CN111690086B - Preparation method of rapid crosslinking type propenyl polyolefin for packaging solar cell - Google Patents
Preparation method of rapid crosslinking type propenyl polyolefin for packaging solar cell Download PDFInfo
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- CN111690086B CN111690086B CN202010563259.2A CN202010563259A CN111690086B CN 111690086 B CN111690086 B CN 111690086B CN 202010563259 A CN202010563259 A CN 202010563259A CN 111690086 B CN111690086 B CN 111690086B
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- catalyst
- polyolefin
- crosslinking
- reactor
- solar cell
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- 238000004132 cross linking Methods 0.000 title claims abstract description 60
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 46
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 10
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims abstract description 14
- 238000005538 encapsulation Methods 0.000 claims abstract description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 55
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 27
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 238000007334 copolymerization reaction Methods 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 16
- 238000009826 distribution Methods 0.000 claims description 13
- 239000004711 α-olefin Substances 0.000 claims description 12
- -1 acryl Chemical group 0.000 claims description 11
- 239000012968 metallocene catalyst Substances 0.000 claims description 9
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 150000004291 polyenes Chemical class 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- GDBLZKMJBVGZTR-UHFFFAOYSA-K Cl[Ti](OC1=C(C=CC=C1)C1=CC=CC=C1)(C1(C(=C(C(=C1C)C)C)C)C)Cl Chemical compound Cl[Ti](OC1=C(C=CC=C1)C1=CC=CC=C1)(C1(C(=C(C(=C1C)C)C)C)C)Cl GDBLZKMJBVGZTR-UHFFFAOYSA-K 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 150000005671 trienes Chemical class 0.000 claims description 3
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 claims description 2
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 229910052744 lithium Chemical group 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims 1
- KGWXYUFIQHXOIL-UHFFFAOYSA-K CC(C)C1=CC=CC(C(C)C)=C1O[Ti](Cl)(Cl)C1(C)C(C)=C(C)C(C)=C1C Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O[Ti](Cl)(Cl)C1(C)C(C)=C(C)C(C)=C1C KGWXYUFIQHXOIL-UHFFFAOYSA-K 0.000 claims 1
- DVZWQGLVEOWFOU-UHFFFAOYSA-N C[Hf]C Chemical compound C[Hf]C DVZWQGLVEOWFOU-UHFFFAOYSA-N 0.000 claims 1
- UGVVIPAIDGTTNN-UHFFFAOYSA-N C[Zr]C Chemical compound C[Zr]C UGVVIPAIDGTTNN-UHFFFAOYSA-N 0.000 claims 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 claims 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 26
- 238000010030 laminating Methods 0.000 abstract description 9
- 239000005022 packaging material Substances 0.000 abstract description 8
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000005086 pumping Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 4
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 4
- DZETZMSAJDMAKS-UHFFFAOYSA-L Cl[Zr]Cl.[CH]1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 Chemical compound Cl[Zr]Cl.[CH]1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 DZETZMSAJDMAKS-UHFFFAOYSA-L 0.000 description 4
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000010096 film blowing Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- VLBCYLMKVRFERM-UHFFFAOYSA-N 6-methylocta-1,5-diene Chemical compound CCC(C)=CCCC=C VLBCYLMKVRFERM-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- OIDRXSLJYDFQAZ-UHFFFAOYSA-N N[Hf].N1=CC=CC=C1 Chemical compound N[Hf].N1=CC=CC=C1 OIDRXSLJYDFQAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- YQRRFEPNTPQQHU-UHFFFAOYSA-L [Cl-].[Cl-].C(C=1C(O)=CC=CC1)=C1C(C=CC=C1)N=[Ti+2]=NC1C(C=CC=C1)=CC=1C(O)=CC=CC1 Chemical compound [Cl-].[Cl-].C(C=1C(O)=CC=CC1)=C1C(C=CC=C1)N=[Ti+2]=NC1C(C=CC=C1)=CC=1C(O)=CC=CC1 YQRRFEPNTPQQHU-UHFFFAOYSA-L 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical compound OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/322—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of solar panels
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a preparation method of rapid crosslinking type propenyl polyolefin for solar cell encapsulation, which utilizes continuous solution polymerization to prepare rapid crosslinking type propenyl polyolefin material by controlling the retention time and the addition amount of raw materials, wherein the crosslinking group is vinyl, 0-30 weight percent of the synthesized propenyl polyolefin does not contain the crosslinking group, and the molar composition of the crosslinking group of 30-70 weight percent of the synthesized propenyl polyolefin is 0.001-10%. The total laminating time of the solar cell packaging material prepared from the crosslinking type propenyl polyolefin material is less than 10min at 145 ℃, and the crosslinking degree after laminating is more than 70%. The fast crosslinking type solar cell packaging polyolefin prepared by the invention can be used for replacing the traditional solar cell packaging material and has the advantages of fast crosslinking speed, good weather resistance and the like.
