CN105670307A - Method for improving water resistance and flexibility of polyvinyl alcohol membrane through polycaprolactone and poly(trimethylene carbonate)-polyvinylpyrrolidone - Google Patents
Method for improving water resistance and flexibility of polyvinyl alcohol membrane through polycaprolactone and poly(trimethylene carbonate)-polyvinylpyrrolidone Download PDFInfo
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- CN105670307A CN105670307A CN201610148959.9A CN201610148959A CN105670307A CN 105670307 A CN105670307 A CN 105670307A CN 201610148959 A CN201610148959 A CN 201610148959A CN 105670307 A CN105670307 A CN 105670307A
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- 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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- 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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- C08G2230/00—Compositions for preparing biodegradable polymers
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention discloses a method for improving the water resistance and flexibility of a polyvinyl alcohol membrane through polycaprolactone and poly(trimethylene carbonate)-polyvinylpyrrolidone. The method comprises the following steps: 1, synthesis of polyvinyl alcohol-polycaprolactone grafted copolymer, wherein carboxyl terminated polycaprolactone mono-dodecyl ether, solvent, a condensing agent and polyvinyl alcohol are added into a dry reactor, a reaction is conducted for 2-4 days at the temperature of 20-32 DEG C while stirring is conducted, the reaction is terminated, and filtration, dialysis and drying are conducted, so that the polyvinyl alcohol-polycaprolactone grafted copolymer is obtained; 2, preparation of the polyvinyl alcohol membrane modified by the polycaprolactone and the poly(trimethylene carbonate)-polyvinylpyrrolidone, wherein the polyvinyl alcohol-polycaprolactone grafted copolymer, the poly(trimethylene carbonate)-polyvinylpyrrolidone and solvent are added into a dry reactor, stirring and mixing are conducted for 50-60 minutes at the temperature of 45-53 DEG C, membrane formation is conducted through a tape casting method, and drying is conducted, so that the membrane is obtained. The method is simple in preparation process and easy to grasp, and water resistance and flexibility of the obtained modified membrane are greatly improved.
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 is the biomaterial with excellent biocompatibility and biodegradability, has good hydrophobicity and compliance. PTMC-polyvinylpyrrolidone is the biomaterial with excellent biocompatibility and biodegradability, PTMC segment has good hydrophobicity and compliance, and polyvinylpyrrolidone segment and polyvinyl alcohol segments have good blended property. First polycaprolactone segment is introduced polyvinyl alcohol segments and form polyvinyl alcohol-polycaprolactone graft copolymer, then again PTMC-polyvinylpyrrolidone is added polyvinyl alcohol-polycaprolactone 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 PTMC-polyvinylpyrrolidone, it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 82000～90000, the molecular weight of polycaprolactone segment is 2000～2300, and the molecular weight of PTMC-polyvinylpyrrolidone is 4500～5200; Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-polycaprolactone graft copolymer: add the polycaprolactone monododecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 20～32 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialyse, drying, obtain object;
2) preparation of the polyvinyl alcohol film of polycaprolactone and PTMC-polyvinyl pyrrolidone modified: add polyvinyl alcohol-polycaprolactone graft copolymer, PTMC-polyvinylpyrrolidone and solvent in dry reactor, under inert atmosphere, after stirring mixing 50～60 minutes in 45～53 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 PTMC-polyvinylpyrrolidone, in step 1), the mol ratio of polycaprolactone monododecyl 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 PTMC-polyvinylpyrrolidone, in step 1), 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 1.08～1.8:1, 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 PTMC-polyvinylpyrrolidone, step 2) in, PTMC-polyvinylpyrrolidone adopts PTMC-polyvinylpyrrolidone diblock copolymer, the weight ratio of PTMC and polyvinylpyrrolidone is 90/10, PTMC-polyvinylpyrrolidone mass percent in Modified Membrane is 1～3%, 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 polycaprolactone and PTMC-polyvinylpyrrolidone improves polyvinyl alcohol film resistance to water and compliance, adopts esterification and blended two kinds of means, 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 graft copolymer
Add the polycaprolactone monododecyl ether (molecular weight is 2000) of 20.2 grams of polyvinyl alcohol (molecular weight is 82000) and 8.9 grams of carboxy blockings at dry reactor, add 290ml dimethyl sulfoxide, add 0.063 gramN,N’-dicyclohexylcarbodiimide, under inert atmosphere, in 20 DEG C of stirring reactions 2 days, terminates reaction, by filtering, dialysis, dry, obtains object;
2) preparation of the polyvinyl alcohol film of polycaprolactone and PTMC-polyvinyl pyrrolidone modified
10 grams of polyvinyl alcohol-polycaprolactone graft copolymers and 37ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the PTMC-polyvinylpyrrolidone (molecular weight is 4500) of Modified Membrane gross weight 1%, under inert atmosphere, in 45 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 13.4% before modified.
