CN106987134A - A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with polycaprolactone - Google Patents
A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with polycaprolactone Download PDFInfo
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- CN106987134A CN106987134A CN201710362960.6A CN201710362960A CN106987134A CN 106987134 A CN106987134 A CN 106987134A CN 201710362960 A CN201710362960 A CN 201710362960A CN 106987134 A CN106987134 A CN 106987134A
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- polycaprolactone
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- polyacrylic acid
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- 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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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- 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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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The present invention, which discloses a kind of MPEGPLA, improves the method for polypropylene sorrel water resistance and compliance with polycaprolactone, using following steps：1）The synthesis of polyacrylic acid MPEGPLA polycaprolactone dual graft copolymers：Hydroxy-end capped MPEGPLA is added in dry reactor, hydroxy-end capped polycaprolactone monododecyl ether, solvent, condensing agent and polyacrylic acid, stirring reaction 2~3 days, terminating reaction obtains object；2）MPEGPLA and Polycaprolactone modified polypropylene sorrel preparation：Polyacrylic acid MPEGPLA polycaprolactone dual grafts copolymer, polycaprolactone monododecyl ether 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）It is tool with polycaprolactone
There are excellent biocompatibility and the biomaterial of biodegradability, with good hydrophobicity and compliance.First will
It is double that MPEGPLA segments and polycaprolactone segment introduce polyacrylic acid segment formation polyacrylic acid-MPEGPLA- polycaprolactones simultaneously
Graft copolymer, then again forms polycaprolactone segment addition polyacrylic acid-MPEGPLA- polycaprolactone dual graft copolymers
Blend, 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 that MPEGPLA improves polypropylene sorrel water resistance and compliance with polycaprolactone, it is characterised in that：Modified Membrane
The molecular weight of middle polyacrylic acid segment is that the molecular weight of 82000~93000, MPEGPLA segments is 2500~2600, polycaprolactone
The molecular weight of segment is 2500~2600；Its method of modifying uses following steps：
1）The synthesis of polyacrylic acid-MPEGPLA- polycaprolactone dual graft copolymers：Added in dry reactor hydroxy-end capped
MPEGPLA, hydroxy-end capped polycaprolactone monododecyl ether, solvent, condensing agent and polyacrylic acid, under inert atmosphere, in
27~34 DEG C of stirring reactions 2~3 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）MPEGPLA and Polycaprolactone modified polypropylene sorrel preparation：In dry reactor add polyacrylic acid-
Under MPEGPLA- polycaprolactone dual grafts copolymer, polycaprolactone monododecyl ether and solvent, inert atmosphere, in 46~51 DEG C
After stirring mixing 50~60 minutes, with the tape casting film forming and drying, object is obtained.
A kind of described MPEGPLA improves the method for polypropylene sorrel water resistance and compliance, step 1 with polycaprolactone）
In, the mol ratio of polycaprolactone monododecyl ether and polyacrylic acid is 15~25:1, MPEGPLA uses the poly- second two of mono methoxy
Alcohol gathers（D,L）Lactic acid copolymer（The weight ratio of polyethylene glycol and PLA is 10/90）, mole of MPEGPLA and polyacrylic acid
Than for 15~25:1.
A kind of described MPEGPLA improves the method for polypropylene sorrel water resistance and compliance, step 1 with polycaprolactone）
In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-（3- diformazan ammonia
Propyl group）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.07~1.8:1, solvent uses dimethyl sulfoxide (DMSO), reactant
Solution concentration is 5~15 g:100 ml.
A kind of described MPEGPLA improves the method for polypropylene sorrel water resistance and compliance, step 2 with polycaprolactone）
In, mass percent of the polycaprolactone monododecyl ether in Modified Membrane is 2~4%, 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 polycaprolactone improve the method for polypropylene sorrel water resistance and compliance, using one kind
Two kinds of means of the reaction that is esterified simultaneously of polymer polymeric monomer different from two kinds and blending, 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 polyacrylic acid-MPEGPLA- polycaprolactone dual graft copolymers
16.3 grams of polyacrylic acid are added in dry reactor（Molecular weight is 82000）, 9.2 grams of hydroxy-end capped MPEGPLA（Point
Son amount is 2500）With 9.2 grams of hydroxy-end capped polycaprolactone monododecyl ethers（Molecular weight is 2500）, add 347 ml diformazans
Base sulfoxide, adds 0.052 gramN,N’Under-dicyclohexylcarbodiimide, inert atmosphere, in 27 DEG C of stirring reactions 2 days, terminate anti-
Should, by filtering, dialysis, dry, obtain object；
2）MPEGPLA and Polycaprolactone modified polypropylene sorrel preparation
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 polycaprolactone monododecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 2500）, inert atmosphere
Under, mixed 50 minutes in 46 DEG C of stirrings, 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 9.6%.
