CN105504322B - A kind of method being improved with PTMC and PPDO to polyvinyl alcohol film water resistance and compliance - Google Patents
A kind of method being improved with PTMC and PPDO to polyvinyl alcohol film water resistance and compliance Download PDFInfo
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- CN105504322B CN105504322B CN201610125104.4A CN201610125104A CN105504322B CN 105504322 B CN105504322 B CN 105504322B CN 201610125104 A CN201610125104 A CN 201610125104A CN 105504322 B CN105504322 B CN 105504322B
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- polyvinyl alcohol
- ptmc
- ppdo
- graft copolymer
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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
- 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
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
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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
- 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
- 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 PPDO to polyvinyl alcohol film water resistance and compliance, using following steps：1）Add PTMC monododecyl ether, solvent, condensing agent and the polyvinyl alcohol of carboxy blocking in reactor, react to obtain polyvinyl alcohol PTMC graft copolymer；2）PPDO monododecyl ether, solvent and the condensing agent of Polyvinyl alcohol PTMC graft copolymer, carboxy blocking in reactor, react to obtain polyvinyl alcohol PTMC PPDO dual graft copolymer；3）Polyvinyl alcohol PTMC PPDO dual graft copolymer, PTMC monododecyl ether and solvent, film forming after mixing, obtain object of the present invention in reactor.Preparation technology of the present invention is simple, is 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 polyvinyl alcohol film water resistance and compliance, belong to thin polymer film
Preparing technical field.
Background technology
Polyvinyl alcohol is a kind of biomaterial with good biocompatibility and biodegradability, polyvinyl alcohol film
It can be used as artificial skin etc., but polyvinyl alcohol film hydrophily is too strong and more stiff, lacks preferable water resistance and compliance, so as to
Its application is limited to a certain extent.PTMC and PPDO are that have excellent biocompatibility
With the biomaterial of biodegradability, there is good hydrophobicity and compliance.First PTMC segment is drawn
Enter polyvinyl alcohol segments and form polyvinyl alcohol-PTMC graft copolymer, then by PPDO segment
Polyvinyl alcohol-poly- Sanya is obtained in the polyvinyl alcohol segments being introduced into polyvinyl alcohol-PTMC graft copolymer
Methyl carbonic-PPDO dual graft copolymer, PTMC segment is then added into polyethylene again
Alcohol-PTMC-PPDO dual graft copolymer forms blend, and modified PVA membrane is made,
So as to drastically increase the water resistance of polyvinyl alcohol film and compliance.
The content of the invention
It is an object of the invention to provide a kind of simple to operate and effect preferably to polyvinyl alcohol film water resistance and submissive
The method that property is improved.Its technical scheme is：
One kind is carried out with PTMC with PPDO to polyvinyl alcohol film water resistance and compliance
Improved method, it is characterised in that：The molecular weight of polyvinyl alcohol segments is 84000~93000 in Modified Membrane, polytrimethylene carbon
The molecular weight of acid esters segment is 2700~2800, and the molecular weight of PPDO segment is 2000~2400；Its modification side
Method uses following steps：
1）The preparation of polyvinyl alcohol-PTMC graft copolymer：Carboxyl envelope is added in dry reactor
PTMC monododecyl ether, solvent, condensing agent and the polyvinyl alcohol at end, under inert atmosphere, in 30~35 DEG C
Stirring reaction 2~3 days, terminating reaction, by filtering, dialysing, dry, obtain object；
2）The preparation of polyvinyl alcohol-PTMC-PPDO dual graft copolymer：It is anti-drying
Answer and polyvinyl alcohol-PTMC graft copolymer, the PPDO list 12 of carboxy blocking are added in device
Alkyl ether, solvent and condensing agent, under inert atmosphere, in 30~34 DEG C of stirring reactions 2~4 days, terminating reaction, by filtering, thoroughly
Analysis, dry, obtain object；
3）The preparation for the polyvinyl alcohol film that PTMC is modified with PPDO：In dry reactor
Interior addition polyvinyl alcohol-PTMC-PPDO dual graft copolymer, PTMC list
Lauryl ether and solvent, under inert atmosphere, after 47~52 DEG C are stirred 50~60 minutes, with the tape casting film forming and do
It is dry, obtain object.
