CN1616505A - Process for preparing chitosan base macroporous high water absorptive resin - Google Patents
Process for preparing chitosan base macroporous high water absorptive resin Download PDFInfo
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- CN1616505A CN1616505A CN 200410080300 CN200410080300A CN1616505A CN 1616505 A CN1616505 A CN 1616505A CN 200410080300 CN200410080300 CN 200410080300 CN 200410080300 A CN200410080300 A CN 200410080300A CN 1616505 A CN1616505 A CN 1616505A
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- water absorptive
- absorptive resin
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- 238000004519 manufacturing process Methods 0.000 title description 4
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- 239000000178 monomer Substances 0.000 claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
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- 238000005406 washing Methods 0.000 claims description 4
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- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
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- 210000003298 dental enamel Anatomy 0.000 claims 1
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- 238000010521 absorption reaction Methods 0.000 abstract description 13
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- 239000007791 liquid phase Substances 0.000 abstract description 3
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- DVLFYONBTKHTER-UHFFFAOYSA-N 3-(N-morpholino)propanesulfonic acid Chemical compound OS(=O)(=O)CCCN1CCOCC1 DVLFYONBTKHTER-UHFFFAOYSA-N 0.000 description 2
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- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to the preparation process of chitosan base macroporous high water absorption resin. After chitosan is dissolved in dilute acetic acid solution, acrylic acid is made to graft on the molecular chain of chitosan under the initiation of ammonium or potassium persulfate and the product is cross-linked with cross-linking agent, so as to produce high water absorption chitosan grafted acrylic resin with distilled water absorption of 560-1210 g/g and physiological saline absorption of 76-125 g/g. The prepared resin is further modified via solvent deposition process to form macroporous structure to raise the water absorbing rate greatly. High efficiency liquid phase chromatographic test shows that the resin has greatly reduced acrylic acid monomer residue.
Description
Affiliated technical field:
The present invention relates to a kind of preparation method of chitosan-based macroporous high water absorptive resin.Be exactly by vinylformic acid crosslinked preparation super absorbent resin after graft copolymerization on the molecular chain of chitosan specifically, adopt solvent precipitation that it is carried out modification and make resin with coarse pored structure.The invention belongs to the synthetic field of macromolecular material.
Technical background:
Super absorbent resin is the class new functional macromolecule material that development in recent years is got up, it is a kind of strong hydrophilic radical that contains, and the material that has appropriately crosslinked tridimensional network on microcosmic, it can absorb water, salt solution and the physiological liquid of own wt hundreds of even thousands of times.
U.S. UCC company began super absorbent resin is applied to agriculture aspect in 1973, and expanded to aspects such as agricultural gardening and soil water-retaining, cultivating seedlings and conveying and breeding.After this countries such as Japan and France have also begun the applied research to this class material in succession.Because the excellent properties of super absorbent resin has obtained widespread use in all respects such as production and lives: as playing soil water-retaining aspect the agricultural gardening, soilless culture promotes seed germination and plant-growth, administers effects such as desert; At medicine and hygiene fields as various organization materials, wound dressings, artificial organs, slow releasing pharmaceutical carrier and physiological hygiene articles for use etc.; Be widely used in petrochemical complex, mine industry, metallurgical industry, environment-protecting industrial, household chemicals industry and the foodstuffs industry at industrial circle; At building field as sealing, water proof, leakproofing material etc.; In addition, super absorbent resin also can be used as extinguish material, fireproof coating material, artificial intelligence hydrogel, water-absorbent dress material etc.
