CN100554330C - The preparation method of polyvinyl alcohol beta-cyclodextrin multipolymer - Google Patents
The preparation method of polyvinyl alcohol beta-cyclodextrin multipolymer Download PDFInfo
- Publication number
- CN100554330C CN100554330C CNB2006101050802A CN200610105080A CN100554330C CN 100554330 C CN100554330 C CN 100554330C CN B2006101050802 A CNB2006101050802 A CN B2006101050802A CN 200610105080 A CN200610105080 A CN 200610105080A CN 100554330 C CN100554330 C CN 100554330C
- Authority
- CN
- China
- Prior art keywords
- cyclodextrin
- beta
- polyvinyl alcohol
- multipolymer
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
A kind of preparation method of polyvinyl alcohol beta-cyclodextrin multipolymer, with the 3.00g polyvinyl alcohol, 10.00g beta-cyclodextrin and 40mL water join in the 150mL three-necked flask, stirring and dissolving under 90 ℃ of heating in water bath, be cooled to 60 ℃ then, and slowly to be added dropwise to concentration be 30%NaOH aqueous solution 30mL, continue to stir 12 hours, is 1: 1 by epoxy chloropropane with beta-cyclodextrin amount of substance ratio, disposable epoxy chloropropane is added in the above-mentioned mixed solution, at 60 ℃ of following stirring reactions after 12 hours, add the acetone termination reaction, get 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 multipolymer.This invention has that preparation is simple, and equipment is not had particular requirement, characteristics such as with low cost.
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, PVA1-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 (1)
1, a kind of preparation method of polyvinyl alcohol beta-cyclodextrin multipolymer, it is characterized in that: with the 3.00g polyvinyl alcohol, 10.00g beta-cyclodextrin and 40mL water join in the 150mL three-necked flask, stirring and dissolving under 90 ℃ of heating in water bath, be cooled to 60 ℃ then, and slowly to be added dropwise to concentration be 30%NaOH aqueous solution 30mL, continue to stir 12 hours, is 1: 1 by epoxy chloropropane with beta-cyclodextrin amount of substance ratio, disposable epoxy chloropropane is added in the above-mentioned mixed solution, at 60 ℃ of following stirring reactions after 12 hours, add the acetone termination reaction, get 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 multipolymer.
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 CN1911998A (en) | 2007-02-14 |
| CN100554330C true CN100554330C (en) | 2009-10-28 |
Family
ID=37721070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101050802A Expired - Fee Related CN100554330C (en) | 2006-08-31 | 2006-08-31 | The preparation method of polyvinyl alcohol beta-cyclodextrin multipolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100554330C (en) |
Families Citing this family (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 |
Citations (3)
| 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 |
| CN1312317A (en) * | 2001-03-27 | 2001-09-12 | 武汉大学 | Biologically degradable henry steudnera tuber film and its making process |
| CN1453303A (en) * | 2002-04-28 | 2003-11-05 | 武汉金宝生物环保科技有限公司 | Biologically degradable starch film and its prepn |
-
2006
- 2006-08-31 CN CNB2006101050802A patent/CN100554330C/en not_active Expired - Fee Related
Patent Citations (3)
| 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 |
| CN1312317A (en) * | 2001-03-27 | 2001-09-12 | 武汉大学 | Biologically degradable henry steudnera tuber film and its making process |
| CN1453303A (en) * | 2002-04-28 | 2003-11-05 | 武汉金宝生物环保科技有限公司 | Biologically degradable starch film and its prepn |
Non-Patent Citations (4)
| Title |
|---|
| 新型环糊精高分子的合成及其药物控制释放机理研究. 黄怡.西北工业大学博士学位论文. 2005 |
| 新型环糊精高分子的合成及其药物控制释放机理研究. 黄怡.西北工业大学博士学位论文. 2005 * |
| 聚乙烯醇固载β-环糊精线性高聚物的合成及其药物控制释放研究. 黄怡，范晓东，张楠楠.高分子学报，第6期. 2004 |
| 聚乙烯醇固载β-环糊精线性高聚物的合成及其药物控制释放研究. 黄怡，范晓东，张楠楠.高分子学报，第6期. 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1911998A (en) | 2007-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dai et al. | Pineapple peel carboxymethyl cellulose/polyvinyl alcohol/mesoporous silica SBA-15 hydrogel composites for papain immobilization | |
| Orasugh et al. | Jute cellulose nano-fibrils/hydroxypropylmethylcellulose nanocomposite: A novel material with potential for application in packaging and transdermal drug delivery system | |
| Mishra et al. | Tamarind xyloglucan: a polysaccharide with versatile application potential | |
| Liu et al. | Preparation and characterization of chitosan by a novel deacetylation approach using glycerol as green reaction solvent | |
| de Oliveira et al. | Development of food packaging bioactive aerogels through the valorization of Gelidium sesquipedale seaweed | |
| Xia et al. | Preparation of hybrid hydrogel containing Ag nanoparticles by a green in situ reduction method | |
| Yang et al. | Synthesis and characterization of temperature sensitive hemicellulose-based hydrogels | |
| Osorio-Madrazo et al. | Kinetics study of the solid-state acid hydrolysis of chitosan: Evolution of the crystallinity and macromolecular structure | |
| Ibrahim et al. | Polysaccharide-based polymer gels and their potential applications | |
| Pareek et al. | Bioconversion to chitosan: A two stage process employing chitin deacetylase from Penicillium oxalicum SAEM-51 | |
| Suenaga et al. | Self-sustaining cellulose nanofiber hydrogel produced by hydrothermal gelation without additives | |
| KR20110059697A (en) | Functional nano starch complexes and their preparation methods | |
| Pereira et al. | Effect of chitin nanowhiskers on mechanical and swelling properties of Gum Arabic hydrogels nanocomposites | |
| WO2008044586A1 (en) | Molded article comprising branched starch | |
| Wang et al. | Formation of composite hydrogel of carboxymethyl konjac glucomannan/gelatin for sustained release of EGCG | |
| Azeez et al. | Recent developments on the application of carbohydrate polymers | |
| Fajardo et al. | Hydrogels nanocomposites based on crystals, whiskers and fibrils derived from biopolymers | |
| Saboktakin et al. | Design and characterization of chitosan nanoparticles as delivery systems for paclitaxel | |
| JP5183860B2 (en) | COMPOSITE MOLDED ARTICLE AND METHOD FOR IMMOBILIZING ACTIVE SUBSTANCES | |
| Song et al. | Long term antibacterial effect cellulose film was modified with polyhexamethylene biguanide (PHMB) | |
| CN100554330C (en) | The preparation method of polyvinyl alcohol beta-cyclodextrin multipolymer | |
| Li et al. | The use of bacterial cellulose from kombucha to produce curcumin loaded Pickering emulsion with improved stability and antioxidant properties | |
| WO2008044588A1 (en) | Branched starch derivative, process for production thereof, and molded article comprising the branched starch derivative | |
| CN105860103A (en) | Preparation method and application of novel nano hydrogel | |
| Goswami et al. | Pullulan films and natural compounds: applications and perspectives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
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 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091028 Termination date: 20120831 |