Described one kind PTMC and PPDO are to polyvinyl alcohol film water resistance and submissive
The method that property is improved, step 1）In, the mol ratio of PTMC monododecyl ether and polyvinyl alcohol is 15
~25:1.
Described one kind PTMC and PPDO are to polyvinyl alcohol film water resistance and submissive
The method that property is improved, step 1）In, condensing agent usesN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl carbon two is sub-
Amine or 3- ethyls -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyvinyl alcohol is 1.07~1.9:1, it is molten
Agent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
Described one kind PTMC and PPDO are to polyvinyl alcohol film water resistance and submissive
The method that property is improved, step 2）In, PPDO monododecyl ether and polyvinyl alcohol-polytrimethylene carbonic acid
The mol ratio of polyvinyl alcohol segments in ester graft copolymer is 15~25:1.
Described one kind PTMC and PPDO are to polyvinyl alcohol film water resistance and submissive
The method that property is improved, step 2）In, condensing agent usesN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl carbon two is sub-
Amine or 3- ethyls -1-（3- dimethylaminopropyls）Carbodiimide, condensing agent and polyvinyl alcohol-PTMC graft copolymerization
The mol ratio of polyvinyl alcohol segments in thing is 1.07~1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5
~15 g:100 ml.
Described one kind PTMC and PPDO are to polyvinyl alcohol film water resistance and submissive
The method that property is improved, step 3）In, mass percent of the PTMC monododecyl ether in Modified Membrane
For 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, described one kind PTMC and PPDO are to polyvinyl alcohol film water resistance and soft
The pliable method being improved, it is simple to operate, be easy to grasp using three kinds of means of two step esterifications and blending；
2nd, described polyvinyl alcohol modification film water resistance and compliance are enhanced.
Embodiment
Embodiment 1
1）The preparation of polyvinyl alcohol-PTMC graft copolymer
18 grams of polyvinyl alcohol are added in dry reactor（Molecular weight is 84000）With poly- three methylene of 10.2 grams of carboxy blockings
Base carbonic ester monododecyl ether（Molecular weight is 2700）, 260 ml dimethyl sulfoxide (DMSO)s are added, add 0.056 gramN,N’- two
Carbodicyclo hexylimide, under inert atmosphere, in 30 DEG C of stirring reactions 2 days, terminating reaction, by filtering, dialysing, drying, obtain
Object；
2）The preparation of polyvinyl alcohol-PTMC-PPDO dual graft copolymer
10 grams of polyvinyl alcohol-PTMC graft copolymer and 4.5 grams of carboxyl envelopes are added in dry reactor
The PPDO monododecyl ether at end（Molecular weight is 2000）, 142 ml dimethyl sulfoxide (DMSO)s are added, add 0.032
GramN,N’- dicyclohexylcarbodiimide, under inert atmosphere, in 30 DEG C of stirring reactions 2 days, terminating reaction, by filtering, dialysing,
Dry, obtain object；
3）The preparation for the polyvinyl alcohol film that PTMC is modified with PPDO
10 grams of polyvinyl alcohol-PTMC-PPDO dual grafts are added in dry reactor
Copolymer and 37 ml dimethyl sulfoxide solvents, it is another to add the PTMC list dodecane for accounting for Modified Membrane gross weight 2%
Base ether（Molecular weight is 2700）, under inert atmosphere, it is stirred in 47 DEG C 50 minutes, with the tape casting film forming, is done in 50 DEG C of vacuum
Object is dried to obtain in dry case.
After tested：The surface contact angle and its elongation at break of object and water of the present invention respectively than improving before modified
12.6 ° and 12.9%.
