium persulphate, sodium bisulfite composite initiator again, wherein in ammonium persulphate, sodium bisulfite composite initiator, the mol ratio of ammonium persulphate and sodium bisulfite is 1:5, and the parts by weight of the ammonium persulphate added, sodium bisulfite composite initiator are 10 parts;
(4) by after reaction solution strong stirring 30s, stop stirring, and under the condition of 60 DEG C, be incubated 4 h complete polyreaction;
(5) by excessive distilled water immersion 48 h of the water-absorbing resin of gained, make it fully swelling, to remove unreacted monomer and lyotrope;
(6) water-absorbing resin of gained is put into refrigerator and cooled to freeze, proceed in freeze drier after solidification completely, lyophilize 24 h, obtained dry chitosan crosslinked polymaleic anhydride High hydrophilous resin.
Embodiment 2
A synthetic method for chitosan crosslinked polymaleic anhydride High hydrophilous resin, said method comprising the steps of:
(1) chitosan of 100 parts is got in single port flask, add 200 parts of deionized waters, 5 parts of acetic acid, after stirring makes chitosan dissolve completely, dropwise add the acetone soln of 100 parts of maleic anhydrides, under room temperature, continue stirring reaction 10 h, linking agent N-Nmaleoyl chitosan is separated out with acetone, at 40 DEG C, be fully dried to constant weight with vacuum drying oven, obtain linking agent N-Nmaleoyl chitosan;
(2) take 5 parts of above-mentioned N-Nmaleoyl chitosans in beaker, add deionized water, be stirred to after linking agent dissolves completely, in beaker, add the vinylformic acid of 10000 parts, mix, with in sodium hydroxide solution and part acrylic acid;
(3) maleic anhydride 100 parts that massfraction is 20% is then added, continue to stir and heat to make the temperature of system rise to 50 DEG C, maleic anhydride is dissolved completely, add ammonium persulphate, sodium bisulfite composite initiator again, wherein in ammonium persulphate, sodium bisulfite composite initiator, the mol ratio of ammonium persulphate and sodium bisulfite is 5:20, and the parts by weight of the ammonium persulphate added, sodium bisulfite composite initiator are 80 parts;
(4) by after reaction solution strong stirring 40s, stop stirring, and under the condition of 60 DEG C, be incubated 4 h complete polyreaction;
(5) by excessive distilled water immersion 48 h of the water-absorbing resin of gained, make it fully swelling, to remove unreacted monomer and lyotrope;
(6) water-absorbing resin of gained is put into refrigerator and cooled to freeze, proceed in freeze drier after solidification completely, lyophilize 24 h, obtained dry chitosan crosslinked polymaleic anhydride High hydrophilous resin.
Embodiment 3
A synthetic method for chitosan crosslinked polymaleic anhydride High hydrophilous resin, said method comprising the steps of:
(1) chitosan of 80 parts is got in single port flask, add 150 parts of deionized waters, 3 parts of acetic acid, after stirring makes chitosan dissolve completely, dropwise add the acetone soln of 80 parts of maleic anhydrides, under room temperature, continue stirring reaction 8h, linking agent N-Nmaleoyl chitosan is separated out with acetone, at 40 DEG C, be fully dried to constant weight with vacuum drying oven, obtain linking agent N-Nmaleoyl chitosan;
(2) take 3 parts of above-mentioned N-Nmaleoyl chitosans in beaker, add deionized water, be stirred to after linking agent dissolves completely, in beaker, add the vinylformic acid of 8000 parts, mix, with in sodium hydroxide solution and part acrylic acid;
(3) maleic anhydride 300 parts that massfraction is 20% is then added, continue to stir and heat to make the temperature of system rise to 50 DEG C, maleic anhydride is dissolved completely, add ammonium persulphate, sodium bisulfite composite initiator again, wherein in ammonium persulphate, sodium bisulfite composite initiator, the mol ratio of ammonium persulphate and sodium bisulfite is 3:16, and the parts by weight of the ammonium persulphate added, sodium bisulfite composite initiator are 70 parts;
(4) by after reaction solution strong stirring 40s, stop stirring, and under the condition of 60 DEG C, be incubated 4 h complete polyreaction;
(5) by excessive distilled water immersion 48 h of the water-absorbing resin of gained, make it fully swelling, to remove unreacted monomer and lyotrope;
(6) water-absorbing resin of gained is put into refrigerator and cooled to freeze, proceed in freeze drier after solidification completely, lyophilize 24 h, obtained dry chitosan crosslinked polymaleic anhydride High hydrophilous resin.
Claims (3)
1. a synthetic method for chitosan crosslinked polymaleic anhydride High hydrophilous resin, is characterized in that, said method comprising the steps of:
(1) chitosan of 10-100 part is got in single port flask, add 50-200 part deionized water, 1-5 part acetic acid, after stirring makes chitosan dissolve completely, dropwise add the acetone soln of 1-100 part maleic anhydride, under room temperature, continue stirring reaction 5 ~ 10 h, linking agent N-Nmaleoyl chitosan is separated out with acetone, at 40 DEG C, be fully dried to constant weight with vacuum drying oven, obtain linking agent N-Nmaleoyl chitosan;
(2) take the above-mentioned N-Nmaleoyl chitosan of 1-5 part in beaker, add deionized water, be stirred to after linking agent dissolves completely, in beaker, add the vinylformic acid of 2000-10000 part, mix, with in sodium hydroxide solution and part acrylic acid;
(3) then add maleic anhydride 100-500 part that massfraction is 20%, continue to stir and heat to make the temperature of system rise to 50 DEG C, maleic anhydride is dissolved completely, then adds ammonium persulphate, sodium bisulfite composite initiator;
(4) by after reaction solution strong stirring 30 ~ 40s, stop stirring, and under the condition of 60 DEG C, be incubated 4 h complete polyreaction;
(5) by excessive distilled water immersion 48 h of the water-absorbing resin of gained, make it fully swelling, to remove unreacted monomer and lyotrope;
(6) water-absorbing resin of gained is put into refrigerator and cooled to freeze, proceed in freeze drier after solidification completely, lyophilize 24 h, obtained dry chitosan crosslinked polymaleic anhydride High hydrophilous resin.
