CN102226001B - Fully biodegradable nano-starch graft polylactic acid - Google Patents
Fully biodegradable nano-starch graft polylactic acid Download PDFInfo
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Abstract
Belonging to the technological field of preparation of fully biodegradable nano-starch based graft copolymer, the invention provides a method for preparing completely biodegradable nano-starch graft polylactic acid copolymer by a click chemistry method. The nano-starch based graft copolymer is prepared by the steps of: subjecting hydroxy functional groups with reactivity in nano-starch to a chemical reaction and introducing azide groups, and performing an azide-alkynyl Husigen cycloaddition reaction with polylactic acid of a triplebond end group. The nano-starch-polylactic acid graft copolymer is prepared through the click chemistry method, and is characterized by high-efficient and controllable reaction, clear and controllable polylactic acid molecular weight and grafting rate, clear copolymer structure, reduced hydrophily of starch, and excellent plasticity and processability.
Description
Technical field:
The invention belongs to the preparing technical field of the nano-starch based polyalcohol of fully biodegradable.
Technical background:
Click chemistry is that Americanized scholar Sharpless proposes, and is a kind of novel method of fast synthetic a large amount of compounds, and purport is the splicing through junior unit, comes fast and reliable ground to accomplish the chemosynthesis of varied molecule.Can obtain molecular diversity simply efficiently in this way.The notion of click chemistry has very big contribution to the field of chemical synthesis, and in the numerous areas of drug development and bio-medical material etc., it has become one of the most useful at present and attracting synthetic theory.
Starch is a kind of important reproducible and biodegradable natural macromolecular material, in foodstuffs industry with other practical application in extremely important, usage quantity is big.Starch source is abundant, and is cheap, but because starch has very strong water-absorbent, can not stablize use for a long time, and its mechanical property and workability are poor simultaneously.After starch reached nano level, its specific surface area increased, and had excellent performance.With the nano-starch modification, its performance improves a lot.POLYACTIC ACID is a kind of material with good biocompatibility, biodegradable and Bioabsorbable.POLYACTIC ACID is a kind of real biological plastics, and its nontoxic, nonirritant has excellent biological compatibility, and biodegradable absorption does not pollute the environment, and plasticity-is good, is prone to machine-shaping.But simultaneously the shortcoming that exists of POLYACTIC ACID has: wetting ability is relatively poor, has reduced the biocompatibility of it and other material.Therefore, people to have opened up one be that raw material comes synthesising biological matrix material frontier with starch and POLYACTIC ACID.Be that two kinds of materials are carried out blend on the one hand, but two kinds of materials are difficult to mix, then in this intermingling material, added various solubilizing agent, like maleic anhydride, ammonium polyphosphate microcapsule, glycerine etc.Biomacromolecules 5 (2004) 1446-1451 have reported with maleic anhydride and have done solubilizing agent that starch and POLYACTIC ACID carry out blend.Also have the binary tertiary blending, POLYACTIC ACID, polycaprolactone and thermoplastic starch are carried out blend like Polymer 49 (2008) 599-609.Also have with after the starch acetylize with polylactic acid blend.The 2nd, cause the lactic acid ring-opening polymerization with starch, Carbohydrate Polymers 77 (2009) 32-40 have reported hydroxylic moiety methyl alkylization in the starch, cause the lactic acid ring-opening polymerization, then deprotection.Also useful electrostatic spinning technique, Materials Letters 65 (2011) 985-987 are fused with starch and POLYACTIC ACID with electrostatic spinning technique.At present, click chemistry method synthesis of nano starch-grafting polylactic acid also of no use, the advantage of this method is that reaction is efficient, and the POLYACTIC ACID percentage of grafting is controlled, and copolymer structure is clear and definite.
Up to the present, about not appearing in the newspapers with click chemistry method synthesis of nano starch-g-POLYACTIC ACID.
