CN109206801A - A kind of polyvinylidene difluoride film and preparation method thereof - Google Patents
A kind of polyvinylidene difluoride film and preparation method thereof Download PDFInfo
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- CN109206801A CN109206801A CN201811129218.1A CN201811129218A CN109206801A CN 109206801 A CN109206801 A CN 109206801A CN 201811129218 A CN201811129218 A CN 201811129218A CN 109206801 A CN109206801 A CN 109206801A
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—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
- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- 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
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
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- 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
- C08K5/00—Use of organic ingredients
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention relates to a kind of polyvinylidene difluoride film and preparation method thereof, formula composition includes the component of following parts by weight: Kynoar, and 60-80 parts；Styrene be 5~10 parts, 5~10 parts of plasticizer, 1-3 parts of stabilizer, antioxidant: 1~5 part；1~10 part of reinforcing agent；Compared with prior art, which not only has excellent weatherability, barrier properties for gases, waterproofness, and degradation, xanthochromia are not susceptible to after irradiating in short term by sunlight, has excellent UV resistance；When preparing the polyvinylidene difluoride film by using double-axes fensile work, so that the carbon fluorine structure unit regularity inside film improves, transparency and mechanical property increase, and thickness is uniform.
Description
Technical field
The present invention relates to a kind of polyvinylidene difluoride films and preparation method thereof.
Background technique
Kynoar (referred to as PVDF) is important a member in fluoroplastics family, steady due to its chemical structure C-F key
Qualitative and higher crystallinity, polyvinylidene fluoride material has the ability of excellent resistance ultraviolet damage, and chemically-resistant is rotten
Erosion has lower water vapor transmittance, currently as Weatherproof ageing-resistant protective film in photovoltaic industry, building trade, change
Work field etc. is widely applied.PVDF thin film is usually placed in the outer surface of required guard block in use, straight with air
Contact, and receive the irradiation of sunlight.Meanwhile the combination of PVDF thin film and component is usually bonded by glue, i.e., in film
Surface coats one layer of glue in advance, then with protected adhering components.Therefore, for the performance requirement of PVDF thin film are as follows: interior
Surface has good adhesive property, and film should have good weatherability to support anti-ultraviolet destruction at the same time.
The performances such as weatherability, barrier properties for gases and the mechanical strength of existing polyvinylidene difluoride film are poor, this be
Become fragile when preparation due to adding other substances meeting film, is hygroscopic, and degradation, xanthochromia occurs after irradiating in short term by sunlight
Deng promoting material property to deteriorate.Therefore, high performance PVDF thin film requires import at present, and most of pvdf membranes are still adopted
With traditional blow molding, preparation is mass produced in the method for curtain coating and pressing mold, is unable to satisfy with social development in science and technology and is increasingly increased
Long material performance requirement.
In view of the above technical problems, it therefore needs to improve.
Summary of the invention
The present invention is to provide a kind of superior weatherability, barrier properties for gases to overcome above-mentioned defect in the prior art
And mechanical strength, while there is the high grade of transparency, polyvinylidene difluoride film in homogeneous thickness and preparation method thereof.
In order to reach the goals above, the technical scheme adopted by the invention is that: a kind of polyvinylidene difluoride film, formula group
At the component including following parts by weight: Kynoar, 60-80 parts；Styrene is 5~10 parts, 5~10 parts of plasticizer, is stablized
1-3 parts of agent, antioxidant: 1~5 part；1~10 part of reinforcing agent.
As a preferred solution of the present invention, formula composition includes the component of following parts by weight: Kynoar,
65-75 parts；Styrene be 6~9 parts, 7~8 parts of plasticizer, 1-2 parts of stabilizer, antioxidant: 1~3 part；1~5 part of reinforcing agent.
As a preferred solution of the present invention, the plasticizer includes DOP plasticizer and ESO plasticizer, DOP plasticizer
Weight ratio with ESO plasticizer is 3:2.
As a preferred solution of the present invention, the stabilizer is barium zinc stabilizer.
As a preferred solution of the present invention, the reinforcing agent includes xylene resin RX-80.
As a preferred solution of the present invention, the antioxidant is divided into primary antioxidant and auxiliary anti-oxidant, weight ratio 2:
3, the primary antioxidant is one of Hinered phenols and sulphur ester antioxidant；Auxiliary anti-oxidant is phosphorous acid salt and phosphite ester
One of kind antioxidant.
As a preferred solution of the present invention, the resistance to compression agent includes aramid fiber or Fanglun slurry cake.
