CN109694444B - Ethylene-vinyl acetate copolymer, method for preparing same, and solar cell packaging sheet using same - Google Patents
Ethylene-vinyl acetate copolymer, method for preparing same, and solar cell packaging sheet using same Download PDFInfo
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- CN109694444B CN109694444B CN201810936716.0A CN201810936716A CN109694444B CN 109694444 B CN109694444 B CN 109694444B CN 201810936716 A CN201810936716 A CN 201810936716A CN 109694444 B CN109694444 B CN 109694444B
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- 239000005038 ethylene vinyl acetate Substances 0.000 title claims abstract description 125
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004806 packaging method and process Methods 0.000 title claims description 6
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 90
- 238000005538 encapsulation Methods 0.000 claims abstract description 10
- 238000004132 cross linking Methods 0.000 claims description 46
- 238000006116 polymerization reaction Methods 0.000 claims description 44
- 125000000217 alkyl group Chemical group 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000003505 polymerization initiator Substances 0.000 claims description 29
- 150000002978 peroxides Chemical class 0.000 claims description 28
- 239000003431 cross linking reagent Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 23
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 20
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 238000009826 distribution Methods 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical group CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims 2
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 claims 1
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 238000003475 lamination Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- 229920005989 resin Polymers 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000000149 argon plasma sintering Methods 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 150000001451 organic peroxides Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000008393 encapsulating agent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- BRQMAAFGEXNUOL-UHFFFAOYSA-N 2-ethylhexyl (2-methylpropan-2-yl)oxy carbonate Chemical compound CCCCC(CC)COC(=O)OOC(C)(C)C BRQMAAFGEXNUOL-UHFFFAOYSA-N 0.000 description 2
- -1 2-ethylhexyl T-butylperoxycarbonate Chemical compound 0.000 description 2
- CARSMBZECAABMO-UHFFFAOYSA-N 3-chloro-2,6-dimethylbenzoic acid Chemical compound CC1=CC=C(Cl)C(C)=C1C(O)=O CARSMBZECAABMO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 150000004978 peroxycarbonates Chemical class 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- FIYMNUNPPYABMU-UHFFFAOYSA-N 2-benzyl-5-chloro-1h-indole Chemical compound C=1C2=CC(Cl)=CC=C2NC=1CC1=CC=CC=C1 FIYMNUNPPYABMU-UHFFFAOYSA-N 0.000 description 1
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 description 1
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 description 1
- ZIDNXYVJSYJXPE-UHFFFAOYSA-N 2-methylbutan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CCC(C)(C)OOC(=O)CCCCCC(C)(C)C ZIDNXYVJSYJXPE-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- 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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- C08K5/14—Peroxides
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- 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
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
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- 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
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- H01L31/049—Protective back sheets
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to an ethylene-vinyl acetate (EVA) copolymer resin, a method of preparing the same, and a solar cell encapsulation sheet using the same. More particularly, the present invention relates to an EVA copolymer resin for a solar cell encapsulating sheet, wherein the High Molecular Weight (HMW) component fraction (F) of the EVA copolymer resin is determined by GPC-LSD deconvolutionHMW) And a Low Molecular Weight (LMW) fraction (F)LMW) Less than 10% and less than 40%, respectively.
Description
Cross-referencing
This application claims priority and benefit of korean patent application No.10-2017-0136867 filed on korean intellectual property office at 20.10.2017 and all the benefits derived therefrom in accordance with 35 u.s.c.119, the entire contents of which are incorporated herein by reference.
Technical Field
The present invention relates to an ethylene-vinyl acetate (EVA) copolymer resin prepared using a polymerization reactor, a method of preparing the same, and a solar cell encapsulation sheet using the same. More particularly, the present invention relates to a resin having an increased crosslinking speed during lamination for manufacturing a solar cell module compared to a general EVA copolymer resin, and a method for preparing the same.
Background
In a solar cell module used in photovoltaic power generation, EVA sheets are generally used on both sides of a cell to protect the cell. In addition, a transparent glass substrate and a sheet having excellent gas barrier properties and weatherability are laminated on one side facing sunlight and the other side, respectively.
In order to ensure weatherability and heat resistance, EVA sheets need to be crosslinked to a certain level or more. During lamination, the crosslinking agent added to prepare the sheet is decomposed and crosslinked to cause a crosslinking reaction. Dialkyl peroxides, peroxycarbonates, peroxyketals, and the like are generally used as crosslinking agents for crosslinking. However, these crosslinking agents have several problems. That is, since the dialkyl peroxide has a high half-life temperature, the lamination requires a relatively long time. In addition, since peroxyketals have a low half-life temperature, lamination times can be shortened, but commercial use is limited because rapid crosslinking reactions can exhibit a number of adverse side effects. At present, peroxycarbonates are most widely used on a commercial basis in view of stability during lamination and weatherability in long-term use. However, in order to increase the productivity of the module, there is an increasing demand for increased lamination speed in the manufacture of solar cell modules. In Japanese patent application No. JP2012212267A, it is proposed to use an organic peroxide which exhibits a low decomposition temperature to increase the crosslinking speed while shortening the time required for crosslinking and adhesion. However, the use of organic peroxides exhibiting a low decomposition temperature has the following disadvantages: the sheet forming temperature may be lowered to prevent decomposition of the organic peroxide during sheet formation, which may reduce sheet productivity, increase defect rate due to generation of bubbles during lamination, and increase amount of remaining crosslinking agent after lamination may cause defects such as high yellowing index.
Korean patent registration No. 10-928441 proposes the use of a mixture of some organic peroxides having a low decomposition temperature to increase the crosslinking speed. However, the proposed attempts still do not solve the problems associated with the rapid crosslinking reaction.
