CN106977948A - A kind of method that PLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance - Google Patents
A kind of method that PLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance Download PDFInfo
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- CN106977948A CN106977948A CN201710376571.9A CN201710376571A CN106977948A CN 106977948 A CN106977948 A CN 106977948A CN 201710376571 A CN201710376571 A CN 201710376571A CN 106977948 A CN106977948 A CN 106977948A
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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
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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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- 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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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The present invention discloses a kind of method that PLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance, using following steps：1）Hydroxy-end capped polycaprolactone monododecyl ether, solvent, condensing agent and polyacrylic acid is added in dry reactor, reacts 2~4 days, obtains polyacrylic acid polycaprolactone graft copolymer；2）Graft copolymer, amino-terminated PLA list tridecyl ether, solvent and condensing agent are added in dry reactor, reacts 2~4 days, obtains polyacrylic acid polylactic acid poly caprolactone dual graft copolymer；3）Dual graft copolymer, PLA list tridecyl 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.It is poly-（D,L）Lactic acid and polycaprolactone can be dropped with excellent biocompatibility and biology
The biomaterial of solution property, with good hydrophobicity and compliance.Polycaprolactone segment is first grafted to polyacrylic acid strand
On obtain poly acrylic acid-poly caprolactone graft copolymer, then polylactic acid chain segment is grafted to the grafting of poly acrylic acid-poly caprolactone altogether
Poly acrylic acid-poly lactic acid-polycaprolactone dual graft copolymer is formed on polyacrylic acid segment in polymers, then again by PLA
Segment adds poly acrylic acid-poly lactic acid-polycaprolactone dual graft copolymer formation blend, and modified polypropene sorrel is made, from
And 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 PLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance, it is characterised in that：
The molecular weight of polyacrylic acid segment is 81000~92000 in Modified Membrane, and the molecular weight of polycaprolactone segment is 2600~2700,
The molecular weight of polylactic acid chain 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 monododecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 28~33 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 lactic acid-polycaprolactone dual graft copolymer：In dry reactor add polyacrylic acid-
Under polycaprolactone graft copolymer, amino-terminated PLA list tridecyl ether, solvent and condensing agent, inert atmosphere, in 28
~31 DEG C of stirring reactions 2~4 days, terminating reaction by filtering, dialysis, is dried, obtains object；
3）The preparation for the polypropylene sorrel that PLA is improved with polycaprolactone：Poly acrylic acid-poly breast is added in dry reactor
It is mixed in 48~51 DEG C of stirrings under acid-polycaprolactone dual graft copolymer, PLA list tridecyl ether and solvent, inert atmosphere
After closing 50~60 minutes, with the tape casting film forming and drying, object is obtained.
The method that a kind of described PLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance, step
Rapid 1）In, the mol ratio of polycaprolactone monododecyl ether and polyacrylic acid is 15~25:1.
The method that a kind of described PLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance, step
Rapid 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-（3- bis-
First aminopropyl）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.06~1.9:1, solvent uses dimethyl sulfoxide (DMSO), instead
It is 5~15 g to answer thing solution concentration:100 ml.
The method that a kind of described PLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance, step
Rapid 2）In, PLA list tridecyl ether is using poly-（D,L）Lactic acid list tridecyl ether, PLA list tridecyl ether and poly- third
The mol ratio of polyacrylic acid segment is 15~25 in olefin(e) acid-polycaprolactone graft copolymer:1.
