CN105670304A - Method for improving water resistance and flexibility of polyvinyl alcohol film by using polycaprolactone and polylactic acid-glycollic acid - Google Patents
Method for improving water resistance and flexibility of polyvinyl alcohol film by using polycaprolactone and polylactic acid-glycollic acid Download PDFInfo
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- CN105670304A CN105670304A CN201610123780.8A CN201610123780A CN105670304A CN 105670304 A CN105670304 A CN 105670304A CN 201610123780 A CN201610123780 A CN 201610123780A CN 105670304 A CN105670304 A CN 105670304A
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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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- 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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- 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
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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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
Abstract
The invention discloses a method for improving the water resistance and flexibility of a polyvinyl alcohol film by using polycaprolactone and polylactic acid-glycollic acid. The method comprises the following steps: 1) adding carboxyl-capped polycaprolactone monododecyl ether, a solvent, a condensing agent and polyvinyl alcohol into a reactor for reacting to obtain a polyvinyl alcohol-polycaprolactone graft copolymer; 2) adding the polyvinyl alcohol-polycaprolactone graft copolymer, carboxyl-capped polylactic acid-glycollic acid monododecyl ether, a solvent and a condensing agent into the reactor for reacting to obtain a polyvinyl alcohol-polycaprolactone-polylactic acid-glycollic acid binary graft copolymer; and 3) adding the polyvinyl alcohol-polycaprolactone-polylactic acid-glycollic acid binary graft copolymer, polycaprolactone monododecyl ether and a solvent into the reactor, and mixing to obtain a film which is the target object. The method disclosed by the invention is simple in preparation technology and easy to master; and the water resistance and flexibility of the obtained modified film are greatly improved.
Description
Technical field
The present invention relates to a kind of method polyvinyl alcohol film water tolerance and kindliness improved, belong to field of polymer film preparing technology.
Background technology
Polyvinyl alcohol a kind of has good biocompatibility and the biomaterial of biodegradability, polyvinyl alcohol film can be used as artificial skin etc., but polyvinyl alcohol film wetting ability is too strong and more stiff, lack good water tolerance and kindliness, thus limit its application to a certain extent. Polycaprolactone and poly-(D, Pfansteihl) oxyacetic acid (weight ratio of lactic acid and oxyacetic acid is 90/10) have excellent biocompatibility and the biomaterial of biodegradability, has good hydrophobicity and kindliness. First polycaprolactone segment is introduced polyvinyl alcohol segments and form polyvinyl alcohol-polycaprolactone graft copolymer, again poly (lactic acid-glycolic acid) segment is introduced and the polyvinyl alcohol segments in polyvinyl alcohol-polycaprolactone graft copolymer obtains polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft multipolymer, and then polycaprolactone segment added polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft multipolymer form blend, obtained modified PVA membrane, thus drastically increase water tolerance and the kindliness of polyvinyl alcohol film.
Summary of the invention
It is an object of the invention to provide a kind of method that polyvinyl alcohol film water tolerance and kindliness are improved by simple to operate and effect preferably. Its technical scheme is:
A kind of method that polyvinyl alcohol film water tolerance and kindliness are improved by polycaprolactone and poly (lactic acid-glycolic acid), it is characterized in that: in modified membrane, the molecular weight of polyvinyl alcohol segments is 83000～94000, the molecular weight of polycaprolactone segment is 2800～2900, and the molecular weight of poly (lactic acid-glycolic acid) segment is 2300～2400; Its method of modifying adopts following step:
1) preparation 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 28～33 DEG C of stirring reactions 2～3 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) preparation of polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft multipolymer: add polyvinyl alcohol-polycaprolactone graft copolymer, the poly (lactic acid-glycolic acid) monododecyl ether of carboxy blocking, solvent and condensing agent in dry reactor, under inert atmosphere, in 26～33 DEG C of stirring reactions 2～4 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
3) preparation of the polyvinyl alcohol film of polycaprolactone and poly (lactic acid-glycolic acid) modification: add polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft multipolymer, polycaprolactone monododecyl ether and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 50～60 minutes in 49～53 DEG C, also dry by casting method film forming, obtain target compound.
