CN116178604A - Preparation method of thermoplastic polyolefin elastomer with high volume resistivity - Google Patents
Preparation method of thermoplastic polyolefin elastomer with high volume resistivity Download PDFInfo
- Publication number
- CN116178604A CN116178604A CN202211415064.9A CN202211415064A CN116178604A CN 116178604 A CN116178604 A CN 116178604A CN 202211415064 A CN202211415064 A CN 202211415064A CN 116178604 A CN116178604 A CN 116178604A
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- China
- Prior art keywords
- volume resistivity
- thermoplastic polyolefin
- polyolefin elastomer
- adsorbent
- catalyst
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Links
- 229920002397 thermoplastic olefin Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 28
- 239000003463 adsorbent Substances 0.000 claims description 57
- 238000001179 sorption measurement Methods 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 17
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 13
- -1 vinyl-bisindenyl-diphenoxy zirconium Chemical compound 0.000 claims description 13
- 239000004711 α-olefin Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 6
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 6
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 claims description 6
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 6
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims description 5
- ZOICEQJZAWJHSI-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boron Chemical compound [B]C1=C(F)C(F)=C(F)C(F)=C1F ZOICEQJZAWJHSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012968 metallocene catalyst Substances 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- 229940106006 1-eicosene Drugs 0.000 claims description 3
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 3
- 229940069096 dodecene Drugs 0.000 claims description 3
- 239000001282 iso-butane Substances 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012005 post-metallocene catalyst Substances 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 230000008020 evaporation Effects 0.000 description 27
- 238000001704 evaporation Methods 0.000 description 27
- 239000000463 material Substances 0.000 description 25
- 238000007670 refining Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VMZMXDNPNZSQOM-UHFFFAOYSA-N C[SiH](C)C[Ti](C)(NC(C)(C)C)C1C=C(C2=CC=CC=C12)C=1NC=CC1 Chemical compound C[SiH](C)C[Ti](C)(NC(C)(C)C)C1C=C(C2=CC=CC=C12)C=1NC=CC1 VMZMXDNPNZSQOM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- FJMJPZLXUXRLLD-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 FJMJPZLXUXRLLD-UHFFFAOYSA-L 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
Abstract
The invention provides a preparation method of a thermoplastic polyolefin elastomer with high volume resistivity, which comprises the following steps: in the process of preparing the thermoplastic polyolefin elastomer, residual catalyst is adsorbed and flash evaporated after the polymerization reaction is completed, so that the thermoplastic polyolefin elastomer with high volume resistivity is obtained. According to the invention, the relation between ash content and volume resistivity is represented, and the volume resistivity is controlled by controlling ash content, so that the problem of leakage current of the photovoltaic module is solved, and the overall progress of the photovoltaic industry in China is improved.
Description
Technical Field
The invention belongs to the technical field of polyolefin, and particularly relates to a preparation method of a thermoplastic polyolefin elastomer with high volume resistivity.
Background
The solar photovoltaic module is a device for converting solar energy into electric energy, but leakage current exists between glass and packaging materials along with the long-term high-voltage action of the module, a large amount of charges are accumulated on the surface of a battery piece, so that the passivation effect of the surface of the battery is deteriorated, and the photoelectric conversion rate is seriously affected. Therefore, the use of high resistivity materials is particularly important in the selection of the encapsulation material. The high resistivity packaging materials currently in use in the market are mostly made from thermoplastic polyolefin elastomers.
The high-resistivity packaging material is a glue film prepared from 95% of thermoplastic polyolefin elastomer and 5% of auxiliary agent. Because the consumption of the thermoplastic polyolefin elastomer is very large in the adhesive film, the development of the thermoplastic polyolefin elastomer with high volume resistivity is the most effective method for improving the volume resistivity of the photovoltaic packaging adhesive film and is the most important means for reducing the electric leakage of the photovoltaic module.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a thermoplastic polyolefin elastomer with high volume resistivity, and the product prepared by the method provided by the present invention has good performance.
The invention provides a preparation method of a thermoplastic polyolefin elastomer with high volume resistivity, which comprises the following steps:
in the process of preparing the thermoplastic polyolefin elastomer, residual catalyst is adsorbed and flash evaporated after the polymerization reaction is completed, so that the thermoplastic polyolefin elastomer with high volume resistivity is obtained.