Adopt nontoxicly, contain the method that to carry out crosslinked preparation super absorbent resin 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 be the important synthesizing high-hydroscopicity resin of a class on the abundant and molecular chain of raw material sources.The Fanta of USDA north institute in 1966 etc. causes W-Gum and acrylonitrile graft copolymer with ceric ammonium nitrate, by making super absorbent resin after the suitable hydrolysis.In recent years, starch and Super Absorbent Resin from Cellulose have been had a large amount of reports, as 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 (CN1,172,124; 1,075,488; 1,058,972; GK 85,100, and 849; 85,104,864; Introduction 85,103,771) etc. is all arranged.This class super absorbent resin is with low cost, and 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 derivatives, 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).With the crosslinked super absorbent resin that makes that carries out after chitosan and the monomer-grafted polymerization of unsaturated ethylene thiazolinyl to a certain degree.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 at present to being that the research report of feedstock production super absorbent resin is few with the chitosan.
Super absorbent resin as medical material and physiological hygiene material are used must possess two primary conditions: high rate of water absorption and less harmful level of residual monomers.By an amount of pore-creating agent of adding in building-up process resin is made cavernous structure and can improve its rate of water absorption, but the adding of pore-creating agent can improve harmful monomeric residual quantity in the resin again.Solvent precipitation is a kind of novel method of the preparation macroporous high water absorptive resin that we invent, it can significantly improve the rate of water absorption of resin and reduce wherein harmful monomeric residual quantity by simple process, have important and practical meanings, adopt this method that super absorbent resin is carried out modification at present and yet there are no report.
The objective of the invention is to prepare a kind of novel super absorbent resin that medical material and physiological hygiene material are used that is suitable for.Prepare super absorbent resin by natural macromolecular material chitosan and acrylic graft copolymer, and adopt solvent precipitation that resin is carried out modification to make resin with coarse pored structure, with the rate of water absorption of raising resin, and the Acrylic Acid Monomer residual quantity in the reduction resin.
Summary of the invention:
The present invention realizes by following two-stage process:
1, the preparation of chitosan graft polyacrylic acid high water absorptive resin.Its method is: after the chitosan powder is fully dissolved in 100～150 milliliters 2wt% dilute acetic acid aqueous solution; the persulfate initiator that under nitrogen protection, adds monomer 1.5～4wt%; react after 30 minutes add with the chitosan mass ratio be 4～15: 1 Acrylic Acid Monomer and the N of monomer 0～0.5wt%; N '-methylene-bisacrylamide linking agent; stopped reaction after reacting 4～10 hours under 50～80 ℃; reaction system is used the ethanol sedimentation product with in 20% the aqueous sodium hydroxide solution and back; by 2500 rev/mins high-speed stirring precipitation is smashed the back and under this stirring velocity, use washing with alcohol repeatedly; filter cake is dispersed in volume ratio behind the suction filtration again and is to soak in 4: 1 the ethanol/water mixed solvent and be further purified in 24 hours, suction filtration also obtains the chitosan graft polyacrylic acid high water absorptive resin with pulverizing after the filter cake vacuum-drying.This resin is inhaled distilled water multiplying power can reach 560～1210 gram/grams, inhales the physiological saline multiplying power and can reach 76～125 gram/grams, and approximately needing to absorb water in 25～40 minutes can be approaching saturated, and the Acrylic Acid Monomer residual quantity is less than 9.20 * 10 in the resin
-3%.
2, adopt solvent precipitation that super absorbent resin is carried out modification.Its method is: with chitosan graft polyacrylic acid high water absorptive resin powder add with its mass ratio be in 50～150: 1 the deionized water, in 25 ℃ water bath with thermostatic control vibrator, resin swelling added after 10～30 hours with the super absorbent resin mass ratio be that 100～300: 1 precipitation agent comes out resin precipitated, with product suction filtration final vacuum drying, be modified product.Modified product is inhaled the distilled water multiplying power in 520～1090 gram/gram scopes, inhales the physiological saline multiplying power in 72～110 gram/gram scopes, and approximately needing to absorb water in 8～15 minutes can be approaching saturated, and the Acrylic Acid Monomer residual quantity is less than 3.82 * 10 in the resin
-3%.
The measuring method of saturated water absorbent rate 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 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 ℃) 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.
