CN105542485A - Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(trimethylene carbonate) and polycaprolactone-polyvinylpyrrolidone - Google Patents
Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(trimethylene carbonate) and polycaprolactone-polyvinylpyrrolidone Download PDFInfo
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- CN105542485A CN105542485A CN201610148961.6A CN201610148961A CN105542485A CN 105542485 A CN105542485 A CN 105542485A CN 201610148961 A CN201610148961 A CN 201610148961A CN 105542485 A CN105542485 A CN 105542485A
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- polyvinyl alcohol
- polycaprolactone
- polyvinylpyrrolidone
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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
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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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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
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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
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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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
- 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
Abstract
The invention discloses a method for modifying the water resistance and flexibility of a polyvinyl alcohol membrane through poly(trimethylene carbonate) and polycaprolactone-polyvinylpyrrolidone. The method includes the following steps of firstly, synthesizing polyvinyl alcohol and poly(trimethylene carbonate) draft copolymers, wherein poly(trimethylene carbonate) monotridecyl ether with the end sealed by a carboxyl group, solvent, condensing agent and polyvinyl alcohol are added into a drying reactor to react for 2-3 days at a temperature of 25-33 DEG C, and the target object is obtained through filtering, dialyzing and drying; secondly, preparing the polyvinyl alcohol membrane modified by poly(trimethylene carbonate) and polycaprolactone-polyvinylpyrrolidone, wherein the polyvinyl alcohol and poly(trimethylene carbonate) draft copolymers, polycaprolactone-polyvinylpyrrolidone and solvent are added into the drying reactor to be mixed for 50-60 minutes at a temperature of 46-50 DEG C, and the membrane is formed through a flow coating method and dried to obtain the target object. The method is simple in preparation process and easy to grasp, and the water resistance and flexibility of the modified membrane are greatly improved.
Description
Technical field
The present invention relates to a kind of method that polyvinyl alcohol film water tolerance and kindliness are improved, belong to field of polymer film preparing technology.
Background technology
Polyvinyl alcohol a kind ofly has good biocompatibility and the biomaterial of biodegradability, polyvinyl alcohol film can be used as artificial skin etc., but polyvinyl alcohol film wetting ability too by force and more stiff, lacks good water tolerance and kindliness, thus limit its application to a certain extent.PTMC has excellent biocompatibility and the biomaterial of biodegradability, has good hydrophobicity and kindliness.Polycaprolactone-polyvinylpyrrolidone has excellent biocompatibility and the biomaterial of biodegradability, and polycaprolactone segment has good hydrophobicity and kindliness, and polyvinylpyrrolidone segment and polyvinyl alcohol segments have good blended property.First PTMC segment is introduced polyvinyl alcohol segments and form polyvinyl alcohol-PTMC graft copolymer, and then polycaprolactone-polyvinylpyrrolidone is added polyvinyl alcohol-PTMC graft copolymer formation blend, obtained modified PVA membrane, thus drastically increase water tolerance and the kindliness of polyvinyl alcohol film.
Summary of the invention
The object of the present invention is to provide a kind of simple to operate and effect preferably to the method that polyvinyl alcohol film water tolerance and kindliness are improved.Its technical scheme is:
A kind of PTMC and polycaprolactone-polyvinylpyrrolidone improve the method for polyvinyl alcohol film water tolerance and kindliness, it is characterized in that: in modified membrane, the molecular weight of polyvinyl alcohol segments is 84000 ~ 90000, the molecular weight of PTMC segment is 2000 ~ 2400, and the molecular weight of polycaprolactone-polyvinylpyrrolidone is 5000 ~ 5500; Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-PTMC graft copolymer: add the PTMC list tridecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 25 ~ 33 DEG C of stirring reactions 2 ~ 3 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) preparation of the polyvinyl alcohol film of PTMC and polycaprolactone-polyvinyl pyrrolidone modified: add polyvinyl alcohol-PTMC graft copolymer, polycaprolactone-polyvinylpyrrolidone and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 50 ~ 60 minutes in 46 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
Described a kind of PTMC and polycaprolactone-polyvinylpyrrolidone improve the method for polyvinyl alcohol film water tolerance and kindliness, and in step 1), the mol ratio of PTMC list tridecyl ether and polyvinyl alcohol is 15 ~ 25:1.
