CN107057376A - A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO - Google Patents
A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO Download PDFInfo
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- CN107057376A CN107057376A CN201710376533.3A CN201710376533A CN107057376A CN 107057376 A CN107057376 A CN 107057376A CN 201710376533 A CN201710376533 A CN 201710376533A CN 107057376 A CN107057376 A CN 107057376A
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- ppdo
- polycaprolactone
- water resistance
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- 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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- 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
Abstract
The present invention discloses a kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO, using following steps:1)Hydroxy-end capped polycaprolactone list tridecyl ether, solvent, condensing agent and polyacrylic acid is added in dry reactor, reacts 2~4 days, obtains polyacrylic acid polycaprolactone graft copolymer;2)Polyacrylic acid polycaprolactone graft copolymer, hydroxy-end capped PPDO monododecyl ether, solvent and condensing agent are added in dry reactor, reacts 2~4 days, obtains polyacrylic acid polycaprolactone PPDO dual graft copolymer;3)Dual graft copolymer, PPDO monododecyl ether and solvent are added in dry reactor, after mixing 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 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 PPDO are can with excellent biocompatibility and biology
The biomaterial of degradability, with good hydrophobicity and compliance.Polycaprolactone segment is first grafted to polyacrylic acid molecule
Obtain poly acrylic acid-poly caprolactone graft copolymer on chain, then by PPDO segment be grafted to poly acrylic acid-poly oneself
Poly acrylic acid-poly caprolactone-PPDO dual graft is formed on polyacrylic acid segment in interior ester graft copolymer to be total to
Polymers, then adds poly acrylic acid-poly caprolactone-PPDO dual graft copolymerization by PPDO segment again
Thing 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 polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO, its feature exists
In:The molecular weight of polyacrylic acid segment is 82000~94000 in Modified Membrane, the molecular weight of polycaprolactone segment for 2500~
2600, the molecular weight of PPDO segment is 2300~2400;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 single tridecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 27~32 DEG C of stirring reactions 2~4 days, terminate anti-
Should, by filtering, dialysis, dry, obtain object;
2)The synthesis of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer:Added in dry reactor poly-
Acrylic acid-polycaprolactone graft copolymer, hydroxy-end capped PPDO monododecyl ether, solvent and condensing agent,
Under inert atmosphere, in 26~31 DEG C of stirring reactions 2~4 days, terminating reaction by filtering, dialysis, was dried, obtains object;
3)The preparation for the polypropylene sorrel that polycaprolactone is improved with PPDO:Polypropylene is added in dry reactor
Acid-polycaprolactone-PPDO dual graft copolymer, PPDO monododecyl ether and solvent, inertia
Under atmosphere, after 45~51 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, object is obtained.
The method that a kind of described polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO,
Step 1)In, the mol ratio of polycaprolactone list tridecyl ether and polyacrylic acid is 15~25:1.
The method that a kind of described polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO,
Step 1)In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-(3-
Dimethylaminopropyl)The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.06~1.8:1, solvent uses dimethyl sulfoxide (DMSO),
Reactant solution concentration is 5~15 g:100 ml.
The method that a kind of described polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO,
Step 2)In, PPDO monododecyl ether and polyacrylic acid chain in poly acrylic acid-poly caprolactone graft copolymer
The mol ratio of section is 15~25:1.
The method that a kind of described polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO,
Step 2)In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-(3-
Dimethylaminopropyl)Carbodiimide, the mol ratio of condensing agent and polyacrylic acid segment in poly acrylic acid-poly caprolactone graft copolymer
For 1.06~1.8:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
The method that a kind of described polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO,
Step 3)In, mass percent of the PPDO monododecyl ether in Modified Membrane is 2~4%, and solvent uses diformazan
Base sulfoxide, mixture solution concentration is 25~30 g:100 ml.
Compared with prior art, its advantage is the present invention:
1st, the method for a kind of described polycaprolactone and PPDO improvement polypropylene sorrel water resistance and compliance, is adopted
It is simple to operate, be easy to grasp with two step esterifications and the means that are combined of blending;
2nd, described polyacrylic acid improvement film water resistance and compliance are enhanced.