A kind of preparation method of the polyvinylidene difluoride film, comprising the following steps:
Step (1), by Kynoar, 60-80 parts；Styrene is 5~10 parts, antioxidant: 1~5 part；1~10 part of reinforcing agent,
5~10 parts of plasticizer, 1-3 parts of stabilizer are separately added into mechanical mixture in high-speed mixer；
Mixture in step (1) is put into double screw extruder and is melted, disperses and extruding pelletization: obtained by step (2)
Raw material particle；
Step (3), by raw material particle be placed in it is quiet under room temperature thin-film material uniformly tiled on glass panels, stand 2h
~3h；After drying, master batch is formed；
Master batch will be added in single screw extrusion machine after melting at 200~230 DEG C by step (4), via film mouth mold, be led to
Cross the molding of curtain coating stretching device, and by film after 150 DEG C of heat treatment shaping through overstretching, cooling and shaping, trimming winding,
To obtain polyvinylidene difluoride film.
As a preferred solution of the present invention, styrene described in above-mentioned preparation process is 24 parts.
As a preferred solution of the present invention, Kynoar described in above-mentioned preparation process is 65 parts.
The beneficial effects of the present invention are:
1. compared with prior art, which not only has excellent weatherability, barrier properties for gases, waterproofness,
And degradation, xanthochromia are not susceptible to after irradiating in short term by sunlight, there is excellent UV resistance；Gather inclined fluorine preparing this
By using double-axes fensile work when vinyl film so that the carbon fluorine structure unit regularity inside film improves, transparency and
Mechanical property increases, and thickness is uniform；
2. it is in use that the polyvinylidene difluoride film material that preparation method of the present invention is prepared overcomes conventional thin-film material
The shortcomings that generation, light transmittance have reached 93% to 96%, and other than light transmittance, polyvinylidene difluoride film material of the invention also has
Stronger ageing-resistant performance；
3. preparation process of the present invention is simple, at low cost, it is conducive to industrialized production.
Specific embodiment
It elaborates below to the embodiment of the present invention.
Embodiment 1: a kind of polyvinylidene difluoride film, formula composition include the component of following parts by weight: Kynoar
62 parts；Styrene is 10 parts, 10 parts of plasticizer, 3 parts of stabilizer, 5 parts of antioxidant；10 parts of reinforcing agent.
Plasticizer includes DOP plasticizer and ESO plasticizer, and the weight ratio of DOP plasticizer and ESO plasticizer is 3:2；Significantly
Enhance the translucency of film entirety of the invention, it is ensured that its fluorescent brightness.
Stabilizer is barium zinc stabilizer, improves the stability of film entirety, increases compound fastness degree.
Reinforcing agent includes xylene resin RX-80, greatly strengthens tensile strength of the invention.
Antioxidant is divided into primary antioxidant and auxiliary anti-oxidant, and weight ratio is 2:3, the primary antioxidant be selected from Hinered phenols and
One of sulphur ester antioxidant, preferably main anti-oxidant are 1010；Auxiliary anti-oxidant agent is selected from phosphorous acid salt and phosphite ester
One of kind antioxidant, preferably auxiliary antioxidant are 168.
Resistance to compression agent includes aramid fiber or Fanglun slurry cake.
A kind of preparation method of polyvinylidene difluoride film, comprising the following steps:
Step 1, by 62 parts of Kynoar, styrene is 10 parts, 10 parts of plasticizer, 3 parts of stabilizer, 5 parts of antioxidant；Reinforcing agent
10 parts are separately added into mechanical mixture in high-speed mixer；
Step 2, the mixture in step 1 is put into double screw extruder to be melted, disperse and extruding pelletization: obtains former material
Expect particle；
Step 3, by raw material particle be placed in it is quiet under room temperature thin-film material uniformly tiled on glass panels, stand 2h~
3h；After drying, master batch is formed；
Step 4, master batch will be added in single screw extrusion machine after being melted at 200~230 DEG C, via film mouth mold, will be passed through
The molding of casting and stretching device, and by film after 150 DEG C of heat treatment shaping through overstretching, cooling and shaping, trimming winding, from
And obtain polyvinylidene difluoride film.
Embodiment 2:
The present embodiment content and 1 content of embodiment are essentially identical, and same section content is not repeating, unlike the first embodiment:
In the present embodiment formula composition by following parts by weight component:
70 parts of Kynoar；
Styrene is 8 parts,
8 parts of plasticizer,
4 parts of stabilizer,
5 parts of antioxidant；
5 parts of reinforcing agent.