Description
Technical Field
The invention belongs to the technical field of polyolefin preparation, and particularly relates to a preparation method of cross-linked polyolefin for solar cell encapsulation.
Background
The polyolefin has the advantages of rich raw materials, low price, easy processing and forming and excellent comprehensive performance, and can be applied to the fields of automobiles, aviation, food, medical appliances and the like. The preparation method comprises gas phase method, slurry method and bulk methodAnd solution process, with the success of the industrialization of metallocene catalysts in the last 90 th century, the solution polymerization process has been widely used. Typical solution polymerization processes include the INSITE process by Dow and the Exxon adiabatic solution polymerization process by Exxon Mobil chemical, under the trade names Engage, respectively TM And Exact TM . The molecular weight and distribution of the polymer and the composition and distribution of the copolymer can be regulated and controlled by regulating and controlling the feeding strategy of each monomer in the polymerization process, so that the polyolefin product with more excellent performance and wider application range is obtained.
Ethylene-vinyl acetate copolymers and polyolefins are widely used as solar cell sealing materials because of their advantages such as transparency, flexibility and insulation properties. The ethylene-vinyl acetate copolymer is easy to degrade and yellow in the long-term use process of the solar cell module, so that the service life of the photovoltaic module in power generation is shortened, and the power generation efficiency is greatly reduced. The polyolefin material has the characteristics of excellent weather resistance, PID (proportion integration differentiation) effect resistance, difficult yellowing and the like due to a saturated hydrocarbon structure, and is an emerging photovoltaic packaging material (CN 106206790A, CN105247689A, CN104995745A, CN104823285B and CN 104530994B). But the saturated hydrocarbon structure also results in slower crosslinking rates relative to ethylene-vinyl acetate copolymers.
At present, few commercial polyolefins specially aiming at photovoltaic packaging films are available on the market, and EnLIGHT is introduced by Dow by utilizing INSITE process of the polyolefins TM The series of polyolefin has strong bonding force with glass and no bubble in lamination, is very suitable for being applied to the encapsulation of thin film components, crystalline silicon components and flexible components, but the prepared polyolefin still has a saturated chain structure and slow crosslinking speed. Therefore, the patent adopts a continuous solution polymerization mode, and prepares a rapid crosslinking type propenyl polyolefin material consisting of two crosslinking groups by controlling the retention time and the addition amount of raw materials, wherein the crosslinking groups are vinyl, the molar composition of the crosslinking groups in the synthesized polyolefin is 0.001-10%, the weight average molecular weight is 1-500 kg/mol, and the molecular weight distribution index is 2.0-15.0;
disclosure of Invention
The invention aims to provide a preparation method of rapid crosslinking type propenyl polyolefin for packaging a solar cell aiming at the defects of the existing production products and technologies.
