CN107011667A - A kind of method being improved with PTMC and poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance - Google Patents
A kind of method being improved with PTMC and poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance Download PDFInfo
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- CN107011667A CN107011667A CN201710362562.4A CN201710362562A CN107011667A CN 107011667 A CN107011667 A CN 107011667A CN 201710362562 A CN201710362562 A CN 201710362562A CN 107011667 A CN107011667 A CN 107011667A
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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
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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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 PTMC 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 2~4 days, terminating reaction obtains object；2）The preparation for the polypropylene sorrel that PTMC is modified with poly (lactic acid-glycolic acid)：Polyacrylic acid poly (lactic acid-glycolic acid) graft copolymer, PTMC 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.PTMC and poly-（D,L）Y（Lactic acid and glycolic mol ratio
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
PTMC segment is added into poly acrylic acid-poly y graft copolymer formation blend again afterwards, is made
Modified polypropene 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：
It is a kind of with PTMC and poly (lactic acid-glycolic acid) polypropylene sorrel water resistance and compliance to be improved
Method, it is characterised in that：The molecular weight of polyacrylic acid segment is 84000~90000 in Modified Membrane, poly (lactic acid-glycolic acid) segment
Molecular weight is 2200~2500, and the molecular weight of PTMC segment is 4800~5300；Its method of modifying use with
Lower 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 27~34 DEG C of stirring reactions 2~4
My god, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The preparation for the polypropylene sorrel that PTMC is modified with poly (lactic acid-glycolic acid)：Added in dry reactor
Poly acrylic acid-poly y graft copolymer, PTMC list tridecyl ether and solvent, inert atmosphere
Under, after 48~53 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, obtain object.
Described one kind PTMC is with poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance
The method being improved, step 1）In, poly (lactic acid-glycolic acid) monododecyl ether is using poly-（D,L）Y list dodecane
Base ether（Lactic acid is 90/10 with glycolic mol ratio）, the mol ratio of poly (lactic acid-glycolic acid) monododecyl ether and polyacrylic acid is
15~25:1.
Described one kind PTMC is with poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance
The method being improved, 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
Using dimethyl sulfoxide (DMSO), reactant solution concentration is 5~15 g:100 ml.
Described one kind PTMC is with poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance
The method being improved, step 2）In, mass percent of the PTMC list tridecyl ether in Modified Membrane is 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 PTMC and poly (lactic acid-glycolic acid) enter to polypropylene sorrel water resistance and compliance
The improved method of row, it is simple to operate, be easy to grasp using two kinds of means of esterification and blending；
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
20.8 grams of polyacrylic acid are added in dry reactor（Molecular weight is 84000）With 9.8 grams of hydroxy-end capped PLA second
Alkyd monododecyl ether（Molecular weight is 2200）, 297 ml dimethyl sulfoxide (DMSO)s are added, 0.063 gram is addedN,N’- two hexamethylenes
Under base carbodiimide, inert atmosphere, in 27 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 PTMC 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 PTMC list tridecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 4800）, indifferent gas
Under 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
11.3 ° and 9.1%.
Embodiment 2
1）The preparation of poly acrylic acid-poly y 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 ethanol
Sour monododecyl ether（Molecular weight is 2300）, 315 ml dimethyl sulfoxide (DMSO)s are added, 0.039 gram is addedN,N’- diisopropyl
Under carbodiimide, inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation for the polypropylene sorrel that PTMC 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 PTMC list tridecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 5000）, it is lazy
Property atmosphere under, in 50 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
12.4 ° and 9.9%.
Embodiment 3
1）The preparation of poly acrylic acid-poly y graft copolymer
21.8 grams of polyacrylic acid are added in dry reactor（Molecular weight is 90000）With 11.4 grams of hydroxy-end capped PLA second
Alkyd monododecyl ether（Molecular weight is 2500）, 328 ml dimethyl sulfoxide (DMSO)s are added, 0.058 gram of 3- ethyls -1- is added（3-
Dimethylaminopropyl）Under carbodiimide, inert atmosphere, in 34 DEG C of stirring reactions 4 days, terminating reaction by filtering, dialysis, was dried,
Obtain object；
2）The preparation for the polypropylene sorrel that PTMC 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 PTMC list tridecyl ether for accounting for Modified Membrane gross weight 3%（Molecular weight is 5300）, indifferent gas
Under atmosphere, 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
12.9 ° and 10.6%.
Claims (4)
1. one kind is improved with PTMC with 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 84000~90000, poly (lactic acid-glycolic acid) segment in Modified Membrane
Molecular weight be 2200~2500, the molecular weight of PTMC segment is 4800~5300；Its method of modifying is used
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 monododecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 27~34 DEG C of stirring reactions 2~4
My god, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The preparation for the polypropylene sorrel that PTMC is modified with poly (lactic acid-glycolic acid)：Added in dry reactor
Poly acrylic acid-poly y graft copolymer, PTMC list tridecyl ether and solvent, inert atmosphere
Under, after 48~53 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, obtain object.
2. one kind PTMC according to claim 1 and poly (lactic acid-glycolic acid) are water-fast to polypropylene sorrel
The method that property and compliance are improved, it is characterised in that：Step 1）In, poly (lactic acid-glycolic acid) monododecyl ether is using poly-
（D,L）Y monododecyl ether（Lactic acid is 90/10 with glycolic mol ratio）, poly (lactic acid-glycolic acid) list dodecyl
The mol ratio of ether and polyacrylic acid is 15~25:1.
3. one kind PTMC according to claim 1 and poly (lactic acid-glycolic acid) are water-fast to polypropylene sorrel
The method that property and compliance are improved, it is characterised in that：Step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-（3- dimethylaminopropyls）Mole of carbodiimide, condensing agent and polyacrylic acid
Than for 1.07~1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. one kind PTMC according to claim 1 and poly (lactic acid-glycolic acid) are water-fast to polypropylene sorrel
The method that property and compliance are improved, it is characterised in that：Step 2）In, PTMC list tridecyl ether is changing
Property film 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 |
|---|---|---|---|
| CN201710362562.4A CN107011667A (en) | 2017-05-22 | 2017-05-22 | A kind of method being improved with PTMC and poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710362562.4A CN107011667A (en) | 2017-05-22 | 2017-05-22 | A kind of method being improved with PTMC 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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| CN107011667A true CN107011667A (en) | 2017-08-04 |
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| CN201710362562.4A Withdrawn CN107011667A (en) | 2017-05-22 | 2017-05-22 | A kind of method being improved with PTMC and poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694476A (en) * | 2016-03-16 | 2016-06-22 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol membrane through poly trimethylene carbonate and poly lactic acid-glycolic acid |
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- 2017-05-22 CN CN201710362562.4A patent/CN107011667A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694476A (en) * | 2016-03-16 | 2016-06-22 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol membrane through poly trimethylene carbonate and poly lactic acid-glycolic acid |
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