CN106987131A - A kind of method being improved with MPEGPLA and polypropylene glycol to polypropylene sorrel water resistance and compliance - Google Patents

A kind of method being improved with MPEGPLA and polypropylene glycol to polypropylene sorrel water resistance and compliance Download PDF

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Publication number
CN106987131A
CN106987131A CN201710362906.1A CN201710362906A CN106987131A CN 106987131 A CN106987131 A CN 106987131A CN 201710362906 A CN201710362906 A CN 201710362906A CN 106987131 A CN106987131 A CN 106987131A
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mpegpla
polypropylene glycol
polypropylene
compliance
water resistance
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申红望
朱国全
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Shandong University of Technology
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Shandong University of Technology
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L87/00Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C08L87/005Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02Macromolecular 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
    • C08G81/024Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/027Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00Compositions for preparing biodegradable polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2387/00Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The present invention discloses a kind of method being improved with MPEGPLA and polypropylene glycol to polypropylene sorrel water resistance and compliance, using following steps:1)The synthesis of polyacrylic acid polypropylene glycol graft copolymer:Add hydroxy-end capped polypropylene glycol monobutyl ether, solvent, condensing agent and polyacrylic acid in dry reactor, stirring reaction 2~3 days, terminating reaction obtains object;2)MPEGPLA and the polypropylene sorrel of polypropylene glycol modified preparation:Polyacrylic acid polypropylene glycol graft copolymer, MPEGPLA 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

One kind is entered with MPEGPLA with polypropylene glycol to polypropylene sorrel water resistance and compliance The improved method of row
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.MPEGPLA(The weight ratio of polyethylene glycol and PLA is 10/90)And polypropylene glycol(Point Son amount more than 2000)It is the biomaterial with excellent biocompatibility and biodegradability, with hydrophobicity and submissive Property.Polypropylene glycol segment is first introduced into polyacrylic acid segment formation poly acrylic acid-poly propane diols graft copolymer, then again will MPEGPLA segments add poly acrylic acid-poly propane diols graft copolymer formation blend, and modified polypropene sorrel is made, so that 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 being improved with MPEGPLA and polypropylene glycol to polypropylene sorrel water resistance and compliance, its feature exists In:The molecular weight of polyacrylic acid segment is 82000~89000 in Modified Membrane, the molecular weight of polypropylene glycol segment for 2300~ The molecular weight of 2400, MPEGPLA segments is 4800~5000;Its method of modifying uses following steps:
1)The synthesis of poly acrylic acid-poly propane diols graft copolymer:Hydroxy-end capped polypropylene glycol is added in dry reactor Under monobutyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 27~33 DEG C of stirring reactions 2~3 days, terminating reaction was led to Filter, dialyse, dry, obtain object;
2)MPEGPLA and the polypropylene sorrel of polypropylene glycol modified preparation:Poly acrylic acid-poly third is added in dry reactor Under glycol graft copolymer, MPEGPLA and solvent, inert atmosphere, after 48~53 DEG C of stirrings are mixed 50~60 minutes, with curtain coating Method film forming and drying, obtain object.
A kind of described side being improved with MPEGPLA and polypropylene glycol to polypropylene sorrel water resistance and compliance Method, step 1)In, the mol ratio of polypropylene glycol monobutyl ether and polyacrylic acid is 15~25:1.
A kind of described side being improved with MPEGPLA and polypropylene glycol to polypropylene sorrel water resistance and compliance Method, 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 is sub- using dimethyl Sulfone, reactant solution concentration is 5~15 g:100 ml.
A kind of described side being improved with MPEGPLA and polypropylene glycol to polypropylene sorrel water resistance and compliance Method, step 2)In, MPEGPLA is poly- using mono methoxy polyethylene glycol(D,L)Lactic acid copolymer(The weight of polyethylene glycol and PLA Amount is than being 10/90), mass percents of the MPEGPLA in Modified Membrane is 1~3%, and solvent uses dimethyl sulfoxide (DMSO), and mixture is molten Liquid concentration is 25~30 g:100 ml.
Compared with prior art, its advantage is the present invention:
1st, a kind of described method being improved with MPEGPLA and polypropylene glycol to polypropylene sorrel water resistance and compliance, 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 propane diols graft copolymer
20.2 grams of polyacrylic acid are added in dry reactor(Molecular weight is 82000)With 10.4 grams of hydroxy-end capped polypropylene glycols Monobutyl ether(Molecular weight is 2300), 301 ml dimethyl sulfoxide (DMSO)s are added, 0.062 gram is addedN,N’- dicyclohexylcarbodiimide, Under inert atmosphere, in 27 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains object;
2)MPEGPLA and the polypropylene sorrel of polypropylene glycol modified preparation
10 grams of poly acrylic acid-poly propane diols graft copolymers and 37 ml dimethyl sulfoxide solvents are added in dry reactor, separately Add the MPEGPLA for accounting for Modified Membrane gross weight 1%(Molecular weight is 4800), under inert atmosphere, in 48 DEG C of stirring mixing 50 minutes, The tape casting film forming is used, 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 12.2 ° and 9.3%.
Embodiment 2
1)The preparation of poly acrylic acid-poly propane diols graft copolymer
21 grams of polyacrylic acid are added in dry reactor(Molecular weight is 85000)With 10.7 grams of hydroxy-end capped polypropylene glycol lists Butyl ether(Molecular weight is 2300), 315 ml dimethyl sulfoxide (DMSO)s are added, 0.039 gram is addedN,N’- DIC, it is lazy Property atmosphere under, in 30 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, and obtains object;
2)MPEGPLA and the polypropylene sorrel of polypropylene glycol modified preparation
10.1 grams of poly acrylic acid-poly propane diols graft copolymers are added in dry reactor and 36.5 ml dimethyl sulfoxide (DMSO)s are molten Agent, it is another to add the MPEGPLA for accounting for Modified Membrane gross weight 2%(Molecular weight is 4900), under inert atmosphere, in 50 DEG C of stirring mixing 55 Minute, the tape casting film forming is used, 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 12.7 ° and 9.8%.
Embodiment 3
1)The preparation of poly acrylic acid-poly propane diols graft copolymer
21.5 grams of polyacrylic acid are added in dry reactor(Molecular weight is 89000)With 10.8 grams of hydroxy-end capped polypropylene glycols Monobutyl ether(Molecular weight is 2400), 325 ml dimethyl sulfoxide (DMSO)s are added, 0.058 gram of 3- ethyls -1- is added(3- diformazans ammonia third Base)Under carbodiimide, inert atmosphere, in 33 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains target Thing;
2)MPEGPLA and the polypropylene sorrel of polypropylene glycol modified preparation
9.6 grams of poly acrylic acid-poly propane diols graft copolymers and 35 ml dimethyl sulfoxide solvents are added in dry reactor, It is another to add the MPEGPLA for accounting for Modified Membrane gross weight 3%(Molecular weight is 5000), under inert atmosphere, in 53 DEG C of 60 points of stirring mixing Clock, uses the tape casting film forming, and 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 13.3 ° and 10.5%.