The method that a kind of described PLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance, step
Rapid 2）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-（3- bis-
First aminopropyl）Carbodiimide, the mol ratio of condensing agent and polyacrylic acid segment in poly acrylic acid-poly caprolactone graft copolymer is
1.06~1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
The method that a kind of described PLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance, step
Rapid 3）In, PLA list tridecyl ether is using poly-（D,L）Lactic acid list tridecyl ether, PLA list tridecyl ether is in modification
Mass percent in film is 2~3%, 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, the method that a kind of described PLA and polycaprolactone are improved to polypropylene sorrel water resistance and compliance, is used
Esterification, amidation process and blending three kinds of means, it is simple to operate, be easy to grasp；
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
15.5 grams of polyacrylic acid are added in dry reactor（Molecular weight is 81000）, 9.2 grams of hydroxy-end capped polycaprolactone lists
Lauryl ether（Molecular weight is 2600）, 247 ml dimethyl sulfoxide (DMSO)s are added, 0.049 gram is addedN,N’- dicyclohexyl carbon two
Under imines, inert atmosphere, in 28 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation of poly acrylic acid-poly lactic acid-polycaprolactone dual graft copolymer
12.1 grams of poly acrylic acid-poly caprolactone graft copolymers, 6.5 grams of amino-terminated PLAs are added in dry reactor
Single tridecyl ether（Molecular weight is 2300）, 186 ml dimethyl sulfoxide (DMSO)s are added, 0.036 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；
3）The preparation for the polypropylene sorrel that PLA is improved with polycaprolactone
10.1 grams of poly acrylic acid-poly lactic acid-polycaprolactone dual graft copolymers and 37 ml dimethyl are added in dry reactor
Sulfoxide solvent, it is another to add the PLA list tridecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 2300）, under inert atmosphere,
Mixed 50 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
12.5 ° and 10.3%.
Embodiment 2
1）The preparation of poly acrylic acid-poly caprolactone graft copolymer
15.1 grams of polyacrylic acid are added in dry reactor（Molecular weight is 87000）, 8.6 grams of hydroxy-end capped polycaprolactone lists
Lauryl ether（Molecular weight is 2600）, 237 ml dimethyl sulfoxide (DMSO)s are added, 0.028 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）The preparation of poly acrylic acid-poly lactic acid-polycaprolactone dual graft copolymer
12.2 grams of poly acrylic acid-poly caprolactone graft copolymers, 6.5 grams of amino-terminated PLAs are added in dry reactor
Single tridecyl ether（Molecular weight is 2400）, 187 ml dimethyl sulfoxide (DMSO)s are added, 0.021 gram is addedN,N’- diisopropyl carbon
Under diimine, inert atmosphere, in 29 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains object；
3）The preparation for the polypropylene sorrel that PLA is improved with polycaprolactone
9.9 grams of poly acrylic acid-poly lactic acid-polycaprolactone dual graft copolymers and 36 ml dimethyl are added in dry reactor
Sulfoxide solvent, it is another to add the PLA list tridecyl ether for accounting for Modified Membrane gross weight 3%（Molecular weight is 2400）, under inert atmosphere,
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
12.9 ° and 10.9%.
Embodiment 3
1）The preparation of poly acrylic acid-poly caprolactone graft copolymer
15.5 grams of polyacrylic acid are added in dry reactor（Molecular weight is 92000）, 8.3 grams of hydroxy-end capped polycaprolactone lists
Lauryl ether（Molecular weight is 2700）, 237 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 33 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 lactic acid-polycaprolactone dual graft copolymer
11.6 grams of poly acrylic acid-poly caprolactone graft copolymers, 5.6 grams of amino-terminated PLAs are added in dry reactor
Single tridecyl ether（Molecular weight is 2400）, 173 ml dimethyl sulfoxide (DMSO)s are added, 0.028 gram of 3- ethyls -1- is added（3- diformazans
Aminopropyl）Under carbodiimide, inert atmosphere, in 31 DEG C of stirring reactions 4 days, terminating reaction by filtering, dialysis, was dried, obtained
Object；
3）The preparation for the polypropylene sorrel that PLA is improved with polycaprolactone
9.5 grams of poly acrylic acid-poly lactic acid-polycaprolactone dual graft copolymers and 35 ml dimethyl are added in dry reactor
Sulfoxide solvent, it is another to add the PLA list tridecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 2400）, 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
13.7 ° and 11.6%.