Preferably, the adsorption is performed in an adsorption column; the pressure in the adsorption process is 3-20 MPa.
Preferably, the temperature in the adsorption process is 100-300 ℃.
Preferably, the adsorbent used in the adsorption process is one or more selected from silicon-aluminum adsorbents, phosphorus-aluminum adsorbents and skeleton heteroatom adsorbents.
Preferably, the particle size of the adsorbent is 1-5 mm.
Preferably, the bulk density of the adsorbent is 0.6 to 1.0g/ml.
Preferably, in the process of preparing the thermoplastic polyolefin elastomer, the relation between the volume resistivity and the ash is:
y=(-0.050±0.010)x+10;
y is the volume resistivity, unit 10 15 Ω·cm,
x is ash content in ppm.
Preferably, the method of polymerization comprises:
carrying out polymerization reaction on the reaction raw materials;
the reaction raw materials preferably include:
ethylene, alpha-olefin, organic solvent, main catalyst and cocatalyst.
Preferably, the alpha-olefin is a linear or branched alpha-olefin with 3-20 carbon atoms, and is selected from one or more of propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and 1-eicosene;
the organic solvent is preferably selected from one or more of n-butane, isobutane, cyclobutane, n-pentane or isopentane;
the main catalyst is preferably one or more of single-active-site metallocene catalyst or post-metallocene catalyst, and is selected from one or more of diphenylcarba bridge-cyclopentadienyl-fluorenyl zirconium dichloride, diphenylcarba bridge-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride, bis [2- (3 ',5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, dicyclopentadienyl-diphenoxy zirconium, vinyl-bisindenyl-diphenoxy zirconium, bis (salicylidene-phenylimino) titanium dichloride, [ N- (3, 5-di-tert-butylsalicylidene) -2-diphenylphosphinophenimine ] titanium trichloride, dimethylsilyl bridge-bisindenyl zirconium dichloride, dimethylsilyl bridge-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, dimethylsilyl bridge-3-pyrrolyl indenyl-tert-butylamino-dimethyl titanium, pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride;
the cocatalyst is preferably selected from one or more of methylaluminoxane compound, modified methylaluminoxane compound, tris (pentafluorophenyl) boron compound, triphenylcarbonium tetrakis (pentafluorophenyl) boron compound, N-dimethylanilinium tetrakis (pentafluorophenyl) boron compound, triisobutylaluminum and trimethylaluminum.
Preferably, the polymerization temperature is 100-200 ℃, the pressure is 1-10 MPa, and the time is 5-150 min.
At present, no preparation method of a thermoplastic polyolefin elastomer with high volume resistivity is reported, and the method is beneficial to solving the leakage current phenomenon of a photovoltaic module and improving the overall progress of the photovoltaic industry in China by representing the relation between ash and the volume resistivity and further controlling the volume resistivity by controlling the ash.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a thermoplastic polyolefin elastomer with high volume resistivity, which comprises the following steps:
in the process of preparing the thermoplastic polyolefin elastomer, residual catalyst is adsorbed and flash evaporated after the polymerization reaction is completed, so that the thermoplastic polyolefin elastomer with high volume resistivity is obtained.
In the research process, it is found that almost all ash is generated by unreacted parts of the catalyst and the cocatalyst in the preparation process, and mainly comprises aluminum, lithium, lead and mercury, wherein the former two account for up to 70% of all ash.
According to the invention, thermoplastic polyolefin elastomers with different ash contents of 50 ppm-300 ppm are prepared, 20-30 groups of data in an ash content interval of 50 ppm-300 ppm are screened, and linear fitting is carried out, so that the formula relation between volume resistivity and ash content is obtained:
y=(-0.050±0.010)x+10
y is the volume resistivity, unit 10 15 Ω·cm,
x is ash content in ppm.