Claims (4)

1. a kind of method being improved with MPEGPLA and polypropylene glycol to polypropylene sorrel water resistance and compliance, its feature It is:The molecular weight of polyacrylic acid segment is 82000~89000 in Modified Membrane, the molecular weight of polypropylene glycol segment for 2300~ The molecular weight of 2400, MPEGPLA segments is 4800~5000;Its method of modifying uses following steps:
1)The synthesis of poly acrylic acid-poly propane diols graft copolymer:Hydroxy-end capped polypropylene glycol is added in dry reactor Under monobutyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 27~33 DEG C of stirring reactions 2~3 days, terminating reaction was led to Filter, dialyse, dry, obtain object;
2)MPEGPLA and the polypropylene sorrel of polypropylene glycol modified preparation:Poly acrylic acid-poly third is added in dry reactor Under glycol graft copolymer, MPEGPLA and solvent, inert atmosphere, after 48~53 DEG C of stirrings are mixed 50~60 minutes, with curtain coating Method film forming and drying, obtain object.
2. one kind according to claim 1 is entered with MPEGPLA with polypropylene glycol to polypropylene sorrel water resistance and compliance The improved method of row, it is characterised in that:Step 1)In, the mol ratio of polypropylene glycol monobutyl ether and polyacrylic acid is 15~25:1.
3. one kind according to claim 1 is entered with MPEGPLA with polypropylene glycol to polypropylene sorrel water resistance and compliance The improved method of row, 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. one kind according to claim 1 is entered with MPEGPLA with polypropylene glycol to polypropylene sorrel water resistance and compliance The improved method of row, it is characterised in that:Step 2)In, MPEGPLA is poly- using mono methoxy polyethylene glycol(D,L)Lactic acid copolymer (The weight ratio of polyethylene glycol and PLA is 10/90), mass percents of the MPEGPLA in Modified Membrane is 1~3%, and solvent is adopted With dimethyl sulfoxide (DMSO), mixture solution concentration is 25~30 g:100 ml.
CN201710362906.1A 2017-05-22 2017-05-22 A kind of method being improved with MPEGPLA and polypropylene glycol to polypropylene sorrel water resistance and compliance Withdrawn CN106987131A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103865074A (en) * 2014-04-11 2014-06-18 山东理工大学 Preparation method of polypeptide-poly(caprolactone-lactide)-MPEGPLA double-graft copolymer
CN105542207A (en) * 2016-03-07 2016-05-04 山东理工大学 Method for improving water resistance and flexibility of polyvinyl alcohol film through polypropylene glycol and polypeptide-polyvinylpyrrolidone

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103865074A (en) * 2014-04-11 2014-06-18 山东理工大学 Preparation method of polypeptide-poly(caprolactone-lactide)-MPEGPLA double-graft copolymer
CN105542207A (en) * 2016-03-07 2016-05-04 山东理工大学 Method for improving water resistance and flexibility of polyvinyl alcohol film through polypropylene glycol and polypeptide-polyvinylpyrrolidone

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
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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Application publication date: 20170728