CN106947264A - A kind of method being improved with polycaprolactone and polypropylene glycol to polypropylene sorrel water resistance and compliance - Google Patents
A kind of method being improved with polycaprolactone and polypropylene glycol to polypropylene sorrel water resistance and compliance Download PDFInfo
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- CN106947264A CN106947264A CN201710362966.3A CN201710362966A CN106947264A CN 106947264 A CN106947264 A CN 106947264A CN 201710362966 A CN201710362966 A CN 201710362966A CN 106947264 A CN106947264 A CN 106947264A
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- polypropylene glycol
- polycaprolactone
- polypropylene
- compliance
- water resistance
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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
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether 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 being improved with polycaprolactone and polypropylene glycol to polypropylene sorrel water resistance and compliance, using following steps:1)The synthesis of polyacrylic acid polypropylene glycol graft copolymer:Add hydroxy-end capped polypropylene glycol monobutyl ether, solvent, condensing agent and polyacrylic acid in dry reactor, stirring reaction 2~4 days, terminating reaction obtains object;2)The preparation of polycaprolactone and the polypropylene sorrel of polypropylene glycol modified:Polyacrylic acid polypropylene glycol 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.Polycaprolactone and polypropylene glycol(Molecular weight more than 2000)It is with excellent bio-compatible
The biomaterial of property and biodegradability, with hydrophobicity and compliance.Polypropylene glycol segment is first introduced into polyacrylic acid chain
Section forms poly acrylic acid-poly propane diols graft copolymer, then again connects polycaprolactone segment addition poly acrylic acid-poly propane diols
Graft copolymer formation blend, is made modified polypropene sorrel, so as to drastically increase the water resistance of polypropylene sorrel and soft
It is pliable.
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 polycaprolactone and polypropylene glycol to polypropylene sorrel water resistance and compliance, its feature exists
In:The molecular weight of polyacrylic acid segment is 83000~89000 in Modified Membrane, the molecular weight of polypropylene glycol segment for 2300~
2500, the molecular weight of polycaprolactone segment is 4800~5600;Its method of modifying uses following steps:
1)The synthesis of poly acrylic acid-poly propane diols graft copolymer:Hydroxy-end capped polypropylene glycol is added in dry reactor
Under monobutyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 25~34 DEG C of stirring reactions 2~4 days, terminating reaction was led to
Filter, dialyse, dry, obtain object;
2)The preparation of polycaprolactone and the polypropylene sorrel of polypropylene glycol modified:Poly acrylic acid-poly is added in dry reactor
Under propane diols graft copolymer, polycaprolactone list tridecyl ether and solvent, inert atmosphere, in 48~53 DEG C stirring mixing 50~
After 60 minutes, with the tape casting film forming and drying, object is obtained.
A kind of described side being improved with polycaprolactone and polypropylene glycol to polypropylene sorrel water resistance and compliance
Method, step 1)In, the mol ratio of polypropylene glycol monobutyl ether and polyacrylic acid is 15~25:1.
A kind of described side being improved with polycaprolactone and polypropylene glycol to polypropylene sorrel water resistance and compliance
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 1.07~1.9:1, solvent is sub- using dimethyl
Sulfone, reactant solution concentration is 5~15 g:100 ml.
A kind of described side being improved with polycaprolactone and polypropylene glycol to polypropylene sorrel water resistance and compliance
Method, step 2)In, mass percent of the polycaprolactone list tridecyl ether in Modified Membrane is 2~3%, 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 method being improved with polycaprolactone and polypropylene glycol to 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 propane diols graft copolymer
20.4 grams of polyacrylic acid are added in dry reactor(Molecular weight is 83000)With 10.4 grams of hydroxy-end capped polypropylene glycols
Monobutyl ether(Molecular weight is 2300), 302 ml dimethyl sulfoxide (DMSO)s are added, 0.063 gram is addedN,N’- dicyclohexylcarbodiimide,
Under inert atmosphere, in 25 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains object;
2)The preparation of polycaprolactone and the polypropylene sorrel of polypropylene glycol modified
10 grams of poly acrylic acid-poly propane diols graft copolymers and 37 ml dimethyl sulfoxide solvents are added in dry reactor, separately
Add the polycaprolactone list tridecyl ether for accounting for Modified Membrane gross weight 2%(Molecular weight is 4800), under inert atmosphere, stirred in 48 DEG C
Mixing 50 minutes is mixed, the tape casting film forming is used, 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 poly acrylic acid-poly propane diols graft copolymer
21 grams of polyacrylic acid are added in dry reactor(Molecular weight is 85000)With 11.2 grams of hydroxy-end capped polypropylene glycol lists
Butyl ether(Molecular weight is 2400), 318 ml dimethyl sulfoxide (DMSO)s are added, 0.039 gram is addedN,N’- DIC, it is lazy
Property atmosphere under, in 30 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, and obtains object;
2)The preparation of polycaprolactone and the polypropylene sorrel of polypropylene glycol modified
10.1 grams of poly acrylic acid-poly propane diols graft copolymers are added in dry reactor and 36.5 ml dimethyl sulfoxide (DMSO)s are molten
Agent, it is another to add the polycaprolactone list tridecyl ether for accounting for Modified Membrane gross weight 2%(Molecular weight is 5200), under inert atmosphere, in 50
DEG C stirring mixing 55 minutes, use the tape casting film forming, object be 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 10.3%.