Therefore, a basic solution for increasing the crosslinking degree and the crosslinking speed by using the inherent properties of the EVA resin is required.
Disclosure of Invention
Embodiments of the present invention provide an ethylene-vinyl acetate (EVA) copolymer resin for a solar cell encapsulation sheet, which can improve module productivity through a higher crosslinking speed during lamination in manufacturing a solar cell module compared to a conventional EVA resin even with a general crosslinking agent, and can reduce the amount of the crosslinking agent through an improved degree of crosslinking, and a method of preparing the same.
Embodiments of the present invention also provide an EVA copolymer resin prepared by the method and an EVA sheet prepared using the EVA copolymer resin.
According to an aspect of the present invention, there is provided an ethylene-vinyl acetate (EVA) copolymer resin for a solar cell encapsulation sheet, wherein a High Molecular Weight (HMW) component fraction (F) of the EVA copolymer resin is determined by GPC-LSD deconvolutionHMW) Less than 10%.
According to another aspect of the present invention, there is provided a method of preparing an ethylene-vinyl acetate (EVA) copolymer resin, the method including: injecting vinyl acetate monomer and ethylene-vinyl acetate (EVA) into a polymerization reactor, adding a polymerization initiator mixture containing two or more peroxide polymerization initiators, and polymerizing at a polymerization temperature of 190 to 250 ℃ and a polymerization pressure of 2600 to 2700kg/cm2And a polymerization time of from 2 to 5 minutes, wherein the peroxide polymerization initiator forms a mixture comprising (a) an alkyl peroxyneodecanoate compound having from 4 to 5 carbon atoms in the peroxide-bonded alkyl group, (B) an alkyl peroxypivalate compound having from 4 to 5 carbon atoms in the peroxide-bonded alkyl group, and (C) an alkyl peroxyhexanoate compound having from 4 to 5 carbon atoms in the peroxide-bonded alkyl group, wherein the weight ratio of the peroxide polymerization initiator mixture comprising (a), (B), and (C) in the first reaction stage is from 30 to 50: 20-40: 20-40, in the second reaction stage 1-20: 10-30: 50-80, and wherein the High Molecular Weight (HMW) fraction (F) of the EVA copolymer resin is determined by GPC-LSD deconvolutionHMW) Less than 10%.
According to still another aspect of the present invention, there is provided an encapsulating sheet for a solar cell, wherein the encapsulating sheet employs an EVA copolymer resin.
As described above, according to the EVA resin preparation method of the present invention, the crosslinking performance of the resin itself can be maximized, so that the encapsulant using the EVA resin of the present invention exhibits an increased crosslinking speed compared to the conventional encapsulant even with the same amount of the crosslinking agent, thereby improving the productivity of the module and realizing mass production. In addition, since the EVA sheet according to the present invention has a relatively high crosslinking rate, excellent weatherability and thermal stability are demonstrated. In addition, since it is not necessary to increase the amount of the crosslinking agent, problems such as yellowing associated with increasing the amount of the crosslinking agent are not caused.
Drawings
FIG. 1 depicts the GPC-LSD plots of the EVA resins prepared in example 2 and comparative examples 1 and 2.
FIG. 2 is a graphical representation of GPC-LSD deconvolution of the EVA resin prepared in example 1.
FIG. 3 is a graphical representation of GPC-LSD deconvolution of the EVA resin prepared in example 2.
FIG. 4 is a graphical representation of GPC-LSD deconvolution of the EVA resin prepared in example 3.
FIG. 5 is a graphical representation of GPC-LSD deconvolution of the EVA resin prepared in comparative example 1.
FIG. 6 is a graphical representation of GPC-LSD deconvolution of the EVA resin prepared in comparative example 2.
Fig. 7 is a graph showing the ODR evaluation results of the solar cell encapsulation sheets using the EVA copolymer resins prepared in examples 1 to 3 and comparative examples 1 and 2.
Detailed Description
Hereinafter, the present invention will be described in more detail.
According to an embodiment of the present invention, there is provided an EVA copolymer resin for a solar cell encapsulation sheet, wherein a High Molecular Weight (HMW) component fraction (F) of the EVA copolymer resin is determined by GPC-LSD deconvolutionHMW) Less than 10%.
If FHMWGreater than or equal to 10%, the rate of intramolecular cross-linking may increase, undesirably decreasing the effective cross-linking rate, due to increased long-chain branching during cross-linking.
According to one embodiment of the invention, the Low Molecular Weight (LMW) component fraction (F) of the EVA copolymer resinLMW) Preferably less than 40%. If FLMW40% or more, the crosslinking rate is highThe degree may be decreased due to an increase in the rate of crosslinking within molecules having a low molecular weight, undesirably decreasing the rate of crosslinking and the rate of crosslinking.
In the present invention, the EVA copolymer resin may have a bimodal molecular weight distribution as determined by Gel Permeation Chromatography (GPC) in view of light scattering chromatography.
Chromatogram deconvolution means that two or more component polymers, where one component polymer may be present in a bulge (hump), shoulder, or tail relative to the Molecular Weight Distribution (MWD) of the other component polymer.
According to an embodiment of the present invention, the EVA copolymer resin preferably has a weight average molecular weight (Mw) of 60000 to 100000g/mole, and a molecular weight distribution (Mw/Mn) of 4.0 to 4.5 as measured by GPC-LSD. If the molecular weight distribution (Mw/Mn) of the EVA copolymer resin is 4 or less, moldability problems, particularly severe necking, may occur. If the molecular weight distribution (Mw/Mn) of the EVA copolymer resin is 4.5 or more, the elasticity of the EVA copolymer resin increases, resulting in an increase in shrinkage during lamination.