Described a kind of PTMC and polycaprolactone-polyvinylpyrrolidone improve the method for polyvinyl alcohol film water tolerance and kindliness, and 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.
Described a kind of PTMC and polycaprolactone-polyvinylpyrrolidone improve the method for polyvinyl alcohol film water tolerance and kindliness, step 2) in, polycaprolactone-polyvinylpyrrolidone adopts polycaprolactone-polyvinylpyrrolidone Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, the weight ratio of polycaprolactone and polyvinylpyrrolidone is 90/10, the mass percent of polycaprolactone-polyvinylpyrrolidone in modified membrane is 2 ~ 4%, solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25 ~ 30g:100ml.
Compared with prior art, its advantage is in the present invention:
1, described PTMC and polycaprolactone-polyvinylpyrrolidone improve the method for polyvinyl alcohol film water tolerance and kindliness, adopt esterification and blended two kinds of means, simple to operate, be easy to grasp;
2, described polyvinyl alcohol modification film water tolerance and kindliness are enhanced.
Embodiment
embodiment 1
1) preparation of polyvinyl alcohol-PTMC graft copolymer
Add the PTMC list tridecyl ether (molecular weight is 2000) of 20.5 grams of polyvinyl alcohol (molecular weight is 84000) and 8.8 grams of carboxy blockings at dry reactor, add 292ml dimethyl sulfoxide (DMSO), then add 0.062 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;
2) preparation of the polyvinyl alcohol film of PTMC and polycaprolactone-polyvinyl pyrrolidone modified
10 grams of polyvinyl alcohol-PTMC graft copolymer and 37ml dimethyl sulfoxide solvent is added in dry reactor, separately add the polycaprolactone-polyvinylpyrrolidone (molecular weight is 5000) accounting for modified membrane gross weight 2%, under inert atmosphere, 50 minutes are uniformly mixed in 46 DEG C, use casting method film forming, in 50 DEG C of vacuum drying ovens, drying obtains target compound.
After tested: the surface contact angle of target compound of the present invention and water and elongation at break thereof are respectively than improve 11.8 ° and 12.7% before modified.
embodiment 2
1) preparation of polyvinyl alcohol-PTMC graft copolymer
Add the PTMC list tridecyl ether (molecular weight is 2200) of 21.2 grams of polyvinyl alcohol (molecular weight is 87000) and 9.7 grams of carboxy blockings at dry reactor, add 300ml dimethyl sulfoxide (DMSO), then add 0.039 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;
2) preparation of the polyvinyl alcohol film of PTMC and polycaprolactone-polyvinyl pyrrolidone modified
10 grams of polyvinyl alcohol-PTMC graft copolymer and 36ml dimethyl sulfoxide solvent is added in dry reactor, separately add the polycaprolactone-polyvinylpyrrolidone (molecular weight is 5300) accounting for modified membrane gross weight 3%, under inert atmosphere, 55 minutes are uniformly mixed in 48 DEG C, use casting method film forming, in 50 DEG C of vacuum drying ovens, drying obtains target compound.
After tested: the surface contact angle of target compound of the present invention and water and elongation at break thereof are respectively than improve 12.4 ° and 13.6% before modified.