Summary of the invention:
In order to solve starch and POLYACTIC ACID is raw material synthesising biological problems of composite, the invention provides a kind of preparation method of nano-starch base grafted polylactic acid of fully biodegradable.Thereby make the nano-starch base polylactic acid fully biodegradable that adopts the inventive method preparation, have excellent mechanical property, workability, improved the biocompatibility and the wetting ability of polymkeric substance simultaneously.
Preparation process is following:
(1) preparation of Terminal Acetylenes base polylactic acid
Rac-Lactide is dissolved in the toluene (wherein, the volume of toluene (ml): the quality of rac-Lactide (g) is 10～20: 1), add stannous octoate, the amount of substance of stannous octoate is the per mille of the amount of substance of monomer rac-Lactide; Add the propiolic alcohol monomer, the amount of substance of propiolic alcohol is identical with the amount of substance of desiring synthetic certain molecular weight POLYACTIC ACID, 120 ℃ of oil baths; Reaction 24～48h, the ethanol sedimentation is filtered; Washing, vacuum-drying 24h obtains the Terminal Acetylenes base polylactic acid.
(2) preparation of nitrine modified Nano starch
The preparation of nitrine modified Nano starch is divided into following two steps:
A. the preparation of methyl sulphonyl nano-starch
Nano-starch after at first will dewatering with methylbenzene azeotropic is dissolved in (wherein, the quality of nano-starch (g): the volume of DMSO 99.8MIN. (ml) is 1: 10～30) in the dimethyl sulfoxide solvent, dropwise drips Methanesulfonyl chloride then; Wherein, the amount of substance of Methanesulfonyl chloride (mol): the amount of substance of hydroxyl (mol) is 0.05～0.2: 1 in the nano-starch, adds triethylamine after mixing again; Wherein the amount of substance of triethylamine is identical with the amount of substance of Methanesulfonyl chloride, reaction 24h, ethanol sedimentation; Filter; Washing, vacuum-drying obtains the methyl sulphonyl nano-starch.
B. the preparation of nitrine modified Nano starch
The methyl sulphonyl nano-starch that a step is obtained is dissolved in the DMSO 99.8MIN., and wherein, the quality (g) of methyl sulphonyl nano-starch material: the volume of DMSO 99.8MIN. (ml) is 1: 10～30; Add sodiumazide then, wherein, the amount of substance of sodiumazide (mol): the amount of substance of the methyl sulphonyl in the methyl sulphonyl nano-starch (mol) is 1～5: 1; Reaction 24～72h, the ethanol sedimentation is filtered; Washing, vacuum-drying obtains nitrine modified Nano starch.
(3) preparation of nano-starch-g-POLYACTIC ACID
Nitrine modified Nano starch and Terminal Acetylenes base polylactic acid are dissolved in respectively in the DMSO 99.8MIN., and wherein, the amount of substance of azido-is identical with the amount of substance of carbon-carbon triple bond in the Terminal Acetylenes base polylactic acid in the nitrine modified Nano starch; Add cupric sulfate pentahydrate and sodium ascorbate, wherein, the amount of substance of cupric sulfate pentahydrate is identical with the amount of substance of azido-in the nitrine modified Nano starch; The amount of substance of sodium ascorbate (mol): the amount of substance of cupric sulfate pentahydrate (mol) is 1～5: 1, and reaction 24～72h adds ion exchange resin; Wherein, the quality of ion exchange resin (g): the quality of cupric sulfate pentahydrate (g) is 10～20: 1, reaction 24h; Filter out insolubles, bubble goes in the primary water to dialyse 5-7 days, changes water every day at least three times; Freeze-drying then obtains nano-starch-g-POLYACTIC ACID.
Starch involved in the present invention comprises W-Gum, tapioca(flour) and yam starch.
The present invention is a raw material with technical grade starch, and its structure comprises pulullan and amylose starch.At the surface grafting POLYACTIC ACID, the wetting ability of starch is weakened, improved the biocompatibility of POLYACTIC ACID, the consistency of the two improves.
