CN105566922A - Method for improving water resistance and compliance of polyvinyl alcohol film with poly trimethylene carbonate and P (CPP-SA)-polyethylene glycol - Google Patents
Method for improving water resistance and compliance of polyvinyl alcohol film with poly trimethylene carbonate and P (CPP-SA)-polyethylene glycol Download PDFInfo
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- CN105566922A CN105566922A CN201610123802.0A CN201610123802A CN105566922A CN 105566922 A CN105566922 A CN 105566922A CN 201610123802 A CN201610123802 A CN 201610123802A CN 105566922 A CN105566922 A CN 105566922A
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- polyvinyl alcohol
- cpp
- ptmc
- polyoxyethylene glycol
- alcohol film
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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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- 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
- 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
- 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
- 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 improving water resistance and compliance of a polyvinyl alcohol film with poly trimethylene carbonate and P (CPP-SA)-polyethylene glycol. The method comprises the following steps: (1) synthesis of a polyvinyl alcohol-poly trimethylene carbonate grafted copolymer: adding carboxyl-blocked poly trimethylene carbonate monododecyl ether, a solvent, a condensing agent and polyvinyl alcohol into a dry reactor, performing stirring reaction for 2 to 4 days at 26 to 34 DEG C, ending the reaction, and filtering, dialyzing and drying to obtain a target object; (2) preparation of a poly trimethylene carbonate and P (CPP-SA)-polyethylene glycol modified polyvinyl alcohol film: adding the polyvinyl alcohol-poly trimethylene carbonate grafted copolymer, the P (CPP-SA)-polyethylene glycol and a solvent into the dry reactor, stirring and mixing at 47 to 53 DEG C for 50to 60 minutes, and then forming the film by using a tape casting method and drying to obtain a target object of the invention. The method disclosed by the invention has a simple preparation process, and easy to master; the obtained modified film is greatly improved in water resistance and compliance.
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.P (CPP-SA)-polyoxyethylene glycol has good biocompatibility and the biomaterial of biodegradability, P (CPP-SA) segment has good hydrophobicity, and polyoxyethylene glycol segment has kindliness and has good blended property with polyvinyl alcohol segments.First PTMC segment is introduced polyvinyl alcohol segments and form polyvinyl alcohol-PTMC graft copolymer, and then P (CPP-SA)-polyoxyethylene glycol 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:
One PTMC and P (CPP-SA)-polyoxyethylene glycol 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 81000 ~ 91000, the molecular weight of PTMC segment is the molecular weight of 2300 ~ 2800, P (CPP-SA)-polyoxyethylene glycol is 4700 ~ 5300; Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-PTMC graft copolymer: add the PTMC monododecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 26 ~ 34 DEG C of stirring reactions 2 ~ 4 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) preparation of the polyvinyl alcohol film of PTMC and P (CPP-SA)-poly ethyldiol modified: add polyvinyl alcohol-PTMC graft copolymer, P (CPP-SA)-polyoxyethylene glycol and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 50 ~ 60 minutes in 47 ~ 53 DEG C, also dry by casting method film forming, obtain target compound.
Described one PTMC and P (CPP-SA)-polyoxyethylene glycol improve the method for polyvinyl alcohol film water tolerance and kindliness, in step 1), the mol ratio of PTMC monododecyl ether and polyvinyl alcohol is 15 ~ 25:1.
Described one PTMC and P (CPP-SA)-polyoxyethylene glycol 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 1.08 ~ 1.8:1, and solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15g:100ml.
Described one PTMC and P (CPP-SA)-polyoxyethylene glycol improve the method for polyvinyl alcohol film water tolerance and kindliness, step 2) in, P (CPP-SA)-polyoxyethylene glycol adopts P (CPP-SA)-polyoxyethylene glycol Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, P (CPP-SA) adopts poly-[1, two (to the carboxyphenoxy) propane-SA of 3-] multipolymer, the mol ratio of CPP and SA is 70/30, P (CPP-SA) is 90/10 with the weight ratio of polyoxyethylene glycol, P (the CPP-SA)-mass percent of polyoxyethylene glycol in modified membrane is 2 ~ 3%, solvent adopts dimethyl sulfoxide (DMSO), mixture solution concentration is 25 ~ 30g:100ml.
Compared with prior art, its advantage is in the present invention:
1, described PTMC and P (CPP-SA)-polyoxyethylene glycol 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 monododecyl ether (molecular weight is 2300) of 19 grams of polyvinyl alcohol (molecular weight is 81000) and 10.1 grams of carboxy blockings at dry reactor, add 285ml dimethyl sulfoxide (DMSO), then add 0.058 gram
n, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 26 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 P (CPP-SA)-poly ethyldiol modified
10 grams of polyvinyl alcohol-PTMC graft copolymer and 37ml dimethyl sulfoxide solvent is added in dry reactor, separately add P (the CPP-SA)-polyoxyethylene glycol (molecular weight is 4700) accounting for modified membrane gross weight 2%, under inert atmosphere, 50 minutes are uniformly mixed in 47 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 12.6 ° and 12.8% before modified.