The method that polyvinyl alcohol film water tolerance and kindliness are improved by described a kind of polycaprolactone and poly (lactic acid-glycolic acid), in step 1), the mol ratio of polycaprolactone monododecyl ether and polyvinyl alcohol is 15～25:1.
The method that polyvinyl alcohol film water tolerance and kindliness are improved by described a kind of polycaprolactone and poly (lactic acid-glycolic acid), 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 1.07～1.9:1, and solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15g:100ml.
The method that polyvinyl alcohol film water tolerance and kindliness are improved by described a kind of polycaprolactone and poly (lactic acid-glycolic acid), step 2) in, poly (lactic acid-glycolic acid) monododecyl ether adopts poly-(D, Pfansteihl) oxyacetic acid monododecyl ether, and the weight ratio of lactic acid and oxyacetic acid is 90/10, the mol ratio of the polyvinyl alcohol segments in poly (lactic acid-glycolic acid) monododecyl ether and polyvinyl alcohol-polycaprolactone graft copolymer is 15～25:1.
The method that polyvinyl alcohol film water tolerance and kindliness are improved by described a kind of polycaprolactone and poly (lactic acid-glycolic acid), step 2) in, condensing agent adoptsN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, the mol ratio of the polyvinyl alcohol segments in condensing agent and polyvinyl alcohol-polycaprolactone graft copolymer is 1.07～1.9:1, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15g:100ml.
The method that polyvinyl alcohol film water tolerance and kindliness are improved by described a kind of polycaprolactone and poly (lactic acid-glycolic acid), in step 3), the mass percent of polycaprolactone monododecyl 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:
The method that polyvinyl alcohol film water tolerance and kindliness are improved by 1, described a kind of polycaprolactone and poly (lactic acid-glycolic acid), adopts two step esterifications and blended three 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-polycaprolactone graft copolymer
Add the polycaprolactone monododecyl ether (molecular weight is 2800) of 18 grams of polyvinyl alcohol (molecular weight is 83000) and 11.3 grams of carboxy blockings at dry reactor, add 275ml dimethyl sulfoxide (DMSO), then add 0.056 gramN,N’-dicyclohexylcarbodiimide, under inert atmosphere, in 28 DEG C of stirring reactions 2 days, termination reaction, by filtering, dialysis, dry, obtains target compound;
2) preparation of polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft multipolymer
Add the poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 2300) of 10 grams of polyvinyl alcohol-polycaprolactone graft copolymer and 5.1 grams of carboxy blockings at dry reactor, add 149ml dimethyl sulfoxide (DMSO), then add 0.031 gramN,N’-dicyclohexylcarbodiimide, under inert atmosphere, in 26 DEG C of stirring reactions 2 days, termination reaction, by filtering, dialysis, dry, obtains target compound;
3) preparation of the polyvinyl alcohol film of polycaprolactone and poly (lactic acid-glycolic acid) modification
10 grams of polyvinyl alcohol-polycaprolactones-poly (lactic acid-glycolic acid) dual graft multipolymer and 37ml dimethyl sulfoxide solvent is added in dry reactor, separately add the polycaprolactone monododecyl ether (molecular weight is 2800) accounting for modified membrane gross weight 2%, under inert atmosphere, it is uniformly mixed 50 minutes in 49 DEG C, using 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 12.3 ° and 12.6% before modified.
