CN106987125A - A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polycaprolactone - Google Patents
A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polycaprolactone Download PDFInfo
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- CN106987125A CN106987125A CN201710362573.2A CN201710362573A CN106987125A CN 106987125 A CN106987125 A CN 106987125A CN 201710362573 A CN201710362573 A CN 201710362573A CN 106987125 A CN106987125 A CN 106987125A
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- polycaprolactone
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- water resistance
- polyacrylic acid
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- 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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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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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- 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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Abstract
The present invention, which discloses a kind of PTMC, improves the method for polypropylene sorrel water resistance and compliance with polycaprolactone, using following steps：1）The synthesis of polyacrylic acid PTMC polycaprolactone dual graft copolymer：Hydroxy-end capped PTMC monododecyl ether is added in dry reactor, hydroxy-end capped polycaprolactone list tridecyl ether, solvent, condensing agent and polyacrylic acid, stirring reaction 2~3 days, terminating reaction obtains object；2）The preparation of PTMC and Polycaprolactone modified polypropylene sorrel：Polyacrylic acid PTMC polycaprolactone dual graft copolymer, polycaprolactone list tridecyl 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.PTMC and polycaprolactone are with excellent biocompatibility and biology
The biomaterial of degradability, with good hydrophobicity and compliance.First by PTMC segment and gather oneself in
Ester segment introduces polyacrylic acid segment formation poly acrylic acid-poly trimethylene carbonate-polycaprolactone dual graft copolymer simultaneously,
Then polycaprolactone segment is added into poly acrylic acid-poly trimethylene carbonate-polycaprolactone dual graft copolymer again to be formed altogether
Mixed thing, 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 PTMC improves polypropylene sorrel water resistance and compliance with polycaprolactone, its feature exists
In：The molecular weight of polyacrylic acid segment is 81000~93000 in Modified Membrane, and the molecular weight of PTMC segment is
2500~2700, the molecular weight of polycaprolactone segment is 2500~2700；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly trimethylene carbonate-polycaprolactone dual graft copolymer：Added in dry reactor
Hydroxy-end capped PTMC monododecyl ether, hydroxy-end capped polycaprolactone list tridecyl ether, solvent, contracting
Under mixture and polyacrylic acid, inert atmosphere, in 25~34 DEG C of stirring reactions 2~3 days, terminating reaction, by filtering, dialysis, dry
It is dry, obtain object；
2）The preparation of PTMC and Polycaprolactone modified polypropylene sorrel：Poly- third is added in dry reactor
Olefin(e) acid-PTMC-polycaprolactone dual graft copolymer, polycaprolactone list tridecyl ether and solvent, indifferent gas
Under atmosphere, after 45~53 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, object is obtained.
A kind of described PTMC improves the side of polypropylene sorrel water resistance and compliance with polycaprolactone
Method, step 1）In, the mol ratio of PTMC monododecyl ether and polyacrylic acid is 15~25:1, polycaprolactone
The mol ratio of single tridecyl ether and polyacrylic acid is 15~25:1.
A kind of described PTMC improves the side of polypropylene sorrel water resistance and compliance with polycaprolactone
Method, 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 1.06~1.8:1, solvent is sub- using dimethyl
Sulfone, reactant solution concentration is 5~15 g:100 ml.
A kind of described PTMC improves the side of polypropylene sorrel water resistance and compliance with polycaprolactone
Method, step 2）In, mass percent of the polycaprolactone list tridecyl ether in Modified Membrane is 1~3%, and solvent uses dimethyl
Sulfoxide, mixture solution concentration is 25~30 g:100 ml.
Compared with prior art, its advantage is the present invention：
1st, a kind of described PTMC and polycaprolactone improve the method for polypropylene sorrel water resistance and compliance,
The two kinds of means of reaction and blending being esterified simultaneously using a kind of polymer polymeric monomer different from two kinds are simple to operate, easy
In 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-polycaprolactone dual graft copolymer
16.3 grams of polyacrylic acid are added in dry reactor（Molecular weight is 81000）, 9.4 grams of hydroxy-end capped polytrimethylenes
Carbonic ester monododecyl ether（Molecular weight is 2500）With 9.4 grams of hydroxy-end capped polycaprolactone list tridecyl ethers（Molecular weight
For 2500）, 349 ml dimethyl sulfoxide (DMSO)s are added, 0.052 gram is addedN,N’Under-dicyclohexylcarbodiimide, inert atmosphere, in
25 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The preparation of PTMC and Polycaprolactone modified polypropylene sorrel
10 grams of poly acrylic acid-poly trimethylene carbonate-polycaprolactone dual graft copolymers and 37 are added in dry reactor
Ml dimethyl sulfoxide solvents, it is another to add the polycaprolactone list tridecyl ether for accounting for Modified Membrane gross weight 1%（Molecular weight is 2500）,
Under inert atmosphere, mixed 50 minutes in 45 DEG C of stirrings, use the tape casting film forming, target is dried to obtain in 50 DEG C of vacuum drying chambers
Thing.
