CN105778113A - Method for preparing polyvinyl alcohol-polycaprolactone-poly trimethylene carbonate double-grafted copolymer micelle - Google Patents
Method for preparing polyvinyl alcohol-polycaprolactone-poly trimethylene carbonate double-grafted copolymer micelle Download PDFInfo
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- CN105778113A CN105778113A CN201610140622.3A CN201610140622A CN105778113A CN 105778113 A CN105778113 A CN 105778113A CN 201610140622 A CN201610140622 A CN 201610140622A CN 105778113 A CN105778113 A CN 105778113A
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- polyvinyl alcohol
- polycaprolactone
- graft copolymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/097—Sulfur containing compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/10—Dispersions; Emulsions
- A61K9/107—Emulsions ; Emulsion preconcentrates; Micelles
- A61K9/1075—Microemulsions or submicron emulsions; Preconcentrates or solids thereof; Micelles, e.g. made of phospholipids or block copolymers
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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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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The invention discloses a method for preparing a method for preparing a polyvinyl alcohol-polycaprolactone-poly trimethylene carbonate double-grafted copolymer micelle. The method comprises the following steps: (1) adding polyvinyl alcohol, carboxyl-terminated polycaprolactone monodod ecyl ether, a solvent and a condensing agent into a reactor, and reacting to obtain polyvinyl alcohol-polycaprolactone grafted copolymer; (2) adding the grafted copolymer, carboxyl-terminated poly trimethylene carbonate mono(tridecyl) ether, the solvent and the condensing agent into the reactor, and reacting to obtain a polyvinyl alcohol-polycaprolactone-poly trimethylene carbonate double-grafted copolymer; (3) adding the double-grafted copolymer and the solvent into the reactor, and dissolving to obtain a polyvinyl alcohol-polycaprolactone-poly trimethylene carbonate double-grafted copolymer stock solution; (4) adding the stock solution into a dialysis bag, placing the dialysis bag into a beaker which contains a selective solvent, conducting displacement for 3 to 4 times, pouring the solution into a volumetric flask with scales, and regulating the solution to the scale to obtain a target object disclosed by the invention. The method is simple in preparation process, and is easy to master; the obtained target object is a novel medicinal carrier.
Description
Technical field
The present invention relates to a kind of method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle, belong to biodegradated polymer materal preparing technical field.
Background technology
Polyvinyl alcohol is a kind of biomaterial with good biocompatibility and biodegradability, has excellent hydrophily, is widely used in medicine and pharmacology aspect.Polycaprolactone and PTMC are the biomaterials with excellent biocompatibility and biodegradability, all have good hydrophobicity, have a wide range of applications at medicine.First it is grafted to polycaprolactone segment on polyvinyl alcohol molecule chain obtain polyvinyl alcohol-polycaprolactone graft copolymer, polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer obtained by being grafted to by PTMC segment again in the polyvinyl alcohol segments in polyvinyl alcohol-polycaprolactone graft copolymer has amphipathic, micella can be self-assembly of in selective solvent, it is a kind of novel pharmaceutical carrier, has broad application prospects in terms of the difficult and complicated cases such as treatment cancer.
Summary of the invention
It is an object of the invention to provide the method that a kind of simple to operate and effect preferably prepares polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle.Its technical scheme is:
A kind of method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle, it is characterized in that: in copolymer, the molecular weight of polyvinyl alcohol segments is 46000～52000, the molecular weight of polycaprolactone segment is 2600～2700, and the molecular weight of PTMC segment is 2100～2400；Its preparation method employing following steps:
1) preparation of polyvinyl alcohol-polycaprolactone graft copolymer: add polyvinyl alcohol, polycaprolactone monododecyl ether, solvent and the condensing agent of carboxy blocking in dry reactor, under inert atmosphere, in 28～34 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialysing, it is dried, obtains object；
2) preparation of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer: add polyvinyl alcohol-polycaprolactone graft copolymer, PTMC list tridecyl ether, solvent and the condensing agent of carboxy blocking in dry reactor, under inert atmosphere, in 27～35 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialysing, it is dried, obtains object；
3) preparation of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer stoste: add polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer and solvent in dry reactor, in 48～52 DEG C of stirring and dissolving 50～60 minutes, obtain object；
4) preparation of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle: under room temperature, stoste is added in bag filter, put it in the 500 milliliters of beakers filling selective solvent, every displacement in 7 hours once, replace 3～4 times, solution display blue light in bag filter, be then poured in the graduated volumetric flask of band, it is adjusted to scale with selective solvent, obtains object.
