CN105542209A - Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and poly(p-dioxanone) - Google Patents
Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and poly(p-dioxanone) Download PDFInfo
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- CN105542209A CN105542209A CN201610148958.4A CN201610148958A CN105542209A CN 105542209 A CN105542209 A CN 105542209A CN 201610148958 A CN201610148958 A CN 201610148958A CN 105542209 A CN105542209 A CN 105542209A
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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
- 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
- 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
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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
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention discloses a method for modifying the water resistance and flexibility of a polyvinyl alcohol membrane through polypeptide and poly(p-dioxanone). The method includes the following steps of firstly, synthesizing polyvinyl alcohol, polypeptide and poly(p-dioxanone) double-draft copolymers, wherein polypeptide homopolymer with the end sealed by a carboxyl group, poly(p-dioxanone) monododecyl ether with the end sealed by a carboxyl group, solvent, condensing agent and polyvinyl alcohol are added into a drying reactor to be stirred and react for 2-4 days at a temperature of 27-33 DEG C, and the target object is obtained through filtering, dialyzing and drying; secondly, preparing the polyvinyl alcohol membrane modified by polypeptide and poly(p-dioxanone), wherein the polyvinyl alcohol, polypeptide and poly(p-dioxanone) double-draft copolymers, poly(p-dioxanone) monododecyl ether and solvent are added into the drying reactor to be stirred and mixed for 50-60 minutes at a temperature of 48-50 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.Poly-peptide has excellent biocompatibility and the biomaterial of biodegradability, has excellent hydrophobicity.PPDO has excellent biocompatibility and the biomaterial of biodegradability, has good hydrophobicity and kindliness.First poly-peptide segment and PPDO segment are introduced polyvinyl alcohol segments simultaneously and form polyvinyl alcohol-poly-peptide-PPDO dual graft multipolymer, and then PPDO segment is added polyvinyl alcohol-poly-peptide-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 poly-peptide 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 84000 ~ 93000, the molecular weight of poly-peptide segment is 2600 ~ 2800, and the molecular weight of PPDO segment is 2600 ~ 2800; Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-poly-peptide-PPDO dual graft multipolymer: add the poly-peptide homopolymer of carboxy blocking, the PPDO monododecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 27 ~ 33 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 poly-peptide and PPDO modification: add polyvinyl alcohol-poly-peptide-PPDO dual graft multipolymer, PPDO monododecyl ether and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 50 ~ 60 minutes in 48 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
Described a kind of poly-peptide and PPDO improve the method for polyvinyl alcohol film water tolerance and kindliness, in step 1), the mol ratio of PPDO monododecyl ether and polyvinyl alcohol is 15 ~ 25:1, poly-peptide homopolymer adopts poly-(r-phenmethyl-Pidolidone ester), poly-(r-ethyl-L-glutamate ester) or poly-(r-methyl-Pidolidone ester), and the mol ratio of poly-peptide homopolymer and polyvinyl alcohol is 15 ~ 25:1.
Described a kind of poly-peptide 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 1.08 ~ 1.9:1, and solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15g:100ml.
Described a kind of poly-peptide and PPDO improve the method for polyvinyl alcohol film water tolerance and kindliness, step 2) in, the mass percent of PPDO monododecyl ether in modified membrane is 2 ~ 3%, 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 poly-peptide 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-poly-peptide-PPDO dual graft multipolymer
18 grams of polyvinyl alcohol (molecular weight is 84000), poly-(r-phenmethyl-Pidolidone ester) (molecular weight is 2600) of 9.9 grams of carboxy blockings and the PPDO monododecyl ether (molecular weight is 2600) of 9.9 grams of carboxy blockings is added at dry reactor, add 354ml dimethyl sulfoxide (DMSO), then add 0.056 gram
n, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 27 DEG C of stirring reactions 2 days, termination reaction, by filtering, dialysis, dry, obtains target compound;
2) preparation of the polyvinyl alcohol film of poly-peptide and PPDO modification
10 grams of polyvinyl alcohol-poly-peptide-PPDO dual graft multipolymer and 37ml dimethyl sulfoxide solvent is added in dry reactor, separately add the PPDO monododecyl 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-poly-peptide-PPDO dual graft multipolymer
21.4 grams of polyvinyl alcohol (molecular weight is 87000), poly-(r-ethyl-L-glutamate ester) (molecular weight is 2700) of 11.8 grams of carboxy blockings and the PPDO monododecyl ether (molecular weight is 2700) of 11.8 grams of carboxy blockings is added at dry reactor, add 433ml dimethyl sulfoxide (DMSO), then add 0.038 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 poly-peptide and PPDO modification
10 grams of polyvinyl alcohol-poly-peptide-PPDO dual graft multipolymer and 36.5ml dimethyl sulfoxide solvent is added in dry reactor, separately add the PPDO monododecyl ether (molecular weight is 2700) accounting for modified membrane gross weight 3%, under inert atmosphere, 55 minutes are uniformly mixed in 49 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 12.9 ° and 13.2% before modified.
