CN108164889A - High-intensity and high-tenacity PVDF solar energy backboard membrane materials and preparation method thereof - Google Patents
High-intensity and high-tenacity PVDF solar energy backboard membrane materials and preparation method thereof Download PDFInfo
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- CN108164889A CN108164889A CN201711175465.0A CN201711175465A CN108164889A CN 108164889 A CN108164889 A CN 108164889A CN 201711175465 A CN201711175465 A CN 201711175465A CN 108164889 A CN108164889 A CN 108164889A
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- intensity
- whisker
- solar energy
- pvdf
- tenacity
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- 239000012528 membrane Substances 0.000 title claims abstract description 49
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 45
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 30
- 239000007822 coupling agent Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 10
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims abstract description 7
- 235000010215 titanium dioxide Nutrition 0.000 claims description 51
- 238000002156 mixing Methods 0.000 claims description 38
- 239000013078 crystal Substances 0.000 claims description 24
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 11
- 238000005469 granulation Methods 0.000 claims description 11
- 230000003179 granulation Effects 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- FUSNPOOETKRESL-ZPHPHTNESA-N (z)-n-octadecyldocos-13-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCC\C=C/CCCCCCCC FUSNPOOETKRESL-ZPHPHTNESA-N 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 4
- 238000010348 incorporation Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- CHBCHAGCVIMDKI-UHFFFAOYSA-N [F].C=C Chemical group [F].C=C CHBCHAGCVIMDKI-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical group CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 9
- 230000007812 deficiency Effects 0.000 abstract description 7
- 238000002310 reflectometry Methods 0.000 abstract description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract 1
- 239000004926 polymethyl methacrylate Substances 0.000 abstract 1
- 238000007781 pre-processing Methods 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 8
- 238000005266 casting Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- OLZDXDPSDUSGIS-UHFFFAOYSA-N sulfinylmagnesium Chemical compound [Mg].S=O OLZDXDPSDUSGIS-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
-
- 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
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
A kind of solar energy backboard field of membrane material of the present invention, and in particular to high-intensity and high-tenacity PVDF solar energy backboard membrane material and preparation method thereof.Including following components：Kynoar, polymethyl acrylate, titanium dioxide, nano inorganic whisker, coupling agent, heat stabilizer, flow ability modifying agent.A diameter of 0.1~0.5 μm of nano inorganic whisker, length are 2~50 μm, and draw ratio is 20~100.The present invention improves PVDF backboards film strength and toughness, solves the problems, such as only to add PMMA and the intensity of titanium dioxide and toughness deficiency, the tensile strength >=50MPa in PVDF backboard membrane material MD directions being prepared, elongation at break >=350%；Tensile strength >=40MPa, elongation at break >=250% in TD directions；Light transmittance is low, improves the reflectivity of sunlight, and then improves utilization rate of the back board module to sunlight.
Description
Technical field
A kind of solar energy backboard field of membrane material of the present invention, and in particular to high-intensity and high-tenacity PVDF solar energy backboard membrane material
Material and preparation method thereof.
Background technology
PVDF has the excellent properties such as the resistant to chemical etching of protrusion, high-low temperature resistant, weatherability, these excellent performances of PVDF
It is made to be particularly suitable for doing solar energy backboard membrane material.But there is difficult film forming, film forming shrinking percentage height, light transmittance in pure PVDF raw materials
The deficiencies of high, usually adds PMMA and film forming modified, addition titanium dioxide reduction film light transmittance is carried out to PVDF, but adds PMMA
Strength and toughness deficiency problem is still had with titanium dioxide, especially film TD directions tensile strength, elongation at break is relatively low.