After tested：The surface contact angle and its elongation at break of object and water of the present invention respectively than improving before modified
11.5 ° and 9.3%.
Embodiment 2
1）The preparation of poly acrylic acid-poly trimethylene carbonate-polycaprolactone dual graft copolymer
21.1 grams of polyacrylic acid are added in dry reactor（Molecular weight is 87000）, 11.4 grams of hydroxy-end capped poly- three methylenes
Base carbonic ester monododecyl ether（Molecular weight is 2600）With 11.4 grams of hydroxy-end capped polycaprolactone list tridecyl ethers（Molecule
Measure as 2600）, 438 ml dimethyl sulfoxide (DMSO)s are added, 0.038 gram is addedN,N’Under-DIC, inert atmosphere,
In 30 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation of PTMC and Polycaprolactone modified polypropylene sorrel
9.9 grams of poly acrylic acid-poly trimethylene carbonate-polycaprolactone dual graft copolymers and 36 are added in dry reactor
Ml dimethyl sulfoxide solvents, it is another to add the polycaprolactone list tridecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 2600）,
Under inert atmosphere, mixed 55 minutes in 48 DEG C of stirrings, use the tape casting film forming, target is dried to obtain in 50 DEG C of vacuum drying chambers
Thing.
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 10.1%.
Embodiment 3
1）The preparation of poly acrylic acid-poly trimethylene carbonate-polycaprolactone dual graft copolymer
23.3 grams of polyacrylic acid are added in dry reactor（Molecular weight is 93000）, 12.4 grams of hydroxy-end capped poly- three methylenes
Base carbonic ester monododecyl ether（Molecular weight is 2700）With 12.4 grams of hydroxy-end capped polycaprolactone list tridecyl ethers（Molecule
Measure as 2700）, 479ml dimethyl sulfoxide (DMSO)s are added, 0.061 gram of 3- ethyls -1- is added（3- dimethylaminopropyls）Carbodiimide, it is lazy
Property atmosphere under, in 34 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, and obtains object；
2）The preparation of PTMC and Polycaprolactone modified polypropylene sorrel
9.5 grams of poly acrylic acid-poly trimethylene carbonate-polycaprolactone dual graft copolymers and 35 are added in dry reactor
Ml dimethyl sulfoxide solvents, it is another to add the polycaprolactone list tridecyl ether for accounting for Modified Membrane gross weight 3%（Molecular weight is 2700）,
Under inert atmosphere, mixed 60 minutes in 53 DEG C of stirrings, use the tape casting film forming, target is dried to obtain in 50 DEG C of vacuum drying chambers
Thing.
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 10.6%.
Claims (4)
1. a kind of PTMC improves the method for polypropylene sorrel water resistance and compliance, its feature with polycaprolactone
It is：The molecular weight of polyacrylic acid segment is 81000~93000, the molecular weight of PTMC segment in Modified Membrane
For 2500~2700, the molecular weight of polycaprolactone segment is 2500~2700；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly trimethylene carbonate-polycaprolactone dual graft copolymer：Added in dry reactor
Hydroxy-end capped PTMC monododecyl ether, hydroxy-end capped polycaprolactone list tridecyl ether, solvent, contracting
Under mixture and polyacrylic acid, inert atmosphere, in 25~34 DEG C of stirring reactions 2~3 days, terminating reaction, by filtering, dialysis, dry
It is dry, obtain object；
2）The preparation of PTMC and Polycaprolactone modified polypropylene sorrel：Poly- third is added in dry reactor
Olefin(e) acid-PTMC-polycaprolactone dual graft copolymer, polycaprolactone list tridecyl ether and solvent, indifferent gas
Under atmosphere, after 45~53 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, object is obtained.
2. a kind of PTMC according to claim 1 and polycaprolactone improve polypropylene sorrel water resistance and
The method of compliance, it is characterised in that：Step 1）In, mole of PTMC monododecyl ether and polyacrylic acid
Than for 15~25:1, the mol ratio of polycaprolactone list tridecyl ether and polyacrylic acid is 15~25:1.
3. a kind of PTMC according to claim 1 improves polypropylene sorrel water resistance with polycaprolactone
And the method for compliance, it is characterised in that：Step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- two is different
Propyl group carbodiimide or 3- ethyls -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.06
~1.8:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. a kind of PTMC according to claim 1 and polycaprolactone improve polypropylene sorrel water resistance and
The method of compliance, it is characterised in that：Step 2）In, mass percent of the polycaprolactone list tridecyl ether in Modified Membrane is
1~3%, solvent uses dimethyl sulfoxide (DMSO), and mixture solution concentration is 25~30 g:100 ml.
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| CN201710362573.2A CN106987125A (en) | 2017-05-22 | 2017-05-22 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polycaprolactone |
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| CN201710362573.2A CN106987125A (en) | 2017-05-22 | 2017-05-22 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polycaprolactone |
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Citations (1)
| 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 |
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| 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 |
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