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US 6,191,240 B1Granted
Catalysts and processes for the polymerization of olefins
AssigneeMontell Technology Company BV
InventorMaurizio Galimberti
Life of this patent
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Abstract
Catalysts for the polymerization of olefins comprise the product of the reaction between: (A) a titanium, zirconium or hafnium product with substituted cyclopentadiene ligands, (B) a mixture of two organometallic aluminium compounds, with at least one of the groups bound to the aluminium being other than a linear alkyl, and (C) water. When used in the polymerization of olefins, these catalysts show higher activities, at short residence times, than corresponding catalysts obtained from the individual components of the above-mentioned mixtures of aluminium compounds.
Claims21
Catalyst for the polymerization of olefins, comprising the product of the reaction between the following components:
- (A) a cyclopentadienyl compound of the formula (I):
- (C5R1x−mH5−x)R2m(C5R1y−mH5−y)nMQ3−n (I)
- in which M is Ti, Zr or Hf, C5R1x−mH5−x and C5R1y−mH5−y are cyclopentadiene rings substituted in the same way or different ways, the substituents R1 which are identical or different are alkyl, alkenyl, aryl, alkylaryl or arylalkyl radicals which have from 1 to 20 carbon atoms and can also contain Si or Ge atoms, or Si (CH3)3 groups, or also two or four substituents R1 of one and the same cyclopentadienylgroup can form one or two rings having from 4 to 6 carbon atoms, R2 is a group forming a bridge link between the two cyclopentadiene rings and is selected from the group consisting of CR32, C2R34, SiR32, Si2R34, GeR32, Ge2R34, R32SiCR32, NR1, and PR1, with the substituents R3 which are identical or different being R1 or hydrogen, or also two or four substituents R3 can form one or two rings having from 3 to 6 carbon atoms, the radicals Q which are identical or different are halogen, hydrogen, R1 or OR1, SR1, NR12 or PR12, m is 0 or 1, n is 0 or 1, being 1, if m=1, x is an integer between (m+1) and 5, and y is an integer between m and 5;
- (B) a mixture composed of:
- (B1) 1-99 mol-% of an organoaluminium compound of the formula (II):
- Al—(CH2—CR4R5R6)3−zHz (II)
- in which R4 is an alkyl, alkenyl or arylalkyl group having from 1 to 10 carbon atoms, R5 is an alkyl, alkenyl or alkylaryl group with a branched chain having from 3 to 10 carbon atoms, or R4 and R5 are fused together to form a ring having from 4 to 6 carbon atoms, R6 is hydrogen or an alkyl, alkenyl or arylalkyl group having from 1 to 10 carbon atoms, and z is 0 or 1;
- (B2) 1-99 mol-% of an organoaluminium compound of the formula (III):
- AlR33−wHw (III)
- in which the radicals R3 which are identical or different are alkyl, alkenyl or alkylaryl radicals which have from 1 to 10 carbon atoms and can also contain Si or Ge atoms, with the proviso that at least one of the substituents R3 is other than a linear alkyl group, and w is 0 or 1, the compounds of the formula (II) defined above being excluded;
- and
- (C) water,
- the molar ratio between the organometallic aluminium compounds and the water being between 1:1 and 100:1.
10 more elements
Catalyst for the polymerization of olefins, comprising the product obtained from contacting the following components:
- (A) a cyclopentadienyl compound of the formula (I)
- (C5R1x−mH5−x)R2m(C5R1y−mH5−y)nMQ3−n (I)
- in which M is Ti, Zr or Hf, C5R1x−mH5−x and C5R1y−mH5−y are cyclopentadienerings substituted in the same way or different ways, the substituents R1 which are identical or different are alkyl, alkenyl, aryl, alkylaryl or arylalkyl radicals which have from 1 to 20 carbon atoms and can also contain Si or Ge atoms, or Si(CH3)3 groups, or also two or four substituents R1 of one and the same cyclopentadienyl group can form one or two rings having from 4 to 6 carbon atoms, R2 is a group forming a bridge link between the two cyclopentadiene rings and is selected from the group consisting of CR32, C2R34, SiR32, Si2R34, GeR32, Ge2R34, R32SiCR32, NR1, and PR1, with the substituents R3 which are identical or different being R1 or hydrogen, or also two or four substituents R3 can form one or two rings having from 3 to 6 carbon atoms, the radicals Q which are identical or different are halogen, hydrogen, R1, OR1, SR1, NR12 or PR12, m is 0 or 1, n is 0 or 1, being 1, if m=1, x is an integer between (m+1) and 5, and an integer between m and 5;
- and
- (B) the product of the reaction between water and a mixture composed of:
- (B1) 10-90 mol-% of an organoaluminium compound of the formula (II):
- Al—(CH2—CR4R5R6)3−zHz (II)
- in which R4 is an alkyl, alkenyl or arylalkyl group having from 1 to 10 carbon atoms, R5 is an alkyl, alkenyl or alkylaryl group with a branched chain having from 3 to 10 carbon atoms, or R4 and R5 are fused together to form a cycle having from 4 to 6 carbon atoms, R6 is hydrogen or an alkyl, alkenyl or arylalkyl group having from 1 to 10 carbon atoms, and z is 0 or 1;
- (B2) 10-90 mol-% of an organoaluminium compound of the formula (III):
- AlR33−wHw (III)
- in which the radicals R3 which are identical or different are alkyl, alkenyl or alkylaryl radicals which have from 1 to 10 carbon atoms and can also contain Si or Ge atoms, with the proviso that at least one of the substituents R3 is other than a linear alkyl group, and w is zero or 1, the compounds of the formula (II) defined above being excluded;
- the molar ratio between the organometallic aluminium compounds and the water being between 1:1 and 100:1.
9 more elements
Dependencies are inferred from the claim text.