Problem is modified for solar energy backboard membrane activeness and quietness, patent CN106159010 discloses a kind of high tensile
PVDF solar energy backboard membranes, in PVDF/PMMA/TiO2On the basis of compounding, anti-impact modifier is added to, using blending of dissolving each other
Technology prepares solar energy backboard membrane, tensile strength (MD) >=50MPa, and tensile strength (TD) >=37MPa effectively increases PVDF trees
The tensile strength of fat.But heat stabilizer or antioxidant are not added in the formula that the patent is provided, the titanium dioxide of addition is to PVDF
The thermal decomposition facilitation of resin cannot inhibit well.It is thin that patent CN201010536756.X discloses a kind of Kynoar
Film special material using reinforced resin (esters of acrylic acid) to PVDF plasticising and toughening, improves the tear-resistant intensity of film.
103240008 A of Chinese patent CN disclose a kind of whisker and strengthen Pvdf Microporous Hollow Fiber Membrane and its preparation
Technique, applied to hollow-fibre membrane, using the form spinning of casting solution.107236232 A of Chinese patent CN, disclose one kind
Polyvinylidene fluoride resin polymer and preparation method thereof uses at least one of sodium metasilicate material, magnesium oxysulfide whisker, potassium titanate crystal whisker
With the composite nucleating agent of mica powder compounding, Shrinkage of Injection Molding is reduced, impact strength is improved, and is applied to injection neck
Domain is not appropriate for as backboard membrane material.
Invention content
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of high-intensity and high-tenacity PVDF solar energy backboard membranes
Material improves the intensity and toughness of PVDF backboard membrane masterbatch, solves the problems, such as prior art intensity and toughness deficiency, tensile strength with
Elongation at break is high, and light transmittance is low, improves the reflectivity of sunlight；The present invention also provides preparation methods.
High-intensity and high-tenacity PVDF solar energy backboard membrane material of the present invention is formed including following components：Gather inclined fluorine
Ethylene, polymethyl acrylate, titanium dioxide, nano inorganic whisker, coupling agent, heat stabilizer and flow ability modifying agent.
Preferably, the component composition including following parts by weight：
Wherein：
A diameter of 0.1~0.5 μm of nano inorganic whisker, length are 2~50 μm, and draw ratio is 20~100.Nano whisker
Different-diameter, length and draw ratio are different to the activeness and quietness effect of composite material, and draw ratio increases in a certain range, compound
Tensile strength of material increases, but when draw ratio is excessive, and dispersion is deteriorated, and generates stress concentration in material internal, is unfavorable for increasing instead
Strong toughening, selects the whisker of above-mentioned size, and activeness and quietness effect is best.Nano inorganic whisker is titanium dioxide crystal whisker, silicon carbide
One in whisker, potassium titanate crystal whisker, aluminium borate whisker, calcium sulfate crystal whiskers, calcium carbonate crystal whisker, alumina whisker or ZnOw
Kind is a variety of.Whisker is a kind of fiber mainly grown into single crystal form, and diameter is very small (micro/nano level), does not contain logical
Defect present in normal material, atomic arrangement high-sequential, the height-oriented structure of whisker make it have high intensity, high-modulus
And high elongation rate, intensity are far above other chopped strands, Material shrinkage can not only be reduced by adding whisker in a polymer matrix
Rate, moreover it is possible to optimize intensity, the toughness of material.
Kynoar is in the copolymer of vinylidene fluoride monomers homopolymer or vinylidene fluoride monomers and other fluorochemical monomers
At least one.
230 DEG C of Kynoar, 5kg melt mass flow rate be 5~30g/10min.
230 DEG C of polymethyl acrylate, 5kg melt mass flow rate for 0.5~25g/10min, preferably 2~
15g/10min。
Titanium dioxide is rutile type titanium white or anatase thpe white powder, preferably rutile type titanium white.
The grain size of titanium dioxide is 100~500nm, preferably 200~400nm.
Coupling agent is one or more in silane coupling agent, titanate coupling agent or aluminate coupling agent.
Flow ability modifying agent is in erucyl amide, stearic amide, stearyl erucamide, calcium stearate or zinc stearate
It is one or more.
Heat stabilizer is Hinered phenols antioxidant 1010 and phosphorous acid esters auxiliary antioxidant 168 is 0.5 by weight：1
~3:1 mixture.1010 be primary antioxidant, and 168 be auxiliary antioxidant, and the two compounding synergy is good, can effectively improve and add
Antioxygenic property during work thermal stability and materials'use.
