CN106947261A - A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polypropylene glycol - Google Patents
A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polypropylene glycol Download PDFInfo
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- CN106947261A CN106947261A CN201710362583.6A CN201710362583A CN106947261A CN 106947261 A CN106947261 A CN 106947261A CN 201710362583 A CN201710362583 A CN 201710362583A CN 106947261 A CN106947261 A CN 106947261A
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- polypropylene glycol
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- polypropylene
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- 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
- C08G81/027—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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
- C08J2471/03—Polyepihalohydrins
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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
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- C08L2203/16—Applications used for films
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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 polypropylene glycol, using following steps：1）The synthesis of polyacrylic acid PTMC polypropylene glycol dual graft copolymer：Add hydroxy-end capped PTMC monododecyl ether, hydroxy-end capped polypropylene glycol monobutyl 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 the polypropylene sorrel of polypropylene glycol modified：Polyacrylic acid PTMC polypropylene glycol dual graft copolymer, polypropylene glycol monobutyl 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 polypropylene glycol（Molecular weight more than 2000）It is with excellent
The biomaterial of biocompatibility and biodegradability, with hydrophobicity and compliance.First by PTMC chain
It is double that section and polypropylene glycol segment introduce polyacrylic acid segment formation poly acrylic acid-poly trimethylene carbonate-polypropylene glycol simultaneously
Graft copolymer, then adds poly acrylic acid-poly trimethylene carbonate-polypropylene glycol dual graft by polypropylene glycol segment again and is total to
Polymers 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 polypropylene glycol, its feature exists
In：The molecular weight of polyacrylic acid segment is 85000~93000 in Modified Membrane, and the molecular weight of PTMC segment is
2700~2900, the molecular weight of polypropylene glycol segment is 2700~2900；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly trimethylene carbonate-polypropylene glycol dual graft copolymer：Added in dry reactor
Hydroxy-end capped PTMC monododecyl ether, hydroxy-end capped polypropylene glycol monobutyl ether, solvent, condensing agent and
Under polyacrylic acid, inert atmosphere, in 25~33 DEG C of stirring reactions 2~3 days, terminating reaction by filtering, dialysis, was dried, obtained
Object；
2）The preparation of PTMC and the polypropylene sorrel of polypropylene glycol modified：Poly- third is added in dry reactor
Under olefin(e) acid-PTMC-polypropylene glycol dual graft copolymer, polypropylene glycol monobutyl ether and solvent, inert atmosphere, in
After 45~52 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 polypropylene glycol
Method, step 1）In, the mol ratio of PTMC monododecyl ether and polyacrylic acid is 15~25:1, polypropylene glycol
The mol ratio of monobutyl ether and polyacrylic acid is 15~25:1.
A kind of described PTMC improves the side of polypropylene sorrel water resistance and compliance with polypropylene glycol
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 polypropylene glycol
Method, step 2）In, mass percent of the polypropylene glycol monobutyl ether in Modified Membrane is 2~3%, and solvent uses dimethyl sulfoxide (DMSO), is mixed
Polymer 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 polypropylene glycol 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-polypropylene glycol dual graft copolymer
17.1 grams of polyacrylic acid are added in dry reactor（Molecular weight is 85000）, 10.4 grams of hydroxy-end capped poly- three methylenes
Base carbonic ester monododecyl ether（Molecular weight is 2700）With 10.4 grams of hydroxy-end capped polypropylene glycol monobutyl ethers（Molecular weight is
2700）, 379 ml dimethyl sulfoxide (DMSO)s are added, 0.052 gram is addedN,N’Under-dicyclohexylcarbodiimide, inert atmosphere, in 25
DEG C stirring reaction 2 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The preparation of PTMC and the polypropylene sorrel of polypropylene glycol modified
10 grams of poly acrylic acid-poly trimethylene carbonate-polypropylene glycol dual graft copolymers and 37 are added in dry reactor
Ml dimethyl sulfoxide solvents, it is another to add the polypropylene glycol monobutyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 2700）, indifferent gas
Under atmosphere, mixed 50 minutes in 45 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
12.1 ° and 9.5%.
