CN1252107C - Konjaku plucosidopolyose graft copolymer, preparing process and use thereof - Google Patents
Konjaku plucosidopolyose graft copolymer, preparing process and use thereof Download PDFInfo
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- CN1252107C CN1252107C CN 02139036 CN02139036A CN1252107C CN 1252107 C CN1252107 C CN 1252107C CN 02139036 CN02139036 CN 02139036 CN 02139036 A CN02139036 A CN 02139036A CN 1252107 C CN1252107 C CN 1252107C
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- Prior art keywords
- konjac glucomannan
- konjac
- graft copolymer
- vinyl
- vinyl monomer
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Links
- 229920002752 Konjac Polymers 0.000 title claims abstract description 54
- 229920000578 graft copolymer Polymers 0.000 title abstract description 24
- 238000000034 method Methods 0.000 title description 7
- 229920002581 Glucomannan Polymers 0.000 claims abstract description 51
- 229940046240 glucomannan Drugs 0.000 claims abstract description 51
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 claims abstract description 50
- 235000010485 konjac Nutrition 0.000 claims abstract description 37
- 241001312219 Amorphophallus konjac Species 0.000 claims abstract description 31
- 235000001206 Amorphophallus rivieri Nutrition 0.000 claims abstract description 31
- 239000000252 konjac Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical group [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 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 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
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 235000013305 food Nutrition 0.000 claims description 3
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims 1
- 239000000017 hydrogel Substances 0.000 abstract description 18
- 150000004676 glycans Chemical class 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 4
- 229920001282 polysaccharide Polymers 0.000 abstract description 4
- 239000005017 polysaccharide Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- -1 functional group compound Chemical class 0.000 abstract description 2
- 239000012429 reaction media Substances 0.000 abstract description 2
- 229930182478 glucoside Natural products 0.000 abstract 1
- 150000008131 glucosides Chemical class 0.000 abstract 1
- 239000012966 redox initiator Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WQZGKKKJIJFFOK-PQMKYFCFSA-N alpha-D-mannose Chemical compound OC[C@H]1O[C@H](O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-PQMKYFCFSA-N 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 150000001720 carbohydrates Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000013268 sustained release Methods 0.000 description 3
- 239000012730 sustained-release form Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 241001278826 Amorphophallus Species 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 208000003556 Dry Eye Syndromes Diseases 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 206010021639 Incontinence Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000599 controlled substance Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 208000030533 eye disease Diseases 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 150000003214 pyranose derivatives Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000004162 soil erosion Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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- Graft Or Block Polymers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
本发明公开了一类生物可降解的魔芋葡苷聚糖接枝共聚物及其制备方法和用途。由魔芋葡苷聚糖水溶液在氧化还原引发剂引发下，与乙烯基单体接枝共聚，多乙烯基官能团化合物为交联剂或通过高温交联，合成得到魔芋葡甘聚糖接枝共聚物。由于魔芋葡苷聚糖为天然水溶性多糖，具有良好的生物相容性和生物可降解性，因而以它作主链得到的水凝胶也具有良好的生物相容性和生物可降解性。制备工艺简便，反应介质为水，生产过程不产生环境污染。魔芋葡苷聚糖来自价廉易得的农产品，本发明也为农副产品的综合利用提供了一条有效途径。在生物化学、医学、农业、日用化工等领域有多种用途。
The invention discloses a kind of biodegradable konjac glucosidan graft copolymer and its preparation method and application. Konjac glucomannan graft copolymer is synthesized by grafting copolymerization of konjac glucomannan aqueous solution with vinyl monomer under the trigger of redox initiator, using polyvinyl functional group compound as crosslinking agent or crosslinking at high temperature . Since konjac glucosidan is a natural water-soluble polysaccharide with good biocompatibility and biodegradability, the hydrogel obtained with it as the main chain also has good biocompatibility and biodegradability. The preparation process is simple and convenient, the reaction medium is water, and the production process does not produce environmental pollution. Konjac glucoside comes from cheap and easy-to-obtain agricultural products, and the invention also provides an effective way for the comprehensive utilization of agricultural and sideline products. It has many uses in biochemistry, medicine, agriculture, daily chemical industry and other fields.
