CN107118569A - A kind of method that poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with polycaprolactone - Google Patents
A kind of method that poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with polycaprolactone Download PDFInfo
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- CN107118569A CN107118569A CN201710376554.5A CN201710376554A CN107118569A CN 107118569 A CN107118569 A CN 107118569A CN 201710376554 A CN201710376554 A CN 201710376554A CN 107118569 A CN107118569 A CN 107118569A
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- 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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- 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 poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with polycaprolactone, using following steps：1）Hydroxy-end capped poly (lactic acid-glycolic acid) list tridecyl ether, solvent, condensing agent and polyacrylic acid is added in dry reactor, reacts 2~4 days, obtains polyacrylic acid poly (lactic acid-glycolic 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 poly (lactic acid-glycolic acid) polycaprolactone 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,L）Y（Lactic acid is 90/10 with glycolic mol ratio）And polycaprolactone
It is the biomaterial with excellent biocompatibility and biodegradability, with good hydrophobicity and compliance.First will
Poly (lactic acid-glycolic acid) segment, which is grafted on polyacrylic acid strand, obtains poly acrylic acid-poly y graft copolymer, then
Poly- third is formed on the polyacrylic acid segment that polycaprolactone segment is grafted in poly acrylic acid-poly y graft copolymer
Olefin(e) acid-poly (lactic acid-glycolic acid)-polycaprolactone dual graft copolymer, then adds poly acrylic acid-poly breast by polycaprolactone segment again
Sour glycolic-polycaprolactone dual graft copolymer formation blend, is made modified polypropene sorrel, so as to drastically increase poly-
The water resistance and compliance of acrylic film.
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 poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with polycaprolactone, it is characterised in that：
The molecular weight of polyacrylic acid segment is 84000~93000 in Modified Membrane, the molecular weight of poly (lactic acid-glycolic acid) segment for 2600~
2700, the molecular weight of polycaprolactone segment is 2400~2500；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly y graft copolymer：Hydroxy-end capped poly- breast is added in dry reactor
Under sour glycolic list tridecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 28~32 DEG C of stirring reactions 2~4
My god, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The synthesis of poly acrylic acid-poly y-polycaprolactone dual graft copolymer：Poly- third is added in dry reactor
Olefin(e) acid-poly (lactic acid-glycolic acid) graft copolymer, hydroxy-end capped polycaprolactone monododecyl ether, solvent and condensing agent, inertia
Under atmosphere, in 27~32 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 poly (lactic acid-glycolic acid) is improved with polycaprolactone：Polypropylene is added in dry reactor
Under acid-poly (lactic acid-glycolic acid)-polycaprolactone dual graft copolymer, polycaprolactone monododecyl ether and solvent, inert atmosphere, in
After 47~52 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 poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with polycaprolactone, step
Rapid 1）In, poly (lactic acid-glycolic acid) list tridecyl ether is using poly-（D,L）Y list tridecyl ether (lactic acid and glycolic
Mol ratio is that 90/10), the mol ratio of poly (lactic acid-glycolic acid) list tridecyl ether and polyacrylic acid is 15~25:1.
The method that a kind of described poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with polycaprolactone, 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 1.07~1.8:1, 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 poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with polycaprolactone, step
Rapid 2）In, polycaprolactone monododecyl ether and polyacrylic acid segment in poly acrylic acid-poly y graft copolymer
Mol ratio is 15~25:1.
