MXPA96000627A - Components and catalysts for olefi polymerization - Google Patents
Components and catalysts for olefi polymerizationInfo
- Publication number
- MXPA96000627A MXPA96000627A MXPA/A/1996/000627A MX9600627A MXPA96000627A MX PA96000627 A MXPA96000627 A MX PA96000627A MX 9600627 A MX9600627 A MX 9600627A MX PA96000627 A MXPA96000627 A MX PA96000627A
- Authority
- MX
- Mexico
- Prior art keywords
- carbon atoms
- radicals
- bis
- methoxymethi
- equal
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 133
- 238000006116 polymerization reaction Methods 0.000 title claims description 26
- 125000004432 carbon atoms Chemical group C* 0.000 claims abstract description 169
- 239000007787 solid Substances 0.000 claims abstract description 61
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 125000003367 polycyclic group Chemical group 0.000 claims abstract 4
- -1 magnesium halide Chemical class 0.000 claims description 147
- 150000001875 compounds Chemical class 0.000 claims description 55
- 150000003254 radicals Chemical class 0.000 claims description 41
- 125000003118 aryl group Chemical group 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 30
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 25
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000001336 alkenes Chemical class 0.000 claims description 22
- 239000011777 magnesium Substances 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229910052749 magnesium Inorganic materials 0.000 claims description 19
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L MgCl2 Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 18
- 125000005842 heteroatoms Chemical group 0.000 claims description 17
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 16
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 150000002829 nitrogen Chemical group 0.000 claims description 13
- 125000004429 atoms Chemical group 0.000 claims description 12
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 150000003609 titanium compounds Chemical class 0.000 claims description 11
- 102100010976 SLC39A2 Human genes 0.000 claims description 10
- 101710017106 SLC39A2 Proteins 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- HSUIVCLOAAJSRE-UHFFFAOYSA-N bis(2-methoxyethyl) benzene-1,2-dicarboxylate Chemical compound COCCOC(=O)C1=CC=CC=C1C(=O)OCCOC HSUIVCLOAAJSRE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- YBYIRNPNPLQARY-UHFFFAOYSA-N Indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N Fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 125000004433 nitrogen atoms Chemical group N* 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N oxygen atom Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000004430 oxygen atoms Chemical group O* 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004434 sulfur atoms Chemical group 0.000 claims description 4
- GJCOSYZMQJWQCA-UHFFFAOYSA-N Xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 150000004291 polyenes Polymers 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- 239000002879 Lewis base Substances 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J Titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- LCMTZHXTJIFQJX-UHFFFAOYSA-N [2-(methoxymethyl)-3,4,5-triphenylcyclopenta-1,4-dien-1-yl]benzene Chemical compound COCC1=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C1C1=CC=CC=C1 LCMTZHXTJIFQJX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 150000007527 lewis bases Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Chemical group CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims 2
- IAKOZHOLGAGEJT-UHFFFAOYSA-N 1,1,1-trichloro-2,2-bis(p-methoxyphenyl)-Ethane Chemical compound C1=CC(OC)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(OC)C=C1 IAKOZHOLGAGEJT-UHFFFAOYSA-N 0.000 claims 1
- NPRGLZSHCQXKDX-UHFFFAOYSA-N 1-(methoxymethyl)-2,3-dimethyl-1H-indene Chemical compound C1=CC=C2C(COC)C(C)=C(C)C2=C1 NPRGLZSHCQXKDX-UHFFFAOYSA-N 0.000 claims 1
- NAEUHJIOGQLWCW-UHFFFAOYSA-N 1-(methoxymethyl)-4,7-dimethyl-1H-indene Chemical compound CC1=CC=C(C)C2=C1C(COC)C=C2 NAEUHJIOGQLWCW-UHFFFAOYSA-N 0.000 claims 1
- MYZIJBJPIHILLG-UHFFFAOYSA-N 1-chloro-9H-fluorene Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2Cl MYZIJBJPIHILLG-UHFFFAOYSA-N 0.000 claims 1
- JQCSUVJDBHJKNG-UHFFFAOYSA-N 1-methoxy-Ethyl Chemical group C[CH]OC JQCSUVJDBHJKNG-UHFFFAOYSA-N 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N Phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 125000004956 cyclohexylene group Chemical group 0.000 claims 1
- 239000000306 component Substances 0.000 abstract 2
- 239000004743 Polypropylene Substances 0.000 description 31
- 229920001155 polypropylene Polymers 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000155 melt Substances 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- 150000002170 ethers Chemical class 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- VNKYTQGIUYNRMY-UHFFFAOYSA-N Methoxypropane Chemical group CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000008079 hexane Substances 0.000 description 8
- 239000011949 solid catalyst Substances 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- GTIIVHODSNYECK-UHFFFAOYSA-N 1,1,1-trifluoropropane Chemical group [CH2]CC(F)(F)F GTIIVHODSNYECK-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000005936 piperidyl group Chemical group 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 230000002194 synthesizing Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N Diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N Hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000002083 X-ray spectrum Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229940077744 antacids containing magnesium compounds Drugs 0.000 description 2
- 210000000436 anus Anatomy 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000536 complexating Effects 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000005712 crystallization Effects 0.000 description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- BZKBCQXYZZXSCO-UHFFFAOYSA-N sodium hydride Inorganic materials [H-].[Na+] BZKBCQXYZZXSCO-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000000707 stereoselective Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- HBMODDNTUPGVFW-UHFFFAOYSA-N (1,3-dimethoxy-2-phenylpropan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(COC)(COC)C1=CC=CC=C1 HBMODDNTUPGVFW-UHFFFAOYSA-N 0.000 description 1
- MZECAZRMUYMCLS-UHFFFAOYSA-N 1,1-bis(phenoxymethyl)indene Chemical compound C1=CC2=CC=CC=C2C1(COC=1C=CC=CC=1)COC1=CC=CC=C1 MZECAZRMUYMCLS-UHFFFAOYSA-N 0.000 description 1
- UUAMLBIYJDPGFU-UHFFFAOYSA-N 1,3-dimethoxypropane Chemical compound COCCCOC UUAMLBIYJDPGFU-UHFFFAOYSA-N 0.000 description 1
- VLWDGUOLMDJDGZ-UHFFFAOYSA-N 1,8-dichloro-2-(methoxymethyl)-9H-fluorene Chemical compound C1=CC=C(Cl)C2=C1C1=CC=C(COC)C(Cl)=C1C2 VLWDGUOLMDJDGZ-UHFFFAOYSA-N 0.000 description 1
- ULIIAVLJDYHAPZ-UHFFFAOYSA-N 1-(1,3-dimethoxypropyl)naphthalene Chemical compound C1=CC=C2C(C(OC)CCOC)=CC=CC2=C1 ULIIAVLJDYHAPZ-UHFFFAOYSA-N 0.000 description 1
- QLCNPFDPCVHMAR-UHFFFAOYSA-N 1-(methoxymethyl)-2,3,6,7-tetramethyl-9H-fluorene Chemical compound CC1=C(C)C=C2C3=CC(C)=C(C)C(COC)=C3CC2=C1 QLCNPFDPCVHMAR-UHFFFAOYSA-N 0.000 description 1
- YHHFOUGKHZQCRR-UHFFFAOYSA-N 1-(methoxymethyl)cyclopenta-1,3-diene Chemical compound COCC1=CC=CC1 YHHFOUGKHZQCRR-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-Hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-Octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- QMWKALSHLPERRD-UHFFFAOYSA-N 1-[methoxy(phenyl)methyl]-1H-indene Chemical compound C1=CC2=CC=CC=C2C1C(OC)C1=CC=CC=C1 QMWKALSHLPERRD-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- SVJCEDKUVMVBKM-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2-methylpentane Chemical compound CCCC(C)(COC)COC SVJCEDKUVMVBKM-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- POWUJINVZSHIGY-UHFFFAOYSA-N 2,6-di(propan-2-yl)piperidine Chemical compound CC(C)C1CCCC(C(C)C)N1 POWUJINVZSHIGY-UHFFFAOYSA-N 0.000 description 1
- 125000004135 2-norbornyl group Chemical group [H]C1([H])C([H])([H])C2([H])C([H])([H])C1([H])C([H])([H])C2([H])* 0.000 description 1
- KGWNRZLPXLBMPS-UHFFFAOYSA-N 2H-1,3-oxazine Chemical compound C1OC=CC=N1 KGWNRZLPXLBMPS-UHFFFAOYSA-N 0.000 description 1
- SBWACGDKPKXCRS-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,2,4,4-tetramethylpentane Chemical compound COCC(C(C)(C)C)(C(C)(C)C)COC SBWACGDKPKXCRS-UHFFFAOYSA-N 0.000 description 1
- MRCDMWYOQNUJCM-UHFFFAOYSA-N 3,3-bis(methoxymethyl)cyclohexa-1,4-diene Chemical compound COCC1(COC)C=CCC=C1 MRCDMWYOQNUJCM-UHFFFAOYSA-N 0.000 description 1
- IXVWCSDATSDISB-UHFFFAOYSA-N 4-cyclohexyl-1-(methoxymethyl)-1H-indene Chemical compound COCC1C=CC2=C1C=CC=C2C1CCCCC1 IXVWCSDATSDISB-UHFFFAOYSA-N 0.000 description 1
- CWVKCYDPJZCDMC-UHFFFAOYSA-N 4-ethyl-1-methoxy-2-(methoxymethyl)-2-methyloctane Chemical compound CCCCC(CC)CC(C)(COC)COC CWVKCYDPJZCDMC-UHFFFAOYSA-N 0.000 description 1
- ZXABOXSKCIQAJG-UHFFFAOYSA-N 5,5-bis(1-butoxyethyl)cyclopenta-1,3-diene Chemical compound CCCCOC(C)C1(C(C)OCCCC)C=CC=C1 ZXABOXSKCIQAJG-UHFFFAOYSA-N 0.000 description 1
- NUPABKVXQKZAHY-UHFFFAOYSA-N 5,5-bis(methoxymethyl)-1,2,3,4-tetramethylcyclopenta-1,3-diene Chemical compound COCC1(COC)C(C)=C(C)C(C)=C1C NUPABKVXQKZAHY-UHFFFAOYSA-N 0.000 description 1
- WPDAVTSOEQEGMS-UHFFFAOYSA-N 9,10-dihydroanthracene Chemical compound C1=CC=C2CC3=CC=CC=C3CC2=C1 WPDAVTSOEQEGMS-UHFFFAOYSA-N 0.000 description 1
- PQRUIZPAUUOIPY-UHFFFAOYSA-N 9,9-bis(methoxymethyl)-2,7-di(propan-2-yl)fluorene Chemical compound C1=C(C(C)C)C=C2C(COC)(COC)C3=CC(C(C)C)=CC=C3C2=C1 PQRUIZPAUUOIPY-UHFFFAOYSA-N 0.000 description 1
- QBVOFHFIKBUUMY-UHFFFAOYSA-N 9,9-bis[methoxy(phenyl)methyl]fluorene Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1(C(OC)C=1C=CC=CC=1)C(OC)C1=CC=CC=C1 QBVOFHFIKBUUMY-UHFFFAOYSA-N 0.000 description 1
- ANGMMFRGIJDWPU-UHFFFAOYSA-N 9-(1-methoxyethyl)-9-(methoxymethyl)fluorene Chemical compound C1=CC=C2C(COC)(C(C)OC)C3=CC=CC=C3C2=C1 ANGMMFRGIJDWPU-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N Anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 241000287523 Ara Species 0.000 description 1
- 101700067048 CDC13 Proteins 0.000 description 1
- 210000001736 Capillaries Anatomy 0.000 description 1
- 241000233001 Carios Species 0.000 description 1
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- APSBXTVYXVQYAB-UHFFFAOYSA-M Dioctyl sodium sulfosuccinate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N Diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 241001146155 Emilia Species 0.000 description 1
- 235000002139 Emilia sonchifolia Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N Norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N Silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N Sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N Tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- PQJUJGAVDBINPI-UHFFFAOYSA-N Thioxanthene Chemical compound C1=CC=C2CC3=CC=CC=C3SC2=C1 PQJUJGAVDBINPI-UHFFFAOYSA-N 0.000 description 1
- RHBLISBUFROBBC-UHFFFAOYSA-N [9-(hydroxymethyl)fluoren-9-yl]methanol Chemical compound C1=CC=C2C(CO)(CO)C3=CC=CC=C3C2=C1 RHBLISBUFROBBC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- UXXXZMDJQLPQPH-UHFFFAOYSA-N bis(2-methylpropyl) carbonate Chemical compound CC(C)COC(=O)OCC(C)C UXXXZMDJQLPQPH-UHFFFAOYSA-N 0.000 description 1
- SWBJZPDGKVYSLT-UHFFFAOYSA-N bis(2-methylpropyl) propanedioate Chemical group CC(C)COC(=O)CC(=O)OCC(C)C SWBJZPDGKVYSLT-UHFFFAOYSA-N 0.000 description 1
- 229910000099 calcium monohydride Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 230000024881 catalytic activity Effects 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000295 complement Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010192 crystallographic characterization Methods 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- NUFBGJAEANEZKW-UHFFFAOYSA-N cyclopropyloxycyclopropane Chemical compound C1CC1OC1CC1 NUFBGJAEANEZKW-UHFFFAOYSA-N 0.000 description 1
- DKMROQRQHGEIOW-UHFFFAOYSA-N diethyl butanedioate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 1
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- YCNSGSUGQPDYTK-UHFFFAOYSA-N ethyl phenyl carbonate Chemical compound CCOC(=O)OC1=CC=CC=C1 YCNSGSUGQPDYTK-UHFFFAOYSA-N 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000000977 initiatory Effects 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HRDXJKGNWSUIBT-UHFFFAOYSA-N methoxybenzene Chemical group [CH2]OC1=CC=CC=C1 HRDXJKGNWSUIBT-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000004437 phosphorous atoms Chemical group 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- 230000001131 transforming Effects 0.000 description 1
Abstract
The present invention relates to catalyst components, solids and catalysts thereof, the catalysts comprise the reaction product of: i. a catalyst component, solid containing an internal donor; an Al-alkyl compound, and optionally, iii. an external donor, the internal donor and / or the external donor are 1, 3-cyclopolyenic diethers, where the carbon atom in position 2 corresponds to a particular cyclic or polycyclic structure containing two or three unsaturation
Description
"COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINS"
Inventor (s): GIAMPIERO MORINI, Italian, domiciled at 215, Via Emilia, 27058 Voghera, Pavia, Italy; ENRICO ALBIZZATI, Italian, domiciled at 64, Via Roma, 28041 Arona, Novara, Italy; GIULIO BALBONTIN, Italian, domiciled at 17 / a, Via Ugo Bassi, 44100 Ferrara, Italy; GIOVANNI BARUZZI, Italian, domiciled at 37, Via Mario Azzi, 44100 Ferrara, Italy and ANTONIO CRISTOFORI, Italian, domiciled at 9, Corso Berlinguer, 45030 Occhiobello, Rovigo, Italy.
