CN106987126A - One kind polycaprolactone is with gathering（Lactide glycolide）The method being improved to polypropylene sorrel water resistance and compliance - Google Patents

One kind polycaprolactone is with gathering（Lactide glycolide）The method being improved to polypropylene sorrel water resistance and compliance Download PDF

Info

Publication number
CN106987126A
CN106987126A CN201710362584.0A CN201710362584A CN106987126A CN 106987126 A CN106987126 A CN 106987126A CN 201710362584 A CN201710362584 A CN 201710362584A CN 106987126 A CN106987126 A CN 106987126A
Authority
CN
China
Prior art keywords
polycaprolactone
lactide
gathering
lactide coglycolide
compliance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201710362584.0A
Other languages
Chinese (zh)
Inventor
林治涛
朱国全
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong University of Technology
Original Assignee
Shandong University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong University of Technology filed Critical Shandong University of Technology
Priority to CN201710362584.0A priority Critical patent/CN106987126A/en
Publication of CN106987126A publication Critical patent/CN106987126A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00—Compositions for preparing biodegradable polymers
    • 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
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • 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

Landscapes

  • 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 one kind polycaprolactone with gathering（Lactide glycolide）The method being improved to 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）Polycaprolactone is with gathering（Lactide glycolide）The preparation of modified polypropylene sorrel：Polyacrylic acid is added in dry reactor to gather（Lactide glycolide）Graft copolymer, polycaprolactone list tridecyl ether 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

One kind polycaprolactone is with gathering（Lactide coglycolide）To polypropylene sorrel water resistance And the method that compliance is improved
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 poly-（D, L- lactide coglycolide）（The weight ratio of lactide and glycolide For 90/10）It is the biomaterial with excellent biocompatibility and biodegradability, with good hydrophobicity and submissive Property.First will be poly-（Lactide coglycolide）Segment introduces polyacrylic acid segment formation poly acrylic acid-poly（Lactide coglycolide）Connect Graft copolymer, then adds poly acrylic acid-poly by polycaprolactone segment again（Lactide coglycolide）Graft copolymer formation blending Thing, is made modified polypropene sorrel, 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：
One kind polycaprolactone is with gathering（Lactide coglycolide）The side being improved to polypropylene sorrel water resistance and compliance Method, it is characterised in that：The molecular weight of polyacrylic acid segment is 83000~91000 in Modified Membrane, is gathered（Lactide coglycolide）Chain The molecular weight of section is 2100~2400, and the molecular weight of polycaprolactone segment is 4800~5500；Its method of modifying uses following step Suddenly：
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）Polycaprolactone is with gathering（Lactide coglycolide）The preparation of modified polypropylene sorrel：Added in dry reactor poly- Acrylic acid-poly-（Lactide coglycolide）Under graft copolymer, polycaprolactone list tridecyl ether and solvent, inert atmosphere, in 47 After~52 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, object is obtained.
Described one kind polycaprolactone is with gathering（Lactide coglycolide）Polypropylene sorrel water resistance and compliance are carried out Improved method, step 1）In, gather（Lactide coglycolide）Monododecyl ether is using poly-（D, L- lactide coglycolide）It is single Lauryl ether（The weight ratio of lactide and glycolide is 90/10）, gather（Lactide coglycolide）Monododecyl ether and poly- third The mol ratio of olefin(e) acid is 15~25:1.
Described one kind polycaprolactone is with gathering（Lactide coglycolide）Polypropylene sorrel water resistance and compliance are carried out Improved method, step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- Ethyl -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.07~1.9:1, solvent is used Dimethyl sulfoxide (DMSO), reactant solution concentration is 5~15 g:100 ml.
Described one kind polycaprolactone is with gathering（Lactide coglycolide）Polypropylene sorrel water resistance and compliance are carried out Improved method, step 2）In, mass percent of the polycaprolactone list tridecyl ether in Modified Membrane is 2~3%, and solvent is adopted With dimethyl sulfoxide (DMSO), mixture solution concentration is 25~30 g:100 ml.
Compared with prior art, its advantage is the present invention：
1st, described one kind polycaprolactone is with gathering（Lactide coglycolide）Polypropylene sorrel water resistance and compliance are changed The method entered, 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
20.4 grams of polyacrylic acid are added in dry reactor（Molecular weight is 83000）It is hydroxy-end capped poly- with 9.5 grams（Third hands over Ester-glycolide）Monododecyl ether（Molecular weight is 2100）, 296 ml dimethyl sulfoxide (DMSO)s are added, 0.063 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）Polycaprolactone is with gathering（Lactide coglycolide）The preparation of modified polypropylene sorrel
9.9 grams of poly acrylic acid-polies are added in dry reactor（Lactide coglycolide）Graft copolymer and 37 ml dimethyl Sulfoxide solvent, it is another to add the polycaprolactone list tridecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 4800）, inert atmosphere Under, mixed 50 minutes in 47 DEG C of stirrings, 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 9.5%.
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 10.3 grams（Lactide- Glycolide）Monododecyl ether（Molecular weight is 2200）, 311 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）Polycaprolactone 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 polycaprolactone list tridecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 5200）, indifferent gas Under atmosphere, mixed 55 minutes in 49 DEG C of stirrings, 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 10.2%.
Embodiment 3
1）Poly acrylic acid-poly（Lactide coglycolide）The preparation of graft copolymer
22.2 grams of polyacrylic acid are added in dry reactor（Molecular weight is 91000）It is hydroxy-end capped poly- with 10.9 grams（Third hands over Ester-glycolide）Monododecyl ether（Molecular weight is 2400）, 328 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）Polycaprolactone is with gathering（Lactide coglycolide）The preparation of modified polypropylene sorrel
9.5 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 polycaprolactone list tridecyl ether for accounting for Modified Membrane gross weight 3%（Molecular weight is 5500）, inert atmosphere Under, mixed 60 minutes in 52 DEG C of stirrings, 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 12.9 ° and 10.7%.

