CN1911998A - Copolymer of polyvinyl alcohol and sugar and its preparation method - Google Patents
Copolymer of polyvinyl alcohol and sugar and its preparation method Download PDFInfo
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- CN1911998A CN1911998A CN 200610105080 CN200610105080A CN1911998A CN 1911998 A CN1911998 A CN 1911998A CN 200610105080 CN200610105080 CN 200610105080 CN 200610105080 A CN200610105080 A CN 200610105080A CN 1911998 A CN1911998 A CN 1911998A
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- polyvinyl alcohol
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Abstract
The present invention is PVA-saccharide copolymer and its preparation process. The copolymer based on PVA chain has saccharide, which may be monose, oligose, cyclodextrin, starch, etc, grafted onto the PVA chain. The preparation process includes the following steps: dissolving PVA and saccharide in hot water and lowering the temperature to 50-70 deg.c after dissolving; adding 30 % concentration water solution of NaOH and stirring for 12 hr at 50-70 deg.c; adding cross-linking agent at 50-70 deg.c, stirring to react for 12 hr, adding proper amount of acetone to terminate reaction and obtain yellow sol and neutralizing with dilute hydrochloric acid solution; separating and purifying the sol, and drying to obtain the PVA-saccharide copolymer. The present invention has simple preparation process, low cost and other features.
Description
Technical field
The present invention relates to multipolymer of polyvinyl alcohol and sugar and preparation method thereof, belong to polymer preparation and Application Areas thereof.
Background technology
Polyvinyl alcohol (Poly (vinyl alcohol) is called for short PVA) is a kind of good pharmaceutical excipient that is obtained through alkali catalyzed alcoholysis by polyvinyl acetate (PVA).It has good water-solubility and film-forming properties, and the mechanical property of its film is good.The very low and nonirritant of safety experiment proof PVA toxicity, the Japan and the U.S. etc. all approved are used for medicine and foodstuffs industry.
PVA has synthetic convenience, safety and low toxicity, quality product and is easy to control, low price, characteristics such as easy to use.Therefore, PVA is the good pharmaceutical excipient that has once more potentiality to be exploited.At present, PVA is mainly used in the film forming material of capsule material, film and the liniment of making minigel etc. in pharmaceutical preparation, and effect is good.PVA is nontoxic and have good adhesiveproperties, in the production and research of pharmaceutical preparation, also often is used to do the tackiness agent of tablet.PVA is used as the framework material of tablet, energy slowly-releasing, controlled release drug.PVA is water-soluble and have very low surface tension, in preparation medicine carrying microballoons or micro-capsule, both can make the pore-creating agent of microballoon or micro-capsule, also can make dispersion medium.Because PVA has nontoxicity and excellent biological compatibility and mechanical property, now has been widely used in bio-medical material.As pharmaceutical carrier, PVA also demonstrates its superior sustained release performance.Simultaneously, glucide nontoxic, have no side effect, good biocompatibility and can degradation in vivo become the small molecules nutritive substance that can be absorbed by body.Starch, cyclodextrin glucides such as (CD) are the bio-medical materials that is widely used.If carbohydrate is incorporated in the PVA polymkeric substance with simple method, can make the performance of PVA obtain changing and improving, after particularly cyclodextrin being incorporated into polyvinyl alcohol polymer, not only make polyvinyl alcohol have the inclusion function of cyclodextrin concurrently, the slow release effect and the cost that improve medicine are lower.Therefore, the PVA product of polyose modification has important use value.
Summary of the invention
The present invention has introduced multipolymer of polyvinyl alcohol and sugar and preparation method thereof.This method is to be raw material with polyvinyl alcohol and sugar, and " one pot " crosslinking reaction can obtain the multipolymer of polyvinyl alcohol and sugar under alkaline condition, and it has, and preparation is simple, and equipment is not had particular requirement, with low cost, characteristics such as polysaccharide supported quantity height.