Embodiment
Embodiment 1
1)The preparation of poly acrylic acid-poly caprolactone graft copolymer
15.8 grams of polyacrylic acid are added in dry reactor(Molecular weight is 82000), 8.9 grams of hydroxy-end capped polycaprolactone lists
Tridecyl ether(Molecular weight is 2500), 247 ml dimethyl sulfoxide (DMSO)s are added, 0.049 gram is addedN,N’- dicyclohexyl carbon two
Under imines, inert atmosphere, in 27 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains object;
2)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer
Added in dry reactor 12.2 grams of poly acrylic acid-poly caprolactone graft copolymers, 6.5 grams it is hydroxy-end capped poly- to two
Oxygen cyclohexanone monododecyl ether(Molecular weight is 2300), 187 ml dimethyl sulfoxide (DMSO)s are added, 0.036 gram is addedN,N’- two
Under carbodicyclo hexylimide, inert atmosphere, in 26 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtained
Object;
3)The preparation for the polypropylene sorrel that polycaprolactone is improved with PPDO
10 grams of poly acrylic acid-poly caprolactone-PPDO dual graft copolymers and 37 ml are added in dry reactor
Dimethyl sulfoxide solvent, it is another to add the PPDO monododecyl ether for accounting for Modified Membrane gross weight 2%(Molecular weight is
2300), under inert atmosphere, in 45 DEG C of stirring mixing 50 minutes, the tape casting film forming is used, is dried to obtain in 50 DEG C of vacuum drying chambers
Object.
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 9.7%.
Embodiment 2
1)The preparation of poly acrylic acid-poly caprolactone graft copolymer
15 grams of polyacrylic acid are added in dry reactor(Molecular weight is 87000), 8.7 grams of hydroxy-end capped polycaprolactone lists ten
Trialkyl ether(Molecular weight is 2600), 236 ml dimethyl sulfoxide (DMSO)s are added, 0.028 gram is addedN,N’- diisopropyl carbon two is sub-
Under amine, inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains object;
2)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer
Added in dry reactor 12.3 grams of poly acrylic acid-poly caprolactone graft copolymers, 6.3 grams it is hydroxy-end capped poly- to two
Oxygen cyclohexanone monododecyl ether(Molecular weight is 2400), 186 ml dimethyl sulfoxide (DMSO)s are added, 0.021 gram is addedN,N’- two
Under diisopropylcarbodiimide, inert atmosphere, in 28 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtained
Object;
3)The preparation for the polypropylene sorrel that polycaprolactone is improved with PPDO
9.9 grams of poly acrylic acid-poly caprolactone-PPDO dual graft copolymers and 36 are added in dry reactor
Ml dimethyl sulfoxide solvents, it is another to add the PPDO monododecyl ether for accounting for Modified Membrane gross weight 3%(Molecular weight is
2400), under inert atmosphere, in 48 DEG C of stirring mixing 55 minutes, the tape casting film forming is used, is dried to obtain in 50 DEG C of vacuum drying chambers
Object.
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 10.4%.
Embodiment 3
1)The preparation of poly acrylic acid-poly caprolactone graft copolymer
15.8 grams of polyacrylic acid are added in dry reactor(Molecular weight is 94000), 8.3 grams of hydroxy-end capped polycaprolactone lists
Tridecyl ether(Molecular weight is 2600), 241 ml dimethyl sulfoxide (DMSO)s are added, 0.041 gram of 3- ethyls -1- is added(3- diformazan ammonia
Propyl group)Under carbodiimide, inert atmosphere, in 32 DEG C of stirring reactions 4 days, terminating reaction by filtering, dialysis, was dried, obtains mesh
Mark thing;
2)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer
Added in dry reactor 11.6 grams of poly acrylic acid-poly caprolactone graft copolymers, 5.6 grams it is hydroxy-end capped poly- to two
Oxygen cyclohexanone monododecyl ether(Molecular weight is 2400), add 171 ml dimethyl sulfoxide (DMSO)s, add 0.028 gram of 3- ethyl-
1-(3- dimethylaminopropyls)Under carbodiimide, inert atmosphere, in 31 DEG C of stirring reactions 4 days, terminating reaction, by filtering, dialysis,
Dry, obtain object;
3)The preparation for the polypropylene sorrel that polycaprolactone is improved with PPDO
9.5 grams of poly acrylic acid-poly caprolactone-PPDO dual graft copolymers and 35 are added in dry reactor
Ml dimethyl sulfoxide solvents, it is another to add the PPDO monododecyl ether for accounting for Modified Membrane gross weight 4%(Molecular weight is
2400), under inert atmosphere, in 51 DEG C of stirring mixing 60 minutes, the tape casting film forming is used, is dried to obtain in 50 DEG C of vacuum drying chambers
Object.