A kind of described method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle, in step 1), polycaprolactone monododecyl ether is 15～25:1 with the mol ratio of polyvinyl alcohol.
A kind of described method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle, in step 1), condensing agent usesN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, condensing agent is 1.08～1.8:1 with the mol ratio of polyvinyl alcohol, and solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15 g/100 ml.
A kind of described method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle, step 2) in, PTMC list tridecyl ether is 15～25:1 with the mol ratio of polyvinyl alcohol segments in polyvinyl alcohol-polycaprolactone graft copolymer.
A kind of described method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle, step 2) in, condensing agent usesN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, condensing agent is 1.07～1.8:1 with the mol ratio of polyvinyl alcohol segments in polyvinyl alcohol-polycaprolactone graft copolymer, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15 g/100 ml.
A kind of described method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle, in step 3), solvent uses dimethyl sulfoxide (DMSO), and original liquid concentration is 1～1.5 mg/ml.
A kind of described method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle, in step 4), bag filter capacity is 5～10 ml, and bag filter molecular cut off is 3500～4000, selective solvent uses distilled water, and solution concentration is 0.1～0.3 mg/ml.
Compared with prior art, its advantage is the present invention:
1, a kind of described method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle, uses the means that two step esterifications and dialysis combine, simple to operate, be prone to grasp；
2, described a kind of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle is a kind of novel pharmaceutical carrier.
Detailed description of the invention
Embodiment
1
1) preparation of polyvinyl alcohol-polycaprolactone graft copolymer
In dry reactor, add 12.2 grams of polyvinyl alcohol (molecular weight is 46000), the polycaprolactone monododecyl ether (molecular weight is 2600) of 12.6 grams of carboxy blockings, add 241 milliliters of dimethyl sulfoxide (DMSO)s, add 0.073 gramN,N’-dicyclohexylcarbodiimide, under inert atmosphere, in 28 DEG C of stirring reactions 2 days, terminates reaction, by filtering, dialysing, is dried, obtains object；
2) preparation of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer
In dry reactor, add 10 grams of polyvinyl alcohol-polycaprolactone graft copolymers, the PTMC list tridecyl ether (molecular weight is 2100) of 8.5 grams of carboxy blockings, add 182 milliliters of dimethyl sulfoxide (DMSO)s, add 0.056 gramN,N’-dicyclohexylcarbodiimide, under inert atmosphere, in 27 DEG C of stirring reactions 2 days, terminates reaction, by filtering, dialysing, is dried, obtains object；
3) preparation of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer stoste
In dry reactor, add 120 milligrams of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymers and 100 milliliters of dimethyl sulfoxide (DMSO)s, in 48 DEG C of stirring and dissolving 50 minutes, obtain object；
4) preparation of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle
Under room temperature, 1 milliliter of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer stoste is added in the bag filter of 5 milliliters of capacity (molecular cut off is 3500), put it in the 500 milliliters of beakers filling distilled water, every displacement in 7 hours once, replace 3 times, solution display blue light in bag filter, be then poured in the graduated 10 milliliters of volumetric flasks of band, it is adjusted to scale with distilled water, obtains object.