The purpose of the invention is realized by the following technical scheme: a preparation method of fast cross-linking type propenyl polyolefin for packaging a solar cell comprises the following steps: under the anhydrous and anaerobic conditions, adding a first part of propylene, a first part of alpha-olefin, a copolymerization catalyst and a cocatalyst into an organic solvent of a first reactor in a multistage continuous reactor, polymerizing at 50-300 ℃, keeping the time for 0.5-180min, then flowing into a subsequent reactor, adding a polyene monomer with a crosslinking group, a second part of propylene and a second part of alpha-olefin into the subsequent reactor, polymerizing at 50-300 ℃, keeping the time for 0.5-180min, and obtaining the fast crosslinking type propenyl polyolefin for packaging the solar cell. Based on the volume of the organic solvent, the adding amount of the first part of propylene, the first part of alpha-olefin, the second part of propylene, the second part of alpha-olefin and the polyene monomer with a crosslinking group is 0.001-10 mol/L, the concentration of the catalyst is 0.1-100 mu mol/L, and the molar ratio of the cocatalyst to the copolymerization catalyst is 50-10000.
Further, the crosslinking group is vinyl, the weight average molecular weight of the prepared fast crosslinking propenyl polyolefin for solar cell encapsulation is 1-500 kg/mol, the molecular weight distribution index is 2.0-15.0, and the fast crosslinking propenyl polyolefin is composed of 0-30 wt% of olefin polymer without crosslinking group and 70-100 wt% of olefin polymer with crosslinking group; in the rapid crosslinking type propenyl polyolefin for packaging the solar cell, the molar content of a crosslinking group is 0.001-10%.
Further, the reactor is a tubular reactor or a kettle type reactor, and the polymerization mode is solution polymerization.
Further, the alpha-olefin is linear or branched alpha-olefin with 4-20 carbon atoms, and comprises butylene, 1-hexene, 1-octene, isoamylene, 2-methylpropene and the like.
Further, the polyene monomer includes a linear diene monomer, a cyclic diene monomer, a linear triene monomer, a cyclic triene monomer, a olefin having a benzene ring, etc., preferably butadiene, 1,5-hexadiene, 1,4-hexadiene, 1,7-octadiene, 1,9-decadiene, 1,4-isoprene, cyclopentadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinylbicyclo [2.2.1] hept-2-ene, styrene, cyclohexadiene, etc.
Furthermore, the copolymerization catalyst is mixed by one or two or more of metallocene catalyst and non-metallocene catalyst according to any proportion. <xnotran> , 5754 zxft 5754- -8- - ) (3- - ) , - , - - - , , , - , [ N- (3252 zxft 3252- ) -2- ] , , - - , - - , - - - , -3- - - , -3- - - , [2- (3 ',5' - ) - ] , (2- -3532 zxft 3532- - ) , , - (2- ) - , ( - (3425 zxft 3425- ) - , </xnotran> Bis (salicylidene-phenylimino) titanium dichloride and the like; the non-metallocene catalyst comprises a bidentate imine pyrrole ligand vanadium catalyst, a pyridine amino hafnium catalyst, a palladium diimine catalyst, neutral salicylaldehyde imine nickel, a phenoxy imine ligand catalyst and a catalyst with a limited geometrical configuration.
Further, the cocatalyst is selected from M (R) 1 ) 3 、M(O)R 1 Wherein M is aluminum, boron or lithium; r is 1 Is an alkyl group of 4 to 10 carbon atoms.
Further, said R 1 Methyl, ethyl, isobutyl are preferred.
Further, the organic solvent is straight-chain alkane, isoparaffin, cycloalkane or aralkane having 3 to 10 carbon atoms.
Further, the organic solvent is preferably n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, isoparaffin oil, toluene, xylene. In still another aspect, the invention also relates to a solar cell packaging material prepared from the rapid crosslinking type propenyl polyolefin material consisting of two crosslinking groups. Specifically, the sheet-shaped or film-shaped packaging material is prepared by one or more methods of calendaring, tape casting, film blowing and biaxial stretching. The solar cell packaging material processed by the synthesized propenyl polyolefin is laminated at 145 ℃, the laminating time is less than 10min, and the crosslinking degree of the polyolefin containing crosslinking groups after lamination is more than 70%.