Can prepare the nano-starch based polyalcohol of the good fully biodegradable of consistency through method provided by the invention.Grafted aliphatic polyester makes the consistency of starch and aliphatic polyester improve; The nano-starch grafted polylactic acid material for preparing a series of different percentage of grafting has certain mechanical strength, have plasticity-and workability, acidproof, alkaline-resisting and water tolerance; Can be used for buffet box and food product pack type; Have wide practical use, way is provided for solving white pollution and oil shortage problem.
Embodiment:
Further specify the present invention through instance below, but the present invention is not limited to this.
Embodiment 1: the preparation of Terminal Acetylenes base polylactic acid
The 7.4930g rac-Lactide is dissolved in the 80ml toluene, adds the 0.2888ml propiolic alcohol, add the 1.3053ml stannous octoate, 120 ℃ of oil baths; Reaction 24h with the sedimentation of 400ml ethanol, filters; Washing with alcohol three times, vacuum-drying 24h obtains molecular weight and is 1500 Terminal Acetylenes base polylactic acid.
Embodiment 2: the preparation of Terminal Acetylenes base polylactic acid
The 6.1862g rac-Lactide is dissolved in the 70ml toluene, adds the 0.1191ml propiolic alcohol, add the 1.0776ml stannous octoate, 120 ℃ of oil baths; Reaction 24h with the sedimentation of 400ml ethanol, filters; Washing with alcohol three times, vacuum-drying 24h obtains molecular weight and is 3000 Terminal Acetylenes base polylactic acid.
Embodiment 3: the preparation of Terminal Acetylenes base polylactic acid
The 2.89g rac-Lactide is dissolved in the 10ml toluene, adds the 0.0167ml propiolic alcohol, add the 0.5034ml stannous octoate, 120 ℃ of oil baths; Reaction 24h with the sedimentation of 100ml ethanol, filters; Washing with alcohol three times, vacuum-drying 24h obtains molecular weight and is 10000 Terminal Acetylenes base polylactic acid.
Embodiment 4: the preparation of methyl sulphonyl nano-starch
Nano-starch 2.5g after will dewatering with methylbenzene azeotropic is dissolved in the 30ml DMSO 99.8MIN., adds the 0.3246ml triethylamine, dropwise drips the 0.1814ml Methanesulfonyl chloride again; Room temperature reaction 24h; With the sedimentation of 300ml ethanol, filter, with ether washing three times; Vacuum-drying 24h obtains percentage of grafting and is 5% methyl sulphonyl nano-starch.
Embodiment 5: the preparation of methyl sulphonyl nano-starch
Nano-starch 3g after will dewatering with methylbenzene azeotropic is dissolved in the 30ml DMSO 99.8MIN., adds the 1.1687ml triethylamine, dropwise drips the 0.6530ml Methanesulfonyl chloride again; Room temperature reaction 24h; With the sedimentation of 300ml ethanol, filter, with ether washing three times; Room temperature vacuum-drying 24h obtains percentage of grafting and is 15% methyl sulphonyl nano-starch.
Embodiment 6: the preparation of methyl sulphonyl nano-starch
Nano-starch 3g after will dewatering with methylbenzene azeotropic is dissolved in the 30ml DMSO 99.8MIN., adds the 1.5583ml triethylamine, dropwise drips the 0.8706ml Methanesulfonyl chloride again; Room temperature reaction 24h; With the sedimentation of 300ml ethanol, filter, with ether washing three times; Room temperature vacuum-drying 24h obtains percentage of grafting and is 20% methyl sulphonyl nano-starch.
Embodiment 7: the preparation of nitrine modified Nano starch
With percentage of grafting is that 5% methyl sulphonyl nano-starch 2g is dissolved in the 20ml DMSO 99.8MIN., adds the 0.6057g sodiumazide, room temperature reaction 72h; With the sedimentation of 200ml ethanol, filter, with ether washing three times; Vacuum-drying 24h obtains percentage of grafting and is 5% nitrine modified Nano starch.