Embodiment
2
1) preparation of polyvinyl alcohol-polycaprolactone graft copolymer
In dry reactor, add 12.3 grams of polyvinyl alcohol (molecular weight is 48000), the polycaprolactone monododecyl ether (molecular weight is 2600) of 12.5 grams of carboxy blockings, add 240 milliliters of dimethyl sulfoxide (DMSO)s, add 0.041 gramN,N’-DIC, under inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminates reaction, by filtering, dialysing, is dried, obtains object；
2) preparation of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer
In dry reactor, add 10.2 grams of polyvinyl alcohol-polycaprolactone graft copolymers, the PTMC list tridecyl ether (molecular weight is 2200) of 8.5 grams of carboxy blockings, add 184 milliliters of dimethyl sulfoxide (DMSO)s, add 0.034 gramN,N’-DIC, under inert atmosphere, in 31 DEG C of stirring reactions 3 days, terminates reaction, by filtering, dialysing, is dried, obtains object；
3) preparation of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer stoste
In dry reactor, add 130 milligrams of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymers and 100 milliliters of dimethyl sulfoxide (DMSO)s, in 50 DEG C of stirring and dissolving 55 minutes, obtain object；
4) preparation of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle
Under room temperature, 1 milliliter of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer stoste is added in the bag filter of 6 milliliters of capacity (molecular cut off is 3700), put it in the 500 milliliters of beakers filling distilled water, every displacement in 7 hours once, replace 4 times, solution display blue light in bag filter, be then poured in the graduated 10 milliliters of volumetric flasks of band, it is adjusted to scale with distilled water, obtains object.
Embodiment
3
1) preparation of polyvinyl alcohol-polycaprolactone graft copolymer
12.4 grams of polyvinyl alcohol (molecular weight is 52000), the polycaprolactone monododecyl ether (molecular weight is 2700) of 11.9 grams of carboxy blockings is added in dry reactor, add 239 milliliters of dimethyl sulfoxide (DMSO)s, add 0.059 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, in 34 DEG C of stirring reactions 4 days, terminate reaction, by filtering, dialysing, be dried, obtain object；
2) preparation of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer
10.3 grams of polyvinyl alcohol-polycaprolactone graft copolymers, the PTMC list tridecyl ether (molecular weight is 2400) of 8.8 grams of carboxy blockings is added in dry reactor, add 183 milliliters of dimethyl sulfoxide (DMSO)s, add 0.046 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, in 35 DEG C of stirring reactions 4 days, terminate reaction, by filtering, dialysing, be dried, obtain object；
3) preparation of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer stoste
In dry reactor, add 140 milligrams of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymers and 100 milliliters of dimethyl sulfoxide (DMSO)s, in 52 DEG C of stirring and dissolving 60 minutes, obtain object；
4) preparation of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle
Under room temperature, 1.2 milliliters of polyvinyl alcohol-polycaprolactones-PTMC dual graft copolymer stoste is added in the bag filter of 7 milliliters of capacity (molecular cut off is 4000), put it in the 500 milliliters of beakers filling distilled water, every displacement in 7 hours once, replace 4 times, solution display blue light in bag filter, be then poured in the graduated 12 milliliters of volumetric flasks of band, it is adjusted to scale with distilled water, obtains object.
Claims (7)
1. the method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle, it is characterized in that: in copolymer, the molecular weight of polyvinyl alcohol segments is 46000～52000, the molecular weight of polycaprolactone segment is 2600～2700, and the molecular weight of PTMC segment is 2100～2400；Its preparation method employing following steps:
1) preparation of polyvinyl alcohol-polycaprolactone graft copolymer: add polyvinyl alcohol, polycaprolactone monododecyl ether, solvent and the condensing agent of carboxy blocking in dry reactor, under inert atmosphere, in 28～34 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialysing, it is dried, obtains object；
2) preparation of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer: add polyvinyl alcohol-polycaprolactone graft copolymer, PTMC list tridecyl ether, solvent and the condensing agent of carboxy blocking in dry reactor, under inert atmosphere, in 27～35 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialysing, it is dried, obtains object；
3) preparation of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer stoste: add polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer and solvent in dry reactor, in 48～52 DEG C of stirring and dissolving 50～60 minutes, obtain object；
4) preparation of polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle: under room temperature, stoste is added in bag filter, put it in the 500 milliliters of beakers filling selective solvent, every displacement in 7 hours once, replace 3～4 times, solution display blue light in bag filter, be then poured in the graduated volumetric flask of band, it is adjusted to scale with selective solvent, obtains object.
A kind of method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle the most according to claim 1, it is characterised in that: in step 1), polycaprolactone monododecyl ether is 15～25:1 with the mol ratio of polyvinyl alcohol.
