CN106977941A - A kind of method being improved with PPDO and poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance - Google Patents
A kind of method being improved with PPDO and poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance Download PDFInfo
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- CN106977941A CN106977941A CN201710362956.XA CN201710362956A CN106977941A CN 106977941 A CN106977941 A CN 106977941A CN 201710362956 A CN201710362956 A CN 201710362956A CN 106977941 A CN106977941 A CN 106977941A
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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 method being improved with PPDO and poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance, using following steps：1）The synthesis of polyacrylic acid poly (lactic acid-glycolic acid) graft copolymer：Add hydroxy-end capped poly (lactic acid-glycolic acid) monododecyl ether, solvent, condensing agent and polyacrylic acid in dry reactor, stirring reaction 2~3 days, terminating reaction obtains object；2）The preparation for the polypropylene sorrel that PPDO is modified with poly (lactic acid-glycolic acid)：Polyacrylic acid poly (lactic acid-glycolic acid) graft copolymer, PPDO list tridecyl ether 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.PPDO and poly-（D,L）Y（The mol ratio of lactic acid and glycolic
For 90/10）It is the biomaterial with excellent biocompatibility and biodegradability, with good hydrophobicity and submissive
Property.Poly (lactic acid-glycolic acid) segment is first introduced into polyacrylic acid segment formation poly acrylic acid-poly y graft copolymer, so
PPDO segment is added into poly acrylic acid-poly y graft copolymer formation blend again afterwards, is made and changes
Property polypropylene sorrel, 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 side being improved with PPDO and poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance
Method, it is characterised in that：The molecular weight of polyacrylic acid segment is 84000~93000 in Modified Membrane, point of poly (lactic acid-glycolic acid) segment
Son amount is 2100~2300, and the molecular weight of PPDO segment is 4800~5800；Its method of modifying uses following step
Suddenly：
1）The synthesis of poly acrylic acid-poly y graft copolymer：Hydroxy-end capped poly- breast is added in dry reactor
Under sour glycolic monododecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 29~33 DEG C of stirring reactions 2~3
My god, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The preparation for the polypropylene sorrel that PPDO is modified with poly (lactic acid-glycolic acid)：Added in dry reactor poly-
Under acrylic acid-poly (lactic acid-glycolic acid) graft copolymer, PPDO list tridecyl ether and solvent, inert atmosphere, in
After 48~53 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, object is obtained.
Described one kind PPDO enters with poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance
The improved method of row, step 1）In, poly (lactic acid-glycolic acid) monododecyl ether is using poly-（D,L）Y list dodecyl
Ether（The mol ratio of lactic acid and glycolic is 90/10）, the mol ratio of poly (lactic acid-glycolic acid) monododecyl ether and polyacrylic acid is
15~25:1.
Described one kind PPDO enters with poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance
The improved method of row, 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 1.07~1.9:1, solvent is adopted
With dimethyl sulfoxide (DMSO), reactant solution concentration is 5~15 g:100 ml.
Described one kind PPDO enters with poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance
The improved method of row, step 2）In, mass percent of the PPDO list tridecyl ether in Modified Membrane be 2~
3%, 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, described one kind is carried out with PPDO and poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance
Improved 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 y graft copolymer
20.7 grams of polyacrylic acid are added in dry reactor（Molecular weight is 84000）With 9.5 grams of hydroxy-end capped PLA second
Alkyd monododecyl ether（Molecular weight is 2100）, 298 ml dimethyl sulfoxide (DMSO)s are added, 0.061 gram is addedN,N’- two hexamethylenes
Under base carbodiimide, inert atmosphere, in 29 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains target
Thing；
2）The preparation for the polypropylene sorrel that PPDO is modified with poly (lactic acid-glycolic acid)
10 grams of poly acrylic acid-poly y graft copolymers are added in dry reactor and 37 ml dimethyl sulfoxide (DMSO)s are molten
Agent, it is another to add the PPDO list tridecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 4800）, inert atmosphere
Under, 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
12.1 ° and 9.4%.
