CN107118570A - A kind of method that PLA improves polypropylene sorrel water resistance and compliance with polycaprolactone - Google Patents
A kind of method that PLA improves polypropylene sorrel water resistance and compliance with polycaprolactone Download PDFInfo
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- CN107118570A CN107118570A CN201710376600.1A CN201710376600A CN107118570A CN 107118570 A CN107118570 A CN 107118570A CN 201710376600 A CN201710376600 A CN 201710376600A CN 107118570 A CN107118570 A CN 107118570A
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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
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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 PLA improves polypropylene sorrel water resistance and compliance with polycaprolactone, using following steps：1）Hydroxy-end capped PLA list tridecyl ether, solvent, condensing agent and polyacrylic acid is added in dry reactor, reacts 2~4 days, obtains polyacrylic acid polylactic acid graft copolymer；2）Graft copolymer, hydroxy-end capped polycaprolactone monododecyl 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, polycaprolactone 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.It is poly-（D, Pfansteihl）With polycaprolactone can be dropped with excellent biocompatibility and biology
The biomaterial of solution property, with good hydrophobicity and compliance.First polylactic acid chain segment is grafted on polyacrylic acid strand
Poly acrylic acid-poly lactic acid graft copolymer is obtained, then polycaprolactone segment is grafted to poly acrylic acid-poly lactic acid graft copolymer
In polyacrylic acid segment on form poly acrylic acid-poly lactic acid-polycaprolactone dual graft copolymer, then again by polycaprolactone chain
Section adds poly acrylic acid-poly lactic acid-polycaprolactone dual graft copolymer formation blend, and modified polypropene sorrel is made, so that
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 improves polypropylene sorrel water resistance and compliance with polycaprolactone, it is characterised in that：Modified Membrane
The molecular weight of middle polyacrylic acid segment is 81000~91000, and the molecular weight of polylactic acid chain segment is 2600~2800, polycaprolactone
The molecular weight of segment is 2400~2500；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly lactic acid graft copolymer：Hydroxy-end capped PLA list ten is added in dry reactor
Under trialkyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 27~31 DEG C of stirring reactions 2~4 days, terminating reaction,
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 polylactic acid graft copolymer, hydroxy-end capped polycaprolactone monododecyl ether, solvent and condensing agent, inert atmosphere, in 26
~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
Under acid-polycaprolactone dual graft copolymer, polycaprolactone monododecyl ether and solvent, inert atmosphere, in 47~51 DEG C of stirrings
After mixing 50~60 minutes, with the tape casting film forming and drying, object is obtained.
A kind of described PLA improves the method for polypropylene sorrel water resistance and compliance, step 1 with polycaprolactone）
In, PLA list tridecyl ether is using poly-（D, Pfansteihl）Single tridecyl ether, PLA list tridecyl ether and polypropylene
The mol ratio of acid is 15~25:1.
A kind of described PLA improves the method for polypropylene sorrel water resistance and compliance, step 1 with polycaprolactone）
In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-（3- diformazan ammonia
Propyl group）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.
A kind of described PLA improves the method for polypropylene sorrel water resistance and compliance, step 2 with polycaprolactone）
In, the mol ratio of polycaprolactone monododecyl ether and polyacrylic acid segment in poly acrylic acid-poly lactic acid graft copolymer is 15
~25:1.
A kind of described PLA improves the method for polypropylene sorrel water resistance and compliance, step 2 with polycaprolactone）
In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-（3- diformazan ammonia
Propyl group）In carbodiimide, condensing agent and poly acrylic acid-poly lactic acid graft copolymer the mol ratio of polyacrylic acid segment for 1.06~
1.8:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
A kind of described PLA improves the method for polypropylene sorrel water resistance and compliance, step 3 with polycaprolactone）
In, mass percent of the polycaprolactone monododecyl ether in Modified Membrane is 2~4%, and solvent uses dimethyl sulfoxide (DMSO), mixing
Thing 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 PLA and polycaprolactone improvement polypropylene sorrel water resistance and compliance, using two step esters
Change reaction and the means that are combined of blending, 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 lactic acid graft copolymer
15.7 grams of polyacrylic acid are added in dry reactor（Molecular weight is 81000）, 9.1 grams of hydroxy-end capped PLA lists ten
Trialkyl ether（Molecular weight is 2600）, 248 ml dimethyl sulfoxide (DMSO)s are added, 0.049 gram is addedN,N’- dicyclohexyl carbon two is sub-
Under amine, 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 lactic acid-polycaprolactone dual graft copolymer
12.2 grams of poly acrylic acid-poly lactic acid graft copolymers, 6.7 grams of hydroxy-end capped polycaprolactones are added in dry reactor
Monododecyl ether（Molecular weight is 2400）, 188 ml dimethyl sulfoxide (DMSO)s are added, 0.036 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；
3）The preparation for the polypropylene sorrel that PLA is improved with polycaprolactone
10 grams of poly acrylic acid-poly lactic acid-polycaprolactone dual graft copolymers are added in dry reactor and 37 ml dimethyl are sub-
Sulfoxide solvent, it is another to add the polycaprolactone monododecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 2400）, under inert atmosphere,
Mixed 50 minutes in 47 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 9.3%.