Causaire: MONTELL NORTH AMERICA INC., Delaware State Corporation, E.U.A., domiciled at 2801 Centerville Road, New Castle County, Delaware, E.U.A.
FIELD OF THE INVENTION
The present invention relates to catalysts for the polymerization of olefins, comprising particular 1,3-diethers.
BACKGROUND OF THE INVENTION
Published European Patent Application No. 361 494 discloses solid catalyst components comprising, as an internal electron donor, an ether containing two or more ether groups, and having reaction characteristics, specific for magnesium chloride, anhydrous and TiCl .. The catalysts obtained from the reaction of these catalyst components with an Al-alkyl compound exhibit high activity and stereospecificity in the polymerization of olefins, and do not require the use of an external electron donor. . Now, it has been found that by reacting an Al-alkyl compound with a catalyst component, a solid comprising magnesium dihalide, in the active form, a titanium compound and a 1,3-diether in which the carbon in position 2 corresponds to a cyclic, specific structure containing two or three unsaturations (structure of the opol iinic), a catalyst is obtained which has a remarkably high catalytic activity and a high level of stereospeci fi city in the polymerization of olefins. In fact, the aforementioned 1,3-diethers with a cyclopolymer structure (subsequently in the present cyclopolyenic 1,3-diethers), which are not described in published European Patent Application No. 361 494, confer upon the above mentioned catalyst a considerably high activity than that obtained by using the ethers known in the art. The addition of an external electron donor to the above catalyst, which contains the cyclo-polyenic 1,3-diether as the internal electron donor, allows to obtain very high levels of stereospecificity, while maintaining high activity. In this way, activity and stereospecific equilibria are obtained which can not be achieved with the ethers known in the art. European Patent Application, published No. 362 705 discloses catalysts comprising the reaction product of a catalyst component, solid comprising a titanium compound and an internal electron donor supported on a magnesium dihalide in the active form, a composed of Al-alkyl, and, as an external electron donor, an ether containing two or more ether groups, and capable of complexing with anhydrous magnesium chloride, under normal conditions in amounts of less than 60 mmol per 100 g of magnesium chloride. These catalysts exhibit high activity and stereospecificity in the polymerization of olefins. Now, it has been found that the performance of the aforementioned catalysts is improved when the aforementioned 1,3-diethers of the above-mentioned, such as the external electron donors are used. In fact, the catalysts obtained by using, as the external electron donors, the 1,3-diethers of the opol i ni eos, mentioned above, which are not described in published European Patent Application No. 362 705, exhibit, in the polymerization of olefins, very high activity and stereospecific equilibria, which can not be obtained with the ethers known in the art.
DESCRIPTION OF THE INVENTION
Accordingly, the present invention provides a solid catalyst component for the polymerization of olefins, this catalyst component, a solid comprising a magnesium halide in the active form, and, supported thereon, a titanium compound. , which contains at least one Ti-halogen bond, and as the internal electron donor compound, a cyclo-polyene 1,3-diether in which the carbon atom in the 2-position corresponds to a cyclic structure or pol cyclic made of 5, 6, or 7 carbon atoms, or of 5-not 6-n 'carbon atoms, or respectively n atoms of nitrogen and n1 heteroatoms selected from the group consisting of N, 0, S and If, where n is 1 or 2, and n 'is 1, 2, or 3, this structure contains two or three unsaturations (cyclopolynic structure), and is optionally condense with other cyclic structures, or substituted with one or more substituents selected from the group consisting of radicale s to which i, 1 i neal or branched; cycloalkyl, aryl, aralkyl, alkaryl and halogen radicals, or is condensed with other cyclic structures and substituted with one or more substituents mentioned above which can also be linked to the condensed cyclic structures; one or more of the above-mentioned alkyl, cycloalkyl, aryl, aralkyl, or alkaryl radicals, and condensed cyclic structures optionally containing one or more heteroatoms, as substituents for the carbon or hydrogen atoms, or both. According to another embodiment, the present invention provides a catalyst for the polymerization of olefins comprising the reaction product of: a) a catalyst component as defined above; b) an Al-alkyl compound, and optionally c) an electron donor compound. According to another embodiment, the present invention provides a catalyst for the polymerization of olefins comprising the reaction product of an Al-alkyl compound and a 1,3-di-ether ether with a catalyst component, sol a) comprising a magnesium halide in active form and supported thereon, a titanium compound, containing at least one Ti-halogen bond and an electron donor compound. The catalyst component a) is a preferred example of the catalyst component a). Preferably, in the cyclopentane 1,3-diethers used in preparing the catalyst component (a), the carbon atoms in positions 1 and 3 are secondary. The above substituents on the cyclopolionic 1,3-diethers are preferably selected from the group consisting of straight or branched radicals of 1 to 20 carbon atoms; cycloalkyl radicals of 3 to 20 carbon atoms; aryl of 6 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms and alkaryl of 7 to 20 carbon atoms; Cl and F. The heteroatoms optionally present in the alkyl, cycloalkyl, aryl, aralkyl, alkaryl radicals, and / or in the condensed cyclic structures are preferably selected from the group consisting of N; 0; S; P; Si and halogens, in particular Cl and F. Among the above-mentioned, particularly preferred cyclopolymeric 1,3-diethers are the compounds of the general formula:
where A, B, C and D are carbon atoms or heteroatoms selected from the group consisting of N, 0,
S and Yes; v, x and y are 0 or 1; u and z are 0 or 1 d 2; with the proviso that when u = 0: i) A, B and C are carbon atoms, and v, x and y are equal to 1; or ii) A is a nitrogen atom, B and C are carbon atoms, v is equal to 0, and x and y are equal to i; or iii) A and B are nitrogen atoms, C is a carbon atom, v and x are equal to 0, and y equals
1; or iv) A and B are carbon atoms, C is a nitrogen atom, v and x are equal to 1, and y is equal to 0; when u = 1: 1) A, B, C and D are carbon atoms, v, x and y are equal to 1, and z equals 2; or 2) A and B are carbon atoms, C is a nitrogen atom, D is an oxygen atom, v and x are equal to 1, and e z are equal to 0; or 3) A, B and C are carbon atoms, D is an atom of oxygen, nitrogen, sulfur or silicon, v, x and y are equal to 1, and z is equal to 0 when D is an oxygen or sulfur atom, equal to 1, when D is a nitrogen atom, and equal to 2 when D is a silicon atom; when u = 2 A, B and C are carbon atoms, D represents two carbon atoms linked together by an individual or double bond, v, x and y are equal to 1, and z is equal to 1, when the pair of atoms Carbon D is linked by a double bond, and equal to 2 when the pair is linked by an individual bond; the radicals R and R, the same or different, are selected from the group consisting of hydrogen; halogens, preferably Cl and F; alkyl radicals of 1 to 20 carbon atoms, linear or branched; cycloalkyl radicals of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkaryl of 7 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; the same or different radicals R are selected from the group consisting of linear or branched alkyl radicals of 1 to 20 carbon atoms; cycloalkyl radicals of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkaryl of 7 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms, and two or more of the radicals R can be attached between yes to form condensed, saturated or unsaturated cyclic structures, optionally substituted with radicals R selected from the group consisting of halogens, preferably Cl and F; alkyl radicals of 1 to 20 carbon atoms, linear or branched; cycloalkyl radicals of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkaryl of 7 to 20 carbon atoms and aralkyl of 7 to 20 carbon atoms; these radicals from R to R which optionally contain one or more heteroatoms as substituents for carbon or hydrogen atoms, or both. Preferably, in the cyclopentenyl 1,3-diethers used in preparing the catalyst component a) all the radicals R in the compounds of the formula (I) are hydrogen, and the two radicals R are methyl. The heteroatoms optionally present in the radicals of R to R are preferably selected from the group consisting of N; 0; S; P; Yes and halogens, in particular Cl and F. Una. The most restricted class of compounds of the formula (I) is constituted by the compounds of the general formula:
