CN105694061A - Method for preparing polyving akohol-polycaprolactone-poly trimethylene carbonate-poly(p-dioxanone) ternary graft copolymer - Google Patents

Method for preparing polyving akohol-polycaprolactone-poly trimethylene carbonate-poly(p-dioxanone) ternary graft copolymer Download PDF

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Publication number
CN105694061A
CN105694061A CN201610118882.0A CN201610118882A CN105694061A CN 105694061 A CN105694061 A CN 105694061A CN 201610118882 A CN201610118882 A CN 201610118882A CN 105694061 A CN105694061 A CN 105694061A
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Prior art keywords
polycaprolactone
polyvinyl alcohol
ptmc
ppdo
poly
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CN201610118882.0A
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Chinese (zh)
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朱国全
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Shandong University of Technology
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Shandong University of Technology
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Priority to CN201610118882.0A priority Critical patent/CN105694061A/en
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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
    • 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
    • C08G2230/00—Compositions for preparing biodegradable polymers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention discloses a method for preparing a polyving akohol-polycaprolactone-poly trimethylene carbonate-poly(p-dioxanone) ternary graft copolymer. The method comprises the steps of adding polyving akohol, carboxyl end capped polycaprolactone mono dodecyl ether, carboxyl end capped poly trimethylene carbonate mono undecyl ether, carboxyl end capped poly(p-dioxanone) mono tridecyl ether, solvent and condensing agent into a dry reactor for stirring reaction lasting 2-4 days at 31-34 DEG C in the inert atmosphere, stopping reaction, and obtaining the target product through filtration, dialysis and drying. The preparing process is simple and easy to grasp, and the target product is a novel degradable biological material.

Description

A kind of preparation method of polyvinyl alcohol-polycaprolactone-PTMC-PPDO three graft copolymer
Technical field
The preparation method that the present invention relates to a kind of polyvinyl alcohol-polycaprolactone-PTMC-PPDO three graft copolymer, belongs to biodegradated polymer materal preparing technical field。
Background technology
Polyvinyl alcohol is a kind of biomaterial with good biocompatibility and biodegradability, has excellent hydrophilic, in medicine extensive application。Polycaprolactone, PTMC and PPDO are to have the biomaterial of excellent biocompatibility and biodegradability, have good hydrophobicity, are widely used at medicine。Polyvinyl alcohol-polycaprolactone-PTMC-PPDO three graft copolymer set that to be grafted on polyvinyl alcohol molecule chain by polycaprolactone segment, PTMC segment and PPDO segment obtained simultaneously advantage of polyvinyl alcohol, polycaprolactone, PTMC and PPDO, it is a kind of there is amphipathic novel degradable biomaterial, certainly will have a good application prospect in preparing sustained-release drug carrier。
Summary of the invention
It is an object of the invention to provide a kind of simple to operate and good polyvinyl alcohol-polycaprolactone-PTMC-PPDO three graft copolymer of effect preparation method。Its technical scheme is:
A kind of preparation method of polyvinyl alcohol-polycaprolactone-PTMC-PPDO three graft copolymer, it is characterized in that: in copolymer, the molecular weight of polyvinyl alcohol segments is 45000～52000, the molecular weight of polycaprolactone segment is 2300～2600, the molecular weight of PTMC segment is 2300～2600, and the molecular weight of PPDO segment is 2300～2600；Its preparation method is as follows:
Polyvinyl alcohol, the polycaprolactone monododecyl ether of carboxy blocking, the PTMC list undecyl ether of carboxy blocking, the PPDO list tridecyl ether of carboxy blocking, solvent and condensing agent is added in dry reactor, under inert atmosphere, in 31～34 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialyse, drying, obtain object。
The preparation method of described a kind of polyvinyl alcohol-polycaprolactone-PTMC-PPDO three graft copolymer, the mol ratio of polycaprolactone monododecyl ether and polyvinyl alcohol is 15～25:1, the mol ratio of PTMC list undecyl ether and polyvinyl alcohol is 15～25:1, and the mol ratio of PPDO list tridecyl ether and polyvinyl alcohol is 15～25:1。
The preparation method of described a kind of polyvinyl alcohol-polycaprolactone-PTMC-PPDO three graft copolymer, condensing agent adoptsN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, the mol ratio of condensing agent and polyvinyl alcohol is 1.07～1.9:1, and solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15g:100ml。
Compared with prior art, its advantage is the present invention:
1, the preparation method of described a kind of polyvinyl alcohol-polycaprolactone-PTMC-PPDO three graft copolymer, adopts a kind of polymer and three kinds of different polymeric monomer to carry out the means of esterification simultaneously, simple to operate, be prone to grasp；
2, described a kind of polyvinyl alcohol-polycaprolactone-PTMC-PPDO three graft copolymer is a kind of novel degradable biomaterial。
Detailed description of the invention
Embodiment 1
The PPDO list tridecyl ether (molecular weight is 2300) of 12.2 grams of polyvinyl alcohol (molecular weight is 45000), the polycaprolactone monododecyl ether (molecular weight is 2300) of 11.3 grams of carboxy blockings, the PTMC list undecyl ether (molecular weight is 2300) of 11.2 grams of carboxy blockings and 11.2 grams of carboxy blockings is added at dry reactor, add 422ml dimethyl sulfoxide, add 0.074 gramN,N’-dicyclohexylcarbodiimide, under inert atmosphere, in 31 DEG C of stirring reactions 2 days, terminates reaction, by filtering, dialysis, dry, obtains object。
Embodiment 2
The PPDO list tridecyl ether (molecular weight is 2400) of 13.2 grams of polyvinyl alcohol (molecular weight is 48000), the polycaprolactone monododecyl ether (molecular weight is 2400) of 11.8 grams of carboxy blockings, the PTMC list undecyl ether (molecular weight is 2400) of 11.8 grams of carboxy blockings and 11.8 grams of carboxy blockings is added at dry reactor, add 443ml dimethyl sulfoxide, add 0.045 gramN,N’-DIC, under inert atmosphere, in 32 DEG C of stirring reactions 3 days, terminates reaction, by filtering, dialysis, dry, obtains object。
Embodiment 3
14.1 grams of polyvinyl alcohol (molecular weight is 52000) are added at dry reactor, 12.8 the polycaprolactone monododecyl ether of gram carboxy blocking (molecular weight is 2600), 12.8 the PPDO list tridecyl ether (molecular weight is 2600) of the PTMC list undecyl ether (molecular weight is 2600) of gram carboxy blocking and 12.8 grams of carboxy blockings, add 462ml dimethyl sulfoxide, add 0.066 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, in 34 DEG C of stirring reactions 4 days, terminate reaction, by filtering, dialysis, dry, obtain object。

