CN105647200A - Method for improving water resistance and flexibility of polyvinyl alcohol film by polycaprolactone and poly(lactic acid-glycolic acid) - Google Patents
Method for improving water resistance and flexibility of polyvinyl alcohol film by polycaprolactone and poly(lactic acid-glycolic acid) Download PDFInfo
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- CN105647200A CN105647200A CN201610149293.9A CN201610149293A CN105647200A CN 105647200 A CN105647200 A CN 105647200A CN 201610149293 A CN201610149293 A CN 201610149293A CN 105647200 A CN105647200 A CN 105647200A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
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- 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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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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Abstract
The invention discloses a method for improving the water resistance and the flexibility of a polyvinyl alcohol film by polycaprolactone and poly(lactic acid-glycolic acid). The method comprises the following steps of (1), the synthesis of a polyvinyl alcohol-polycaprolactone-poly(lactic acid-glycolic acid) double graft copolymer: adding carboxyl-terminated polycaprolactone monododecyl ether, carboxyl-terminated poly(lactic acid-glycolic acid) monotridecyl ether, a solvent, a condensating agent and polyvinyl alcohol into a dry reactor, subjecting an obtained first mixture to a reaction for 2 to 4 days, ending the reaction, and obtaining a target object through filtration, dialysis and drying; (2), the preparation of the polyvinyl alcohol film modified by the polycaprolactone and the poly(lactic acid-glycolic acid): adding the polyvinyl alcohol-polycaprolactone-poly(lactic acid-glycolic acid) double graft copolymer, poly(lactic acid-glycolic acid) monotridecyl ether and a solvent into a dry reactor, mixing an obtained second mixture for 50 to 60 minutes, afterwards, forming the film by using a tape casting method and drying the film, so as to obtain a target object of the invention. The method is simple in preparation process and is easy to master; the water resistance and the flexibility of the obtained modified film are increased greatly.
Description
Technical field
The present invention relates to a kind of method that polyvinyl alcohol film resistance to water and compliance are improved, belong to field of polymer film preparing technology.
Background technology
Polyvinyl alcohol is a kind of biomaterial with good biocompatibility and biodegradability, polyvinyl alcohol film can be used as artificial skin etc., but polyvinyl alcohol film hydrophilic is too strong and more stiff, lack good resistance to water and compliance, thus limiting its application to a certain extent. Polycaprolactone and poly-(D, Pfansteihl) glycolic (weight ratio of lactic acid and glycolic is 90/10) are the biomaterials with excellent biocompatibility and biodegradability, have good hydrophobicity and compliance. First polycaprolactone segment and poly (lactic acid-glycolic acid) segment are simultaneously introduced polyvinyl alcohol segments and form polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft copolymer, then again poly (lactic acid-glycolic acid) segment is added polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft copolymer and form blend, prepare modified PVA membrane, thus drastically increasing resistance to water and the compliance of polyvinyl alcohol film.
Summary of the invention
It is an object of the invention to provide the method that polyvinyl alcohol film resistance to water and compliance are improved by a kind of simple to operate and effect preferably. Its technical scheme is:
A kind of method that polycaprolactone improves polyvinyl alcohol film resistance to water and compliance with poly (lactic acid-glycolic acid), it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 89000��95000, the molecular weight of polycaprolactone segment is 2800��2900, and the molecular weight of poly (lactic acid-glycolic acid) segment is 2800��2900; Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft copolymer: add the polycaprolactone monododecyl ether of carboxy blocking, the poly (lactic acid-glycolic acid) list tridecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 29��33 DEG C of stirring reactions 2��4 days, terminate reaction, by filtering, dialyse, drying, obtain object;
2) preparation of the polyvinyl alcohol film that polycaprolactone is modified with poly (lactic acid-glycolic acid): add polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft copolymer, poly (lactic acid-glycolic acid) list tridecyl ether and solvent in dry reactor, under inert atmosphere, after stirring mixing 50��60 minutes in 50��55 DEG C, by the tape casting film forming and dry, obtain object.
The method that described a kind of polycaprolactone improves polyvinyl alcohol film resistance to water and compliance with poly (lactic acid-glycolic acid), in step 1), the mol ratio of polycaprolactone monododecyl ether and polyvinyl alcohol is 15��25:1, poly (lactic acid-glycolic acid) list tridecyl ether adopts poly-(D, Pfansteihl) glycolic list tridecyl ether, and the weight ratio of lactic acid and glycolic is 90/10, the mol ratio of poly (lactic acid-glycolic acid) list tridecyl ether and polyvinyl alcohol is 15��25:1.
The method that described a kind of polycaprolactone improves polyvinyl alcohol film resistance to water and compliance with poly (lactic acid-glycolic acid), 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 1.08��1.8:1, and solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5��15g:100ml.