Accurately take by weighing the super absorbent resin of 0.1000 gram oven dry, adds 10 milliliters 0.9% physiological saline, vibrated 1 hour on constant temperature oscillator, make the abundant swelling of resin, use filter paper filtering, filtrate is to be measured.Harmful Acrylic Acid Monomer determination of residual amount method in the resin: the 1100 series of high efficiency chromatographic analyzer of liquid phase systems that adopt U.S. Agilent company.Chromatographic column adopting Diamonsil
TM(diamond)-C18 (5 μ, 250 * 4.6mm), be moving phase with MOPS (3-(N-morpholino) propanesulfonic acid) ion pair reagent (PH=5.80) of 0.02 mol, flow velocity 0.8 ml/min detects wavelength 210 nanometers, hand sampling, sample size 20 microlitres.
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 polymerization 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; Adopt simple solvent precipitation that super absorbent resin is carried out modification, modification after product rate of water absorption improves greatly, and the vinylformic acid residual quantity significantly reduces.
Description of drawings:
Accompanying drawing one is the electromicroscopic photograph of resin before and after the modification, and as seen from the figure, resin surface is the structure of small pore-like before the modification, and tangible change had taken place its structure after resin carried out modification, had formed loose macropore.
Accompanying drawing two is the rate of water absorption curve of resin before and after the modification, and as seen from the figure, the rate of water absorption of resin significantly improves after the modification.
Accompanying drawing three is the monomeric high-efficient liquid phase chromatogram of residual acrylic acid in the resin before and after the modification, as seen from the figure, after the modification in the resin Acrylic Acid Monomer residual quantity significantly reduce, and be significantly less than by soxhlet extraction and handle residual acrylic acid content in the resin of back.
Embodiment:
Below in conjunction with embodiment patent of the present invention is elaborated:
Embodiment 1:
With the chitosan powder in 120 milliliters 2% dilute acetic acid aqueous solution fully after the dissolving; under nitrogen protection, add monomer 3.3wt% ammonium persulfate initiator and 65 ℃ down reaction add after 30 minutes with the chitosan mass ratio be 10: 1 Acrylic Acid Monomer and the N of monomer 0.16wt%; N '-methylene-bisacrylamide; stopped reaction after reacting 5.5 hours under 65 ℃; reaction system is used the ethanol sedimentation product with in 20% the aqueous sodium hydroxide solution and back; by 2500 rev/mins high-speed stirring precipitation is smashed the back and under this stirring velocity, use washing with alcohol repeatedly; suction filtration and filter cake is dispersed in volume ratio is to soak in 4: 1 the ethanol/water mixed solvent to be further purified in 24 hours, behind the suction filtration with filter cake vacuum-drying and pulverize and obtain the white powder product.This product is inhaled distilled water multiplying power can reach 1180 gram/grams, inhales the physiological saline multiplying power and can reach 120 gram/grams, and need about 32 minutes absorbing water can be approaching saturated, records that the vinylformic acid residual quantity is 6.78 * 10 in the resin
-3%, the mean pore size that adopts scanning electron microscope to record resin is 9.3 ± 3.0 microns.
Embodiment 2:
With the chitosan powder in 120 milliliters 2% dilute acetic acid aqueous solution fully after the dissolving; under nitrogen protection, add monomer 2.5wt% Potassium Persulphate and 60 ℃ down reaction add after 30 minutes with the chitosan mass ratio be 12: 1 Acrylic Acid Monomer and the N of monomer 0.14wt%; N '-methylene-bisacrylamide; stopped reaction after reacting 6 hours under 60 ℃; reaction system is used the ethanol sedimentation product with in 20% the aqueous sodium hydroxide solution and back; by 2500 rev/mins high-speed stirring precipitation is smashed the back and under this stirring velocity, use washing with alcohol repeatedly; suction filtration and filter cake is dispersed in volume ratio is to soak in 4: 1 the ethanol/water mixed solvent to be further purified in 24 hours, behind the suction filtration with filter cake vacuum-drying and pulverize and obtain the white powder product.This product is inhaled distilled water multiplying power can reach 1065 gram/grams, inhales the physiological saline multiplying power and can reach 108 gram/grams, and need about 27 minutes absorbing water can be approaching saturated, records that the vinylformic acid residual quantity is 8.24 * 10 in the resin
-3%, the mean pore size that adopts scanning electron microscope to record resin is 9.5 ± 4.1 microns.