Embodiment 2
1) preparation of polyvinyl alcohol-polycaprolactone graft copolymer
Add the polycaprolactone monododecyl ether (molecular weight is 2100) of 21.3 grams of polyvinyl alcohol (molecular weight is 87000) and 9.6 grams of carboxy blockings at dry reactor, add 308ml dimethyl sulfoxide, add 0.039 gramN,N’-DIC, under inert atmosphere, in 27 DEG C of stirring reactions 3 days, terminates reaction, by filtering, dialysis, dry, obtains object;
2) preparation of the polyvinyl alcohol film of polycaprolactone and PTMC-polyvinyl pyrrolidone modified
10 grams of polyvinyl alcohol-polycaprolactone graft copolymers and 36ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the PTMC-polyvinylpyrrolidone (molecular weight is 4700) of Modified Membrane gross weight 2%, under inert atmosphere, in 47 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 12.9 ° and 13.8% before modified.
Embodiment 3
1) preparation of polyvinyl alcohol-polycaprolactone graft copolymer
The polycaprolactone monododecyl ether (molecular weight is 2300) of 22 grams of polyvinyl alcohol (molecular weight is 90000) and 10.2 grams of carboxy blockings is added at dry reactor, add 301ml dimethyl sulfoxide, add 0.059 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, in 32 DEG C of stirring reactions 4 days, terminate reaction, by filtering, dialyse, drying, obtain object;
2) preparation of the polyvinyl alcohol film of polycaprolactone and PTMC-polyvinyl pyrrolidone modified
9.6 grams of polyvinyl alcohol-polycaprolactone graft copolymers and 34.5ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the PTMC-polyvinylpyrrolidone (molecular weight is 5200) of Modified Membrane gross weight 3%, under inert atmosphere, in 53 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 14.3% before modified.
Claims (4)
1. the method that a polycaprolactone improves polyvinyl alcohol film resistance to water and compliance with PTMC-polyvinylpyrrolidone, it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 82000～90000, the molecular weight of polycaprolactone segment is 2000～2300, and the molecular weight of PTMC-polyvinylpyrrolidone is 4500～5200; Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-polycaprolactone graft copolymer: add the polycaprolactone monododecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 20～32 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialyse, drying, obtain object;
2) preparation of the polyvinyl alcohol film of polycaprolactone and PTMC-polyvinyl pyrrolidone modified: add polyvinyl alcohol-polycaprolactone graft copolymer, PTMC-polyvinylpyrrolidone and solvent in dry reactor, under inert atmosphere, after stirring mixing 50～60 minutes in 45～53 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 PTMC-polyvinylpyrrolidone, it is characterized in that: in step 1), the mol ratio of polycaprolactone monododecyl 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 PTMC-polyvinylpyrrolidone, it is characterised in that: in step 1), 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 1.08～1.8:1, 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 PTMC-polyvinylpyrrolidone, it is characterized in that: step 2) in, PTMC-polyvinylpyrrolidone adopts PTMC-polyvinylpyrrolidone diblock copolymer, the weight ratio of PTMC and polyvinylpyrrolidone is 90/10, PTMC-polyvinylpyrrolidone mass percent in Modified Membrane is 1～3%, solvent adopts dimethyl sulfoxide, mixture solution concentration is 25～30g:100ml.
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| CN201610148959.9A CN105670307A (en) | 2016-03-16 | 2016-03-16 | Method for improving water resistance and flexibility of polyvinyl alcohol membrane through polycaprolactone and poly(trimethylene carbonate)-polyvinylpyrrolidone |
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| CN201610148959.9A CN105670307A (en) | 2016-03-16 | 2016-03-16 | Method for improving water resistance and flexibility of polyvinyl alcohol membrane through polycaprolactone and poly(trimethylene carbonate)-polyvinylpyrrolidone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106987132A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PTMC |
| 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819905A (en) * | 2014-03-07 | 2014-05-28 | 山东理工大学 | Method for modifying hydrophilia of polypeptide membrane through adopting poly trimethylene carbonate and polyvinylpyrrolidone |
| 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 |
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- 2016-03-16 CN CN201610148959.9A patent/CN105670307A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819905A (en) * | 2014-03-07 | 2014-05-28 | 山东理工大学 | Method for modifying hydrophilia of polypeptide membrane through adopting poly trimethylene carbonate and polyvinylpyrrolidone |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106987132A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PTMC |
| 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: 20160615 |