The invention has the beneficial effects that: the continuous solution polymerization technology of the single-active-center-based metallocene catalyst system synthesizes the rapid crosslinking type propenyl polyolefin material by controlling the retention time and the addition amount of the raw materials, and overcomes the defect of low crosslinking speed of the metallocene polyolefin packaging material. The rapid crosslinking solar cell packaging propylene-based polyolefin material prepared by the invention can be used for replacing the traditional solar cell packaging material, has the advantages of high crosslinking speed, good weather resistance and the like, and has high industrial value.
Detailed Description
The present invention is illustrated by the following specific examples, which are merely exemplary and should not be construed as limiting the invention.
The molecular weights (Mw and Mn) of the polymers and their distribution indices (PDI) were determined by high temperature gel permeation chromatography (PL-GPC 220). 1,2,4-trichlorobenzene is used as solvent to prepare 0.1-0.3 wt% polymer solution at 150 deg.C, polystyrene with narrow molecular weight distribution is used as standard sample, and the flow rate of the solvent is 1.0ml/min, and the determination is carried out at 150 deg.C.
The solar module template was assembled by a vacuum laminator (TDCZ-Y-4) at a lamination temperature of 145 ℃.
The degree of crosslinking is calculated according to ASTM D2765-2016.
Example 1
The tubular and kettle reactors were connected in series for continuous solution polymerization, with the tubular reactor volume being 330ml and the kettle reactor volume being 300ml.
The tubular and tank reactors were purged with 10mmol/L of triisobutylaluminum Isopar E solution, after removal of water oxygen, the reactors and oil bath were opened, the temperature of both reactors was raised to 140 ℃ and the stirring speed was set to 1000rpm. And opening a feed valve and a discharge valve of the reactor, opening a high-pressure chemical metering pump, continuously pumping the solvent into the reactor, and allowing the propylene to flow into the reactor through a flow meter at a constant speed until the pressure in the two reactors is stabilized at 4MPa. Pumping rac-dimethylsilicon bridged-bis (2-methyl-4-phenyl-indenyl) zirconium dichloride catalyst solution, methylaluminoxane solution and octene into a tubular reactor, pumping rac-dimethylsilicon bridged-bis (2-methyl-4-phenyl-indenyl) zirconium dichloride catalyst solution, methylaluminoxane solution and 5-ethylidene-2 norbornene into a kettle reactor, and discharging the material discharge flow of the tubular reactor after the system is stabilized through the kettle reactor. The concentration of the copolymerization catalyst in the tubular reactor is 5umol/L, the concentration of the cocatalyst is 15mmol/L, the molar ratio of the cocatalyst to the main catalyst is 3000, the feeding concentration of the first part of propylene is 0.83mol/L, the feeding concentration of the first part of octene is 1.1mol/L, the concentration of the copolymerization catalyst in the tank reactor is 10umol/L, the concentration of the cocatalyst is 10mmol/L, the molar ratio of the cocatalyst to the main catalyst is 1000, the feeding concentration of the second part of propylene is 0.83mol/L, the feeding concentration of the second part of octene is 1.1mol/L, the feeding concentration of 5-ethylidene-2 norbornene is 0.02mol/L, the temperature of the two reactors is controlled at 140 ℃, the pressure is controlled at 4MPa, and the total residence time of materials in the reactors is 10min. The continuously flowing-out material is washed by a large amount of acidified ethanol, filtered, pumped to dryness and dried in vacuum at 60 ℃ for more than 8 hours. The molecular weight of the product is 90kg/mol, the molecular weight distribution is 3.6, the polyolefin containing crosslinking groups accounts for 80%, the dried sample is prepared into an encapsulation film by a hot-pressing film-forming mode, the laminating time is 8.5min, and the crosslinking degree is 74%.
Example 2
The tubular and kettle reactors were connected in series for continuous solution polymerization, with the tubular reactor volume being 330ml and the kettle reactor volume being 300ml.