A kind of preparation method of polyvinylidene difluoride film, comprising the following steps:
Step 1, by 70 parts of Kynoar, styrene is 8 parts, 8 parts of plasticizer, 4 parts of stabilizer, and 5 parts of antioxidant, reinforcing agent 5
Part is separately added into mechanical mixture in high-speed mixer；
Step 2, the mixture in step 1 is put into double screw extruder to be melted, disperse and extruding pelletization: obtains former material
Expect particle；
Step 3, by raw material particle be placed in it is quiet under room temperature thin-film material uniformly tiled on glass panels, stand 2h~
3h；After drying, master batch is formed；
Step 4, master batch will be added in single screw extrusion machine after being melted at 200~230 DEG C, via film mouth mold, will be passed through
The molding of casting and stretching device, and by film after 150 DEG C of heat treatment shaping through overstretching, cooling and shaping, trimming winding, from
And obtain polyvinylidene difluoride film.
Embodiment 3:
The present embodiment content and 1 content of embodiment are essentially identical, and same section content is not repeating, unlike the first embodiment:
In the present embodiment formula composition by following parts by weight component:
75 parts of Kynoar；
Styrene is 5 parts,
5 parts of plasticizer,
2 parts of stabilizer,
3 parts of antioxidant；
10 parts of reinforcing agent.
A kind of preparation method of polyvinylidene difluoride film, comprising the following steps:
Step 1, by 75 parts of Kynoar, styrene is 5 parts, 5 parts of plasticizer, 2 parts of stabilizer, and 3 parts of antioxidant, reinforcing agent 10
Part is separately added into mechanical mixture in high-speed mixer；
Step 2, the mixture in step 1 is put into double screw extruder to be melted, disperse and extruding pelletization: obtains former material
Expect particle；
Step 3, by raw material particle be placed in it is quiet under room temperature thin-film material uniformly tiled on glass panels, stand 2h~
3h；After drying, master batch is formed；
Step 4, master batch will be added in single screw extrusion machine after being melted at 200~230 DEG C, via film mouth mold, will be passed through
The molding of casting and stretching device, and by film after 150 DEG C of heat treatment shaping through overstretching, cooling and shaping, trimming winding, from
And obtain polyvinylidene difluoride film.
Embodiment 4:
The present embodiment content and 3 content of embodiment are essentially identical, and same section content is not repeating, as different from Example 3:
In the present embodiment formula composition by following parts by weight component:
75 parts of Kynoar,
Styrene is 5 parts,
6 parts of plasticizer,
1 part of stabilizer,
3 parts of antioxidant,
10 parts of reinforcing agent.
A kind of preparation method of polyvinylidene difluoride film, comprising the following steps:
Step 1, by 75 parts of Kynoar, styrene is 5 parts, 6 parts of plasticizer, 1 part of stabilizer, and 3 parts of antioxidant, reinforcing agent 10
Part is separately added into mechanical mixture in high-speed mixer；
Step 2, the mixture in step 1 is put into double screw extruder to be melted, disperse and extruding pelletization: obtains former material
Expect particle；
Step 3, by raw material particle be placed in it is quiet under room temperature thin-film material uniformly tiled on glass panels, stand 2h~
3h；After drying, master batch is formed；
Step 4, master batch will be added in single screw extrusion machine after being melted at 200~230 DEG C, via film mouth mold, will be passed through
The molding of casting and stretching device, and by film after 150 DEG C of heat treatment shaping through overstretching, cooling and shaping, trimming winding, from
And obtain polyvinylidene difluoride film.
As different from Example 3: adjusting the component of the parts by weight of plasticizer to 6 parts by 5 parts in this programme, stabilizer
The components of parts by weight adjusted by 2 parts to 1 part, it has been found that can be improved of the invention after adjusting above two component
The translucency of film entirety, it is ensured that its fluorescent brightness.
Embodiment 5:
The present embodiment content and 4 content of embodiment are essentially identical, and same section content is not repeating, as different from Example 4:
In the present embodiment formula composition by following parts by weight component:
Kynoar, 75 parts；
Styrene is 5 parts,
6 parts of plasticizer,
3 parts of stabilizer,
3 parts of antioxidant；
8 parts of reinforcing agent.
A kind of preparation method of polyvinylidene difluoride film, comprising the following steps:
Step 1, by Kynoar, 75 parts；Styrene is 5 parts, 6 parts of plasticizer, 3 parts of stabilizer, 3 parts of antioxidant；Reinforcing agent 8
Part is separately added into mechanical mixture in high-speed mixer；
Step 2, the mixture in step 1 is put into double screw extruder to be melted, disperse and extruding pelletization: obtains former material
Expect particle；
Step 3, by raw material particle be placed in it is quiet under room temperature thin-film material uniformly tiled on glass panels, stand 2h~
3h；After drying, master batch is formed；
Step 4, master batch will be added in single screw extrusion machine after being melted at 200~230 DEG C, via film mouth mold, will be passed through
The molding of casting and stretching device, and by film after 150 DEG C of heat treatment shaping through overstretching, cooling and shaping, trimming winding, from
And obtain polyvinylidene difluoride film.