embodiment 2
1) preparation of polyvinyl alcohol-PTMC graft copolymer
Add the PTMC monododecyl ether (molecular weight is 2500) of 21 grams of polyvinyl alcohol (molecular weight is 85000) and 11.4 grams of carboxy blockings at dry reactor, add 305ml dimethyl sulfoxide (DMSO), then add 0.039 gram
n, N '-DIC, under inert atmosphere, in 30 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 P (CPP-SA)-poly ethyldiol modified
10 grams of polyvinyl alcohol-PTMC graft copolymer and 36ml dimethyl sulfoxide solvent is added in dry reactor, separately add P (the CPP-SA)-polyoxyethylene glycol (molecular weight is 5000) accounting for modified membrane gross weight 2%, under inert atmosphere, 55 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 13.2 ° and 12.6% before modified.
embodiment 3
1) preparation of polyvinyl alcohol-PTMC graft copolymer
The PTMC monododecyl ether (molecular weight is 2800) of 22.1 grams of polyvinyl alcohol (molecular weight is 91000) and 12.5 grams of carboxy blockings is added at dry reactor, add 331ml dimethyl sulfoxide (DMSO), add 0.061 gram of 3-ethyl-1-(3-dimethylaminopropyl again) carbodiimide, under inert atmosphere, in 34 DEG C of stirring reactions 4 days, termination reaction, by filtration, dialysis, drying, obtains target compound;
2) preparation of the polyvinyl alcohol film of PTMC and P (CPP-SA)-poly ethyldiol modified
9.5 grams of polyvinyl alcohol-PTMC graft copolymer and 34ml dimethyl sulfoxide solvent is added in dry reactor, separately add P (the CPP-SA)-polyoxyethylene glycol (molecular weight is 5300) accounting for modified membrane gross weight 3%, under inert atmosphere, 60 minutes are uniformly mixed in 53 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 12.4% before modified.
Claims (4)
1. one kind is improved the method for polyvinyl alcohol film water tolerance and kindliness with PTMC and P (CPP-SA)-polyoxyethylene glycol, it is characterized in that: in modified membrane, the molecular weight of polyvinyl alcohol segments is 81000 ~ 91000, the molecular weight of PTMC segment is the molecular weight of 2300 ~ 2800, P (CPP-SA)-polyoxyethylene glycol is 4700 ~ 5300; Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-PTMC graft copolymer: add the PTMC monododecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 26 ~ 34 DEG C of stirring reactions 2 ~ 4 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) preparation of the polyvinyl alcohol film of PTMC and P (CPP-SA)-poly ethyldiol modified: add polyvinyl alcohol-PTMC graft copolymer, P (CPP-SA)-polyoxyethylene glycol and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 50 ~ 60 minutes in 47 ~ 53 DEG C, also dry by casting method film forming, obtain target compound.
2. one PTMC according to claim 1 and P (CPP-SA)-polyoxyethylene glycol improve the method for polyvinyl alcohol film water tolerance and kindliness, it is characterized in that: in step 1), the mol ratio of PTMC monododecyl ether and polyvinyl alcohol is 15 ~ 25:1.
3. one PTMC according to claim 1 and P (CPP-SA)-polyoxyethylene glycol 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 1.08 ~ 1.8:1, and solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15g:100ml.
4. one PTMC according to claim 1 and P (CPP-SA)-polyoxyethylene glycol improve the method for polyvinyl alcohol film water tolerance and kindliness, it is characterized in that: step 2) in, P (CPP-SA)-polyoxyethylene glycol adopts P (CPP-SA)-polyoxyethylene glycol Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, P (CPP-SA) adopts poly-[1, two (to the carboxyphenoxy) propane-SA of 3-] multipolymer, the mol ratio of CPP and SA is 70/30, P (CPP-SA) is 90/10 with the weight ratio of polyoxyethylene glycol, P (the CPP-SA)-mass percent of polyoxyethylene glycol in modified membrane is 2 ~ 3%, solvent adopts dimethyl sulfoxide (DMSO), mixture solution concentration is 25 ~ 30g:100ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610123802.0A CN105566922A (en) | 2016-03-07 | 2016-03-07 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly trimethylene carbonate and P (CPP-SA)-polyethylene glycol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610123802.0A CN105566922A (en) | 2016-03-07 | 2016-03-07 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly trimethylene carbonate and P (CPP-SA)-polyethylene glycol |
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| CN105566922A true CN105566922A (en) | 2016-05-11 |
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| CN201610123802.0A Pending CN105566922A (en) | 2016-03-07 | 2016-03-07 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly trimethylene carbonate and P (CPP-SA)-polyethylene glycol |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947259A (en) * | 2017-05-22 | 2017-07-14 | 山东理工大学 | A kind of method being improved with MPEGPLA and PTMC to polypropylene sorrel water resistance and compliance |
| CN106947261A (en) * | 2017-05-22 | 2017-07-14 | 山东理工大学 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
| CN106977932A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with condensing model |
| CN107011668A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PTMC |
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| CN101544757A (en) * | 2009-04-20 | 2009-09-30 | 西北工业大学 | Amphiphilic polyanhydride polymer and preparation method 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) |
| 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
- 2016-03-07 CN CN201610123802.0A patent/CN105566922A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101544757A (en) * | 2009-04-20 | 2009-09-30 | 西北工业大学 | Amphiphilic polyanhydride polymer and preparation method 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) |
| 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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| 任杰: "《可降解与吸收材料》", 31 October 2003 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947259A (en) * | 2017-05-22 | 2017-07-14 | 山东理工大学 | A kind of method being improved with MPEGPLA and PTMC to polypropylene sorrel water resistance and compliance |
| CN106947261A (en) * | 2017-05-22 | 2017-07-14 | 山东理工大学 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
| CN106977932A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with condensing model |
| CN107011668A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PTMC |
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Application publication date: 20160511 |
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