CN105694474A - Method for improving water resisting property and flexibility of polyvinyl alcohol film by means of poly trimethylene carbonate and poly lactic acid-glycolic acid - Google Patents
Method for improving water resisting property and flexibility of polyvinyl alcohol film by means of poly trimethylene carbonate and poly lactic acid-glycolic acid Download PDFInfo
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- CN105694474A CN105694474A CN201610125952.5A CN201610125952A CN105694474A CN 105694474 A CN105694474 A CN 105694474A CN 201610125952 A CN201610125952 A CN 201610125952A CN 105694474 A CN105694474 A CN 105694474A
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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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 resisting property and flexibility of a polyvinyl alcohol film by means of poly trimethylene carbonate and poly lactic acid-glycolic acid. The method comprises the following steps that firstly, carboxyl end capped poly trimethylene carbonate single lauryl ether, solvent, a condensing agent and polyvinyl alcohol are added into a reactor, and after reaction, polyvinyl alcohol-poly trimethylene carbonate grafted copolymer is obtained; secondly, the polyvinyl alcohol-poly trimethylene carbonate grafted copolymer, carboxyl end capped poly lactic acid-glycolic acid single lauryl ether, solvent and a condensing agent are added into the reactor, and after reaction, polyvinyl alcohol-poly trimethylene carbonate poly lactic acid-glycolic acid bi-grafted copolymer is obtained; thirdly, the polyvinyl alcohol-poly trimethylene carbonate poly lactic acid-glycolic acid bi-grafted copolymer, poly trimethylene carbonate single lauryl ether and solvent are added into the reactor and mixed to form the film, and the target object is obtained. The preparing technology is simple and easy to grasp, and the water resisting property and flexibility of the modified film are greatly improved.
Description
Technical field
The present invention relates to a kind of method that polyvinyl alcohol film resistance to water and compliance are improved, belong to field of polymer film preparing technology。
Background technology
Polyvinyl alcohol is a kind of biomaterial with good biocompatibility and biodegradability, polyvinyl alcohol film can be used as artificial skin etc., but polyvinyl alcohol film hydrophilic is too strong and more stiff, lack good resistance to water and compliance, thus limiting its application to a certain extent。PTMC and poly-(D, Pfansteihl) glycolic (weight ratio of lactic acid and glycolic is 90/10) are the biomaterials with excellent biocompatibility and biodegradability, have good hydrophobicity and compliance。First PTMC segment is introduced polyvinyl alcohol segments and form polyvinyl alcohol-PTMC graft copolymer, again poly (lactic acid-glycolic acid) segment is introduced and the polyvinyl alcohol segments in polyvinyl alcohol-PTMC graft copolymer obtains polyvinyl alcohol-PTMC-poly (lactic acid-glycolic acid) dual graft copolymer, then again PTMC segment is added polyvinyl alcohol-PTMC-poly (lactic acid-glycolic acid) dual graft copolymer and form blend, prepare modified PVA membrane, thus drastically increasing resistance to water and the compliance of polyvinyl alcohol film。
Summary of the invention
It is an object of the invention to provide the method that polyvinyl alcohol film resistance to water and compliance are improved by a kind of simple to operate and effect preferably。Its technical scheme is:
A kind of method that polyvinyl alcohol film resistance to water and compliance are improved by PTMC and poly (lactic acid-glycolic acid), it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 83000～93000, the molecular weight of PTMC segment is 2500～2800, and the molecular weight of poly (lactic acid-glycolic acid) segment is 2100～2200；Its method of modifying adopts following steps:
1) preparation 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 30～34 DEG C of stirring reactions 2～3 days, terminate reaction, by filtering, dialyse, drying, obtain object；
2) preparation of polyvinyl alcohol-PTMC-poly (lactic acid-glycolic acid) dual graft copolymer: add polyvinyl alcohol-PTMC graft copolymer, the poly (lactic acid-glycolic acid) monododecyl ether of carboxy blocking, solvent and condensing agent in dry reactor, under inert atmosphere, in 30～33 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialyse, drying, obtain object；