Embodiment 2
1) preparation of polyvinyl alcohol-polycaprolactone graft copolymer
Add the polycaprolactone monododecyl ether (molecular weight is 2800) of 18.2 grams of polyvinyl alcohol (molecular weight is 88000) and 10.8 grams of carboxy blockings at dry reactor, add 276ml dimethyl sulfoxide (DMSO), then add 0.032 gramN,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 polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft multipolymer
Add the poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 2300) of 10.3 grams of polyvinyl alcohol-polycaprolactone graft copolymer and 4.9 grams of carboxy blockings at dry reactor, add 147ml dimethyl sulfoxide (DMSO), then add 0.019 gramN,N’-DIC, under inert atmosphere, in 30 DEG C of stirring reactions 3 days, termination reaction, by filtering, dialysis, dry, obtains target compound;
3) preparation of the polyvinyl alcohol film of polycaprolactone and poly (lactic acid-glycolic acid) modification
9.8 grams of polyvinyl alcohol-polycaprolactones-poly (lactic acid-glycolic acid) dual graft multipolymer and 36ml dimethyl sulfoxide solvent is added in dry reactor, separately add the polycaprolactone monododecyl ether (molecular weight is 2800) accounting for modified membrane gross weight 3%, under inert atmosphere, it is uniformly mixed 55 minutes in 51 DEG C, using 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 13.2% before modified.
Embodiment 3
1) preparation of polyvinyl alcohol-polycaprolactone graft copolymer
The polycaprolactone monododecyl ether (molecular weight is 2900) of 18.3 grams of polyvinyl alcohol (molecular weight is 94000) and 10.3 grams of carboxy blockings is added at dry reactor, add 266ml dimethyl sulfoxide (DMSO), add 0.049 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 polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft multipolymer
The poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 2400) of 10 grams of polyvinyl alcohol-polycaprolactone graft copolymer and 4.7 grams of carboxy blockings is added at dry reactor, add 146ml dimethyl sulfoxide (DMSO), add 0.027 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, obtains target compound;
3) preparation of the polyvinyl alcohol film of polycaprolactone and poly (lactic acid-glycolic acid) modification
9.5 grams of polyvinyl alcohol-polycaprolactones-poly (lactic acid-glycolic acid) dual graft multipolymer and 35ml dimethyl sulfoxide solvent is added in dry reactor, separately add the polycaprolactone monododecyl ether (molecular weight is 2900) accounting for modified membrane gross weight 4%, under inert atmosphere, it is uniformly mixed 60 minutes in 53 DEG C, using 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 13.7 ° and 14.1% before modified.
Claims (6)
1. method polyvinyl alcohol film water tolerance and kindliness improved with polycaprolactone and poly (lactic acid-glycolic acid), it is characterized in that: in modified membrane, the molecular weight of polyvinyl alcohol segments is 83000～94000, the molecular weight of polycaprolactone segment is 2800～2900, and the molecular weight of poly (lactic acid-glycolic acid) segment is 2300～2400; Its method of modifying adopts following step:
1) preparation 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 28～33 DEG C of stirring reactions 2～3 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) preparation of polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft multipolymer: add polyvinyl alcohol-polycaprolactone graft copolymer, the poly (lactic acid-glycolic acid) monododecyl ether of carboxy blocking, solvent and condensing agent in dry reactor, under inert atmosphere, in 26～33 DEG C of stirring reactions 2～4 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
3) preparation of the polyvinyl alcohol film of polycaprolactone and poly (lactic acid-glycolic acid) modification: add polyvinyl alcohol-polycaprolactone-poly (lactic acid-glycolic acid) dual graft multipolymer, polycaprolactone monododecyl ether and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 50～60 minutes in 49～53 DEG C, also dry by casting method film forming, obtain target compound.
2. the method that polyvinyl alcohol film water tolerance and kindliness are improved by a kind of polycaprolactone according to claim 1 and poly (lactic acid-glycolic acid), 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 polyvinyl alcohol film water tolerance and kindliness are improved by a kind of polycaprolactone according to claim 1 and poly (lactic acid-glycolic acid), 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 1.07～1.9:1, and solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15g:100ml.
4. the method that polyvinyl alcohol film water tolerance and kindliness are improved by a kind of polycaprolactone according to claim 1 and poly (lactic acid-glycolic acid), it is characterized in that: step 2) in, poly (lactic acid-glycolic acid) monododecyl ether adopts poly-(D, Pfansteihl) oxyacetic acid monododecyl ether, and the weight ratio of lactic acid and oxyacetic acid is 90/10, the mol ratio of the polyvinyl alcohol segments in poly (lactic acid-glycolic acid) monododecyl ether and polyvinyl alcohol-polycaprolactone graft copolymer is 15～25:1.