Embodiment 2
1）The preparation of poly acrylic acid-poly trimethylene carbonate-polypropylene glycol dual graft copolymer
20.3 grams of polyacrylic acid are added in dry reactor（Molecular weight is 87000）, 11.9 grams of hydroxy-end capped poly- three methylenes
Base carbonic ester monododecyl ether（Molecular weight is 2800）With 11.9 grams of hydroxy-end capped polypropylene glycol monobutyl ethers（Molecular weight is
2800）, 442 ml dimethyl sulfoxide (DMSO)s are added, 0.036 gram is addedN,N’Under-DIC, inert atmosphere, in 30
DEG C stirring reaction 3 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The preparation of PTMC and the polypropylene sorrel of polypropylene glycol modified
9.9 grams of poly acrylic acid-poly trimethylene carbonate-polypropylene glycol dual graft copolymers and 36 are added in dry reactor
Ml dimethyl sulfoxide solvents, it is another to add the polypropylene glycol monobutyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 2800）, 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
12.9 ° and 10.3%.
Embodiment 3
1）The preparation of poly acrylic acid-poly trimethylene carbonate-polypropylene glycol dual graft copolymer
22 grams of polyacrylic acid are added in dry reactor（Molecular weight is 93000）, 12.8 grams of hydroxy-end capped polytrimethylenes
Carbonic ester monododecyl ether（Molecular weight is 2900）With 12.8 grams of hydroxy-end capped polypropylene glycol monobutyl ethers（Molecular weight is
2900）, 476ml dimethyl sulfoxide (DMSO)s are added, 0.058 gram of 3- ethyls -1- is added（3- dimethylaminopropyls）Carbodiimide, indifferent gas
Under atmosphere, in 33 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation of PTMC and the polypropylene sorrel of polypropylene glycol modified
9.5 grams of poly acrylic acid-poly trimethylene carbonate-polypropylene glycol dual graft copolymers and 35 are added in dry reactor
Ml dimethyl sulfoxide solvents, it is another to add the polypropylene glycol monobutyl ether for accounting for Modified Membrane gross weight 3%（Molecular weight is 2900）, indifferent gas
Under atmosphere, mixed 60 minutes in 52 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
13.3 ° and 11.2%.
Claims (4)
1. a kind of PTMC improves the method for polypropylene sorrel water resistance and compliance, its feature with polypropylene glycol
It is：The molecular weight of polyacrylic acid segment is 85000~93000, the molecular weight of PTMC segment in Modified Membrane
For 2700~2900, the molecular weight of polypropylene glycol segment is 2700~2900；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly trimethylene carbonate-polypropylene glycol dual graft copolymer：Added in dry reactor
Hydroxy-end capped PTMC monododecyl ether, hydroxy-end capped polypropylene glycol monobutyl ether, solvent, condensing agent and
Under polyacrylic acid, inert atmosphere, in 25~33 DEG C of stirring reactions 2~3 days, terminating reaction by filtering, dialysis, was dried, obtained
Object；
2）The preparation of PTMC and the polypropylene sorrel of polypropylene glycol modified：Poly- third is added in dry reactor
Under olefin(e) acid-PTMC-polypropylene glycol dual graft copolymer, polypropylene glycol monobutyl ether and solvent, inert atmosphere, in
After 45~52 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 polypropylene glycol 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 polypropylene glycol monobutyl ether and polyacrylic acid is 15~25:1.
3. a kind of PTMC according to claim 1 improves polypropylene sorrel water resistance with polypropylene glycol
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 polypropylene glycol improve polypropylene sorrel water resistance and
The method of compliance, it is characterised in that：Step 2）In, mass percent of the polypropylene glycol monobutyl 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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| Application Number | Priority Date | Filing Date | Title |
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| CN201710362583.6A CN106947261A (en) | 2017-05-22 | 2017-05-22 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
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| CN201710362583.6A CN106947261A (en) | 2017-05-22 | 2017-05-22 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
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Citations (3)
| 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 |
| CN105542207A (en) * | 2016-03-07 | 2016-05-04 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film through polypropylene glycol and polypeptide-polyvinylpyrrolidone |
| CN105566922A (en) * | 2016-03-07 | 2016-05-11 | 山东理工大学 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly trimethylene carbonate and P (CPP-SA)-polyethylene glycol |
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2017
- 2017-05-22 CN CN201710362583.6A patent/CN106947261A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105542207A (en) * | 2016-03-07 | 2016-05-04 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film through polypropylene glycol and polypeptide-polyvinylpyrrolidone |
| CN105566922A (en) * | 2016-03-07 | 2016-05-11 | 山东理工大学 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly trimethylene carbonate and P (CPP-SA)-polyethylene glycol |
| 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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