CN107365465A - Polyvinylidene difluoride film materials - Google Patents
Polyvinylidene difluoride film materials Download PDFInfo
- Publication number
- CN107365465A CN107365465A CN201710557190.0A CN201710557190A CN107365465A CN 107365465 A CN107365465 A CN 107365465A CN 201710557190 A CN201710557190 A CN 201710557190A CN 107365465 A CN107365465 A CN 107365465A
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- CN
- China
- Prior art keywords
- polyvinylidene difluoride
- film materials
- difluoride film
- film
- antioxidant
- 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.)
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to the technical field of Kynoar, more particularly to a kind of polyvinylidene difluoride film materials.This polyvinylidene difluoride film materials, the weight percent composition of the materials are as follows：Kynoar 55 93%, titanium dioxide 0 35%, acrylate copolymer 5 40%, antioxidant 0.1 0.8%.The polymethyl methacrylate that this polyvinylidene difluoride film materials replace being commonly used using acrylate copolymer, greatly improve the ability of film article wet and heat ageing resistant, the film hydrothermal aging post yellowing that the material special for polyvinylidene fluoride film prepared using the present invention is produced is small, and transverse breakage percent retention of elongation is substantially improved.
Description
Technical field
It is easy to use blown film or casting film-forming the present invention relates to one kind, it is good to be made mechanical property, good weatherability, Gao Heng
To the polyvinylidene difluoride film of elongation at break conservation rate, more particularly to a kind of polyvinylidene difluoride film materials.
Background technology
Kynoar（PVDF）It is to be only second to polytetrafluoroethylene (PTFE)（PTFE）Fluororesin in second largest resin, be by inclined
The thermoplastic fluoroelastomer plastics that fluoride monomers homopolymerization or copolymerization form.Because it has excellent chemical resistance, weatherability, resistance to
The characteristic such as oxidisability and the radiativity of resistance to ray, while also possess good mechanical performance, therefore in solar battery back film etc.
Various fields, which are obtained for, to be widely applied.
But because PVDF costs are higher, easily by catalytic degradation when individually being processed with titanium dioxide, transverse breakage is stretched after film forming
The long low defect of rate, need to generally blending and modifying be carried out to it in process.Prior art generally uses polymethylacrylic acid
Methyl esters（PMMA）Blending and modifying is carried out to it, improves PVDF processing characteristics, and substantially increases the initial horizontal of finished films
To elongation at break.But due to the deficiency of PMMA itself wet and heat ageing resistant performances, the transverse breakage elongation of finished films is passing through
Go through wet and heat ageing resistant experiment（PCT）After can deep fades, make the risk that Transverse Cracks during it is long-term use of out of doors be present.
The content of the invention
A kind of present invention seek to address that drawbacks described above, there is provided polyvinylidene difluoride film materials.
In order to overcome defect present in background technology, the technical solution adopted for the present invention to solve the technical problems is：
This polyvinylidene difluoride film materials, the weight percent composition of the materials are as follows：Kynoar 55-93%, titanium dioxide 0-35%,
Acrylate copolymer 5-40%, antioxidant 0.1-0.8%.
According to another embodiment of the invention, the molecular weight for further comprising the Kynoar is 10-80 ten thousand.
According to another embodiment of the invention, it is rutile type titanium white to further comprise the titanium dioxide, average grain
Footpath is 0.05-0.8 microns.
According to another embodiment of the invention, further comprise that described acrylate copolymer is methyl methacrylate
The copolymer of two or more monomer in ester, acrylate, organosilicon.
According to another embodiment of the invention, further comprise the antioxidant for Hinered phenols antioxidant, monothioester
The combination of one or both of kind antioxidant or phosphite ester kind antioxidant compounding.
The beneficial effects of the invention are as follows：This polyvinylidene difluoride film materials are replaced general at present using acrylate copolymer
All over the polymethyl methacrylate used, the ability of film article wet and heat ageing resistant is greatly improved, is prepared using the present invention
The film hydrothermal aging post yellowing of material special for polyvinylidene fluoride film production is small, and transverse breakage percent retention of elongation is substantially improved.
Embodiment
The weight percent composition of this polyvinylidene difluoride film materials is as follows：Kynoar 55-93%, titanium dioxide 0-
35%, acrylate copolymer 5-40%, antioxidant 0.1-0.8%.
The molecular weight of Kynoar is 10-80 ten thousand.
Titanium dioxide is rutile type titanium white, and average grain diameter is 0.05-0.8 microns.
Acrylate copolymer is two or more monomer in methyl methacrylate, acrylate, organosilicon
Copolymer.
Antioxidant is one or both of Hinered phenols antioxidant, monothioester kind antioxidant or phosphite ester kind antioxidant
The combination of compounding.
Embodiment
The formula of embodiment is referring to table 1.
The raw material wherein used is described as follows：
Fluoroethylene resin（PVDF）：Solef 6008, supplier are：Su Wei companies of the U.S..
Titanium dioxide（TiO2）：R-104, supplier are：Du pont company.
Methyl methacrylate（PMMA）：CM-207, supplier are：Zhenjiang Qi Mei companies.
Acrylate copolymer：S-2100, supplier are：Mitsubishi chemistry
Antioxidant：Antioxidant 1076, irgasfos 168, supplier are：BASF Aktiengesellschaft.