The research of the invention discovers that the refining of raw materials and the dosage of the catalyst have certain influence on ash, but the two procedures of the mature polymerization process for preparing the thermoplastic elastomer are basically fixed, are not suitable to be changed, and have great influence on the product performance if the procedures are changed. The invention creatively discovers that the most effective way of controlling ash is to add a residual catalyst adsorption tower procedure in the post-treatment process, after the polymerization reaction of the materials in the reaction kettle is completed, the materials firstly flow through the residual catalyst adsorption tower, and the adsorption tower adsorbs most of the residual catalyst in the polymer and then enters a flash evaporation procedure.
In the present invention, the adsorption is preferably performed in an adsorption column; the pressure in the adsorption process is preferably 3-20 MPa, more preferably 4-8 MPa, and most preferably 5-6 MPa; the temperature is preferably 100 to 300 ℃, more preferably 120 to 190 ℃, and most preferably 140 to 160 ℃; the adsorbent used in the adsorption process is preferably one or more of silicon-aluminum adsorbents, phosphorus-aluminum adsorbents and skeleton heteroatom adsorbents, and more preferably silicon-aluminum adsorbents, such as 13X type products provided by the new material technology company of the Fangfang Nake; the particle size of the adsorbent is preferably in the form of spherical particles of 1 to 5mm, more preferably 2 to 4mm, most preferably 3mm; the bulk density is preferably 0.6 to 1.0g/ml, more preferably 0.7 to 0.9g/ml, most preferably 0.8g/ml.
In the present invention, the method of polymerization preferably comprises:
the reaction raw materials are subjected to polymerization reaction.
In the present invention, the material phase of the raw material may be a gas phase or a liquid phase; the reaction raw materials preferably include:
ethylene, alpha-olefin, organic solvent, main catalyst and cocatalyst.
In the present invention, the α -olefin is preferably a linear or branched α -olefin having 3 to 20 carbon atoms, more preferably 5 to 15, still more preferably 8 to 12, most preferably 10; more preferably, one or more selected from propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
In the present invention, the organic solvent is preferably selected from one or more of n-butane, isobutane, cyclobutane, n-pentane or isopentane.
In the present invention, the main catalyst is preferably one or more of single site metallocene catalyst or post-metallocene catalyst, more preferably one or more selected from diphenylcarbobridge-cyclopentadienyl-fluorenyl zirconium dichloride, diphenylcarbobridge-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride, bis [2- (3 ',5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, dicyclopentadienyl-diphenoxyzirconium, vinyl-bisindenyl-diphenoxyzirconium, bis (salicylidene-phenylimino) titanium dichloride, [ N- (3, 5-di-tert-butylsalicylidene) -2-diphenylphosphinophenimine ] titanium trichloride, dimethylsilyl-bisindenyl zirconium dichloride, dimethylsilyl-bridged-tetramethyl cyclopentadienyl-tert-butylamino-dimethyl titanium, dimethylsilyl-3-pyrrolyl indenyl-tert-butylamino-dimethyl titanium, pentamethyl cyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, pentamethyl cyclopentadienyl- (2, 6-diisophenoxy) -titanium dichloride.
In the present invention, the cocatalyst is preferably one or more selected from methylaluminoxane compounds, modified methylaluminoxane compounds, tris (pentafluorophenyl) boron compounds, triphenylcarbonium tetrakis (pentafluorophenyl) boron compounds, N-dimethylanilinium tetrakis (pentafluorophenyl) boron compounds, triisobutylaluminum, trimethylaluminum.
In the present invention, the molar ratio of the alpha-olefin to ethylene or other alpha-olefin is preferably 1: (1 to 4), more preferably 1: (2-3); the molar ratio of the cocatalyst to the main catalyst is preferably (3 to 10000) to 1, more preferably (10 to 8000): 1, more preferably (50 to 6000): 1, more preferably (100 to 4000): 1, more preferably (500 to 3000): 1, more preferably (1000 to 2000): 1, most preferably 1500:1, a step of; the volume ratio of the organic solvent to the monomer raw material (ethylene and/or alpha-olefin) is (5-20) to 1, more preferably (10-15): 1, most preferably (12 to 13): 1, a step of; the concentration of the procatalyst in the solvent is preferably 0.5 to 1.5. Mu. Mol/L, more preferably 0.8 to 1.2. Mu. Mol/L, and most preferably 1.0. Mu. Mol/L.