Description
Technical field
The present invention relates to konjac glucomannan graft copolymer and its production and use.
Background technology
Amorphophallus aroid, its stem tuber are rich in deposit property polysaccharide konjaku glucomannan (Konjac glucomannan writes a Chinese character in simplified form and makes KGM).Rhizoma amorphophalli glucomannan is the main component of konjaku powder, accounts for the heavy 50%-60% of dry product.
As far back as the 60-80 age in last century, Japanese scholar did many researchs to the structure and the character of Rhizoma amorphophalli glucomannan, and the result shows that Rhizoma amorphophalli glucomannan is a main chain by D-seminose and D-glucose with β-1,4 pyranose glycosidic bond banded mixed polysaccharide, at the C of main chain seminose
3Exist by β-1,3 key bonded branched structure on the position, approximately on per 32 saccharide residues 3 left and right sides side chains are arranged; side chain has only the length of several residues; and have acetyl group on some saccharide residue, have one on per approximately 19 saccharide residues, combine in the mode of ester.The constitutive molar ratio of seminose and glucose is about 1.5-1.7 in the Rhizoma amorphophalli glucomannan, is generally 1.6, and different varieties is different with the molecular weight of the Rhizoma amorphophalli glucomannan in source, and the molecular weight that different measuring methods obtains is also different.
The schematic construction of Rhizoma amorphophalli glucomannan is as follows:
By following formula as can be known, the konjak portuguese gansu polyose glycan molecule contains active-OH base, can be by esterification, nitrated, etherificate, chemical modifications such as grafting prepare novel konjak portuguese gansu polyose sugar derivatives, improve the viscosity of its water-sol, stable and various performances make it have the new function that is fit for various uses, thereby enlarge its range of application; Also can be by blend, crosslinked and composite modified and other material generation chemistry or physical bond, thus good novel material obtained.
Rhizoma amorphophalli glucomannan has many good properties as a kind of natural macromolecule amylose, such as biocompatibility, and film-forming properties, biodegradable etc.Can be applicable to food, biochemistry, medicine and daily life all respects.For example konjac glucomannan can be used as hydrophilizing agent, thickening material, stablizer, emulsifying agent, suspension agent, gelifying agent etc., is widely used in foodstuffs industry.Also can be used as preservative film, chromatographic column filler, wound lapping, medical optical facility, gel rubber sustained-release material, various goods such as mould material.In addition, be to adapt to the needs of new technology application development, all kinds of researchs that Rhizoma amorphophalli glucomannan is carried out functional modification are well afoot also.
Macromolecule hydrogel is the network size of hydrophilic high mol, its swellable and keep large quantity of moisture and don't dissolving in water.Hydrogel has caused scientific worker's common concern in many purposes in fields such as biological chemistry, medical science, agricultural, daily-use chemical industry.Most of up to now hydrogels are nonbiodegradable, and this has limited their application aspect medicine and environmental protection.Preparation biodegradable hydrogel has several different methods, and wherein to prepare hydrogel by grafting, crosslinking reaction be a kind of simple and effective method to the natural hydrophilic polymkeric substance, and resulting polymers has excellent biological compatibility and biological degradability.At present research is more starch, amylopectin, dextran, chitosan etc.
Summary of the invention
The purpose of this invention is to provide biodegradable konjac glucomannan graft copolymer of a class and its production and use.
The present invention adopts water-soluble konjac glucomannan and graft copolymerization of vinyl monomer, crosslinked method to prepare the biodegradable hydrogel.
Technical scheme provided by the invention is: konjac glucomannan grafted multipolymer, by the konjac glucomannan aqueous solution under water soluble oxidized reduction initiator causes, with graft copolymerization of vinyl monomer, many vinyl-functional compound is linking agent or passes through high-temperature cross-linking, synthetic obtaining.