According to an embodiment of the present invention, the EVA copolymer resin preferably contains 22 to 35 wt% vinyl acetate monomer and has a Melt Index (MI) of 0.4 to 4.0g/10min as measured according to ASTM D1238 at 125 ℃ and 2.16kg load.
If the content of the vinyl acetate monomer is less than 22% by weight, the EVA copolymer resin has poor elasticity and flexibility, resulting in undesirable damage to the solar cell when manufacturing a solar cell module, and low light transmittance, undesirably making the EVA copolymer resin unfavorable for use in a solar cell encapsulation sheet. If the vinyl acetate monomer content is more than 35% by weight, electrical insulation properties may deteriorate, moisture permeability may increase and the amount of generated acetic acid may increase, causing serious damage to the solar cell module, and mechanical properties may deteriorate, making the EVA copolymer resin unfavorable for use in a solar cell encapsulation sheet.
If the Melt Index (MI) is less than 0.4g/10min, the workability is poor, making it difficult to form a sheet using the EVA copolymer resin. If the Melt Index (MI) is greater than 4.0g/10min, the EVA copolymer resin may flow out of the module during lamination, undesirably producing a defective module product.
According to an embodiment of the present invention, there is provided a method of preparing an EVA copolymer resin, the method including: injecting vinyl acetate monomer and Ethylene Vinyl Acetate (EVA) into a polymerization reactor; adding a polymerization initiator mixture comprising two or more peroxide polymerization initiators; and a polymerization temperature of 190 to 250 ℃ and a polymerization pressure of 2600 to 2700kg/cm2And a polymerization time of from 2 to 5 minutes, wherein the peroxide polymerization initiator forms a mixture comprising (a) an alkyl peroxyneodecanoate compound having from 4 to 5 carbon atoms in the peroxide-bonded alkyl group, (B) an alkyl peroxypivalate compound having from 4 to 5 carbon atoms in the peroxide-bonded alkyl group, and (C) an alkyl peroxyhexanoate compound having from 4 to 5 carbon atoms in the peroxide-bonded alkyl group, the weight ratio of the peroxide polymerization initiator mixture comprising (a), (B), and (C) being from 30 to 50 in the first reaction stage: 20-40: 20-40, in the second reaction stage 1-20: 10-30: 50-80 and a High Molecular Weight (HMW) fraction (F) of EVA copolymer resin as determined by GPC-LSD deconvolutionHMW) Less than 10%.
The EVA copolymer resin of the present invention is polymerized in a polymerization reactor composed of at least two reactors, and ethylene and vinyl acetate are preferably injected only into the first-stage reactor connected to a monomer input port in the polymerization reactor.
In a polymerization reactor composed of at least two reactors, the reactor connected to the monomer input port is referred to as a first-stage reactor, and the other reactors are referred to as a second-stage reactor and a third-stage reactor in this order depending on the number of reactors.
In addition, the polymerization reactor may include a monomer input port connected to one end of the polymerization reactor and a copolymer resin output port connected to the other end of the polymerization reactor.
A peroxide polymerization initiator used as a polymerization initiator is injected into the polymerization reactor, and the reaction is initiated after the peroxide polymerization initiator is injected. Due to the reaction heat from the injection point of the peroxide polymerization initiator, the polymerization temperature may rise sharply, and the ethylene monomer, vinyl acetate monomer and resulting polymer may flow along the reactor, with the heat and reaction temperature being controlled accordingly by heat exchange with cooling water from the reactor wall. The reactants and polymer passing through the first stage reactor are transferred to the next stage reactor where the peroxide mixture as a polymerization initiator is again injected to carry out further reaction. However, the ethylene monomer and vinyl acetate monomer are preferably injected into the reactor only in the first reaction stage, and not in the subsequent reaction stages. If the monomer is injected into a subsequent reactor after the first stage reactor, the Molecular Weight Distribution (MWD) is increased, undesirably decreasing the degree of crosslinking. Thereafter, the polymer and the unreacted monomer were finally discharged to the outlet of the reactor to be separated, and then passed through an extruder, thereby obtaining a pelletized resin.
In the preparation method of the EVA copolymer resin according to the present invention, a polymerization initiator including two or more peroxide polymerization initiators is preferably added at a concentration of 1000 to 3000 ppm. If the concentration of the polymerization initiator is less than 1000ppm, the reaction temperature during polymerization is low, undesirably resulting in low conversion to the EVA copolymer resin and making it difficult to control the molecular weight. If the concentration of the polymerization initiator is more than 3000ppm, the reaction temperature during polymerization is very high, the resin may be decomposed, and the decomposition of vinyl acetate may generate acetic acid, which may damage the reaction radical, undesirably impairing safety problems.
In the method of preparing an EVA copolymer resin according to the present invention, specific examples of the alkyl peroxyneodecanoate compound (a) suitable for use as an initiator may include t-amyl peroxyneodecanoate, t-butyl peroxyneodecanoate (TBPND), etc., specific examples of the alkyl peroxypivalate compound (B) suitable for use as an initiator may include t-amyl peroxypivalate, t-butyl peroxypivalate, etc., and specific examples of the alkyl peroxyhexanoate compound (C) suitable for use as an initiator may include t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-amyl peroxy-3, 5, 5-trimethylhexanoate, t-butyl peroxy-2-ethylhexanoate (TBPO), t-butyl peroxy-3, 5, 5-Trimethylhexanoate (TBPIN), etc.