3) preparation of the polyvinyl alcohol film that PTMC is modified with poly (lactic acid-glycolic acid): add polyvinyl alcohol-PTMC-poly (lactic acid-glycolic acid) dual graft copolymer, PTMC monododecyl ether and solvent in dry reactor, under inert atmosphere, after stirring mixing 50～60 minutes in 47～53 DEG C, by the tape casting film forming and dry, obtain object。
The method that polyvinyl alcohol film resistance to water and compliance are improved by described a kind of PTMC and poly (lactic acid-glycolic acid), in step 1), the mol ratio of PTMC monododecyl ether and polyvinyl alcohol is 15～25:1。
The method that polyvinyl alcohol film resistance to water and compliance are improved by described a kind of PTMC 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 1.07～1.8:1, and solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15g:100ml。
The method that polyvinyl alcohol film resistance to water and compliance are improved by described a kind of PTMC and poly (lactic acid-glycolic acid), step 2) in, poly (lactic acid-glycolic acid) monododecyl ether adopts poly-(D, Pfansteihl) glycolic monododecyl ether, and the weight ratio of lactic acid and glycolic is 90/10, the mol ratio of the polyvinyl alcohol segments in poly (lactic acid-glycolic acid) monododecyl ether and polyvinyl alcohol-PTMC graft copolymer is 15～25:1。
The method that polyvinyl alcohol film resistance to water and compliance are improved by described a kind of PTMC 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-PTMC graft copolymer is 1.07～1.8:1, solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15g:100ml。
The method that polyvinyl alcohol film resistance to water and compliance are improved by described a kind of PTMC and poly (lactic acid-glycolic acid), in step 3), PTMC monododecyl ether mass percent in Modified Membrane is 2～4%, solvent adopts dimethyl sulfoxide, and mixture solution concentration is 25～30g:100ml。
Compared with prior art, its advantage is the present invention:
1, the method that polyvinyl alcohol film resistance to water and compliance are improved by described a kind of PTMC and poly (lactic acid-glycolic acid), adopts two step esterifications and blended three kinds of means, simple to operate, be prone to grasp；
2, described polyvinyl alcohol modification film resistance to water and compliance are enhanced。
Detailed description of the invention
Embodiment 1
1) preparation of polyvinyl alcohol-PTMC graft copolymer
Add the PTMC monododecyl ether (molecular weight is 2500) of 18 grams of polyvinyl alcohol (molecular weight is 83000) and 10 grams of carboxy blockings at dry reactor, add 260ml dimethyl sulfoxide, add 0.056 gramN,N’-dicyclohexylcarbodiimide, under inert atmosphere, in 30 DEG C of stirring reactions 2 days, terminates reaction, by filtering, dialysis, dry, obtains object；
2) preparation of polyvinyl alcohol-PTMC-poly (lactic acid-glycolic acid) dual graft copolymer
Add the poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 2100) of 10 grams of polyvinyl alcohol-PTMC graft copolymers and 4.6 grams of carboxy blockings at dry reactor, add 144ml dimethyl sulfoxide, add 0.031 gramN,N’-dicyclohexylcarbodiimide, under inert atmosphere, in 30 DEG C of stirring reactions 2 days, terminates reaction, by filtering, dialysis, dry, obtains object；
3) preparation of the polyvinyl alcohol film that PTMC is modified with poly (lactic acid-glycolic acid)
10 grams of polyvinyl alcohol-PTMC-poly (lactic acid-glycolic acid) dual graft copolymers and 37ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the PTMC monododecyl ether (molecular weight is 2500) of Modified Membrane gross weight 2%, under inert atmosphere, in 47 DEG C of stirring mixing 50 minutes, use the tape casting film forming, dry in 50 DEG C of vacuum drying ovens and obtain object。
After tested: the surface contact angle of object of the present invention and water and elongation at break thereof are respectively than improve 12.1 ° and 12.4% before modified。
Embodiment 2
1) preparation of polyvinyl alcohol-PTMC graft copolymer
Add the PTMC monododecyl ether (molecular weight is 2700) of 18.2 grams of polyvinyl alcohol (molecular weight is 88000) and 9.8 grams of carboxy blockings at dry reactor, add 265ml dimethyl sulfoxide, add 0.032 gramN,N’-DIC, under inert atmosphere, in 32 DEG C of stirring reactions 3 days, terminates reaction, by filtering, dialysis, dry, obtains object；
2) preparation of polyvinyl alcohol-PTMC-poly (lactic acid-glycolic acid) dual graft copolymer
