CN106947260A - A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with PLA - Google Patents
A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with PLA Download PDFInfo
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- CN106947260A CN106947260A CN201710362575.1A CN201710362575A CN106947260A CN 106947260 A CN106947260 A CN 106947260A CN 201710362575 A CN201710362575 A CN 201710362575A CN 106947260 A CN106947260 A CN 106947260A
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- ppdo
- pla
- water resistance
- polyacrylic acid
- polypropylene sorrel
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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 that PPDO improves polypropylene sorrel water resistance and compliance with PLA, using following steps：1）The synthesis of polyacrylic acid PPDO graft copolymer：Add hydroxy-end capped PPDO list tridecyl ether, solvent, condensing agent and polyacrylic acid in dry reactor, stirring reaction 2~3 days, terminating reaction obtains object；2）The preparation of PPDO and polylactic acid modified polypropylene sorrel：Polyacrylic acid PPDO graft copolymer, PLA monododecyl 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.PPDO and poly-（D,L）Lactic acid is with excellent biocompatibility and life
The biomaterial of Biodegradable, with good hydrophobicity and compliance.PPDO segment is first introduced poly- third
Olefin(e) acid segment formation poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer, then again by polylactic acid chain segment add polyacrylic acid-
PPDO 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 method that PPDO improves polypropylene sorrel water resistance and compliance with PLA, it is characterised in that：
The molecular weight of polyacrylic acid segment is 81000~93000 in Modified Membrane, the molecular weight of PPDO segment for 2000~
2100, the molecular weight of polylactic acid chain segment is 5300~6100；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 list tridecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 25~29 DEG C of stirring reactions 2
~3 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation of PPDO and polylactic acid modified polypropylene sorrel：Polypropylene is added in dry reactor
Under acid-PPDO graft copolymer, PLA monododecyl ether and solvent, inert atmosphere, stirred in 45~50 DEG C
After mixing mixing 50~60 minutes, with the tape casting film forming and drying, object is obtained.
The method that a kind of described PPDO improves polypropylene sorrel water resistance and compliance with PLA, step
Rapid 1）In, the mol ratio of PPDO list tridecyl ether and polyacrylic acid is 15~25:1.
The method that a kind of described PPDO improves polypropylene sorrel water resistance and compliance with PLA, step
Rapid 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-（3- bis-
First aminopropyl）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.06~1.9:1, solvent uses dimethyl sulfoxide (DMSO), instead
It is 5~15 g to answer thing solution concentration:100 ml.
The method that a kind of described PPDO improves polypropylene sorrel water resistance and compliance with PLA, step
Rapid 2）In, PLA monododecyl ether is using poly-（D, Pfansteihl）Monododecyl ether, PLA monododecyl ether is changing
Property film in mass percent be 2~4%, solvent uses dimethyl sulfoxide (DMSO), and mixture solution concentration is 25~30 g:100 ml.
Compared with prior art, its advantage is the present invention：
1st, the method that a kind of described PPDO and PLA improve polypropylene sorrel water resistance and compliance, is used
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 8.8 grams
Cyclohexanone list tridecyl ether（Molecular weight is 2000）, 285 ml dimethyl sulfoxide (DMSO)s are added, 0.062 gram is addedN,N’- two rings
Under hexyl carbodiimide, inert atmosphere, in 25 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains mesh
Mark thing；
2）The preparation of PPDO and polylactic acid modified polypropylene sorrel
10.1 grams of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymers are added in dry reactor and 37 ml dimethyl are sub-
Sulfoxide solvent, it is another to add the PLA monododecyl ether for accounting for Modified Membrane gross weight 2%（Molecular weight is 5300）, under inert atmosphere, in
45 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
12.2 ° and 9.5%.
Embodiment 2
1）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer
21.1 grams of polyacrylic acid are added in dry reactor（Molecular weight is 85000）It is hydroxy-end capped poly- to dioxy with 9.9 grams
Cyclohexanone list tridecyl ether（Molecular weight is 2100）, 309 ml dimethyl sulfoxide (DMSO)s are added, 0.039 gram is addedN,N’- two is different
Under propyl group carbodiimide, inert atmosphere, in 27 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains mesh
Mark thing；
2）The preparation of PPDO and polylactic acid modified polypropylene sorrel
10 grams of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymers are added in dry reactor and 36.5 ml dimethyl are sub-
Sulfoxide solvent, it is another to add the PLA monododecyl ether for accounting for Modified Membrane gross weight 3%（Molecular weight is 5500）, under inert atmosphere, in
47 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
12.8 ° and 10.1%.
