CN106947259A - A kind of method being improved with MPEGPLA and PTMC to polypropylene sorrel water resistance and compliance - Google Patents
A kind of method being improved with MPEGPLA and PTMC to polypropylene sorrel water resistance and compliance Download PDFInfo
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- CN106947259A CN106947259A CN201710362563.9A CN201710362563A CN106947259A CN 106947259 A CN106947259 A CN 106947259A CN 201710362563 A CN201710362563 A CN 201710362563A CN 106947259 A CN106947259 A CN 106947259A
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- ptmc
- mpegpla
- compliance
- water resistance
- polypropylene sorrel
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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
- 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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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Abstract
The present invention discloses a kind of method being improved with MPEGPLA and PTMC to polypropylene sorrel water resistance and compliance, using following steps：1）The synthesis of polyacrylic acid PTMC graft copolymer：Add hydroxy-end capped PTMC monododecyl ether, solvent, condensing agent and polyacrylic acid in dry reactor, stirring reaction 2~3 days, terminating reaction obtains object；2）The preparation for the polypropylene sorrel that MPEGPLA is modified with PTMC：Polyacrylic acid PTMC 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 being 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.
PTMC segment is first introduced into the formation poly acrylic acid-poly trimethylene carbonate graft copolymerization of polyacrylic acid segment
Thing, then adds poly acrylic acid-poly trimethylene carbonate graft copolymer formation blend by MPEGPLA segments again, is made
Modified polypropene sorrel, 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 being improved with MPEGPLA and PTMC to polypropylene sorrel water resistance and compliance,
It is characterized in that：The molecular weight of polyacrylic acid segment is 82000~89000 in Modified Membrane, PTMC segment
Molecular weight is that the molecular weight of 2100~2400, MPEGPLA segments is 4600~5000；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 26~32 DEG C of stirrings
Reaction 2~3 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The preparation for the polypropylene sorrel that MPEGPLA is modified with PTMC：Poly- third is added in dry reactor
Under olefin(e) acid-PTMC graft copolymer, MPEGPLA and solvent, inert atmosphere, in 46~52 DEG C of stirring mixing 50
After~60 minutes, with the tape casting film forming and drying, object is obtained.
Described one kind is changed with MPEGPLA with PTMC to polypropylene sorrel water resistance and compliance
The method entered, step 1）In, the mol ratio of PTMC monododecyl ether and polyacrylic acid is 15~25:1.
Described one kind is changed with MPEGPLA with PTMC to polypropylene sorrel water resistance and compliance
The method entered, 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 1.07~1.9:1, solvent uses two
Methyl sulfoxide, reactant solution concentration is 5~15 g:100 ml.
Described one kind is changed with MPEGPLA with PTMC to polypropylene sorrel water resistance and compliance
The method entered, step 2）In, MPEGPLA is poly- using mono methoxy polyethylene glycol（D,L）Lactic acid copolymer（Polyethylene glycol and poly- breast
The weight ratio of acid is 10/90）, mass percents of the MPEGPLA in Modified Membrane is 1~3%, and solvent uses dimethyl sulfoxide (DMSO), is mixed
Polymer solution concentration is 25~30 g:100 ml.
Compared with prior art, its advantage is the present invention：
1st, described one kind is improved with MPEGPLA and PTMC to polypropylene sorrel water resistance and compliance
Method, using esterification and blending two kinds of means, it is simple to operate, be easy to grasp；
2nd, described polyacrylic acid modified film water resistance and compliance are enhanced.
Embodiment
Embodiment 1
1）The preparation of poly acrylic acid-poly trimethylene carbonate graft copolymer
20.2 grams of polyacrylic acid are added in dry reactor（Molecular weight is 82000）With 9.3 grams of hydroxy-end capped poly- three methylenes
Base carbonic ester monododecyl ether（Molecular weight is 2100）, 294 ml dimethyl sulfoxide (DMSO)s are added, 0.061 gram is addedN,N’- two
Under carbodicyclo hexylimide, inert atmosphere, in 26 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtained
Object；
2）The preparation for the polypropylene sorrel that MPEGPLA is modified with PTMC
10 grams of poly acrylic acid-poly trimethylene carbonate graft copolymers are added in dry reactor and 37 ml dimethyl are sub-
Sulfoxide solvent, it is another to add the MPEGPLA for accounting for Modified Membrane gross weight 1%（Molecular weight is 4600）, it is mixed in 46 DEG C of stirrings under inert atmosphere
Close 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
11.8 ° and 9.7%.