Embodiment 2
1）The preparation of polyvinyl alcohol-PTMC graft copolymer
18.2 grams of polyvinyl alcohol are added in dry reactor（Molecular weight is 88000）With the poly- Sanya of 9.8 grams of carboxy blockings
Methyl carbonic monododecyl ether（Molecular weight is 2700）, 263 ml dimethyl sulfoxide (DMSO)s are added, add 0.033 gramN,N’-
DIC, under inert atmosphere, in 32 DEG C of stirring reactions 3 days, terminating reaction, by filtering, dialysing, drying, obtain
To object；
2）The preparation of polyvinyl alcohol-PTMC-PPDO dual graft copolymer
10.3 grams of polyvinyl alcohol-PTMC graft copolymer and 4.6 grams of carboxyls are added in dry reactor
The PPDO monododecyl ether of end-blocking（Molecular weight is 2200）, 147 ml dimethyl sulfoxide (DMSO)s are added, are added
0.019 gramN,N’- DIC, under inert atmosphere, in 32 DEG C of stirring reactions 3 days, terminating reaction, by filtering,
Dialysis, dry, obtain object；
3）The preparation for the polyvinyl alcohol film that PTMC is modified with PPDO
9.8 grams of polyvinyl alcohol-PTMC-PPDO dual grafts are added in dry reactor
Copolymer and 36 ml dimethyl sulfoxide solvents, it is another to add the PTMC list dodecane for accounting for Modified Membrane gross weight 3%
Base ether（Molecular weight is 2700）, under inert atmosphere, it is stirred in 49 DEG C 55 minutes, with the tape casting film forming, is done in 50 DEG C of vacuum
Object is dried to obtain in dry case.
After tested：The surface contact angle and its elongation at break of object and water of the present invention respectively than improving before modified
13.1 ° and 13.4%.
Embodiment 3
1）The preparation of polyvinyl alcohol-PTMC graft copolymer
18.3 grams of polyvinyl alcohol are added in dry reactor（Molecular weight is 93000）With the poly- Sanya of 10.3 grams of carboxy blockings
Methyl carbonic monododecyl ether（Molecular weight is 2800）, 264 ml dimethyl sulfoxide (DMSO)s are added, add 0.049 gram of 3- second
Base -1-（3- dimethylaminopropyls）Carbodiimide, under inert atmosphere, in 35 DEG C of stirring reactions 2 days, terminating reaction, by filtering, thoroughly
Analysis, dry, obtain object；
2）The preparation of polyvinyl alcohol-PTMC-PPDO dual graft copolymer
10 grams of polyvinyl alcohol-PTMC graft copolymer and 4.7 grams of carboxyl envelopes are added in dry reactor
The PPDO monododecyl ether at end（Molecular weight is 2400）, 146 ml dimethyl sulfoxide (DMSO)s are added, add 0.027
Gram 3- ethyls -1-（3- dimethylaminopropyls）Carbodiimide, under inert atmosphere, in 34 DEG C of stirring reactions 4 days, terminating reaction, pass through
Filtering, dialysis, dry, obtain object；
3）The preparation for the polyvinyl alcohol film that PTMC is modified with PPDO
9.5 grams of polyvinyl alcohol-PTMC-PPDO dual grafts are added in dry reactor
Copolymer and 35 ml dimethyl sulfoxide solvents, it is another to add the PTMC list dodecane for accounting for Modified Membrane gross weight 4%
Base ether（Molecular weight is 2800）, under inert atmosphere, it is stirred in 52 DEG C 60 minutes, with the tape casting film forming, is done in 50 DEG C of vacuum
Object is dried to obtain in dry case.
After tested：The surface contact angle and its elongation at break of object and water of the present invention respectively than improving before modified
13.6 ° and 14.1%.
Claims (6)
1. one kind is changed with PTMC with PPDO to polyvinyl alcohol film water resistance and compliance
The method entered, it is characterised in that：The molecular weight of polyvinyl alcohol segments is 84000~93000 in Modified Membrane, polytrimethylene carbonic acid
The molecular weight of ester segment is 2700~2800, and the molecular weight of PPDO segment is 2000~2400；Its method of modifying
Using following steps：
1）The preparation of polyvinyl alcohol-PTMC graft copolymer：Carboxy blocking is added in dry reactor
PTMC monododecyl ether, solvent, condensing agent and polyvinyl alcohol, under inert atmosphere, in 30~35 DEG C of stirrings
Reaction 2~3 days, terminating reaction, by filtering, dialysing, dry, obtain object；
2）The preparation of polyvinyl alcohol-PTMC-PPDO dual graft copolymer：In dry reactor
Interior addition polyvinyl alcohol-PTMC graft copolymer, the PPDO list dodecyl of carboxy blocking
Ether, solvent and condensing agent, under inert atmosphere, in 30~34 DEG C of stirring reactions 2~4 days, terminating reaction, by filtering, dialysing, doing
It is dry, obtain object；
3）The preparation for the polyvinyl alcohol film that PTMC is modified with PPDO：Add in dry reactor
Enter polyvinyl alcohol-PTMC-PPDO dual graft copolymer, PTMC list 12
Alkyl ether and solvent, under inert atmosphere, after 47~52 DEG C are stirred 50~60 minutes, with the tape casting film forming and drying, obtain
To object.