The method that a kind of described poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with polycaprolactone, step
Rapid 2）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-（3- bis-
First aminopropyl）Carbodiimide, mole of condensing agent and polyacrylic acid segment in poly acrylic acid-poly y graft copolymer
Than for 1.07~1.8:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
The method that a kind of described poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with polycaprolactone, step
Rapid 3）In, mass percent of the polycaprolactone monododecyl ether in Modified Membrane is 2~4%, and solvent uses dimethyl sulfoxide (DMSO),
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 poly (lactic acid-glycolic acid) and polycaprolactone improvement polypropylene sorrel water resistance and compliance, is used
Two step esterifications 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 y graft copolymer
16 grams of polyacrylic acid are added in dry reactor（Molecular weight is 84000）, 9.1 grams of hydroxy-end capped poly (lactic acid-glycolic acid)s
Single tridecyl ether（Molecular weight is 2600）, 251 ml dimethyl sulfoxide (DMSO)s are added, 0.049 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）The preparation of poly acrylic acid-poly y-polycaprolactone dual graft copolymer
Added in dry reactor 12.2 grams of poly acrylic acid-poly y graft copolymers, 6.7 grams it is hydroxy-end capped poly-
Caprolactone monododecyl ether（Molecular weight is 2400）, 189 ml dimethyl sulfoxide (DMSO)s are added, 0.035 gram is addedN,N’- two rings
Under hexyl carbodiimide, inert atmosphere, in 27 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains mesh
Mark thing；
3）The preparation for the polypropylene sorrel that poly (lactic acid-glycolic acid) is improved with polycaprolactone
10.1 grams of poly acrylic acid-poly y-polycaprolactone dual graft copolymers and 37 ml are added in dry reactor
Dimethyl sulfoxide solvent, it is another to add the polycaprolactone monododecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 2400）, it is lazy
Property atmosphere under, in 47 DEG C stirring mixing 50 minutes, use the tape casting film forming, object be 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
12.6 ° and 9.6%.
Embodiment 2
1）The preparation of poly acrylic acid-poly y graft copolymer
15 grams of polyacrylic acid are added in dry reactor（Molecular weight is 87000）, 8.7 grams of hydroxy-end capped poly (lactic acid-glycolic acid)s
Single tridecyl ether（Molecular weight is 2700）, 238 ml dimethyl sulfoxide (DMSO)s are added, 0.028 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；
2）The preparation of poly acrylic acid-poly y-polycaprolactone dual graft copolymer
Added in dry reactor 12.1 grams of poly acrylic acid-poly y graft copolymers, 6.4 grams it is hydroxy-end capped poly-
Caprolactone monododecyl ether（Molecular weight is 2400）, 186 ml dimethyl sulfoxide (DMSO)s are added, 0.022 gram is addedN,N’- two is different
Under propyl group carbodiimide, inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains mesh
Mark thing；
3）The preparation for the polypropylene sorrel that poly (lactic acid-glycolic acid) is improved with polycaprolactone
9.9 grams of poly acrylic acid-poly y-polycaprolactone dual graft copolymers and 36 ml are added in dry reactor
Dimethyl sulfoxide solvent, it is another to add the polycaprolactone monododecyl ether for accounting for Modified Membrane gross weight 3%（Molecular weight is 2400）, it is lazy
Property atmosphere under, in 49 DEG C stirring mixing 55 minutes, use the tape casting film forming, object be 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
13.3 ° and 10.3%.
Embodiment 3
1）The preparation of poly acrylic acid-poly y graft copolymer
15.8 grams of polyacrylic acid are added in dry reactor（Molecular weight is 93000）, 8.5 grams of hydroxy-end capped PLA ethanol
Sour list tridecyl ether（Molecular weight is 2700）, 243 ml dimethyl sulfoxide (DMSO)s are added, 0.041 gram of 3- ethyls -1- is added（3- bis-
First aminopropyl）Under carbodiimide, inert atmosphere, in 32 DEG C of stirring reactions 4 days, terminating reaction by filtering, dialysis, was dried, obtained
To object；
2）The preparation of poly acrylic acid-poly y-polycaprolactone dual graft copolymer
Added in dry reactor 11.6 grams of poly acrylic acid-poly y graft copolymers, 5.7 grams it is hydroxy-end capped poly-
Caprolactone monododecyl ether（Molecular weight is 2500）, 173 ml dimethyl sulfoxide (DMSO)s are added, 0.028 gram of 3- ethyls -1- is added
（3- dimethylaminopropyls）Under carbodiimide, inert atmosphere, in 32 DEG C of stirring reactions 4 days, terminating reaction, by filtering, dialysis, dry
It is dry, obtain object；
3）The preparation for the polypropylene sorrel that poly (lactic acid-glycolic acid) is improved with polycaprolactone
9.5 grams of poly acrylic acid-poly y-polycaprolactone dual graft copolymers and 35 ml are added in dry reactor
Dimethyl sulfoxide solvent, it is another to add the polycaprolactone monododecyl ether for accounting for Modified Membrane gross weight 4%（Molecular weight is 2500）, it is lazy
Property atmosphere under, in 52 DEG C stirring mixing 60 minutes, use the tape casting film forming, object be 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
13.9 ° and 10.8%.
