RU96108407A

RU96108407A - CATALYSTS AND POLYMERIZATION PROCESSES OF OLEFINS

Info

Publication number: RU96108407A
Application number: RU96108407/04A
Authority: RU
Inventors: Тициано Далл'оццо; Маурицио Галимберти; Луиджи Рескони; Энрико Альбиццати; Джанни Пеннини
Original assignee: Монтелл Текнолоджи Компани Б.В.
Priority date: 1994-07-20
Filing date: 1995-07-18
Publication date: 1998-07-20

Claims

1. The catalyst for the polymerization of olefins containing the reaction product obtained by contact of the following components:
(A) compounds of cyclopentadienyl of the formula I
(C ₅ R

\binom{1}{xm}

H _5-x ) R

\binom{2}{m}

(C ₅ R

\binom{1}{ym}

H _5-y ) _n MQ _3-n ,
where M represents Ti, Zr or Hf;
C ₅ R

\binom{1}{xm}

H _5-x and C ₅ R

\binom{1}{ym}

H _5-y are the same or differently substituted cyclopentadienyl rings, the substituents R ¹ , identical or different, are alkyl, alkenyl, aryl, alkylaryl or arylalkyl radicals with 1 to 20 carbon atoms, which may also contain Si or Ge atoms, or Si (CH ₃ ) ₃ groups, or two or four R ¹ substituents of the same cyclopentadienyl group can also form one or two cycles with 4 to 6 carbon atoms;
R ² represents a group which, as a bridge, binds two cyclopentadienyl rings and is selected from CR

\binom{3}{2}

, C ₂ R

\binom{3}{4}

SiR

\binom{3}{2}

, Si ₂ R

\binom{3}{4}

GeR

\binom{3}{2}

, Ge ₂ R

\binom{3}{4}

, R

\binom{3}{2}

SiCR

\binom{3}{2}

, NR ¹ and PR ¹ , where R ³ substituents are the same or different, wherein R ¹ or hydrogen or two or four R ³ substituents can also form one or two rings with 3 to 6 carbon atoms;
Q, identical or different, are halogen, hydrogen, R ¹ , OR ¹ , SR ¹ , NR

\binom{1}{2}

or PR

\binom{1}{2}

;
m is 0 or 1;
n = 0 or 1, with n - 1 if m = 1;
x is an integer from (m + 1) to 5;
y is an integer from m to 5;
(B) an organometallic aluminum compound of formula II
Al (CH ₂ -CR ⁴ R ⁵ R ⁶ ) _w R

\binom{7}{y}

H _z
where the groups CH ₂ - CR ⁴ R ⁵ R ⁶ ) are the same or different;
R ⁴ represents an alkyl, alkenyl or arylalkyl group with 1 to 10 carbon atoms;
R ⁵ represents an alkyl, alkenyl, aryl, arylalkyl or alkylaryl group with 3 to 50 carbon atoms, and it is different from a straight chain alkyl or alkenyl group and, optionally, R ¹ and R ⁵ merged together may form a ring from 4 to 6 carbon atoms;
R ⁶ represents hydrogen or alkyl, alkenyl or an arylalkyl group with 1 to 10 carbon atoms;
R ⁷ , identical or different, are alkyl, alkenyl, aryl, arylalkyl or alkylaryl radicals with 1 to 10 carbon atoms and they may also optionally contain Si or Ge atoms;
w is 1, 2 or 3;
z is 0 or 1;
y = 3w-z;
(C) water;
while the molar ratio of the organometallic compound of aluminum and water is from 1: 1 to 100: 1.

2. The catalyst according to claim 1, characterized in that the molar ratio of the organometallic compound of aluminum and water is 2.

3. The catalyst according to claim 1 or 2, characterized in that the molar ratio of aluminum of said organometallic aluminum compound to metal M of said cyclopentadienyl compound is 50-10,000.

4. The catalyst according to any one of claims 1 to 3, characterized in that in said cyclopentadienyl compound of formula I, metal M is Zr.

5. The catalyst according to any one of claims 1 to 4, characterized in that in said cyclopentadienyl compound of the formula I m = 0, groups C ₅ R

\binom{1}{xm}

H _5-x and C ₅ R

\binom{1}{ym}

H _{5-y is} selected from pentamethylcyclopentadienyl, indenyl and 4, 5, 6, 7-tetrahydroindenyl groups, and Q substituents are chlorine atoms or methyl groups.

6. The catalyst according to any one of claims 1 to 5, characterized in that in said cyclopentadienyl compound of the formula I m = 1, groups C ₅ R

\binom{1}{xm}

H _5-x and C ₅ R

\binom{1}{ym}

H _{5-y is} selected from tetramethylcyclopentadienyl, indenyl and 4, 5, 6, 7-tetrahydroindenyl, 2-methyl-4,5,6,7-tetrahydroindenyl, 4,7-dimethyl-4,5,6,7-tetrahydroindenyl, 2,4,7-trimethyl-4,5,6,7-tetrahydroindenyl and fluorenyl groups, R ² represents a (CH ₃ ) ₂ Si or C ₂ H ₄ group, and the substituents Q represent chlorine atoms or methyl groups.

