CN107011671A - A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with PLA - Google Patents
A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with PLA Download PDFInfo
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- CN107011671A CN107011671A CN201710362691.3A CN201710362691A CN107011671A CN 107011671 A CN107011671 A CN 107011671A CN 201710362691 A CN201710362691 A CN 201710362691A CN 107011671 A CN107011671 A CN 107011671A
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- Prior art keywords
- pla
- ptmc
- water resistance
- tridecyl ether
- polyacrylic acid
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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
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The present invention, which discloses a kind of PTMC, improves the method for polypropylene sorrel water resistance and compliance with PLA, using following steps：1）The synthesis of polyacrylic acid PTMC PLA dual graft copolymer：Hydroxy-end capped PTMC monododecyl ether is added in dry reactor, hydroxy-end capped PLA list tridecyl ether, solvent, condensing agent and polyacrylic acid, stirring reaction 2~3 days, terminating reaction obtains object；2）The preparation of PTMC and polylactic acid modified polypropylene sorrel：Polyacrylic acid PTMC PLA dual graft copolymer, PLA 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）Lactic acid be with excellent biocompatibility and
The biomaterial of biodegradability, with good hydrophobicity and compliance.First by PTMC segment and poly-
Lactic acid segment introduces polyacrylic acid segment formation poly acrylic acid-poly trimethylene carbonate-PLA dual graft copolymer simultaneously,
Then polylactic acid chain segment is added into poly acrylic acid-poly trimethylene carbonate-PLA dual graft copolymer formation blend again,
Modified polypropene sorrel is made, 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 PLA, its feature exists
In：The molecular weight of polyacrylic acid segment is 83000~93000 in Modified Membrane, and the molecular weight of PTMC segment is
2600~2800, the molecular weight of polylactic acid chain segment is 2600~2800；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly trimethylene carbonate-PLA dual graft copolymer：Hydroxyl is added in dry reactor
PTMC monododecyl ether, hydroxy-end capped PLA list tridecyl ether, solvent, the condensing agent of base end-blocking
And polyacrylic acid, under inert atmosphere, in 27~34 DEG C of stirring reactions 2~3 days, terminating reaction by filtering, dialysis, was dried, obtained
To object；
2）The preparation of PTMC and polylactic acid modified polypropylene sorrel：Polypropylene is added in dry reactor
Under acid-PTMC-PLA dual graft copolymer, PLA list tridecyl ether and solvent, inert atmosphere, in
After 47~51 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 PTMC improves polypropylene sorrel water resistance and compliance with PLA,
Step 1）In, the mol ratio of PTMC monododecyl ether and polyacrylic acid is 15~25:1, PLA list ten
Trialkyl ether is using poly-（D, Pfansteihl）The mol ratio of single tridecyl ether, PLA list tridecyl ether and polyacrylic acid is 15
~25:1.
The method that a kind of described PTMC improves polypropylene sorrel water resistance and compliance with PLA,
Step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-（3-
Dimethylaminopropyl）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.07~1.9:1, solvent uses dimethyl sulfoxide (DMSO),
Reactant solution concentration is 5~15 g:100 ml.
The method that a kind of described PTMC improves polypropylene sorrel water resistance and compliance with PLA,
Step 2）In, PLA list tridecyl ether is using poly-（D, Pfansteihl）Single tridecyl ether, PLA list tridecyl ether exists
Mass percent in Modified Membrane is 1~3%, and 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 PLA improve the method for polypropylene sorrel water resistance and compliance, adopt
With a kind of reaction that is esterified simultaneously of polymer polymeric monomer different from two kinds and two kinds of means are blended, 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-PLA dual graft copolymer
16.7 grams of polyacrylic acid are added in dry reactor（Molecular weight is 83000）, 9.6 grams of hydroxy-end capped polytrimethylenes
Carbonic ester monododecyl ether（Molecular weight is 2600）With 9.6 grams of hydroxy-end capped PLA list tridecyl ethers（Molecular weight is
2600）, 358 ml dimethyl sulfoxide (DMSO)s are added, 0.052 gram is addedN,N’Under-dicyclohexylcarbodiimide, inert atmosphere, in 27
DEG C stirring reaction 2 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The preparation of PTMC and polylactic acid modified polypropylene sorrel
10 grams of poly acrylic acid-poly trimethylene carbonate-PLA dual graft copolymers and 37 ml are added in dry reactor
Dimethyl sulfoxide solvent, it is another to add the PLA list tridecyl ether for accounting for Modified Membrane gross weight 1%（Molecular weight is 2600）, inertia
Under atmosphere, mixed 50 minutes in 47 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
11.9 ° and 9.3%.