Embodiment 3:
The reaction process of present embodiment is with example 1, but omits the step of filter cake being soaked with ethanol/water mixed solvent 24 hours.It is 930 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 102 gram/grams, records that the vinylformic acid residual quantity is 8.33 * 10 in the resin
-3%.
Embodiment 4:
The reaction process of present embodiment is with example 2, but omits the step of filter cake being soaked with ethanol/water mixed solvent 24 hours.It is 825 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 97 gram/grams, records that the vinylformic acid residual quantity is 8.95 * 10 in the resin
-3%.
Embodiment 5:
This example is to adopt solvent precipitation to carry out modification to the super absorbent resin that embodiment 1 makes, take by weighing 1.00 gram super absorbent resin powder, add 100 ml deionized water, in 25 ℃ water bath with thermostatic control vibrator resin swelling being added 180 milliliters of precipitation agents after 24 hours comes out resin precipitated, with product suction filtration final vacuum drying, promptly obtain modified product.It is 1050 gram/grams that this product is inhaled distilled water multiplying power, and inhaling the physiological saline multiplying power be to 106 gram/grams, and need about 10 minutes absorbing water can be approaching saturated, records that the vinylformic acid residual quantity is 1.83 * 10 in the resin
-3%, the mean pore size that adopts scanning electron microscope to record resin is 36.2 ± 11.6 microns.
Embodiment 6:
This example is to adopt solvent precipitation to carry out modification to the super absorbent resin that embodiment 2 makes, take by weighing 1.00 gram super absorbent resin powder, add 120 ml deionized water, in 25 ℃ water bath with thermostatic control vibrator resin swelling being added 200 milliliters of precipitation agents after 24 hours comes out resin precipitated, with product suction filtration final vacuum drying, promptly obtain modified product.It is 1022 gram/grams that this product is inhaled distilled water multiplying power, and inhaling the physiological saline multiplying power be to 102 gram/grams, and need about 9 minutes absorbing water can be approaching saturated, records that the vinylformic acid residual quantity is 2.35 * 10 in the resin
-3%, the mean pore size that adopts scanning electron microscope to record resin is 47.8 ± 17.1 microns.
Claims (8)
1, a kind of preparation method of chitosan-based macroporous high water absorptive resin.With chitosan in 2% dilute acetic acid aqueous solution fully after the dissolving; under nitrogen protection, add persulfate initiator; react and add Acrylic Acid Monomer and linking agent after 30 minutes; stopped reaction after reacting 4～10 hours under 50～80 ℃; with in the reaction system and back ethanol sedimentation product; and with product by washing purifying final vacuum drying, at last the resin that obtains is carried out modification, obtain final product.
2, the preparation method of a kind of chitosan-based macroporous high water absorptive resin as claimed in claim 1 is characterized in adding N in polymerization system, N '-methylene-bisacrylamide is a linking agent.
3, the preparation method of a kind of chitosan-based macroporous high water absorptive resin as claimed in claim 1 is characterized in adding ammonium persulphate in polymerization system or Potassium Persulphate is an initiator.
4, the preparation method of a kind of chitosan-based macroporous high water absorptive resin as claimed in claim 1 is characterized in before the reaction chitosan fully being dissolved by dilute acetic acid solution.
5, the preparation method of a kind of chitosan-based macroporous high water absorptive resin as claimed in claim 1, be characterized in after reaction finishes product being smashed precipitation and repetitive scrubbing by high-speed stirring after with ethanol sedimentation, again filter cake be further purified with the immersion of ethanol/water mixing solutions behind the suction filtration.