wherein the radicals from R to R have the meanings defined above for formula (I), which include the preferred cases. In particular, two or more of the radicals R can be joined together to form one or more condensed cyclic structures, preferably benzene, optionally substituted by radicals R The specific examples of compounds comprised in the formula (II) are:
1, l-bis (methoxymethyl) -cyclopentadiene; 1,1-bis (methoxymethyl) -2,3,4,5-tetramethylcyclopentadiene; 1, l-bis (methoxymethyl) -2,3,4,5-tetraphenylcyclopentadiene; 1, l-bis (methoxymethyl) -2,2,4,5-tetrafluorocyclopentadiene 1,1-bis (methoxy-meth) -3,4-dicyclopentylcyclopentadiene; 1,1-bis (methox imeti i ndeno; 1 -bi s (methoxymethi -2, 3-dimeti 1 i ndeno; 1,1 -bi s (methoxymethi -4,5,6,7-tetrahydroindene; 1,1 -bi s (methoxymethi-2,3,6; 7-tetrafluoroindene; 1,1-bis (methoxymethi-4, -dimet i 1 indene; 1,1-bis (methox imeti -3,6-dimeti-1-indene; 1,1-bis (methoxymethyl-4-phenol indene; 1,1-bis (methox imeti-4-phenyl-2-methylindene; 1,1-bis (methoxymethyl-4-cyclohexyl indene; 1,1-bis (methyloxy-7- (3,3 , 3-trifluoropropyl) indene; 1,1-bis (methoxymethi-7-trimethylsilyldenene; 1,1-bis (methoxymethi-7-trifluoromet lindene; 1.1 -bi s (methoxymethi-4,7-dimeti1-4,5,6, 7-tetrahydroindene;
1,1-bis (methoxymethi-7-methy1 i ndeno; 1.1 -bi s (methoxymethi-7-cyclopentyl ndene; 1,1-b s (methoxymethi-7-isopropylindene; 1,1-b s (methoxymethi-7 -cyclohexylindene, 1,1-bis (methoxymethi-7-tert-butyl 1 i ndene, 1,1-bis (methoxymethi-7-te? -butyl-2-methylindene; 1,1-bis (methoxymethi-7) -pheni 1 i ndeno; 1,1-bis (methoxymethi-2-phenyl-1-ndene; 1,1-bis (methoxymethi-1H-benz [e] indene; 1.1 -bi s (methoxymethi-1H-2-methyl) lbenz [e] indene; 9,9 -bi s (methoxymethyl f 1 -oreno;
9,9-b-s (methoxymethyl-2,3,6,7-tetramethylfluorene; 9,9-b s (methoxymethi-2,3,4,5,6,7-hexafluorofluorene; 9,9-bis ( methoxymethylene -2, 3-benzofluorene; 9,9-bi s (methoxymethyl-2,3,6,7-dibenzofluorene; 9,9-bi s (methoxymethyl) -2,7-diisopropylfluorene; 9,9-bi s (methoxymethyl-1, 8-dichlorofluorene; 9,9-b s (methoxy-methylene-2,7-dicyclopentyl-fluorene; 9,9-b-s (methoxy-methylene-1,8-difluorofluorene; methoxy methi-1,2,3,4-tetrahydrofluorene; 9,9-b s (methoxymethi-1,2,3,4,5,6,7,8-octahydrofluorene;
9,9-bis (methoxymethyl) 4-tert-butyl-1-chloro-urethane Other examples of cyclopolymer 1,3-diethers included in the above definitions are:
1,1-bis (1-butoxyethyl) -cyclopentadiene; 1,1-bis (1'-isopropoxy-n.propyl) cyclopentadiene; 1-methoxymethi 1-1 - (1'-methoxyethyl) -2,4,5,5-tetramethyl cyclopentadiene; 1, l-bis (alpha-methoxybenzyl) indene; 1, 1-bis (phenoxymethyl) indene; l. l -b i s O '-metox i et i l J -d. d-d i c l o ro i ndeno; 1,1-bis (phenoxymethyl) -3,6-dicyclohexyldedene; 1-methoxy i met i 1-1 - (1'-methoxy eti 1) -7-tert-butyl 1 i ndene; 1,1-b i s [2- (2'-methoxypropyl)] - -methyl-1-indene; 3,3-bis (methoxymethyl) -3H-2-methybenz [e] indene; 9,9-bis (alpha-methoxybenzyl) fluorene;
9,9-bis (1'-isopropoxy-n.butyl) -4,5-diphenyl-fluorene;
9,9-bis (1'-methoxyeti1) fluorene; 9- (methoxymethi 1) -9- (1'-methoxy-ethi-1) -2,3,6,7-tetrafluoro-f-1-loreno; 9-methox imeti 1-9-pentoxymethyl fluorene; 9-me tox i meti 1-9-ethoxethene 1 fluorene; 9-methoxymethyl-9- (1'-methoxyethyl) -fluorene; 9-methoxymethi 1 -9- [2- (2-methoxypropyl)] - fl uorene; 1,1-bis-methoxymethyl-2, 5-cyclohexadiene; 1,1-bis methoxymethi benzonaphthene; 7,7-bis methoxymethi 2, 5-norbornadiene; 9,9-bis methoxymethi-1,4-methanodi idronaphthalene; 4, 4-bi s methoxymethi-4H-cyclopenta [d, e, f] phenanthrene; 9,9-bis methoxymethi 9,10-dihydroanthracene; 7,7-bis methoxymethi-7H-benz [d, e] anthracene; 1,1-bis methoxymethi 1, -dihi dron afta lene; 4,4-bis methoxymethi-1-pheny1-3,4-dihydronaphthalene; 4,4-bis methoxymethi-1-phenyl-1,4-dihydrophthalene; 5, 5-bi s methoxymethi-1,3,6-cycloheptatriene; 5, 5-bi s methoxymethi-10,11-dihydro-5 H -dibenzo [a, d] ci-clohept no; 5, 5-bi-methoxymethi-5H-dibenzo [a, d] cycloheptene; 9,9-bis methoxymethi xanthene; 9,9-bis methoxymethi-2,3,6,7-tetramethylxanthene; 9,9-bis-1'-methoxyisobutyl) thioxanthene; 4, 4-bi-methoxymethi 1-1, 4-phenyl;
9, 9-bi s (methoxy eti 1) -N-ter buti 1-9, 10-d i idroacridine;
4, 4-bi s (methoxy methy1-1, 4-chromene; 4, 4-bi s (methoxy eti 1 -1,, 4-oxazi na; 1, 1 -bi s (methoxy and methy1 benzo-2 3, 1-oxazine; 5, 5-bi s (methoxymethyl-1,5-pyridine; 5, 5-bi s (methoxy-methyl-1,6,7-dimethyl-1,5-pyrindine; , 2-bis (methoxymethi 1 -3,4,5-trifluoroisopyrrole; 4,4-bis (1'-methoxyeti) benzo-N-phenyl-1,4-dihydropyridine;
The cyclopolionic 1,3-diethers according to the present invention can be prepared by first synthesizing the cyclopropyl ether by reacting the desired cyclopolyne with paraformaldehyde in the presence of sodium alcoholate (as described by B). WESSLEN, ACTA CHEM SCAND. 21 (1967) 718-20), and then by transforming the dimethylol derivative into the corresponding diether by means of alkylation, cycloalkyl ation or arylation, according to known techniques, such as by the reaction of the dimethylol derivative with an aryl, alkyl or cycloalkyl halide in the presence of a strong base, such as NaH, in appropriate solvent, such as tetrahydrofuran. The electron donor compound present in the catalyst component, solid a) can be a Lewis base containing one or more electro-negative groups where the electron donating atoms are selected from the group consisting of N, 0, S , P, As or Sn. Examples of the electron donor compounds mentioned above are widely described in the art. Preferred electron-donor compounds that can be extracted with Al-triethyl from the catalyst component a) for at least 70 mol%, the surface area (BET) 2 of the extraction solid product is at least 20 m / g, and that varies in general from 100 to 300 m / g. Examples of the electron donor compounds mentioned above are described in USP 4,522,930, and comprise ethers, ketones, lactones, compounds containing N, P and / or S atoms, and specific types of esters. In addition to the esters of USP No. 4,522,930, the esters described in European Patent No. 045977 can be used. Phthalic acid esters are particularly suitable, such as diisobutyl phthalate, dioctyl and diphenyl, benzyl phthalate 1-butyl the; the esters of maloic acid such as diisobutyl and diethyl malonate; alkyl and aryl pivalates; alkyl, cycloalkyl, and aryl maleates; alkyl and aryl carbonates such as diisobutyl carbonate, ethyl phenyl carbonate and diphenyl carbonate; the succinic acid esters such as mono and diethyl succinate. Phthalic acid esters are preferred. Also useful in the catalyst component a) are the electron donor compounds described in European Patent Application No. 361494. Said compounds are ethers containing two or more ether groups, and which, under normal conditions are capable of complexing with Anhydrous magnesium chloride for less than 60 mmoles per 100 g of chloride and with TiCl. do not suffer from substitution reactions, or only for less than 50% in moles. The tests that allow verification of the above reactivity criteria are reported below.
Test of formation of complements of the ethers with tyspi 2 *
In a 100 ml glass flask with a mechanical stirrer with fixed blades are introduced under a nitrogen atmosphere, in the order: 70 ml of anhydrous n-heptane 12 mmole of MgCl 2. anhydrous, activated as described below 2 mmole of ether.
The content is allowed to react at 60 ° C for 4 hours (stirring speed at 400 rpm). It is then filtered and washed at room temperature with 100 ml of n-heptane, after which it is dried with a mechanical pump. The solid is characterized, after it has been treated with 100 ml of ethanol, by means of a quantitative gas chromatographic analysis for the analysis of the amount of ether.
Testing the reaction with TiCl
Into a 25 ml test tube with a magnetic stirrer and nitrogen atmosphere are introduced: 10 ml anhydrous n-heptane 5 mmoles TiCl * 1 mmole donor. The content is to react at 70 C for 30 minutes, after which it is cooled to 25 C and decomposed with 90 ml of ethanol. The obtained solutions are analyzed by means of gas chrography using the normal internal method, with a Cario Erba Mega Series HRGC 5300 gas chrograph with a CP-SIL 5 CB chrompack 25 meter capillary column.