Embodiment 3
1)The preparation of poly acrylic acid-poly propane diols graft copolymer
21.6 grams of polyacrylic acid are added in dry reactor(Molecular weight is 89000)With 11.5 grams of hydroxy-end capped polypropylene glycols
Monobutyl ether(Molecular weight is 2500), 329 ml dimethyl sulfoxide (DMSO)s are added, 0.058 gram of 3- ethyls -1- is added(3- diformazans ammonia third
Base)Under carbodiimide, inert atmosphere, in 34 DEG C of stirring reactions 4 days, terminating reaction by filtering, dialysis, was dried, obtains target
Thing;
2)The preparation of polycaprolactone and the polypropylene sorrel of polypropylene glycol modified
9.5 grams of poly acrylic acid-poly propane diols graft copolymers and 35 ml dimethyl sulfoxide solvents are added in dry reactor,
It is another to add the polycaprolactone list tridecyl ether for accounting for Modified Membrane gross weight 3%(Molecular weight is 5600), under inert atmosphere, in 53 DEG C
Stirring 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
13.5 ° and 10.8%.
Claims (4)
1. a kind of method being improved with polycaprolactone and polypropylene glycol to polypropylene sorrel water resistance and compliance, its feature
It is:The molecular weight of polyacrylic acid segment is 83000~89000 in Modified Membrane, the molecular weight of polypropylene glycol segment for 2300~
2500, the molecular weight of polycaprolactone segment is 4800~5600;Its method of modifying uses following steps:
1)The synthesis of poly acrylic acid-poly propane diols graft copolymer:Hydroxy-end capped polypropylene glycol is added in dry reactor
Under monobutyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 25~34 DEG C of stirring reactions 2~4 days, terminating reaction was led to
Filter, dialyse, dry, obtain object;
2)The preparation of polycaprolactone and the polypropylene sorrel of polypropylene glycol modified:Poly acrylic acid-poly is added in dry reactor
Under propane diols graft copolymer, polycaprolactone list tridecyl ether and solvent, inert atmosphere, in 48~53 DEG C stirring mixing 50~
After 60 minutes, with the tape casting film forming and drying, object is obtained.
2. one kind polycaprolactone according to claim 1 enters with polypropylene glycol to polypropylene sorrel water resistance and compliance
The improved method of row, it is characterised in that:Step 1)In, the mol ratio of polypropylene glycol monobutyl ether and polyacrylic acid is 15~25:1.
3. one kind polycaprolactone according to claim 1 enters with polypropylene glycol to polypropylene sorrel water resistance and compliance
The improved method of row, 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 1.07~
1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. one kind polycaprolactone according to claim 1 enters with polypropylene glycol to polypropylene sorrel water resistance and compliance
The improved method of row, it is characterised in that:Step 2)In, mass percent of the polycaprolactone list tridecyl ether in Modified Membrane is
2~3%, solvent uses dimethyl sulfoxide (DMSO), and mixture solution concentration is 25~30 g:100 ml.
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CN201710362966.3A CN106947264A (en) | 2017-05-22 | 2017-05-22 | A kind of method being improved with polycaprolactone and polypropylene glycol to polypropylene sorrel water resistance and compliance |
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CN201710362966.3A CN106947264A (en) | 2017-05-22 | 2017-05-22 | A kind of method being improved with polycaprolactone and polypropylene glycol to polypropylene sorrel water resistance and compliance |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103865086A (en) * | 2014-03-04 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide membrane by polycaprolactone and polypropylene glycol |
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- 2017-05-22 CN CN201710362966.3A patent/CN106947264A/en not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103865086A (en) * | 2014-03-04 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide membrane by polycaprolactone and polypropylene glycol |
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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Application publication date: 20170714 |