Embodiment 2
1）The preparation of poly acrylic acid-poly lactic acid graft copolymer
15.1 grams of polyacrylic acid are added in dry reactor（Molecular weight is 87000）, 8.8 grams of hydroxy-end capped PLA lists ten
Trialkyl ether（Molecular weight is 2700）, 237 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 lactic acid-polycaprolactone dual graft copolymer
12.1 grams of poly acrylic acid-poly lactic acid graft copolymers, 6.5 grams of hydroxy-end capped polycaprolactones are added in dry reactor
Monododecyl ether（Molecular weight is 2400）, 186 ml dimethyl sulfoxide (DMSO)s are added, 0.021 gram is addedN,N’- diisopropyl carbon
Under diimine, inert atmosphere, in 30 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 polycaprolactone monododecyl ether for accounting for Modified Membrane gross weight 3%（Molecular weight is 2400）, inert atmosphere
Under, 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
12.8 ° and 10.2%.
Embodiment 3
1）The preparation of poly acrylic acid-poly lactic acid graft copolymer
15.2 grams of polyacrylic acid are added in dry reactor（Molecular weight is 91000）, 8.8 grams of hydroxy-end capped PLA lists ten
Trialkyl ether（Molecular weight is 2800）, 239 ml dimethyl sulfoxide (DMSO)s are added, 0.041 gram of 3- ethyls -1- is added（3- diformazans ammonia third
Base）Under carbodiimide, inert atmosphere, in 31 DEG C of stirring reactions 4 days, terminating reaction by filtering, dialysis, was dried, obtains target
Thing；
2）The preparation of poly acrylic acid-poly lactic acid-polycaprolactone dual graft copolymer
11.5 grams of poly acrylic acid-poly lactic acid graft copolymers, 5.8 grams of hydroxy-end capped polycaprolactones are added in dry reactor
Monododecyl ether（Molecular weight is 2500）, 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 polycaprolactone monododecyl ether for accounting for Modified Membrane gross weight 4%（Molecular weight is 2500）, inert atmosphere
Under, 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
13.6 ° and 10.8%.
Claims (6)
1. a kind of method that PLA improves polypropylene sorrel water resistance and compliance with polycaprolactone, it is characterised in that：It is modified
The molecular weight of polyacrylic acid segment is 81000~91000 in film, and the molecular weight of polylactic acid chain segment is 2600~2800, is gathered in oneself
The molecular weight of ester segment is 2400~2500；Its modification method uses following steps：
1）The synthesis of poly acrylic acid-poly lactic acid graft copolymer：Hydroxy-end capped PLA list ten is added in dry reactor
Under trialkyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 27~31 DEG C of stirring reactions 2~4 days, terminating reaction,
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 polylactic acid graft copolymer, hydroxy-end capped polycaprolactone monododecyl ether, solvent and condensing agent, inert atmosphere, in 26
~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
Under acid-polycaprolactone dual graft copolymer, polycaprolactone monododecyl ether and solvent, inert atmosphere, in 47~51 DEG C of stirrings
After mixing 50~60 minutes, with the tape casting film forming and drying, object is obtained.
2. a kind of PLA according to claim 1 improves the side of polypropylene sorrel water resistance and compliance with polycaprolactone
Method, it is characterised in that：Step 1）In, PLA list tridecyl ether is using poly-（D, Pfansteihl）Single tridecyl ether, PLA
The mol ratio of single tridecyl ether and polyacrylic acid is 15~25:1.
3. a kind of PLA according to claim 1 and polycaprolactone improve polypropylene sorrel water resistance and compliance
Method, it is characterised in that：Step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl carbon two is sub-
Amine or 3- ethyls -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.06~1.8:1, it is molten
Agent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. a kind of PLA according to claim 1 improves the side of polypropylene sorrel water resistance and compliance with polycaprolactone
Method, it is characterised in that：Step 2）In, polycaprolactone monododecyl ether and in poly acrylic acid-poly lactic acid graft copolymer poly- third
The mol ratio of olefin(e) acid segment is 15~25:1.
5. a kind of PLA according to claim 1 and polycaprolactone improve polypropylene sorrel water resistance and compliance
Method, it is characterised in that：Step 2）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl carbon two is sub-
Amine or 3- ethyls -1-（3- dimethylaminopropyls）Carbodiimide, condensing agent and polypropylene in poly acrylic acid-poly lactic acid graft copolymer
The mol ratio of sour segment is 1.06~1.8:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100
ml。
6. a kind of PLA according to claim 1 improves the side of polypropylene sorrel water resistance and compliance with polycaprolactone
Method, it is characterised in that：Step 3）In, mass percent of the polycaprolactone monododecyl ether in Modified Membrane is 2~4%, solvent
Using dimethyl sulfoxide (DMSO), mixture solution concentration is 25~30 g:100 ml.
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| CN201710376600.1A CN107118570A (en) | 2017-05-25 | 2017-05-25 | A kind of method that PLA improves polypropylene sorrel water resistance and compliance with polycaprolactone |
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| CN201710376600.1A CN107118570A (en) | 2017-05-25 | 2017-05-25 | A kind of method that PLA improves polypropylene sorrel water resistance and compliance with polycaprolactone |
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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 |
| 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 |
| CN105670309A (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 polypeptide and polycaprolactone |
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2017
- 2017-05-25 CN CN201710376600.1A patent/CN107118570A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN105670309A (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 polypeptide and polycaprolactone |
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