2. one kind PTMC according to claim 1 and PPDO are resistance to polyvinyl alcohol film
The method that water-based and compliance is improved, it is characterised in that：Step 1）In, PTMC monododecyl ether with
The mol ratio of polyvinyl alcohol is 15~25:1.
3. one kind PTMC according to claim 1 is with PPDO to polyvinyl alcohol film
The method that water resistance and compliance are improved, it is characterised in that：Step 1）In, condensing agent usesN,N’- dicyclohexyl carbon two
Imines,N,N’- DIC or 3- ethyls -1-（3- dimethylaminopropyls）Carbodiimide, condensing agent and polyvinyl alcohol
Mol ratio be 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 PPDO are resistance to polyvinyl alcohol film
The method that water-based and compliance is improved, it is characterised in that：Step 2）In, PPDO monododecyl ether is with gathering
The mol ratio of polyvinyl alcohol segments in vinyl alcohol-PTMC graft copolymer is 15~25:1.
5. one kind PTMC according to claim 1 is with PPDO to polyvinyl alcohol film
The method that water resistance and compliance are improved, it is characterised in that：Step 2）In, condensing agent usesN,N’- dicyclohexyl carbon two
Imines,N,N’- DIC or 3- ethyls -1-（3- dimethylaminopropyls）Carbodiimide, condensing agent and polyvinyl alcohol-
The mol ratio of polyvinyl alcohol segments in PTMC graft copolymer is 1.07~1.9:1, solvent uses diformazan
Base sulfoxide, reactant solution concentration are 5~15 g:100 ml.
6. one kind PTMC according to claim 1 and PPDO are resistance to polyvinyl alcohol film
The method that water-based and compliance is improved, it is characterised in that：Step 3）In, PTMC monododecyl ether exists
Mass percent in Modified Membrane is 2~4%, 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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| CN201610125104.4A CN105504322B (en) | 2016-03-07 | 2016-03-07 | A kind of method being improved with PTMC and PPDO to polyvinyl alcohol film water resistance and compliance |
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| CN201610125104.4A CN105504322B (en) | 2016-03-07 | 2016-03-07 | A kind of method being improved with PTMC and PPDO to polyvinyl alcohol film water resistance and compliance |
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| CN105504322B true CN105504322B (en) | 2018-02-02 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106977939A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method being improved with PTMC and PPDO to polypropylene sorrel water resistance and compliance |
| CN107011673A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with PPDO |
| CN106987132A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PTMC |
| CN106977943A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with PPDO |
| CN106987136A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PTMC |
| CN106947265A (en) * | 2017-05-25 | 2017-07-14 | 山东理工大学 | A kind of method that PPDO is improved with PTMC to polypropylene sorrel water resistance and compliance |
| CN107118571A (en) * | 2017-05-25 | 2017-09-01 | 山东理工大学 | A kind of method that PLA is improved with PTMC to polypropylene sorrel water resistance and compliance |
| CN106987140A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with PTMC |
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| CN103881398B (en) * | 2014-03-24 | 2016-06-29 | 山东理工大学 | A kind of method that PTMC improves polyvinyl alcohol film resistance to water with PPDO |
| CN104479158B (en) * | 2015-01-06 | 2017-09-08 | 山东理工大学 | A kind of method that PPDO improves poly- peptide film hydrophily and compliance with polyethylene glycol |
| CN104559213B (en) * | 2015-01-06 | 2017-03-08 | 山东理工大学 | A kind of method that PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol |
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