7. The catalyst according to any one of paragraphs. 1 to 6, characterized in that in said organometallic aluminum compound of formula II, R ⁴ is a methyl or ethyl group, R ^{5 is} selected from a branched alkyl, alkenyl or alkylaryl group containing 3 to 20 carbon atoms, preferably from 4 to 10 carbon atoms and optionally substituted phenyl groups, R ⁶ is hydrogen, and R ⁷ is an alkyl group containing from 1 to 5 carbon atoms.

8. The catalyst according to any one of claims 1 to 7, characterized in that said organometallic aluminum compound of formula II is selected from:
tris (2,4,4-trimethylpentyl) aluminum,
bis (2,4,4-trimethylpentyl) aluminum hydride,
isobutyl bis (2-phenylpropyl) aluminum,
diisobutyl- (2-phenylpropyl) aluminum,
isobutyl bis (2,4,4-trimethylpentyl) aluminum and
diisobutyl- (2,4,4-trimethylpentyl) aluminum.

9. The catalyst according to any one of claims 1 to 8, characterized in that in said organometallic compound of formula II, said (CH ₂ -CR ⁴ R ⁵ R ⁶ ) group is a derivative of the oligomerization product of lower α-olefins, such as propylene or 1- butene.

10. The catalyst according to claim 9, characterized in that in said organometallic compound of formula II w = 1 or 2.

11. The catalyst for the polymerization of olefins containing the product obtained by contacting the following components:
(A) compounds of cyclopentadienyl of the formula I
(C ₅ R

\binom{1}{xm}

H _5-x ) R

\binom{2}{m}

(C ₅ R

\binom{1}{ym}

H _5-y ) _n MQ _3-n ,
where M represents Ti, Zr or Hf, C ₅ R

\binom{1}{xm}

H _5-x and C ₅ R

\binom{1}{ym}

H _5-y are equally or differently substituted cyclopentadienyl rings;
R ¹ , identical or different, are alkyl, alkenyl, aryl, alkylaryl or arylalkyl radicals with 1 to 20 carbon atoms, which may also contain Si or Ge atoms, or Si (CH ₃ ) ₃ groups, or two or four R substituents ^{1 of} the same cyclopentadienyl group can also form one or two cycles with 4 to 6 carbon atoms;
R ² represents a group which, as a bridge, binds two cyclopentadienyl rings and is selected from CR

\binom{3}{2}

, C ₂ R

\binom{3}{4}

SiR

\binom{3}{2}

, Si ₂ R

\binom{3}{4}

GeR

\binom{3}{2}

, Ge ₂ R

\binom{3}{4}

, R

\binom{3}{2}

SiCR

\binom{3}{2}

, NR ¹ and PR ¹ , where R ³ substituents are the same or different, wherein R ¹ or hydrogen or two or four R ¹ substituents can also form one or two rings with 3 to 6 carbon atoms;
Q, identical or different, are halogen, hydrogen, R ¹ , OR ¹ , SR ¹ , NR

\binom{1}{2}

or PR

\binom{1}{2}

;
m is 0 or 1;
n = 0 or 1, and n = 1, if m - 1;
x is an integer from (m + 1) to 5;
y is an integer from m to 5;
(B) a reaction product between water and an organometallic aluminum compound of formula II
Al (CH ₂ -CR ⁴ R ⁵ R ⁶ ) _w R

\binom{7}{y}

H _z
where the groups (CH ₂ -CR ⁴ R ⁵ R ⁶ ) are the same or different;
R ⁴ represents an alkyl, alkenyl or arylalkyl group with 1 to 10 carbon atoms;
R ⁵ represents an alkyl, alkenyl, aryl, arylalkyl or alkylaryl group with 3 to 50 carbon atoms, and it is different from a straight chain alkyl or alkenyl group and, optionally, R ⁴ and R ⁵ merged together may form a ring from 4 to 6 carbon atoms;
R ⁶ represents hydrogen or alkyl, alkenyl or an arylalkyl group with 1 to 10 carbon atoms;
R ⁷ , identical or different, are alkyl, alkenyl, aryl, arylalkyl or alkylaryl radicals with 1 to 10 carbon atoms and they may also optionally contain Si or Ge atoms;
w is 1, 2 or 3;
z is 0 or 1;
y = 3w-z,
while the molar ratio of the specified organometallic compounds of aluminum and water is from 1: 1 to 100: 1.

12. The process of polymerization of an olefin in the presence of a catalyst according to any one of claims 1 to 11.

13. The process of claim 12, wherein said olefin is an α-olefin of formula CH ₂ = CHR, in which R is hydrogen or an alkyl radical containing from 1 to 20 carbon atoms.

14. The process according to item 13, wherein the homopolymerization of ethylene.

15. The process according to p. 13, characterized in that ethylene is copolymerized with an α-olefin of the formula CH ₂ = CHR, in which R is a linear, branched or cyclic alkyl radical containing from 1 to 20 carbon atoms, or with a cycolefin and, optionally with polyene.

16. The process of claim 15, wherein said α-olefin is selected from propylene, 1-butene, 4-methyl-1-pentene, 1-hexane and 1-octene.

17. The process according to p. 15 or 16, characterized in that an elastomeric ethylene copolymer is obtained, said copolymer containing 15 to 85 mol% of monomeric ethylene units, and the rest up to 100%, are monomeric units of one or more α-olefins and / or a non-conjugated diolefin capable of cyclopolymerization.

18. The process according to 17, characterized in that the said copolymer contains 0.1 to 5 mol.% Monomer units derived from polyenes.