CN107057373A - A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid) - Google Patents
A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid) Download PDFInfo
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- CN107057373A CN107057373A CN201710362933.9A CN201710362933A CN107057373A CN 107057373 A CN107057373 A CN 107057373A CN 201710362933 A CN201710362933 A CN 201710362933A CN 107057373 A CN107057373 A CN 107057373A
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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 that PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid), using following steps：1）The synthesis of polyacrylic acid PTMC graft copolymer：Add hydroxy-end capped PTMC list tridecyl 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 PTMC graft copolymer, poly (lactic acid-glycolic acid) monododecyl 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.PTMC segment first is introduced into polyacrylic acid segment formation poly acrylic acid-poly trimethylene carbonate to be grafted
Copolymer, then again forms poly (lactic acid-glycolic acid) segment addition poly acrylic acid-poly trimethylene carbonate graft copolymer altogether
Mixed thing, 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：
A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid), it is special
Levy and be：The molecular weight of polyacrylic acid segment is 80000~89000, the molecule of PTMC segment in Modified Membrane
Measure as 2300~2400, the molecular weight of poly (lactic acid-glycolic acid) segment is 5300~6100；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly trimethylene carbonate graft copolymer：Added in dry reactor hydroxy-end capped
Under PTMC list tridecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 28~32 DEG C of stirrings
Reaction 2~4 days, 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 trimethylene carbonate graft copolymer, poly (lactic acid-glycolic acid) monododecyl ether and solvent, inert atmosphere
Under, after 45~52 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, obtain object.
A kind of described PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid)
Method, step 1）In, the mol ratio of PTMC list tridecyl ether and polyacrylic acid is 15~25:1.
A kind of described PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid)
Method, step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- second
Base -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.06~1.9:1, solvent uses two
Methyl sulfoxide, reactant solution concentration is 5~15 g:100 ml.
A kind of described PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid)
Method, step 2）In, poly (lactic acid-glycolic acid) monododecyl ether is using poly-（D,L）Y monododecyl ether（Breast
Acid is 90/10 with glycolic mol ratio）, mass percent of the poly (lactic acid-glycolic acid) monododecyl ether in Modified Membrane be 2~
4%, 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, a kind of described PTMC and poly (lactic acid-glycolic acid) improve polypropylene sorrel water resistance and compliance
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 trimethylene carbonate graft copolymer
18.6 grams of polyacrylic acid are added in dry reactor（Molecular weight is 80000）With 9.8 grams of hydroxy-end capped poly- three methylenes
Base carbonic ester list tridecyl ether（Molecular weight is 2300）, 283 ml dimethyl sulfoxide (DMSO)s are added, 0.061 gram is addedN,N’- two
Under carbodicyclo hexylimide, inert atmosphere, in 28 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtained
Object；
2）The preparation for the polypropylene sorrel that PTMC is modified with poly (lactic acid-glycolic acid)
10 grams of poly acrylic acid-poly trimethylene carbonate graft copolymers are added in dry reactor and 37 ml dimethyl are sub-
Sulfoxide solvent, it is another to add the poly (lactic acid-glycolic acid) monododecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 5300）, indifferent gas
Under atmosphere, mixed 50 minutes in 45 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
11.6 ° and 8.7%.
Embodiment 2
1）The preparation of poly acrylic acid-poly trimethylene carbonate graft copolymer
21 grams of polyacrylic acid are added in dry reactor（Molecular weight is 85000）With 10.6 grams of hydroxy-end capped polytrimethylenes
Carbonic ester list tridecyl ether（Molecular weight is 2300）, 314 ml dimethyl sulfoxide (DMSO)s are added, 0.039 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；
2）The preparation for the polypropylene sorrel that PTMC is modified with poly (lactic acid-glycolic acid)
10 grams of poly acrylic acid-poly trimethylene carbonate graft copolymers and 36.5 ml dimethyl are added in dry reactor
Sulfoxide solvent, it is another to add the poly (lactic acid-glycolic acid) monododecyl ether for accounting for Modified Membrane gross weight 3%（Molecular weight is 5700）, inertia
Under atmosphere, 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
12.1 ° and 9.8%.