The preparation method of high-intensity and high-tenacity PVDF solar energy backboard membrane material of the present invention, includes the following steps：
(1) titanium dioxide and nano inorganic whisker are pre-processed using coupling agent：By coupling agent and titanium dioxide and receive
Rice inorganic crystal whisker mixes in high-speed mixer, obtains prefinished products；
(2) prefinished products and heat stabilizer that obtain Kynoar, polymethyl acrylate, step (1) and
Flow ability modifying agent mixes in high-speed mixer；Obtained mixture is obtained in carrying out melt-processed granulation on double screw extruder
To the special master batch of backboard membrane；
(3) the special master batch of backboard membrane is cast or Blown Film on a single-screw extruder.
Wherein：
Incorporation time in step (1) is 5-20min, and mixing temperature is 60-80 DEG C, rotating speed 800-2000r/min.
Incorporation time in step (2) is 10-30min, and mixing temperature is 40-80 DEG C, rotating speed 800-2000r/min,
Prilling temperature is 180-220 DEG C.
Extrusion temperature in step (3) is 170-210 DEG C.
As a kind of perferred technical scheme, high-intensity and high-tenacity PVDF solar energy backboard membrane material of the present invention
Preparation method, step are as follows：
(1) titanium dioxide and nano inorganic whisker are pre-processed using coupling agent：By coupling agent and titanium dioxide and receive
Rice inorganic crystal whisker mixes 5-20min, 60-80 DEG C of mixing temperature in high-speed mixer, and rotating speed 800-2000r/min is obtained pre-
The titanium dioxide of processing and nano inorganic whisker；
(2) titanium of pretreatment for obtaining Kynoar (PVDF), polymethyl acrylate (PMMA), step (1)
White powder and nano inorganic whisker, heat stabilizer, flow ability modifying agent mix 10-30min, mixing temperature 40- in high-speed mixer
80 DEG C, rotating speed 800-2000r/min；Obtained mixture is in progress melt-processed granulation, prilling temperature on double screw extruder
180-220 DEG C, obtain the special master batch of backboard membrane；
(3) the special master batch of backboard membrane is cast or Blown Film on a single-screw extruder, 170-210 DEG C of extrusion temperature.
Compared with prior art, the present invention has the following advantages：
(1) present invention is improved by adding nano inorganic whisker using the distinctive activeness and quietness effect of nano inorganic whisker
The intensity and toughness of PVDF backboard membrane masterbatch are solved the problems, such as only to add PMMA and the intensity of titanium dioxide and toughness deficiency, is prepared into
Tensile strength >=the 50MPa in PVDF backboard membrane material MD directions arrived, elongation at break >=350%；The tensile strength in TD directions
>=40MPa, elongation at break >=250%；The nano inorganic whisker of addition is white simultaneously, and light transmittance is low, relative to other thoroughly
The high activeness and quietness modifying agent of light rate, addition nano inorganic whisker can prepare the lower backboard membrane of light transmittance, improve sunlight
Reflectivity, and then improve back board module to the utilization rate of sunlight.The present invention is extrusion by melting, and addition whisker increases in addition to enhancing
Outside tough effect, other comprehensive functions are also achieved, as the light transmittance of backboard membrane material is lower, processing heat stability improves.
(2) present invention is improved by adding nano inorganic whisker using the distinctive activeness and quietness effect of nano inorganic whisker
The intensity and toughness of PVDF backboard membrane masterbatch solve the problems, such as only to add PMMA and the intensity of titanium dioxide and toughness deficiency；Titanium dioxide
With nano inorganic whisker collective effect, the backboard membrane light transmittance that can make preparation is lower, improves the reflectivity of sunlight, Jin Erti
High back board module is to the utilization rate of sunlight.The use of heat stabilizer and a titanium dioxide additive amount part are by inorganic crystal whisker simultaneously
It substitutes, improves the processing heat stability of backboard membrane material.
Specific embodiment
With reference to embodiment, the present invention will be further described.
