CN106987138A - A kind of method that MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance - Google Patents
A kind of method that MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance Download PDFInfo
- Publication number
- CN106987138A CN106987138A CN201710376535.2A CN201710376535A CN106987138A CN 106987138 A CN106987138 A CN 106987138A CN 201710376535 A CN201710376535 A CN 201710376535A CN 106987138 A CN106987138 A CN 106987138A
- Authority
- CN
- China
- Prior art keywords
- mpegpla
- ptmc
- polyacrylic acid
- poly
- water resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- External Artificial Organs (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
The present invention discloses a kind of method that MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance, using following steps：1）Hydroxy-end capped PTMC monododecyl ether, solvent, condensing agent and polyacrylic acid is added in dry reactor, stirring reaction 2~4 days obtains polyacrylic acid PTMC graft copolymer；2）Polyacrylic acid PTMC graft copolymer, amino-terminated MPEGPLA, solvent and condensing agent, stirring reaction 2~4 days are added in dry reactor, polyacrylic acid MPEGPLA PTMC dual graft copolymers are obtained；3）Dual graft copolymer, MPEGPLA and solvent are added in dry reactor, after stirring is mixed 50~60 minutes, with the tape casting film forming and drying, object of the present invention is obtained.Preparation technology of the present invention is simple, be easy to grasp, and gained Modified Membrane water resistance and compliance are greatly improved.
Description
Technical field
The present invention relates to a kind of method improved to polypropylene sorrel water resistance and compliance, belong to thin polymer film
Preparing technical field.
Background technology
Polyacrylic acid is a kind of biomaterial with good biocompatibility and biodegradability, polypropylene sorrel
It can be used as artificial skin etc., but polypropylene sorrel hydrophily is too strong and more stiff, lacks preferable water resistance and compliance, so that
Its application is limited to a certain extent.MPEGPLA（The weight ratio of polyethylene glycol and PLA is 10/90）With polytrimethylene carbon
Acid esters is the biomaterial with excellent biocompatibility and biodegradability, with good hydrophobicity and compliance.
First PTMC segment is grafted on polyacrylic acid strand and obtains poly acrylic acid-poly trimethylene carbonate and connects
Graft copolymer, then MPEGPLA segments are grafted to the polyacrylic acid in poly acrylic acid-poly trimethylene carbonate graft copolymer
Polyacrylic acid-MPEGPLA- PTMC dual graft copolymers are formed on segment, then again add MPEGPLA segments
Enter polyacrylic acid-MPEGPLA- PTMC dual grafts copolymer formation blend, modified polypropene sorrel be made,
So as to drastically increase the water resistance and compliance of polypropylene sorrel.
The content of the invention
It is preferable to polypropylene sorrel water resistance and submissive it is an object of the invention to provide a kind of simple to operate and effect
The method that property is improved.Its technical scheme is：
A kind of method that MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance, its
It is characterised by：The molecular weight of polyacrylic acid segment is 83000~93000 in Modified Membrane, point of PTMC segment
Son amount is that the molecular weight of 2500~2700, MPEGPLA segments is 2300~2400；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly trimethylene carbonate graft copolymer：Added in dry reactor hydroxy-end capped
Under PTMC monododecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 27~33 DEG C of stirrings
Reaction 2~4 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The synthesis of polyacrylic acid-MPEGPLA- PTMC dual graft copolymers：Added in dry reactor
Poly acrylic acid-poly trimethylene carbonate graft copolymer, amino-terminated MPEGPLA, solvent and condensing agent, inert atmosphere
Under, in 26~30 DEG C of stirring reactions 2~4 days, terminating reaction by filtering, dialysis, was dried, obtains object；
3）The preparation for the polypropylene sorrel that MPEGPLA is improved with PTMC：Poly- third is added in dry reactor
Under olefin(e) acid-MPEGPLA- PTMC dual grafts copolymer, MPEGPLA and solvent, inert atmosphere, in 46~50 DEG C
After stirring mixing 50~60 minutes, with the tape casting film forming and drying, object is obtained.
A kind of described MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance
Method, step 1）In, the mol ratio of PTMC monododecyl ether and polyacrylic acid is 15~25:1.
A kind of described MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance
Method, step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- second
Base -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.06~1.9:1, solvent uses two
Methyl sulfoxide, reactant solution concentration is 5~15 g:100 ml.
A kind of described MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance
Method, step 2）In, MPEGPLA is poly- using mono methoxy polyethylene glycol（D,L）Lactic acid copolymer（Polyethylene glycol and PLA
Weight ratio be 10/90）, polyacrylic acid segment in MPEGPLA and poly acrylic acid-poly trimethylene carbonate graft copolymer
Mol ratio is 15~25:1.