Embodiment 3
1）The preparation of poly acrylic acid-poly trimethylene carbonate graft copolymer
21.3 grams of polyacrylic acid are added in dry reactor（Molecular weight is 89000）With 10.8 grams of hydroxy-end capped poly- three methylenes
Base carbonic ester list tridecyl ether（Molecular weight is 2400）, add 319 ml dimethyl sulfoxide (DMSO)s, add 0.058 gram of 3- ethyl-
1-（3- dimethylaminopropyls）Under carbodiimide, inert atmosphere, in 32 DEG C of stirring reactions 4 days, terminating reaction, by filtering, dialysis,
Dry, obtain object；
2）The preparation for the polypropylene sorrel that PTMC is modified with poly (lactic acid-glycolic acid)
9.6 grams of poly acrylic acid-poly trimethylene carbonate graft copolymers are added in dry reactor and 35 ml dimethyl are sub-
Sulfoxide solvent, it is another to add the poly (lactic acid-glycolic acid) monododecyl ether for accounting for Modified Membrane gross weight 4%（Molecular weight is 6100）, indifferent gas
Under atmosphere, mixed 60 minutes in 52 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 10.4%.
Claims (4)
1. a kind of method that PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid), its
It is characterised by：The molecular weight of polyacrylic acid segment is 80000~89000 in Modified Membrane, point of PTMC segment
Son amount is 2300~2400, and the molecular weight of poly (lactic acid-glycolic acid) segment is 5300~6100；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly trimethylene carbonate graft copolymer：Added in dry reactor hydroxy-end capped
Under PTMC list tridecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 28~32 DEG C of stirrings
Reaction 2~4 days, 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 trimethylene carbonate graft copolymer, poly (lactic acid-glycolic acid) monododecyl ether and solvent, inert atmosphere
Under, after 45~52 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, obtain object.
It is water-fast that 2. a kind of PTMC according to claim 1 improves polypropylene sorrel with poly (lactic acid-glycolic acid)
The method of property and compliance, it is characterised in that：Step 1）In, PTMC list tridecyl ether and polyacrylic acid
Mol ratio is 15~25:1.
It is water-fast that 3. a kind of PTMC according to claim 1 improves polypropylene sorrel with poly (lactic acid-glycolic acid)
The method of property and compliance, it is characterised in that：Step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- two
Diisopropylcarbodiimide or 3- ethyls -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is
1.06~1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
It is water-fast that 4. a kind of PTMC according to claim 1 improves polypropylene sorrel with poly (lactic acid-glycolic acid)
The method of property and compliance, it is characterised in that：Step 2）In, poly (lactic acid-glycolic acid) monododecyl ether is using poly-（D,L）Lactic acid
Glycolic monododecyl ether（Lactic acid is 90/10 with glycolic mol ratio）, poly (lactic acid-glycolic acid) monododecyl ether is in modification
Mass percent in film is 2~4%, and 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 |
|---|---|---|---|
| CN201710362933.9A CN107057373A (en) | 2017-05-22 | 2017-05-22 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid) |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710362933.9A CN107057373A (en) | 2017-05-22 | 2017-05-22 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid) |
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| Publication Number | Publication Date |
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| CN107057373A true CN107057373A (en) | 2017-08-18 |
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| CN201710362933.9A Withdrawn CN107057373A (en) | 2017-05-22 | 2017-05-22 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid) |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105647193A (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 polylactic acid-glycolic acid and polypeptide |
| CN105694474A (en) * | 2016-03-07 | 2016-06-22 | 山东理工大学 | Method for improving water resisting property and flexibility of polyvinyl alcohol film by means of poly trimethylene carbonate and poly lactic acid-glycolic acid |
-
2017
- 2017-05-22 CN CN201710362933.9A patent/CN107057373A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105647193A (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 polylactic acid-glycolic acid and polypeptide |
| CN105694474A (en) * | 2016-03-07 | 2016-06-22 | 山东理工大学 | Method for improving water resisting property and flexibility of polyvinyl alcohol film by means of poly trimethylene carbonate 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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