Embodiment 2
1）The preparation of poly acrylic acid-poly y graft copolymer
21.2 grams of polyacrylic acid are added in dry reactor（Molecular weight is 86000）With 10.1 grams of hydroxy-end capped PLA second
Alkyd monododecyl ether（Molecular weight is 2200）, 312 ml dimethyl sulfoxide (DMSO)s are added, 0.039 gram is addedN,N’- diisopropyl
Under base carbodiimide, inert atmosphere, in 31 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains target
Thing；
2）The preparation for the polypropylene sorrel that PPDO is modified with poly (lactic acid-glycolic acid)
10.1 grams of poly acrylic acid-poly y graft copolymers are added in dry reactor and 36.5 ml dimethyl are sub-
Sulfoxide solvent, it is another to add the PPDO list tridecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 5400）, inertia
Under atmosphere, mixed 55 minutes in 50 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
12.7 ° and 10.1%.
Embodiment 3
1）The preparation of poly acrylic acid-poly y graft copolymer
22.8 grams of polyacrylic acid are added in dry reactor（Molecular weight is 93000）With 10.6 grams of hydroxy-end capped PLA second
Alkyd monododecyl ether（Molecular weight is 2300）, 331 ml dimethyl sulfoxide (DMSO)s are added, 0.059 gram of 3- ethyls -1- is added（3-
Dimethylaminopropyl）Under carbodiimide, inert atmosphere, in 33 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried,
Obtain object；
2）The preparation for the polypropylene sorrel that PPDO is modified with poly (lactic acid-glycolic acid)
9.5 grams of poly acrylic acid-poly y graft copolymers are added in dry reactor and 35 ml dimethyl sulfoxide (DMSO)s are molten
Agent, it is another to add the PPDO list tridecyl ether for accounting for Modified Membrane gross weight 3%（Molecular weight is 5800）, 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
13.3 ° and 10.8%.
Claims (4)
- With PPDO and poly (lactic acid-glycolic acid) polypropylene sorrel water resistance and compliance are improved 1. a kind of Method, it is characterised in that：The molecular weight of polyacrylic acid segment is 84000~93000 in Modified Membrane, poly (lactic acid-glycolic acid) segment Molecular weight is 2100~2300, and the molecular weight of PPDO segment is 4800~5800；Its method of modifying is using following Step：1）The synthesis of poly acrylic acid-poly y graft copolymer：Hydroxy-end capped poly- breast is added in dry reactor Under sour glycolic monododecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 29~33 DEG C of stirring reactions 2~3 My god, terminating reaction by filtering, dialysis, is dried, obtains object；2）The preparation for the polypropylene sorrel that PPDO is modified with poly (lactic acid-glycolic acid)：Added in dry reactor poly- Under acrylic acid-poly (lactic acid-glycolic acid) graft copolymer, PPDO list tridecyl ether and solvent, inert atmosphere, in After 48~53 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, object is obtained.
- 2. one kind PPDO according to claim 1 is with poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance And the method that compliance is improved, it is characterised in that：Step 1）In, poly (lactic acid-glycolic acid) monododecyl ether is using poly-（D, L）Y monododecyl ether（The mol ratio of lactic acid and glycolic is 90/10）, poly (lactic acid-glycolic acid) list dodecyl The mol ratio of ether and polyacrylic acid is 15~25:1.
- 3. one kind PPDO according to claim 1 is with poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance And the method that compliance is improved, it is characterised in that：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 For 1.07~1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
- 4. one kind PPDO according to claim 1 is with poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance And the method that compliance is improved, it is characterised in that：Step 2）In, PPDO list tridecyl ether is in Modified Membrane In mass percent be 2~3%, solvent uses dimethyl sulfoxide (DMSO), and mixture solution concentration is 25~30 g:100 ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710362956.XA CN106977941A (en) | 2017-05-22 | 2017-05-22 | A kind of method being improved with PPDO and poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710362956.XA CN106977941A (en) | 2017-05-22 | 2017-05-22 | A kind of method being improved with PPDO and poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance |
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| Publication Number | Publication Date |
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| CN106977941A true CN106977941A (en) | 2017-07-25 |
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| CN201710362956.XA Withdrawn CN106977941A (en) | 2017-05-22 | 2017-05-22 | A kind of method being improved with PPDO and poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105542479A (en) * | 2016-03-07 | 2016-05-04 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film through poly(p-dioxanone) and poly lactic acid-glycolic acid |
| CN105542482A (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(p-dioxanone) and poly(lactic acid-glycolic acid) |
-
2017
- 2017-05-22 CN CN201710362956.XA patent/CN106977941A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105542479A (en) * | 2016-03-07 | 2016-05-04 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film through poly(p-dioxanone) and poly lactic acid-glycolic acid |
| CN105542482A (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(p-dioxanone) and poly(lactic acid-glycolic acid) |
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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Application publication date: 20170725 |