The tubular and tank reactors were purged with 10mmol/L triisobutylaluminum Isopar E solution, after removal of water oxygen, the reactors and the oil bath were opened, the temperature of both reactors was raised to 90 ℃ and the stirring speed was set to 1000rpm. And opening a feed valve and a discharge valve of the reactor, opening a high-pressure chemical metering pump, continuously pumping the solvent into the reactor, and allowing the propylene to flow into the reactor through a flow meter at a constant speed until the pressure in the two reactors is stabilized at 2MPa. The method comprises the following steps of pumping pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride catalyst solution, modified methylaluminoxane solution and octene into a tubular reactor, pumping pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride catalyst solution, modified methylaluminoxane solution and 6-methyl-1,5-octadiene into a kettle type reactor, and discharging material discharged from the tubular reactor and discharged through the kettle type reactor after a system is stable. The concentration of the copolymerization catalyst in the tubular reactor is 4umol/L, the concentration of the cocatalyst is 12mmol/L, the molar ratio of the cocatalyst to the main catalyst is 3000, the feeding concentration of the first part of propylene is 0.7mol/L, the feeding concentration of the first part of octene is 0.9mol/L, the concentration of the copolymerization catalyst in the tank reactor is 8umol/L, the concentration of the cocatalyst is 8mmol/L, the molar ratio of the cocatalyst to the main catalyst is 1000, the feeding concentration of the second part of propylene is 0.7mol/L, the feeding concentration of the second part of octene is 0.9mol/L, the feeding concentration of 5-ethylidene-2 norbornene is 0.008mol/L, the temperature of the two reactors is controlled at 90 ℃, the pressure is controlled at 2MPa, and the total retention time of materials in the reactors is 10min. The continuously flowing-out material is washed by a large amount of acidified ethanol, filtered, pumped to dryness and dried in vacuum at 60 ℃ for more than 8 hours. The molecular weight of the product is 120kg/mol, the molecular weight distribution is 3.5, the polyolefin containing crosslinking groups accounts for 90%, the dried sample is prepared into an encapsulation film in a film blowing mode, the laminating time is 8.5min, and the crosslinking degree is 72%.
Example 3
The tubular and kettle reactors were connected in series for continuous solution polymerization, with the tubular reactor volume being 330ml and the kettle reactor volume being 300ml.
The tubular and tank reactors were purged with 10mmol/L of triisobutylaluminum Isopar E solution, after removal of water oxygen, the reactors and oil bath were opened, the temperature of both reactors was raised to 120 ℃ and the stirring speed was set to 1000rpm. And opening a feed valve and a discharge valve of the reactor, opening a high-pressure chemical metering pump, continuously pumping the solvent into the reactor, and allowing the propylene to flow into the reactor through a flow meter at a constant speed until the pressure in the two reactors is stabilized at 4MPa. Pumping diphenyl carbon bridge group-cyclopentadienyl-fluorenyl zirconium dichloride catalyst solution, methylaluminoxane solution and octene into a tubular reactor, pumping diphenyl carbon bridge group-cyclopentadienyl-fluorenyl zirconium dichloride catalyst solution, methylaluminoxane solution and 1,5-cyclooctadiene into a kettle type reactor, and discharging material discharged flow of the tubular reactor and discharging the material again through the kettle type reactor after the system is stable. The concentration of the copolymerization catalyst in the tubular reactor is 3umol/L, the concentration of the cocatalyst is 15mmol/L, the molar ratio of the cocatalyst to the main catalyst is 5000, the feeding concentration of the first part of propylene is 1.2mol/L, the feeding concentration of the first part of octene is 1.0mol/L, the concentration of the copolymerization catalyst in the tank reactor is 3umol/L, the concentration of the cocatalyst is 9mmol/L, the molar ratio of the cocatalyst to the main catalyst is 3000, the feeding concentration of the second part of propylene is 1.2mol/L, the feeding concentration of the second part of octene is 1.0mol/L, the feeding concentration of 1,5-cyclooctadiene is 0.005mol/L, the temperature of the two reactors is controlled at 120 ℃, the pressure is controlled at 4MPa, and the total residence time of materials in the reactors is 10min. The continuously outflowing material was washed with a large amount of acidified ethanol, filtered, drained and vacuum dried at 60 ℃ for over 8 hours. The molecular weight of the product is 80kg/mol, the molecular weight distribution is 3.8, the polyolefin containing crosslinking groups accounts for 72%, and a dried sample is prepared into an encapsulation film by a casting film forming mode, the laminating time is 15min, and the crosslinking degree is 73%.