Examples of the peroxide polymerization initiator more preferably usable in the present invention may include t-butyl peroxyneodecanoate (TBND), t-butyl peroxypivalate (TBPV), t-butyl peroxy-2-ethylhexanoate (TBPO) and t-butyl peroxy-3, 5, 5-Trimethylhexanoate (TBPIN), and each peroxide is diluted in a paraffin-based solvent to be used. Furthermore, the individual peroxides are used in the form of mixtures.
In the peroxide polymerization initiator according to the present invention, the weight ratio of the peroxide polymerization initiator mixture used in the first stage is (a): (B) the method comprises the following steps (C) 30-50: 20-40: 20-40, (a) an alkyl peroxyneodecanoate compound having 4 to 5 carbon atoms in the peroxide-bonded alkyl group, (B) an alkyl peroxypivalate compound having 4 to 5 carbon atoms in the peroxide-bonded alkyl group, and (C) an alkyl peroxyhexanoate compound having 4 to 5 carbon atoms in the peroxide-bonded alkyl group, and the reaction stage weight ratios after the first reaction stage are (a): (B) the method comprises the following steps (C) 1-20: 10-30: 50-80.
In the two or more peroxide polymerization initiators used in the present invention, if the mixing ratio of the alkyl peroxyhexanoate compound (C) in the weight ratio of the peroxide mixture used in the first reaction stage is less than 20, the Molecular Weight Distribution (MWD) becomes broad, and if it is more than 40, an excessive reaction may occur, which is problematic in terms of reaction control. Meanwhile, if the mixing ratio of the alkyl peroxyneodecanoate compound (a) in the weight ratio of the peroxide initiator mixture used in the second reaction stage is more than 20%, the yield of the module may be lowered, which is undesirable. Further, if the weight ratio of the peroxide polymerization initiator in the peroxide mixture is out of the above range, it is difficult to appropriately control the molecular weight and obtain desired crosslinking properties, which is not preferable.
In the preparation method of the EVA copolymer resin according to the present invention, t-butyl peroxyneodecanoate (TBND) is most preferably used as the alkyl peroxyneodecanoate compound (a) in the peroxide polymerization initiator mixture, t-butyl peroxypivalate (TBPV) is most preferably used as the alkyl peroxypivalate compound (B), and most preferably one selected from t-butyl peroxy-2-ethylhexanoate (TBPO) and t-butyl peroxy-3, 5, 5-Trimethylhexanoate (TBPIN) is used as the alkyl peroxyhexanoate compound (C).
In the method of preparing the EVA copolymer resin according to the present invention, the polymerization is preferably performed at a temperature of 190 to 250 ℃. If the polymerization temperature is less than 190 ℃, the EVA conversion is low and the desired level of weight average molecular weight and molecular weight distribution cannot be obtained. If the polymerization temperature is higher than 250 deg.C, it is difficult to obtain a desired weight average molecular weight level, which is undesirable.
In the method for preparing an EVA copolymer resin according to the present invention, the polymerization pressure is preferably 2600 to 2700kg/cm2Within the range of (1). If the polymerization pressure is less than 2600kg/cm2The reaction may not be sufficiently performed or the processing stability may be lowered, which is undesirable. If the polymerization pressure is greater than 2700kg/cm2Stability problems may arise due to performance limitations of the high pressure pump.
In the method of preparing the EVA copolymer resin according to the present invention, the polymerization time is preferably in the range of 2 to 5 minutes. If the polymerization time is less than 2 minutes, the EVA conversion is low and the weight average molecular weight level is low, both of which are undesirable. If the polymerization time is more than 5 minutes, it is not easy to control the polymerization pressure and undesirable gel formation may occur.
The present invention provides an EVA copolymer resin prepared by the method of preparing an EVA copolymer resin.
The EVA copolymer resin prepared under polymerization conditions has a Melt Index (MI) of 0.4 to 4.0g/10min measured according to ASTM D1238 at 125 ℃ and 2.16kg load, a weight average molecular weight (Mw) of 60000 to 100000g/mol as measured by GPC-LSD, a molecular weight distribution (Mw/Mn) of 4.0 to 4.5.
If the molecular weight distribution is less than 4.0, the extrusion load is high and severe necking occurs after die extrusion. If the molecular weight distribution is 4.5 or more, the elasticity of the EVA copolymer resin increases, resulting in an increase in shrinkage during lamination, thereby lowering light transmittance.
In the present invention, the EVA copolymer resin preferably has a Melt Index (MI) of 0.4 to 4.0g/10min measured according to ASTM D1238 at 125 ℃ under a load of 2.16 kg.
If the Melt Index (MI) of the EVA copolymer resin is less than 0.4g/10min, poor extrusion processability is exhibited. If the Melt Index (MI) is greater than 4.0g/10min, the EVA copolymer resin may flow out of the module during lamination, which is referred to as an edge flow phenomenon.
In the present invention, the EVA copolymer resin preferably has a weight average molecular weight (Mw) of 60000 to 100000 g/mol. If the weight average molecular weight (Mw) of the EVA copolymer resin is less than 60000g/mol, the mechanical properties of the EVA copolymer resin may not be achieved. If the weight average molecular weight (Mw) of the EVA copolymer resin is greater than 100000g/mol, the EVA copolymer resin may have poor transparency, gel agglomeration occurs, light transmittance is reduced, and microcracks may occur during lamination.
The invention provides a packaging sheet for a solar cell, which adopts EVA copolymer resin. The packaging sheet may be a front sheet or a back sheet.
The EVA copolymer encapsulating sheet is prepared in the form of a sheet by the following steps: the EVA copolymer resin is mixed with various additives including a crosslinking agent, a co-crosslinking agent, a silane coupling agent, an antioxidant, a light stabilizer, a UV absorber, etc., and the mixture is melt-kneaded in a temperature range higher than the melting point of the EVA copolymer resin and lower than the decomposition temperature of an organic peroxide as a crosslinking agent.
