CN105566648A - Method for preparing polyving akohol-polycaprolactone-polypeptide double graft copolymer - Google Patents
Method for preparing polyving akohol-polycaprolactone-polypeptide double graft copolymer Download PDFInfo
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- CN105566648A CN105566648A CN201610118880.1A CN201610118880A CN105566648A CN 105566648 A CN105566648 A CN 105566648A CN 201610118880 A CN201610118880 A CN 201610118880A CN 105566648 A CN105566648 A CN 105566648A
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- polycaprolactone
- polyvinyl alcohol
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- peptide
- graft copolymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Organic Chemistry (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
The invention discloses a method for preparing a polyving akohol-polycaprolactone-polypeptide double graft copolymer, comprising the following steps of 1) preparation of a polyving akohol-polycaprolactone graft copolymer: adding polyving akohol, carboxyl terminated polycaprolactone mono lauryl ethers, solvents and condensing agents in a drying reactor, reacting for 2-4 days by stirring at 26-34 DEG C in the inert atmosphere, stopping the reaction, and filtering, dialyzing and drying to obtain a target object; 2) preparation of the polyving akohol-polycaprolactone-polypeptide double graft copolymer: adding the polyving akohol-polycaprolactone graft copolymer, carboxyl terminated polypeptide homopolymers, solvents and condensing agents in the drying reactor, reacting for 2-4 days by stirring at 25-30 DEG C in the inert atmosphere, stopping the reaction, and filtering, dialyzing and drying to obtain the target object. The method preparing the polyving akohol-polycaprolactone-polypeptide double graft copolymer is simple in process and easy to master, and the obtained target object is a novel degradable biological material.
Description
Technical field
The present invention relates to a kind of method preparing polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer, belong to biodegradated polymer materal preparing technical field.
Background technology
Polyvinyl alcohol a kind ofly has good biocompatibility and the biomaterial of biodegradability, has excellent wetting ability, be widely used in medicine and pharmacology aspect.Polycaprolactone and poly-peptide have excellent biocompatibility and the biomaterial of biodegradability, all has good hydrophobicity, have a wide range of applications at medicine.First polycaprolactone segment is grafted on polyvinyl alcohol molecule chain and obtains polyvinyl alcohol-polycaprolactone graft copolymer, again poly-peptide segment is grafted to the advantage of polyvinyl alcohol-polycaprolactone that the polyvinyl alcohol segments in polyvinyl alcohol-polycaprolactone graft copolymer obtains-poly-peptide dual graft multipolymer set polyvinyl alcohol, polycaprolactone and poly-peptide three, be a kind of there is amphipathic novel degradable biomaterial, preparing in sustained-release drug carrier and certainly will have a good application prospect.
Summary of the invention
A kind of simple to operate and effect is the object of the present invention is to provide to prepare the method for polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer preferably.Its technical scheme is:
A kind of method preparing polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer, it is characterized in that: in multipolymer, the molecular weight of polyvinyl alcohol segments is 41000 ~ 51000, the molecular weight of polycaprolactone segment is 2400 ~ 2600, and the molecular weight of poly-peptide segment is 2000 ~ 2300; Its preparation method adopts following steps:
1) preparation of polyvinyl alcohol-polycaprolactone graft copolymer: add polyvinyl alcohol, the polycaprolactone monododecyl ether of carboxy blocking, solvent and condensing agent in dry reactor, under inert atmosphere, in 26 ~ 34 DEG C of stirring reactions 2 ~ 4 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) preparation of polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer: add polyvinyl alcohol-polycaprolactone graft copolymer, the poly-peptide homopolymer of carboxy blocking, solvent and condensing agent in dry reactor, under inert atmosphere, in 25 ~ 30 DEG C of stirring reactions 2 ~ 4 days, termination reaction, by filtration, dialysis, drying, obtain target compound.
A kind of described method preparing polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer, in step 1), the mol ratio of polycaprolactone monododecyl ether and polyvinyl alcohol is 15 ~ 25:1.
A kind of described method preparing polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer, in step 1), condensing agent adopts
n, N '-dicyclohexylcarbodiimide,
n, N '-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, the mol ratio of condensing agent and polyvinyl alcohol is 1.07 ~ 1.8:1, and solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15g:100ml.