embodiment 3
1) preparation of polyvinyl alcohol-PTMC graft copolymer
The PTMC list tridecyl ether (molecular weight is 2400) of 22 grams of polyvinyl alcohol (molecular weight is 90000) and 10.6 grams of carboxy blockings is added at dry reactor, add 310ml dimethyl sulfoxide (DMSO), add 0.058 gram of 3-ethyl-1-(3-dimethylaminopropyl again) carbodiimide, under inert atmosphere, in 33 DEG C of stirring reactions 2 days, termination reaction, by filtration, dialysis, drying, obtains target compound;
2) preparation of the polyvinyl alcohol film of PTMC and polycaprolactone-polyvinyl pyrrolidone modified
9.5 grams of polyvinyl alcohol-PTMC graft copolymer and 35ml dimethyl sulfoxide solvent is added in dry reactor, separately add the polycaprolactone-polyvinylpyrrolidone (molecular weight is 5500) accounting for modified membrane gross weight 4%, under inert atmosphere, 60 minutes are uniformly mixed in 50 DEG C, use casting method film forming, in 50 DEG C of vacuum drying ovens, drying obtains target compound.
After tested: the surface contact angle of target compound of the present invention and water and elongation at break thereof are respectively than improve 13.5 ° and 14.9% before modified.
Claims (4)
1. a PTMC and polycaprolactone-polyvinylpyrrolidone improve the method for polyvinyl alcohol film water tolerance and kindliness, it is characterized in that: in modified membrane, the molecular weight of polyvinyl alcohol segments is 84000 ~ 90000, the molecular weight of PTMC segment is 2000 ~ 2400, and the molecular weight of polycaprolactone-polyvinylpyrrolidone is 5000 ~ 5500; Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-PTMC graft copolymer: add the PTMC list tridecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 25 ~ 33 DEG C of stirring reactions 2 ~ 3 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) preparation of the polyvinyl alcohol film of PTMC and polycaprolactone-polyvinyl pyrrolidone modified: add polyvinyl alcohol-PTMC graft copolymer, polycaprolactone-polyvinylpyrrolidone and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 50 ~ 60 minutes in 46 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
2. a kind of PTMC according to claim 1 and polycaprolactone-polyvinylpyrrolidone improve the method for polyvinyl alcohol film water tolerance and kindliness, it is characterized in that: in step 1), the mol ratio of PTMC list tridecyl ether and polyvinyl alcohol is 15 ~ 25:1.
3. a kind of PTMC according to claim 1 and polycaprolactone-polyvinylpyrrolidone improve the method for polyvinyl alcohol film water tolerance and kindliness, it is characterized in that: in step 1), and 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 PTMC according to claim 1 and polycaprolactone-polyvinylpyrrolidone improve the method for polyvinyl alcohol film water tolerance and kindliness, it is characterized in that: step 2) in, polycaprolactone-polyvinylpyrrolidone adopts polycaprolactone-polyvinylpyrrolidone Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, the weight ratio of polycaprolactone and polyvinylpyrrolidone is 90/10, the mass percent of polycaprolactone-polyvinylpyrrolidone in modified membrane is 2 ~ 4%, solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25 ~ 30g:100ml.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610148961.6A CN105542485A (en) | 2016-03-16 | 2016-03-16 | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(trimethylene carbonate) and polycaprolactone-polyvinylpyrrolidone |
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| CN201610148961.6A CN105542485A (en) | 2016-03-16 | 2016-03-16 | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(trimethylene carbonate) and polycaprolactone-polyvinylpyrrolidone |
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| CN105542485A true CN105542485A (en) | 2016-05-04 |
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Cited By (1)
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| CN106977947A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PTMC |
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| 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 |
| CN104559213A (en) * | 2015-01-06 | 2015-04-29 | 山东理工大学 | Method for improving hydrophily and flexibility of polypeptide membrane by poly(trimethylene carbonate) and polyethylene glycol |
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2016
- 2016-03-16 CN CN201610148961.6A patent/CN105542485A/en active Pending
Patent Citations (3)
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| 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 |
| CN104559213A (en) * | 2015-01-06 | 2015-04-29 | 山东理工大学 | Method for improving hydrophily and flexibility of polypeptide membrane by poly(trimethylene carbonate) and polyethylene glycol |
Non-Patent Citations (1)
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| 李翠珍: "CRP与ROP联用制备PCL嵌段共聚物及其性能和应用研究", 《华东理工大学博士学位论文》 * |
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| CN106977947A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PTMC |
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