The method that described a kind of polycaprolactone improves polyvinyl alcohol film resistance to water and compliance with poly (lactic acid-glycolic acid), step 2) in, poly (lactic acid-glycolic acid) list tridecyl ether adopts poly-(D, Pfansteihl) glycolic list tridecyl ether, and the weight ratio of lactic acid and glycolic is 90/10, poly (lactic acid-glycolic acid) list tridecyl ether mass percent in Modified Membrane is 2��4%, and solvent adopts dimethyl sulfoxide, and mixture solution concentration is 25��30g:100ml.
Compared with prior art, its advantage is the present invention:
1, the method that described a kind of polycaprolactone and poly (lactic acid-glycolic acid) improve polyvinyl alcohol film resistance to water and compliance, adopts reaction and blended two kinds of means that a kind of polymer and two kinds of different polymeric monomer carry out being esterified simultaneously, simple to operate, be prone to grasp;
2, described polyvinyl alcohol modification film resistance to water and compliance are enhanced.
Detailed description of the invention
Embodiment 1
1) preparation of polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft copolymer
The poly (lactic acid-glycolic acid) list tridecyl ether (molecular weight is 2800) of 18.2 grams of polyvinyl alcohol (molecular weight is 89000), the polycaprolactone monododecyl ether (molecular weight is 2800) of 10.5 grams of carboxy blockings and 10.5 grams of carboxy blockings is added at dry reactor, add 366ml dimethyl sulfoxide, add 0.055 gram of N, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 29 DEG C of stirring reactions 2 days, terminate reaction, by filtering, dialyse, drying, obtain object;
2) preparation of the polyvinyl alcohol film that polycaprolactone is modified with poly (lactic acid-glycolic acid)
10 grams of polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft copolymers and 37ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the poly (lactic acid-glycolic acid) list tridecyl ether (molecular weight is 2800) of Modified Membrane gross weight 2%, under inert atmosphere, in 50 DEG C of stirring mixing 50 minutes, use the tape casting film forming, dry in 50 DEG C of vacuum drying ovens and obtain object.
After tested: the surface contact angle of object of the present invention and water and elongation at break thereof are respectively than improve 12.4 �� and 12.1% before modified.
Embodiment 2
1) preparation of polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft copolymer
The poly (lactic acid-glycolic acid) list tridecyl ether (molecular weight is 2800) of 21.7 grams of polyvinyl alcohol (molecular weight is 92000), the polycaprolactone monododecyl ether (molecular weight is 2800) of 11.7 grams of carboxy blockings and 11.7 grams of carboxy blockings is added at dry reactor, add 442ml dimethyl sulfoxide, add 0.038 gram of N, N '-DIC, under inert atmosphere, in 31 DEG C of stirring reactions 3 days, terminate reaction, by filtering, dialyse, drying, obtain object;
2) preparation of the polyvinyl alcohol film that polycaprolactone is modified with poly (lactic acid-glycolic acid)
9.9 grams of polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft copolymers and 36ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the poly (lactic acid-glycolic acid) list tridecyl ether (molecular weight is 2800) of Modified Membrane gross weight 3%, under inert atmosphere, in 53 DEG C of stirring mixing 55 minutes, use the tape casting film forming, dry in 50 DEG C of vacuum drying ovens and obtain object.
After tested: the surface contact angle of object of the present invention and water and elongation at break thereof are respectively than improve 13.2 �� and 12.9% before modified.
Embodiment 3
1) preparation of polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft copolymer
The poly (lactic acid-glycolic acid) list tridecyl ether (molecular weight is 2900) of 22 grams of polyvinyl alcohol (molecular weight is 95000), the polycaprolactone monododecyl ether (molecular weight is 2900) of 12.4 grams of carboxy blockings and 12.4 grams of carboxy blockings is added at dry reactor, add 456ml dimethyl sulfoxide, add 0.057 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, in 33 DEG C of stirring reactions 4 days, terminate reaction, by filtering, dialyse, drying, obtain object;
2) preparation of the polyvinyl alcohol film that polycaprolactone is modified with poly (lactic acid-glycolic acid)
9.6 grams of polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft copolymers and 35ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the poly (lactic acid-glycolic acid) list tridecyl ether (molecular weight is 2900) of Modified Membrane gross weight 4%, under inert atmosphere, in 55 DEG C of stirring mixing 60 minutes, use the tape casting film forming, dry in 50 DEG C of vacuum drying ovens and obtain object.
After tested: the surface contact angle of object of the present invention and water and elongation at break thereof are respectively than improve 13.5 �� and 13.3% before modified.