Embodiment 8: the preparation of nitrine modified Nano starch
With percentage of grafting is that 15% methyl sulphonyl nano-starch 3.614g is dissolved in the 40ml DMSO 99.8MIN., adds the 3.2834g sodiumazide, room temperature reaction 72h; With the sedimentation of 400ml ethanol, filter, with ether washing three times; Vacuum-drying 24h obtains percentage of grafting and is 15% nitrine modified Nano starch.
Embodiment 9: the preparation of nitrine modified Nano starch
With percentage of grafting is that 20% methyl sulphonyl nano-starch 2.5g is dissolved in the 30ml DMSO 99.8MIN., adds the 3.0284g sodiumazide, room temperature reaction 72h; With the sedimentation of 300ml ethanol, filter, with ether washing three times; Vacuum-drying 24h obtains percentage of grafting and is 20% nitrine modified Nano starch.
Embodiment 10: the preparation of nano-starch-g-POLYACTIC ACID
With percentage of grafting is that 5% nitrine modified Nano starch 0.3g and molecular weight are that 3000 Terminal Acetylenes base polylactic acid 0.8385g is dissolved in the 20ml DMSO 99.8MIN., adds the 0.0698g cupric sulfate pentahydrate, adds sodium ascorbate 0.2769g; 40 ℃ of reactions of oil bath 72h adds ion exchange resin 1g, room temperature reaction 24h again; Filter out insolubles, water was changed three times in primary water dialysis in one day; Freeze-drying after five days obtains percentage of grafting and is 5%, molecular weight is the nano-starch-g-POLYACTIC ACID of 3000 Terminal Acetylenes base polylactic acids.
Embodiment 11: the preparation of nano-starch-g-POLYACTIC ACID
With percentage of grafting is that 15% nitrine modified Nano starch 0.3g and molecular weight are that 3000 Terminal Acetylenes base polylactic acid 2.5155g is dissolved in the 30ml DMSO 99.8MIN., adds the 0.2094g cupric sulfate pentahydrate, adds sodium ascorbate 0.8306g; 40 ℃ of reactions of oil bath 72h adds ion exchange resin 2g, room temperature reaction 24h again; Filter out insolubles, water was changed three times in primary water dialysis in one day; Freeze-drying after five days obtains percentage of grafting and is 15%, molecular weight is the nano-starch-g-POLYACTIC ACID of 3000 Terminal Acetylenes base polylactic acids.
Embodiment 12: the preparation of nano-starch-g-POLYACTIC ACID
With percentage of grafting is that 20% nitrine modified Nano starch 0.1g and molecular weight are that 1500 Terminal Acetylenes base polylactic acid 0.559g is dissolved in the 20ml DMSO 99.8MIN., adds the 0.093g cupric sulfate pentahydrate, adds sodium ascorbate 0.3691g; 40 ℃ of reactions of oil bath 72h adds ion exchange resin 1g, room temperature reaction 24h again; Filter out insolubles, water was changed three times in primary water dialysis in one day; Freeze-drying after five days obtains percentage of grafting and is 20%, molecular weight is the nano-starch-g-POLYACTIC ACID of 1500 Terminal Acetylenes base polylactic acids.