A kind of described MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance
Method, step 2）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- second
Base -1-（3- dimethylaminopropyls）Carbodiimide, condensing agent and in poly acrylic acid-poly trimethylene carbonate graft copolymer poly- third
The mol ratio of olefin(e) acid segment is 1.06~1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100
ml。
A kind of described MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance
Method, step 3）In, MPEGPLA is poly- using mono methoxy polyethylene glycol（D,L）Lactic acid copolymer（Polyethylene glycol and PLA
Weight ratio be 10/90）, mass percents of the MPEGPLA in Modified Membrane is 2~3%, and solvent uses dimethyl sulfoxide (DMSO), mixing
Thing solution concentration is 25~30 g:100 ml.
Compared with prior art, its advantage is the present invention：
1st, a kind of described MPEGPLA and PTMC are improved to polypropylene sorrel water resistance and compliance
Method, using esterification, amidation process and blending three kinds of means, it is simple to operate, be easy to grasp；
2nd, described polyacrylic acid improvement film water resistance and compliance are enhanced.
Embodiment
Embodiment 1
1）The preparation of poly acrylic acid-poly trimethylene carbonate graft copolymer
16.2 grams of polyacrylic acid are added in dry reactor（Molecular weight is 83000）, 9.1 grams of hydroxy-end capped polytrimethylenes
Carbonic ester monododecyl ether（Molecular weight is 2500）, 254 ml dimethyl sulfoxide (DMSO)s are added, 0.051 gram is addedN,N’- two rings
Under hexyl carbodiimide, inert atmosphere, in 27 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains mesh
Mark thing；
2）The preparation of polyacrylic acid-MPEGPLA- PTMC dual graft copolymers
Dry reactor add 12 grams of poly acrylic acid-poly trimethylene carbonate graft copolymers, 6.6 grams it is amino-terminated
MPEGPLA（Molecular weight is 2300）, 186 ml dimethyl sulfoxide (DMSO)s are added, 0.036 gram is addedN,N’- dicyclohexyl carbon two is sub-
Under amine, inert atmosphere, in 26 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains object；
3）The preparation for the polypropylene sorrel that MPEGPLA is improved with PTMC
10 grams of polyacrylic acid-MPEGPLA- PTMC dual graft copolymers and 37 are added in dry reactor
Ml dimethyl sulfoxide solvents, it is another to add the MPEGPLA for accounting for Modified Membrane gross weight 2%（Molecular weight is 2300）, under inert atmosphere, in
46 DEG C of stirrings are mixed 50 minutes, use the tape casting film forming, object is dried to obtain in 50 DEG C of vacuum drying chambers.
After tested：The surface contact angle and its elongation at break of object and water of the present invention respectively than improving before modified
12.5 ° and 9.4%.
Embodiment 2
1）The preparation of poly acrylic acid-poly trimethylene carbonate graft copolymer
15 grams of polyacrylic acid are added in dry reactor（Molecular weight is 87000）, 8.6 grams of hydroxy-end capped polytrimethylene carbon
Acid esters monododecyl ether（Molecular weight is 2600）, 235 ml dimethyl sulfoxide (DMSO)s are added, 0.028 gram is addedN,N’- diisopropyl
Under base carbodiimide, inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains target
Thing；
2）The preparation of polyacrylic acid-MPEGPLA- PTMC dual graft copolymers
Dry reactor add 12.2 grams of poly acrylic acid-poly trimethylene carbonate graft copolymers, 6.4 grams it is amino-terminated
MPEGPLA（Molecular weight is 2400）, 185 ml dimethyl sulfoxide (DMSO)s are added, 0.021 gram is addedN,N’- diisopropyl carbon two is sub-
Under amine, inert atmosphere, in 28 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains object；
3）The preparation for the polypropylene sorrel that MPEGPLA is improved with PTMC
9.9 grams of polyacrylic acid-MPEGPLA- PTMC dual graft copolymers and 36 are added in dry reactor
Ml dimethyl sulfoxide solvents, it is another to add the MPEGPLA for accounting for Modified Membrane gross weight 3%（Molecular weight is 2400）, under inert atmosphere, in
48 DEG C of stirrings are mixed 55 minutes, use the tape casting film forming, object is dried to obtain in 50 DEG C of vacuum drying chambers.
After tested：The surface contact angle and its elongation at break of object and water of the present invention respectively than improving before modified
13.1 ° and 9.9%.