Synthetic method of the present invention is as follows:
PVA, sugar and water are joined in the three-necked flask, and stirring and dissolving under 80～90 ℃ of heating in water bath is cooled to 50～70 ℃ then, and slowly to drip concentration be the 30%NaOH aqueous solution, continues to stir 12h.
Press linking agent and sugar unit amount of substance ratio, disposable linking agent added in the above-mentioned mixed solution, behind 50～70 ℃ of following stirring reaction 12h, add the proper amount of acetone termination reaction, yellow sol, neutralize with dilute hydrochloric acid.Gained colloidal sol is separated and purifies, and drying promptly gets the multipolymer of PVA and sugar.
Embodiment implementation procedure of the present invention is described in detail by following examples:
Embodiment one: polyvinyl alcohol beta-cyclodextrin copolymer 1
3.00g PVA, 10.00g β-CD and 40mL water are joined in the 150mL three-necked flask, and stirring and dissolving under 90 ℃ of heating in water bath is cooled to 60 ℃ then, and slowly to be added dropwise to concentration be 30%NaOH aqueous solution 30mL, continues to stir 12h.
Is 1: 1 by epoxy chloropropane (Epi) with β-CD amount of substance ratio, disposable Epi is added in the above-mentioned mixed solution, behind 60 ℃ of following stirring reaction 12h, adds the proper amount of acetone termination reaction, faint yellow colloidal sol, neutralize with dilute hydrochloric acid.Gained colloidal sol is separated and purify with the ethanol precipitation method, then solvent is drained, vacuum-drying promptly gets polyvinyl alcohol beta-cyclodextrin copolymer 1.
1H NMR (300MHz, D
2O): δ 4.9 (s, 7H, β-CD 1-H), 3.3～3.9 (m, 74H, β-CD, linker and PVA2-H), 1.5 (t, 54H, PVA 1-H).
Embodiment two: polyvinyl alcohol beta-cyclodextrin multipolymer 2
Is 1: 2 with Epi with β-CD amount of substance ratio, and it is synthetic to press embodiment one, gets beta-cyclodextrin polyvinyl alcohol copolymer 2.
1H NMR (300MHz, D
2O): δ 4.9 (s, 7H, β-CD 1-H), 3.3～3.9 (m, 81H, β-CD, linker and PVA2-H), 1.5 (t, 48H, PVA 1-H).
Embodiment three: polyvinyl alcohol beta-cyclodextrin multipolymer 3
Is 1: 4 with Epi with β-CD amount of substance ratio, and it is synthetic to press embodiment one, gets beta-cyclodextrin polyvinyl alcohol copolymer 3.
1H NMR (300MHz, D
2O): δ 4.9 (s, 7H, β-CD 1-H), 3.3～3.9 (m, 69H, β-CD, linker and PVA2-H), 1.5 (t, 27H, PVA 1-H).
Embodiment four: polyvinyl alcohol beta-cyclodextrin multipolymer 4
Is 1: 7 with Epi with β-CD amount of substance ratio, and it is synthetic to press embodiment one, gets gel beta-cyclodextrin polyvinyl alcohol copolymer 4.
Embodiment five: polyvinyl alcohol beta-cyclodextrin multipolymer 5
Is 1: 10 with Epi with β-CD amount of substance ratio, and it is synthetic to press embodiment one, gets gel beta-cyclodextrin polyvinyl alcohol copolymer 5.
Embodiment six: polyvinyl alcohol beta-cyclodextrin starch copolymer
3.00g PVA, 5.00g β-CD, 5.00g starch and 40mL water are joined in the 150mL three-necked flask, and stirring and dissolving under 90 ℃ of heating in water bath is cooled to 60 ℃ then, and slowly to be added dropwise to concentration be 30%NaOH aqueous solution 30mL, continues to stir 12h.