As different from Example 4: the component of the parts by weight of reinforcing agent being adjusted by 10 parts to 8 parts in this programme, is stablized
The component of the parts by weight of agent is adjusted by 1 part to 3 parts, it has been found that the present invention can be improved after adjusting above two component
Film entirety tensile strength.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention；Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of polyvinylidene difluoride film, it is characterised in that: its formula composition includes the component of following parts by weight: polyvinylidene fluoride
Alkene, 60-80 parts；Styrene be 5~10 parts, 5~10 parts of plasticizer, 1-3 parts of stabilizer, antioxidant: 1~5 part；Reinforcing agent 1~
10 parts.
2. a kind of polyvinylidene difluoride film according to claim 1, it is characterised in that: its formula composition includes following weight
The component of part: Kynoar, 65-75 parts；Styrene be 6~9 parts, 7~8 parts of plasticizer, 1-2 parts of stabilizer, antioxidant: 1
~3 parts；1~5 part of reinforcing agent.
3. a kind of polyvinylidene difluoride film according to claim 1, it is characterised in that: the plasticizer includes DOP plasticising
The weight ratio of agent and ESO plasticizer, DOP plasticizer and ESO plasticizer is 3:2.
4. a kind of polyvinylidene difluoride film according to claim 1, it is characterised in that: the stabilizer is stablized for barium zinc
Agent.
5. a kind of polyvinylidene difluoride film according to claim 1, it is characterised in that: the reinforcing agent includes dimethylbenzene tree
Rouge RX-80.
6. a kind of polyvinylidene difluoride film according to claim 1, it is characterised in that: the antioxidant is divided into primary antioxidant
And auxiliary anti-oxidant, weight ratio 2:3, the primary antioxidant is one of Hinered phenols and sulphur ester antioxidant；Auxiliary anti-oxidant
It is one of phosphorous acid salt and phosphite ester antioxidant.
7. a kind of polyvinylidene difluoride film according to claim 1, it is characterised in that: the resistance to compression agent includes aramid fiber
Or Fanglun slurry cake.
8. the preparation method of -7 any polyvinylidene difluoride films according to claim 1, which is characterized in that including following
Step:
Step (1), by Kynoar, 60-80 parts；Styrene is 5~10 parts, antioxidant: 1~5 part；1~10 part of reinforcing agent,
5~10 parts of plasticizer, 1-3 parts of stabilizer are separately added into mechanical mixture in high-speed mixer；
Mixture in step (1) is put into double screw extruder and is melted, disperses and extruding pelletization: obtained by step (2)
Raw material particle；
Step (3), by raw material particle be placed in it is quiet under room temperature thin-film material uniformly tiled on glass panels, stand 2h
~3h；After drying, master batch is formed；
Master batch will be added in single screw extrusion machine after melting at 200~230 DEG C by step (4), via film mouth mold, be led to
Cross the molding of curtain coating stretching device, and by film after 150 DEG C of heat treatment shaping through overstretching, cooling and shaping, trimming winding,
To obtain polyvinylidene difluoride film.
9. the preparation method of polyvinylidene difluoride film described in one kind according to claim 8, it is characterised in that: prepared
Styrene described in journey is 24 parts.
10. the preparation method of polyvinylidene difluoride film described in one kind according to claim 8, it is characterised in that: preparation
The Kynoar is 65 parts in the process.
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| CN201811129218.1A CN109206801A (en) | 2018-09-27 | 2018-09-27 | A kind of polyvinylidene difluoride film and preparation method thereof |
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| CN201811129218.1A CN109206801A (en) | 2018-09-27 | 2018-09-27 | A kind of polyvinylidene difluoride film and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114953537A (en) * | 2022-07-27 | 2022-08-30 | 三三智能科技(日照)有限公司 | PVDF piezoelectric film tape casting process capable of controlling thickness |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010554A (en) * | 2010-11-09 | 2011-04-13 | 杭州福膜新材料科技有限公司 | Material special for polyvinylidene fluoride film |
-
2018
- 2018-09-27 CN CN201811129218.1A patent/CN109206801A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010554A (en) * | 2010-11-09 | 2011-04-13 | 杭州福膜新材料科技有限公司 | Material special for polyvinylidene fluoride film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114953537A (en) * | 2022-07-27 | 2022-08-30 | 三三智能科技(日照)有限公司 | PVDF piezoelectric film tape casting process capable of controlling thickness |
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