Example 4
The two-kettle series continuous solution polymerization, the volume of the kettle type reactor is 300ml.
The tank reactor was rinsed with 10mmol/L triisobutylaluminum Isopar E solution, after removal of the water oxygen, the reactor and the oil bath were opened, the temperature of both reactors was raised to 140 ℃ and the stirring speed was set to 1000rpm. And opening a feed valve and a discharge valve of the reactor, opening a high-pressure chemical metering pump, continuously pumping the solvent into the reactor, and allowing the propylene to flow into the reactor through a flow meter at a constant speed until the pressure in the two reactors is stabilized at 4MPa. Rac-dimethylsilicon bridged-bis (2-methyl-4-phenyl-indenyl) zirconium dichloride catalyst solution, modified methylaluminoxane solution, octene were pumped into kettle 1, rac-dimethylsilicon bridged-bis (2-methyl-4-phenyl-indenyl) zirconium dichloride catalyst solution, methylaluminoxane solution, 5-ethylidene-2 norbornene were pumped into kettle 2, after the system had stabilized, the contents of kettle 1 were discharged through kettle 2 and discharged. The concentration of the copolymerization catalyst in the kettle 1 is 10umol/L, the concentration of the cocatalyst is 20mmol/L, the molar ratio of the cocatalyst to the main catalyst is 2000, the feed concentration of the first part of propylene is 0.83mol/L, the feed concentration of the first part of octene is 1.1mol/L, the concentration of the copolymerization catalyst in the kettle 2 is 5umol/L, the concentration of the cocatalyst is 10mmol/L, the molar ratio of the cocatalyst to the main catalyst is 2000, the feed concentration of the second part of propylene is 0.83mol/L, the feed concentration of the second part of octene is 1.1mol/L, the feed concentration of 5-ethylidene-2 norbornene is 0.008mol/L, the temperature of the two reactors is controlled at 140 ℃, the pressure is controlled at 4MPa, and the total residence time of materials in the reactors is 12min. The continuously outflowing material was washed with a large amount of acidified ethanol, filtered, drained and vacuum dried at 60 ℃ for over 8 hours. The molecular weight of the product is 85kg/mol, the molecular weight distribution is 3.6, the polyolefin containing crosslinking groups accounts for 75%, the dried sample is prepared into an encapsulation film by a biaxial stretching mode, the laminating time is 12min, and the crosslinking degree is 74%.
Example 5
The two-kettle series continuous solution polymerization, the volume of the kettle type reactor is 300ml.
The tank reactor was rinsed with 10mmol/L of triisobutylaluminum Isopar E solution, after removal of the water oxygen the reactor and the oil bath were opened, the temperature of both reactors was raised to 90 ℃ and the stirring speed was set to 1000rpm. And opening a feed valve and a discharge valve of the reactor, opening a high-pressure chemical metering pump, continuously pumping the solvent into the reactor, and allowing the propylene to flow into the reactor through a flow meter at a constant speed until the pressure in the two reactors is stabilized at 2MPa. The method comprises the following steps of pumping pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride catalyst solution, modified methylaluminoxane solution and octene into a kettle 1, pumping pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride catalyst solution, methylaluminoxane solution and 6-methyl-1,5-octadiene into a kettle 2, and discharging materials in the kettle 1 after the system is stable and the materials flow out of the kettle 2 and then are discharged. The concentration of the copolymerization catalyst in the kettle 1 is 4umol/L, the concentration of the cocatalyst is 12mmol/L, the molar ratio of the cocatalyst to the main catalyst is 3000, the feeding concentration of the first part of propylene is 0.7mol/L, the feeding concentration of the first part of octene is 0.9mol/L, the concentration of the copolymerization catalyst in the kettle 2 is 8umol/L, the concentration of the cocatalyst is 8mmol/L, the molar ratio of the cocatalyst to the main catalyst is 1000, the feeding concentration of the second part of propylene is 0.7mol/L, the feeding concentration of the second part of octene is 0.9mol/L, the feeding concentration of 5-ethylidene-2 norbornene is 0.002mol/L, the temperature of the two reactors is controlled at 90 ℃, the pressure is controlled at 2MPa, and the total retention time of the materials in the reactors is 12min. The continuously flowing-out material is washed by a large amount of acidified ethanol, filtered, pumped to dryness and dried in vacuum at 60 ℃ for more than 8 hours. The molecular weight of the product is 100kg/mol, the molecular weight distribution is 5.3, the polyolefin containing crosslinking groups accounts for 85%, the dried sample is prepared into an encapsulation film in a film blowing mode, the laminating time is 8min, and the crosslinking degree is 68%.