A kind of method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle the most according to claim 1, it is characterised in that: in step 1), condensing agent usesN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, condensing agent is 1.08～1.8:1 with the mol ratio of polyvinyl alcohol, and solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15 g/100 ml.
A kind of method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle the most according to claim 1, it is characterized in that: step 2) in, PTMC list tridecyl ether is 15～25:1 with the mol ratio of polyvinyl alcohol segments in polyvinyl alcohol-polycaprolactone graft copolymer.
A kind of method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle the most according to claim 1, it is characterised in that: step 2) in, condensing agent usesN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, condensing agent is 1.07～1.8:1 with the mol ratio of polyvinyl alcohol segments in polyvinyl alcohol-polycaprolactone graft copolymer, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15 g/100 ml.
A kind of method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle the most according to claim 1, it is characterised in that: in step 3), solvent uses dimethyl sulfoxide (DMSO), and original liquid concentration is 1～1.5 mg/ml.
A kind of method preparing polyvinyl alcohol-polycaprolactone-PTMC dual graft copolymer micelle the most according to claim 1, it is characterized in that: in step 4), bag filter capacity is 5～10 ml, bag filter molecular cut off is 3500～4000, selective solvent uses distilled water, and solution concentration is 0.1～0.3 mg/ml.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106986996A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of polyacrylic acid polycaprolactone gathers（Lactide glycolide）The preparation method of copolymer micelle |
| CN106986999A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of method for preparing polyacrylic acid PTMC MPEGPLA copolymer micelles |
| CN107118368A (en) * | 2017-05-25 | 2017-09-01 | 山东理工大学 | A kind of preparation method of polyacrylic acid PTMC polycaprolactone polypropylene glycol copolymers micella |
| CN107118362A (en) * | 2017-05-22 | 2017-09-01 | 山东理工大学 | A kind of preparation method of polyacrylic acid polycaprolactone MPEGPLA copolymer micelles |
| CN107118365A (en) * | 2017-05-22 | 2017-09-01 | 山东理工大学 | A kind of preparation method of polyacrylic acid polycaprolactone PTMC copolymer micelle |
| CN107118363A (en) * | 2017-05-22 | 2017-09-01 | 山东理工大学 | A kind of preparation method of polyacrylic acid polycaprolactone copolymer of poly lactic acid micella |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865091A (en) * | 2014-03-24 | 2014-06-18 | 山东理工大学 | Method for improving water resisting performance of polyvinyl alcohol film from polycaprolactone and polylactic acid |
| 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 |
| CN104114600A (en) * | 2011-12-15 | 2014-10-22 | 道达尔研究技术弗吕公司 | Process for the preparation of defined functional lactic acid oligomers |
-
2016
- 2016-03-14 CN CN201610140622.3A patent/CN105778113A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104114600A (en) * | 2011-12-15 | 2014-10-22 | 道达尔研究技术弗吕公司 | Process for the preparation of defined functional lactic acid oligomers |
| CN103865091A (en) * | 2014-03-24 | 2014-06-18 | 山东理工大学 | Method for improving water resisting performance of polyvinyl alcohol film from polycaprolactone and polylactic acid |
| 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 (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106986996A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of polyacrylic acid polycaprolactone gathers（Lactide glycolide）The preparation method of copolymer micelle |
| CN106986999A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of method for preparing polyacrylic acid PTMC MPEGPLA copolymer micelles |
| CN107118362A (en) * | 2017-05-22 | 2017-09-01 | 山东理工大学 | A kind of preparation method of polyacrylic acid polycaprolactone MPEGPLA copolymer micelles |
| CN107118365A (en) * | 2017-05-22 | 2017-09-01 | 山东理工大学 | A kind of preparation method of polyacrylic acid polycaprolactone PTMC copolymer micelle |
| CN107118363A (en) * | 2017-05-22 | 2017-09-01 | 山东理工大学 | A kind of preparation method of polyacrylic acid polycaprolactone copolymer of poly lactic acid micella |
| CN107118368A (en) * | 2017-05-25 | 2017-09-01 | 山东理工大学 | A kind of preparation method of polyacrylic acid PTMC polycaprolactone polypropylene glycol copolymers micella |
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Application publication date: 20160720 |