CN101091796A - Method for synthesizing lactide copolymer grafted by beta cyclodextrin - Google Patents
Method for synthesizing lactide copolymer grafted by beta cyclodextrin Download PDFInfo
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- CN101091796A CN101091796A CNA2007101043875A CN200710104387A CN101091796A CN 101091796 A CN101091796 A CN 101091796A CN A2007101043875 A CNA2007101043875 A CN A2007101043875A CN 200710104387 A CN200710104387 A CN 200710104387A CN 101091796 A CN101091796 A CN 101091796A
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Abstract
The present invention discloses a method for synthesizing beta-cyclodextrin grafted lactide copolymer, belonging to the field of biomedical high-molecular material technology. Said method includes the following steps: mixing heat-cyclodextrin, sodium hydroxide and water according to the mass ratio of 10:3-5:15-25; making them be quickly dissolved into a transparent solution; stirring to make reaction for 2-24h at 20deg.C-50deg.C; adding epoxy-chloropropane into the reaction system according to that the mole ratio of beta-cyclodextrin and epoxy-chloropropane is 1:10-20 and continuously stirring to make reaction for 2-6h; microwave heating and concentrating reaction system, then adding proper quantity of acetone to dilute said reaction system to obtain paste-like material, then adding lactide into the paste-like material, fully stirring them, utilizing microwave to irradiate and heat said reaction system, stirring to make reaction so as to obtain the invented product.
Description
Technical field
The present invention relates to a kind of method for preparing lactide copolymer grafted by beta cyclodextrin, belong to the biological medical polymer material technical field.
Background of invention
Polylactic acid has good biocompatibility and biological degradability, has caused great concern and input as the research of materials such as slow releasing pharmaceutical carrier and tissue engineering bracket.The problem that exists as slow-release material is how to improve drug loading, how to obtain needed drug release rate, and how to prolong drug release time etc., these problems all with matrix material hydrophilic, hydrophobicity is relevant.In order to improve the hydrophilic of polylactic acid, manyly at present to regulate to introduce Polyethylene Glycol, the defective of this class material is that Polyethylene Glycol itself can not biodegrade, if long term in human body, will have unpredictable side effect.As timbering material, the hydrophobicity of polylactic acid has a strong impact on adhesiveness and the affinity of cell to timbering material.Beta-schardinger dextrin-is a starch decomposition products, not only has characteristics such as nontoxic, biodegradable absorption, cyclodextrin cavity can also with many molecule forming bag mixtures, institute's inclusion molecule is had slow release, Stabilization.Earlier beta-schardinger dextrin-is prepared into soluble prepolymer as main chain, again the lactide glycerol polymerization is got on to obtain the polylactic acid side chain, obtain amphipathic copolymer.The content of, hydrophobic component hydrophilic by regulating, can regulate copolymer degradation speed, therefore can expect that this amphipathic copolymer not only has totally biodegradable, nontoxic, advantage such as degradation rate is controlled as a kind of novel medicament delivery vehicles or tissue engineering bracket material, cyclodextrin cavity also has the envelope Stabilization to some drugs molecule, polypeptide etc.Therefore, the preparation of copolymer grafted by beta cyclodextrin lactide will provide a kind of novel bio-medical material, be expected at the medicine and pharmacology field and have important and wide application prospect.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing copolymer grafted by beta cyclodextrin lactide, particularly a kind of elder generation is prepared into soluble prepolymer with beta-schardinger dextrin-, again lactide graft copolymerization is got on, and with microwave heating pasty state copolymerization system, utilize polarity low boiling easy volatile solvent that the moisture content in the reaction system is taken out of fast, make water and the low boiling point solvent reaction system that after finishing heat transfer effect, speeds away, the new preparation method that glycerol polymerization is carried out, its feature comprises following process:
With beta-schardinger dextrin-, 10: 3～5: 15～25 mixing that sodium hydroxide and water are pressed mass ratio, feed way is: beta-schardinger dextrin-is added in the entry fully stir earlier, adding sodium hydroxide again stirs to make and is clear solution rapidly, 20 ℃～50 ℃ following stirring reactions 2～24 hours, be 1: 10～20 with epoxychloropropane by the mol ratio of beta-schardinger dextrin-and epoxychloropropane again, add reaction system and continued stirring reaction 2～6 hours, obtain the water soluble Beta-cyclodextrin performed polymer, microwave heating concentrates, add proper amount of acetone again and be diluted to pasty state, adding lactide fully stirs, utilize microwave that the pasty state reaction system is carried out irradiated heat, stir, gained solid water dissolution filter with the oxolane precipitation, is drying to obtain lactide copolymer grafted by beta cyclodextrin.The microwave exposure frequency is 2450MHZ.Microwave power is 70～700 watts.