In the present invention, the polymerization is preferably carried out in a reaction vessel; the polymerization temperature is preferably 100 to 200 ℃, more preferably 130 to 180 ℃, and most preferably 140 to 160 ℃; the pressure of the polymerization is preferably 1 to 10MPa, more preferably 2 to 10MPa, still more preferably 3 to 6MPa, and most preferably 4 to 5MPa; the polymerization time is preferably 5 to 150 minutes, more preferably 10 to 130 minutes, more preferably 10 to 100 minutes, more preferably 10 to 80 minutes, more preferably 10 to 30 minutes, and most preferably 20 minutes.
In the present invention, the flash evaporation is preferably performed in a flash evaporation kettle, and the flash evaporation kettle is preferably selected from a falling-strip type flash evaporation kettle, a flash evaporation kettle with double helical stirring blades, and a flash evaporation kettle with single helical stirring blades; more preferably, the flash tank is of a type with double helical stirring blades, and the flash tank is more uniformly stirred and volatilized more water than a single helical type. In the invention, the pressure in the kettle is preferably controlled to be 0.1-5 MPa, more preferably 0.5-4 MPa, more preferably 1-3 MPa, and most preferably 2MPa in the flash evaporation process; the pressure difference between the inside and the outside of the kettle is preferably controlled to be 1-10 MPa, more preferably 2-8 MPa, more preferably 3-6 MPa, and most preferably 4-5 MPa; the temperature of the flash evaporation is preferably 120-200 ℃, more preferably 140-180 ℃, and most preferably 160 ℃; the flash evaporation time is preferably 3 to 30min, more preferably 5 to 25min, still more preferably 10 to 20min, and most preferably 15min.
In the present invention, the method for producing a thermoplastic polyolefin elastomer having a high volume resistivity preferably comprises:
after the reaction raw materials are refined, the refined raw materials enter a reaction kettle to carry out polymerization reaction, then pass through a catalyst adsorption tower, then carry out flash evaporation, and finally the extruder is devolatilized.
In the invention, the refining of the raw materials preferably adopts a refining agent; the refining agent is preferably one or more selected from dechlorination adsorbent, deoxidization adsorbent, dehydration adsorbent, desulfurization adsorbent, CO-removal adsorbent, acetylene-removal adsorbent, methane-removal adsorbent and methanol-removal adsorbent; the bulk density of the refining agent is preferably 0.5 to 1.0kg/L, more preferably 0.6 to 0.9kg/L, and most preferably 0.7kg/L.
In the present invention, the dechlorination adsorbent preferably contains SiO 2 、Al 2 O 3 At least one of active ingredients such as Na, K, cu, mn, mg and Ti; the desulfurization adsorbent is preferably an A-type, X-type or Y-type adsorbent, more preferably a DCH-02 desulfurization adsorbent, and is available from the New Material technology Co., ltd; the deoxidizing adsorbent is preferably an HTO-01 deoxidizing adsorbent, and is available from the new materials technology Co., ltd; the dehydration adsorbent is preferably a 3A dehydration adsorbent available from the New Material technology Co., ltd; the CO-free adsorbent is preferably a 5A adsorbent and/or a transition metal-loaded particle adsorbent; the transition metal particles in the transition metal particle-loaded adsorbent are preferably copper particles and/or iron particles; the acetylene removal adsorbent is preferably a supported catalyst for supporting metal active components, and is required to be used in a hydrogen atmosphere to catalyze the reaction process of acetylene and hydrogen; the metal active component is preferably at least one of Ni, pd and Pt, and the carrier is preferably Al 2 O 3 A carrier; the methanol removal catalyst is an A-type, X-type or Y-type adsorbent, more preferably a TC-4 methanol removal catalyst, and can be purchased from the new materials technology Co., ltd.
In the invention, the devolatilization of the extruder is preferably carried out in a double-screw extruder, a multistage devolatilization device is preferably adopted, the devolatilization efficiency is higher than that of single-stage devolatilization, the removal of small molecules is more thorough, and the VOC can be obviously reduced; the multi-stage devolatilization device is preferably 2-5 stages of devolatilization, more preferably 3-4 stages; the order of the cylinder on each stage of screw is preferably 5-15, more preferably 8-12, and most preferably 10; the number of the vacuumizing holes is preferably 4-7, more preferably 5-6; the vacuum pressure is preferably-0.09 to 0MPa, more preferably-0.09 to-0.03 MPa, and most preferably-0.09 to-0.06 MPa.
