Solid catalyst component, catalyst comprising said solid component, and process for the (co)polymerization of α-olefins

Patent metadata

Field	Value
Publication number	US-9944726-B2
Application number	US-201514932743-A
Country	US
Kind code	B2
Filing date	Nov 4, 2015
Priority date	Dec 27, 2010
Publication date	Apr 17, 2018
Grant date	Apr 17, 2018

Abstract

A solid catalyst component for the (co)polymerization of α-olefins having general formula (I):

Zr n MAl x Cl y Mg p   (I)

wherein:
M represents titanium (Ti), vanadium (V), or mixtures thereof; n is a number ranging from 0.01 to 2; x is a number ranging from 0.1 to 4; y is a number ranging from 5 to 53; p is a number ranging from 0 to 15;

obtained by means of a process comprising putting at least one zirconium arene in contact with at least one metal compound and, optionally, with at least one compound of magnesium.

Said solid catalyst component can be advantageously used as a solid component in a catalyst for the (co)polymerization of α-olefins.
Said catalyst can be advantageously used in a process for the (co)polymerization of α-olefins.

First claim

The invention claimed is:

1. A solid catalyst component for the (co)polymerization of α-olefins, the solid catalyst component having general formula (I):
Zr n MAl x Cl y Mg p   (I)

wherein:
M represents titanium (Ti);
n is a number ranging from 0.01 to 2;
x is a number ranging from 0.1 to 4;
y is a number ranging from 5 to 53;
p is a number ranging from 0 to 15;
obtained by means of a process which comprises putting the following components in contact:

(A) at least one zirconium alkyl-arene having general formula (III) or (IIIa):
Zr(η 6 -arene) 2 Al q′ X r′ R s′   (III)

Zr(η 6 -arene)Al q′ X r′ R s′   (IIIa)

wherein:
arene represents a benzene, or a benzene substituted with from 1 to 6 linear or branched C 1 -C 6 alkyl groups, or mixtures thereof;
X represents chlorine;
R represents a linear or branched C 1 -C 10 alkyl group;
q′ is a number ranging from 2 to 6;
r′ is a number ranging from 2 to 20; and
s′ is a number ranging from 2 to 6;

(B) at least one compound selected from:
alkoxides or chloroalkoxides having general formula M(OR 1 ) t Cl 4−t wherein M represents titanium, R 1 represents a linear or branched C 1 -C 10 alkyl group, t is a number ranging from 1 to 4;
carboxylates or chlorocarboxylates having general formula (IV):
M(OOCR 2 ) t Cl 4−t   (IV)

wherein M represents titanium, R 2 represents a linear or branched C 1 -C 10 alkyl group, t is a number ranging from 1 to 4; or the carboxylate group OOCR 2 in general formula (IV) is selected from:
carboxylate groups having general formula (V):

wherein R′ 1 , R′ 2 , R′ 3 , R′ 4 and R′ 5 , each independently, represent a hydrogen atom; a halogen atom selected from chlorine, bromine, fluorine, or iodine; a monofunctional hydrocarbyl radical as such or having at least one of its hydrogen atoms substituted with a halogen atom selected from chlorine, bromine, fluorine, or iodine; with the proviso that at least one of the substituents from R′ 1 to R′ 5 represents chlorine, bromine, fluorine, or iodine, or a monofunctional hydrocarbyl radical having at least one of its hydrogen atoms substituted with a halogen atom selected from chlorine, bromine, fluorine, or iodine; t′ and u′ are numbers ranging from 0 to 10; and optionally,

(C) at least one magnesium compound selected from:
magnesium dialkyls having general formula MgR 3 R 4 wherein R 3 and R 4 , each independently, represent a linear or branched C 1 -C 10 alkyl group; and
complexes of magnesium chloride having general formula MgCl 2 L u wherein L represents tetrahydrofuran (THF), or 1,2-dimethoxyethane (DME); and u is a number ranging from 1 to 4.

2. The solid catalyst component according to claim 1 , wherein q′ is 3 in the case of zirconium alkyl-arene having general formula (III), 2 in the case of zirconium alkyl-arene having general formula (IIIa).

3. The solid catalyst component according to claim 1 , wherein r′ is 9 in the case of zirconium alkyl-arene having general formula (III), 6 in the case of zirconium alkyl-arene having general formula (IIIa).

4. The solid catalyst component according to claim 1 , wherein s′ is 2.

5. The solid catalyst component according to claim 1 , wherein compounds (A), (B) and, optionally (C), are used in the following molar ratios (0.5-2):(1):(0-12), respectively.

6. The solid catalyst component according to claim 1 , wherein in the zirconium alkyl-arene having general formula (III) or (IIIa), said arene is selected from: benzene, toluene, ortho-xylene, meta-xylene, para-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene (mesitylene), hexamethylbenzene, or mixtures thereof.