5. the method that polyvinyl alcohol film water tolerance and kindliness are improved by a kind of polycaprolactone according to claim 1 and poly (lactic acid-glycolic acid), it is characterised in that: step 2) in, condensing agent adoptsN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, the mol ratio of the polyvinyl alcohol segments in condensing agent and polyvinyl alcohol-polycaprolactone graft copolymer is 1.07～1.9:1, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15g:100ml.
6. the method that polyvinyl alcohol film water tolerance and kindliness are improved by a kind of polycaprolactone according to claim 1 and poly (lactic acid-glycolic acid), it is characterized in that: in step 3), the mass percent of polycaprolactone monododecyl ether in modified membrane is 2～4%, solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25～30g:100ml.
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| CN201610123780.8A CN105670304A (en) | 2016-03-07 | 2016-03-07 | Method for improving water resistance and flexibility of polyvinyl alcohol film by using polycaprolactone and polylactic acid-glycollic acid |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977936A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of polycaprolactone is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance |
| CN106977950A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with PPDO |
| CN106977951A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that poly (lactic acid-glycolic acid) is improved with polycaprolactone to polypropylene sorrel water resistance and compliance |
| CN106977931A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
| CN106987124A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of method being improved with polycaprolactone and PLA to polypropylene sorrel water resistance and compliance |
| CN107011675A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid) |
| CN107011678A (en) * | 2017-05-25 | 2017-08-04 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with polycaprolactone |
| CN107057377A (en) * | 2017-05-25 | 2017-08-18 | 山东理工大学 | A kind of method that MPEGPLA is improved with polypropylene glycol to polypropylene sorrel water resistance and compliance |
| CN107118568A (en) * | 2017-05-25 | 2017-09-01 | 山东理工大学 | A kind of method that polypropylene glycol is improved with polycaprolactone to polypropylene sorrel water resistance and compliance |
| CN107118569A (en) * | 2017-05-25 | 2017-09-01 | 山东理工大学 | A kind of method that poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with polycaprolactone |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103865274A (en) * | 2014-03-14 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide film by poly(lactic acid-glycolic acid) and poly(caprolactone-lactide) |
| CN103865275A (en) * | 2014-04-11 | 2014-06-18 | 山东理工大学 | Method for improving the water resistance of polyethylene glycol film modified by polylactic acid and polyvinyl alcohol |
| 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) |
-
2016
- 2016-03-07 CN CN201610123780.8A patent/CN105670304A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865274A (en) * | 2014-03-14 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide film by poly(lactic acid-glycolic acid) and poly(caprolactone-lactide) |
| 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 |
| 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) |
| CN103865275A (en) * | 2014-04-11 | 2014-06-18 | 山东理工大学 | Method for improving the water resistance of polyethylene glycol film modified by polylactic acid and polyvinyl alcohol |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977936A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of polycaprolactone is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance |
| CN106977931A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
| CN106987124A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of method being improved with polycaprolactone and PLA to polypropylene sorrel water resistance and compliance |
| CN107011675A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid) |
| CN106977950A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with PPDO |
| CN106977951A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that poly (lactic acid-glycolic acid) is improved with polycaprolactone to polypropylene sorrel water resistance and compliance |
| CN107011678A (en) * | 2017-05-25 | 2017-08-04 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with polycaprolactone |
| CN107057377A (en) * | 2017-05-25 | 2017-08-18 | 山东理工大学 | A kind of method that MPEGPLA is improved with polypropylene glycol to polypropylene sorrel water resistance and compliance |
| CN107118568A (en) * | 2017-05-25 | 2017-09-01 | 山东理工大学 | A kind of method that polypropylene glycol is improved with polycaprolactone to polypropylene sorrel water resistance and compliance |
| CN107118569A (en) * | 2017-05-25 | 2017-09-01 | 山东理工大学 | A kind of method that poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with polycaprolactone |
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Application publication date: 20160615 |