The number of each material is parts by weight in following embodiment；Extrusion temperature refers to screw rod melt zone in following embodiment
Temperature.
Comparative example
0.5 part of silane coupling agent and 10 parts of titanium dioxides are mixed into 15min in high-speed mixer, 60 DEG C of mixing temperature mixes
Conjunction machine rotating speed 1200r/min, obtains coupling agent pre-processing titanium white powder；By 70 parts of PVDF, 20 parts of PMMA, pre-processing titanium white powder, 1 part
Stearyl erucamide, 1.5 parts of antioxidant (1010:168=1:0.5) 20min, mixing temperature are mixed in high-speed mixer
50 DEG C, mixing machine rotating speed 1500r/min, mixture is obtained in progress melt-processed granulation, temperature 195 on double screw extruder
DEG C, the special master batch of backboard membrane is obtained in casting film-forming on single screw extrusion machine, 195 DEG C of temperature, 25 μm of film thickness.
Embodiment 1
0.5 part of silane coupling agent and 10 parts of titanium dioxides and 5 parts of calcium sulfate crystal whiskers are mixed into 15min in high-speed mixer,
60 DEG C of mixing temperature, mixing machine rotating speed 800r/min, obtains coupling agent pre-processing titanium white powder and calcium sulfate crystal whiskers；By 60 parts
PVDF, 25 parts of PMMA, obtained pre-processing titanium white powder and titanium dioxide crystal whisker, 1 part of stearyl erucamide, 1.5 parts of antioxygens
Agent (1010:168=1:0.5) 10min is mixed in high-speed mixer, 50 DEG C of mixing temperature, mixing machine rotating speed 1200r/nim,
It obtains mixture and obtains the special master batch of backboard membrane in single spiral shell in progress melt-processed granulation, 200 DEG C of temperature on double screw extruder
Casting film-forming on bar extruder, 200 DEG C of temperature, 25 μm of film thickness.
Embodiment 2
1 part of silane coupling agent and 5 parts of titanium dioxides and 10 parts of titanium dioxide crystal whiskers are mixed into 10min in high-speed mixer,
65 DEG C of mixing temperature, mixing machine rotating speed 1000r/min, obtains coupling agent pre-processing titanium white powder and titanium dioxide crystal whisker；By 65 parts
PVDF, 20 parts of PMMA, obtained pre-processing titanium white powder and titanium dioxide crystal whisker, 1.5 parts of stearyl erucamides, 1.8 parts it is anti-
Oxygen agent (1010:168=1:0.8) 15min, 60 DEG C of mixing temperature, mixing machine rotating speed 1500r/ are mixed in high-speed mixer
Nim, obtain mixture on double screw extruder carry out melt-processed granulation, 210 DEG C of temperature, obtain the special master batch of backboard membrane in
Casting film-forming on single screw extrusion machine, 190 DEG C of temperature, 25 μm of film thickness.
Embodiment 3
1.5 parts of silane coupling agents and 12 parts of titanium dioxides and 3 parts of alumina whiskers are mixed into 20min in high-speed mixer,
70 DEG C of mixing temperature, mixing machine rotating speed 1200r/min, obtains coupling agent pre-processing titanium white powder and alumina whisker；By 70 parts
PVDF, 15 parts of PMMA, obtained pre-processing titanium white powder and alumina whisker, 0.5 part of stearyl erucamide, 1.0 parts of antioxygens
Agent (1010:168=0.5:0.5) 30min, 40 DEG C of mixing temperature, mixing machine rotating speed 1800r/ are mixed in high-speed mixer
Nim, obtain mixture on double screw extruder carry out melt-processed granulation, 220 DEG C of temperature, obtain the special master batch of backboard membrane in
Casting film-forming on single screw extrusion machine, 210 DEG C of temperature, 25 μm of film thickness.