2. the synthetic method of a kind of chitosan crosslinked polymaleic anhydride High hydrophilous resin according to claim 1, it is characterized in that, in the ammonium persulphate added in step (3), sodium bisulfite composite initiator, the mol ratio of ammonium persulphate and sodium bisulfite is 1-10:5-20.
3. the synthetic method of a kind of chitosan crosslinked polymaleic anhydride High hydrophilous resin according to claim 1, is characterized in that, the ammonium persulphate added in step (3), the parts by weight of sodium bisulfite composite initiator are 10-80 part.
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| CN105949370A (en) * | 2016-07-01 | 2016-09-21 | 青岛科技大学 | High-strength rapid water absorption resin and preparation method thereof |
| CN106551772A (en) * | 2016-11-24 | 2017-04-05 | 东台市苏中电工机械有限公司 | A kind of railway locomotive rain-proof cloth |
| CN113402631A (en) * | 2021-06-18 | 2021-09-17 | 青岛市农业科学研究院 | Preparation method and application of alkaline seed coating agent film-forming agent |
| US11136490B2 (en) | 2017-11-10 | 2021-10-05 | China University Of Petroleum (East China) | PH sensitive water-absorbent resin suitable for oil well cement slurry and application thereof |
| CN113663653A (en) * | 2021-07-02 | 2021-11-19 | 浙江工业大学 | Copolymer based on rotten pine bark and preparation method and application thereof |
| CN113712039A (en) * | 2021-10-14 | 2021-11-30 | 长沙尚洁环保科技有限公司 | Chlorine dioxide slow-release material and preparation method thereof |
| WO2022065843A1 (en) * | 2020-09-25 | 2022-03-31 | 주식회사 엘지화학 | Biodegradable super absorbent polymer and preparation method therefor |
| CN114711101A (en) * | 2022-04-08 | 2022-07-08 | 凯盛浩丰农业有限公司 | Application of water-retaining agent for vegetable transplantation in vegetable transplantation |
| CN114920606A (en) * | 2022-04-27 | 2022-08-19 | 兰州石化职业技术学院 | Preparation method of adsorption type degradable soil moisture preservation slow release fertilizer based on modified wheat straw |
| WO2024005426A1 (en) * | 2022-06-28 | 2024-01-04 | 주식회사 엘지화학 | Biodegradable super absorbent polymer and preparation method thereof |
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- 2014-12-25 CN CN201410818719.6A patent/CN104558442A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105949370A (en) * | 2016-07-01 | 2016-09-21 | 青岛科技大学 | High-strength rapid water absorption resin and preparation method thereof |
| CN106551772A (en) * | 2016-11-24 | 2017-04-05 | 东台市苏中电工机械有限公司 | A kind of railway locomotive rain-proof cloth |
| US11136490B2 (en) | 2017-11-10 | 2021-10-05 | China University Of Petroleum (East China) | PH sensitive water-absorbent resin suitable for oil well cement slurry and application thereof |
| WO2022065843A1 (en) * | 2020-09-25 | 2022-03-31 | 주식회사 엘지화학 | Biodegradable super absorbent polymer and preparation method therefor |
| CN114901714A (en) * | 2020-09-25 | 2022-08-12 | 株式会社Lg化学 | Biodegradable superabsorbent polymer and method for producing the same |
| CN113402631A (en) * | 2021-06-18 | 2021-09-17 | 青岛市农业科学研究院 | Preparation method and application of alkaline seed coating agent film-forming agent |
| CN113402631B (en) * | 2021-06-18 | 2023-02-28 | 青岛市农业科学研究院 | Preparation method and application of alkaline seed coating agent film-forming agent |
| CN113663653A (en) * | 2021-07-02 | 2021-11-19 | 浙江工业大学 | Copolymer based on rotten pine bark and preparation method and application thereof |
| CN113663653B (en) * | 2021-07-02 | 2024-02-23 | 浙江工业大学 | Copolymer based on decomposed pine bark and preparation method and application thereof |
| CN113712039A (en) * | 2021-10-14 | 2021-11-30 | 长沙尚洁环保科技有限公司 | Chlorine dioxide slow-release material and preparation method thereof |
| CN114711101A (en) * | 2022-04-08 | 2022-07-08 | 凯盛浩丰农业有限公司 | Application of water-retaining agent for vegetable transplantation in vegetable transplantation |
| CN114920606A (en) * | 2022-04-27 | 2022-08-19 | 兰州石化职业技术学院 | Preparation method of adsorption type degradable soil moisture preservation slow release fertilizer based on modified wheat straw |
| CN114920606B (en) * | 2022-04-27 | 2024-01-12 | 兰州石化职业技术学院 | Preparation method of adsorption type degradable soil moisture conservation slow release fertilizer based on modified wheat straw |
| WO2024005426A1 (en) * | 2022-06-28 | 2024-01-04 | 주식회사 엘지화학 | Biodegradable super absorbent polymer and preparation method thereof |
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