7. The solid catalyst component according to claim 1 , wherein in the zirconium alkyl-arene having general formula (III) or (IIIa), said group R is selected from: ethyl, butyl, iso-butyl, n-octyl.

8. The solid catalyst component according to claim 1 , wherein said alkoxides or chloro-alkoxides having general formula M(OR 1 ) t Cl 4−t are selected from: titanium tetra-ethoxide; titanium tetra-propoxide; titanium tetra-n-butoxide; titanium tetra-iso-butoxide; or their relative chlorides; or mixtures thereof.

9. The solid catalyst component according to claim 1 , wherein said carboxylates or chloro-carboxylates having general formula (IV) are selected from: titanium tetra-n-decanoate; titanium tetra-n-undecanoate; titanium tetra-isobutyrate; titanium tetra-2-ethyl-hexanoate; titanium tetra-2,2-dimethylpropanoate; titanium tetra-versatate; titanium tetra-3-ethyl-pentanoate; titanium tetra-citronellate; titanium tetra-naphthenate; titanium tetra-2-phenyl-butyrate; or their relative chlorides; or mixtures thereof.

10. The solid catalyst component according to claim 1 , wherein said magnesium dialkyls having general formula MgR 3 R 4 are selected from: magnesium butyl-octyl [(n-C 4 H 9 ) 1,5 (n-(C 8 H 17 ) 0.5 Mg], magnesium ethyl-butyl [(n-C 2 H 5 )(n-(C 4 H 9 )Mg], magnesium di-butyl [n-(C 4 H 9 ) 2 Mg], or mixtures thereof.

11. The solid catalyst component according to claim 1 , wherein said magnesium chloride complexes having general formula MgCl 2 L u are selected from: magnesium-tetrahydrofuran chloride complex, magnesium 1,2-dimethoxyethane chloride complex, magnesium-pyrane chloride complexes, magnesium-ether ethyl chloride complexes, magnesium-di-octylether chloride complexes, magnesium-di-butylether chloride complexes, or mixtures thereof.

12. The solid catalyst component according to claim 1 , wherein said process comprises putting components (A), (B), and, optionally, (C), in contact with at least one organic chloro-derivative (D) which is selected from:
(a) di- or poly-chloroalkanes;
(b) alkyl esters of aliphatic carboxylic acids di- or tri-chloro-substituted on the carbon in alpha position with respect to the carboxyl; or
(c) monochloro triphenylmethane or dichloro diphenylmethane carrying a carboxyalkyl group in para position of at least one of the phenyl rings.

13. The solid catalyst component according to claim 12 , wherein the compounds (A), (B), and, optionally, (C) and (D), are used in the following molar ratios (0.5-2):(1):(0-12):(0-40), respectively.

14. The solid catalyst component according to claim 12 , wherein said process comprises putting components (A), (B), and, optionally, (C) and (D), in contact with at least one aluminium alkyl chloride (E) which is selected from those having general formula:
Al(R 13 ) w Cl 3−w
wherein R 13 represents a linear or branched C 1 -C 20 alkyl group; w is 1 or 2.

15. The solid catalyst component according to claim 14 , wherein the compounds (A), (B), and, optionally, (C) and (D) and (E), are used in the following molar ratios (0.5-2):(1):(0-12):(0-40):(0-40), respectively.

16. The solid catalyst component of claim 1 , wherein the zirconium alkyl-arene has the general formula (III) or (IIIa):
Zr(η 6 -arene) 2 Al q ′X r ′R s′   (Ill)

Zr(η 6 -arene)Al q′ X r′ R s′   (IIIa)

wherein:
arene represents a benzene, or a benzene substituted with from 1 to 6 linear or branched C 1 -C 6 alkyl groups, or mixtures thereof;
X represents a halogen atom selected from chlorine, bromine, fluorine, iodine;
R represents a linear or branched C 1 -C 10 alkyl group;
q′ is a number ranging from 2 to 6;
r′ is a number ranging from 2 to 20;
s′ is a number ranging from 2 to 6.

17. The solid catalyst component of claim 1 , wherein the zirconium alkyl-arene having general fo

Assignees

• Polimeri Europa Spa
• Versalis Spa

Inventors

• Sommazzi Anna
• Masi Francesco
• Pampaloni Guido
• Renili Filippo
• Marchetti Fabio
• Raspolli Galletti Anna Maria

Classifications

• C07F17/00

  Metallocenes · CPC title

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F10/02 Primary

  Ethene · CPC title

• C08F4/6552

  and metals of C08F4/64 or compounds thereof · CPC title

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title