Example 6
The two-kettle series continuous solution polymerization is carried out, and the volume of the kettle type reactor is 300ml.
The tank reactor was rinsed with 10mmol/L of triisobutylaluminum Isopar E solution, after removal of the water oxygen the reactor and the oil bath were opened, the temperature of both reactors was raised to 120 ℃ and the stirring speed was set to 1000rpm. And opening a feed valve and a discharge valve of the reactor, opening a high-pressure chemical metering pump, continuously pumping the solvent into the reactor, and allowing the propylene to flow into the reactor through a flow meter at a constant speed until the pressure in the two reactors is stabilized at 4MPa. Diphenyl carbon bridge group-cyclopentadienyl-fluorenyl zirconium dichloride catalyst solution, methylaluminoxane solution and octene are pumped into a kettle 1, diphenyl carbon bridge group-cyclopentadienyl-fluorenyl zirconium dichloride catalyst solution, modified methylaluminoxane solution and 1,5-cyclooctadiene are pumped into a kettle 2, and after the system is stable, the material of the kettle 1 is discharged and flows through the kettle 2 and then is discharged. The concentration of the copolymerization catalyst in the kettle 1 is 3umol/L, the concentration of the cocatalyst is 15mmol/L, the molar ratio of the cocatalyst to the main catalyst is 5000, the feeding concentration of the first part of propylene is 1.2mol/L, the feeding concentration of the first part of octene is 1.0mol/L, the concentration of the copolymerization catalyst in the kettle 2 is 4umol/L, the concentration of the cocatalyst is 9mmol/L, the molar ratio of the cocatalyst to the main catalyst is 2250, the feeding concentration of the second part of propylene is 1.2mol/L, the feeding concentration of the second part of octene is 0.8mol/L, the feeding concentration of 1,5-cyclooctadiene is 0.1mol/L, the temperature of the two reactors is controlled at 120 ℃, the pressure is controlled at 4MPa, and the total residence time of the materials in the reactors is 12min. The continuously outflowing material was washed with a large amount of acidified ethanol, filtered, drained and vacuum dried at 60 ℃ for over 8 hours. The molecular weight of the product is 200kg/mol, the molecular weight distribution is 6.4, the polyolefin containing crosslinking groups accounts for 80%, the dried sample is prepared into an encapsulation film by a hot-pressing film-forming mode, the laminating time is 8min, and the crosslinking degree is 74%.
Claims (11)
1. A preparation method of rapid crosslinking type propenyl polyolefin for solar cell encapsulation is characterized by comprising the following steps: under the anhydrous and anaerobic conditions, adding a first part of propylene, a first part of alpha-olefin, a copolymerization catalyst and a cocatalyst into an organic solvent of a first reactor in a multistage continuous reactor, polymerizing at 50-300 ℃, keeping the time for 0.5-180min, then flowing into a subsequent reactor, adding a polyene monomer with a crosslinking group, a second part of propylene and a second part of alpha-olefin into the subsequent reactor, polymerizing at 50-300 ℃, keeping the time for 0.5-180min, and obtaining the fast crosslinking type propenyl polyolefin for packaging the solar cell; based on the volume of the organic solvent, the adding amount of the first part of propylene, the first part of alpha-olefin, the second part of propylene, the second part of alpha-olefin and the polyene monomer with a crosslinking group is 0.001-10 mol/L, the concentration of the catalyst is 0.1-100 mu mol/L, and the molar ratio of the cocatalyst to the copolymerization catalyst is 50-10000.