The invention has the advantages that: with microwave heating pasty state copolymerization system, utilize polarity low boiling easy volatile solvent that the moisture content in the reaction system is taken out of fast, make water and the low boiling point solvent reaction system that after finishing heat transfer effect, speeds away, thereby glycerol polymerization is carried out, with compare with the conventional method of microwave heating solution reaction system, it is simple to have technology, characteristics such as efficient energy-saving.
This research obtains grant of national natural science foundation (project approval number 50563002)
The specific embodiment
With embodiment the present invention is illustrated below.
Embodiment 1: 20 gram beta-schardinger dextrin-s are added in 50 ml deionized water, and thermal agitation makes rapid dispersion, adds 6 gram sodium hydroxide and stirs, and makes to be dissolved as clear solution rapidly.Room temperature (30 ℃) electromagnetic agitation reaction 3 hours, added 20 milliliters of epoxychloropropane room temperature electromagnetic agitation 2 hours, used microwave heating, stirring, reaction instead 3 minutes, reaction system concentrates, the reuse acetone diluted becomes pasty state, adds 3 gram lactides and fully stirs, microwave heating, stirring, reaction 90 seconds, obtain white solid, the water dissolution filter, obtain required product with oxolane precipitation.Infrared spectrum analysis is at 1740CM
-1Near carbonyl characteristic absorption from lactide is arranged, at 580CM
-1Near characteristic absorption from cyclodextrin is arranged, all the other are evident as the stack (seeing accompanying drawing 1) that two components absorb.
Embodiment 2: 20 gram beta-schardinger dextrin-s are added in 50 ml deionized water, and thermal agitation makes rapid dispersion, adds 6 gram sodium hydroxide and stirs, and makes to be dissolved as clear solution rapidly.50 ℃ of electromagnetic agitation were reacted 1.5 hours, added 50 ℃ of electromagnetic agitation of 20 milliliters of epoxychloropropane 1 hour, used microwave heating, stirring, reaction instead 90 seconds, reaction system concentrates, and the reuse acetone diluted becomes pasty state, adds 10 gram lactides and fully stirs, microwave heating, stirring, reaction 90 seconds, reaction system is molten, stir solidify white solid, the water dissolution filter, obtain required product with the oxolane precipitation.Infrared spectrum analysis is at 1740CM
-1Near carbonyl characteristic absorption from lactide is arranged, at 580CM
-1Near characteristic absorption from cyclodextrin is arranged, all the other are evident as the stack (seeing accompanying drawing 2) that two components absorb.
Claims (4)
1, a kind of method for preparing lactide copolymer grafted by beta cyclodextrin, it is characterized in that: beta-schardinger dextrin-, sodium hydroxide and water are pressed mass ratio 10: 3～5: 15～25 mix, make and be dissolved as clear solution rapidly, 20 ℃～50 ℃ following stirring reactions 2～24 hours, be 1: 10～20 with epoxychloropropane by the mol ratio of beta-schardinger dextrin-and epoxychloropropane again, add reaction system and continued stirring reaction 2～6 hours, obtain water solublity beta-schardinger dextrin-performed polymer.Microwave heating concentration response system, add proper amount of acetone diluting reaction system again to pasty state, adding lactide then fully stirs, utilize microwave that reaction system is carried out irradiated heat, stirring, the gained solid is with water dissolution, filtration, with the oxolane precipitation, and it is lactide copolymer grafted to filter, be drying to obtain cyclodextrin.