Embodiment 4
2 parts of silane coupling agents and 15 parts of titanium dioxides and 1 part of silicon carbide whisker in high-speed mixer are mixed into 25min, are mixed
75 DEG C of temperature is closed, mixing machine rotating speed 1500r/min obtains coupling agent pre-processing titanium white powder and silicon carbide whisker；By 75 parts of PVDF,
9 parts of PMMA, obtained pre-processing titanium white powder and silicon carbide whisker, 2 parts of stearyl erucamides, 3 parts of antioxidant (1010:168
=2:1) 10min, 80 DEG C of mixing temperature are mixed in high-speed mixer, mixing machine rotating speed 800r/nim obtains mixture in double
Melt-processed granulation is carried out on screw extruder, 200 DEG C of temperature obtains the special master batch of backboard membrane in being cast on single screw extrusion machine
Film forming, 195 DEG C of temperature, 25 μm of film thickness.
Embodiment 5
By 3 parts of silane coupling agents and 10 parts of titanium dioxides and 3 parts of titanium dioxide crystal whiskers, 2 parts of alumina whiskers in mixed at high speed
30min, 80 DEG C of mixing temperature are mixed in machine, mixing machine rotating speed 1800r/min obtains coupling agent prefinished products；By 80 parts
PVDF, 5 parts of PMMA, obtained prefinished products, 3 parts of stearyl erucamides, 2.5 parts of antioxidant (1010:168=1.5:
1) 25min, 60 DEG C of mixing temperature are mixed in high-speed mixer, mixing machine rotating speed 1500r/nim obtains mixture in twin-screw
Melt-processed granulation is carried out on extruder, 200 DEG C of temperature obtains the special master batch of backboard membrane in being cast on single screw extrusion machine
Film, 195 DEG C of temperature, 25 μm of film thickness.
Embodiment 6
By 0.5 part of silane coupling agent and 5 parts of titanium dioxides and 5 parts of titanium dioxide crystal whiskers, 5 parts of alumina whiskers in 70 DEG C of high speeds
15min, 60 DEG C of mixing temperature are mixed in mixing machine, mixing machine rotating speed 1200r/min obtains coupling agent prefinished products；By 65
Part PVDF, 20 parts of PMMA, obtained prefinished products, 1 part of stearyl erucamide, 2 parts of antioxidant (1010:168=1:1)
15min, 60 DEG C of mixing temperature are mixed in high-speed mixer, mixing machine rotating speed 1500r/nim obtains mixture and squeezed in twin-screw
Going out on machine progress melt-processed granulation, 205 DEG C of temperature obtains the special master batch of backboard membrane in casting film-forming on single screw extrusion machine,
195 DEG C of temperature, 25 μm of film thickness.
Embodiment 7
0.5 part of silane coupling agent and 15 parts of titanium dioxides and 5 parts of calcium carbonate crystal whiskers are mixed into 20min in high-speed mixer,
80 DEG C of mixing temperature, mixing machine rotating speed 1000r/min, obtains coupling agent pre-processing titanium white powder and calcium carbonate crystal whisker；By 70 parts
PVDF, 10 parts of PMMA, obtained pre-processing titanium white powder and calcium carbonate crystal whisker, 1 part of stearyl erucamide, 1.5 parts of antioxidant
(1010:168=0.5:1) 20min, 70 DEG C of mixing temperature are mixed in high-speed mixer, mixing machine rotating speed 1800r/nim is obtained
The special master batch of backboard membrane is obtained in single screw rod in progress melt-processed granulation, 205 DEG C of temperature on double screw extruder to mixture
Casting film-forming on extruder, 195 DEG C of temperature, 25 μm of film thickness.
The various embodiments described above formula is listed in table 1.
1 Example formulations of table
Mechanical property, light transmittance, weatherability (yellowness index) are carried out to the film that comparative example and embodiment 1-7 obtain to survey
Examination, test result are as shown in table 2：
2 comparative example of table and embodiment 1-7 test results
Claims (10)
1. a kind of high-intensity and high-tenacity PVDF solar energy backboard membrane material, it is characterised in that：It is formed including following components：Gather inclined fluorine
Ethylene, polymethyl acrylate, titanium dioxide, nano inorganic whisker, coupling agent, heat stabilizer and flow ability modifying agent.