The comparative example of table 1 and embodiment list of ingredients
| Material name | Comparative example | Embodiment 1 | Embodiment 2 |
| PVDF 6008 | 69.7 | 69.7 | 79.7 |
| Titanium dioxide R-104 | 15 | 15 | 0 |
| PMMA CM-207 | 15 | 0 | 0 |
| S-2100 | 0 | 15 | 20 |
| Antioxidant 1076 | 0.1 | 0.1 | 0.1 |
| Irgasfos 168 | 0.2 | 0.2 | 0.2 |
Weigh PVDF, titanium dioxide, PMMA, acrylate copolymer, the antioxidant of corresponding ratio respectively according to formula table 1 Suo Shi
1076th, irgasfos 168, high speed dispersor mixing is added to, mixing speed 700r/min, mixing time is 20 minutes, is obtained
Uniform compound.Obtained uniform compound is added into double screw extruder and carries out plastifying fusion extrusion, melting extrusion temperature 205
DEG C, screw speed 400r/min, material special for polyvinylidene fluoride film is obtained after pelletizing.
Obtained material special for polyvinylidene fluoride film is dried 2 hours under the conditions of 105 DEG C, and squeezed under the conditions of 220 DEG C
Go out to be cast into 25 micron thickness films.Then by ASTM D882 standards to certain PCT ageing times（PCT aging conditions：121
DEG C, 2atm, 100%RH）Front and rear film batten carries out extension test, by ASTM E313-05 standards to PCT agings（PCT agings
Condition：121 DEG C, 2atm, 100%RH, 96 hours）Front and rear film batten carries out xanthochromia test, as a result as shown in table 2.
The comparative example of table 2 and embodiment the performance test results
| Test event | Comparative example | Embodiment 1 | Embodiment 2 |
| Transverse breakage elongation, %（Before PCT） | 571.5 | 437 | 495 |
| Transverse breakage elongation, %（After PCT48H） | 10 | 245 | 176 |
| Transverse breakage elongation, %（After PCT96H） | 8.5 | 387 | 453 |
| Yellowness index Δ b（After PCT96H） | 2.2 | 0.6 | 0.5 |
Compare comparative example and embodiment can be seen that using polyvinylidene difluoride film prepared by PP Pipe Compound of the present invention in PCT agings
Transverse breakage elongation is substantially improved afterwards, and xanthochromia also decreases, and significantly improves the wet and heat ageing resistant of polyvinylidene difluoride film
Performance, solve the problems, such as transverse breakage elongation deep fades after the PCT agings that current PVDF thin film generally faces, reduce family
The risk of outer long-term use of Transverse Cracks.
Claims (5)
- A kind of 1. polyvinylidene difluoride film materials, it is characterised in that：The weight percent composition of the materials is as follows：Kynoar 55-93%, titanium dioxide 0-35%, acrylate copolymer 5-40%, antioxidant 0.1-0.8%.
- 2. polyvinylidene difluoride film materials as claimed in claim 1, it is characterised in that：The molecular weight of the Kynoar is 10-80 ten thousand.
- 3. polyvinylidene difluoride film materials as claimed in claim 1, it is characterised in that：The titanium dioxide is rutile titanium dioxide Powder, average grain diameter are 0.05-0.8 microns.
- 4. polyvinylidene difluoride film materials as claimed in claim 1, it is characterised in that：Described acrylate copolymer is first The copolymer of two or more monomer in base methyl acrylate, acrylate, organosilicon.
- 5. polyvinylidene difluoride film materials as claimed in claim 1, it is characterised in that：The antioxidant is Hinered phenols antioxygen The combination of one or both of agent, monothioester kind antioxidant or phosphite ester kind antioxidant compounding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710557190.0A CN107365465A (en) | 2017-07-10 | 2017-07-10 | Polyvinylidene difluoride film materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710557190.0A CN107365465A (en) | 2017-07-10 | 2017-07-10 | Polyvinylidene difluoride film materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107365465A true CN107365465A (en) | 2017-11-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710557190.0A Pending CN107365465A (en) | 2017-07-10 | 2017-07-10 | Polyvinylidene difluoride film materials |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696309A (en) * | 2009-10-13 | 2010-04-21 | 常熟市冠日新材料有限公司 | Fluorine-contained film and preparation method thereof |
| CN101964371A (en) * | 2010-09-02 | 2011-02-02 | 常熟市冠日新材料有限公司 | Insulating back plate for novel solar cell |
| CN102311595A (en) * | 2010-07-02 | 2012-01-11 | 沈辉 | Fluorine-containing membrane applied to photovoltaic industry |
| CN102432963A (en) * | 2011-08-17 | 2012-05-02 | 常州荣晟新材料科技有限公司 | Fluorinated weather-resistant film for solar photovoltaic battery back plate and preparation method of fluorinated weather-resistant film |
| CN103965708A (en) * | 2014-04-04 | 2014-08-06 | 赤壁市雄意达涂料有限公司 | Fluorocarbon finish and preparation method thereof |
-
2017
- 2017-07-10 CN CN201710557190.0A patent/CN107365465A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696309A (en) * | 2009-10-13 | 2010-04-21 | 常熟市冠日新材料有限公司 | Fluorine-contained film and preparation method thereof |
| CN102311595A (en) * | 2010-07-02 | 2012-01-11 | 沈辉 | Fluorine-containing membrane applied to photovoltaic industry |
| CN101964371A (en) * | 2010-09-02 | 2011-02-02 | 常熟市冠日新材料有限公司 | Insulating back plate for novel solar cell |
| CN102432963A (en) * | 2011-08-17 | 2012-05-02 | 常州荣晟新材料科技有限公司 | Fluorinated weather-resistant film for solar photovoltaic battery back plate and preparation method of fluorinated weather-resistant film |
| CN103965708A (en) * | 2014-04-04 | 2014-08-06 | 赤壁市雄意达涂料有限公司 | Fluorocarbon finish and preparation method thereof |
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Application publication date: 20171121 |