CN107011676A - A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with polypropylene glycol - Google Patents

A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with polypropylene glycol Download PDF

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Publication number
CN107011676A
CN107011676A CN201710362969.7A CN201710362969A CN107011676A CN 107011676 A CN107011676 A CN 107011676A CN 201710362969 A CN201710362969 A CN 201710362969A CN 107011676 A CN107011676 A CN 107011676A
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polypropylene glycol
polycaprolactone
polypropylene
compliance
water resistance
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林治涛
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
    • C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • 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)
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Abstract

The present invention, which discloses a kind of polycaprolactone, improves the method for polypropylene sorrel water resistance and compliance with polypropylene glycol, using following steps：1）The synthesis of polyacrylic acid polycaprolactone polypropylene glycol dual graft copolymer：Add hydroxy-end capped polycaprolactone monododecyl ether, 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）The preparation of polycaprolactone and the polypropylene sorrel of polypropylene glycol modified：Polyacrylic acid polycaprolactone polypropylene glycol dual graft copolymer, polypropylene glycol monobutyl 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

A kind of polycaprolactone and polypropylene glycol improve polypropylene sorrel water resistance and compliance Method
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.Polycaprolactone and polypropylene glycol（Molecular weight more than 2000）It is with excellent bio-compatible The biomaterial of property and biodegradability, with hydrophobicity and compliance.First by polycaprolactone segment and polypropylene glycol segment Polyacrylic acid segment formation poly acrylic acid-poly caprolactone-polypropylene glycol dual graft copolymer is introduced simultaneously, then again by poly- the third two Alcohol segment adds poly acrylic acid-poly caprolactone-polypropylene glycol dual graft copolymer formation blend, and modified polyacrylic acid is made Film, 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 polycaprolactone improves polypropylene sorrel water resistance and compliance with polypropylene glycol, it is characterised in that：It is modified The molecular weight of polyacrylic acid segment is 85000~92000 in film, and the molecular weight of polycaprolactone segment is 2700~2800, poly- third The molecular weight of glycol segment is 2700~2800；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly caprolactone-polypropylene glycol dual graft copolymer：Added in dry reactor hydroxy-end capped Polycaprolactone monododecyl ether, hydroxy-end capped polypropylene glycol monobutyl ether, solvent, condensing agent and polyacrylic acid, indifferent gas Under atmosphere, in 29~33 DEG C of stirring reactions 2~3 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation of polycaprolactone and the polypropylene sorrel of polypropylene glycol modified：Poly acrylic acid-poly is added in dry reactor It is mixed in 49~52 DEG C of stirrings under caprolactone-polypropylene glycol dual graft copolymer, polypropylene glycol monobutyl ether and solvent, inert atmosphere After closing 50~60 minutes, with the tape casting film forming and drying, object is obtained.
A kind of described polycaprolactone improves the method for polypropylene sorrel water resistance and compliance, step 1 with polypropylene glycol） In, the mol ratio of polycaprolactone monododecyl ether and polyacrylic acid is 15~25:1, polypropylene glycol monobutyl ether and polyacrylic acid Mol ratio be 15~25:1.
A kind of described polycaprolactone improves the method for polypropylene sorrel water resistance and compliance, step 1 with polypropylene glycol） In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-（3- diformazan ammonia Propyl group）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.06~1.8:1, solvent uses dimethyl sulfoxide (DMSO), reactant Solution concentration is 5~15 g:100 ml.
A kind of described polycaprolactone improves the method for polypropylene sorrel water resistance and compliance, step 2 with polypropylene glycol） In, mass percent of the polypropylene glycol monobutyl ether in Modified Membrane is 2~3%, and solvent uses dimethyl sulfoxide (DMSO), mixture solution Concentration is 25~30 g:100 ml.
Compared with prior art, its advantage is the present invention：
1st, a kind of described polycaprolactone and polypropylene glycol improve the method for polypropylene sorrel water resistance and compliance, using one kind Two kinds of means of the reaction that is esterified simultaneously of polymer polymeric monomer different from two kinds and blending, 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 caprolactone-polypropylene glycol dual graft copolymer
17.1 grams of polyacrylic acid are added in dry reactor（Molecular weight is 85000）, 10.5 grams of hydroxy-end capped polycaprolactones Monododecyl ether（Molecular weight is 2700）With 10.5 grams of hydroxy-end capped polypropylene glycol monobutyl ethers（Molecular weight is 2700）, add 381 ml dimethyl sulfoxide (DMSO)s, add 0.052 gramN,N’Under-dicyclohexylcarbodiimide, inert atmosphere, in 29 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation of polycaprolactone and the polypropylene sorrel of polypropylene glycol modified
10 grams of poly acrylic acid-poly caprolactone-polypropylene glycol dual graft copolymers and 37 ml dimethyl are added in dry reactor Sulfoxide solvent, it is another to add the polypropylene glycol monobutyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 2700）, under inert atmosphere, in 49 DEG C stirring mixing 50 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 11.9 ° and 10.2%.
Embodiment 2
1）The preparation of poly acrylic acid-poly caprolactone-polypropylene glycol dual graft copolymer
20.3 grams of polyacrylic acid are added in dry reactor（Molecular weight is 87000）, 11.8 grams of hydroxy-end capped polycaprolactones Monododecyl ether（Molecular weight is 2800）With 11.8 grams of hydroxy-end capped polypropylene glycol monobutyl ethers（Molecular weight is 2800）, add 441 ml dimethyl sulfoxide (DMSO)s, add 0.036 gramN,N’Under-DIC, inert atmosphere, in 31 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation of polycaprolactone and the polypropylene sorrel of polypropylene glycol modified
9.9 grams of poly acrylic acid-poly caprolactone-polypropylene glycol dual graft copolymers and 36 ml diformazans are added in dry reactor Base sulfoxide solvent, it is another to add the polypropylene glycol monobutyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 2800）, under inert atmosphere, in 50 DEG C of stirrings are mixed 55 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 12.5 ° and 10.8%.
Embodiment 3
1）The preparation of poly acrylic acid-poly caprolactone-polypropylene glycol dual graft copolymer
21.5 grams of polyacrylic acid are added in dry reactor（Molecular weight is 92000）, 12.4 grams of hydroxy-end capped polycaprolactones Monododecyl ether（Molecular weight is 2800）With 12.4 grams of hydroxy-end capped polypropylene glycol monobutyl ethers（Molecular weight is 2800）, add 463ml dimethyl sulfoxide (DMSO)s, add 0.056 gram of 3- ethyls -1-（3- dimethylaminopropyls）Under carbodiimide, inert atmosphere, in 33 DEG C stirring reaction 2 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The preparation of polycaprolactone and the polypropylene sorrel of polypropylene glycol modified
9.5 grams of poly acrylic acid-poly caprolactone-polypropylene glycol dual graft copolymers and 35 ml diformazans are added in dry reactor Base sulfoxide solvent, it is another to add the polypropylene glycol monobutyl ether for accounting for Modified Membrane gross weight 3%（Molecular weight is 2800）, under inert atmosphere, in 52 DEG C of stirrings are mixed 60 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 13.4 ° and 11.7%.