Claims (3)
1. the preparation method of a nano-starch grafted polylactic acid, its step and condition are following:
1. the preparation of Terminal Acetylenes base polylactic acid
Rac-Lactide is dissolved in the toluene, and wherein, the volume mL of toluene: the quality g of rac-Lactide is 10～20: 1, adds stannous octoate; The amount of substance of stannous octoate is the per mille of the amount of substance of monomer rac-Lactide, adds the propiolic alcohol monomer, and the amount of substance of propiolic alcohol is identical with the amount of substance of desiring synthetic certain molecular weight POLYACTIC ACID, 120 ℃ of oil baths; Reaction 24～48h, the ethanol sedimentation is filtered; Washing, vacuum-drying 24h obtains the Terminal Acetylenes base polylactic acid;
2. the preparation of nitrine modified Nano starch
The preparation of nitrine modified Nano starch comprises following two steps:
A. the preparation of methyl sulphonyl nano-starch
Nano-starch after at first will dewatering with methylbenzene azeotropic is dissolved in the dimethyl sulfoxide solvent, and wherein, the quality g of nano-starch: the volume mL of DMSO 99.8MIN. is 1: 10～30; Dropwise drip Methanesulfonyl chloride then, wherein, the amount of substance mol of Methanesulfonyl chloride: the amount of substance mol of hydroxyl is 0.05～0.2: 1 in the nano-starch; Add triethylamine after mixing again, wherein the amount of substance of triethylamine is identical with the amount of substance of Methanesulfonyl chloride, reaction 24h; The ethanol sedimentation is filtered, washing; Vacuum-drying obtains the methyl sulphonyl nano-starch;
B. the preparation of nitrine modified Nano starch
The methyl sulphonyl nano-starch that a step is obtained is dissolved in the DMSO 99.8MIN., and wherein, the quality g of methyl sulphonyl nano-starch material: the volume mL of DMSO 99.8MIN. is 1: 10～30; Add sodiumazide then, wherein, the amount of substance mol of sodiumazide: the amount of substance mol of the methyl sulphonyl in the methyl sulphonyl nano-starch is 1～5: 1; Reaction 24～72h, the ethanol sedimentation is filtered; Washing, vacuum-drying obtains nitrine modified Nano starch;
3. the preparation of nano-starch-g-POLYACTIC ACID
Nitrine modified Nano starch and Terminal Acetylenes base polylactic acid are dissolved in respectively in the DMSO 99.8MIN., and wherein, the amount of substance of azido-is identical with the amount of substance of carbon-carbon triple bond in the Terminal Acetylenes base polylactic acid in the nitrine modified Nano starch; Add cupric sulfate pentahydrate and sodium ascorbate, wherein, the amount of substance of cupric sulfate pentahydrate is identical with the amount of substance of azido-in the nitrine modified Nano starch; The amount of substance mol of sodium ascorbate: the amount of substance mol of cupric sulfate pentahydrate is 1～5: 1, and reaction 24～72h adds ion exchange resin; Wherein, the quality g of ion exchange resin: the quality g of cupric sulfate pentahydrate is 10～20: 1, reaction 24h; Filter out insolubles, bubble goes in the primary water to dialyse 5-7 days, changes water every day at least three times; Freeze-drying then obtains nano-starch-g-POLYACTIC ACID.
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| CN108410435B (en) * | 2018-03-12 | 2019-09-24 | 中国石油大学(华东) | A kind of drilling fluid nano-starch fluid loss additive and preparation method thereof |
| CN110734553A (en) * | 2019-10-10 | 2020-01-31 | 山东顺通环保材料有限公司徐州分公司 | Preparation method of degradable super absorbent resins |
| KR102508277B1 (en) * | 2021-02-15 | 2023-03-09 | 대상 주식회사 | Thermoplastic starch composition, manufacturing method thereof, and use thereof |
| CN114672055B (en) * | 2022-04-25 | 2023-01-03 | 安徽紫金新材料科技股份有限公司 | Preparation of degradable hydrophobic film with terminal cationic starch as base material |
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| CN1693341A (en) * | 2005-04-30 | 2005-11-09 | 中国科学院长春应用化学研究所 | Process for preparing surface lactic acid graft modified starch and aliphatic polyester graft copolymer |
| CN101942118A (en) * | 2010-10-25 | 2011-01-12 | 曾广胜 | Plant fiber starch fully-biodegradable material and preparation method thereof |
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| CN1693341A (en) * | 2005-04-30 | 2005-11-09 | 中国科学院长春应用化学研究所 | Process for preparing surface lactic acid graft modified starch and aliphatic polyester graft copolymer |
| CN101942118A (en) * | 2010-10-25 | 2011-01-12 | 曾广胜 | Plant fiber starch fully-biodegradable material and preparation method thereof |
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