CN106977936A - A kind of polycaprolactone is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance - Google Patents
A kind of polycaprolactone is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance Download PDFInfo
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- CN106977936A CN106977936A CN201710362693.2A CN201710362693A CN106977936A CN 106977936 A CN106977936 A CN 106977936A CN 201710362693 A CN201710362693 A CN 201710362693A CN 106977936 A CN106977936 A CN 106977936A
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- polycaprolactone
- gathering
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- lactide
- 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
- 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 polycaprolactone with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance, 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）Polycaprolactone is with gathering（Lactide glycolide）The preparation of modified polypropylene sorrel：Polyacrylic acid polycaprolactone graft copolymer is added in dry reactor, is gathered（Lactide glycolide）Monododecyl ether and solvent, after stirring is mixed 50~60 minutes, with the tape casting film forming and drying, obtain object of the present invention.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 poly-（D, L- lactide coglycolide）（The weight ratio of lactide and glycolide
For 90/10）It is the biomaterial with excellent biocompatibility and biodegradability, with good hydrophobicity and submissive
Property.Polycaprolactone segment is first introduced into polyacrylic acid segment formation poly acrylic acid-poly caprolactone graft copolymer, then again will be poly-
（Lactide coglycolide）Segment adds poly acrylic acid-poly caprolactone graft copolymer formation blend, and modified polyacrylic acid is made
Film, 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 polycaprolactone is with gathering（Lactide coglycolide）The method for improving polypropylene sorrel water resistance and compliance, its feature
It is：The molecular weight of polyacrylic acid segment is 82000~91000 in Modified Membrane, the molecular weight of polycaprolactone segment for 2000~
2400, gather（Lactide coglycolide）The molecular weight of segment is 5300~6000；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 28~34 DEG C of stirring reactions 2~3 days, terminate anti-
Should, by filtering, dialysis, dry, obtain object；
2）Polycaprolactone is with gathering（Lactide coglycolide）The preparation of modified polypropylene sorrel：Added in dry reactor poly-
It is acrylic acid-polycaprolactone graft copolymer, poly-（Lactide coglycolide）Under monododecyl ether and solvent, inert atmosphere, in 46
After~53 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, object is obtained.
A kind of described polycaprolactone is with gathering（Lactide coglycolide）Improve the side of polypropylene sorrel water resistance and compliance
Method, step 1）In, the mol ratio of polycaprolactone list tridecyl ether and polyacrylic acid is 15~25:1.
A kind of described polycaprolactone is with gathering（Lactide coglycolide）Improve the side of 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 1.06~1.8:1, solvent is sub- using dimethyl
Sulfone, reactant solution concentration is 5~15 g:100 ml.
A kind of described polycaprolactone is with gathering（Lactide coglycolide）Improve the side of polypropylene sorrel water resistance and compliance
Method, step 2）In, gather（Lactide coglycolide）Monododecyl ether is using poly-（D, L- lactide coglycolide）Single dodecyl
Ether（The weight ratio of lactide and glycolide is 90/10）, gather（Lactide coglycolide）Matter of the monododecyl ether in Modified Membrane
It is 2~4% to measure percentage, and 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, a kind of described polycaprolactone is with gathering（Lactide coglycolide）Improve the side of polypropylene sorrel water resistance and compliance
Method, 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
19.6 grams of polyacrylic acid are added in dry reactor（Molecular weight is 82000）With 8.9 grams of hydroxy-end capped polycaprolactones
Single tridecyl ether（Molecular weight is 2000）, 285 ml dimethyl sulfoxide (DMSO)s are added, 0.061 gram is addedN,N’- dicyclohexyl carbon
Under diimine, inert atmosphere, in 28 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）Polycaprolactone is with gathering（Lactide coglycolide）The preparation of modified polypropylene sorrel
10.1 grams of poly acrylic acid-poly caprolactone graft copolymers and 37 ml dimethyl sulfoxide solvents are added in dry reactor,
Another add accounts for the poly- of Modified Membrane gross weight 2%（Lactide coglycolide）Monododecyl ether（Molecular weight is 5300）, inert atmosphere
Under, 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
11.9 ° and 9.4%.
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
Tridecyl 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 30 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）Polycaprolactone is with gathering（Lactide coglycolide）The preparation of modified polypropylene sorrel
10 grams of poly acrylic acid-poly caprolactone graft copolymers and 36.5 ml dimethyl sulfoxide solvents are added in dry reactor,
Another add accounts for the poly- of Modified Membrane gross weight 3%（Lactide coglycolide）Monododecyl ether（Molecular weight is 5600）, inert atmosphere
Under, mixed 55 minutes in 49 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
12.2 ° and 10.2%.