The preparation method of above-mentioned konjac glucomannan grafted multipolymer, by the konjac glucomannan aqueous solution under water soluble oxidized reduction initiator causes, with graft copolymerization of vinyl monomer, with many vinyl-functional compound is linking agent or by high-temperature cross-linking, syntheticly obtains konjac glucomannan grafted copolymer aquagel.
Above-mentioned graft copolymerization vinyl monomer is vinylformic acid, methacrylic acid, acrylamide, N-N-isopropylacrylamide, vinyl cyanide or vinylacetic acid.
Above-mentioned water soluble oxidized reduction initiator is ceric ammonium nitrate or persulphate.
Above-mentioned linking agent is many vinyl-functional compound N, N '-methylene-bisacrylamide, diacrylate binaryglycol ester, Ethylene glycol dimethacrylate or diethyleneglycol dimethacrylate(DEGDMA); Its consumption is the 0.03-2.0% of vinyl monomer weight.
Above-mentioned graft copolymerization temperature is 25-90 ℃, is preferably 35-50 ℃.
The concentration of above-mentioned konjak portuguese gansu polyose sugar aqueous solution is 0.1-2.0% (mass percent), is preferably 0.5-1.0% (mass percent).
The konjac glucomannan grafted copolymer aquagel of gained of the present invention can be applicable to biological chemistry, medical science, agricultural, food, filed of daily-use chemical industry.
The structure of graftomer is through infrared spectra (FT-IR), scanning electron microscope analysis, and measured water-intake rate.
The present invention adopts water-soluble konjac glucomannan by preparing the biodegradable hydrogel with graft copolymerization of vinyl monomer, crosslinked method first.Because konjac glucomannan is water-soluble polysaccharide, has excellent biological compatibility and biodegradability, thereby also has excellent biological compatibility and biodegradability with it as the hydrogel that main chain obtains.Preparation technology is easy, and reaction medium is a water, and production process does not produce environmental pollution.Konjac glucomannan is from agricultural-food cheap and easy to get, and the present invention also provides an effective way for the comprehensive utilization of agricultural byproducts.
Konjac glucomannan graft copolymer of the present invention has following purposes:
1, resulting hydrogel has biocompatibility and biological degradability, can be used as bio-medical material.For example controlled drug delivery system, tissue engineering material, contact lens, dentistry imbibition material, operation bandage, sanitary belt, nursing pad etc.
2, make physiological hygiene articles for use, for example sanitary towel, diaper, adult-incontinence articles, disinfected paper napkin etc. as High hydrophilous resin.
3, be used for agricultural gardening material,, can improve soil moisture conservation, the performance of keeping humidity of soil, promote the formation of crumb structure, improve the plantation surviving rate of short of rain or areas with soil-erosion problems such as desert, deserted mountain for example with mixing with soil.It is carried out coating to seed handle, can improve seed humidity, temperature condition on every side, improve seedling rate, shorten and emerge the cycle.Also can be used as the chemical fertilizer sustained release drug.
4, as filtration, parting material.
5, as antistatic fiber, sealing material and filler.
6, in petroleum industry is produced, the control leakage as the oil dehydrating agent, can be removed small amount of moisture contained in the petroleum-type product effectively.
7, as curing compound.
8, otherwise application, for example spices sustained release dosage, deodorizing composition, vegetables and fruits are fresh-keeping, moisture adsorbent of various wrapping material, paper for kitchen, sludge curing treatment agent etc.
Description of drawings
Fig. 1 is the infrared spectra of konjaku powder;
Fig. 2 is the infrared spectra of konjaku powder graft acrylic acid of the present invention;
Fig. 3 is the stereoscan photograph of konjaku powder;
Fig. 4 is the stereoscan photograph of konjaku powder graft acrylic acid of the present invention.
Embodiment
The konjac glucomannan grafted copolymer aquagel of the present invention is to be reduced under initiator (as ceric ammonium nitrate or persulphate etc.) causes in water soluble oxidized by the konjak portuguese gansu polyose sugar aqueous solution, with graft copolymerization of vinyl monomer, with many vinyl-functional compound is that linking agent is crosslinked, or obtains by high-temperature cross-linking is synthetic.