Claims (4)

1. a kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with polypropylene glycol, it is characterised in that：Change Property film in the molecular weight of polyacrylic acid segment be 85000~92000, the molecular weight of polycaprolactone segment is 2700~2800, is gathered The molecular weight of propane diols segment is 2700~2800；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly caprolactone-polypropylene glycol dual graft copolymer：Added in dry reactor hydroxy-end capped Polycaprolactone monododecyl ether, hydroxy-end capped polypropylene glycol monobutyl ether, solvent, condensing agent and polyacrylic acid, indifferent gas Under atmosphere, in 29~33 DEG C of stirring reactions 2~3 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation of polycaprolactone and the polypropylene sorrel of polypropylene glycol modified：Poly acrylic acid-poly is added in dry reactor It is mixed in 49~52 DEG C of stirrings under caprolactone-polypropylene glycol dual graft copolymer, polypropylene glycol monobutyl ether and solvent, inert atmosphere After closing 50~60 minutes, with the tape casting film forming and drying, object is obtained.
2. a kind of polycaprolactone according to claim 1 and polypropylene glycol improve polypropylene sorrel water resistance and compliance Method, it is characterised in that：Step 1）In, the mol ratio of polycaprolactone monododecyl ether and polyacrylic acid is 15~25:1, gather The mol ratio of propylene glycol monobutyl ether and polyacrylic acid is 15~25:1.
3. a kind of polycaprolactone according to claim 1 improves polypropylene sorrel water resistance and compliance with polypropylene glycol Method, it is characterised in that：Step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl carbon two Imines or 3- ethyls -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.06~1.8:1, Solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. a kind of polycaprolactone according to claim 1 and polypropylene glycol improve polypropylene sorrel water resistance and compliance Method, it is characterised in that：Step 2）In, mass percent of the polypropylene glycol monobutyl ether in Modified Membrane is 2~3%, and solvent is used Dimethyl sulfoxide (DMSO), mixture solution concentration is 25~30 g:100 ml.
CN201710362969.7A 2017-05-22 2017-05-22 A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with polypropylene glycol Withdrawn CN107011676A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103834180A (en) * 2014-03-04 2014-06-04 山东理工大学 Method for improving flexibility of polypeptide membrane by using polycaprolactone and polypropylene glycol
CN103865273A (en) * 2014-03-10 2014-06-18 山东理工大学 Method for improving flexibility of polypeptide membrane by polypropylene glycol and poly-trimethylene carbonate
CN104479157A (en) * 2015-01-06 2015-04-01 山东理工大学 Method for improving hydrophilia and flexibility of polypeptide membrane through polycaprolactone and polyethylene glycol
CN104559214A (en) * 2015-01-06 2015-04-29 山东理工大学 Method for improving hydrophily and flexibility of polypeptide membrane by polypropylene glycol and polyacrylic acid

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103834180A (en) * 2014-03-04 2014-06-04 山东理工大学 Method for improving flexibility of polypeptide membrane by using polycaprolactone and polypropylene glycol
CN103865273A (en) * 2014-03-10 2014-06-18 山东理工大学 Method for improving flexibility of polypeptide membrane by polypropylene glycol and poly-trimethylene carbonate
CN104479157A (en) * 2015-01-06 2015-04-01 山东理工大学 Method for improving hydrophilia and flexibility of polypeptide membrane through polycaprolactone and polyethylene glycol
CN104559214A (en) * 2015-01-06 2015-04-29 山东理工大学 Method for improving hydrophily and flexibility of polypeptide membrane by polypropylene glycol and polyacrylic acid

Non-Patent Citations (1)

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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: 20170804