Claims (6)
1. a kind of method that PLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance, its feature exists
In：The molecular weight of polyacrylic acid segment is 81000~92000 in Modified Membrane, the molecular weight of polycaprolactone segment for 2600~
2700, the molecular weight of polylactic acid chain 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 monododecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 28~33 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 lactic acid-polycaprolactone dual graft copolymer：In dry reactor add polyacrylic acid-
Under polycaprolactone graft copolymer, amino-terminated PLA list tridecyl ether, solvent and condensing agent, inert atmosphere, in 28
~31 DEG C of stirring reactions 2~4 days, terminating reaction by filtering, dialysis, is dried, obtains object；
3）The preparation for the polypropylene sorrel that PLA is improved with polycaprolactone：Poly acrylic acid-poly breast is added in dry reactor
It is mixed in 48~51 DEG C of stirrings under acid-polycaprolactone dual graft copolymer, PLA list tridecyl ether and solvent, inert atmosphere
After closing 50~60 minutes, with the tape casting film forming and drying, object is obtained.
2. a kind of PLA according to claim 1 changes with polycaprolactone to polypropylene sorrel water resistance and compliance
Good method, it is characterised in that：Step 1）In, the mol ratio of polycaprolactone monododecyl ether and polyacrylic acid is 15~25:
1。
3. a kind of PLA according to claim 1 is carried out with polycaprolactone to polypropylene sorrel water resistance and compliance
The method of improvement, 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~
1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. a kind of PLA according to claim 1 changes with polycaprolactone to polypropylene sorrel water resistance and compliance
Good method, it is characterised in that：Step 2）In, PLA list tridecyl ether is using poly-（D,L）Lactic acid list tridecyl ether, gathers
The mol ratio of lactic acid list tridecyl ether and polyacrylic acid segment in poly acrylic acid-poly caprolactone graft copolymer is 15~25:
1。
5. a kind of PLA according to claim 1 is carried out with polycaprolactone to polypropylene sorrel water resistance and compliance
The method of improvement, it is characterised in that：Step 2）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl
Carbodiimide or 3- ethyls -1-（3- dimethylaminopropyls）Carbodiimide, condensing agent and poly acrylic acid-poly caprolactone graft copolymer
The mol ratio of middle polyacrylic acid segment is 1.06~1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15
g:100 ml。
6. a kind of PLA according to claim 1 changes with polycaprolactone to polypropylene sorrel water resistance and compliance
Good method, it is characterised in that：Step 3）In, PLA list tridecyl ether is using poly-（D,L）Lactic acid list tridecyl ether, gathers
Mass percent of the lactic acid list tridecyl ether in Modified Membrane is 2~3%, and solvent uses dimethyl sulfoxide (DMSO), and mixture solution is dense
Spend for 25~30 g:100 ml.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710376571.9A CN106977948A (en) | 2017-05-25 | 2017-05-25 | A kind of method that PLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance |
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| CN201710376571.9A CN106977948A (en) | 2017-05-25 | 2017-05-25 | A kind of method that PLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486806A (en) * | 2009-02-17 | 2009-07-22 | 四川大学 | Natural polymer / degradable polymer composite material and preparation thereof |
| CN102408578A (en) * | 2011-09-22 | 2012-04-11 | 福建师范大学 | Preparation method for super hydrophobic biodegradable compound film and product thereof |
| CN105647195A (en) * | 2016-03-07 | 2016-06-08 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by polytrimethylene carbonate and polycaprolactone |
-
2017
- 2017-05-25 CN CN201710376571.9A patent/CN106977948A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486806A (en) * | 2009-02-17 | 2009-07-22 | 四川大学 | Natural polymer / degradable polymer composite material and preparation thereof |
| CN102408578A (en) * | 2011-09-22 | 2012-04-11 | 福建师范大学 | Preparation method for super hydrophobic biodegradable compound film and product thereof |
| CN105647195A (en) * | 2016-03-07 | 2016-06-08 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by polytrimethylene carbonate and polycaprolactone |
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Application publication date: 20170725 |