Embodiment 2
1）The preparation of poly acrylic acid-poly trimethylene carbonate graft copolymer
21 grams of polyacrylic acid are added in dry reactor（Molecular weight is 85000）With 10.3 grams of hydroxy-end capped polytrimethylenes
Carbonic ester monododecyl ether（Molecular weight is 2200）, 312 ml dimethyl sulfoxide (DMSO)s are added, 0.038 gram is addedN,N’- two is different
Under propyl group carbodiimide, inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains mesh
Mark thing；
2）The preparation for the polypropylene sorrel that MPEGPLA is modified with PTMC
9.9 grams of poly acrylic acid-poly trimethylene carbonate graft copolymers and 36.5 ml dimethyl are added in dry reactor
Sulfoxide solvent, it is another to add the MPEGPLA for accounting for Modified Membrane gross weight 2%（Molecular weight is 4800）, under inert atmosphere, in 48 DEG C of stirrings
Mixing 55 minutes, uses 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
12.2 ° and 10.3%.
Embodiment 3
1）The preparation of poly acrylic acid-poly trimethylene carbonate graft copolymer
21.5 grams of polyacrylic acid are added in dry reactor（Molecular weight is 89000）With 10.8 grams of hydroxy-end capped poly- three methylenes
Base carbonic ester monododecyl ether（Molecular weight is 2400）, add 321 ml dimethyl sulfoxide (DMSO)s, add 0.058 gram of 3- ethyl-
1-（3- dimethylaminopropyls）Under carbodiimide, inert atmosphere, in 32 DEG C of stirring reactions 2 days, terminating reaction, by filtering, dialysis,
Dry, obtain object；
2）The preparation for the polypropylene sorrel that MPEGPLA is modified with PTMC
9.5 grams of poly acrylic acid-poly trimethylene carbonate graft copolymers are added in dry reactor and 35 ml dimethyl are sub-
Sulfoxide solvent, it is another to add the MPEGPLA for accounting for Modified Membrane gross weight 3%（Molecular weight is 5000）, it is mixed in 52 DEG C of stirrings under inert atmosphere
Close 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
12.9 ° and 10.8%.
Claims (4)
1. a kind of side being improved with MPEGPLA and PTMC to polypropylene sorrel water resistance and compliance
Method, it is characterised in that：The molecular weight of polyacrylic acid segment is 82000~89000, PTMC segment in Modified Membrane
Molecular weight be that the molecular weight of 2100~2400, MPEGPLA segments is 4600~5000；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 26~32 DEG C of stirrings
Reaction 2~3 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The preparation for the polypropylene sorrel that MPEGPLA is modified with PTMC：Poly- third is added in dry reactor
Under olefin(e) acid-PTMC graft copolymer, MPEGPLA and solvent, inert atmosphere, in 46~52 DEG C of stirring mixing 50
After~60 minutes, with the tape casting film forming and drying, object is obtained.
2. it is according to claim 1 it is a kind of with MPEGPLA and PTMC to polypropylene sorrel water resistance and
The method that compliance is improved, it is characterised in that：Step 1）In, PTMC monododecyl ether and polypropylene
The mol ratio of acid is 15~25:1.
3. it is according to claim 1 it is a kind of with MPEGPLA and PTMC to polypropylene sorrel water resistance and
The method that compliance is 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
For 1.07~1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. it is according to claim 1 it is a kind of with MPEGPLA and PTMC to polypropylene sorrel water resistance and
The method that compliance is improved, it is characterised in that：Step 2）In, MPEGPLA is poly- using mono methoxy polyethylene glycol（D,L）Breast
Acid copolymer（The weight ratio of polyethylene glycol and PLA is 10/90）, mass percents of the MPEGPLA in Modified Membrane be 1~
3%, solvent uses dimethyl sulfoxide (DMSO), and mixture solution concentration is 25~30 g:100 ml.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710362563.9A CN106947259A (en) | 2017-05-22 | 2017-05-22 | A kind of method being improved with MPEGPLA and PTMC to polypropylene sorrel water resistance and compliance |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710362563.9A CN106947259A (en) | 2017-05-22 | 2017-05-22 | A kind of method being improved with MPEGPLA and PTMC to polypropylene sorrel water resistance and compliance |
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| Publication Number | Publication Date |
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| CN106947259A true CN106947259A (en) | 2017-07-14 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105542481A (en) * | 2016-03-16 | 2016-05-04 | 山东理工大学 | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(trimethylene carbonate) and polycaprolactone |
| CN105566922A (en) * | 2016-03-07 | 2016-05-11 | 山东理工大学 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly trimethylene carbonate and P (CPP-SA)-polyethylene glycol |
| CN105647195A (en) * | 2016-03-07 | 2016-06-08 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by polytrimethylene carbonate and polycaprolactone |
| 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
- 2017-05-22 CN CN201710362563.9A patent/CN106947259A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566922A (en) * | 2016-03-07 | 2016-05-11 | 山东理工大学 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly trimethylene carbonate and P (CPP-SA)-polyethylene glycol |
| CN105647195A (en) * | 2016-03-07 | 2016-06-08 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by polytrimethylene carbonate and polycaprolactone |
| 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 |
| CN105542481A (en) * | 2016-03-16 | 2016-05-04 | 山东理工大学 | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(trimethylene carbonate) and polycaprolactone |
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