Claims (6)
1. a kind of method that poly (lactic acid-glycolic acid) improves polypropylene sorrel water resistance and compliance with polycaprolactone, its feature exists
In：The molecular weight of polyacrylic acid segment is 84000~93000 in Modified Membrane, and the molecular weight of poly (lactic acid-glycolic acid) segment is 2600
~2700, the molecular weight of polycaprolactone segment is 2400~2500；Its modification method uses following steps：
1）The synthesis of poly acrylic acid-poly y graft copolymer：Hydroxy-end capped poly- breast is added in dry reactor
Under sour glycolic list tridecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 28~32 DEG C of stirring reactions 2~4
My god, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The synthesis of poly acrylic acid-poly y-polycaprolactone dual graft copolymer：Poly- third is added in dry reactor
Olefin(e) acid-poly (lactic acid-glycolic acid) graft copolymer, hydroxy-end capped polycaprolactone monododecyl ether, solvent and condensing agent, inertia
Under atmosphere, in 27~32 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 poly (lactic acid-glycolic acid) is improved with polycaprolactone：Polypropylene is added in dry reactor
Under acid-poly (lactic acid-glycolic acid)-polycaprolactone dual graft copolymer, polycaprolactone monododecyl ether and solvent, inert atmosphere, in
After 47~52 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, object is obtained.
2. a kind of poly (lactic acid-glycolic acid) according to claim 1 improves polypropylene sorrel water resistance and submissive with polycaprolactone
The method of property, it is characterised in that：Step 1）In, poly (lactic acid-glycolic acid) list tridecyl ether is using poly-（D,L）Y list
Tridecyl ether (lactic acid with glycolic mol ratio be 90/10), poly (lactic acid-glycolic acid) list tridecyl ether and polyacrylic acid rub
You are than being 15~25:1.
3. a kind of poly (lactic acid-glycolic acid) according to claim 1 improves polypropylene sorrel water resistance and soft with polycaprolactone
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 1.07~
1.8:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. a kind of poly (lactic acid-glycolic acid) according to claim 1 improves polypropylene sorrel water resistance and submissive with polycaprolactone
The method of property, it is characterised in that：Step 2）In, polycaprolactone monododecyl ether is grafted with poly acrylic acid-poly y
The mol ratio of polyacrylic acid segment is 15~25 in copolymer:1.
5. a kind of poly (lactic acid-glycolic acid) according to claim 1 improves polypropylene sorrel water resistance and soft with polycaprolactone
Pliable method, 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 the grafting of poly acrylic acid-poly y are common
The mol ratio of polyacrylic acid segment is 1.07~1.8 in polymers:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5
~15 g:100 ml.
6. a kind of poly (lactic acid-glycolic acid) according to claim 1 improves polypropylene sorrel water resistance and submissive with polycaprolactone
The method of property, it is characterised in that：Step 3）In, mass percent of the polycaprolactone monododecyl ether in Modified Membrane be 2~
4%, solvent uses dimethyl sulfoxide (DMSO), and mixture solution concentration is 25~30 g:100 ml.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865091A (en) * | 2014-03-24 | 2014-06-18 | 山东理工大学 | Method for improving water resisting performance of polyvinyl alcohol film from polycaprolactone and polylactic 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) |
| 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 |
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2017
- 2017-05-25 CN CN201710376554.5A patent/CN107118569A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865091A (en) * | 2014-03-24 | 2014-06-18 | 山东理工大学 | Method for improving water resisting performance of polyvinyl alcohol film from polycaprolactone and polylactic acid |
| 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: 20170901 |