CN106987127A - 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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- CN106987127A CN106987127A CN201710362662.7A CN201710362662A CN106987127A CN 106987127 A CN106987127 A CN 106987127A CN 201710362662 A CN201710362662 A CN 201710362662A CN 106987127 A CN106987127 A CN 106987127A
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- polycaprolactone
- ppdo
- water resistance
- polyacrylic acid
- polypropylene sorrel
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- 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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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The present invention discloses a kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO, using following steps:1)The synthesis of polyacrylic acid polycaprolactone graft copolymer:Add hydroxy-end capped polycaprolactone list tridecyl ether, solvent, condensing agent and polyacrylic acid in dry reactor, stirring reaction 2~3 days, terminating reaction obtains object;2)The preparation for the polypropylene sorrel that polycaprolactone is modified with PPDO:Polyacrylic acid polycaprolactone graft copolymer, PPDO 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.Polycaprolactone and PPDO are can with excellent biocompatibility and biology
The biomaterial of degradability, with good hydrophobicity and compliance.Polycaprolactone segment is first introduced into polyacrylic acid segment shape
Into poly acrylic acid-poly caprolactone graft copolymer, PPDO segment is then added into poly acrylic acid-poly caprolactone again
Graft copolymer formation blend, is made modified polypropene sorrel, thus drastically increase polypropylene sorrel water resistance 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 that polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO, its feature exists
In:The molecular weight of polyacrylic acid segment is 80000~92000 in Modified Membrane, the molecular weight of polycaprolactone segment for 2000~
2200, the molecular weight of PPDO segment is 5000~6000;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 26~33 DEG C of stirring reactions 2~3 days, terminate anti-
Should, by filtering, dialysis, dry, obtain object;
2)The preparation for the polypropylene sorrel that polycaprolactone is modified with PPDO:Polypropylene is added in dry reactor
Under acid-polycaprolactone graft copolymer, PPDO monododecyl ether and solvent, inert atmosphere, in 45~51 DEG C
After stirring mixing 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, 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 that a kind of described polycaprolactone and PPDO improve polypropylene sorrel water resistance and compliance, is adopted
With 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
18.6 grams of polyacrylic acid are added in dry reactor(Molecular weight is 80000)With 8.7 grams of hydroxy-end capped polycaprolactones
Single tridecyl ether(Molecular weight is 2000), 273 ml dimethyl sulfoxide (DMSO)s are added, 0.062 gram is addedN,N’- dicyclohexyl carbon
Under diimine, inert atmosphere, in 26 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains object;
2)The preparation for the polypropylene sorrel that polycaprolactone is modified with PPDO
10.1 grams of poly acrylic acid-poly caprolactone graft copolymers and 37 ml dimethyl sulfoxide solvents are added in dry reactor,
It is another to add the PPDO monododecyl ether for accounting for Modified Membrane gross weight 2%(Molecular weight is 5000), under inert 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
11.4 ° and 9.1%.
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 9.8 grams of hydroxy-end capped polycaprolactone lists
Tridecyl ether(Molecular weight is 2100), 307 ml dimethyl sulfoxide (DMSO)s are added, 0.039 gram is addedN,N’- diisopropyl carbon two
Under imines, inert atmosphere, in 29 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains object;
2)The preparation for the polypropylene sorrel that polycaprolactone is modified with PPDO
10 grams of poly acrylic acid-poly caprolactone graft copolymers and 36.5 ml dimethyl sulfoxide solvents are added in dry reactor,
It is another to add the PPDO monododecyl ether for accounting for Modified Membrane gross weight 3%(Molecular weight is 5500), under inert 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 9.6%.
Embodiment 3
1)The preparation of poly acrylic acid-poly caprolactone graft copolymer
22.6 grams of polyacrylic acid are added in dry reactor(Molecular weight is 92000)With 10.1 grams of hydroxy-end capped polycaprolactones
Single tridecyl ether(Molecular weight is 2200), 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 33 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtained
Object;
2)The preparation for the polypropylene sorrel that polycaprolactone is modified with PPDO
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 PPDO monododecyl ether for accounting for Modified Membrane gross weight 4%(Molecular weight is 6000), under inert atmosphere,
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 10.3%.
Claims (4)
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 80000~92000 in Modified Membrane, the molecular weight of polycaprolactone segment for 2000~
2200, the molecular weight of PPDO segment is 5000~6000;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 26~33 DEG C of stirring reactions 2~3 days, terminate anti-
Should, by filtering, dialysis, dry, obtain object;
2)The preparation for the polypropylene sorrel that polycaprolactone is modified with PPDO:Polypropylene is added in dry reactor
Under acid-polycaprolactone graft copolymer, PPDO monododecyl ether and solvent, inert atmosphere, in 45~51 DEG C
After stirring mixing 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 improves polypropylene sorrel water resistance and soft with PPDO
Pliable method, it is characterised in that:Step 1)In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl
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, 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)
Publication number | Priority date | Publication date | Assignee | Title |
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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) |
CN105778523A (en) * | 2016-03-16 | 2016-07-20 | 山东理工大学 | Method for improving water tolerance and flexibility of polyvinyl alcohol membrane with poly (p-dioxanone) and polycaprolactone-polyvinyl pyrrolidone |
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2017
- 2017-05-22 CN CN201710362662.7A patent/CN106987127A/en not_active Withdrawn
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) |
CN105778523A (en) * | 2016-03-16 | 2016-07-20 | 山东理工大学 | Method for improving water tolerance and flexibility of polyvinyl alcohol membrane with poly (p-dioxanone) and polycaprolactone-polyvinyl pyrrolidone |
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