The magnesium chloride used in the complex formation test with the ethers is prepared as follows. In a 1 liter vibrating mixing jar (Vibraton de Siebtechnik) containing 1.8 kg of 16 mm diameter steel spheres, 50 g of anhydrous gC ^ and 6.8 ml of 1.2 g of nitrogen are introduced under nitrogen. dichloroethane (DCE). The content is milled at room temperature for 96 hours, after which the recovered solid is kept under vacuum in the mechanical pump for 16 hours at 50 C. Characterization of the solid: maximum mean width of the reflection D110 = 1..15 cm. Presence of a halo with greater intensity at 2T =
32. Surface area (B.E.T.) = 125 / g Residual DCE = 2.5% by weight. Examples of ethers having the characteristics indicated above are the 1,3-diethers of the formula
where R ,, and 3 are the same or different and are alkyl radicals of 1 to 18 carbon atoms, cycloalkyl of 3 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, aralkyl of 7 to 18 carbon atoms, linear or branched alkaryls, and R ~ or R., can be a hydrogen atom. Preferably, R, is an alkyl radical of 1 to 6 carbon atoms, and more particularly a methyl. Further, when R is methyl, ethyl, propyl, or isopropyl, R3 may be ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, methyl-1-cyclohexyl, phenyl. , or benzyl; when R "is hydrogen, R3 may be ethyl, butyl, sec-butyl, tert-butyl, 2-ethyl-1-hexy-1, cyclohexylhexyl, di-phenyl-1-methyl, 1-phenyl-1-phenyl, naphthyl, 1 -decahydronaphthi lo; R and Ro can be the same and can be ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, phenyl, benzyl, cyclohexyl, cyclopentyl. Specific examples of ethers, which can be used advantageously include: 2- (2-eti-1-hexy-1) -1,3-dimethoxy-propane, 2-isopyr-1, 3-dimethoxy-propane, 2-buty-1- 1, 3-dimethoxy propane, 2-sec-buty 1-1, 3-dimethoxy propane, 2-cyclohexy 1-1, 3-dimethoxy propane, 2-pheny1-1, 3-dime-toxipropane, 2-te? -buti 1-1, 3-dimethoxypropane, 2-cumyl-1,3-di methoxy and propane, 2- (2-fe ni leti l) -1,3-dimethoxypropane, 2- (2-ci cl ohexi 1 eti 1) -1, 3-dimethoxy propane, 2- (p-chlorophenyl) * 1,3-dimethoxy propane, 2- (di-phenylmethyl) -!, 3-dimethoxy propane, 2 (1-naphthyl) - 1, 3-dimethoxy propane, 2 (p-flourofeni1) -1,3-dimethoxy propane, 2 (1-decahydronaphthyl) -l, 3-di methoxypropane, 2 (? -te? -butyl pheni 1) -1 , 3-dimethoxy propane, 2,2-di-cyclohexylo-1,3-dimethoxy propane, 2, 2-di eti 1-1, 3-dimethoxy propane, 2,2-di-propi 1-1, 3-dimethoxy propane, 2, 2-dibuti 1-1, 3-di me to-xipropano, 2, 2-di eti 1-1, 3-di ethoxy propane, 2, 2-di ci cl open-ti 1-1, 3-dimethoxypropane, 2, 2-dipropyl 1-1, 3-diethoxypropane , 2, 2-dibuti 1-1, 3-di ethoxy prop anus, 2-met i 1 -2-eti 1-1, 3-di ethoxy propane, 2-methyl-2-propyl-1,3- dimethoxypropane, -methi 1-2-benzyl 1-1, 3-dimethoxy propane, 2- ethi 1-2-pheny1-1, 3-d imethoxy propane, 2-met i 1 -2 -ci cl or exi 1 - 1,3-Di methoxypropylene, 2-methyl 1-2 methylene cyclic ohexy 1-1, 3-dimethoxy propane, 2,2-bis (p-chlorophen i 1) -1,3-dimethoxy propane, 2 2-bis (2-phenylethi) -1,3-dimethoxypropane, 2,2-bis (2-cyclohexyethyl) -1,3-dimethoxy propane, 2- ethyl 1-2-i sobuty 1-1,3-di methoxy propane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2,2-bis (-ethyl exyl) -!, 3-dimethoxy propane, 2, 2-bi s (p-methyl-1-phenyl) 1) -1, 3-di methoxy propane, 2-methy1 -2-i sopropi 1 -1,3-dimethoxypropane, 2, 2-di i sobuti 1-1, 3-dimethoxy propane, 2, 2-di fen i 1-1, 3-di methoxy i propane, 2, 2-di benzyl 1 -1, 3-di methoxy propane, 2-isopropi 1-2-cyclopenti 1-1, 3-di methoxy propane, 2,2 -bis (cyclohexylmethyl) -l, 3-dimethoxypropane, 2, 2-di i sobuti 1-1, 3-di-styxypropane, 2, 2-di i sobuti 1 -1, 3-di butoxy-pr opane, 2-i sobuti 1-2-i sopropi 1-1, 3-di methoxy and propane.
2, -di -sec-buty 1-1, 3-dimethoxy propane, 2,2-di-tert-butyl-1,3-di methoxypropane, 2, -di neopenti 1 -1, 3-di methoxy propane , 2-i sopropi 1-2-i sopenti 1-1, 3-dimethoxy propane, 2-phenyl 1-2-benzyl 1-1, 3-d imethoxy propane, 2-cyclohexyl-2-cyclohexyl-methylated 1-1 , 3-di methoxy and propane. The preparation of the catalyst components, solids a) and a) can be carried out using various methods. For example, the magnesium halide (used anhydrous, containing less than 1% water), the titanium compound, and the electron donor compound are milled together under conditions that cause activation of the magnesium halide; The ground product is then made to react one or more times with TiCl. in excess, optionally in the presence of an electron donor, at a temperature ranging from 80 to 135 C, and then repeatedly washing with a hydrocarbon (e.g. such as hexane), until no chlorine ions can be detected in the washing liquid. According to another method, the anhydrous magnesium halide is pre-activated according to known methods and then reacted by an excess of TiCl. containing the electron donor compound and optionally an aliphatic, cycloaliphatic, aromatic or chlorinated hydrocarbon solvent (for example: hexane, heptane, cyclohexane, toluene, ethylbenzene, chlorobenzene, dichloroethane). In this case also the operation takes place at a temperature between 80 ° and 135 ° C. The reaction with TiCl ^, in the presence or absence of an electron donor, is optionally repeated and the solid is then washed with hexane to remove the unreacted TiCl ». According to another method, an adduct of MgCl.nroh (particularly in the form of spheroidal particles) where n is in general from 1 to 3, and ROH is an alcohol, such as for example, ethanol, butanol, isobutapol, is made that reacts with an excess of TiCl. containing the electron donor compound and optionally one of the hydrocarbon solvents mentioned above. The reaction temperature is initially from 0 to 25 C, and then increases to 80-135 C. After the reaction, the solid is reacted once more with TiCl ", in the presence or absence of the electron donor, then separated and washed with a hydrocarbon until no chlorine ions are detected in the wash liquid. According to yet another method, the magnesium alcoholates and chloroalcoholates (can be prepared by the chloroalcoholates particularly as described in USP No. 4,220, 554) are made to react with TiCl. in excess, which contains an electron donor compound, operating under the reaction conditions already described. According to another method, complexes of magnesium halides with titanium alcoholates, the complex MgCl2.2Ti (0C4Hg) 4 is a typical example) are reacted, in a hydrocarbon solution, with TiCl., In excess, containing a electron donor compound, the separated solid product is reacted again with excess TiCl ", in the presence or absence of the electron donor, and then separated and washed with hexane. The reaction with TiCl. It is carried out at a temperature ranging from 80 ° to 130 ° C. According to a variant, the titanium alcoholate complex and MgC1 ~ is reacted in a hydrocarbon solution with polyhydroxy loxane; the separated solid product is reacted at 50 ° C with silicon tetrachloride containing the electron donor compound; the solid is then reacted with excess TiCl »in the presence or absence of the electron donor, operating at 80 -130 C. Regardless of the specific preparation method, after the last reaction with TiCl. in the presence of the electron donor, it is preferred to separate the solid obtained (for example, by means of filtration), and to react it with an excess of TiCl.
at temperatures that vary from 80 to 135 ° C, before washing it with the hydrocarbon solvent. Finally, it is possible to react the TiCl. in excess and containing the electron donor with porous resins such as styrene-di vi ni 1 benzene, partially crosslinked, in the form of spherical particles or porous inorganic oxides such as silica and alumina impregnated with solutions of magnesium compounds or soluble complexes in organic solvents.
The porous resins which can be used are described in published European Patent Application No. 344755. The reaction with TiCl is carried out at 80-100 C. After removing the excess of TiCl, the reaction is repeated and the solid then it is washed with a hydro-catheter. The molar ratio of the MgCl / / electron donor used in the reactions indicated above generally varies from 4: 1 to 12: 1. The electron-donor compound is fixed to the magnesium halide in a cation ranging generally from 1 to 20 mol%. In particular, the cyclopolyenic 1,3-diether is fixed to the magnesium halide in a cation ranging in general from 5 to 20 mol%. In the catalyst components, solids a) and a) the Mg / Ti ratio is in general from 30: 1 to 4: 1; in the components supported on resins or in inorganic oxides the ratio can be different and usually varies from 20: 1 to 2: 1. The titanium compounds that can be used for the preparation of catalyst components a) and a) are halogen halides and alcoholates. Titanium tetrachloride is the preferred compound. Satisfactory results can also be obtained with trihalides, particularly TiCl, HR, TiCl.-, ARA, and with halogen alcoholates such as TiCl, OR, where R is, for example, a phenyl radical. The above reactions cause the formation of magnesium halide in active form. In addition to these reactions other reactions are known in the literature that lead to the formation of magnesium halide in the active form initiating magnesium compounds different from the halides. The active form of the magnesium halides present in the catalyst components of the invention is recognizable by the fact that in the X-ray spectrum of the catalyst component, the main reflection of the intensity appearing in the spectrum of the halides of non-active magnesium (which have surface areas less than 3 m / g) is not present for a long time, but instead there is a halo with the position of the maximum intensity changed with respect to the position of the main reflection of the intensity, or by the fact that the main reflection of the intensity has a maximum mean width at least 30% greater than one of the corresponding reflection of the non-activated Mg halide. The most active forms are those in which the halo appears in the X-ray spectrum of the solid catalyst component. Among the magnesium halides, chloride is the preferred compound. In the case of the active forms of magnesium chloride, the halo appears in the place of reflection that in the spectrum of activated magnesium chloride lies at the interplanar distance of 2.56.
A. The catalyst components a) and a) form, by reaction with the Al-alkyl compounds, catalysts which can be used in the polymerization of olefins CH ~ β CHR, where R is hydrogen or an alkyl radical of 1 to 6 carbon atoms, or an aryl radical, or mixtures of these olefins or of olefins and diolefins. However, the present invention requires the use of an external electron donor with the compo-? catalyst (a), at least when the latter is different from the catalyst component a). The Al-alkyl compounds comprise Al-trialkyls such as Al-triethyl, Al-t-i and -butbutyl, Al-tri-n-butyl, Al -triocti 1 o. Alkyl, linear or cyclic alkyl compounds containing one or more Al atoms attached to another with 0, N, or S atoms may also be used. Examples of these compounds are:
(CA), A1-O-Al (CA), (i-C4H.) »A1-O-Al (i-CA) i
where n is a number from 1 to 20; the compounds of AIR OR1 where R 'is an aryl radical of 6 to 20 carbon atoms substituted at position 2 and / or 6, and R is an alkyl radical of 1 to 6 carbon atoms, and compounds of A1R ~ H where R is an alkyl radical of 1 to 6 carbon atoms.
The Al-alkyl compound is used in Al / Ti ratios which generally vary from 1 to 1000. The trialkyl compounds can also be used in mixtures with Al-alkyl halides such as AlEtgCl and AlEt3 / 2C13, 2. The polymerization of olefins is carried out according to known methods by operating in the liquid phase constituted by one or more monomers, or by a solution of one or more monomers in an aliphatic or aromatic hydrocarbon solvent, or in gas phase, or also by combining the polymerization stages in the liquid phase and in the gas phase. The temperature of (co) poly erization is usable in-te from 0 to 150 ° C; particularly from 60 ° to 100 ° C. The operation occurs at atmospheric pressure or higher. The catalysts can be pre-contacted with small amounts of olefins (prepolymerization). The prepolymerization improves the performance of the catalysts as well as the morphology of the polymers. The prepolymerization is carried out by keeping the catalysts in suspension in a hydrocarbon solvent (for example, hexane or heptane), adding an olefin, and operating at temperatures ranging from room temperature to 60 C producing an amount of polymer in general from 0.5 to 3 times and weight of the catalyst. It can also be carried out in the liquid monomer, under the temperature conditions indicated above, and producing quantities of polymer that can reach 1000 g per g of the catalyst component. When the catalyst component a) is to be used in the stereoregular polymerization of olefins, particularly propylene, an external electron donor can be added to the Al-alkyl, this external electron donor compound which is selected preferentially from the group consisting of silicon compounds containing at least one Si-OR bond (R = hydrocarbon radical); 2, 2, 6, 6-tetramethyl 1 pi peri-di na; 2,6-diisopropylpiperidine; esters of carboxylic acid, such as ethanediol and ethi-1-benzoate, and di- and polyethers. Preferably, the silicon compounds having the formula R n Si (0R) 4_n where n is 1 or 2, the 4 radicals or radical R, the same or different, are alkyl radicals from 1 to 12 atoms, cycloalkyl from 3 to 12 carbon atoms, aryl of 6 to 12 carbon atoms, alkaryl of 7 to 12 carbon atoms or aralkyl, radical is
where R and R are the same or different and have the meanings given above for R, or are joined together to form a cyclic structure; the radicals
R are the same or different and are alkyl radicals of 1 to 6 carbon atoms. Optionally, the radicals R to R may contain one or more halogens, in particular Cl and F, as substituents for the hydrogen atoms.