Embodiment 3
1）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer
22.6 grams of polyacrylic acid are added in dry reactor（Molecular weight is 93000）It is hydroxy-end capped poly- to dioxy with 9.3 grams
Cyclohexanone list tridecyl ether（Molecular weight is 2100）, 319 ml dimethyl sulfoxide (DMSO)s are added, 0.058 gram of 3- ethyls -1- is added
（3- dimethylaminopropyls）Under carbodiimide, inert atmosphere, in 29 DEG C of stirring reactions 2 days, terminating reaction, by filtering, dialysis, dry
It is dry, obtain object；
2）The preparation of PPDO and polylactic acid modified polypropylene sorrel
9.6 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 PLA monododecyl ether for accounting for Modified Membrane gross weight 4%（Molecular weight is 6100）, under inert atmosphere, in 50
DEG C stirring mixing 60 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
13.4 ° and 10.7%.
Claims (4)
1. a kind of method that PPDO improves polypropylene sorrel water resistance and compliance with PLA, its feature exists
In：The molecular weight of polyacrylic acid segment is 81000~93000 in Modified Membrane, and the molecular weight of PPDO segment is
2000~2100, the molecular weight of polylactic acid chain segment is 5300~6100；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 list tridecyl ether, solvent, condensing agent and polyacrylic acid, inert atmosphere, in 25~29 DEG C of stirring reactions 2
~3 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation of PPDO and polylactic acid modified polypropylene sorrel：Polypropylene is added in dry reactor
Under acid-PPDO graft copolymer, PLA monododecyl ether and solvent, inert atmosphere, stirred in 45~50 DEG C
After mixing mixing 50~60 minutes, with the tape casting film forming and drying, object is obtained.
2. a kind of PPDO according to claim 1 improves polypropylene sorrel water resistance and submissive with PLA
The method of property, it is characterised in that：Step 1）In, the mol ratio of PPDO list tridecyl ether and polyacrylic acid is 15
~25:1.
3. a kind of PPDO according to claim 1 improves polypropylene sorrel water resistance and submissive with PLA
The method of property, it is characterised in that：Step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl carbon
Diimine or 3- ethyls -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.06~1.9:
1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. a kind of PPDO according to claim 1 improves polypropylene sorrel water resistance and submissive with PLA
The method of property, it is characterised in that：Step 2）In, PLA monododecyl ether is using poly-（D, Pfansteihl）Monododecyl ether,
Mass percent of the PLA monododecyl ether in Modified Membrane is 2~4%, and solvent uses dimethyl sulfoxide (DMSO), mixture solution
Concentration is 25~30 g:100 ml.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710362575.1A CN106947260A (en) | 2017-05-22 | 2017-05-22 | A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with PLA |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710362575.1A CN106947260A (en) | 2017-05-22 | 2017-05-22 | A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with PLA |
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| Publication Number | Publication Date |
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| CN106947260A true CN106947260A (en) | 2017-07-14 |
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| CN201710362575.1A Withdrawn CN106947260A (en) | 2017-05-22 | 2017-05-22 | A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with PLA |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865275A (en) * | 2014-04-11 | 2014-06-18 | 山东理工大学 | Method for improving the water resistance of polyethylene glycol film modified by polylactic acid and polyvinyl alcohol |
| CN105542479A (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 poly(p-dioxanone) and poly lactic acid-glycolic acid |
| CN105566663A (en) * | 2016-03-07 | 2016-05-11 | 山东理工大学 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly (p-dioxanone) and P (CPP-SA)-polyethylene glycol |
-
2017
- 2017-05-22 CN CN201710362575.1A patent/CN106947260A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865275A (en) * | 2014-04-11 | 2014-06-18 | 山东理工大学 | Method for improving the water resistance of polyethylene glycol film modified by polylactic acid and polyvinyl alcohol |
| CN105542479A (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 poly(p-dioxanone) and poly lactic acid-glycolic acid |
| CN105566663A (en) * | 2016-03-07 | 2016-05-11 | 山东理工大学 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly (p-dioxanone) and P (CPP-SA)-polyethylene glycol |
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