embodiment 3
1) preparation of polyvinyl alcohol-poly-peptide-PPDO dual graft multipolymer
22.2 grams of polyvinyl alcohol (molecular weight is 93000), poly-(r-methyl-Pidolidone ester) (molecular weight is 2800) of 12.1 grams of carboxy blockings and the PPDO monododecyl ether (molecular weight is 2800) of 12.1 grams of carboxy blockings is added at dry reactor, add 455ml dimethyl sulfoxide (DMSO), add 0.056 gram of 3-ethyl-1-(3-dimethylaminopropyl again) carbodiimide, under inert atmosphere, in 33 DEG C of stirring reactions 4 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) preparation of the polyvinyl alcohol film of poly-peptide and PPDO modification
9.5 grams of polyvinyl alcohol-poly-peptide-PPDO dual graft multipolymer and 35ml dimethyl sulfoxide solvent is added in dry reactor, separately add the PPDO monododecyl ether (molecular weight is 2800) accounting for modified membrane gross weight 3%, 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 13.4 ° and 14.2% before modified.
Claims (4)
1. a poly-peptide 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 84000 ~ 93000, the molecular weight of poly-peptide segment is 2600 ~ 2800, and the molecular weight of PPDO segment is 2600 ~ 2800; Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-poly-peptide-PPDO dual graft multipolymer: add the poly-peptide homopolymer of carboxy blocking, the PPDO monododecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 27 ~ 33 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 poly-peptide and PPDO modification: add polyvinyl alcohol-poly-peptide-PPDO dual graft multipolymer, PPDO monododecyl ether and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 50 ~ 60 minutes in 48 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
2. a kind of poly-peptide 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 PPDO monododecyl ether and polyvinyl alcohol is 15 ~ 25:1, poly-peptide homopolymer adopts poly-(r-phenmethyl-Pidolidone ester), poly-(r-ethyl-L-glutamate ester) or poly-(r-methyl-Pidolidone ester), and the mol ratio of poly-peptide homopolymer and polyvinyl alcohol is 15 ~ 25:1.
3. a kind of poly-peptide 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 1.08 ~ 1.9:1, and solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15g:100ml.
4. a kind of poly-peptide 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 monododecyl ether in modified membrane is 2 ~ 3%, solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25 ~ 30g:100ml.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610148958.4A CN105542209A (en) | 2016-03-16 | 2016-03-16 | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and poly(p-dioxanone) |
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|---|---|---|---|
| CN201610148958.4A CN105542209A (en) | 2016-03-16 | 2016-03-16 | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and poly(p-dioxanone) |
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| CN105542209A true CN105542209A (en) | 2016-05-04 |
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| CN201610148958.4A Pending CN105542209A (en) | 2016-03-16 | 2016-03-16 | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and poly(p-dioxanone) |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911380A (en) * | 2012-10-29 | 2013-02-06 | 北京爱美客生物科技有限公司 | Hyaluronan and biodegradable high polymer modified material and preparation method |
| CN103788607A (en) * | 2014-03-07 | 2014-05-14 | 山东理工大学 | Method for improving hydrophilicity of polypeptide film through p-dioxanone and waterborne polyurethane |
| CN103865089A (en) * | 2014-03-10 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide membrane by polylactic acid and polydioxanone |
| 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 |
| CN104479158A (en) * | 2015-01-06 | 2015-04-01 | 山东理工大学 | Method for improving hydrophilia and flexibility of polypeptide membrane through polydioxanone and polyethylene glycol |
-
2016
- 2016-03-16 CN CN201610148958.4A patent/CN105542209A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911380A (en) * | 2012-10-29 | 2013-02-06 | 北京爱美客生物科技有限公司 | Hyaluronan and biodegradable high polymer modified material and preparation method |
| CN103788607A (en) * | 2014-03-07 | 2014-05-14 | 山东理工大学 | Method for improving hydrophilicity of polypeptide film through p-dioxanone and waterborne polyurethane |
| CN103865089A (en) * | 2014-03-10 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide membrane by polylactic acid and polydioxanone |
| 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 |
| CN104479158A (en) * | 2015-01-06 | 2015-04-01 | 山东理工大学 | Method for improving hydrophilia and flexibility of polypeptide membrane through polydioxanone and polyethylene glycol |
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