RU95122079A - METAL-CELL CATALYTIC SYSTEMS ON A SUBSTRATE FOR POLYMERIZATION OF OLEFINS, THEIR RECEIVING AND APPLICATION - Google Patents

Claims (23)

1. The catalytic system on the carrier, comprising: (a) the product of the reaction of one or more metallocenes with alumoxane;

where M ¹ denotes a metal of group 4, 5 or 6 of the Periodic table;
R ¹ and R ^{2 are the} same or different and represent a hydrogen atom, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₆ -C ₁₀ aryl group, a C ₆ -C ₁₀ aryloxy group, a C ₂ - A C ₁₀ -alkenyl group, a C ₇ -C ₄₀ arylalkyl group, a C ₇ -C ₄₀ alkylaryl group, a C ₈ -C ₄₀ arylalkenyl group or a halogen atom;
R ³ and R ⁴ denote hydrogen atoms;
R ⁵ and R ^{6 are the} same or different, preferably the same, and represent a halogen atom, a C ₁ -C ₁₀ -alkyl group which may be halogenated, a C ₆ -C ₁₀ -aryl group which may be halogenated, C ₂ -C ₁₀ -alkenyl group, C ₇ -C ₄₀ arylalkyl group, C ₇ -C ₄₀ alkylaryl group, C ₈ -C ₄₀ arylalkenyl group, -NR radical $\genfrac{}{}{0ex}{}{\text{15}}{\text{2}}$ ,, -SR ¹⁵ , -OR ¹⁵ , -OSiR $\genfrac{}{}{0ex}{}{\text{15}}{\text{3}}$ or -PR $\genfrac{}{}{0ex}{}{\text{15}}{\text{2}}$ ,, where R ¹⁵ denotes a halogen atom, a C ₁ -C _{10 is an} alkyl group or a C ₆ -C ₁₀ aryl group;
R ⁷ means

= BR ¹¹ , = AlR ¹¹ , -Ge-, -Sn-, -O-, -S-, = SO, = S0 ₂ , = NR ¹¹ , = CO, PR ¹¹ or = P (O) R ¹¹ , where R ¹¹ , R ¹² and R ^{13 are the} same or different and represent a hydrogen atom or
halogen atom, C ₁ -C ₂₀ -alkyl group, C ₁ -C ₂₀ -fluoroalkyl group, C ₆ -C ₃₀ -aryl group, C ₆ -C ₃₀ -fluoroaryl group, C ₁ -C ₂₀ alkoxy group, C ₂ - A C ₂₀ alkenyl group, a C ₇ -C ₄₀ arylalkyl group, a C ₈ -C ₄₀ arylalkenyl group, a C ₇ -C ₄₀ alkylaryl group, or
R ¹¹ and R ¹² , or R ¹¹ and R ¹³ together with the atoms connecting them can form cyclic systems;
M ² is an atom of silicon, germanium or tin;
R ⁸ and R ^{9 are the} same or different and have the same meaning as R ¹¹ ; m and n are the same or different and represent 0, 1 or 2, the sum
m and n is 0, 1 or 2;
R ¹⁰ radicals are the same or different and have the same meanings as R ¹¹ , R ¹² and R ¹³ , where two adjacent radicals R ¹⁰ can be associated with the formation of a ring system,
(b) a porous carrier; and (c) an optionally prepolymerized olefin monomer (s). 2. A process for producing a propylene homo- or copolymer, the molecular weight of which is about 100,000 g / mol or more, the melting point is about 140 ^° C or higher, the bulk density is about 0.30 g / cm ³ or more, by polymerization of propylene or by copolymerization mixtures of propylene with one or more other olefin polymerization reaction at a temperature of about 45 ^o C or above, under a polymerization pressure of 0.5-100 bar in the gas phase, bulk or suspension in the presence of (a) the reaction product of one or more metallocenes s with an alumoxane, said reaction product obtained by the introduction of said metallocene component (s) into contact with alumoxane in a suitable solvent, wherein the metallocene has the general formula

where M ¹ denotes a metal of group IV, V or VI of the Periodic table;
R ¹ and R ^{2 are the} same or different and represent a hydrogen atom, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₆ -C ₁₀ aryl group, a C ₆ -C ₁₀ aryloxy group, a C ₂ - A C ₁₀ alkenyl group, a C ₇ -C ₄₀ arylalkyl group, a C ₇ -C ₄₀ alkylaryl group, a C ₈ -C ₄₀ arylalkenyl group or a halogen atom;
R ³ and R ⁴ denote hydrogen atoms; R ⁵ and R ^{6 are the} same or different, preferably the same, and represent a halogen atom, a C ₁ -C ₁₀ -alkyl group which may be halogenated, a C ₆ -C ₁₀ -aryl group which may be halogenated, C ₂ -C ₁₀ -alkenyl group, C ₇ -C ₄₀ arylalkyl group, C ₇ -C ₄₀ alkylaryl group, C ₈ -C ₄₀ arylalkenyl group, -NR radical $\genfrac{}{}{0ex}{}{\text{15}}{\text{2}}$ , -SR ¹⁵ , -OR ¹⁵ , -OSiR $\genfrac{}{}{0ex}{}{\text{15}}{\text{3}}$ or -PR $\genfrac{}{}{0ex}{}{\text{15}}{\text{2}}$ where R ¹⁵ denotes a halogen atom, a C ₁ -C _{10 is an} alkyl group or a C ₆ -C ₁₀ aryl group;
R ⁷ means