Examples of these compounds are: (ter-buti 1) 2Si (0CH3) 2; (cyclohexyl) 2 Si (0CH 3) 2; (isopropyl) 2 Si (0CH 3) 2; (sec-butyl) 2 Si (0CH 3) 2; (cyclohexyl) (meti 1) Si (0CH3) 2; (Cyclopentyl SiiOCH.,) ^; (isopropyl) (methyl) Si (0CH3) 2; (n-butyl) 2 Si (0CH 3) 2; (isobutyl) 2 Si (0CH 3) 2; (sec-butyl) 2 Si (0CH 3) 2; (ter-buti 1) (met l) Si (0CH3) 2; (ter-amyl) (methyl) Si (0CH3) 2; (ter-hexyl) (methyl) Si (0CH3) 2; (2-norbornyl) (methyl) Si (0CH3) 2; (ter-buti 1) (cyclopentyl) Si (0CH3) 2;
2-norbornyl) (cyclopentyl) Si (0CH3) ?; ter-butyl) Si (0CH3) 3; tert-butyl) Si (0C2H5) 3; 2-norborni 1) Si (0CH3) 3; 2-norborn l) Si (0CH2H5) 3; ter-hexyl) Si (OCH3) 3; ter-hexyl) Si (OC2Hc) 3; tert-butyl) (2-met i Ipiperidi 1) Si (OCH 3) 2; ter-buti 1) (3-meth i piperidyl) Si (OCH) ?; ter-butyl 1) (4-methypiperidi 1) Si (OCH 3) 2; ter-hexyl) (piperidyl) Si (0CH3) 2? tei-hexyl) (pyrrolidinyl) Si (0CH3) 2; methyl) (3,3,3-trifluoropopyl) Si (0CH3)?; isopropyl) (3,3,3-trifluoropropyl) Si (0CH) 2 n-butyl) (3,3,3-trifluoropropyl) Si (OCH 3) 2; isobutyl) (3,3,3-trifluoropropyl) Si (0CH 3) 2; sec-buti1) (3,3,3-trifluoropropyl) Si (0CH3) 2 tei-butyl) (3,3,3-trifluoropropyl) Si (0CH3) 2 3, 3, 3-tri fluoropropyl) (piperidyl) Si ( OCH3) 2; 3,3,3-trifluoropropy) (2-methylpiperidyl) Si (0CH) 2; 3, 3, 3-tr fluoropropy) (2-ethi Ipiperidi 1) Si (0CH3) 2; 3,3,3-trifluoropropy) (3-methylpiperidyl) Si (0CH3) 2; 3,3,3-trifluoropropy) (4-methylpiperidyl) Si (0CH3) 2; 3,3,3-trifluoropropy) 2 Si (0CH 3) 2.
Examples of preferred dieters that can be used as external electron donors with the catalyst component a) are the compounds of the general formula
RV? Rv ?? \ C O "» 1
A A D? V DV DVI DVII DVIII DIX, where R, R, R, R, R and R are the same or different, and are hydrogen; alkyl radicals of 1 to 18 carbon atoms, linear or branched, cycloalkyl radicals of 3 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, aralkyl of 7 to 18 carbon atoms, or alkaryl, with the proviso that only IV V. »X XI one of R and R can be hydrogen; R and R have IV V the meanings given as R and R, except for hydrogen, with the proviso that when the radicals from IX X IX IV R to R are hydrogen and R and R are methyl, R is not methyl; in addition, two or more of the radicals from R to R can be joined to form a cyclic structure.
Preferably in the above formula, R and R are methyl and R and R are the same or different and are selected from the group consisting of isopropyl, isobutyl, tert-butyl; cyclohexyl; isopentyl; ci cl ohexi 1 eti 1 o; pentyl; ci cl openti 1 o; heptyl; 1,5- dimeti 1 exi lo; 3, 7-dimeti locti 1 o; phenyl; cyclohexylmethyl; and propyl. Specific examples of the above mentioned diethers are: 2, 2-di i sobuti 1 -1, 3-dimethoxy-propane; 2-i sopropi 1-2-i sopent i 1-1, 3-di ethoxy propane; 2, 2-di i sopropi 1-1, 3-dimethoxy propane; 2-i sopropi 1-2-c i clohexylmethyl 1-1, 3-dimethoxy propane; 2, 2-di-phenyl-1-1, 3-dimethoxy-propane. Additional examples of dieterers having the aforementioned formula are listed in published European Patent Application No. 362 705. Particularly preferred for use as external electron donors with the catalyst component a) are 1,3-diethyl esters. ionic clopol. The molar ratio of the compound of Al -a ^ -qu-j ^ 'to the external electron donor is generally from 5: 1 to 100: 1, and preferably from 10: 1 to 30: 1; the ratio can be wider, for example from 0.5: 1 to 100: 1, during the prepolymerization phase. The catalysts find particular application
JK * tion in the polymerization of olefins CH2 = CHR where R is an alkyl radical of 1 to 6 carbon atoms or aryl. In particular, the catalysts are suitable for the polymerization of propylene or its copolymerization with ethylene or other alpha-olefins. By carrying out the polymerization in the liquid monomer, operating with Al / Ti ratios in less than 50, it is possible to obtain, thanks to the high productivity of the catalysts of the present invention,
propylene homopolymers and copolymers, hyperpuros, useful in the electronic field (capacitor grade). The catalysts of the present invention are also suitable for the production of polyethylenes and copolymers of ethylene with alpha-olefins, such as
1-butene, 1-hexene, and 1-octene. The following examples are given in order to illustrate and not limit the invention. Unless stated otherwise, the percentages in the examples are expressed by weight. 20 The melt flow rate (MRF) for polypropylene is determined in accordance with ASTM D1238, condition L. The intrinsic viscosity [f] is determined in tetrahydronaphthalene at 135 C. 25 A In order to determine the fraction insoluble in af-xylene at 25 C (XI%), 2.5 g of polymer are dissolved under agitation in 250 ml of xylene at 135 ° C, and after 20 minutes they are allowed to cool to 25 ° C. After 30 minutes the precipitated polymer is filtered and dried under reduced pressure at 80 C until the constant weight is reached.
Synthesis of 9, 9-bi s (hydroxymethi 1) fl uoreno
In a 500 ml flask, in an anhydrous atmosphere, enter in the order: 100 ml of dimethyl sulfoxide (DMSO) distilled in CaH, 8 g of paraformaldehyde (produced anhydrous at room temperature environment at a pressure of 2 torr for 8 hours), and 1.4 g of sodium ethylate dissolved in 6 ml of ethanol. After cooling the solution with an ice bath (the melting temperature of the DMSO / EtOH mixture is 13 ° C), while the suspension is maintained under stirring, 100 ml of a solution of 16 g fluorene is added. in DMSO, in a period of thirty seconds. After three minutes from the start of the addition of the fluorene solution in DMSO, the reaction is stopped with 1.5 ml of 37% HCl, and then diluted with 400 ml of water.
The mixture is saturated with NaCl, and 9,9-bi s (hydroxymethyl) -fluorene is extracted with ethyl acetate. The organic phase is then made anhydrous with anhydrous a2SO4 and the solvent is completely distilled. After crystallization by means of toluene, 15.2 g of the product are obtained (yield: 70%). The NMR spectrum] H in CDC13, at 200 MHz and using tetramethi 1 - if 1 year (TMS) as an internal standard, showed the following: 7.77 ppm, doublet, aromatic 2H 7.62 ppm, doubled, 2H aromatic 7.41 ppm, tri pte, aromatic 2H 7.32 ppm, triplet, aromatic 2H 3.99 ppm, doublet, 4H CH2 0.25 ppm. triplet. 2H OH.
Synthesis of 9, 9-bi s (methoxymethi 1) f luoreno
100 ml of tetrahydrofuran (THF), 11.3 g of 9,9-bis (hydroxymethyl) 1-fluorine, and 31.1 ml of CH. Are introduced into a 100 ml flask. 1. While stirring and operating at room temperature is maintained, 4 g of 60% by weight NaH in mineral oil are added over a period of 2 hours and 30 minutes, and the contents are then allowed to react for 1 hour and 30 minutes. minutes By distillation the unreacted CH-, 1 is recovered, and the remaining content is diluted with 100 ml of water; the resulting floating solid is filtered and dried under vacuum at 40 C. By means of the crystallization of ethanol, 11.3 g of product are obtained (yield: 90 Z). The NMR spectrum] H in CDCU, at 200 MHz and using TMS as an internal standard, showed the following: 7.75 ppm, doublet, aromatic 2H 7.6dif ppm, doublet, aromatic 2H 7.39 ppm, triplet, aromatic 2H 7.29 ppm, triplet, 2H aromatics 3.64 ppm, singlet, 4H CH2 3.55 ppm. if ngul ete, 6H CH o.
Example 1
In a 500 ml cylindrical glass reactor equipped with a filtration barrier, 225 ml of TiCl are introduced at 0 ° C, and while under stirring in a period of 15 minutes, 10.1 g (54 mmol) of MgCl2.2.1 C2H50H, my croespheroidal obtained as described below.
At the end of the addition, the temperature is 70 C, and 9 mmoles of 9, 9-bi s (methoxymethi 1) -fluorene are introduced. The temperature is increased to 100 ° C and after 2 hours, the TiCl is removed by filtration. 200 ml of TiCl are added. and 9 mmoles of 9, 9-bi s (methoxymethi 1) -fluorene; after 1 hour at 120 ° C the contents are filtered again and another 200 ml of TiCl are added, continuing the treatment at 120 ° C for one more hour; finally, the contents are filtered and washed at 60 ° C with n-heptane until all the chlorine ions disappear from the filtrate. The catalyst component obtained in this way contains: Ti = 3.5% by weight; 9, 9-bi s (methoxymethi 1) fl uoreno = 16.2% by weight. The MgC 12 - 2.1 C2H, -0H my croespheroidal is prepared as follows. 48 g of anhydrous gClp, 77 g of anhydrous C 2 H α OH, and 830 ml of kerosene are fed, in inert gas and at room temperature, in a 2 liter autoclave equipped with a turbine agitator and extraction tube. The content is heated to 120 C, while stirring to form the adduct between MgC ^ and the alcohol that melts and remains mixed with the dispersion Sgepte. The nitrogen pressure inside the autoclave is maintained at 15 atm. The autoclave extraction tube is heated externally to 120 ° C with a heating jacket, has an internal diameter of 1 mm, and is 3 meters long from one end of the heating jacket to the other. Then, the mixture is made to flow through the tube at a speed of 7m / sec ca. At the outlet of the tube, the dispersion is collected in a 5 1 flask, under agitation, containing 2.5 1 of kerosene, and cooled externally by means of a liner maintained at an initial temperature of -40 ° C. The final temperature of the dispersion is 0 ° C. The spherical solid product that constituted the dispersed phase of the emulsion that separates by means of sedimentation and filtration, and then washed with heptane and dried. All these operations are carried out in an atmosphere of inert gas. 130 g of MgCl2.3 C2Hc0H are obtained in the form of spherical solid particles with a maximum diameter of 50 microns or less. Alcohol is removed from the product obtained in this way, at temperatures that gradually increase from 50 ° C to 100 ° C in nitrogen stream until the alcohol content is reduced to 2.1 moles per mole of MgCl 2. In a 4-liter autoclave, previously purged with gaseous propylene at 70 C for 1 hour, 70 ml of anhydrous n-hexane containing 7 mmole of alu-mi nio-triethyl are introduced at room temperature and in propylene stream. 4 mg of the catalyst component, alone prepared as described above. The autoclave is closed, 1.7 NI of hydrogen and 1.2 kg of liquid propylene are introduced; the agitator is set in motion and the temperature is increased to 70 ° C in a period of 5 minutes. After 2 hours at 70 ° C, the stirring is stopped, the unpolymerized monomer is removed, and the contents are cooled to room temperature. 380 g of polypropylene are discharged from the autoclave, this polypropylene has an insoluble fraction of xylene at 25 C (X.I.) = 97.7%, and a melt index MFR / L = 4.5 g / 10 min. The polymer yield is 95,000 g of polypropylene / g of solid catalyst component.
