CN106977934A - A kind of method being improved with condensing model and PLA to polypropylene sorrel water resistance and compliance - Google Patents
A kind of method being improved with condensing model and PLA to polypropylene sorrel water resistance and compliance Download PDFInfo
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- CN106977934A CN106977934A CN201710362682.4A CN201710362682A CN106977934A CN 106977934 A CN106977934 A CN 106977934A CN 201710362682 A CN201710362682 A CN 201710362682A CN 106977934 A CN106977934 A CN 106977934A
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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
- C08J2473/00—Characterised by the use of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08J2459/00 - C08J2471/00; Derivatives of such polymers
- C08J2473/02—Polyanhydrides
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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 method being improved with condensing model and PLA to polypropylene sorrel water resistance and compliance, using following steps：1）The synthesis of polyacrylic acid polylactic acid graft copolymer：Add hydroxy-end capped PLA monododecyl ether, solvent, condensing agent and polyacrylic acid in dry reactor, stirring reaction 2~3 days, terminating reaction obtains object；2）The preparation of condensing model and polylactic acid modified polypropylene sorrel：Polyacrylic acid polylactic acid graft copolymer, condensing model 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.Condensing model is the biomaterial with excellent biocompatibility and biodegradability,
With good hydrophobicity.It is poly-（D,L）Lactic acid is the biomaterial with excellent biocompatibility and biodegradability, tool
There is good hydrophobicity and compliance.Polylactic acid chain segment first is introduced into polyacrylic acid segment formation poly acrylic acid-poly lactic acid to be grafted
Copolymer, then adds poly acrylic acid-poly lactic acid graft copolymer formation blend by condensing model segment again, is made modified poly- third
Olefin(e) acid 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 method being improved with condensing model and PLA to polypropylene sorrel water resistance and compliance, it is characterised in that：
The molecular weight of polyacrylic acid segment is 82000~87000 in Modified Membrane, and the molecular weight of polylactic acid chain segment is 2100~2400, is gathered
The molecular weight of acid anhydrides segment is 4800~5000；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 dialkyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 28~32 DEG C of stirring reactions 2~3 days, terminating reaction,
By filtering, dialysis, dry, obtain object；
2）The preparation of condensing model and polylactic acid modified polypropylene sorrel：Poly acrylic acid-poly lactic acid is added in dry reactor
Under graft copolymer, condensing model and solvent, inert atmosphere, in 48~52 DEG C stirring mixing 50~60 minutes after, with the tape casting into
Film and drying, obtain object.
A kind of described method being improved with condensing model and PLA to polypropylene sorrel water resistance and compliance, step
Rapid 1）In, PLA monododecyl ether is using poly-（D, Pfansteihl）Monododecyl ether, PLA monododecyl ether is with gathering
The mol ratio of acrylic acid is 15~25:1.
A kind of described method being improved with condensing model and PLA 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 1.07~1.9:1, solvent uses dimethyl sulfoxide (DMSO), instead
It is 5~15 g to answer thing solution concentration:100 ml.
A kind of described method being improved with condensing model and PLA to polypropylene sorrel water resistance and compliance, step
Rapid 2）In, condensing model is using poly- [1,3- pair（To carboxyphenoxy）Propane-SA] copolymer,（1,3- is double（To carboxyl benzene oxygen
Base）The mol ratio of propane and SA is 70/30, and mass percent of the condensing model in Modified Membrane is 1~3%, and solvent uses two
Methyl sulfoxide, mixture solution concentration is 25~30 g:100 ml.
Compared with prior art, its advantage is the present invention：
1st, a kind of described method being improved with condensing model and PLA to polypropylene sorrel water resistance and compliance, is used
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 lactic acid graft copolymer
20.2 grams of polyacrylic acid are added in dry reactor（Molecular weight is 82000）With 9.4 grams of hydroxy-end capped PLA lists
Lauryl ether（Molecular weight is 2100）, 296 ml dimethyl sulfoxide (DMSO)s are added, 0.062 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 condensing model and polylactic acid modified polypropylene sorrel
10 grams of poly acrylic acid-poly lactic acid graft copolymers and 37 ml dimethyl sulfoxide solvents are added in dry reactor, it is another to add
Enter to account for the condensing model of Modified Membrane gross weight 1%（Molecular weight is 4800）, under inert atmosphere, in 48 DEG C of stirring mixing 50 minutes, with stream
Prolong method 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 9.5%.
Embodiment 2
1）The preparation of poly acrylic acid-poly lactic acid graft copolymer
21 grams of polyacrylic acid are added in dry reactor（Molecular weight is 85000）With 10.7 grams of hydroxy-end capped PLA lists ten
Dialkyl ether（Molecular weight is 2300）, 316 ml dimethyl sulfoxide (DMSO)s are added, 0.039 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 condensing model and polylactic acid modified polypropylene sorrel
10.1 grams of poly acrylic acid-poly lactic acid graft copolymers and 36.5 ml dimethyl sulfoxide solvents are added in dry reactor,
It is another to add the condensing model for accounting for Modified Membrane gross weight 2%（Molecular weight is 4900）, under inert atmosphere, in 50 DEG C of stirring mixing 55 minutes,
The tape casting film forming is used, 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 10.1%.