In the invention, the temperature of each barrel in the extrusion process of the extruder is preferably controlled to be 150-250 ℃, more preferably 180-220 ℃ and most preferably 200 ℃; the rotation speed is preferably controlled to 50 to 200rpm, more preferably 100 to 150ppm, most preferably 120 to 130ppm; the flow rate of the polymer in the screw is preferably controlled to be 10 to 200kg/h, more preferably 50 to 150kg/h, still more preferably 80 to 120kg/h, most preferably 100kg/h; the residence time is preferably 3 to 30 minutes, more preferably 5 to 25 minutes, more preferably 10 to 20 minutes, and most preferably 15 minutes.
According to the invention, the relation between ash content and volume resistivity is represented, and the volume resistivity is controlled by controlling ash content, so that the problem of leakage current of the photovoltaic module is solved, and the overall progress of the photovoltaic industry in China is improved.
Example 1
Refining raw materials: 1-octene and ethylene (the molar ratio of 1-octene to ethylene is 1:2, the total amount of ethylene and octene is 200 kg), a metallocene catalyst diphenyl carbon bridge-cyclopentadienyl-fluorenyl zirconium dichloride (the concentration in a solvent is 1 mu mol/L), a cocatalyst methylaluminoxane compound (the molar ratio of cocatalyst to main catalyst is 100:1), a solvent is n-hexane (the using amount ratio of solvent to 1-octene is 10 mL: 1 mL), a refining agent is dechlorinated adsorbent (activated alumina adsorbent of the company of the Fabry-Navigator) a deoxidized adsorbent (HTO-01 deoxidized adsorbent of the company of the Fabry-Navigator), a dehydration adsorbent (3A dehydrated adsorbent of the company of the Fabry-Navigator), a desulfurization adsorbent (DCH-02 desulfurization adsorbent of the company of the Fabry-Navigator), a CO-removal adsorbent (5A adsorbent of the company of the Fabry-Navigator), a dec-Navigator (HTO-01) and a new material of the company of the laboratory Navigator-Navigator, a new material of the laboratory-Navigator-4) and a new material of the laboratory-Navigator-4;
reaction conditions in the polymerization reactor: the temperature is 150 ℃, the pressure is 3MPa, and the reaction time is 20min;
the reaction materials after the polymerization reaction flow through a residual catalyst adsorption tower and then enter flash evaporation, and the main parameters of the adsorption tower are as follows:
the operating pressure of the catalyst adsorption tower is 4MPa, the temperature is 120 ℃, the adsorbent is 13X of silicon aluminum (13X type product provided by the new materials technology Co., ltd., the gallery Nake) and has the particle size of 2mm, the bulk density of 0.7g/ml and the appearance of sphere;
the flash evaporation process is as follows: the pressure in the kettle is controlled to be 3MPa, the pressure difference is controlled to be 10MPa, and the flash evaporation is carried out for 10min at 140 ℃.
Twin-screw extrusion control: selecting a three-stage devolatilization device, wherein the number of barrel steps on each stage of screw is 7, the number of vacuumizing ports is 4, the vacuumizing pressure is-0.082 MPa, the temperature of each barrel is controlled to 180 ℃, the rotating speed is controlled to 60rpm, the flow rate of the polymer in the screw is controlled to 40kg/h, and the residence time is 10min.
Example 2
The reaction conditions in the raw material refining and polymerization reactor were the same as in example 1.
The reaction materials after the polymerization reaction flow through a residual catalyst adsorption tower and then enter flash evaporation, and the main parameters of the adsorption tower are as follows:
the operating pressure of the catalyst adsorption tower is 4MPa, the temperature is 120 ℃, and the adsorbent is AlPO of phosphorus-aluminum type 4 (AlPO of the biological medicine technology Co., ltd., of Wuhank 4 ) The particle size is 2mm, the bulk density is 0.7g/ml, and the appearance is spherical;
the flash evaporation and twin screw extrusion processes were the same as in example 1.