The vinyl monomer that the present invention adopts is vinylformic acid, methacrylic acid, acrylamide, N-N-isopropylacrylamide, vinyl cyanide or vinylacetic acid.When being monomer, behind the graft reaction, become acid amides or acid through sodium hydroxide hydrolysis with the vinyl cyanide.Many vinyl-functional compound is N, N '-methylene-bisacrylamide, or diacrylate binaryglycol ester, or Ethylene glycol dimethacrylate, or diethyleneglycol dimethacrylate(DEGDMA).
Concrete synthetic route of the present invention is schematically as follows:
The konjac glucomannan vinyl monomer
Vinyl monomer and corresponding R ' and R outline as follows in the formula:
Vinyl monomer R ' R
Vinylformic acid H COOH
Methacrylic acid CH
3COOH
Acrylamide H CONH
2
N-N-isopropylacrylamide H CONHCH (CH
3)
2
Vinyl cyanide H CN
Vinylacetic acid H CH
2COOH
Embodiment one:
Synthesizing of Rhizoma amorphophalli glucomannan/acrylic acid graft copolymer
Accurately take by weighing the konjaku powder of 0.10 gram, compound concentration is 0.5% the aqueous solution, and in about 50 ℃, place the enough time, KGM is uniformly dispersed, the Acrylic Acid Monomer that adds 1.77 mol then, the back that stirs add 2.19 mmoles/liter initiator solution (ceric ammonium nitrate+nitric acid) and 10.37 mmoles/liter linking agent N, N '-methylene-bisacrylamide, stir and, obtain water white hydrogel in 45-50 ℃ of following reaction stopped reaction after 2 hours.
To react the gained hydrogel with distilled water immersion, washing, under 60 ℃, dry then crude product.Again with desciccate with acetone in soxhlet's extractor extracting 24 hours to remove homopolymer, under 60 ℃, dry required pure graft copolymer, store for future use.
The mensuration of percentage of grafting
Percentage of grafting is the massfraction that grafted branches accounts for the konjak portuguese gansu polyose sugar substrate, is calculated as follows:
G％＝(M
g-M
0)/M
0*100％
G% is a percentage of grafting in the formula; M
gQuality for graft copolymer after the grafting; M
0Quality for Rhizoma amorphophalli glucomannan sample before the grafting.
The mensuration of pick up
Buffered soln with Sodium phosphate dibasic and potassium primary phosphate preparation pH=7.4.Accurately take by weighing a certain amount of pure graft copolymer in the 100ml beaker, add above-mentioned damping fluid 50ml then, make the gel suction, up to swelling equilibrium.Pick up is calculated as follows:
Pick up=(M
2-M
1)/M
1* 100%
M in the formula
1For dry-eye disease weighs; M
2For quality is M
1Dry-eye disease water absorption and swelling balance after jello heavy.
Recording percentage of grafting according to aforesaid method is 97%, and pick up is 71 times.
Infrared spectra
By FTIR8000 (day island proper Tianjin) spectrometer measurement, after pure graft copolymerization matter sample is pulverized, by the KBr compressing tablet.
Scanning electron microscope
With the exterior appearance of the pure graft copolymer of Hitachi SX-650 (Japan) sem observation, understand its structure.Take pictures behind the sample metal spraying.
