CN107011665A - 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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- CN107011665A CN107011665A CN201710362548.4A CN201710362548A CN107011665A CN 107011665 A CN107011665 A CN 107011665A CN 201710362548 A CN201710362548 A CN 201710362548A CN 107011665 A CN107011665 A CN 107011665A
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- ptmc
- polycaprolactone
- 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 that PTMC improves polypropylene sorrel water resistance and compliance with polycaprolactone, using following steps：1）The synthesis of polyacrylic acid PTMC graft copolymer：Add hydroxy-end capped PTMC list tridecyl ether, solvent, condensing agent and polyacrylic acid in dry reactor, stirring reaction 2~3 days, terminating reaction obtains object；2）The preparation of PTMC and Polycaprolactone modified polypropylene sorrel：Polyacrylic acid PTMC graft 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.PTMC and polycaprolactone are with excellent biocompatibility and biology
The biomaterial of degradability, with good hydrophobicity and compliance.PTMC segment is first introduced poly- third
Olefin(e) acid segment formation poly acrylic acid-poly trimethylene carbonate graft copolymer, then adds poly- third by polycaprolactone segment again
Olefin(e) acid-PTMC graft copolymer formation 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 PTMC improves polypropylene sorrel water resistance and compliance with polycaprolactone, its feature exists
In：The molecular weight of polyacrylic acid segment is 81000~91000 in Modified Membrane, and the molecular weight of PTMC segment is
2100~2300, the molecular weight of polycaprolactone segment is 5100~6000；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 list tridecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 25~31 DEG C of stirrings
Reaction 2~3 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The preparation of PTMC and Polycaprolactone modified polypropylene sorrel：Poly- third is added in dry reactor
Under olefin(e) acid-PTMC graft copolymer, polycaprolactone monododecyl ether and solvent, inert atmosphere, in 46~
After 50 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 list 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 monododecyl ether in Modified Membrane is 2~4%, 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, the method that a kind of described PTMC and polycaprolactone improve polypropylene sorrel water resistance and compliance,
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
19.6 grams of polyacrylic acid are added in dry reactor（Molecular weight is 81000）With 9.2 grams of hydroxy-end capped poly- three methylenes
Base carbonic ester list tridecyl ether（Molecular weight is 2100）, 284 ml dimethyl sulfoxide (DMSO)s are added, 0.062 gram is addedN,N’- two
Under carbodicyclo hexylimide, inert atmosphere, in 25 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtained
Object；
2）The preparation of PTMC and Polycaprolactone modified polypropylene sorrel
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 polycaprolactone monododecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 5100）, under inert atmosphere,
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
10.8 ° and 8.8%.
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 10.1 grams of hydroxy-end capped polytrimethylenes
Carbonic ester list tridecyl ether（Molecular weight is 2200）, 311 ml dimethyl sulfoxide (DMSO)s are added, 0.039 gram is addedN,N’- two is different
Under propyl group carbodiimide, inert atmosphere, in 28 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains mesh
Mark thing；
2）The preparation of PTMC and Polycaprolactone modified polypropylene sorrel
10 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 polycaprolactone monododecyl ether for accounting for Modified Membrane gross weight 3%（Molecular weight is 5500）, 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
11.6 ° and 9.2%.
Embodiment 3
1）The preparation of poly acrylic acid-poly trimethylene carbonate graft copolymer
22.3 grams of polyacrylic acid are added in dry reactor（Molecular weight is 91000）With 10.3 grams of hydroxy-end capped poly- three methylenes
Base carbonic ester list tridecyl ether（Molecular weight is 2300）, add 326 ml dimethyl sulfoxide (DMSO)s, add 0.058 gram of 3- ethyl-
1-（3- dimethylaminopropyls）Under carbodiimide, inert atmosphere, in 31 DEG C of stirring reactions 2 days, terminating reaction, by filtering, dialysis,
Dry, obtain object；
2）The preparation of PTMC and Polycaprolactone modified polypropylene sorrel
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 polycaprolactone monododecyl ether for accounting for Modified Membrane gross weight 4%（Molecular weight is 6000）, under inert atmosphere,
Mixed 60 minutes in 50 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
12.4 ° and 9.9%.
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 81000~91000, the molecular weight of PTMC segment in Modified Membrane
For 2100~2300, the molecular weight of polycaprolactone segment is 5100~6000；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 list tridecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 25~31 DEG C of stirrings
Reaction 2~3 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The preparation of PTMC and Polycaprolactone modified polypropylene sorrel：Poly- third is added in dry reactor
Under olefin(e) acid-PTMC graft copolymer, polycaprolactone monododecyl ether and solvent, inert atmosphere, in 46~
After 50 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 list tridecyl ether and polyacrylic acid
Than for 15~25:1.
3. 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, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl
Base carbodiimide or 3- ethyls -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid be 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 monododecyl ether in Modified Membrane is
2~4%, 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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| CN201710362548.4A CN107011665A (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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| CN201710362548.4A CN107011665A (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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| CN201710362548.4A Withdrawn CN107011665A (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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- 2017-05-22 CN CN201710362548.4A patent/CN107011665A/en not_active Withdrawn
Patent 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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