CN106977954A - A kind of method that MPEGPLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance - Google Patents
A kind of method that MPEGPLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance Download PDFInfo
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- CN106977954A CN106977954A CN201710376612.4A CN201710376612A CN106977954A CN 106977954 A CN106977954 A CN 106977954A CN 201710376612 A CN201710376612 A CN 201710376612A CN 106977954 A CN106977954 A CN 106977954A
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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
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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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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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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- 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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Abstract
The present invention discloses a kind of method that MPEGPLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance, using following steps：1）Hydroxy-end capped polycaprolactone monododecyl ether, solvent, condensing agent and polyacrylic acid is added in dry reactor, stirring reaction 2~4 days obtains polyacrylic acid polycaprolactone graft copolymer；2）Polyacrylic acid polycaprolactone graft copolymer, amino-terminated MPEGPLA, solvent and condensing agent, stirring reaction 2~4 days are added in dry reactor, polyacrylic acid MPEGPLA polycaprolactone 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）It is tool with polycaprolactone
There are excellent biocompatibility and the biomaterial of biodegradability, with good hydrophobicity and compliance.Oneself will first be gathered
Lactone segment, which is grafted on polyacrylic acid strand, obtains poly acrylic acid-poly caprolactone graft copolymer, then by MPEGPLA segments
Polyacrylic acid-MPEGPLA- is formed on the polyacrylic acid segment being grafted in poly acrylic acid-poly caprolactone graft copolymer and gathers oneself
Lactone dual graft copolymer, then adds polyacrylic acid-MPEGPLA- polycaprolactone dual graft copolymers by MPEGPLA segments again
Blend is formed, modified polypropene sorrel is 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 polycaprolactone to polypropylene sorrel water resistance and compliance, it is characterised in that：
The molecular weight of polyacrylic acid segment is 83000~94000 in Modified Membrane, and the molecular weight of polycaprolactone segment is 2600~2700,
The molecular weight of MPEGPLA segments is 2300~2500；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly caprolactone graft copolymer：Hydroxy-end capped polycaprolactone is added in dry reactor
Under monododecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 27~34 DEG C of stirring reactions 2~4 days, terminate anti-
Should, by filtering, dialysis, dry, obtain object；
2）The synthesis of polyacrylic acid-MPEGPLA- polycaprolactone dual graft copolymers：In dry reactor add polyacrylic acid-
It is anti-in 26~31 DEG C of stirrings under polycaprolactone graft copolymer, amino-terminated MPEGPLA, solvent and condensing agent, inert atmosphere
Answer 2~4 days, terminating reaction, by filtering, dialysis, dry, obtain object；
3）The preparation for the polypropylene sorrel that MPEGPLA is improved with polycaprolactone：In dry reactor add polyacrylic acid-
Under MPEGPLA- polycaprolactone dual grafts copolymer, MPEGPLA and solvent, inert atmosphere, in 46~51 DEG C stirring mixing 50~
After 60 minutes, with the tape casting film forming and drying, object is obtained.
The method that a kind of described MPEGPLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance,
Step 1）In, the mol ratio of polycaprolactone monododecyl ether and polyacrylic acid is 15~25:1.
The method that a kind of described MPEGPLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance,
Step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-（3-
Dimethylaminopropyl）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.07~1.9:1, solvent uses dimethyl sulfoxide (DMSO),
Reactant solution concentration is 5~15 g:100 ml.
The method that a kind of described MPEGPLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance,
Step 2）In, MPEGPLA is poly- using mono methoxy polyethylene glycol（D,L）Lactic acid copolymer（The weight of polyethylene glycol and PLA
Than for 10/90）, in MPEGPLA and poly acrylic acid-poly caprolactone graft copolymer the mol ratio of polyacrylic acid segment for 15~
25:1。
The method that a kind of described MPEGPLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance,
Step 2）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-（3-
Dimethylaminopropyl）Carbodiimide, the mol ratio of condensing agent and polyacrylic acid segment in poly acrylic acid-poly caprolactone graft copolymer
For 1.07~1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
The method that a kind of described MPEGPLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance,
Step 3）In, MPEGPLA is poly- using mono methoxy polyethylene glycol（D,L）Lactic acid copolymer（The weight of polyethylene glycol and PLA
Than for 10/90）, mass percents of the MPEGPLA in Modified Membrane is 2~3%, and solvent uses dimethyl sulfoxide (DMSO), mixture solution
Concentration is 25~30 g:100 ml.