2. The preparation method according to claim 1, wherein the crosslinking group is vinyl, and the prepared fast crosslinking type acryl-based polyolefin for solar cell encapsulation has a weight average molecular weight of 1 to 500kg/mol, a molecular weight distribution index of 2.0 to 15.0, and consists of 0 to 30% by weight of an olefin polymer having no crosslinking group and 70 to 100% by weight of an olefin polymer having a crosslinking group; in the rapid crosslinking type propenyl polyolefin for packaging the solar cell, the mol content of a crosslinking group is 0.001-10%.
3. The process according to claim 1, wherein the reactor is a tubular reactor or a tank reactor, and the polymerization is a solution polymerization.
4. The method according to claim 1, wherein the α -olefin is a linear or branched α -olefin having 4 to 20 carbon atoms, and includes butene, 1-hexene, 1-octene, and isopentene.
5. The method according to claim 1, wherein the polyene monomer comprises a linear diene monomer, a cyclic diene monomer, a linear triene monomer, a cyclic triene monomer, and a triene having a benzene ring.
6. The method of claim 5, wherein the polyene monomer is selected from butadiene, 1,5-hexadiene, 1,4-hexadiene, 1,7-octadiene, 1,9-decadiene, 1,4-isoprene, cyclopentadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinylbicyclo [2.2.1] hept-2-ene, styrene, cyclohexadiene.
7. The preparation method of the catalyst according to claim 1, wherein the copolymerization catalyst is prepared by mixing one, two or more of metallocene catalyst and non-metallocene catalyst according to any proportion; the metallocene catalyst comprises bisindenyl dimethyl zirconium, dimethyl cyclopentadienyl-tetramethyl cyclopentadienyl-tert-butylamino-dimethyl titanium, bisindenyl zirconium dichloride, biscyclopentadienyl dimethyl hafnium, biscyclopentadienyl-bis-phenoxy zirconium, [ N- (3,5-di-tert-butylsalicylidene) -2-diphenylphosphino-phenylimine ] titanium trichloride, ethylenebridging bisindenyl zirconium dichloride, dimethyl bridging-3-pyrrolyl indenyl-tert-butylamino-dimethyl titanium, bis [2- (3 ',5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, bis (2-methyl-4,5-phenyl-indenyl) zirconium dichloride, dimethyl bridging bisindenyl zirconium dichloride, pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, (pentamethylcyclopentadienyl- (2,6-diisopropylphenoxy) -titanium dichloride, bis (salicylidene-phenylimine) titanium dichloride, the non-metallocene catalyst comprises bisindenyl vanadium catalyst, pyridinium amino hafnium catalyst, palladium imine catalyst, nickel bis (salicylaldiminine) palladium catalyst, salicylaldiminine catalyst, and a geometric configuration-defined ligand.
8. The method of claim 1, wherein the cocatalyst is selected from the group consisting of M (R) 1 ) 3 、M(O)R 1 Wherein M is aluminum, boron or lithium; r is 1 Is an alkyl group of 4 to 10 carbon atoms.
9. The method according to claim 8, wherein R is 1 Is an isobutyl group.
10. The method according to claim 1, wherein the organic solvent is a linear alkane, an isoparaffin, a cycloalkane, or an arylalkane having 3 to 10 carbon atoms.
11. The method according to claim 10, wherein the organic solvent is preferably n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, isoparaffin oil, toluene, xylene.
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| CN107075209A (en) * | 2014-09-30 | 2017-08-18 | 埃克森美孚化学专利公司 | The amorphous propene ethylene diene terpolymer composition of low ethene |
| CN109535323A (en) * | 2018-09-29 | 2019-03-29 | 浙江大学 | A kind of novel pectination propylene based polyolefm process for preparation of thermoplastic elastomer |
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