6, the preparation method of a kind of chitosan-based macroporous high water absorptive resin as claimed in claim 1 is characterized in adopting solvent precipitation that prepared super absorbent resin is carried out modification.
7, to the measuring method of Acrylic Acid Monomer residual quantity in a kind of chitosan-based macroporous high water absorptive resin as claimed in claim 1, being characterized in adopting high performance liquid chromatography, is moving phase with the ion pair reagent.
8, the preparation method of a kind of chitosan-based macroporous high water absorptive resin as claimed in claim 1 is characterized in that this polyreaction can carry out in the polymerization reactor of general stainless steel or enamel lining, reaction temperature and, be easy to control, process is simple.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100803001A CN1300200C (en) | 2004-09-30 | 2004-09-30 | Process for preparing chitosan base macroporous high water absorptive resin |
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|---|---|---|---|
| CNB2004100803001A CN1300200C (en) | 2004-09-30 | 2004-09-30 | Process for preparing chitosan base macroporous high water absorptive resin |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168937B (en) * | 2007-11-28 | 2010-05-19 | 华南理工大学 | Guar gum-acrylic acid water absorption resin coating moisture absorbing paper and preparation method thereof |
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| CN101641153B (en) * | 2007-04-05 | 2012-08-15 | 株式会社日本触媒 | Granular water absorbent comprising water absorbing resin as the main component |
| CN103071460A (en) * | 2013-01-09 | 2013-05-01 | 中科院广州化学有限公司 | Chitosan crosslinking adsorbent as well as preparation method and application thereof |
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| CN108219070A (en) * | 2017-12-29 | 2018-06-29 | 中国科学院海洋研究所 | A kind of novel salt tolerant super absorbent resin and preparation method thereof |
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1142415C (en) * | 2001-04-13 | 2004-03-17 | 黄元伟 | Improved thermometer and its making method |
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|---|---|---|---|---|
| CN101641153B (en) * | 2007-04-05 | 2012-08-15 | 株式会社日本触媒 | Granular water absorbent comprising water absorbing resin as the main component |
| CN101168937B (en) * | 2007-11-28 | 2010-05-19 | 华南理工大学 | Guar gum-acrylic acid water absorption resin coating moisture absorbing paper and preparation method thereof |
| CN101773819A (en) * | 2010-03-04 | 2010-07-14 | 中国海洋大学 | Resin preparation process for removing residual heavy metal arsenic in laminaria seaweed extract |
| CN102229689A (en) * | 2011-05-11 | 2011-11-02 | 华侨大学 | Preparation method of absorbent resin with bacteriostasis function |
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| CN106117428A (en) * | 2016-06-25 | 2016-11-16 | 陈毅忠 | A kind of method utilizing Limax to prepare water-absorbing resin |
| CN107056986A (en) * | 2017-03-30 | 2017-08-18 | 池州学院 | A kind of chitosan-based high hydroscopic resin process for cleanly preparing |
| CN108219070A (en) * | 2017-12-29 | 2018-06-29 | 中国科学院海洋研究所 | A kind of novel salt tolerant super absorbent resin and preparation method thereof |
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| CN108925929A (en) * | 2018-06-15 | 2018-12-04 | 黄钱英 | The minimizing technology of remains of pesticide parathion-methyl in a kind of honey |
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| CN110606690A (en) * | 2019-09-23 | 2019-12-24 | 长安大学 | Enhanced concrete internal curing high water absorption microsphere material and preparation method thereof |
| CN110746541A (en) * | 2019-11-05 | 2020-02-04 | 深圳市乐闵科技有限公司 | High-salt-tolerance super absorbent resin and preparation method and application thereof |
| CN113735653A (en) * | 2021-09-09 | 2021-12-03 | 苏农（广德）生物科技有限公司 | Slow-release fertilizer capable of preventing and treating plant diseases and processing technology thereof |
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