In the present invention, the solar cell encapsulating sheet includes 0.3 to 1.0 parts by weight of a crosslinking agent, 0.3 to 1.0 parts by weight of a co-crosslinking agent, and 0.3 to 1.0 parts by weight of a silane coupling agent, and 1.0 to 5.0 parts by weight of a white pigment, based on the total weight of the EVA copolymer resin.
In this context, 2-ethylhexyl tert-butylperoxycarbonate (TBEC, tert-butyl peroxy-2-ethylhexyl carbonate) is preferably used as the crosslinking agent, and triallyl isocyanurate (TAICROS) is preferably used as the co-crosslinking agent. Furthermore, methacryloxypropyltrimethoxysilane is preferably used as the silane coupling agent.
In the lamination process for manufacturing a solar cell module by using the encapsulant material, a transparent glass substrate, a top EVA copolymer sheet, a bottom EVA copolymer sheet, and a gas barrier backsheet are stacked and adhered by heating and crosslinking the stack under preset temperature and pressure conditions. In order to achieve a target crosslinking rate in the process, the lamination process should be carried out at a preset temperature for a preset duration, and the crosslinking time required for the process plays an important role in the overall module productivity.
In the present invention, 0.5 parts by weight of each of 2-ethylhexyl tert-butylperoxycarbonate (TBEC) as a crosslinking agent and triallyl isocyanurate (taicrs) as a co-crosslinking agent was fed to the EVA copolymer resin. The torque difference (MH-ML), i.e., the difference between the highest torque value and the lowest torque value, was 2.0dNm or more, and the torque value was obtained by measuring the change in elastic modulus using an Oscillating Disc Rheometer (ODR) with time scanning at 150 ℃ (see table 2 and fig. 7).
The difference (MH-ML) of the EVA copolymer resin measured at 150 ℃ is preferably 2.0 dNm. If the difference (MH-ML) is less than 2.5, the degree of crosslinking is not sufficiently high, resulting in poor heat resistance. Thus, there is a fear that creep or yellowing occurs at the time of field installation of the solar cell module.
In general, the degree of crosslinking of the solar cell encapsulating sheet can also be evaluated by measuring the xylene soluble component and using ODR. In this case, the crosslinking degree was evaluated as a weight ratio of the xylene soluble component to the total weight of the specimen of 85%, and about 85% was set as a target crosslinking degree. The crosslinker to be dosed to the EVA copolymer resin is then determined and the lamination conditions adjusted accordingly. If the degree of crosslinking is as low as 83% or less, long-term physical properties may deteriorate. If the degree of crosslinking is as high as 90% or more, the hardness of the sheet may increase, undesirably decreasing the impact-absorbing ability. In the case of a low degree of crosslinking, it is necessary to input an additional crosslinking agent or to increase the laminating time and temperature. In this case, however, an increased amount of residual crosslinking agent after lamination, yellowing, and generation of bubbles may undesirably occur. In addition, increases in lamination time and temperature undesirably reduce module productivity.
The present invention will be understood in more detail with reference to examples and comparative examples, and the following examples and comparative examples are provided only for describing the present invention and are not intended to limit the scope of the present invention.
Measurement of physical Properties
Various physical properties of the EVA copolymer resins prepared in examples 1 to 3 and comparative examples 1 and 2 were measured according to the following methods and standards.
1) Melt Index (MI): MI was measured according to ASTM D1238 at 125 ℃ under a load of 2.16 kg.
2) Content of VA: the Vinyl Acetate (VA) content was measured by fourier transform infrared spectroscopy (FT-IR).
3) GPC-LSD: gel Permeation Chromatography (GPC) as used herein is a high temperature (150 ℃) chromatography system, i.e., Polymer Laboratories model PL-220 equipped with a refractometer as a Refractive Index (RI) detector. A dual angle system is additionally used as a light scatter detector, having a wavelength of 658nm and being capable of measuring both rayleigh scatter angles of 15 ° and 90 °. Three olexis columns of 30cm length and 7.5cm length filled with 13 microbeads with different pore sizes may be used. Alternatively, a suitable high temperature GPC column at a level equivalent to an olexis column or an olexis guard column may be employed. The sample carousel chamber was operated at 120 °, the column separation was operated at 150 °, and the retention time in the temperature equilibrated chamber before injection was set to 5 minutes. The developing solvent for chromatography or the solvent for sample preparation was Trichlorobenzene (TCB) containing 125ppm of antioxidant, and the solvent used was bubbled with nitrogen. The GPC flow rate was set at 1 ml/min. The light scatter detector and the concentration detector are arranged in series. The inter-detector delay (IDD) resulting from the arrangement of the two detectors, i.e. the light scattering detector and the concentration detector, was calibrated by analyzing a linear polystyrene monomer standard with a molecular weight distribution of about 1 and a molecular weight (Mw) of about 200000. To ensure analytical reliability, at least three samples were prepared and used for the analysis. Polystyrene standards were purchased from Polymer Laboratories and injected after dissolving slowly at a concentration of 1mg/ml for 2 hours while stirring at 140 ℃.
