CN107011666A - A kind of method being improved with polycaprolactone and PPDO to polypropylene sorrel water resistance and compliance - Google Patents
A kind of method being improved with polycaprolactone and PPDO to polypropylene sorrel water resistance and compliance Download PDFInfo
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- CN107011666A CN107011666A CN201710362561.XA CN201710362561A CN107011666A CN 107011666 A CN107011666 A CN 107011666A CN 201710362561 A CN201710362561 A CN 201710362561A CN 107011666 A CN107011666 A CN 107011666A
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- ppdo
- polycaprolactone
- water resistance
- polyacrylic 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
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- 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
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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
- 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
- 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
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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
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- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
The present invention discloses a kind of method being improved with polycaprolactone and PPDO to polypropylene sorrel water resistance and compliance, using following steps：1）The synthesis of polyacrylic acid PPDO graft copolymer：Add hydroxy-end capped PPDO monododecyl ether, solvent, condensing agent and polyacrylic acid in dry reactor, stirring reaction 2~3 days, terminating reaction obtains object；2）The preparation for the polypropylene sorrel that polycaprolactone is modified with PPDO：Polyacrylic acid PPDO graft copolymer, polycaprolactone list tridecyl 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
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 PPDO are can with excellent biocompatibility and biology
The biomaterial of degradability, with good hydrophobicity and compliance.PPDO segment is first introduced into polyacrylic acid
Segment formation poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer, then adds poly acrylic acid-poly by polycaprolactone segment again
Lanthanum Isopropoxide graft copolymer formation blend, is made modified polypropene sorrel, so as to drastically increase polyacrylic acid
The water resistance and compliance of film.
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 polycaprolactone and PPDO to polypropylene sorrel water resistance and compliance, its
It is characterised by：The molecular weight of polyacrylic acid segment is 81000~92000, the molecule of PPDO segment in Modified Membrane
Measure as 2100~2200, the molecular weight of polycaprolactone segment is 4700~5300；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer：Hydroxy-end capped gather is added in dry reactor
Under Lanthanum Isopropoxide monododecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 27~33 DEG C of stirring reactions 2
~3 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation for the polypropylene sorrel that polycaprolactone is modified with PPDO：Polypropylene is added in dry reactor
Under acid-PPDO graft copolymer, polycaprolactone list tridecyl ether and solvent, inert atmosphere, in 46~51 DEG C
After stirring mixing 50~60 minutes, with the tape casting film forming and drying, object is obtained.
Described one kind is changed with polycaprolactone with PPDO to polypropylene sorrel water resistance and compliance
The method entered, step 1）In, the mol ratio of PPDO monododecyl ether and polyacrylic acid is 15~25:1.
Described one kind is changed with polycaprolactone with PPDO to polypropylene sorrel water resistance and compliance
The method entered, step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- second
Base -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.07~1.9:1, solvent uses two
Methyl sulfoxide, reactant solution concentration is 5~15 g:100 ml.
Described one kind is changed with polycaprolactone with PPDO to polypropylene sorrel water resistance and compliance
The method entered, step 2）In, mass percent of the polycaprolactone list tridecyl ether in Modified Membrane is 2~3%, and solvent is used
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 is improved with polycaprolactone and PPDO to polypropylene sorrel water resistance and compliance
Method, 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 Lanthanum Isopropoxide graft copolymer
19.4 grams of polyacrylic acid are added in dry reactor（Molecular weight is 81000）It is hydroxy-end capped poly- to dioxy with 9.4 grams
Cyclohexanone monododecyl ether（Molecular weight is 2100）, 288 ml dimethyl sulfoxide (DMSO)s are added, 0.061 gram is addedN,N’- two rings
Under hexyl carbodiimide, inert atmosphere, in 27 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains mesh
Mark thing；
2）The preparation for the polypropylene sorrel that polycaprolactone is modified with PPDO
10 grams of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymers and 37 ml dimethyl sulfoxide (DMSO)s are added in dry reactor
Solvent, it is another to add the polycaprolactone list tridecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 4700）, under inert atmosphere, in
46 DEG C of stirrings are mixed 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
12.3 ° and 9.5%.
