CN106977937A - A kind of MPEGPLA is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance - Google Patents

A kind of MPEGPLA is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance Download PDF

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Publication number
CN106977937A
CN106977937A CN201710362893.8A CN201710362893A CN106977937A CN 106977937 A CN106977937 A CN 106977937A CN 201710362893 A CN201710362893 A CN 201710362893A CN 106977937 A CN106977937 A CN 106977937A
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mpegpla
gathering
lactide coglycolide
poly
compliance
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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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    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The present invention discloses a kind of MPEGPLA with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance, using following steps：1）Polyacrylic acid gathers（Lactide glycolide）The synthesis of graft copolymer：Hydroxy-end capped gather is added in dry reactor（Lactide glycolide）Monododecyl ether, solvent, condensing agent and polyacrylic acid, stirring reaction 2~3 days, terminating reaction obtains object；2）MPEGPLA is with gathering（Lactide glycolide）The preparation of modified polypropylene sorrel：Polyacrylic acid is added in dry reactor to gather（Lactide glycolide）Graft copolymer, MPEGPLA and solvent, after stirring is mixed 50~60 minutes, with the tape casting film forming and drying, obtain object of the present invention.Preparation technology of the present invention is simple, be easy to grasp, and gained Modified Membrane water resistance and compliance are greatly improved.

Description

A kind of MPEGPLA is with gathering（Lactide coglycolide）Improve polypropylene sorrel water resistance and The method of compliance
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）With it is poly-（D, L- third is handed over Ester-glycolide）（The weight ratio of lactide and glycolide is 90/10）It is with excellent biocompatibility and biodegradability Biomaterial, with good hydrophobicity and compliance.First will be poly-（Lactide coglycolide）Segment introduces polyacrylic acid segment Form poly acrylic acid-poly（Lactide coglycolide）Graft copolymer, then adds poly acrylic acid-poly by MPEGPLA segments again （Lactide coglycolide）Graft copolymer formation blend, is made modified polypropene sorrel, so as to drastically increase polypropylene The water resistance and compliance of 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 MPEGPLA is with gathering（Lactide coglycolide）The method for improving polypropylene sorrel water resistance and compliance, its feature exists In：The molecular weight of polyacrylic acid segment is 82000~89000 in Modified Membrane, is gathered（Lactide coglycolide）The molecular weight of segment is The molecular weight of 2200~2400, MPEGPLA segment is 4600~5000；Its method of modifying uses following steps：
1）Poly acrylic acid-poly（Lactide coglycolide）The synthesis of graft copolymer：Added in dry reactor hydroxy-end capped It is poly-（Lactide coglycolide）Under monododecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 28~33 DEG C of stirrings Reaction 2~3 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）MPEGPLA is with gathering（Lactide coglycolide）The preparation of modified polypropylene sorrel：Poly- third is added in dry reactor Olefin(e) acid-poly-（Lactide coglycolide）Under graft copolymer, MPEGPLA and solvent, inert atmosphere, in 47~52 DEG C of stirring mixing After 50~60 minutes, with the tape casting film forming and drying, object is obtained.
A kind of described MPEGPLA is with gathering（Lactide coglycolide）Improve the side of polypropylene sorrel water resistance and compliance Method, step 1）In, gather（Lactide coglycolide）Monododecyl ether is using poly-（D, L- lactide coglycolide）Single dodecyl Ether（The weight ratio of lactide and glycolide is 90/10）, gather（Lactide coglycolide）Monododecyl ether and polyacrylic acid rub You are than being 15~25:1.
A kind of described MPEGPLA is with gathering（Lactide coglycolide）Improve the side of 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 1.06~1.9:1, solvent is sub- using dimethyl Sulfone, reactant solution concentration is 5~15 g:100 ml.
A kind of described MPEGPLA is with gathering（Lactide coglycolide）Improve the side of 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 MPEGPLA is with gathering（Lactide coglycolide）The method for improving 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）Poly acrylic acid-poly（Lactide coglycolide）The preparation of graft copolymer
20.2 grams of polyacrylic acid are added in dry reactor（Molecular weight is 82000）It is hydroxy-end capped poly- with 9.9 grams（Third hands over Ester-glycolide）Monododecyl ether（Molecular weight is 2200）, 297 ml dimethyl sulfoxide (DMSO)s are added, 0.062 gram is addedN,N’- Under dicyclohexylcarbodiimide, inert atmosphere, in 28 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtained To object；
2）MPEGPLA is with gathering（Lactide coglycolide）The preparation of modified polypropylene sorrel
10 grams of poly acrylic acid-polies are added in dry reactor（Lactide coglycolide）Graft copolymer and 37 ml dimethyl are sub- Sulfoxide solvent, it is another to add the MPEGPLA for accounting for Modified Membrane gross weight 1%（Molecular weight is 4600）, it is mixed in 47 DEG C of stirrings under inert atmosphere Close 50 minutes, 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 9.3%.
Embodiment 2
1）Poly acrylic acid-poly（Lactide coglycolide）The preparation of graft copolymer
21 grams of polyacrylic acid are added in dry reactor（Molecular weight is 85000）It is hydroxy-end capped poly- with 10.8 grams（Lactide- Glycolide）Monododecyl ether（Molecular weight is 2300）, 317 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）MPEGPLA is with gathering（Lactide coglycolide）The preparation of modified polypropylene sorrel
10.1 grams of poly acrylic acid-polies are added in dry reactor（Lactide coglycolide）Graft copolymer and 36.5 ml diformazans Base sulfoxide solvent, it is another to add the MPEGPLA for accounting for Modified Membrane gross weight 2%（Molecular weight is 4800）, under inert atmosphere, stirred in 50 DEG C Mixing 55 minutes is mixed, 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 9.9%.
Embodiment 3
1）Poly acrylic acid-poly（Lactide coglycolide）The preparation of graft copolymer
21.5 grams of polyacrylic acid are added in dry reactor（Molecular weight is 89000）It is hydroxy-end capped poly- with 10.8 grams（Third hands over Ester-glycolide）Monododecyl ether（Molecular weight is 2400）, 315 ml dimethyl sulfoxide (DMSO)s are added, 0.058 gram of 3- second is added Base -1-（3- dimethylaminopropyls）Under carbodiimide, inert atmosphere, in 33 DEG C of stirring reactions 2 days, terminating reaction, by filtering, thoroughly Analyse, dry, obtain object；
2）MPEGPLA is with gathering（Lactide coglycolide）The preparation of modified polypropylene sorrel
9.6 grams of poly acrylic acid-polies are added in dry reactor（Lactide coglycolide）Graft copolymer and 35 ml dimethyl Sulfoxide solvent, it is another to add the MPEGPLA for accounting for Modified Membrane gross weight 3%（Molecular weight is 5000）, under inert atmosphere, in 52 DEG C of stirrings Mixing 60 minutes, uses 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 13.2 ° and 10.4%.