2, " beta-schardinger dextrin-, sodium hydroxide and water are mixed by mass ratio 10: 3～5: 15～25 " according to claim 1, it is characterized in that: the feed way during mixing is, earlier cyclodextrin is added in the entry and fully stir, add sodium hydroxide again and stir to make and be clear solution rapidly.
3, method according to claim 1 is characterized in that: the microwave exposure frequency is 2450MHZ.
4, method according to claim 1 is characterized in that: described microwave power is 70～700 watts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101043875A CN100496612C (en) | 2007-05-11 | 2007-05-11 | Method for synthesizing lactide copolymer grafted by beta cyclodextrin |
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| CNB2007101043875A CN100496612C (en) | 2007-05-11 | 2007-05-11 | Method for synthesizing lactide copolymer grafted by beta cyclodextrin |
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| CN101091796A true CN101091796A (en) | 2007-12-26 |
| CN100496612C CN100496612C (en) | 2009-06-10 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102926277A (en) * | 2012-11-14 | 2013-02-13 | 湖南中烟工业有限责任公司 | Application of Beta-cyclodextrin-g-lactic acid copolymer |
| CN102987564A (en) * | 2012-12-12 | 2013-03-27 | 湖南中烟工业有限责任公司 | Cigarette filtering rod additive for reducing content of ammonia in mainstream smoke as well preparation method and application thereof |
| CN105602543A (en) * | 2015-10-22 | 2016-05-25 | 中国石油化工股份有限公司 | Acid fracturing temporary plugging agent and preparation method thereof |
| CN105924658A (en) * | 2016-05-09 | 2016-09-07 | 南京科技职业学院 | Method for preparing crosslinking cyclodextrin polymer material through microwave assisting |
| CN108329660A (en) * | 2017-01-20 | 2018-07-27 | 深圳市虹彩新材料科技有限公司 | Grafted by beta cyclodextrin object and its preparation method and application |
| CN108619574A (en) * | 2018-06-05 | 2018-10-09 | 佛山皖阳生物科技有限公司 | A kind of preparation method of high-adhesiveness nano bone repair hydrogel material |
-
2007
- 2007-05-11 CN CNB2007101043875A patent/CN100496612C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102926277A (en) * | 2012-11-14 | 2013-02-13 | 湖南中烟工业有限责任公司 | Application of Beta-cyclodextrin-g-lactic acid copolymer |
| CN102926277B (en) * | 2012-11-14 | 2015-05-20 | 湖南中烟工业有限责任公司 | Application of Beta-cyclodextrin-g-lactic acid copolymer |
| CN102987564A (en) * | 2012-12-12 | 2013-03-27 | 湖南中烟工业有限责任公司 | Cigarette filtering rod additive for reducing content of ammonia in mainstream smoke as well preparation method and application thereof |
| CN102987564B (en) * | 2012-12-12 | 2014-04-16 | 湖南中烟工业有限责任公司 | Cigarette filtering rod additive for reducing content of ammonia in mainstream smoke as well preparation method and application thereof |
| CN105602543A (en) * | 2015-10-22 | 2016-05-25 | 中国石油化工股份有限公司 | Acid fracturing temporary plugging agent and preparation method thereof |
| CN105602543B (en) * | 2015-10-22 | 2020-11-06 | 中国石油化工股份有限公司 | Acid fracturing temporary plugging agent and preparation method thereof |
| CN105924658A (en) * | 2016-05-09 | 2016-09-07 | 南京科技职业学院 | Method for preparing crosslinking cyclodextrin polymer material through microwave assisting |
| CN105924658B (en) * | 2016-05-09 | 2018-08-17 | 南京科技职业学院 | A kind of method that microwave radiation technology prepares cross linked ciclodextrines polymer material |
| CN108329660A (en) * | 2017-01-20 | 2018-07-27 | 深圳市虹彩新材料科技有限公司 | Grafted by beta cyclodextrin object and its preparation method and application |
| CN108619574A (en) * | 2018-06-05 | 2018-10-09 | 佛山皖阳生物科技有限公司 | A kind of preparation method of high-adhesiveness nano bone repair hydrogel material |
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| Publication number | Publication date |
|---|---|
| CN100496612C (en) | 2009-06-10 |
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