Infrared spectra is seen Fig. 1, Fig. 2.Fig. 1 is the infrared spectrum of grafted Rhizoma amorphophalli glucomannan not.Fig. 1 is at 2924.9cm
-1The place is the C-H vibration peak of methyl in the Rhizoma amorphophalli glucomannan, 1733.8cm
-1The place then is the absorption peak of carbonyl.876.1cm
-1And 807.3cm
-1The place is the characteristic absorption band of seminose.Fig. 2 is at 2933.6cm
-1The place is the C-H vibration peak of methylene radical in the graft copolymer, 1708.4cm
-1The place is the absorption peak of carboxyl.Fig. 2 compared to Figure 1,1733.8cm
-1The absorption peak of place's carbonyl is by 1708.4cm
-1The absorption peak of place's carboxyl is covered and is only shown 1708.4cm
-1The broad peak at place.876.1cm
-1And 807.3cm
-1Lower wave number 872.4cm is shifted at the peak at place
-1And 798.0cm
-1The place.Show that graft copolymerization has taken place for Rhizoma amorphophalli glucomannan and vinylformic acid.
Fig. 3, Fig. 4 are respectively before the grafting and the konjac glucomannan stereoscan photograph after the grafting, and the surface ratio of Rhizoma amorphophalli glucomannan is more coarse before the grafting, present the consistent particulate phase structure of rule; And the smooth surface of konjac glucomannan grafted acrylic acid multipolymer demonstrates cross linked porous network-like structure, and its hole is dark and the aperture is not of uniform size.The preceding Rhizoma amorphophalli glucomannan of texture ratio grafting that shows Rhizoma amorphophalli glucomannan acrylic acid graft copolymer has very big change.
1708.4cm
-1The absorption peak of place's carboxyl is covered and is only shown 1708.4cm
-1The broad peak at place.876.1cm
-1And 807.3cm
-1Lower wave number 872.4cm is shifted at the peak at place
-1And 798.0cm
-1The place.Show that graft copolymerization has taken place for Rhizoma amorphophalli glucomannan and vinylformic acid.
Embodiment two:
Synthesizing of Rhizoma amorphophalli glucomannan/methacrylic acid graft copolymer
Accurately take by weighing the konjaku powder of 0.20 gram, compound concentration is 1.0% the aqueous solution, and in about 50 ℃, place the enough time, KGM is uniformly dispersed, the methacrylic acid monomer that adds 1.77 mol then, the back that stirs add 2.19 mmoles/liter initiator solution (ceric ammonium nitrate+nitric acid) and linking agent 10.37 mmoles/liter N, N '-methylene-bisacrylamide, stir and, obtain water white hydrogel in 45-50 ℃ of following reaction stopped reaction after 2 hours.
To react the gained hydrogel with distilled water immersion, washing, under 60 ℃, dry then crude product.Again with desciccate with acetone in soxhlet's extractor extracting 24 hours to remove homopolymer, under 60 ℃, dry pure graft copolymer.
Embodiment three:
Synthesizing of Rhizoma amorphophalli glucomannan/acrylamide grafted copolymer
In having the there-necked flask of agitator, add 0.20 gram konjaku powder and water, stir and to be made into 0.5% the aqueous solution down and, konjaku powder to be uniformly dispersed, feed nitrogen 50 ℃ of insulations, add 0.12 gram ceric ammonium nitrate (being dissolved in the nitric acid), stir after 20 minutes, add 10 gram acrylamides and 0.17 gram N, N '-methylene-bisacrylamide, react stopped reaction after 2.5 hours, get gel.
To react the gained hydrogel with distilled water immersion, washing, under 60 ℃, dry then crude product.Again with desciccate with acetone in soxhlet's extractor extracting 24 hours to remove homopolymer, under 60 ℃, dry pure graft copolymer.
Embodiment four:
Synthesizing of Rhizoma amorphophalli glucomannan/N-isopropylacrylamide graft copolymer
In having the there-necked flask of agitator, add 0.20 gram konjaku powder and water, stir and to be made into 0.5% the aqueous solution down and, konjaku powder to be uniformly dispersed, feed nitrogen 50 ℃ of insulations, add 0.12 gram ceric ammonium nitrate (being dissolved in the nitric acid), stir after 20 minutes, add 10 gram N-N-isopropylacrylamide and 0.17 gram N, N '-methylene-bisacrylamide, react stopped reaction after 2.5 hours, get gel.