Compared with prior art, its advantage is the present invention：
1st, the method that a kind of described MPEGPLA and polycaprolactone are improved to polypropylene sorrel water resistance and compliance, is adopted
With 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 caprolactone graft copolymer
16.2 grams of polyacrylic acid are added in dry reactor（Molecular weight is 83000）, 9.3 grams of hydroxy-end capped polycaprolactone lists
Lauryl ether（Molecular weight is 2600）, 256 ml dimethyl sulfoxide (DMSO)s are added, 0.051 gram is addedN,N’- dicyclohexyl carbon two
Under imines, inert atmosphere, in 27 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation of polyacrylic acid-MPEGPLA- polycaprolactone dual graft copolymers
12 grams of poly acrylic acid-poly caprolactone graft copolymers, 6.5 grams of amino-terminated MPEGPLA are added in dry reactor（Point
Son amount is 2300）, 185 ml dimethyl sulfoxide (DMSO)s are added, 0.036 gram is addedN,N’- dicyclohexylcarbodiimide, inert atmosphere
Under, 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 polycaprolactone
10 grams of polyacrylic acid-MPEGPLA- polycaprolactone dual graft copolymers and 37 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 2300）, under inert atmosphere, in 46 DEG C of stirrings
Mixing 50 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
11.9 ° and 9.9%.
Embodiment 2
1）The preparation of poly acrylic acid-poly caprolactone graft copolymer
15 grams of polyacrylic acid are added in dry reactor（Molecular weight is 87000）, 8.7 grams of hydroxy-end capped polycaprolactone lists ten
Dialkyl ether（Molecular weight is 2600）, 237 ml dimethyl sulfoxide (DMSO)s are added, 0.028 gram is addedN,N’- diisopropyl carbon two is sub-
Under amine, inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation of polyacrylic acid-MPEGPLA- polycaprolactone dual graft copolymers
12.1 grams of poly acrylic acid-poly caprolactone graft copolymers, 6.4 grams of amino-terminated MPEGPLA are added in dry reactor
（Molecular weight is 2400）, 185 ml dimethyl sulfoxide (DMSO)s are added, 0.021 gram is addedN,N’- DIC, indifferent gas
Under 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 polycaprolactone
9.9 grams of polyacrylic acid-MPEGPLA- polycaprolactone dual graft copolymers and 36 ml dimethyl are added in dry reactor
Sulfoxide solvent, 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
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
12.6 ° and 10.5%.
Embodiment 3
1）The preparation of poly acrylic acid-poly caprolactone graft copolymer
15.8 grams of polyacrylic acid are added in dry reactor（Molecular weight is 94000）, 8.3 grams of hydroxy-end capped polycaprolactone lists
Lauryl ether（Molecular weight is 2700）, 239 ml dimethyl sulfoxide (DMSO)s are added, 0.041 gram of 3- ethyls -1- is added（3- diformazan ammonia
Propyl group）Under carbodiimide, inert atmosphere, in 34 DEG C of stirring reactions 4 days, terminating reaction by filtering, dialysis, was dried, obtains mesh
Mark thing；
2）The preparation of polyacrylic acid-MPEGPLA- polycaprolactone dual graft copolymers
11.6 grams of poly acrylic acid-poly caprolactone graft copolymers, 5.8 grams of amino-terminated MPEGPLA are added in dry reactor
（Molecular weight is 2500）, 174 ml dimethyl sulfoxide (DMSO)s are added, 0.029 gram of 3- ethyls -1- is added（3- dimethylaminopropyls）Carbon two
Under imines, inert atmosphere, in 31 DEG C of stirring reactions 4 days, terminating reaction by filtering, dialysis, was dried, obtains object；
3）The preparation for the polypropylene sorrel that MPEGPLA is improved with polycaprolactone
9.5 grams of polyacrylic acid-MPEGPLA- polycaprolactone dual graft copolymers and 35 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 2500）, under inert atmosphere, in 51 DEG C of stirrings
Mixing 60 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
13.4 ° and 10.9%.
