CN105542483A - Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(trimethylene carbonate) and poly(p-dioxanone) - Google Patents
Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(trimethylene carbonate) and poly(p-dioxanone) Download PDFInfo
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- CN105542483A CN105542483A CN201610148914.1A CN201610148914A CN105542483A CN 105542483 A CN105542483 A CN 105542483A CN 201610148914 A CN201610148914 A CN 201610148914A CN 105542483 A CN105542483 A CN 105542483A
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- polyvinyl alcohol
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- dioxanone
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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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- 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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- 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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- 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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- 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
- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/06—Biodegradable
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- 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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Abstract
The invention discloses a method for modifying the water resistance and flexibility of a polyvinyl alcohol membrane through poly(trimethylene carbonate) and poly(p-dioxanone). The method includes the following steps of firstly, adding poly(trimethylene carbonate) monododecyl ether with the end sealed by a carboxyl group, poly(p-dioxanone) monotridecyl ether with the end sealed by a carboxyl group, solvent, condensing agent and polyvinyl alcohol into a drying reactor to be stirred and react for 2-4 days at a temperature of 31-34 DEG C to obtain polyvinyl alcohol, poly(trimethylene carbonate) and poly(p-dioxanone) double-draft copolymers; secondly, adding the polyvinyl alcohol, poly(trimethylene carbonate) and poly(p-dioxanone) double-draft copolymers, poly(p-dioxanone) monotridecyl ether and solvent into the drying reactor to be stirred and mixed for 50-60 minutes at a temperature of 48-53 DEG C, and forming the membrane and drying the membrane 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 and PPDO have excellent biocompatibility and the biomaterial of biodegradability, has good hydrophobicity and kindliness.First PTMC segment and PPDO segment are introduced polyvinyl alcohol segments simultaneously and form polyvinyl alcohol-PTMC-PPDO dual graft multipolymer, and then PPDO segment is added polyvinyl alcohol-PTMC-PPDO dual graft multipolymer 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 PPDO 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 87000 ~ 93000, the molecular weight of PTMC segment is 2600 ~ 2700, and the molecular weight of PPDO segment is 2600 ~ 2700; Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-PTMC-PPDO dual graft multipolymer: add the PTMC monododecyl ether of carboxy blocking, the PPDO list tridecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 31 ~ 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 PPDO modification: add polyvinyl alcohol-PTMC-PPDO dual graft multipolymer, PPDO list tridecyl ether and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 50 ~ 60 minutes in 48 ~ 53 DEG C, also dry by casting method film forming, obtain target compound.
Described a kind of PTMC and PPDO 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, and the mol ratio of PPDO list tridecyl ether and polyvinyl alcohol is 15 ~ 25:1.
Described a kind of PTMC and PPDO 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 PPDO improve the method for polyvinyl alcohol film water tolerance and kindliness, step 2) in, the mass percent of PPDO list tridecyl ether 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 a kind of PTMC and PPDO improve the method for polyvinyl alcohol film water tolerance and kindliness, adopt a kind of polymkeric substance polymeric monomer different from two kinds to carry out the reaction of esterification and blended two kinds of means simultaneously, 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-PPDO dual graft multipolymer
18.1 grams of polyvinyl alcohol (molecular weight is 87000), the PTMC monododecyl ether (molecular weight is 2600) of 10.1 grams of carboxy blockings and the PPDO list tridecyl ether (molecular weight is 2600) of 10.1 grams of carboxy blockings is added at dry reactor, add 355ml dimethyl sulfoxide (DMSO), then add 0.055 gram
n, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 31 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 PPDO modification
10 grams of polyvinyl alcohol-PTMC-PPDO dual graft multipolymers and 37ml dimethyl sulfoxide solvent is added in dry reactor, separately add the PPDO list tridecyl ether (molecular weight is 2600) accounting for modified membrane gross weight 2%, under inert atmosphere, 50 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 12.5 ° and 12.7% before modified.
embodiment 2
1) preparation of polyvinyl alcohol-PTMC-PPDO dual graft multipolymer
21.6 grams of polyvinyl alcohol (molecular weight is 89000), the PTMC monododecyl ether (molecular weight is 2700) of 11.8 grams of carboxy blockings and the PPDO list tridecyl ether (molecular weight is 2700) of 11.8 grams of carboxy blockings is added at dry reactor, add 443ml dimethyl sulfoxide (DMSO), then add 0.038 gram
n, N '-DIC, under inert atmosphere, in 32 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 PPDO modification
10 grams of polyvinyl alcohol-PTMC-PPDO dual graft multipolymers and 36ml dimethyl sulfoxide solvent is added in dry reactor, separately add the PPDO list tridecyl ether (molecular weight is 2700) accounting for modified membrane gross weight 3%, 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 13.3 ° and 13.6% before modified.