Example 2
The procedure of Example 1 is used, except that the hexane suspension introduced into the polymerization autoclave is composed as follows: 70 ml of anhydrous n-hexane, 7 mmole of al-nium-o-triethyl, 5.3 mg of a component of catalyst, solid prepared as described in Example 1, and 0.35 mmoles di ci cl openti 1 -dimethoxysilane. 403 g of polypropylene having X.I. - 99% and a melt index MFR / L = 4.2 g / 10 min. The polymer yield is 76,000 g of poly i propi 1 ene / g of catalyst component, soldered.
Comparative example 1
The procedure of Example 1 is used, but in this case to prepare the catalyst component, solid, two equal aliquots are used at 9 mmoles each of 2-i sopropi 1 -2-i soprenti 1 -1, 3-dimethoxy propane , instead of 9, 9-bi s (methoxymethi 1) fl uoreno. The solid catalyst component obtained in this manner contains: Ti = 3.6% by weight; 2-i sopropi 1-2-i sopenti 1-1, 3-dimethoxy-propane = 12.7% by weight. The polymerization is then carried out as described in Example 1, using 5.7 mg of the catalyst component, solid mentioned above. 400 g of polypropylene having an X.I. = 98.0% and an MFR / L fusion index = 5.1 g / 10 min. The polymer yield is 70,000 g of poly ipropy 1 ene / g of catalyst component, solid.
Comparative example 2
The procedure of Example 2 is used, but in this case the hexane suspension introduced into the polymerization autoclave is composed as follows: 70 ml of anhydrous n-hexane, 7 mmoles of 1 to 1 nio-tri eti 1 or, 7.0 mg of the catalyst component, solid prepared as described in Comparative Example 1, and 0.35 mmoles of di ci cl openti 1 dimethoxy if 1 anus. 350 g of polypropylene having an X.I. = 98.9 Z. and a melt index of MFR / L = 5.5 g / 10 min. The polymer yield is 50,000 g of poly i propi 1 ene / g tasting component! i zador, sun gone.
Example 3
In the autoclave described in Example 1, previously purged with gaseous propylene at 70 C for 1 hour, they are introduced at room temperature in the order: 4.1 g of ethylene, 1.2 1 of liquid propylene, and 0.34 1 of hydrogen. The agitator is set in motion, the temperature is increased to 70 C in a period of 5 minutes, and by means of a steel syringe pressurized with nitrogen, a suspension composed of 10 ml of anhydrous n-hexane, 4 mmoles of al umi nio-tri eti lo.
and 4 mg of a catalyst component, solid prepared as described in Example 1. Stirring is maintained for 1.5 hours at 70 C and 32.7 bar, while a propylene / ethanol mixture containing 5.9% moles is fed. of ethylene. At the end, the agitation is interrupted, the unpolymerized monomers are removed, and the contents are cooled to room temperature. 600 g of copolymer having an ethylene content of 4% by weight, X.I. = 91.6 7, and an intrinsic viscosity [n = 1.59 dl / g. The copolymer yield is 150,000 g of propylene-ethylene copolymer / g of catalyst component, solid.
Comparative example 3
Example 3 is repeated, but using in this case, 4.1 mg of the catalyst component, solid prepared according to Comparative Example 1 (containing 2-i sopropi 1-2-i sopenti 1-1, 3-dimethoxy propane in place of 9, 9-bi s (methoxymethi 1) f luorene). 420 g of copolymer having an ethylene content of 3.9% by weight, X.I. = 90.7%, and intrinsic viscosity [?] = 1.55 dl / g. The yield of copolymer is 102,000 g of propylene-1-ene / g copolymer of catalyst component, solid.
Example 4
Example 2 is repeated using 5.2 mg of the catalyst component, solid of Example 1, but in this case the hexane suspension of the catalyst contains 0.35 mmoles of 2-i sopropi 1 -2-i sopenti 1-1, 3-dimethoxy propane instead of 0.35 mmoles of di ci clopenti Id imethoxi if 1 year. 314 g of polypropylene having X.I. are obtained. = 99.0%. The polymer yield is 60,000 g of Q pol i propi 1 ene / g of catalyst component.
Comparative Example 4
Example 1 is repeated, but in this case to prepare the catalyst component, solid, two aliquots equal to 9 mmole each of 2,2-diisobute 1-1, 3-dimethoxypropane are used instead of 9. , 9-bi s (methoxymethi 1) -fluorene. The product obtained comprises: Ti = 2.8% by weight; 2, 2-di i sobuti 1-1, 3-dimethoxypropane = or 14.7% by weight. Using 6.1 mg of the solid catalyst component, 260 g of polypropylene having X.I. - 96.9% and a melt index MFR / L = 4.9 g / 10 min. The polymer yield is 42,600 g of polypropylene / g of catalyst component. 5 Comparative example 5
Example 1 is repeated, but in this case the solid catalyst component is prepared by using two aliquots equal to 9 mmoles each of 2, 2-di i sopen-ti 1-1, 3-dimethoxypropane instead of 9, 9-bi s (methoxymethi 1) -fluorene. The product contains: Ti = 2.6% by weight; 2, 2-di i sopenti 1 -1, 3-d imethoxy propane = 17.6% by weight. By using 7.3 mg of the catalyst component, solid, 332 g of polypropylene having an X.I. = 95.2% and a melt index MFR / L = 5.2 g / 10 min. The polymer yield is 45,400 g of pol i propi 1 ene / g of the catalyst component.
Comparative example 6
Example 1 is repeated, but in this case the catalyst component, solid is prepared by using two aliquots equal to 9 mmoles each of 2-isopropyl-2-cyclohexy 1-1, 3-dimethoxy propane instead of 9.9. -bis (me-toxi eti 1) fluorene. The product obtained contains: Ti = 3.2 Z in weight; 2-i sopropi 1-2-cyclohexy 1-1,3-dimethoxypropane = 13.2% by weight. When using 6.5 mg of the catalyst component, solid, 261 g of polypropylene having X.I. = 97.2% and a melting index MFR / L = 5.9 g / 10 m n. The yield is 40,200 g of pol i propi 1 ene / g of catalyst component.
Example 5
In a 500 ml cylindrical glass reactor equipped with a filtration barrier, at 0 C, 225 ml of TiCl are introduced and while stirring in a period of 15 minutes, 10.1 g, (54 mmoles) of MgC are introduced. 1 • 2.1 C2H5OH my croesferoidal obtained as described in Example 1. At the end of the addition, the temperature is brought to 40 C and 9 mmoles of di-sobutyl phthalate is introduced. The temperature is increased to 100 ° C in the course of 1 hour, and stirring is continued for an additional 2 hours. Then, the TiCl. it is removed by filtration, 200 ml of TiCl are added »while stirring at 120 C for one more hour. Finally, the contents are filtered and washed at 60 C with n-heptane until all the chlorine ions disappear from the filtrate. The catalyst component obtained in this way contains: Ti = 3.3% by weight; diisobutyl phthalate = 8.2% by weight.
In a 4 liter autoclave, previously purged with propylene gas at 70 ° C for 1 hour, 70 ml of anhydrous n-hexane containing 7 mmole of aluminum-triethyl and 0.35 mmole are introduced at room temperature and in propylene stream. of 9, 9-bi s (methoxymethi 1) -fluorene, and 10 mg of the catalyst component, solid prepared as described above. The autoclave is closed, 1.7 NI of hydrogen, 1.2 kg of liquid propylene are introduced; the agitator is set in motion and the temperature is increased to 70 ° C in a period of 5 minutes. After 2 hours at 70 C, the stirring is stopped, the unpolymerized monomer is removed, and the contents are cooled to room temperature. 450 g of polypropylene are charged from the autoclave, said propylene has a fraction insoluble in xylene at 25 ° C (X.I.) = 97.5% and a melt index MFR / L = 5.0 g / 10 min. The polymer yield is 45,000 g of polypropylene / g of the catalyst component, solid.
Comparative example 7
Example 5 is repeated using 8.9 mg of the catalyst component, solid of Example 5, but in this case 0.35 mmoles of 2-i sopropi 1, 2-i sopenti 1 -1, 3-d imethoxy i propane is used as the compound external electron donor with al umi n io-tr i eti lo (instead of 9, 9-bis (methoxymethi 1) f luorene). 339 g of polypropylene are obtained, this polypropylene has an X.I. 97.7% and a melt index MFR / L = 5.2 g / 10 min. The polymer yield is of. 38,000 g of polypropylene / g of catalyst component, sol.
In a glass reactor, cylindrical of 500 ml, equipped with a filtration barrier is introduced at 0 C 225 ml of TiCl ^ and while there is stirring in a period of 15 minutes, 10.1 g (54 mmoles), of MgC 1 > 2.1 C2H (-0H my croespheride obtained as described in Example 1. At the end of the addition, the temperature is brought to 70 ° C and 9 mmoles of 2-isopropyl-2-isopenti 1-1, 3-di are introduced. Methoxy propane The temperature is increased to 100 C and after 2 hours the TiCl is removed by filtration, an additional 200 ml of TiCl is added and 9 mmoles of 2-isopro-pi 1-2-i sopenti 1-1 are added. 3-dimethoxypropane, after one hour at 120 ° C, the contents are filtered again and another 200 ml of TiCl are added continuing with the treatment.
at 120 ° C for one hour; finally the content is filtered and washed at 60 C with n-heptane until all the chlorine ions disappear from the filtrate. The catalyst component, solid obtained in this manner, contains: Ti = 3.6% by weight; 2-i sobuti 1 -2-i sopenti 1 -1, 3-dimethoxy -propane = 12.7% by weight. By carrying out the polymerization as described in Example 5, and using 9.7 mg of the catalyst component described above, 484 g of the polymer having X.I. = 99% and a melt index MFR / L - 5. I g / 10 min. The polymer yield is 50,000 g of pol i propi 1 ene / g of the catalyst cotiponent, solid.
Example 7
Example 6 is repeated but in this case using 5.3 mg of the catalyst component, solid of Example 1. 371 g of polypropylene having an X.I. are obtained. = * 99.1% and MFR / L = 5.1 g / 10 min. The polymer yield is 70,000 9 of ponpropylene / g of the catalyst component.
Comparative example 8
Comparative Example 7 is repeated, but in this case, 0.35 mmoles of 2, 2-di i sobuti 1-1, 3-d imethoxy propane are used as the compound: external electron donor with alu-nio-tri eti 1 or. Using 9.5 mg of the catalyst component, solid, 290 g of polypropylene having an X.I. = 97.0% and a melt index MFR / L = 5.6 g / 10 min. The yield is 30,500 g of polypropylene / g of the catalyst component.
Comparative example 9
Comparative Example 7 is repeated, but in this case 0.35 mmoles of 2-i sopropi 1-2-i sobuti 1-1, 3-dimethoxy propane is used as the external electron donor compound with aluminum-triethyl. Using 10 mg of the catalyst component, solid, 353 g of polypropylene having an X.I. = 97.2% and a melt index MFR / L = 4.6 g / 10 min. The yield is 35,300 g of polypropylene / g of the catalyst component.
Comparative Example 10
Example 7 is repeated, but in this case 0.35 mmoles of 2, 2-di i sopropi 1 -1, 3-dimethoxy propane is used as the external electron donor compound with the umium-triethylumone. Using 10.2 mg of the catalyst component, solid, 403 g of polypropylene having an X.I. = 98% and a melt index MFR / L = 5.1 g / 10 min. The yield is 39,500 g of polypropylene / g of the catalyst component.