Add the poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 2200) of 10.3 grams of polyvinyl alcohol-PTMC graft copolymers and 4.6 grams of carboxy blockings at dry reactor, add 143ml dimethyl sulfoxide, add 0.019 gramN,N’-DIC, under inert atmosphere, in 32 DEG C of stirring reactions 3 days, terminates reaction, by filtering, dialysis, dry, obtains object；
3) preparation of the polyvinyl alcohol film that PTMC is modified with poly (lactic acid-glycolic acid)
9.8 grams of polyvinyl alcohol-PTMC-poly (lactic acid-glycolic acid) dual graft copolymers and 36ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the PTMC monododecyl ether (molecular weight is 2700) of Modified Membrane gross weight 3%, under inert atmosphere, in 49 DEG C of stirring mixing 55 minutes, use the tape casting film forming, dry in 50 DEG C of vacuum drying ovens and obtain object。
After tested: the surface contact angle of object 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 graft copolymer
The PTMC monododecyl ether (molecular weight is 2800) of 18.3 grams of polyvinyl alcohol (molecular weight is 93000) and 10.3 grams of carboxy blockings is added at dry reactor, add 263ml dimethyl sulfoxide, add 0.049 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, in 34 DEG C of stirring reactions 2 days, terminate reaction, by filtering, dialyse, drying, obtain object；
2) preparation of polyvinyl alcohol-PTMC-poly (lactic acid-glycolic acid) dual graft copolymer
The poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 2200) of 10 grams of polyvinyl alcohol-PTMC graft copolymers and 4.4 grams of carboxy blockings is added at dry reactor, add 141ml dimethyl sulfoxide, add 0.027 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, in 33 DEG C of stirring reactions 4 days, terminate reaction, by filtering, dialyse, drying, obtain object；
3) preparation of the polyvinyl alcohol film that PTMC is modified with poly (lactic acid-glycolic acid)
9.5 grams of polyvinyl alcohol-PTMC-poly (lactic acid-glycolic acid) dual graft copolymers and 35ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the PTMC monododecyl ether (molecular weight is 2800) of Modified Membrane gross weight 4%, under inert atmosphere, in 53 DEG C of stirring mixing 60 minutes, use the tape casting film forming, dry in 50 DEG C of vacuum drying ovens and obtain object。
After tested: the surface contact angle of object of the present invention and water and elongation at break thereof are respectively than improve 13.8 ° and 14.3% before modified。
Claims (6)
1. method polyvinyl alcohol film resistance to water and compliance improved with PTMC and poly (lactic acid-glycolic acid), it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 83000～93000, the molecular weight of PTMC segment is 2500～2800, and the molecular weight of poly (lactic acid-glycolic acid) segment is 2100～2200；Its method of modifying adopts following steps:
1) preparation 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 30～34 DEG C of stirring reactions 2～3 days, terminate reaction, by filtering, dialyse, drying, obtain object；
2) preparation of polyvinyl alcohol-PTMC-poly (lactic acid-glycolic acid) dual graft copolymer: add polyvinyl alcohol-PTMC graft copolymer, the poly (lactic acid-glycolic acid) monododecyl ether of carboxy blocking, solvent and condensing agent in dry reactor, under inert atmosphere, in 30～33 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialyse, drying, obtain object；
3) preparation of the polyvinyl alcohol film that PTMC is modified with poly (lactic acid-glycolic acid): add polyvinyl alcohol-PTMC-poly (lactic acid-glycolic acid) dual graft copolymer, PTMC monododecyl ether and solvent in dry reactor, under inert atmosphere, after stirring mixing 50～60 minutes in 47～53 DEG C, by the tape casting film forming and dry, obtain object。
2. the method that polyvinyl alcohol film resistance to water and compliance are improved by a kind of PTMC according to claim 1 and poly (lactic acid-glycolic acid), it is characterized in that: in step 1), the mol ratio of PTMC monododecyl ether and polyvinyl alcohol is 15～25:1。
3. the method that polyvinyl alcohol film resistance to water and compliance are improved by a kind of PTMC 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 1.07～1.8:1, and solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15g:100ml。
4. the method that polyvinyl alcohol film resistance to water and compliance are improved by a kind of PTMC 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) glycolic monododecyl ether, and the weight ratio of lactic acid and glycolic is 90/10, the mol ratio of the polyvinyl alcohol segments in poly (lactic acid-glycolic acid) monododecyl ether and polyvinyl alcohol-PTMC graft copolymer is 15～25:1。