To react the gained hydrogel with distilled water immersion, washing, under 60 ℃, dry then crude product.Again with desciccate with acetone in soxhlet's extractor extracting 24 hours to remove homopolymer, under 60 ℃, dry pure graft copolymer.
Embodiment five:
Synthesizing of Rhizoma amorphophalli glucomannan/acrylonitrile graft copolymer
In having the there-necked flask of agitator, add 0.20 gram konjaku powder and water, stir and be made into 0.5% the aqueous solution down and, konjaku powder be uniformly dispersed 45 ℃ of insulations, feed nitrogen, add 0.12 gram ceric ammonium nitrate (being dissolved in the nitric acid), stir after 10 minutes, adjust the temperature to 35 ℃, add 10 gram vinyl cyanide, react stopped reaction after 3 hours, filter washing, get graft copolymer after the drying.
Graft copolymer is scattered in the water, adds NaOH, 90 ℃ are reacted down to even thick liquid, use the HCl acidifying, washing.Regulating pH with NaOH again is about 7.130 ℃ of dryings 15 minutes, water-fast hydrogel.
Embodiment six:
Synthesizing of Rhizoma amorphophalli glucomannan/vinylacetic acid graft copolymer
In having the there-necked flask of agitator, add 0.20 gram konjaku powder and water, stir and to be made into 0.5% the aqueous solution down and, konjaku powder to be uniformly dispersed, feed nitrogen 45 ℃ of insulations, add 0.12 gram ceric ammonium nitrate (being dissolved in the nitric acid), stir after 10 minutes, adjust the temperature to 35 ℃, add 10 gram vinylacetic acids and 0.17 gram Ethylene glycol dimethacrylate, react stopped reaction after 2.5 hours, get gel.
To react the gained hydrogel with distilled water immersion, washing, under 60 ℃, dry then crude product.Again with desciccate with acetone in soxhlet's extractor extracting 24 hours to remove homopolymer, under 60 ℃, dry pure graft copolymer.
Redox in the foregoing description urges the agent ceric ammonium nitrate can use persulphate (as Sodium Persulfate, Potassium Persulphate etc.) to substitute.
Claims (8)
1. konjac glucomannan grafted multipolymer, under water soluble oxidized reduction initiator caused, with graft copolymerization of vinyl monomer, many vinyl-functional compound was linking agent or passes through high-temperature cross-linking, synthetic obtaining by the konjac glucomannan aqueous solution; Linking agent is many vinyl-functional compound N, N-methylene-bisacrylamide, diacrylate binaryglycol ester, Ethylene glycol dimethacrylate or diethyleneglycol dimethacrylate(DEGDMA); Dosage of crosslinking agent is the 0.03-2.0% of vinyl monomer weight.
2. the preparation method of the described konjac glucomannan grafted multipolymer of claim 1, it is characterized in that: by the konjac glucomannan aqueous solution under water soluble oxidized reduction initiator causes, with graft copolymerization of vinyl monomer, with many vinyl-functional compound is linking agent or by high-temperature cross-linking, syntheticly obtains konjac glucomannan grafted multipolymer.
3. preparation method according to claim 2 is characterized in that: the graft copolymerization vinyl monomer is vinylformic acid, methacrylic acid, acrylamide, N-N-isopropylacrylamide, vinyl cyanide or vinylacetic acid.
4. according to claim 2 or 3 described preparation methods, it is characterized in that: water soluble oxidized reduction initiator is ceric ammonium nitrate or persulphate.
5. according to claim 2 or 3 described preparation methods, it is characterized in that: the graft copolymerization temperature is 25-90 ℃.
6. according to claim 2 or 3 described preparation methods, it is characterized in that: the graft copolymerization temperature is 35-50 ℃.
7. according to claim 2 or 3 described preparation methods, it is characterized in that: the mass percent concentration of konjak portuguese gansu polyose sugar aqueous solution is 0.1-2.0%.
8. the application of the described konjac glucomannan grafted multipolymer of claim 1 in biological chemistry, medical science, agricultural, food, filed of daily-use chemical industry.
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