Comparative example 11
Comparative example 7 is repeated, but in this case 0.35 mmoles of 2-ethi 1-2-buti 1-1, 3-di-methoxy propane are used as the external electron donor compound with the alumo-triethylone. Using 9.8 mg of the catalyst component} solid, 307 g of polypropylene having an X.I. = 95.2% and a melt index MFR / L = 5.1 g / 10 min. The yield is 31,300 g of polypropylene / g of the catalyst component.
Comparative example 1_2_
Comparative Example 7 is repeated, but in this case 0.35 mmoles of 2,2-di-phenyl-1, 3-dimethoxypropane is used as the external electron donor compound with the umium-tri-ethyl ether. Using 8.7 mg of the catalyst component, solid, 347 g of polypropylene having an X is obtained. I. = 98.0% and a melt index MFR / L = 3.1 g / 10 min. The yield is 40,000 g of pol i propi 1 ene / g of catalyst component.
Comparative Example 13
Comparative Example 7 is repeated, but in this case 0.35 mmoles of 2-i sopropi 1-2-cihexhexyl-1, 3-dimethoxy propane is used as the external electron donor compound with the umium-tri-diol. 1 o. Using 9.1 mg of the catalyst component, solid, 297 g of polypropylene having an X.I. = 98% and a melt index MFR / L - 3.8 g / 10 min. The yield is 32,600 g of polypropylene / g of catalyst component.
Comparative Example 14
Comparative Example 7 is repeated, but in this case 0.35 mmoles of 2, 2-d c i c lopenti 1 -1, 3-dimethoxypropane is used as the external electron donor compound with the ali ni o-tri eti 1 o. Using 9.6 mg of the solid catalyst component, 385 g of polypropylene having an X.I. = 97.9% and a melt index MFR / L = 3.2 g / 10 min. The yield is 40,100 g of polypropylene / g of Catalyst component.
It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.
Having described the invention as above, the content of the following is claimed as property:
Claims (29)
1. A catalyst component, solid for the polymerization of olefins, characterized in that it comprises a magnesium halide in active form, and supported thereon, a titanium compound containing at least one Ti -hal bond and a 1,3-diether the opol i in which the carbon atom in position 2 corresponds to a cyclic or polycyclic structure composed of 5, 6, or 7 carbon atoms, or 5-n, or 6-n 'carbon atoms, and respectively n atoms of nitrogen and n 'heteroatoms selected from the group consisting of N, 0, S and Si, where n is 1 or 2 and n' is 1, 2 or 3, this structure contains two or three nsaturations ( cyclopolylic structure) and optionally is condensed with other cyclic structures, or substituted with one or more substituents selected from the group consisting of linear or branched alkyl radicals, cycloalkyl, aryl, aralkyl, alkaryl and halogen radicals, or is condensed with other est cyclic structures and substituted with one or more of the aforementioned substituents which can also be attached to the condensed cyclic structures; one or more of the aforementioned alkyl, cycloalkyl, aryl, aralkyl, or alkaryl radicals and the condensed cyclic structures optionally containing one or more heteroatoms as substitutes for the carbon or hydrogen atoms, or both.
2. The catalyst component, solid according to the rei indication 1, characterized in that the carbon atoms in positions 1 and 3 in the 1,3-diether cyclic opylene are secondary.
3. The catalyst component, solid according to claim 1, characterized in that the substituents in 1,3-diether c i c 1 opol iinic are selected from the group consisting of alkyl radicals of 1 to 20 carbon atoms; cycloalkyl of 3 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; aralkyl of 7 to 20 carbon atoms and alkaryl of 7 to 20 carbon atoms, linear or branched; Cl and F.
4. The catalyst component, solid according to claim 1, characterized in that the cyclopolynic 1,3-diether is selected from the compounds of the general formula: where A, B, C and D are carbon atoms or heteroatoms selected from the group consisting of N, 0, S and Yes; v, x and y are 0 or 1; u and z are 0 or 1 or 2; with the proviso that when u = 0: i) A, B and C are carbon atoms and v, x and y are equal to 1; or ii) A is a nitrogen atom, B and C are carbon atoms, v is equal to 0 and x and y are equal to 1; or iii) A and B are nitrogen atoms, C is a carbon atom, v and x are equal to 0 and y is equal to 1; or iv) A and B are carbon atoms, C is a nitrogen atom, v and x are equal to 1 e and is equal to 0; when u = 1 1) A, B, C and D are carbon atoms, v, x and y are equal to 1 and z equals 2; or 2) A and B are carbon atoms, C is a nitrogen atom, D is an oxygen atom, v and x are equal to 1, and e z are equal to 0; or 3) A, B and C are carbon atoms, D is an oxygen, nitrogen, sulfur or silicon atom, v, x and y are equal to 1 and z is equal to 0, when D is an oxygen atom or an atom of sulfur, is equal to 1 when D is a nitrogen atom, and is equal to 2 when D is a silicon atom; when u = 2: A, B and C are carbon atoms, D represents two carbon atoms linked together by an individual or double bond, v, x and y are equal to 1 and z is equal to 1, when the pair of atoms of Carbon D is linked by a double bond, and is equal to 2, when this pair is linked by an individual bond; the radicals R and R, the same or different, are selected from the group consisting of hydrogen; halogens; alkyl radicals of 1 to 20 carbon atoms, linear or branched; cycloalkyl radicals of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkaryl of 7 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; R radicals, the same or different, are selected from the group consisting of linear or branched alkyl radicals of 1 to 20 carbon atoms; cycloalkyl radicals of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkaryl of 7 to 20 carbon atoms and aralkyl of 7 to 20 carbon atoms, and two or more of the radicals R can be attached to each other to form condensed, saturated or unsaturated cyclic structures, optionally substituted with radicals R selected from the group consisting of halogens or linear or branched alkyl radicals of 1 to 20 carbon atoms; cycloalkyl radicals of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkaryl of 7 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; these radicals from R to R optionally contain one or more heteroatoms as substitutes for the carbon or hydrogen atoms or both.
5. The catalyst component, solid according to claim 4, characterized in that the cyclopolynic 1,3-diether is selected from the compounds of the general formula: wherein the radicals R and R, the same or different, are selected from the group consisting of hydrogen; halogens; alkyl radicals of 1 to 20 carbon atoms, linear or branched; cycloalkyl radicals of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkaryl of 7 to 20 carbon atoms and aralkyl of 7 to 20 carbon atoms; the same or different radicals R are selected from the group consisting of linear or branched alkyl radicals of 1 to 20 carbon atoms; cycloalkyl radicals of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkaryl of 7 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, and two or more of the radicals R can be attached to each other to form cyclic or condensed, saturated or unsaturated structures, optionally substituted with R radicals selected from the group consisting of halogens; alkyl radicals of 1 to 20 carbon atoms, linear or branched; cycloalkyl radicals of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkaryl of 7 to 20 carbon atoms and aralkyl of 7 to 20 carbon atoms; these radicals from R to R optionally contain one or more heteroatoms as substitutes for the carbon and hydrogen atoms, or both.
6. The catalyst component, solid, according to claim 5, characterized in that the 1,3-diether ci c 1 opol iini co is selected from the group consisting of: 1 - . 1 -bi s (methoxymethi -cylpentadi ene; 1 -bi s (methoxymethi-2,3,3,5-tetramethylcyclopentadiene; 1 -bi s (methoxymethi-2,3,4,5-tetraphenylcyclopentadiene; (methoxymethiindene; 1-bi s (methoxymethi -2, 3-d imeti 1 indene; 1-bi s (methoxymethi-4,7-dimethylindene; 1-bi s (methoxymethi-4-phene 1-2-methy1 ndene 1 -bi s (methoxymethi -7- (3,3,3-trifluoropropyl) indene; 1 -bis (methoxymethi-7-trimethylsilyldene; 1 -bi s (methoxymethi-7-trifluoromethylindene; -bi metox imeti -7-met i 1 i ndeno; -b-methoxymethi-7-cyclopentyl indene; -b-methoxymethyl-7-isopropyl-1-indene; -b-methoxymethyl-7-c-clohexyl indene; -b-methoxymethyl-7-tert-butyl indene; -b-methoxymethyl-7-tert-butyl-2-methylindene; -b-methoxymethyl-7-phenylindene; -b-methoxymethyl-2-phenyl-1-ndene; 9-b methox imeti f 1 ororen; 9-b-methoxymethyl-2,3,6,7-tetramethyl-fluorene; 9-b-methoxymethi-2,3,4,5,6,7-hexafluorofluorene; 9-b methoxymethi-2, 3-benzofl-orine; 9-b methoxymethi -2, 3, 6, 7-d i benzofl ororen; 9-b-methoxymethyl-2,7-diisopropyl-fluorene; 9-b methoxymethi-1, 8-di chlorofl-orine; 9-b-methoxymethyl-2,7-dicyclopentyl-fluorene; 9-b methoxymethi -1,8-difluorofluorene; 9-b methoxy met i -1,2, 3, 4-tetrahydrofl-orine; 9-b methoxymethi-1,2,3,4,5,6,7,8-octahydrofluorene; 9-b-methoxymethyl-4-tert-butylphluoro.
7. The catalyst component, solid according to claim 4, characterized in that the cyclopolyenic 1,3-diether is selected from the group consisting of 9, 9-bi s (methoxymethi 1) xanthene and 9,9-bis (methoxymethyl) ) -2,3,6,7-tetramethylxanthene.
8. The catalyst component, solid according to claim 1, characterized in that the titanium compound is selected from the group consisting of halogen halides and alcoholates.
9. The catalyst component, solid according to claim 8, characterized in that the titanium compound is titanium tetrachloride.
10. The catalyst component, solid according to the rei indication 1, characterized in that the 1,3-diether cyclohexylene is present in amounts ranging from 5 to 20 mol% with respect to the magnesium halide i.
11. The catalyst component, solid according to claim 1, characterized in that the Mg / Ti ratio is from 30: 1 to 4: 1.
12. A catalyst for the polymerization of olefins, characterized in that it comprises the reaction product: a) the catalyst component, solid of claim 1, with b) an Al-alkyl compound, and optionally c) a donor compound. electrons different from the 1,3-diethers ci cl opol i e n i eos.
13. The catalyst according to claim 12, characterized in that the Al-alkyl compound b) is an Al -tri to 1i.
14. The catalyst according to claim 12, characterized in that the electron-donor compound c) is selected from the group consisting of silicon compounds, which contain at least one Si-OR bond, where R is a hydrocarbon radical, 2,2,6,6-tetramethylpiperidine, 2,6-di i sopropi 1 pi peri-di, and esters of carboxylic acids.
15. The catalyst according to claim 12, characterized in that the electron donor compound c) is selected from the compounds having the general formula: »VI R VII \ and - OR 'XI , VIII where RIV, RV, RVI. R I1 IX and R are the same, and they are hydrogen; alkyl radicals of 1 to 18 carbon atoms, cycloalkyl of 3 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, aralkyl of 7 to 18 carbon atoms or alkapol, 1 i 1 is branched, with the proviso that only one of R and R can be hydrogen; R and R have the same meanings as for R and R, except for hydrogen, with the proviso that when the V IX * • X XI radicals from R to R are hydrogen and R and R are methyl, R is not methyl; in addition, two or more of the radicals R to R can be joined to form a cyclic structure.