= BR ¹¹ , = AlR ¹¹ , -Ge-, -Sn-, -O-, -S-, = SO, = SO ₂ , = NR ¹¹ , = CO, PR ¹¹ or = P (O) R ¹¹ ,
where R ¹¹ , R ¹² and R ^{13 are the} same or different and represent a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ fluoroalkyl group, a C ₆ -C ₃₀ aryl group, C ₆ - C ₃₀ -ftorarilnuyu group, a C ₁ -C ₂₀ alkoxy, C ₂ - C ₂₀ alkenyl group, a C ₇ -C ₄₀ -arilalkilnuyu group, a C ₈ -C ₄₀ -arilalkenilnuyu group, a C ₇ -C ₄₀ -alkylaryl group, or R ¹¹ and R ¹² or R ¹¹ and R ¹³ together with the atoms connecting them can form cyclic systems;
M ² is an atom of silicon, germanium or tin;
R ⁸ and R ^{9 are the} same or different and have the same meaning as R ¹¹ ; m and n are the same or different and represent 0, 1 or 2, the sum
m and n is 0, 1 or 2;
and the radicals R ^{10 are the} same or different and have the same meanings as R ¹¹ , R ¹² and R ¹³ , where two additional adjacent radicals R ¹⁰ can be linked together to form a ring system;
(b) a porous carrier; and (c) an optionally prepolymerized olefin monomer (s).  3. Catalytic system according to claim 1 or 2, prepolymerized with olefin monomer. 4. The catalytic system according to any one of the preceding paragraphs, where m is equal to n and is equal to 0, and M ² denotes an atom of silicon. 5. The catalytic system according to any one of the preceding paragraphs, where each of R ⁵ and R ⁶ denotes C ₁ -C ₁₀ -alkyl. 6. The catalytic system according to any one of the preceding paragraphs, where the three radicals R ¹⁰ are hydrogen atoms, and one represents a C ₆ -C ₃₀ -aryl group. 7. The catalytic system according to any one of the preceding paragraphs, where two adjacent radicals R ¹⁰ form a condensed 4,5-benzene ring, and the other two radicals R ¹⁰ are hydrogen atoms. 8. The catalytic system according to any one of the preceding paragraphs, where at least one of the radicals R ¹⁰ is a C ₁ -C ₁₀ -alkyl.  9. The catalytic system according to any one of the preceding paragraphs, where the metallocene component is selected from the group that mainly covers racemic dimethylsilanediylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride; racemic dimethylsilanediylbis (2-methylindenyl) zirconium dichloride; racemic dimethylsilanediyl bis (2-methyl-4,6-benzoindenyl) zirconium dichloride and racemic dimethylsilanediyl bis (2-methyl-4-phenylindenyl) zirconium dichloride.  10. The catalytic system according to any one of the preceding paragraphs, where the olefin monomer (s) is ethylene.  11. Catalytic system for PP. 1-9, where the olefin monomer (s) is a propylene.  12. Catalytic system for PP. 1-9, where the olefin monomer (s) includes at least two different monomers containing 2-8 carbon atoms.  13. The catalytic system according to any one of the preceding paragraphs, where the amount of olefin monomer (s) is from about 10 to about 1000 wt.% Based on the weight of the unpolymerized catalyst on the carrier.  14. The catalytic system of Claim 13, wherein the amount of the olefin monomer (s) is from about 100 to about 300% by weight, based on the weight of the unpolymerized catalyst on the carrier.  15. The catalytic system according to any one of the preceding paragraphs, where the molar ratio between aluminum alumoxane and metal metallocene is from about 12: 1 to about 1000: 1.  16. The catalyst according to claim 15, where the ratio is from about 50: 1 to about 500: 1.  17. The method according to claim 2, wherein the propylene is polymerized to isotactic polypropylene.  18. The method according to claim 2 or 17, where mixtures of propylene with other polymerizable olefins are polymerized to polypropylene copolymers. 19. Isotactic polymers of propylene, obtained in accordance with the method according to claims. 2, 17 or 18 are characterized by a weight average mol. m. about 100,000 g / mol or more, a melting point of about 140 ^o C or higher and a bulk density of about 0.30 g / cm ³ or more.  20. Isotactic polypropylene, obtained in the presence of a catalytic system according to any one of paragraphs. 1-16.  21. A method of producing a catalytic system on a carrier, which includes the steps a) of preparing a metallocene / alumoxane mixture in a suitable solvent, where the metallocene component is defined in 1 or 3-16; b) contacting the mixture in a suitable solvent with a porous carrier; c) removal of practically all solvent from the formed suspension; g) obtaining a catalytic system on a carrier and e) optional prepolymerization of a catalytic system on a carrier using one or more olefin monomers. 22. The method according to claim 2, wherein the catalytic system is prepolymerized to obtain a polypropylene polymer or its copolymers characterized by a mol. m. about 100,000 or more, melting point about 140.degree ^{. C.} or higher and bulk density of about 0.30 g / cm ³ or more.  23. The use of polymers obtained by the method defined in paragraph 2 or 17-20, in molded products, films or fibers.