Claims (3)

1. the preparation method of polyvinyl alcohol-polycaprolactone-PTMC-PPDO three graft copolymer, it is characterized in that: in copolymer, the molecular weight of polyvinyl alcohol segments is 45000～52000, the molecular weight of polycaprolactone segment is 2300～2600, the molecular weight of PTMC segment is 2300～2600, and the molecular weight of PPDO segment is 2300～2600；Its preparation method is as follows:
Polyvinyl alcohol, the polycaprolactone monododecyl ether of carboxy blocking, the PTMC list undecyl ether of carboxy blocking, the PPDO list tridecyl ether of carboxy blocking, solvent and condensing agent is added in dry reactor, under inert atmosphere, in 31～34 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialyse, drying, obtain object。
2. the preparation method of a kind of polyvinyl alcohol-polycaprolactone-PTMC-PPDO three graft copolymer according to claim 1, it is characterized in that: the mol ratio of polycaprolactone monododecyl ether and polyvinyl alcohol is 15～25:1, the mol ratio of PTMC list undecyl ether and polyvinyl alcohol is 15～25:1, and the mol ratio of PPDO list tridecyl ether and polyvinyl alcohol is 15～25:1。
3. the preparation method of a kind of polyvinyl alcohol-polycaprolactone-PTMC-PPDO three graft copolymer according to claim 1, it is characterised in that: condensing agent adoptsN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, the mol ratio of condensing agent and polyvinyl alcohol is 1.07～1.9:1, and solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15g:100ml。
CN201610118882.0A 2016-03-03 2016-03-03 Method for preparing polyving akohol-polycaprolactone-poly trimethylene carbonate-poly(p-dioxanone) ternary graft copolymer Pending CN105694061A (en)

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CN201610118882.0A CN105694061A (en) 2016-03-03 2016-03-03 Method for preparing polyving akohol-polycaprolactone-poly trimethylene carbonate-poly(p-dioxanone) ternary graft copolymer

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CN201610118882.0A CN105694061A (en) 2016-03-03 2016-03-03 Method for preparing polyving akohol-polycaprolactone-poly trimethylene carbonate-poly(p-dioxanone) ternary graft copolymer

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106987007A (en) * 2017-05-25 2017-07-28 山东理工大学 A kind of method for preparing polyacrylic acid PPDO polycaprolactone PTMC copolymer micelle

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080107744A1 (en) * 2006-11-06 2008-05-08 Jack Fa-De Chu Injectable hollow tissue filler
CN102482461A (en) * 2009-05-19 2012-05-30 瓦克化学股份公司 Bioplastics
CN103054809A (en) * 2011-12-22 2013-04-24 苏州雷纳药物研发有限公司 Curcumin-particle-containing sustained-release microsphere with high medicament loading capacity as well as preparation method and application thereof
CN103881398A (en) * 2014-03-24 2014-06-25 山东理工大学 Method for improving water resistance of polyvinyl alcohol film by using poly(trimethylene carbonate) and poly(p-dioxanone)
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080107744A1 (en) * 2006-11-06 2008-05-08 Jack Fa-De Chu Injectable hollow tissue filler
CN102482461A (en) * 2009-05-19 2012-05-30 瓦克化学股份公司 Bioplastics
CN103054809A (en) * 2011-12-22 2013-04-24 苏州雷纳药物研发有限公司 Curcumin-particle-containing sustained-release microsphere with high medicament loading capacity as well as preparation method and application thereof
CN103881398A (en) * 2014-03-24 2014-06-25 山东理工大学 Method for improving water resistance of polyvinyl alcohol film by using poly(trimethylene carbonate) and poly(p-dioxanone)
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106987007A (en) * 2017-05-25 2017-07-28 山东理工大学 A kind of method for preparing polyacrylic acid PPDO polycaprolactone PTMC copolymer micelle

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Application publication date: 20160622