CN105694474B - A kind of method being improved with polytrimethylene carbonate and poly (lactic acid-glycolic acid) to polyvinyl alcohol film water resistance and compliance - Google Patents
A kind of method being improved with polytrimethylene carbonate and poly (lactic acid-glycolic acid) to polyvinyl alcohol film water resistance and compliance Download PDFInfo
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- CN105694474B CN105694474B CN201610125952.5A CN201610125952A CN105694474B CN 105694474 B CN105694474 B CN 105694474B CN 201610125952 A CN201610125952 A CN 201610125952A CN 105694474 B CN105694474 B CN 105694474B
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- polyvinyl alcohol
- poly
- polytrimethylene carbonate
- lactic acid
- glycolic 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
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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
Abstract
The present invention discloses a kind of method being improved with polytrimethylene carbonate and poly (lactic acid-glycolic acid) to polyvinyl alcohol film water resistance and compliance, using following steps：1）Add polytrimethylene carbonate monododecyl ether, solvent, condensing agent and the polyvinyl alcohol of carboxy blocking in reactor, react to obtain polyvinyl alcohol polytrimethylene carbonate graft copolymer；2）Poly (lactic acid-glycolic acid) monododecyl ether, solvent and the condensing agent of Polyvinyl alcohol polytrimethylene carbonate graft copolymer, carboxy blocking in reactor react to obtain polyvinyl alcohol polytrimethylene carbonate poly (lactic acid-glycolic acid) dual graft copolymer；3）Polyvinyl alcohol polytrimethylene carbonate poly (lactic acid-glycolic acid) dual graft copolymer, polytrimethylene carbonate monododecyl ether and solvent, form a film after mixing, obtain object of the present invention in reactor.Preparation process 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 methods 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, lack preferable water resistance and compliance, so as to
Its application is limited to a certain extent.Polytrimethylene carbonate and poly-（D, Pfansteihl）Glycolic（The weight of lactic acid and glycolic
Amount is than being 90/10）That there is excellent biocompatibility and the biomaterial of biodegradability, have good hydrophobicity and
Compliance.Polytrimethylene carbonate segment is first introduced into polyvinyl alcohol segments and forms polyvinyl alcohol-polytrimethylene carbonate
Graft copolymer, then poly (lactic acid-glycolic acid) segment is introduced into gathering in polyvinyl alcohol-polytrimethylene carbonate graft copolymer
Polyvinyl alcohol-polytrimethylene carbonate-poly (lactic acid-glycolic acid) dual graft copolymer is obtained on vinyl alcohol segment, it then again will be poly-
Trimethylene carbonate segment adds in polyvinyl alcohol-polytrimethylene carbonate-poly (lactic acid-glycolic acid) dual graft copolymer and is formed
Modified PVA membrane is made, so as to greatly improve the water resistance of polyvinyl alcohol film and compliance in blend.
Invention content
The purpose of the present invention is to provide a kind of easy to operate and effect preferably to polyvinyl alcohol film water resistance and submissive
The method that property is improved.Its technical solution is：
It is a kind of that polyvinyl alcohol film water resistance and compliance are changed with poly (lactic acid-glycolic acid) with polytrimethylene carbonate
Into method, it is characterised in that：The molecular weight of polyvinyl alcohol segments is 83000~93000 in Modified Membrane, polytrimethylene carbonic acid
The molecular weight of ester segment is 2500~2800, and the molecular weight of poly (lactic acid-glycolic acid) segment is 2100~2200；Its method of modifying is adopted
Use following steps：
1）The preparation of polyvinyl alcohol-polytrimethylene carbonate graft copolymer：Carboxyl envelope is added in dry reactor
Polytrimethylene carbonate monododecyl ether, solvent, condensing agent and the polyvinyl alcohol at end, under inert atmosphere, in 30~34 DEG C
It is stirred to react 2~3 days, terminates reaction, by filtering, dialysing, drying, obtain object；
2）The preparation of polyvinyl alcohol-polytrimethylene carbonate-poly (lactic acid-glycolic acid) dual graft copolymer：In dry reaction
The poly (lactic acid-glycolic acid) list dodecyl of polyvinyl alcohol-polytrimethylene carbonate graft copolymer, carboxy blocking is added in device
Ether, solvent and condensing agent under inert atmosphere, are stirred to react 2~4 days in 30~33 DEG C, terminate reaction, by filtering, dialysing, doing
It is dry, obtain object；
3）The preparation for the polyvinyl alcohol film that polytrimethylene carbonate is modified with poly (lactic acid-glycolic acid)：In dry reactor
Add in polyvinyl alcohol-polytrimethylene carbonate-poly (lactic acid-glycolic acid) dual graft copolymer, polytrimethylene carbonate list 12
Alkyl ether and solvent, under inert atmosphere, it is stirred 50 in 47~53 DEG C~after sixty minutes, it is formed a film and dried with the tape casting, obtained
To object.