16. A catalyst for the polymerization of olefins characterized in that it comprises the reaction product between: a1) a soldered tasting component comprising a magnesium halide in the active form, and supported thereon, a titanium compound which contains at least one Ti-halogen bond, and an electron donor compound; b) an Al-alkyl compound; c) a 1,3-diether cyclic opylene in which the carbon atom in position 2 corresponds to a cyclic or polycyclic structure composed of 5, 6, or 7 carbon atoms, or 5-no 6 -n 'carbon atoms and respectively n atoms of nitrogen and n' heteroatoms selected from the group consisting of N, 0, S and Si, where n is 1 or 2, and n 'is 1, 2 or 3, this structure contains two or three unsaturations (cyclopolyenic structure), and optionally condensed with other cyclic structures, or substituted with one or more substituents selected from the group consisting of linear or branched alkyl radicals; cycloalkyl, aryl, aralkyl, alkaryl, and halogen radicals, or is condensed with other cyclic structures and substituted with one or more substituents mentioned above, which can also be attached to the condensed cyclic structures; one or more of the aforementioned alkyl, cycloalkyl, aryl, aralkyl or alkaryl radicals and the condensed cyclic structures optionally contain one or more heteroatoms as substitutes for the carbon or hydrogen atoms, or both.
17. The catalyst according to claim 16, characterized in that the substituents in the cyclopolynic 1,3-diether c) are selected from the group consisting of straight or branched alkyl radicals of 1 to 20 carbon atoms; cycloalkyl radicals of 3 to 20 carbon atoms; aryl of 6 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms and alkaryl of 7 to 20 carbon atoms; Cl and F.
18. The catalyst according to claim 16, characterized in that the cyclo-polyene 1,3-diether c) is selected from the compounds of the general formula: where A, B, C and D are carbon or heteroatom atoms selected from the group consisting of N, 0, S and Yes; v, x, e and are 0 or 1; u and z are either 0 or 1 or 2; with the proviso that when u = 0: A, B and C are carbon atoms, and v, are equal to 1; or 1 A is a nitrogen atom, B and C are carbon atoms, v is equal to 0 and x and y are equal to 1; or 1 i) A and B are nitrogen atoms, C is a carbon atom, v and x are equal to 0 and y is equal to 1; iv) A and B are carbon atoms, C is a carbon atom, v and x are equal to l and y is equal to 0; when u = 1: 1) A, B, C and D are carbon atoms, v, x and y are equal to 1 and z equals 2; or 2) A and B are carbon atoms, C is a nitrogen atom, D is an oxygen atom, v and x are equal to 1, and e z are equal to 0; or 3) A, B and C are carbon atoms, D is an oxygen, nitrogen, sulfur or silicon atom, v, x and y are equal to 1 and z is equal to 0, when D is an oxygen or sulfur atom, like a 1, when D is a nitrogen atom and equal to 2 when D is a silicon atom; when u = 2: A, B and C are carbon atoms, D represents two carbon atoms linked together by an individual or double bond, v, x and y are equal to 1 and z is equal to 1 when the pair of carbon atoms D is linked by a double bond and equal 2 when this pair is linked by an individual link; the radicals R and R, the same or different, are selected from the group consisting of hydrogen; halogens; alkyl radicals of 1 to 20 carbon atoms, linear or branched; cycloalkyl radicals of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms. alkaryl of 7 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; R radicals, the same or different, are selected from the group consisting of linear or branched alkyl radicals of 1 to 20 carbon atoms; cycloalkyl radicals of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkaryl of 7 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms, and two or more of the radicals R can be attached between yes to form condensed, saturated or unsaturated cyclic structures, optionally substituted with radicals R selected from the group consisting of halogens; alkyl radicals of 1 to 20 carbon atoms, linear or branched; cycloalkyl radicals of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkaryl of 7 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; these radicals from R to R optionally contain one or more heteroatoms as substitutes for the carbon or hydrogen atoms, or both.
19. The catalyst according to claim 18, characterized in that the cyclopolyneric 1,3-diether c) is selected from the compounds of the general formula: ^ &t 5? «*» wherein the radicals R and R, the same or different, are selected from the group consisting of hydrogen; halogens; alkyl radicals of 1 to 10 carbon atoms, linear or branched, cycloalkyl radicals of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkaryl of 7 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms carbon; R radicals, the same or different, are selected from the group consisting of linear or branched alkyl radicals of 1 to 10 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkaryl from 7 to 20 carbon atoms, and aralkyl radicals from 7 to 20 carbon atoms, and two or more of the radicals can be linked together to form condensed, saturated, or unsaturated cyclic structures, optionally substituted with radicals R selected from of the group consisting of halogen; alkyl radicals of 1 to 20 carbon atoms, linear to branched; cycloalkyl radicals of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkaryl of 7 to 20 carbon atoms and aralkyl of 7 to 20 carbon atoms; these radicals from R to R optionally contain one or more heteroatoms as substitutes for the carbon or hydrogen atoms, or both.
20. The catalyst according to claim 19, characterized in that the cyclo-polyene 1,3-diether c) is selected from the group consisting of: l-bis (methoxymeth? '1) -cyclopentadiene; 1-bis (methoxymethyl) -2,3,4,5-tetramethylcyclicpentadiene; 1-bis (methoxymethyl) -2,3,4,5-tetraphenylcyclopentadiene; l-bis (methoxymethyl) i ndene; 1-bis (methoxymethyl) -2,3-dimethylindene; 1-bis (methoxymethyl) -4,7-dimethylindene; 1-bi s (methoxymethi 1) -4-phen i 1-2-methyl-1-indene; 1,1-bis methoxymethyl 1) -7- (3,3,3-trifluoropropyl) indene; 1,1-bis-methoxymethyl-1) -7-trimethylsilicon; 1,1-bis-methoxymethyl) -7-trifluoromethyl indene; 1,1-bis methox imet i 1) -7-meti 1 i ndeno; 1,1-bis methoxymethi l) -7-c i c l open t i l i ndeno; 1,1-bis methoxymethi l) -7-i sop rop? ' 1 i nde no; 1,1-bis methox imeti 1) - 7 -c i c > 1 o h e x i 1 i n d o n; 1,1-bis methoxymethi 1) -7-te i-butyl i-ndene; 1,1-bis-methoxymethyl-l) -7-tert-butyl-2- methylidene; 1,1-bis methoxymethi 1) -7-phenyl-1-indene; 1,1-bis-methoxymethyl-l) -2-phenyl-indene; 9,9-bis methox imeti 1) f 1 -oreno; 9,9-bis methoxymethi 1) -2, 3, 6, 7-tetrametheluorene; 9,9-bis methoxymethyl) -2,3,4,5,6,7-hexafluorofluorene; 9,9-bis methox imeti l) -2,3-benzofl-orine; 9,9-bis methoxymethyl) -2,3,6,7-dibenzofluorene; 9,9-bis methoxymethi 1) -2,7-d-isopropyl-fluorene; 9,9-bis methoxymethi 1) -1,8-d i chlorofluorene; 9,9-bis-methoxymethyl-l) -2,7-dicyclopentyl-fluorene; 9,9-bis methoxymethyl) -1,8-difluorofluorene; 9,9-bis methoxymethyl) -1,2,3,4-tetrahydrofluorene; 9,9-bis-methoxymethyl-1) -l, 2,3,4,5,6,7,8-octahydrofluorene; 9,9-bis methoxymethyl) -4) te -butyl fluorene; 1,1-bis to fa-methoxy benz 1) indene; 1,1-bis 1'-methoxy i eti 1) -5,6-dichloroindene; 9, 9-bi s (a lfa-ethoxy benz 1) f 1 -oreno; 9,9-bis (1'-methoxyethanol) fl uoreno; 9- (me toxymethyl) -9- (1-methoxyethyl) -2,3,6,7-tetrafluoro-f-1-loreno; 9-methoxymethi 1-9-pentoxymethyl-1 fluorene; 9-methoxymethi 1-9-ethoxymethi 1 f 1 orinole; 9-methox imeti 1-9- (l 'methoxy eti l) -f1-uorene;
21. The catalyst according to claim 18, characterized in that the 1,3-diether cyclo-polyn i co c) is selected from the group consisting of 9, 9-bi s (methoxymethi 1) xanthene, and 9, 9 -bi s (methoxymethi 1) -2, 3, 6, 7-tetramethyl xanthene.
22. The catalyst according to claim 16, characterized in that the Al-alkyl compound is an Al-tri-alkyl.
23. The catalyst according to the rei indication 16, characterized in that the titanium compound supported on the catalyst component, solid a) is selected from the group consisting of halogen halides and alcoholates.
24. The catalyst according to claim 16, characterized in that the electron donor compound supported on the catalyst component, solid a) is a Lewis base containing one or more electronegative groups where the electron donor atoms are selected from the group consisting of N, 0, S, P, As or Sn.
25. The catalyst according to claim 24, characterized in that the electron donor compound, supported on the catalyst component,
Solid a) is an electron donor compound that can be extracted with Al-triethyl from the catalyst component a) by at least 70 mole%, the surface area (BET) of the solid product of the extraction which is at least 20 / g. 26. The catalyst according to claim 24, characterized in that the electron-donor compound supported on the catalyst component, 1 only 1"or" ** "•) is an ester of phthalic acid.
27. The catalyst according to claim 24, characterized in that the electron donor compound supported on the catalyst component, solid a) is an ether containing two or more groups «E e, and * -fl« .ft-J? At normal temperatures, complex is formed with anhydrous magnesium chloride for less than 60 mmoles per 100 g of chloride and with TiCl 'does not undergo substitution reactions, or only for less than 50% by mol.
28. The catalyst according to claim 24, characterized in that the electron-donor compound supported on the catalyst component, solid a) is a 1,3-diether with the opol iinic acid in which the carbon atom at the 2-position corresponds to a cyclic or polycyclic structure composed of 5, 6 or 7 carbon atoms, or 5-not 6-n 'carbon atoms or respectively n atoms of nitrogen and n' heteroatoms selected from the group consisting of N, 0 , S and Si, where n is 1 or 2 and n 'is 1, 2 or 3, this structure contains two or three unsaturations (cyclopolyenic structure) optionally condensed with other cyclic structures, or substituted with one or more substituents selected from group consisting of linear or branched alkyl radicals; cycloalkyl, aryl, aralkyl, alkaryl and halogen radicals, or is condensed with other cyclic structures and substituted with one or more of the aforementioned substituents which can also be attached to the cyclic condense structures; one or more of the alkyl, cycloalkyl, aryl, aralkyl or alkaryl radicals mentioned above. and condensed cyclic structures optionally containing one or more heteroatoms as substitutes for the carbon or hydrogen atoms, or both.
29. A process for the polymerization of olefins of CH? = CHR, where R is hydrogen or an alkyl radical of 1 to 6 carbon atoms, or an aryl radical, or mixtures of these olefins or of these olefins and diolefins, the process is characterized in that it is carried out in the liquid phase in the presence or not of an aliphatic aromatic hydrocarbon solvent, or in gas phase, or by combining the polymerization steps in the liquid phase in the gas phase, in the presence of a catalyst as defined in claims 12 and 16. In testimony of which I sign the present in this Mexico City D.F. on February 16, 1996. By: MONTELL NORTH AMER ICA__IHC ^ - Representative
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT95MI000317 IT1274251B (en) | 1995-02-21 | 1995-02-21 | Catalyst component for stereospecificity for olefin! polymerisation - contg. cyclo:polyenic 1,3-di:ether with poly:cyclic structure, magnesium halide in active form and titanium cpd., for high activity |
| IT95MI000318 IT1274252B (en) | 1995-02-21 | 1995-02-21 | Catalyst component for stereospecificity for olefin! polymerisation - contg. cyclo:polyenic 1,3-di:ether with poly:cyclic structure, magnesium halide in active form and titanium cpd., for high activity |
| MIMI95A00317 | 1995-02-21 | ||
| MIMI95A00318 | 1995-02-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MX9600627A MX9600627A (en) | 1997-07-31 |
| MXPA96000627A true MXPA96000627A (en) | 1997-12-01 |
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