Claims (6)
1. a kind of method that MPEGPLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance, its feature exists
In：The molecular weight of polyacrylic acid segment is 83000~94000 in Modified Membrane, the molecular weight of polycaprolactone segment for 2600~
The molecular weight of 2700, MPEGPLA segments is 2300~2500；Its modification method uses following steps：
1）The synthesis of poly acrylic acid-poly caprolactone graft copolymer：Hydroxy-end capped polycaprolactone is added in dry reactor
Under monododecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 27~34 DEG C of stirring reactions 2~4 days, terminate anti-
Should, by filtering, dialysis, dry, obtain object；
2）The synthesis of polyacrylic acid-MPEGPLA- polycaprolactone dual graft copolymers：In dry reactor add polyacrylic acid-
It is anti-in 26~31 DEG C of stirrings under polycaprolactone graft copolymer, amino-terminated MPEGPLA, solvent and condensing agent, inert atmosphere
Answer 2~4 days, terminating reaction, by filtering, dialysis, dry, obtain object；
3）The preparation for the polypropylene sorrel that MPEGPLA is improved with polycaprolactone：In dry reactor add polyacrylic acid-
Under MPEGPLA- polycaprolactone dual grafts copolymer, MPEGPLA and solvent, inert atmosphere, in 46~51 DEG C stirring mixing 50~
After 60 minutes, with the tape casting film forming and drying, object is obtained.
2. a kind of MPEGPLA according to claim 1 is carried out with polycaprolactone to polypropylene sorrel water resistance and compliance
The method of improvement, it is characterised in that：Step 1）In, the mol ratio of polycaprolactone monododecyl ether and polyacrylic acid for 15~
25:1。
3. a kind of MPEGPLA according to claim 1 is carried out with polycaprolactone to polypropylene sorrel water resistance and compliance
The method of improvement, it is characterised in that：Step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl
Carbodiimide or 3- ethyls -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid be 1.07~
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 is carried out with polycaprolactone to polypropylene sorrel water resistance and compliance
The method of improvement, 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 and in poly acrylic acid-poly caprolactone graft copolymer poly- third
The mol ratio of olefin(e) acid segment is 15~25:1.
5. a kind of MPEGPLA according to claim 1 is carried out with polycaprolactone to polypropylene sorrel water resistance and compliance
The method of improvement, it is characterised in that：Step 2）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl
Carbodiimide or 3- ethyls -1-（3- dimethylaminopropyls）Carbodiimide, condensing agent and poly acrylic acid-poly caprolactone graft copolymer
The mol ratio of middle polyacrylic acid segment is 1.07~1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15
g:100 ml。
6. a kind of MPEGPLA according to claim 1 is carried out with polycaprolactone to polypropylene sorrel water resistance and compliance
The method of improvement, 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%, and solvent is adopted
With dimethyl sulfoxide (DMSO), mixture solution concentration is 25~30 g:100 ml.
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| CN201710376612.4A CN106977954A (en) | 2017-05-25 | 2017-05-25 | A kind of method that MPEGPLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865074A (en) * | 2014-04-11 | 2014-06-18 | 山东理工大学 | Preparation method of polypeptide-poly(caprolactone-lactide)-MPEGPLA double-graft copolymer |
| CN104448843A (en) * | 2015-01-06 | 2015-03-25 | 山东理工大学 | Method for improving hydrophilia and flexibility of poly peptide film through polycaprolactone and polyacrylic acid |
-
2017
- 2017-05-25 CN CN201710376612.4A patent/CN106977954A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865074A (en) * | 2014-04-11 | 2014-06-18 | 山东理工大学 | Preparation method of polypeptide-poly(caprolactone-lactide)-MPEGPLA double-graft copolymer |
| CN104448843A (en) * | 2015-01-06 | 2015-03-25 | 山东理工大学 | Method for improving hydrophilia and flexibility of poly peptide film through polycaprolactone and polyacrylic acid |
Non-Patent Citations (1)
| Title |
|---|
| 蔡邦肖等: "高分离性能聚丙烯酸膜制备工艺的初步研究", 《第一届全国化学工程与生物化工年会论文摘要集(上)》 * |
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