A kind of described method preparing polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer, step 2) in, gather peptide homopolymer and adopt poly-(r-phenmethyl-Pidolidone ester), poly-(r-ethyl-L-glutamate ester) or poly-(r-methyl-Pidolidone ester), the mol ratio of gathering polyvinyl alcohol segments in peptide homopolymer and polyvinyl alcohol-polycaprolactone graft copolymer is 15 ~ 25:1.
A kind of described method preparing polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer, step 2) in, condensing agent adopts
n, N '-dicyclohexylcarbodiimide,
n, N '-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, in condensing agent and polyvinyl alcohol-polycaprolactone graft copolymer, the mol ratio of polyvinyl alcohol segments is 1.07 ~ 1.8:1, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15g:100ml.
Compared with prior art, its advantage is in the present invention:
1, a kind of described method preparing polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer, adopts the means of two step esterifications, simple to operate, be easy to grasp;
2, described a kind of polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer is a kind of novel degradable biomaterial.
Embodiment
embodiment 1
1) preparation of polyvinyl alcohol-polycaprolactone graft copolymer
In dry reactor, add the polycaprolactone monododecyl ether (molecular weight is 2400) of 12.1 grams of polyvinyl alcohol (molecular weight is 41000), 13.1 grams of carboxy blockings, add 241 milliliters of dimethyl sulfoxide (DMSO), then add 0.075 gram
n, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 26 DEG C of stirring reactions 2 days, termination reaction, by filtering, dialysis, dry, obtains target compound;
2) preparation of polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer
In dry reactor, add poly-(r-phenmethyl-Pidolidone ester) (molecular weight is 2000) of 10 grams of polyvinyl alcohol-polycaprolactone graft copolymer, 8.8 grams of carboxy blockings, add 187 milliliters of dimethyl sulfoxide (DMSO), then add 0.061 gram
n, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 25 DEG C of stirring reactions 2 days, termination reaction, by filtering, dialysis, dry, obtains target compound.
embodiment 2
1) preparation of polyvinyl alcohol-polycaprolactone graft copolymer
In dry reactor, add the polycaprolactone monododecyl ether (molecular weight is 2500) of 12.3 grams of polyvinyl alcohol (molecular weight is 46000), 12.5 grams of carboxy blockings, add 245 milliliters of dimethyl sulfoxide (DMSO), then add 0.042 gram
n, N '-DIC, under inert atmosphere, in 30 DEG C of stirring reactions 3 days, termination reaction, by filtering, dialysis, dry, obtains target compound;
2) preparation of polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer
In dry reactor, add poly-(r-ethyl-L-glutamate ester) (molecular weight is 2200) of 10.2 grams of polyvinyl alcohol-polycaprolactone graft copolymer, 9.1 grams of carboxy blockings, add 194 milliliters of dimethyl sulfoxide (DMSO), then add 0.035 gram
n, N '-DIC, under inert atmosphere, in 28 DEG C of stirring reactions 3 days, termination reaction, by filtering, dialysis, dry, obtains target compound.
embodiment 3
1) preparation of polyvinyl alcohol-polycaprolactone graft copolymer
The polycaprolactone monododecyl ether (molecular weight is 2600) of 12.4 grams of polyvinyl alcohol (molecular weight is 51000), 11.6 grams of carboxy blockings is added in dry reactor, add 239 milliliters of dimethyl sulfoxide (DMSO), add 0.057 gram of 3-ethyl-1-(3-dimethylaminopropyl again) carbodiimide, under inert atmosphere, in 34 DEG C of stirring reactions 4 days, termination reaction, by filtration, dialysis, drying, obtains target compound;
2) preparation of polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer
Poly-(r-methyl-Pidolidone ester) (molecular weight is 2300) of 10.2 grams of polyvinyl alcohol-polycaprolactone graft copolymer, 8.5 grams of carboxy blockings is added in dry reactor, add 186 milliliters of dimethyl sulfoxide (DMSO), add 0.046 gram of 3-ethyl-1-(3-dimethylaminopropyl again) carbodiimide, under inert atmosphere, in 30 DEG C of stirring reactions 4 days, termination reaction, by filtration, dialysis, drying, obtains target compound.