4) GPC-LSD deconvolution: ethylene-vinyl acetate copolymers with long chain branches were distinguished by analysis of the GPC-LSD chromatographic response curves. The response to a Light Scattering (LS) detector is generally evaluated for samples treated with calibrated GPC over a range of sample molecular weights. As shown in fig. 1, the LS chromatogram of a sample having a concentration normalized by the above method represents two or more component polymers, wherein the Molecular Weight Distribution (MWD) of one component polymer relative to the other component polymer may be present as a bulge, shoulder, or tail. Thus, the LS chromatogram can be separated into the most likely peaks of the relevant molecular weight components (fig. 2, 3 and 4). Origin 9.1 software was used for peak separation. Peak broadening may depend on column conditions, concentration and molecular weight of the injected sample, flow rate, etc. Furthermore, many decomposition algorithms may lead to different results depending on the assumptions and methods used. The algorithm used in the present invention is optimized for decomposition into the three most likely MWD components (high molecular weight component-HMW, medium molecular weight component-MMW and low molecular weight component-LMW) under the following conditions of the LS chromatogram isolated under the analysis conditions described above. A Gaussian function is used as the curve fitting model, and the algorithm used in the present invention is based on R of the cumulative fitted peak drawn by recombining the three fitted curves2A value of 0.999 or more.
The area ratio of each peak was calculated by dividing the peak area obtained by integrating each separated peak by the total peak area.
< equation 1>
FHMW+FMMW+FLMW＝100
Conditions for sheet preparation
0.3 part by weight of Ciba Chimassorb 81 (2-hydroxy-4-octyloxy-benzophenone) as a UV absorber, 0.1 part by weight of Ciba Tinuvin 770 (bis-2, 2,6, 6-tetramethyl-4-piperidyl sebacate) as a UV stabilizer were mixed with 100 parts by weight of the EVA copolymer resin prepared in examples 1 to 3 and comparative examples 1 and 2. To the resulting mixture were added 0.5 parts by weight of Archeox TBEC (2-ethylhexyl T-butylperoxycarbonate) as a crosslinking agent, 0.5 parts by weight of TAICROS (triallyl isocyanurate) as a co-crosslinking agent, 0.3 parts by weight of Docong OFS 6030 (methacryloxypropyl trimethoxysiloxane) as a silane coupling agent, and mixed together, followed by extrusion using a single screw extruder having a screw diameter of 40mm and a T-die width of 400mm at an extrusion temperature of 100 ℃ and a screw rotation speed of 50rpm, thereby preparing an encapsulated sheet having a thickness of 450 μm.
1) Difference between highest torque value and lowest torque value (MH-ML): the degree of crosslinking and the rate of crosslinking were measured using an Oscillating Disk Rheometer (ODR) of the Alpha technique. For the encapsulated sheets with additives, a time sweep was performed at 150 ℃, which is equal to the lamination temperature. The measurements were carried out under preset conditions, including a frequency of 1.67Hz and a vibration angle of 6.98% at the time of oscillation.
2) Evaluation of the degree of moisture crosslinking: some of the bottom sheets prepared by the preparation method were sampled and then subjected to vacuum conditions at 150 ℃ for 6 minutes and crosslinked by using a laminator with a pressure of 1 bar for 11 minutes. A sample of the crosslinked sheet was soaked in boiling xylene for 4 hours and then dried for 12 hours, and then the weight reduction of the sample was measured and the xylene insoluble component was calculated from the weight reduction to evaluate the degree of crosslinking.
Example 1
In the first reaction stage, 72% by weight of ethylene monomer and 28% by weight of vinyl acetate monomer are injected into a reactor, tert-butyl peroxyneodecanoate (TBND), tert-butylperoxypivalate (TBND)Butyl ester (TBPV) and tert-butyl peroxy-2-ethylhexanoate (TBPO) were mixed in a weight ratio of 45:30:25, and the resulting mixture was injected into the reactor as a radical initiator. In the second reaction stage, tert-butyl peroxyneodecanoate (TBND), tert-butyl peroxypivalate (TBPV) and tert-butyl peroxy-2-ethylhexanoate (TBPO) were mixed in a weight ratio of 10:20:70, and 2000ppm of the resulting mixture was weighed with respect to the ethylene monomer and the vinyl acetate monomer, and then continuously injected into the reactor using a high-temperature pump. In the range of 2650kg/cm2The polymerization pressure, the polymerization temperature of 230 c and the polymerization time of 4 minutes. High molecular weight fraction (F) of EVA copolymer resin prepared as determined by GPC-LSD deconvolutionHMW) 8.2%, fraction of low molecular weight component (F)LMW) The content was 28.6%.
Example 2
In the first reaction stage, 72% by weight of ethylene monomer and 28% by weight of vinyl acetate monomer were injected into a reactor, tert-butyl peroxyneodecanoate (TBND), tert-butyl peroxypivalate (TBPV), tert-butyl peroxy-2-ethylhexanoate (TBPO) and tert-butyl peroxy-3, 5, 5-Trimethylhexanoate (TBPIN) were mixed in a weight ratio of 40:30:25:5, and the resulting mixture was injected into the reactor as a radical initiator. In the second reaction stage, tert-butyl peroxyneodecanoate (TBND), tert-butyl peroxypivalate (TBPV), tert-butyl peroxy-2-ethylhexanoate (TBPO) and tert-butyl peroxy-3, 5, 5-Trimethylhexanoate (TBPIN) were mixed in a weight ratio of 10:20:60:10, 2000ppm of the resulting mixture was weighed against the ethylene monomer and vinyl acetate monomer, and then continuously injected into the reactor using a high temperature pump. In the range of 2650kg/cm2The polymerization pressure, the polymerization temperature of 240 c and the polymerization time of 4 minutes. High molecular weight fraction (F) of EVA copolymer resin prepared as determined by GPC-LSD deconvolutionHMW) 8.0%, fraction of low molecular weight component (F)LMW) The content was 37.2%.