Claims (4)
1. the method that a polycaprolactone improves polyvinyl alcohol film resistance to water and compliance with poly (lactic acid-glycolic acid), it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 89000��95000, the molecular weight of polycaprolactone segment is 2800��2900, and the molecular weight of poly (lactic acid-glycolic acid) segment is 2800��2900; Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft copolymer: add the polycaprolactone monododecyl ether of carboxy blocking, the poly (lactic acid-glycolic acid) list tridecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 29��33 DEG C of stirring reactions 2��4 days, terminate reaction, by filtering, dialyse, drying, obtain object;
2) preparation of the polyvinyl alcohol film that polycaprolactone is modified with poly (lactic acid-glycolic acid): add polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft copolymer, poly (lactic acid-glycolic acid) list tridecyl ether and solvent in dry reactor, under inert atmosphere, after stirring mixing 50��60 minutes in 50��55 DEG C, by the tape casting film forming and dry, obtain object.
2. the method that a kind of polycaprolactone according to claim 1 improves polyvinyl alcohol film resistance to water and compliance with poly (lactic acid-glycolic acid), it is characterized in that: in step 1), the mol ratio of polycaprolactone monododecyl ether and polyvinyl alcohol is 15��25:1, poly (lactic acid-glycolic acid) list tridecyl ether adopts poly-(D, Pfansteihl) glycolic list tridecyl ether, and the weight ratio of lactic acid and glycolic is 90/10, the mol ratio of poly (lactic acid-glycolic acid) list tridecyl ether and polyvinyl alcohol is 15��25:1.
3. the method that a kind of polycaprolactone according to claim 1 improves polyvinyl alcohol film resistance to water and compliance with poly (lactic acid-glycolic acid), 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 1.08��1.8:1, and solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5��15g:100ml.
4. the method that a kind of polycaprolactone according to claim 1 improves polyvinyl alcohol film resistance to water and compliance with poly (lactic acid-glycolic acid), it is characterized in that: step 2) in, poly (lactic acid-glycolic acid) list tridecyl ether adopts poly-(D, Pfansteihl) glycolic list tridecyl ether, and the weight ratio of lactic acid and glycolic is 90/10, poly (lactic acid-glycolic acid) list tridecyl ether mass percent in Modified Membrane is 2��4%, and solvent adopts dimethyl sulfoxide, and mixture solution concentration is 25��30g:100ml.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610149293.9A CN105647200A (en) | 2016-03-16 | 2016-03-16 | Method for improving water resistance and flexibility of polyvinyl alcohol film by polycaprolactone and poly(lactic acid-glycolic acid) |
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| CN201610149293.9A CN105647200A (en) | 2016-03-16 | 2016-03-16 | Method for improving water resistance and flexibility of polyvinyl alcohol film by polycaprolactone and poly(lactic acid-glycolic acid) |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977951A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that poly (lactic acid-glycolic acid) is improved with polycaprolactone to polypropylene sorrel water resistance and compliance |
| CN106977936A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of polycaprolactone is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance |
| CN106987124A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of method being improved with polycaprolactone and PLA to polypropylene sorrel water resistance and compliance |
| CN107011675A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid) |
| CN107118569A (en) * | 2017-05-25 | 2017-09-01 | 山东理工大学 | A kind of method that poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with polycaprolactone |
| CN107118564A (en) * | 2017-05-22 | 2017-09-01 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PLA |
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| 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 |
| CN103865275A (en) * | 2014-04-11 | 2014-06-18 | 山东理工大学 | Method for improving the water resistance of polyethylene glycol film modified by polylactic acid and polyvinyl alcohol |
| CN103865274A (en) * | 2014-03-14 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide film by poly(lactic acid-glycolic acid) and poly(caprolactone-lactide) |
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2016
- 2016-03-16 CN CN201610149293.9A patent/CN105647200A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103865274A (en) * | 2014-03-14 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide film by poly(lactic acid-glycolic acid) and poly(caprolactone-lactide) |
| 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 |
| CN103865275A (en) * | 2014-04-11 | 2014-06-18 | 山东理工大学 | Method for improving the water resistance of polyethylene glycol film modified by polylactic acid and polyvinyl alcohol |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977936A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of polycaprolactone is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance |
| CN106987124A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of method being improved with polycaprolactone and PLA to polypropylene sorrel water resistance and compliance |
| CN107011675A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid) |
| CN107118564A (en) * | 2017-05-22 | 2017-09-01 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PLA |
| CN106977951A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that poly (lactic acid-glycolic acid) is improved with polycaprolactone to polypropylene sorrel water resistance and compliance |
| CN107118569A (en) * | 2017-05-25 | 2017-09-01 | 山东理工大学 | A kind of method that poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with polycaprolactone |
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Application publication date: 20160608 |