Example 3
The reaction conditions in the raw material refining and polymerization reactor were the same as in example 1.
The reaction materials after the polymerization reaction flow through a residual catalyst adsorption tower and then enter flash evaporation, and the main parameters of the adsorption tower are as follows:
the operation pressure of the catalyst adsorption tower is 4MPa, the temperature is 120 ℃, the adsorbent is framework hetero atom ZSM-5 (ZSM-5 of Shandong ziyi nano technology Co., ltd.), the particle size is 2mm, the bulk density is 0.7g/ml, and the appearance is spherical;
the flash evaporation and twin screw extrusion processes were the same as in example 1.
Example 4
The reaction conditions in the raw material refining and polymerization reactor were the same as in example 1.
The reaction materials after the polymerization reaction flow through a residual catalyst adsorption tower and then enter flash evaporation, and the main parameters of the adsorption tower are as follows:
the operating pressure of the catalyst adsorption tower is 8MPa, the temperature is 120 ℃, the adsorbent is framework hetero atom ZSM-5 (ZSM-5 of Shandong ziyi nano technology Co., ltd.), the particle size is 2mm, the bulk density is 0.7g/ml, and the appearance is spherical;
the flash evaporation and twin screw extrusion processes were the same as in example 1.
Example 5
The reaction conditions in the raw material refining and polymerization reactor were the same as in example 1.
The reaction materials after the polymerization reaction flow through a residual catalyst adsorption tower and then enter flash evaporation, and the main parameters of the adsorption tower are as follows:
the operation pressure of the catalyst adsorption tower is 8MPa, the temperature is 190 ℃, the adsorbent is framework hetero atom ZSM-5, the particle size is 2mm, the bulk density is 0.7g/ml, and the appearance is spherical;
the flash evaporation and twin screw extrusion processes were the same as in example 1.
Comparative example 1
A thermoplastic polyolefin elastomer was produced according to the method of example 1, which differs from example 1 in that no catalyst adsorption column was provided, and the material of the reaction vessel was discharged and then directly subjected to flash evaporation.
Comparative example 2
A thermoplastic polyolefin elastomer was produced according to the method of example 2, except that a catalyst adsorption column was not provided, and the material of the reaction vessel was directly introduced into flash evaporation after flowing out.
Comparative example 3
A thermoplastic polyolefin elastomer was produced according to the method of example 3, except that the catalyst adsorption column was not provided, and the material of the reaction vessel was directly introduced into flash evaporation after flowing out.
Comparative example 4
A thermoplastic polyolefin elastomer was produced according to the method of example 4, except that the catalyst adsorption column was not provided, and the material of the reaction vessel was directly introduced into flash evaporation after flowing out.
Comparative example 5
A thermoplastic polyolefin elastomer was produced according to the method of example 5, except that the catalyst adsorption column was not provided, and the material of the reaction vessel was directly introduced into flash evaporation after flowing out.
Performance detection
Ash and volume resistivity of the thermoplastic polyolefin elastomer prepared in the examples and comparative examples of the present invention were measured by: ash content: GB/T9345.1-2008 plastic ash content determination; volume resistivity: GB/T1410-2006 solid insulating material volume resistivity and surface resistivity test method.
The detection results are as follows:
by comparing the examples with the comparative examples, it can be found that: the residual catalyst adsorption tower is arranged, and compared with the adsorption tower without the residual catalyst, the ash content of the thermoplastic polyolefin elastomer is obviously reduced, and the volume resistivity is obviously increased. By comparing example 1, example 2, example 3 with each other, it can be found that: the silicon-aluminum adsorbent has better adsorption effect, and the thermoplastic polyolefin elastomer has lower ash content and higher volume resistivity. By comparing example 3 with example 4, it can be found that: the pressure of the residual catalyst adsorption tower is increased, ash content can be reduced, and volume resistivity can be improved. By comparison of example 4 with example 5, it can be found that: the temperature of the residual catalyst adsorption tower is increased, ash content can be reduced, and volume resistivity can be improved. In the present invention, setting the residual catalyst adsorption tower is very important for lowering ash and increasing volume resistivity, wherein the silicon-aluminum type adsorbent has the best effect, and as the temperature and pressure in the adsorption tower are increased, ash is slightly lowered, volume resistivity is slightly increased, but the temperature and pressure are increased, so that comprehensive consideration is required for energy consumption.