Embodiment 3
1）The preparation of poly acrylic acid-poly trimethylene carbonate graft copolymer
15.5 grams of polyacrylic acid are added in dry reactor（Molecular weight is 93000）, 8.3 grams of hydroxy-end capped polytrimethylenes
Carbonic ester monododecyl ether（Molecular weight is 2700）, 239 ml dimethyl sulfoxide (DMSO)s are added, 0.041 gram of 3- ethyls -1- is added
（3- dimethylaminopropyls）Under carbodiimide, inert atmosphere, in 33 DEG C of stirring reactions 4 days, terminating reaction, by filtering, dialysis, dry
It is dry, obtain object；
2）The preparation of polyacrylic acid-MPEGPLA- PTMC dual graft copolymers
Dry reactor add 11.6 grams of poly acrylic acid-poly trimethylene carbonate graft copolymers, 5.6 grams it is amino-terminated
MPEGPLA（Molecular weight is 2400）, 173 ml dimethyl sulfoxide (DMSO)s are added, 0.028 gram of 3- ethyls -1- is added（3- diformazans ammonia third
Base）Under carbodiimide, inert atmosphere, in 30 DEG C of stirring reactions 4 days, terminating reaction by filtering, dialysis, was dried, obtains target
Thing；
3）The preparation for the polypropylene sorrel that MPEGPLA is improved with PTMC
9.5 grams of polyacrylic acid-MPEGPLA- PTMC dual graft copolymers and 35 are added in dry reactor
Ml dimethyl sulfoxide solvents, it is another to add the MPEGPLA for accounting for Modified Membrane gross weight 2%（Molecular weight is 2400）, under inert atmosphere, in
50 DEG C of stirrings are mixed 60 minutes, use the tape casting film forming, object is dried to obtain in 50 DEG C of vacuum drying chambers.
After tested：The surface contact angle and its elongation at break of object and water of the present invention respectively than improving before modified
13.7 ° and 10.4%.
Claims (6)
1. a kind of method that MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance,
It is characterized in that：The molecular weight of polyacrylic acid segment is 83000~93000 in Modified Membrane, PTMC segment
Molecular weight is that the molecular weight of 2500~2700, MPEGPLA segments is 2300~2400；Its modification method uses following steps：
1）The synthesis of poly acrylic acid-poly trimethylene carbonate graft copolymer：Added in dry reactor hydroxy-end capped
Under PTMC monododecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 27~33 DEG C of stirrings
Reaction 2~4 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The synthesis of polyacrylic acid-MPEGPLA- PTMC dual graft copolymers：Added in dry reactor
Poly acrylic acid-poly trimethylene carbonate graft copolymer, amino-terminated MPEGPLA, solvent and condensing agent, inert atmosphere
Under, in 26~30 DEG C of stirring reactions 2~4 days, terminating reaction by filtering, dialysis, was dried, obtains object；
3）The preparation for the polypropylene sorrel that MPEGPLA is improved with PTMC：Poly- third is added in dry reactor
Under olefin(e) acid-MPEGPLA- PTMC dual grafts copolymer, MPEGPLA and solvent, inert atmosphere, in 46~50 DEG C
After stirring mixing 50~60 minutes, with the tape casting film forming and drying, object is obtained.
2. a kind of MPEGPLA according to claim 1 and PTMC are to polypropylene sorrel water resistance and soft
The pliable method improved, it is characterised in that：Step 1）In, PTMC monododecyl ether and polyacrylic acid
Mol ratio be 15~25:1.
3. a kind of MPEGPLA according to claim 1 and PTMC are to polypropylene sorrel water resistance and soft
The pliable method improved, it is characterised in that：Step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’-
DIC or 3- ethyls -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is
1.06~1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. a kind of MPEGPLA according to claim 1 and PTMC are to polypropylene sorrel water resistance and soft
The pliable method improved, it is characterised in that：Step 2）In, MPEGPLA is poly- using mono methoxy polyethylene glycol（D,L）Lactic acid
Copolymer（The weight ratio of polyethylene glycol and PLA is 10/90）, MPEGPLA connects with poly acrylic acid-poly trimethylene carbonate
The mol ratio of polyacrylic acid segment is 15~25 in graft copolymer:1.
5. a kind of MPEGPLA according to claim 1 and PTMC are to polypropylene sorrel water resistance and soft
The pliable method improved, it is characterised in that：Step 2）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’-
DIC or 3- ethyls -1-（3- dimethylaminopropyls）Carbodiimide, condensing agent and poly acrylic acid-poly trimethylene
The mol ratio of polyacrylic acid segment is 1.06~1.9 in carbonic acid ester graft copolymer:1, solvent uses dimethyl sulfoxide (DMSO), reactant
Solution concentration is 5~15 g:100 ml.