After tested:The surface contact angle and its elongation at break of object and water of the present invention respectively than improving before modified
13.4 ° and 11.3%.
Claims (6)
1. a kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO, its feature exists
In:The molecular weight of polyacrylic acid segment is 82000~94000 in Modified Membrane, the molecular weight of polycaprolactone segment for 2500~
2600, the molecular weight of PPDO segment is 2300~2400;Its modification method uses following steps:
1)The synthesis of poly acrylic acid-poly caprolactone graft copolymer:Hydroxy-end capped polycaprolactone is added in dry reactor
Under single tridecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 27~32 DEG C of stirring reactions 2~4 days, terminate anti-
Should, by filtering, dialysis, dry, obtain object;
2)The synthesis of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer:Added in dry reactor poly-
Acrylic acid-polycaprolactone graft copolymer, hydroxy-end capped PPDO monododecyl ether, solvent and condensing agent,
Under inert atmosphere, in 26~31 DEG C of stirring reactions 2~4 days, terminating reaction by filtering, dialysis, was dried, obtains object;
3)The preparation for the polypropylene sorrel that polycaprolactone is improved with PPDO:Polypropylene is added in dry reactor
Acid-polycaprolactone-PPDO dual graft copolymer, PPDO monododecyl ether and solvent, inertia
Under atmosphere, after 45~51 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, object is obtained.
2. a kind of polycaprolactone according to claim 1 improves polypropylene sorrel water resistance and soft with PPDO
Pliable method, it is characterised in that:Step 1)In, the mol ratio of polycaprolactone list tridecyl ether and polyacrylic acid for 15~
25:1。
3. a kind of polycaprolactone according to claim 1 and PPDO 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 polycaprolactone according to claim 1 improves polypropylene sorrel water resistance and soft with PPDO
Pliable method, it is characterised in that:Step 2)In, PPDO monododecyl ether and poly acrylic acid-poly caprolactone
The mol ratio of polyacrylic acid segment is 15~25 in graft copolymer:1.
5. a kind of polycaprolactone according to claim 1 and PPDO improve polypropylene sorrel water resistance and
The method of compliance, it is characterised in that:Step 2)In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl
Base carbodiimide or 3- ethyls -1-(3- dimethylaminopropyls)Carbodiimide, condensing agent and poly acrylic acid-poly caprolactone graft copolymerization
The mol ratio of polyacrylic acid segment is 1.06~1.8 in thing:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~
15 g:100 ml。
6. a kind of polycaprolactone according to claim 1 improves polypropylene sorrel water resistance and soft with PPDO
Pliable method, it is characterised in that:Step 3)In, quality percentage of the PPDO monododecyl ether in Modified Membrane
Than for 2~4%, solvent uses dimethyl sulfoxide (DMSO), mixture solution concentration is 25~30 g:100 ml.
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Citations (3)
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CN105542208A (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 polycaprolactone and poly(p-dioxanone) |
CN105585852A (en) * | 2016-03-16 | 2016-05-18 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film through polycaprolactone and poly(p-dioxanone) |
CN105670308A (en) * | 2016-03-16 | 2016-06-15 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol membrane through polycaprolactone and poly (p-dioxanone)-polyvinylpyrrolidone |
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2017
- 2017-05-25 CN CN201710376533.3A patent/CN107057376A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105542208A (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 polycaprolactone and poly(p-dioxanone) |
CN105585852A (en) * | 2016-03-16 | 2016-05-18 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film through polycaprolactone and poly(p-dioxanone) |
CN105670308A (en) * | 2016-03-16 | 2016-06-15 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol membrane through polycaprolactone and poly (p-dioxanone)-polyvinylpyrrolidone |
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