CN106987130A - A kind of method being improved with PTMC and polycaprolactone to polypropylene sorrel water resistance and compliance - Google Patents
A kind of method being improved with PTMC and polycaprolactone to polypropylene sorrel water resistance and compliance Download PDFInfo
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- CN106987130A CN106987130A CN201710362895.7A CN201710362895A CN106987130A CN 106987130 A CN106987130 A CN 106987130A CN 201710362895 A CN201710362895 A CN 201710362895A CN 106987130 A CN106987130 A CN 106987130A
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- polycaprolactone
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- water resistance
- polyacrylic acid
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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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- 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
- 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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- 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
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The present invention discloses a kind of method being improved with PTMC and polycaprolactone to polypropylene sorrel water resistance and compliance, using following steps:1)The synthesis of polyacrylic acid polycaprolactone graft copolymer:Add hydroxy-end capped polycaprolactone monododecyl 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 polycaprolactone graft copolymer, PTMC 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.Polycaprolactone segment is first introduced into polyacrylic acid segment
Formed poly acrylic acid-poly caprolactone graft copolymer, then again by PTMC segment add poly acrylic acid-poly oneself
Interior ester graft copolymer formation blend, is made modified polypropene sorrel, so as to drastically increase the water-fast of polypropylene sorrel
Property and compliance.
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 PTMC and polycaprolactone to polypropylene sorrel water resistance and compliance,
It is characterized in that:The molecular weight of polyacrylic acid segment is 82000~91000 in Modified Membrane, and the molecular weight of polycaprolactone segment is
2100~2400, the molecular weight of PTMC segment is 4600~5200;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 26~31 DEG C of stirring reactions 2~3 days, terminate anti-
Should, by filtering, dialysis, dry, obtain object;
2)The preparation of PTMC and Polycaprolactone modified polypropylene sorrel:Poly- third is added in dry reactor
Under olefin(e) acid-polycaprolactone graft copolymer, PTMC list tridecyl ether and solvent, inert atmosphere, in 46~
After 51 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, object is obtained.
Described one kind is carried out with PTMC with polycaprolactone to polypropylene sorrel water resistance and compliance
Improved method, step 1)In, the mol ratio of polycaprolactone monododecyl ether and polyacrylic acid is 15~25:1.
Described one kind is carried out with PTMC with polycaprolactone to polypropylene sorrel water resistance and compliance
Improved method, step 1)In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3-
Ethyl -1-(3- dimethylaminopropyls)The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.07~1.8:1, solvent is used
Dimethyl sulfoxide (DMSO), reactant solution concentration is 5~15 g:100 ml.
Described one kind is carried out with PTMC with polycaprolactone to polypropylene sorrel water resistance and compliance
Improved method, step 2)In, mass percent of the PTMC list tridecyl ether in Modified Membrane be 1~
3%, solvent uses dimethyl sulfoxide (DMSO), and mixture solution concentration is 25~30 g:100 ml.
Compared with prior art, its advantage is the present invention:
1st, described one kind is changed with PTMC and polycaprolactone to polypropylene sorrel water resistance and compliance
The method entered, 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 caprolactone graft copolymer
20 grams of polyacrylic acid are added in dry reactor(Molecular weight is 82000)With 9.5 grams of hydroxy-end capped polycaprolactone lists
Lauryl ether(Molecular weight is 2100), 291 ml dimethyl sulfoxide (DMSO)s are added, 0.062 gram is addedN,N’- dicyclohexyl carbon two
Under imines, inert atmosphere, in 26 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains object;
2)The preparation of PTMC and Polycaprolactone modified polypropylene sorrel
10 grams of poly acrylic acid-poly caprolactone graft copolymers and 37 ml dimethyl sulfoxide solvents are added in dry reactor, separately
Add the PTMC list tridecyl ether for accounting for Modified Membrane gross weight 1%(Molecular weight is 4600), 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
11.2 ° and 9.6%.
Embodiment 2
1)The preparation of poly acrylic acid-poly caprolactone graft copolymer
21 grams of polyacrylic acid are added in dry reactor(Molecular weight is 85000)With 10.2 grams of hydroxy-end capped polycaprolactone lists
Lauryl ether(Molecular weight is 2200), 311 ml dimethyl sulfoxide (DMSO)s are added, 0.039 gram is addedN,N’- diisopropyl carbon two
Under imines, inert atmosphere, in 28 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
10.1 grams of poly acrylic acid-poly caprolactone graft copolymers are added in dry reactor and 36.5 ml dimethyl sulfoxide (DMSO)s are molten
Agent, it is another to add the PTMC list tridecyl ether for accounting for Modified Membrane gross weight 2%(Molecular weight is 4800), indifferent gas
Under atmosphere, 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
11.8 ° and 10.3%.
Embodiment 3
1)The preparation of poly acrylic acid-poly caprolactone graft copolymer
22.3 grams of polyacrylic acid are added in dry reactor(Molecular weight is 91000)With 10.8 grams of hydroxy-end capped polycaprolactones
Monododecyl ether(Molecular weight is 2400), 323 ml dimethyl sulfoxide (DMSO)s are added, 0.058 gram of 3- ethyls -1- is added(3- diformazans
Aminopropyl)Under carbodiimide, inert atmosphere, in 31 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
9.5 grams of poly acrylic acid-poly caprolactone graft copolymers and 35 ml dimethyl sulfoxide solvents are added in dry reactor,
It is another to add the PTMC list tridecyl ether for accounting for Modified Membrane gross weight 3%(Molecular weight is 5200), 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
12.4 ° and 10.9%.
Claims (4)
1. a kind of side being improved with PTMC and polycaprolactone to polypropylene sorrel water resistance and compliance
Method, it is characterised in that:The molecular weight of polyacrylic acid segment is 82000~91000, the molecular weight of polycaprolactone segment in Modified Membrane
For 2100~2400, the molecular weight of PTMC segment is 4600~5200;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 26~31 DEG C of stirring reactions 2~3 days, terminate anti-
Should, by filtering, dialysis, dry, obtain object;
2)The preparation of PTMC and Polycaprolactone modified polypropylene sorrel:Poly- third is added in dry reactor
Under olefin(e) acid-polycaprolactone graft copolymer, PTMC list tridecyl ether and solvent, inert atmosphere, in 46~
After 51 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, object is obtained.
2. one kind PTMC according to claim 1 and polycaprolactone to polypropylene sorrel water resistance and
The method that compliance is improved, it is characterised in that:Step 1)In, mole of polycaprolactone monododecyl ether and polyacrylic acid
Than for 15~25:1.
3. one kind PTMC according to claim 1 and polycaprolactone 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 1.07~1.8:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. one kind PTMC according to claim 1 and polycaprolactone to polypropylene sorrel water resistance and
The method that compliance is improved, it is characterised in that:Step 2)In, PTMC list tridecyl ether is in Modified Membrane
In mass percent be 1~3%, solvent uses dimethyl sulfoxide (DMSO), and mixture solution concentration is 25~30 g:100 ml.
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Citations (2)
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 |
CN105542183A (en) * | 2016-03-09 | 2016-05-04 | 山东理工大学 | Preparation method of polyvinyl alcohol-polycaprolactone-poly(trimethylene carbonate) dual-grafted copolymer micelle |
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2017
- 2017-05-22 CN CN201710362895.7A patent/CN106987130A/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105542183A (en) * | 2016-03-09 | 2016-05-04 | 山东理工大学 | Preparation method of polyvinyl alcohol-polycaprolactone-poly(trimethylene carbonate) dual-grafted copolymer micelle |
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 |
Non-Patent Citations (1)
Title |
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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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