Claims (4)

1. a kind of MPEGPLA is with gathering（Lactide coglycolide）The method for improving polypropylene sorrel water resistance and compliance, its feature It is：The molecular weight of polyacrylic acid segment is 82000~89000 in Modified Membrane, is gathered（Lactide coglycolide）The molecular weight of segment It is 4600~5000 for the molecular weight of 2200~2400, MPEGPLA segments；Its method of modifying uses following steps：
1）Poly acrylic acid-poly（Lactide coglycolide）The synthesis of graft copolymer：Added in dry reactor hydroxy-end capped It is poly-（Lactide coglycolide）Under monododecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 28~33 DEG C of stirrings Reaction 2~3 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）MPEGPLA is with gathering（Lactide coglycolide）The preparation of modified polypropylene sorrel：Poly- third is added in dry reactor Olefin(e) acid-poly-（Lactide coglycolide）Under graft copolymer, MPEGPLA and solvent, inert atmosphere, in 47~52 DEG C of stirring mixing After 50~60 minutes, with the tape casting film forming and drying, object is obtained.
2. a kind of MPEGPLA according to claim 1 is with gathering（Lactide coglycolide）Improve polypropylene sorrel water resistance and The method of compliance, it is characterised in that：Step 1）In, gather（Lactide coglycolide）Monododecyl ether is using poly-（D, L- third is handed over Ester-glycolide）Monododecyl ether（The weight ratio of lactide and glycolide is 90/10）, gather（Lactide coglycolide）Single 12 The mol ratio of alkyl ether and polyacrylic acid is 15~25:1.
3. a kind of MPEGPLA according to claim 1 is with gathering（Lactide coglycolide）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 1.06~ 1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. a kind of MPEGPLA according to claim 1 is with gathering（Lactide coglycolide）Improve polypropylene sorrel water resistance and The method of compliance, 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.
CN201710362893.8A 2017-05-22 2017-05-22 A kind of MPEGPLA is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance Withdrawn CN106977937A (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
CN103865071A (en) * 2014-03-24 2014-06-18 山东理工大学 Preparation method of polypeptide-poly trimethylene carbonate-MPEGPLA (mono-methoxyl poly(ethylene glycol)-poly(lactic acid) dual-graft copolymer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103865071A (en) * 2014-03-24 2014-06-18 山东理工大学 Preparation method of polypeptide-poly trimethylene carbonate-MPEGPLA (mono-methoxyl poly(ethylene glycol)-poly(lactic acid) dual-graft copolymer
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

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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