Claims (5)
1. prepare the method for polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer for one kind, it is characterized in that: in multipolymer, the molecular weight of polyvinyl alcohol segments is 41000 ~ 51000, the molecular weight of polycaprolactone segment is 2400 ~ 2600, and the molecular weight of poly-peptide segment is 2000 ~ 2300; Its preparation method adopts following steps:
1) preparation of polyvinyl alcohol-polycaprolactone graft copolymer: add polyvinyl alcohol, the polycaprolactone monododecyl ether of carboxy blocking, solvent and condensing agent in dry reactor, under inert atmosphere, in 26 ~ 34 DEG C of stirring reactions 2 ~ 4 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) preparation of polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer: add polyvinyl alcohol-polycaprolactone graft copolymer, the poly-peptide homopolymer of carboxy blocking, solvent and condensing agent in dry reactor, under inert atmosphere, in 25 ~ 30 DEG C of stirring reactions 2 ~ 4 days, termination reaction, by filtration, dialysis, drying, obtain target compound.
2. a kind of method preparing polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer according to claim 1, it is characterized in that: in step 1), the mol ratio of polycaprolactone monododecyl ether and polyvinyl alcohol is 15 ~ 25:1.
3. a kind of method preparing polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer according to claim 1, it is characterized in that: in step 1), condensing agent adopts
n, N '-dicyclohexylcarbodiimide,
n, N '-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, the mol ratio of condensing agent and polyvinyl alcohol is 1.07 ~ 1.8:1, and solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15g:100ml.
4. a kind of method preparing polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer according to claim 1, it is characterized in that: step 2) in, gather peptide homopolymer and adopt poly-(r-phenmethyl-Pidolidone ester), poly-(r-ethyl-L-glutamate ester) or poly-(r-methyl-Pidolidone ester), the mol ratio of gathering polyvinyl alcohol segments in peptide homopolymer and polyvinyl alcohol-polycaprolactone graft copolymer is 15 ~ 25:1.
5. a kind of method preparing polyvinyl alcohol-polycaprolactone-poly-peptide dual graft multipolymer according to claim 1, is characterized in that: step 2) in, condensing agent adopts
n, N '-dicyclohexylcarbodiimide,
n, N '-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, in condensing agent and polyvinyl alcohol-polycaprolactone graft copolymer, the mol ratio of polyvinyl alcohol segments is 1.07 ~ 1.8:1, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15g:100ml.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107033605A (en) * | 2017-05-22 | 2017-08-11 | 山东理工大学 | A kind of method being improved with MPEGPLA and polycaprolactone to polypropylene sorrel water resistance and compliance |
Citations (3)
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CN102181060A (en) * | 2011-03-20 | 2011-09-14 | 山东理工大学 | Polyvinyl alcohol-polypeptide-polyethylene glycol graft copolymer and preparation method thereof |
CN103601878A (en) * | 2013-11-25 | 2014-02-26 | 沈阳药科大学 | High-stability polyethylene glycol-polyester polymer and application thereof |
CN103937269A (en) * | 2014-03-24 | 2014-07-23 | 山东理工大学 | Method for modifying water proofness of polyvinyl alcohol membrane by polypeptide and polycaprolactone |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102181060A (en) * | 2011-03-20 | 2011-09-14 | 山东理工大学 | Polyvinyl alcohol-polypeptide-polyethylene glycol graft copolymer and preparation method thereof |
CN103601878A (en) * | 2013-11-25 | 2014-02-26 | 沈阳药科大学 | High-stability polyethylene glycol-polyester polymer and application thereof |
CN103937269A (en) * | 2014-03-24 | 2014-07-23 | 山东理工大学 | Method for modifying water proofness of polyvinyl alcohol membrane by polypeptide and polycaprolactone |
Non-Patent Citations (1)
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周嘉嘉 等: "两亲多糖纳米胶束作为药物缓释载体的制备及释药研究", 《中山大学学报(医学科学版)》 * |
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CN107033605A (en) * | 2017-05-22 | 2017-08-11 | 山东理工大学 | A kind of method being improved with MPEGPLA and polycaprolactone to polypropylene sorrel water resistance and compliance |
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Application publication date: 20160511 |