According to the invention, the relation between ash content and volume resistivity is represented, and the volume resistivity is controlled by controlling ash content, so that the problem of leakage current of the photovoltaic module is solved, and the overall progress of the photovoltaic industry in China is improved.
While the invention has been described and illustrated with reference to specific embodiments thereof, the description and illustration is not intended to limit the invention. It will be apparent to those skilled in the art that various changes may be made in this particular situation, material, composition of matter, substance, method or process without departing from the true spirit and scope of the invention as defined by the following claims, so as to adapt the objective, spirit and scope of the present application. All such modifications are intended to be within the scope of this appended claims. Although the methods disclosed herein have been described with reference to particular operations being performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form an equivalent method without departing from the teachings of the present disclosure. Thus, unless specifically indicated herein, the order and grouping of operations is not a limitation of the present application.
Claims (10)
1. A method of preparing a thermoplastic polyolefin elastomer of high volume resistivity comprising:
in the process of preparing the thermoplastic polyolefin elastomer, residual catalyst is adsorbed and flash evaporated after the polymerization reaction is completed, so that the thermoplastic polyolefin elastomer with high volume resistivity is obtained.
2. The method according to claim 1, wherein the adsorption is performed in an adsorption column; the pressure in the adsorption process is 3-20 MPa.
3. The method according to claim 1, wherein the temperature during the adsorption is 100-300 ℃.
4. The method according to claim 1, wherein the adsorbent used in the adsorption process is one or more selected from the group consisting of silica-alumina adsorbents, phosphorus-alumina adsorbents and skeletal heteroatom adsorbents.
5. The method of claim 4, wherein the adsorbent has a particle size of 1 to 5mm.
6. The method of claim 4, wherein the adsorbent has a bulk density of 0.6 to 1.0g/ml.
7. The method of claim 1, wherein the thermoplastic polyolefin elastomer is prepared by a process having a volume resistivity and ash relationship of:
y=(-0.050±0.010)x+10;
y is the volume resistivity, unit 10 15 Ω·cm,
x is ash content in ppm.
8. The method of claim 1, wherein the method of polymerizing comprises:
carrying out polymerization reaction on the reaction raw materials;
the reaction raw materials preferably include:
ethylene, alpha-olefin, organic solvent, main catalyst and cocatalyst.
9. The method according to claim 8, wherein the alpha-olefin is a linear or branched alpha-olefin having 3 to 20 carbon atoms, and is selected from one or more of propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene, and 1-eicosene;
the organic solvent is preferably selected from one or more of n-butane, isobutane, cyclobutane, n-pentane or isopentane;
the main catalyst is preferably one or more of single-active-site metallocene catalyst or post-metallocene catalyst, and is selected from one or more of diphenylcarba bridge-cyclopentadienyl-fluorenyl zirconium dichloride, diphenylcarba bridge-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride, bis [2- (3 ',5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, dicyclopentadienyl-diphenoxy zirconium, vinyl-bisindenyl-diphenoxy zirconium, bis (salicylidene-phenylimino) titanium dichloride, [ N- (3, 5-di-tert-butylsalicylidene) -2-diphenylphosphinophenimine ] titanium trichloride, dimethylsilyl bridge-bisindenyl zirconium dichloride, dimethylsilyl bridge-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, dimethylsilyl bridge-3-pyrrolyl indenyl-tert-butylamino-dimethyl titanium, pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride;
the cocatalyst is preferably selected from one or more of methylaluminoxane compound, modified methylaluminoxane compound, tris (pentafluorophenyl) boron compound, triphenylcarbonium tetrakis (pentafluorophenyl) boron compound, N-dimethylanilinium tetrakis (pentafluorophenyl) boron compound, triisobutylaluminum and trimethylaluminum.
10. The method according to claim 8, wherein the polymerization is carried out at a temperature of 100 to 200 ℃, a pressure of 1 to 10MPa, and a time of 5 to 150 minutes.
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