Claims (4)

1. one kind polycaprolactone is with gathering（Lactide coglycolide）The side being improved to polypropylene sorrel water resistance and compliance Method, it is characterised in that：The molecular weight of polyacrylic acid segment is 83000~91000 in Modified Membrane, is gathered（Lactide coglycolide）Chain The molecular weight of section is 2100~2400, and the molecular weight of polycaprolactone segment is 4800~5500；Its method of modifying uses following step Suddenly：
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）Polycaprolactone is with gathering（Lactide coglycolide）The preparation of modified polypropylene sorrel：Added in dry reactor poly- Acrylic acid-poly-（Lactide coglycolide）Under graft copolymer, polycaprolactone list tridecyl ether and solvent, inert atmosphere, in 47 After~52 DEG C of stirrings are mixed 50~60 minutes, with the tape casting film forming and drying, object is obtained.
2. one kind polycaprolactone according to claim 1 is with gathering（Lactide coglycolide）To polypropylene sorrel water resistance And the method that compliance is improved, it is characterised in that：Step 1）In, gather（Lactide coglycolide）Monododecyl ether is used It is poly-（D, L- lactide coglycolide）Monododecyl ether（The weight ratio of lactide and glycolide is 90/10）, gather（Lactide-second Lactide）The mol ratio of monododecyl ether and polyacrylic acid is 15~25:1.
3. one kind polycaprolactone according to claim 1 is with gathering（Lactide coglycolide）To polypropylene sorrel water resistance And the method that compliance is improved, it is characterised in that：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 For 1.07~1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. one kind polycaprolactone according to claim 1 is with gathering（Lactide coglycolide）To polypropylene sorrel water resistance And the method that compliance is improved, it is characterised in that：Step 2）In, matter of the polycaprolactone list tridecyl ether in Modified Membrane It is 2~3% to measure percentage, and solvent uses dimethyl sulfoxide (DMSO), and mixture solution concentration is 25~30 g:100 ml.
CN201710362584.0A 2017-05-22 2017-05-22 One kind polycaprolactone is with gathering（Lactide glycolide）The method being improved to polypropylene sorrel water resistance and compliance Withdrawn CN106987126A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710362584.0A CN106987126A (en) 2017-05-22 2017-05-22 One kind polycaprolactone is with gathering（Lactide glycolide）The method being improved to polypropylene sorrel water resistance and compliance

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710362584.0A CN106987126A (en) 2017-05-22 2017-05-22 One kind polycaprolactone is with gathering（Lactide glycolide）The method being improved to polypropylene sorrel water resistance and compliance

Publications (1)

Publication Number Publication Date
CN106987126A true CN106987126A (en) 2017-07-28

Family

ID=59420484

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710362584.0A Withdrawn CN106987126A (en) 2017-05-22 2017-05-22 One kind polycaprolactone is with gathering（Lactide glycolide）The method being improved to polypropylene sorrel water resistance and compliance

Country Status (1)

Country Link
CN (1) CN106987126A (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103865091A (en) * 2014-03-24 2014-06-18 山东理工大学 Method for improving water resisting performance of polyvinyl alcohol film from polycaprolactone and polylactic acid

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103865091A (en) * 2014-03-24 2014-06-18 山东理工大学 Method for improving water resisting performance of polyvinyl alcohol film from polycaprolactone and polylactic acid

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）》 *

Similar Documents

Publication Publication Date Title
CN106987126A (en) One kind polycaprolactone is with gathering（Lactide glycolide）The method being improved to polypropylene sorrel water resistance and compliance
CN106977936A (en) A kind of polycaprolactone is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance
CN106977937A (en) A kind of MPEGPLA is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance
CN106977954A (en) A kind of method that MPEGPLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance
CN107118567A (en) A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with polylactide
CN106977939A (en) A kind of method being improved with PTMC and PPDO to polypropylene sorrel water resistance and compliance
CN107011666A (en) A kind of method being improved with polycaprolactone and PPDO to polypropylene sorrel water resistance and compliance
CN106977951A (en) A kind of method that poly (lactic acid-glycolic acid) is improved with polycaprolactone to polypropylene sorrel water resistance and compliance
CN106987135A (en) A kind of method that poly (lactic acid-glycolic acid) is improved with PPDO to polypropylene sorrel water resistance and compliance
CN107011672A (en) A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with polycaprolactone
CN107011676A (en) A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with polypropylene glycol
CN106987129A (en) A kind of MPEGPLA is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance
CN106977941A (en) A kind of method being improved with PPDO and poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance
CN107118564A (en) A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PLA
CN106947263A (en) A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid)
CN106977942A (en) A kind of MPEGPLA is with gathering（Lactide glycolide）Improve the method for polypropylene sorrel water resistance and compliance
CN106977938A (en) A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polypropylene glycol
CN107011673A (en) A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with PPDO
CN106977934A (en) A kind of method being improved with condensing model and PLA to polypropylene sorrel water resistance and compliance
CN107011680A (en) A kind of method that polycaprolactone is improved with PTMC to polypropylene sorrel water resistance and compliance
CN107011665A (en) A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with polycaprolactone
CN107011675A (en) A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with poly (lactic acid-glycolic acid)
CN106977935A (en) A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with polypropylene glycol
CN106947266A (en) A kind of method that polypropylene glycol improves polypropylene sorrel water resistance and compliance with polycaprolactone
CN106977940A (en) A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with PLA

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20170728