Embodiment 3
1）The preparation of poly acrylic acid-poly caprolactone graft copolymer
22.2 grams of polyacrylic acid are added in dry reactor（Molecular weight is 91000）With 10.9 grams of hydroxy-end capped polycaprolactones
Single tridecyl ether（Molecular weight is 2400）, 328 ml dimethyl sulfoxide (DMSO)s are added, 0.057 gram of 3- ethyls -1- is added（3- diformazans
Aminopropyl）Under carbodiimide, inert atmosphere, in 34 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtained
Object；
2）Polycaprolactone is with gathering（Lactide coglycolide）The preparation of modified polypropylene sorrel
9.6 grams of poly acrylic acid-poly caprolactone graft copolymers and 35 ml dimethyl sulfoxide solvents are added in dry reactor,
Another add accounts for the poly- of Modified Membrane gross weight 4%（Lactide coglycolide）Monododecyl ether（Molecular weight is 6000）, inert atmosphere
Under, mixed 60 minutes in 53 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
12.8 ° and 10.9%.
Claims (4)
1. a kind of polycaprolactone is with gathering（Lactide coglycolide）The method for improving polypropylene sorrel water resistance and compliance, it is special
Levy and be：The molecular weight of polyacrylic acid segment is 82000~91000 in Modified Membrane, and the molecular weight of polycaprolactone segment is 2000
~2400, gather（Lactide coglycolide）The molecular weight of segment is 5300~6000；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 28~34 DEG C of stirring reactions 2~3 days, terminate anti-
Should, by filtering, dialysis, dry, obtain object；
2）Polycaprolactone is with gathering（Lactide coglycolide）The preparation of modified polypropylene sorrel：Added in dry reactor poly-
It is acrylic acid-polycaprolactone graft copolymer, poly-（Lactide coglycolide）Under monododecyl ether and solvent, inert atmosphere, in 46
After~53 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 is with gathering（Lactide coglycolide）Improve polypropylene sorrel water resistance
And the method for compliance, it is characterised in that：Step 1）In, the mol ratio of polycaprolactone list tridecyl ether and polyacrylic acid is 15
~25:1.
3. a kind of polycaprolactone according to claim 1 is with gathering（Lactide coglycolide）Improve polypropylene sorrel water resistance
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 polycaprolactone according to claim 1 is with gathering（Lactide coglycolide）Improve polypropylene sorrel water resistance
And the method for compliance, it is characterised in that：Step 2）In, gather（Lactide coglycolide）Monododecyl ether is using poly-（D, L- third
Lactide-co-glycolides）Monododecyl ether（The weight ratio of lactide and glycolide is 90/10）, gather（Lactide coglycolide）Single ten
Mass percent of the dialkyl ether in Modified Membrane is 2~4%, and solvent uses dimethyl sulfoxide (DMSO), mixture solution concentration is 25~
30 g:100 ml。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710362693.2A CN106977936A (en) | 2017-05-22 | 2017-05-22 | A kind of polycaprolactone is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710362693.2A CN106977936A (en) | 2017-05-22 | 2017-05-22 | A kind of polycaprolactone is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance |
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| CN106977936A true CN106977936A (en) | 2017-07-25 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105647200A (en) * | 2016-03-16 | 2016-06-08 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by polycaprolactone and poly(lactic acid-glycolic acid) |
| CN105669987A (en) * | 2016-02-29 | 2016-06-15 | 山东理工大学 | Preparation method for polyvinyl alcohol-poly(lactide-glycolide) graft copolymer |
| CN105670304A (en) * | 2016-03-07 | 2016-06-15 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by using polycaprolactone and polylactic acid-glycollic acid |
-
2017
- 2017-05-22 CN CN201710362693.2A patent/CN106977936A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669987A (en) * | 2016-02-29 | 2016-06-15 | 山东理工大学 | Preparation method for polyvinyl alcohol-poly(lactide-glycolide) graft copolymer |
| CN105670304A (en) * | 2016-03-07 | 2016-06-15 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by using polycaprolactone and polylactic acid-glycollic acid |
| CN105647200A (en) * | 2016-03-16 | 2016-06-08 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by polycaprolactone and poly(lactic acid-glycolic acid) |
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Application publication date: 20170725 |