embodiment 3
1) preparation of polyvinyl alcohol-PTMC-PPDO dual graft multipolymer
22.1 grams of polyvinyl alcohol (molecular weight is 93000), the PTMC monododecyl ether (molecular weight is 2700) of 12 grams of carboxy blockings and the PPDO list tridecyl ether (molecular weight is 2700) of 12 grams of carboxy blockings is added at dry reactor, add 453ml dimethyl sulfoxide (DMSO), add 0.058 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, obtain target compound;
2) preparation of the polyvinyl alcohol film of PTMC and PPDO modification
9.5 grams of polyvinyl alcohol-PTMC-PPDO dual graft multipolymers and 35ml dimethyl sulfoxide solvent is added in dry reactor, separately add the PPDO list tridecyl ether (molecular weight is 2700) accounting for modified membrane gross weight 4%, 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 13.8 ° and 14.1% before modified.
Claims (4)
1. a PTMC and PPDO 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 87000 ~ 93000, the molecular weight of PTMC segment is 2600 ~ 2700, and the molecular weight of PPDO segment is 2600 ~ 2700; Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-PTMC-PPDO dual graft multipolymer: add the PTMC monododecyl ether of carboxy blocking, the PPDO list tridecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 31 ~ 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 PPDO modification: add polyvinyl alcohol-PTMC-PPDO dual graft multipolymer, PPDO list tridecyl ether and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 50 ~ 60 minutes in 48 ~ 53 DEG C, also dry by casting method film forming, obtain target compound.
2. a kind of PTMC according to claim 1 and PPDO 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, and the mol ratio of PPDO list tridecyl ether and polyvinyl alcohol is 15 ~ 25:1.
3. a kind of PTMC according to claim 1 and PPDO 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 PPDO improve the method for polyvinyl alcohol film water tolerance and kindliness, it is characterized in that: step 2) in, the mass percent of PPDO list tridecyl ether in modified membrane is 2 ~ 4%, solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25 ~ 30g:100ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610148914.1A CN105542483B (en) | 2016-03-16 | 2016-03-16 | A kind of method that polytrimethylene carbonate improves polyvinyl alcohol film water resistance and compliance with polydioxanone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610148914.1A CN105542483B (en) | 2016-03-16 | 2016-03-16 | A kind of method that polytrimethylene carbonate improves polyvinyl alcohol film water resistance and compliance with polydioxanone |
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| CN105542483A true CN105542483A (en) | 2016-05-04 |
| CN105542483B CN105542483B (en) | 2018-07-13 |
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| CN201610148914.1A Expired - Fee Related CN105542483B (en) | 2016-03-16 | 2016-03-16 | A kind of method that polytrimethylene carbonate improves polyvinyl alcohol film water resistance and compliance with polydioxanone |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977938A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
| CN106977953A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that PLA is improved with PPDO to polypropylene sorrel water resistance and compliance |
| CN106977945A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that polypropylene glycol improves polypropylene sorrel water resistance and compliance with PTMC |
| CN106977943A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with PPDO |
| CN106987140A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with PTMC |
| CN106987141A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that PLA improves polypropylene sorrel water resistance and compliance with PPDO |
| CN106987137A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that polypropylene glycol is improved with PTMC to polypropylene sorrel water resistance and compliance |
| 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 |
| CN107118566A (en) * | 2017-05-22 | 2017-09-01 | 山东理工大学 | A kind of method being improved with PPDO and polypropylene glycol to polypropylene sorrel water resistance and compliance |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977938A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
| CN106977943A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with PPDO |
| 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 |
| CN107118566A (en) * | 2017-05-22 | 2017-09-01 | 山东理工大学 | A kind of method being improved with PPDO and polypropylene glycol to polypropylene sorrel water resistance and compliance |
| CN106977953A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that PLA is improved with PPDO to polypropylene sorrel water resistance and compliance |
| CN106977945A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that polypropylene glycol improves polypropylene sorrel water resistance and compliance with PTMC |
| CN106987140A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with PTMC |
| CN106987141A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that PLA improves polypropylene sorrel water resistance and compliance with PPDO |
| CN106987137A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that polypropylene glycol is improved with PTMC to polypropylene sorrel water resistance and compliance |
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