5. the method that polyvinyl alcohol film resistance to water and compliance are improved by a kind of PTMC 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-PTMC graft copolymer is 1.07～1.8:1, solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15g:100ml。
6. the method that polyvinyl alcohol film resistance to water and compliance are improved by a kind of PTMC according to claim 1 and poly (lactic acid-glycolic acid), it is characterized in that: in step 3), PTMC monododecyl ether mass percent in Modified Membrane is 2～4%, solvent adopts dimethyl sulfoxide, and mixture solution concentration is 25～30g:100ml。
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| CN201610125952.5A CN105694474B (en) | 2016-03-07 | 2016-03-07 | A kind of method being improved with polytrimethylene carbonate and poly (lactic acid-glycolic acid) to polyvinyl alcohol film water resistance and compliance |
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| CN201610125952.5A CN105694474B (en) | 2016-03-07 | 2016-03-07 | A kind of method being improved with polytrimethylene carbonate and poly (lactic acid-glycolic acid) to polyvinyl alcohol film water resistance and compliance |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947265A (en) * | 2017-05-25 | 2017-07-14 | 山东理工大学 | A kind of method that PPDO is improved with PTMC to polypropylene sorrel water resistance and compliance |
| 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 |
| CN106977944A (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 PTMC to polypropylene sorrel water resistance and compliance |
| CN106977940A (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 PLA |
| CN106987138A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance |
| CN106987128A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of method being improved with PTMC and PLA to polypropylene sorrel water resistance and compliance |
| CN106987136A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PTMC |
| CN106987142A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with PTMC |
| CN107011679A (en) * | 2017-05-25 | 2017-08-04 | 山东理工大学 | A kind of method that MPEGPLA is improved with PPDO to polypropylene sorrel water resistance and compliance |
| CN107011677A (en) * | 2017-05-25 | 2017-08-04 | 山东理工大学 | A kind of method that PLA improves polypropylene sorrel water resistance and compliance with PTMC |
| CN107057374A (en) * | 2017-05-22 | 2017-08-18 | 山东理工大学 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid) |
| CN107057373A (en) * | 2017-05-22 | 2017-08-18 | 山东理工大学 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid) |
| CN107118571A (en) * | 2017-05-25 | 2017-09-01 | 山东理工大学 | A kind of method that PLA is improved with PTMC to polypropylene sorrel water resistance and compliance |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106987128A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of method being improved with PTMC and PLA to polypropylene sorrel water resistance and compliance |
| 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 |
| CN107057373A (en) * | 2017-05-22 | 2017-08-18 | 山东理工大学 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid) |
| CN106977940A (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 PLA |
| CN107057374A (en) * | 2017-05-22 | 2017-08-18 | 山东理工大学 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid) |
| CN106987136A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PTMC |
| CN106947265A (en) * | 2017-05-25 | 2017-07-14 | 山东理工大学 | A kind of method that PPDO is improved with PTMC to polypropylene sorrel water resistance and compliance |
| CN106987142A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with PTMC |
| CN107011679A (en) * | 2017-05-25 | 2017-08-04 | 山东理工大学 | A kind of method that MPEGPLA is improved with PPDO to polypropylene sorrel water resistance and compliance |
| CN107011677A (en) * | 2017-05-25 | 2017-08-04 | 山东理工大学 | A kind of method that PLA improves polypropylene sorrel water resistance and compliance with PTMC |
| CN106987138A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance |
| CN106977944A (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 PTMC to polypropylene sorrel water resistance and compliance |
| CN107118571A (en) * | 2017-05-25 | 2017-09-01 | 山东理工大学 | A kind of method that PLA is improved with PTMC to polypropylene sorrel water resistance and compliance |
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