Embodiment 3
1）The preparation of poly acrylic acid-poly lactic acid graft copolymer
20.7 grams of polyacrylic acid are added in dry reactor（Molecular weight is 87000）With 10.8 grams of hydroxy-end capped PLA lists
Lauryl ether（Molecular weight is 2400）, 313 ml dimethyl sulfoxide (DMSO)s are added, 0.058 gram of 3- ethyls -1- is added（3- diformazan ammonia
Propyl group）Under carbodiimide, inert atmosphere, in 32 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains mesh
Mark thing；
2）The preparation of condensing model and polylactic acid modified polypropylene sorrel
9.6 grams of poly acrylic acid-poly lactic acid graft copolymers and 35 ml dimethyl sulfoxide solvents are added in dry reactor, separately
Add the condensing model for accounting for Modified Membrane gross weight 3%（Molecular weight is 5000）, under inert atmosphere, in 52 DEG C of stirring mixing 60 minutes, 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
13.3 ° and 10.8%.
Claims (4)
1. a kind of method being improved with condensing model and PLA to polypropylene sorrel water resistance and compliance, its feature exists
In：The molecular weight of polyacrylic acid segment is 82000~87000 in Modified Membrane, and the molecular weight of polylactic acid chain segment is 2100~2400,
The molecular weight of condensing model segment is 4800~5000；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 dialkyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 28~32 DEG C of stirring reactions 2~3 days, terminating reaction,
By filtering, dialysis, dry, obtain object；
2）The preparation of condensing model and polylactic acid modified polypropylene sorrel：Poly acrylic acid-poly lactic acid is added in dry reactor
Under graft copolymer, condensing model and solvent, inert atmosphere, in 48~52 DEG C stirring mixing 50~60 minutes after, with the tape casting into
Film and drying, obtain object.
2. one kind according to claim 1 is changed with condensing model with PLA to polypropylene sorrel water resistance and compliance
The method entered, it is characterised in that：Step 1）In, PLA monododecyl ether is using poly-（D, Pfansteihl）Monododecyl ether,
The mol ratio of PLA monododecyl ether and polyacrylic acid is 15~25:1.
3. one kind according to claim 1 is changed with condensing model with PLA to polypropylene sorrel water resistance and compliance
The method entered, it is characterised in that：Step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl carbon
Diimine or 3- ethyls -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.07~1.9:
1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. one kind according to claim 1 is changed with condensing model with PLA to polypropylene sorrel water resistance and compliance
The method entered, it is characterised in that：Step 2）In, condensing model is using poly- [1,3- pair（To carboxyphenoxy）Propane-SA] altogether
Polymers,（1,3- is double（To carboxyphenoxy）The mol ratio of propane and SA is 70/30, quality of the condensing model in Modified Membrane
Percentage is 1~3%, and solvent uses dimethyl sulfoxide (DMSO), and mixture solution concentration is 25~30 g:100 ml.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710362682.4A CN106977934A (en) | 2017-05-22 | 2017-05-22 | A kind of method being improved with condensing model and PLA to polypropylene sorrel water resistance and compliance |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710362682.4A CN106977934A (en) | 2017-05-22 | 2017-05-22 | A kind of method being improved with condensing model and PLA to polypropylene sorrel water resistance and compliance |
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| CN106977934A true CN106977934A (en) | 2017-07-25 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559215A (en) * | 2015-01-06 | 2015-04-29 | 山东理工大学 | Method for improving hydrophily and flexibility of polypeptide membrane by polylactic acid and polyethylene glycol |
| CN105566664A (en) * | 2016-03-16 | 2016-05-11 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by using poly(trimethylene carbonate) and polyanhydride (P(CPP-SA))-polyvinylpyrrolidone |
-
2017
- 2017-05-22 CN CN201710362682.4A patent/CN106977934A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559215A (en) * | 2015-01-06 | 2015-04-29 | 山东理工大学 | Method for improving hydrophily and flexibility of polypeptide membrane by polylactic acid and polyethylene glycol |
| CN105566664A (en) * | 2016-03-16 | 2016-05-11 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by using poly(trimethylene carbonate) and polyanhydride (P(CPP-SA))-polyvinylpyrrolidone |
Non-Patent Citations (1)
| Title |
|---|
| 蔡邦肖等: "高分离性能聚丙烯酸膜制备工艺的初步研究", 《第一届全国化学工程与生物化工年会论文摘要集（上）》 * |
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