A kind of use polytrimethylene carbonate is with poly (lactic acid-glycolic acid) to polyvinyl alcohol film water resistance and compliance
The method being improved, step 1）In, the molar ratio of polytrimethylene carbonate monododecyl ether and polyvinyl alcohol for 15~
25:1。
A kind of use polytrimethylene carbonate is with poly (lactic acid-glycolic acid) to polyvinyl alcohol film water resistance and compliance
The method being improved, step 1）In, condensing agent usesN,N’Dicyclohexylcarbodiimide,N,N’Diisopropylcarbodiimide
Or 3- ethyls -1-（3- dimethylaminopropyls）The molar ratio of carbodiimide, condensing agent and polyvinyl alcohol is 1.07~1.8:1, solvent
Using dimethyl sulfoxide (DMSO), a concentration of 5~15 g of reactant solution:100 ml.
A kind of use polytrimethylene carbonate is with poly (lactic acid-glycolic acid) to polyvinyl alcohol film water resistance and compliance
The method being improved, step 2）In, poly (lactic acid-glycolic acid) monododecyl ether is using poly-（D, Pfansteihl）Glycolic list 12
Alkyl ether, and the weight ratio of lactic acid and glycolic is 90/10, poly (lactic acid-glycolic acid) monododecyl ether and polyvinyl alcohol-poly- three
The molar ratio of polyvinyl alcohol segments in carbonate graft copolymer is 15~25:1.
A kind of use polytrimethylene carbonate is with poly (lactic acid-glycolic acid) to polyvinyl alcohol film water resistance and compliance
The method being improved, step 2）In, condensing agent usesN,N’Dicyclohexylcarbodiimide,N,N’Diisopropylcarbodiimide
Or 3- ethyls -1-（3- dimethylaminopropyls）Carbodiimide, condensing agent and polyvinyl alcohol-polytrimethylene carbonate graft copolymer
In polyvinyl alcohol segments molar ratio be 1.07~1.8:1, solvent use dimethyl sulfoxide (DMSO), reactant solution a concentration of 5~
15 g:100 ml。
A kind of use polytrimethylene carbonate is with poly (lactic acid-glycolic acid) to polyvinyl alcohol film water resistance and compliance
The method being improved, step 3）In, mass percent of the polytrimethylene carbonate monododecyl ether in Modified Membrane is 2
~4%, solvent uses dimethyl sulfoxide (DMSO), a concentration of 25~30 g of mixture solution:100 ml.
Compared with prior art, the present invention its advantage is：
1st, it is described it is a kind of with polytrimethylene carbonate and poly (lactic acid-glycolic acid) to polyvinyl alcohol film water resistance and submissive
Property the method that is improved, it is easy to operate, be easy to grasp using three kinds of means of two step esterifications and blending；
2nd, the polyvinyl alcohol modification film water resistance and compliance are enhanced.
Specific embodiment
Embodiment 1
1）The preparation of polyvinyl alcohol-polytrimethylene carbonate graft copolymer
18 grams of polyvinyl alcohol are added in dry reactor（Molecular weight is 83000）With the polytrimethylene of 10 grams of carboxy blockings
Carbonic ester monododecyl ether（Molecular weight is 2500）, 260 ml dimethyl sulfoxide (DMSO)s are added in, add 0.056 gramN,N’- two rings
Hexyl carbodiimide under inert atmosphere, is stirred to react 2 days in 30 DEG C, terminates reaction, by filtering, dialysing, drying, obtains mesh
Mark object；
2）The preparation of polyvinyl alcohol-polytrimethylene carbonate-poly (lactic acid-glycolic acid) dual graft copolymer
10 grams of polyvinyl alcohol-polytrimethylene carbonate graft copolymer and 4.6 grams of carboxyl envelopes are added in dry reactor
The poly (lactic acid-glycolic acid) monododecyl ether at end（Molecular weight is 2100）, 144 ml dimethyl sulfoxide (DMSO)s are added in, add 0.031 gramN,N’Dicyclohexylcarbodiimide under inert atmosphere, is stirred to react 2 days in 30 DEG C, terminates reaction, by filtering, dialysing, doing
It is dry, obtain object；
3）The preparation for the polyvinyl alcohol film that polytrimethylene carbonate is modified with poly (lactic acid-glycolic acid)
10 grams of polyvinyl alcohol-polytrimethylene carbonate-poly (lactic acid-glycolic acid) dual grafts are added in dry reactor to be total to
Polymers and 37 ml dimethyl sulfoxide solvents, it is another to add in the polytrimethylene carbonate list dodecyl for accounting for Modified Membrane total weight 2%
Ether（Molecular weight is 2500）, under inert atmosphere, it is stirred in 47 DEG C 50 minutes, is formed a film with the tape casting, in 50 DEG C of vacuum drying
Object is dried to obtain in 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
12.1 ° and 12.4%.