Embodiment 2
1）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA dual graft copolymer
20.7 grams of polyacrylic acid are added in dry reactor（Molecular weight is 87000）, 11.7 grams of hydroxy-end capped poly- three methylenes
Base carbonic ester monododecyl ether（Molecular weight is 2700）With 11.7 grams of hydroxy-end capped PLA list tridecyl ethers（Molecular weight
For 2700）, 441 ml dimethyl sulfoxide (DMSO)s are added, 0.038 gram is addedN,N’Under-DIC, inert atmosphere, in
30 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The preparation of PTMC and polylactic acid modified polypropylene sorrel
9.9 grams of poly acrylic acid-poly trimethylene carbonate-PLA dual graft copolymers and 36 are added in dry reactor
Ml dimethyl sulfoxide solvents, it is another to add the PLA list tridecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 2700）, 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
12.5 ° and 10.2%.
Embodiment 3
1）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA dual graft copolymer
23 grams of polyacrylic acid are added in dry reactor（Molecular weight is 93000）, 12.7 grams of hydroxy-end capped polytrimethylenes
Carbonic ester monododecyl ether（Molecular weight is 2800）With 12.7 grams of hydroxy-end capped PLA list tridecyl ethers（Molecular weight is
2800）, 483 ml dimethyl sulfoxide (DMSO)s are added, 0.061 gram of 3- ethyls -1- is added（3- dimethylaminopropyls）Carbodiimide, inertia
Under atmosphere, in 34 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation of PTMC and polylactic acid modified polypropylene sorrel
9.5 grams of poly acrylic acid-poly trimethylene carbonate-PLA dual graft copolymers and 35 are added in dry reactor
Ml dimethyl sulfoxide solvents, it is another to add the PLA list tridecyl ether for accounting for Modified Membrane gross weight 3%（Molecular weight is 2800）, it is lazy
Property atmosphere under, in 51 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
12.8 ° and 10.6%.
Claims (4)
1. a kind of method that PTMC improves polypropylene sorrel water resistance and compliance with PLA, its feature exists
In：The molecular weight of polyacrylic acid segment is 83000~93000 in Modified Membrane, and the molecular weight of PTMC segment is
2600~2800, the molecular weight of polylactic acid chain segment is 2600~2800；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly trimethylene carbonate-PLA dual graft copolymer：Hydroxyl is added in dry reactor
PTMC monododecyl ether, hydroxy-end capped PLA list tridecyl ether, solvent, the condensing agent of base end-blocking
And polyacrylic acid, under inert atmosphere, in 27~34 DEG C of stirring reactions 2~3 days, terminating reaction by filtering, dialysis, was dried, obtained
To object；
2）The preparation of PTMC and polylactic acid modified polypropylene sorrel：Polypropylene is added in dry reactor
Under acid-PTMC-PLA dual graft copolymer, PLA list tridecyl ether and solvent, inert atmosphere, in
After 47~51 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, object is obtained.
2. a kind of PTMC according to claim 1 improves polypropylene sorrel water resistance and soft with PLA
Pliable method, it is characterised in that：Step 1）In, the mol ratio of PTMC monododecyl ether and polyacrylic acid
For 15~25:1, PLA list tridecyl ether is using poly-（D, Pfansteihl）Single tridecyl ether, PLA list tridecyl ether
Mol ratio with polyacrylic acid is 15~25:1.
3. a kind of PTMC according to claim 1 and PLA improve polypropylene sorrel water resistance and
The method of compliance, it is characterised in that：Step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl
Base carbodiimide or 3- ethyls -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid be 1.07~
1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. a kind of PTMC according to claim 1 improves polypropylene sorrel water resistance and soft with PLA
Pliable method, it is characterised in that：Step 2）In, PLA list tridecyl ether is using poly-（D, Pfansteihl）Single tridecyl
Ether, mass percent of the PLA list tridecyl ether in Modified Membrane is 1~3%, and solvent uses dimethyl sulfoxide (DMSO), mixture
Solution concentration is 25~30 g:100 ml.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710362691.3A CN107011671A (en) | 2017-05-22 | 2017-05-22 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with PLA |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710362691.3A CN107011671A (en) | 2017-05-22 | 2017-05-22 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with PLA |
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| Publication Number | Publication Date |
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| CN107011671A true CN107011671A (en) | 2017-08-04 |
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| CN201710362691.3A Withdrawn CN107011671A (en) | 2017-05-22 | 2017-05-22 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with PLA |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865275A (en) * | 2014-04-11 | 2014-06-18 | 山东理工大学 | Method for improving the water resistance of polyethylene glycol film modified by polylactic acid and polyvinyl alcohol |
| 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 |
| 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 |
-
2017
- 2017-05-22 CN CN201710362691.3A patent/CN107011671A/en not_active Withdrawn
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 |
| CN103865275A (en) * | 2014-04-11 | 2014-06-18 | 山东理工大学 | Method for improving the water resistance of polyethylene glycol film modified by polylactic acid and polyvinyl alcohol |
| 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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Application publication date: 20170804 |
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