Embodiment 2
1）The preparation of polyacrylic acid-MPEGPLA- polycaprolactone dual graft copolymers
21 grams of polyacrylic acid are added in dry reactor（Molecular weight is 87000）, 11.2 grams of hydroxy-end capped MPEGPLA（Point
Son amount is 2600）With 11.2 grams of hydroxy-end capped polycaprolactone monododecyl ethers（Molecular weight is 2600）, add 436 ml bis-
Methyl sulfoxide, adds 0.038 gramN,N’Under-DIC, inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminate
Reaction, by filtering, dialysis, dries, obtains object；
2）MPEGPLA and Polycaprolactone modified polypropylene sorrel preparation
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 polycaprolactone monododecyl ether for accounting for Modified Membrane gross weight 3%（Molecular weight is 2600）, inert atmosphere
Under, mixed 55 minutes in 48 DEG C of stirrings, 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
12.3 ° and 10.2%.
Embodiment 3
1）The preparation of polyacrylic acid-MPEGPLA- polycaprolactone dual graft copolymers
23.2 grams of polyacrylic acid are added in dry reactor（Molecular weight is 93000）, 11.6 grams of hydroxy-end capped MPEGPLA
（Molecular weight is 2600）With 11.6 grams of hydroxy-end capped polycaprolactone monododecyl ethers（Molecular weight is 2600）, add 463 ml
Dimethyl sulfoxide (DMSO), adds 0.061 gram of 3- ethyls -1-（3- dimethylaminopropyls）Under carbodiimide, inert atmosphere, in 34 DEG C of stirrings
Reaction 2 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）MPEGPLA and Polycaprolactone modified polypropylene sorrel preparation
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 polycaprolactone monododecyl ether for accounting for Modified Membrane gross weight 4%（Molecular weight is 2600）, inert atmosphere
Under, mixed 60 minutes in 51 DEG C of stirrings, 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
12.8 ° and 10.7%.
Claims (4)
1. a kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with polycaprolactone, it is characterised in that：It is modified
The molecular weight of polyacrylic acid segment is that the molecular weight of 82000~93000, MPEGPLA segments is 2500~2600 in film, is gathered in oneself
The molecular weight of ester segment is 2500~2600；Its method of modifying uses following steps：
1）The synthesis of polyacrylic acid-MPEGPLA- polycaprolactone dual graft copolymers：Added in dry reactor hydroxy-end capped
MPEGPLA, hydroxy-end capped polycaprolactone monododecyl ether, solvent, condensing agent and polyacrylic acid, under inert atmosphere, in
27~34 DEG C of stirring reactions 2~3 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）MPEGPLA and Polycaprolactone modified polypropylene sorrel preparation：In dry reactor add polyacrylic acid-
Under MPEGPLA- polycaprolactone dual grafts copolymer, polycaprolactone monododecyl ether and solvent, inert atmosphere, in 46~51 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 polycaprolactone improve polypropylene sorrel water resistance and compliance
Method, it is characterised in that：Step 1）In, the mol ratio of polycaprolactone monododecyl ether and polyacrylic acid is 15~25:1,
MPEGPLA is poly- using mono methoxy polyethylene glycol（D,L）Lactic acid copolymer（The weight ratio of polyethylene glycol and PLA is 10/
90）, the mol ratio of MPEGPLA and polyacrylic acid is 15~25:1.
3. a kind of MPEGPLA according to claim 1 and polycaprolactone improve polypropylene sorrel water resistance and compliance
Method, it is characterised in that：Step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl carbon two is sub-
Amine or 3- ethyls -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.07~1.8:1, it is molten
Agent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. a kind of MPEGPLA according to claim 1 and polycaprolactone improve polypropylene sorrel water resistance and compliance
Method, it is characterised in that：Step 2）In, mass percent of the polycaprolactone monododecyl ether in Modified Membrane is 2~4%, molten
Agent 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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| CN201710362960.6A CN106987134A (en) | 2017-05-22 | 2017-05-22 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with polycaprolactone |
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| CN201710362960.6A CN106987134A (en) | 2017-05-22 | 2017-05-22 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with polycaprolactone |
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Citations (1)
| 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 |
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- 2017-05-22 CN CN201710362960.6A patent/CN106987134A/en not_active Withdrawn
Patent Citations (1)
| 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 |
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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