Embodiment 2
1）The preparation of polyvinyl alcohol-polytrimethylene carbonate 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）, 265 ml dimethyl sulfoxide (DMSO)s are added in, add 0.032 gramN,N’-
Diisopropylcarbodiimide under inert atmosphere, is stirred to react 3 days in 32 DEG C, terminates reaction, by filtering, dialysing, drying, is obtained
To object；
2）The preparation of polyvinyl alcohol-polytrimethylene carbonate-poly (lactic acid-glycolic acid) dual graft copolymer
10.3 grams of polyvinyl alcohol-polytrimethylene carbonate graft copolymer and 4.6 grams of carboxyls are added in dry reactor
The poly (lactic acid-glycolic acid) monododecyl ether of sealing end（Molecular weight is 2200）, 143 ml dimethyl sulfoxide (DMSO)s are added in, add 0.019
GramN,N’Diisopropylcarbodiimide under inert atmosphere, is stirred to react 3 days in 32 DEG C, terminates reaction, by filtering, dialysing,
It is dry, obtain object；
3）The preparation for the polyvinyl alcohol film that polytrimethylene carbonate is modified with poly (lactic acid-glycolic acid)
9.8 grams of polyvinyl alcohol-polytrimethylene carbonate-poly (lactic acid-glycolic acid) dual grafts are added in dry reactor to be total to
Polymers and 36 ml dimethyl sulfoxide solvents, it is another to add in the polytrimethylene carbonate list dodecyl for accounting for Modified Membrane total weight 3%
Ether（Molecular weight is 2700）, under inert atmosphere, it is stirred in 49 DEG C 55 minutes, is formed a film with the tape casting, in 50 DEG C of vacuum drying
Object is dried to obtain in 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
13.3 ° and 13.6%.
Embodiment 3
1）The preparation of polyvinyl alcohol-polytrimethylene carbonate 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）, 263 ml dimethyl sulfoxide (DMSO)s are added in, add 0.049 gram of 3- second
Base -1-（3- dimethylaminopropyls）Carbodiimide under inert atmosphere, is stirred to react 2 days in 34 DEG C, terminates reaction, by filtering, thoroughly
Analysis, drying, obtain object；
2）The preparation of polyvinyl alcohol-polytrimethylene carbonate-poly (lactic acid-glycolic acid) dual graft copolymer
10 grams of polyvinyl alcohol-polytrimethylene carbonate graft copolymer and 4.4 grams of carboxyl envelopes are added in dry reactor
The poly (lactic acid-glycolic acid) monododecyl ether at end（Molecular weight is 2200）, 141 ml dimethyl sulfoxide (DMSO)s are added in, add 0.027 gram
3- ethyls -1-（3- dimethylaminopropyls）Carbodiimide under inert atmosphere, is stirred to react 4 days in 33 DEG C, is terminated reaction, was passed through
Filter, dialysis, drying, obtain object；
3）The preparation for the polyvinyl alcohol film that polytrimethylene carbonate is modified with poly (lactic acid-glycolic acid)
9.5 grams of polyvinyl alcohol-polytrimethylene carbonate-poly (lactic acid-glycolic acid) dual grafts are added in dry reactor to be total to
Polymers and 35 ml dimethyl sulfoxide solvents, it is another to add in the polytrimethylene carbonate list dodecyl for accounting for Modified Membrane total weight 4%
Ether（Molecular weight is 2800）, under inert atmosphere, it is stirred in 53 DEG C 60 minutes, is formed a film with the tape casting, in 50 DEG C of vacuum drying
Object is dried to obtain in 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
13.8 ° and 14.3%.