6. a kind of MPEGPLA according to claim 1 and PTMC are to polypropylene sorrel water resistance and soft
The pliable method improved, it is characterised in that：Step 3）In, MPEGPLA is poly- using mono methoxy polyethylene glycol（D,L）Lactic acid
Copolymer（The weight ratio of polyethylene glycol and PLA is 10/90）, mass percents of the MPEGPLA in Modified Membrane is 2~3%,
Solvent uses dimethyl sulfoxide (DMSO), and mixture solution concentration is 25~30 g:100 ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710376535.2A CN106987138A (en) | 2017-05-25 | 2017-05-25 | A kind of method that MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710376535.2A CN106987138A (en) | 2017-05-25 | 2017-05-25 | A kind of method that MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106987138A true CN106987138A (en) | 2017-07-28 |
Family
ID=59419959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710376535.2A Pending CN106987138A (en) | 2017-05-25 | 2017-05-25 | A kind of method that MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106987138A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559216A (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 polyacrylic acid |
| CN105694474A (en) * | 2016-03-07 | 2016-06-22 | 山东理工大学 | Method for improving water resisting property and flexibility of polyvinyl alcohol film by means of poly trimethylene carbonate and poly lactic acid-glycolic acid |
-
2017
- 2017-05-25 CN CN201710376535.2A patent/CN106987138A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559216A (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 polyacrylic acid |
| CN105694474A (en) * | 2016-03-07 | 2016-06-22 | 山东理工大学 | Method for improving water resisting property and flexibility of polyvinyl alcohol film by means of poly trimethylene carbonate and poly lactic acid-glycolic acid |
Non-Patent Citations (1)
| Title |
|---|
| YANHUI MA ET AL: "Polymer Micelles from Poly(acrylic acid)-graft-polystyrene", 《MACROMOLECULES》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106987138A (en) | A kind of method that MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance | |
| CN106947259A (en) | A kind of method being improved with MPEGPLA and PTMC to polypropylene sorrel water resistance and compliance | |
| CN106987137A (en) | A kind of method that polypropylene glycol is improved with PTMC to polypropylene sorrel water resistance and compliance | |
| CN107033605A (en) | A kind of method being improved with MPEGPLA and polycaprolactone to polypropylene sorrel water resistance and compliance | |
| CN106977954A (en) | A kind of method that MPEGPLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance | |
| CN107118571A (en) | A kind of method that PLA is improved with PTMC to polypropylene sorrel water resistance and compliance | |
| CN107011680A (en) | A kind of method that polycaprolactone is improved with PTMC to polypropylene sorrel water resistance and compliance | |
| CN107011679A (en) | A kind of method that MPEGPLA is improved with PPDO to polypropylene sorrel water resistance and compliance | |
| CN107118568A (en) | A kind of method that polypropylene glycol is improved with polycaprolactone to polypropylene sorrel water resistance and compliance | |
| CN107011665A (en) | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polycaprolactone | |
| CN106977940A (en) | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with PLA | |
| CN106987128A (en) | A kind of method being improved with PTMC and PLA to polypropylene sorrel water resistance and compliance | |
| CN106987136A (en) | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PTMC | |
| CN106947265A (en) | A kind of method that PPDO is improved with PTMC to polypropylene sorrel water resistance and compliance | |
| CN106977928A (en) | A kind of method being improved with MPEGPLA and PPDO to polypropylene sorrel water resistance and compliance | |
| CN106977944A (en) | A kind of method that poly (lactic acid-glycolic acid) is improved with PTMC to polypropylene sorrel water resistance and compliance | |
| CN107118570A (en) | A kind of method that PLA improves polypropylene sorrel water resistance and compliance with polycaprolactone | |
| CN106987134A (en) | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with polycaprolactone | |
| CN106987130A (en) | A kind of method being improved with PTMC and polycaprolactone to polypropylene sorrel water resistance and compliance | |
| CN107011672A (en) | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with polycaprolactone | |
| CN106977951A (en) | A kind of method that poly (lactic acid-glycolic acid) is improved with polycaprolactone to polypropylene sorrel water resistance and compliance | |
| CN107057376A (en) | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO | |
| CN106977938A (en) | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polypropylene glycol | |
| CN107011673A (en) | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with PPDO | |
| CN107011678A (en) | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with polycaprolactone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170728 |