Embodiment 2
1）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer
21 grams of polyacrylic acid are added in dry reactor（Molecular weight is 85000）It is hydroxy-end capped poly- to dioxy ring with 9.8 grams
Hexanone monododecyl ether（Molecular weight is 2100）, 308 ml dimethyl sulfoxide (DMSO)s are added, 0.039 gram is addedN,N’- diisopropyl
Under base carbodiimide, inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains target
Thing；
2）The preparation for the polypropylene sorrel that polycaprolactone is modified with PPDO
10.1 grams of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymers and 36.5 ml dimethyl are added in dry reactor
Sulfoxide solvent, it is another to add the polycaprolactone list tridecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 5000）, inert atmosphere
Under, mixed 55 minutes in 48 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
12.8 ° and 9.9%.
Embodiment 3
1）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer
22.5 grams of polyacrylic acid are added in dry reactor（Molecular weight is 92000）It is hydroxy-end capped poly- to dioxy with 10.2 grams
Cyclohexanone monododecyl ether（Molecular weight is 2200）, 323 ml dimethyl sulfoxide (DMSO)s are added, 0.058 gram of 3- ethyls -1- is added
（3- dimethylaminopropyls）Under carbodiimide, inert atmosphere, in 33 DEG C of stirring reactions 2 days, terminating reaction, by filtering, dialysis, dry
It is dry, obtain object；
2）The preparation for the polypropylene sorrel that polycaprolactone is modified with PPDO
9.5 grams of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymers and 35 ml dimethyl sulfoxide (DMSO)s are added in dry reactor
Solvent, it is another to add the polycaprolactone list tridecyl ether for accounting for Modified Membrane gross weight 3%（Molecular weight is 5300）, under inert atmosphere, in
51 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
13.3 ° and 10.5%.
Claims (4)
1. a kind of method being improved with polycaprolactone and PPDO to polypropylene sorrel water resistance and compliance,
It is characterized in that：The molecular weight of polyacrylic acid segment is 81000~92000 in Modified Membrane, point of PPDO segment
Son amount is 2100~2200, and the molecular weight of polycaprolactone segment is 4700~5300；Its method of modifying uses following steps：
1）The synthesis of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer：Hydroxy-end capped gather is added in dry reactor
Under Lanthanum Isopropoxide monododecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 27~33 DEG C of stirring reactions 2
~3 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation for the polypropylene sorrel that polycaprolactone is modified with PPDO：Polypropylene is added in dry reactor
Under acid-PPDO graft copolymer, polycaprolactone list tridecyl ether and solvent, inert atmosphere, in 46~51 DEG C
After stirring mixing 50~60 minutes, with the tape casting film forming and drying, object is obtained.
2. one kind polycaprolactone according to claim 1 and PPDO are to polypropylene sorrel water resistance and soft
The pliable method being improved, it is characterised in that：Step 1）In, PPDO monododecyl ether and polyacrylic acid
Mol ratio is 15~25:1.
3. one kind polycaprolactone according to claim 1 and PPDO are to polypropylene sorrel water resistance and soft
The pliable method being 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 is
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 and PPDO are to polypropylene sorrel water resistance and soft
The pliable method being improved, it is characterised in that：Step 2）In, quality hundred of the polycaprolactone list tridecyl ether in Modified Membrane
Divide than being 2~3%, solvent uses dimethyl sulfoxide (DMSO), mixture solution concentration is 25~30 g:100 ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710362561.XA CN107011666A (en) | 2017-05-22 | 2017-05-22 | A kind of method being improved with polycaprolactone and PPDO to polypropylene sorrel water resistance and compliance |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710362561.XA CN107011666A (en) | 2017-05-22 | 2017-05-22 | A kind of method being improved with polycaprolactone and PPDO to polypropylene sorrel water resistance and compliance |
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| Publication Number | Publication Date |
|---|---|
| CN107011666A true CN107011666A (en) | 2017-08-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710362561.XA Withdrawn CN107011666A (en) | 2017-05-22 | 2017-05-22 | A kind of method being improved with polycaprolactone and PPDO to polypropylene sorrel water resistance and compliance |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105542208A (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 polycaprolactone and poly(p-dioxanone) |
| CN105585852A (en) * | 2016-03-16 | 2016-05-18 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film through polycaprolactone and poly(p-dioxanone) |
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2017
- 2017-05-22 CN CN201710362561.XA patent/CN107011666A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105542208A (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 polycaprolactone and poly(p-dioxanone) |
| CN105585852A (en) * | 2016-03-16 | 2016-05-18 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film through polycaprolactone and poly(p-dioxanone) |
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