Is 1: 8 by Epi with β-CD amount of substance ratio, disposable Epi is added in the above-mentioned mixed solution, behind 60 ℃ of following stirring reaction 12h, adds the proper amount of acetone termination reaction, light yellow gel, neutralize with dilute hydrochloric acid.Gained colloidal sol is separated and purify with the ethanol precipitation method, then solvent is drained, vacuum-drying promptly gets polyvinyl alcohol beta-cyclodextrin starch copolymer gel.
Claims (5)
1, polyvinyl alcohol and the multipolymer of sugar and the method for preparation thereof is characterized in that polyvinyl alcohol and glucide copolymerization.
2, the multipolymer of polyvinyl alcohol according to claim 1 and carbohydrate, sugar can be glucides such as monose, oligose, cyclodextrin, starch, linking agent be epoxy chloropropane or can be under alkaline condition can with the linking agent of hydroxyl reaction.
3, described polyvinyl alcohol of claim 1 and sugared multipolymer is characterized in that preparation technology may further comprise the steps:
(1) polyvinyl alcohol and sugar are dissolved in hot water jointly, treat all to be cooled to 50～70 ℃ after the dissolving;
(2) add concentration at 50～70 ℃ and be about the 30%NaOH aqueous solution, NaOH concentration is 10～25% in the reaction system, stirs 12h;
(3) add linking agent at 50～70 ℃, stirring reaction 12h adds the proper amount of acetone termination reaction, neutralizes with dilute hydrochloric acid.Gained colloidal sol is separated and purifies, then solvent is drained, drying promptly gets the multipolymer of polyvinyl alcohol and sugar.
4, multipolymer according to claim 3 is synthetic, and the ratio that changes polyvinyl alcohol and polysaccharide can obtain water solubility copolymer or can be by water swollen copolymer gel.
5, multipolymer according to claim 3 is synthetic, and the ratio that changes epoxy chloropropane and polysaccharide can obtain water solubility copolymer or can be by water swollen copolymer gel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101050802A CN100554330C (en) | 2006-08-31 | 2006-08-31 | The preparation method of polyvinyl alcohol beta-cyclodextrin multipolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101050802A CN100554330C (en) | 2006-08-31 | 2006-08-31 | The preparation method of polyvinyl alcohol beta-cyclodextrin multipolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1911998A true CN1911998A (en) | 2007-02-14 |
| CN100554330C CN100554330C (en) | 2009-10-28 |
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| CNB2006101050802A Expired - Fee Related CN100554330C (en) | 2006-08-31 | 2006-08-31 | The preparation method of polyvinyl alcohol beta-cyclodextrin multipolymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284896B (en) * | 2007-12-28 | 2010-06-02 | 北京航空航天大学 | Chitosan oligosaccharide-poly L-beta-indole alanine graft copolymer homogeneous phase synthetic method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3072425B1 (en) * | 1999-07-26 | 2000-07-31 | 村田機械株式会社 | Roll paper empty core transfer device |
| CN1114654C (en) * | 2001-03-27 | 2003-07-16 | 武汉大学 | Biologically degradable henry steudnera tuber film and its making process |
| CN1181123C (en) * | 2002-04-28 | 2004-12-22 | 武汉金宝生物环保科技有限公司 | Biologically degradable starch film and its prepn |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284896B (en) * | 2007-12-28 | 2010-06-02 | 北京航空航天大学 | Chitosan oligosaccharide-poly L-beta-indole alanine graft copolymer homogeneous phase synthetic method |
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| CN100554330C (en) | 2009-10-28 |
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Assignee: Shaanxi Research Design Institute OF Petroleum and Chemical Industry Assignor: Shaanxi Normal University Contract record no.: 2011610000129 Denomination of invention: Copolymer of polyvinyl alcohol and beta-cyclodextrin preparation method Granted publication date: 20091028 License type: Exclusive License Open date: 20070214 Record date: 20110721 |
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Granted publication date: 20091028 Termination date: 20120831 |