2. high-intensity and high-tenacity PVDF solar energy backboard membrane material according to claim 1, it is characterised in that：Including following
The component composition of parts by weight：
3. high-intensity and high-tenacity PVDF solar energy backboard membrane material according to claim 1, it is characterised in that：Nano inorganic
A diameter of 0.1~0.5 μm of whisker, length are 2~50 μm, and draw ratio is 20~100.
4. high-intensity and high-tenacity PVDF solar energy backboard membrane material according to claim 1, it is characterised in that：Nano inorganic
Whisker is titanium dioxide crystal whisker, silicon carbide whisker, potassium titanate crystal whisker, aluminium borate whisker, calcium sulfate crystal whiskers, calcium carbonate crystal whisker, oxygen
It is one or more in change al whisker or ZnOw.
5. high-intensity and high-tenacity PVDF solar energy backboard membrane material according to claim 1, it is characterised in that：Polyvinylidene fluoride
Alkene is vinylidene fluoride monomers homopolymer or at least one of vinylidene fluoride monomers and the copolymer of other fluorochemical monomers；Gather inclined fluorine
230 DEG C of ethylene, 5kg melt mass flow rate be 5~30g/10min.
6. high-intensity and high-tenacity PVDF solar energy backboard membrane material according to claim 1, it is characterised in that：Poly- methyl-prop
230 DEG C of diluted acid methyl esters, 5kg melt mass flow rate be 0.5~25g/10min.
7. high-intensity and high-tenacity PVDF solar energy backboard membrane material according to claim 1, it is characterised in that：Titanium dioxide is
Rutile type titanium white or anatase thpe white powder；The grain size of titanium dioxide is 100~500nm.
8. high-intensity and high-tenacity PVDF solar energy backboard membrane material according to claim 1, it is characterised in that：Coupling agent is
It is one or more in silane coupling agent, titanate coupling agent or aluminate coupling agent；Flow ability modifying agent is erucyl amide, tristearin
It is one or more in sour amide, stearyl erucamide, calcium stearate or zinc stearate；Heat stabilizer resists for Hinered phenols
Oxygen agent 1010 and phosphorous acid esters auxiliary antioxidant 168 are 0.5 by weight：1~3:1 mixture.
9. a kind of preparation method of any high-intensity and high-tenacity PVDF solar energy backboard membrane materials of claim 1-8,
It is characterized in that：Include the following steps：
(1) titanium dioxide and nano inorganic whisker are pre-processed using coupling agent：By coupling agent and titanium dioxide and nanometer nothing
Machine whisker mixes in high-speed mixer, obtains prefinished products；
(2) prefinished products and heat stabilizer that obtain Kynoar, polymethyl acrylate, step (1) and flowing
Modifying agent mixes in high-speed mixer；Obtained mixture is carried on the back in carrying out melt-processed granulation on double screw extruder
The special master batch of plate film；
(3) the special master batch of backboard membrane is cast or Blown Film on a single-screw extruder.
10. the preparation method of high-intensity and high-tenacity PVDF solar energy backboard membrane material according to claim 9, feature exist
In：
Incorporation time in step (1) is 5-20min, and mixing temperature is 60-80 DEG C, rotating speed 800-2000r/min；
Incorporation time in step (2) is 10-30min, and mixing temperature is 40-80 DEG C, rotating speed 800-2000r/min, is granulated
Temperature is 180-220 DEG C；
Extrusion temperature in step (3) is 170-210 DEG C.
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| CN109560165A (en) * | 2018-11-14 | 2019-04-02 | 宁波高新区州致科技有限公司 | A kind of composite membrane used for solar batteries and preparation method thereof |
| CN112549595A (en) * | 2020-12-04 | 2021-03-26 | 宁波东旭成新材料科技有限公司 | Preparation method of reflecting film |
| CN112768542A (en) * | 2021-01-05 | 2021-05-07 | 浙江中聚材料有限公司 | Insulated solar photovoltaic backboard and preparation process thereof |
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