Claims (6)
1. a kind of be improved polyvinyl alcohol film water resistance and compliance with poly (lactic acid-glycolic acid) with polytrimethylene carbonate
Method, it is characterised in that：The molecular weight of polyvinyl alcohol segments is 83000~93000 in Modified Membrane, polytrimethylene carbonate
The molecular weight of segment is 2500~2800, and the molecular weight of poly (lactic acid-glycolic acid) segment is 2100~2200；Its method of modifying uses
Following steps：
1）The preparation of polyvinyl alcohol-polytrimethylene carbonate graft copolymer：Carboxy blocking is added in dry reactor
Polytrimethylene carbonate monododecyl ether, solvent, condensing agent and polyvinyl alcohol, under inert atmosphere, in 30~34 DEG C of stirrings
Reaction 2~3 days terminates reaction, by filtering, dialysing, drying, obtains object；
2）The preparation of polyvinyl alcohol-polytrimethylene carbonate-poly (lactic acid-glycolic acid) dual graft copolymer：In dry reactor
Add in the poly (lactic acid-glycolic acid) monododecyl ether, molten of polyvinyl alcohol-polytrimethylene carbonate graft copolymer, carboxy blocking
Agent and condensing agent under inert atmosphere, are stirred to react 2~4 days in 30~33 DEG C, terminate reaction, by filtering, dialysing, drying, are obtained
To object, wherein, poly (lactic acid-glycolic acid) monododecyl ether is using poly-（D, Pfansteihl）Glycolic monododecyl ether, and breast
The weight ratio of acid and glycolic is 90/10；
3）The preparation for the polyvinyl alcohol film that polytrimethylene carbonate is modified with poly (lactic acid-glycolic acid)：It is added in dry reactor
Polyvinyl alcohol-polytrimethylene carbonate-poly (lactic acid-glycolic acid) dual graft copolymer, polytrimethylene carbonate list dodecyl
Ether and solvent, under inert atmosphere, it is stirred 50 in 47~53 DEG C~after sixty minutes, it is formed a film and dried with the tape casting, obtain mesh
Mark object.
It is 2. according to claim 1 a kind of water-fast to polyvinyl alcohol film with polytrimethylene carbonate and poly (lactic acid-glycolic acid)
The method that property and compliance are improved, it is characterised in that：Step 1）In, polytrimethylene carbonate monododecyl ether is with gathering
The molar ratio of vinyl alcohol is 15~25:1.
It is 3. according to claim 1 a kind of water-fast to polyvinyl alcohol film with polytrimethylene carbonate and poly (lactic acid-glycolic acid)
The method that property and compliance are improved, it is characterised in that：Step 1）In, condensing agent usesN,N’Dicyclohexylcarbodiimide,N,N’Diisopropylcarbodiimide or 3- ethyls -1-（3- dimethylaminopropyls）Mole of carbodiimide, condensing agent and polyvinyl alcohol
Than being 1.07~1.8:1, solvent uses dimethyl sulfoxide (DMSO), a concentration of 5~15 g of reactant solution:100 ml.
It is 4. according to claim 1 a kind of water-fast to polyvinyl alcohol film with polytrimethylene carbonate and poly (lactic acid-glycolic acid)
The method that property and compliance are improved, it is characterised in that：Step 2）In, poly (lactic acid-glycolic acid) monododecyl ether and polyethylene
The molar ratio of polyvinyl alcohol segments in alcohol-polytrimethylene carbonate graft copolymer is 15~25:1.
It is 5. according to claim 1 a kind of water-fast to polyvinyl alcohol film with polytrimethylene carbonate and poly (lactic acid-glycolic acid)
The method that property and compliance are improved, it is characterised in that：Step 2）In, condensing agent usesN,N’Dicyclohexylcarbodiimide,N,N’Diisopropylcarbodiimide or 3- ethyls -1-（3- dimethylaminopropyls）Carbodiimide, condensing agent and polyvinyl alcohol-poly- three
The molar ratio of polyvinyl alcohol segments in carbonate graft copolymer is 1.07~1.8:1, solvent is sub- using dimethyl
Sulfone, a concentration of 5~15 g of reactant solution:100 ml.
It is 6. according to claim 1 a kind of water-fast to polyvinyl alcohol film with polytrimethylene carbonate and poly (lactic acid-glycolic acid)
The method that property and compliance are improved, it is characterised in that：Step 3）In, polytrimethylene carbonate monododecyl ether is changing
Property film in mass percent for 2~4%, solvent uses dimethyl sulfoxide (DMSO), a concentration of 25~30 g of mixture solution:100 ml.
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| CN201610125952.5A CN105694474B (en) | 2016-03-07 | 2016-03-07 | A kind of method being improved with polytrimethylene carbonate and poly (lactic acid-glycolic acid) to polyvinyl alcohol film water resistance and compliance |
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| CN201610125952.5A CN105694474B (en) | 2016-03-07 | 2016-03-07 | A kind of method being improved with polytrimethylene carbonate and poly (lactic acid-glycolic acid) to polyvinyl alcohol film water resistance and compliance |
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| CN107057373A (en) * | 2017-05-22 | 2017-08-18 | 山东理工大学 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid) |
| CN107057374A (en) * | 2017-05-22 | 2017-08-18 | 山东理工大学 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid) |
| CN106987128A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of method being improved with PTMC and PLA to polypropylene sorrel water resistance and compliance |
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| 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 |
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| CN106987138A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance |
| 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 |
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