Example 3
72% by weight of ethylene monomer and 28% by weight of acetic acid were injected in a double injection ratio of 70:30 in the first and second reaction stages, respectivelyVinyl ester monomer is injected into the reactor. In the first reaction stage, tert-butyl peroxyneodecanoate (TBND), tert-butyl peroxypivalate (TBPV) and tert-butyl peroxy-2-ethylhexanoate (TBPO) were injected in a weight ratio of 45:30:25 as radical initiator. In the second reaction stage, tert-butyl peroxyneodecanoate (TBND), tert-butyl peroxypivalate (TBPV) and tert-butyl peroxy-2-ethylhexanoate (TBPO) were mixed in a weight ratio of 15:25:60, and 2000ppm of the resulting mixture was weighed against the ethylene monomer and vinyl acetate monomer, and then continuously injected into the reactor using a high temperature pump. In the range of 2650kg/cm2The polymerization pressure, the polymerization temperature of 230 c and the polymerization time of 4 minutes. High molecular weight fraction (F) of EVA copolymer resin prepared as determined by GPC-LSD deconvolutionHMW) 5.6%, fraction of low molecular weight component (F)LMW) It was 34.2%.
Comparative example 1
An EVA copolymer resin was prepared under substantially the same polymerization conditions as in example 1, except that t-butyl peroxyneodecanoate (TBND), t-butyl peroxypivalate (TBPV), and t-butyl peroxy-2-ethylhexanoate (TBPO) were injected as radical initiators at a weight ratio of 30:10:5 in the first reaction stage, and t-butyl peroxyneodecanoate (TBND), t-butyl peroxypivalate (TBPV), and t-butyl peroxy-2-ethylhexanoate (TBPO) were mixed at a weight ratio of 30:10:60 in the second reaction stage and the resulting mixture was injected. High molecular weight fraction (F) of EVA copolymer resin prepared as determined by GPC-LSD deconvolutionHMW) 12.9%, fraction of low molecular weight component (F)LMW) The content was found to be 23.2%.
Comparative example 2
The EVA copolymer resin used in comparative example 2 is an EVA product for solar cells, commercially available from TPC under the trade name VF 024. The EVA product has a VA content of 28.6% and a Melt Index (MI) of 3.3 as measured according to ASTM D1238 at 125 ℃ and 2.16kg load. The VA content and MI compared to the EVA copolymer resin prepared in example 2 were substantially the same as those of the EVA copolymer resin prepared in example 2. Macromolecules of EVA products as determined by GPC-LSD deconvolutionAmount component fraction (F)HMW) 15% of low molecular weight component fraction (F)LMW) It was 59.4%.
TABLE 1
The EVA copolymer resins prepared under the conditions defined in the examples and comparative examples were evaluated for various physical properties using the above-described measurement methods, solar cell encapsulation sheets were molded using the prepared EVA copolymer resins, various physical properties related to solar cell modules were evaluated, and the evaluation results are listed in table 2.
TABLE 2
As shown in table 2, the EVA copolymer resin prepared in the examples of the present invention has a bimodal molecular weight distribution in view of a light scattering chromatogram determined by GPC. Herein, the High Molecular Weight (HMW) fraction (F) of the EVA copolymer resin as determined by GPC-LSD deconvolutionHMW) And a Low Molecular Weight (LMW) fraction (F)LMW) Less than 10% and less than 40%, respectively.
As confirmed from the Oscillating Disc Rheometer (ODR) data of EVA sheets prepared by adding a crosslinking agent and an additive for solar cell sheets, each EVA sheet has a torque difference (MH-ML) value of 2.0dNm or more, a crosslinking time of 11 minutes or less, and all weight ratios of xylene soluble components are 85% or more, indicating that the EVA copolymer sheet of the present invention shows a relatively short crosslinking time and a relatively high degree of crosslinking compared to the EVA resins prepared in comparative examples 1 and 2.
In the EVA copolymer sheet according to the present invention, a crosslinking agent may be used in a reduced amount due to relatively rapid crosslinking and a relatively high degree of crosslinking, and the time required for lamination may be shortened, thereby increasing module productivity and improving long-term physical properties of a solar cell module.
In contrast, in the EVA copolymer resin prepared in comparative example 1, the Molecular Weight Distribution (MWD) is 4.2, which is in the range of 4.0 to 4.5, i.e., the MWD range of the EVA copolymer resin of the present invention. However, since the EVA copolymer resin prepared in comparative example 1 had a high molecular weight component fraction (F) of 10% or moreHMW) And thus the EVA copolymer resin prepared in comparative example 1 has a relatively low degree of crosslinking.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Claims (10)
1. An ethylene-vinyl acetate EVA copolymer resin for a solar cell encapsulation sheet, wherein a GPC-LSD deconvolution is performed using a Gaussian function as a curve fitting model to decompose a GPC-LSD chromatogram of the EVA copolymer resin into a high molecular weight component HMW peak, a medium molecular weight component MMW peak, and a low molecular weight component LMW peak,
and, calculating a high molecular weight component HMW fraction F of the EVA copolymer resin using equation 1HMWAnd a low molecular weight component LMW fraction F of the EVA copolymer resinLMW，
< equation 1>
FHMW+FMMW+FLMW＝100
High molecular weight component HMW fraction F of the EVA copolymer resin as determined by GPC-LSD deconvolutionHMWLess than 10%, and a LMW fraction F of the low molecular weight component of the EVA copolymer resin as determined by GPC-LSD deconvolutionLMWLess than 40%.
2. The EVA copolymer resin according to claim 1, wherein the molecular weight distribution Mw/Mn of the EVA copolymer resin is in the range of 4.0 to 4.5.
3. A method of making an ethylene-vinyl acetate EVA copolymer resin, comprising:
injecting vinyl acetate monomer and ethylene monomer into a polymerization reactor;
adding a polymerization initiator mixture comprising at least three peroxide polymerization initiators; and
at a polymerization temperature of 190 to 250 ℃ and a polymerization pressure of 2600 to 2700kg/cm2And a polymerization time of 2 to 5 minutes,
wherein the peroxide polymerization initiator forms a mixture comprising A an alkyl peroxyneodecanoate compound having 4 to 5 carbon atoms in the peroxide-bonded alkyl group, B an alkyl peroxypivalate compound having 4 to 5 carbon atoms in the peroxide-bonded alkyl group, and C an alkyl peroxyhexanoate compound having 4 to 5 carbon atoms in the peroxide-bonded alkyl group,
wherein the weight ratio of alkyl peroxyneodecanoate compound a, alkyl peroxypivalate compound B, and alkyl peroxyhexanoate compound C in the peroxide polymerization initiator mixture is 30-50: 20-40: 20-40, in the second reaction stage 1-20: 10-30: 50 to 80, and
performing GPC-LSD deconvolution by using a Gaussian function as a curve fitting model, decomposing a GPC-LSD chromatogram of the EVA copolymer resin into a high molecular weight component HMW peak, a medium molecular weight component MMW peak and a low molecular weight component LMW peak,
and, calculating a high molecular weight component HMW fraction F of the EVA copolymer resin using equation 1HMWAnd a low molecular weight component LMW fraction F of the EVA copolymer resinLMW，
< equation 1>
FHMW+FMMW+FLMW＝100
Wherein the high molecular weight component HMW fraction F of the EVA copolymer resin is determined by GPC-LSD deconvolutionHMWLess than 10%, and a LMW fraction F of the low molecular weight component of the EVA copolymer resin as determined by GPC-LSD deconvolutionLMWLess than 40%.
4. The method of claim 3 wherein the EVA copolymer resin has a molecular weight distribution, Mw/Mn, in the range of from 4.0 to 4.5.
5. The process of claim 3 wherein in the peroxide polymerization initiator mixture, the alkyl peroxyneodecanoate compound A is t-butyl peroxyneodecanoate TBND, the alkyl peroxypivalate compound B is t-butyl peroxypivalate TBPV, and the alkyl peroxyhexanoate compound C is one selected from the group consisting of t-butyl peroxy-2-ethylhexanoate TBPO and t-butyl peroxy-3, 5, 5-trimethylhexanoate TBPIN.
6. The method of claim 3, wherein the polymerization initiator is added at a concentration of 1000 to 3000 ppm.
7. An encapsulating sheet for a solar cell, wherein the encapsulating sheet employs the EVA copolymer resin according to claim 1 or 2.
8. The encapsulating sheet of claim 7, comprising based on the total weight of the EVA copolymer resin
0.3 to 1.0 parts by weight of a crosslinking agent;
0.3 to 1.0 part by weight of a co-crosslinking agent; and
0.3 to 1.0 part by weight of a silane coupling agent.
9. The packaging sheet according to claim 7, wherein a torque difference obtained by measuring a change in elastic modulus with a time sweep at 150 ℃ by an oscillating disc rheometer is equal to or greater than 2.0dNm,
the torque difference is the difference between the highest torque value and the lowest torque value.
10. The packaging sheet according to claim 7, wherein the degree of crosslinking is evaluated at a value of 85% or more, which is obtained by a method of measuring the weight of the xylene soluble component after crosslinking at a temperature in the range of 130 ℃ to 160 ℃.
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| KR1020170136867A KR102055982B1 (en) | 2017-10-20 | 2017-10-20 | Ethylenevinylacetate copolymer for solar light, the method of preparing the same, and Encapsulant sheet for solar cell employing the same |
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| CN113402647B (en) * | 2020-12-31 | 2023-10-13 | 中国科学院长春应用化学研究所 | Regulation and control method and synthesis method of synthetic EVA with controllable release of free radical, EVOH resin and synthesis method thereof |
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| CN105669886A (en) * | 2014-12-03 | 2016-06-15 | 韩华道达尔有限公司 | Ethylene vinyl acetate copolymer for solar cell encapsulant and the method of manufacturing the copolymer |
| KR20160092288A (en) * | 2015-01-27 | 2016-08-04 | 한화토탈 주식회사 | Method for manufacturing Ethylene Vinyl Acetate Copolymer and Ethylene Vinyl Acetate Copolymer manufactured by the same |
| CN106916242A (en) * | 2015-12-24 | 2017-07-04 | 韩华道达尔有限公司 | The manufacture method and resin and encapsulating material for solar cell piece of EVAc resin |
| CN106947013A (en) * | 2016-01-06 | 2017-07-14 | 韩华道达尔有限公司 | The EVAc resin for preparing the method for EVAc resin and being prepared using this method |
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| KR101757565B1 (en) | 2015-12-29 | 2017-07-12 | 한화토탈 주식회사 | Method for manufacturing polyethylene or polyethylene vinylacetate copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105669886A (en) * | 2014-12-03 | 2016-06-15 | 韩华道达尔有限公司 | Ethylene vinyl acetate copolymer for solar cell encapsulant and the method of manufacturing the copolymer |
| KR20160092288A (en) * | 2015-01-27 | 2016-08-04 | 한화토탈 주식회사 | Method for manufacturing Ethylene Vinyl Acetate Copolymer and Ethylene Vinyl Acetate Copolymer manufactured by the same |
| CN106916242A (en) * | 2015-12-24 | 2017-07-04 | 韩华道达尔有限公司 | The manufacture method and resin and encapsulating material for solar cell piece of EVAc resin |
| CN106947013A (en) * | 2016-01-06 | 2017-07-14 | 韩华道达尔有限公司 | The EVAc resin for preparing the method for EVAc resin and being prepared using this method |
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