Supported Ziegler Natta procatalyst for ethylene polymerisation

Patent metadata

Field	Value
Publication number	US-10457758-B2
Application number	US-201314652414-A
Country	US
Kind code	B2
Filing date	Dec 20, 2013
Priority date	Dec 21, 2012
Publication date	Oct 29, 2019
Grant date	Oct 29, 2019

Abstract

Supported Ziegler-Natta ethylene polymerization procatalyst comprising special bi-(oxygen containing ring) compounds as internal donor, as well as a process for preparing the same and use of such a procatalyst for preparing a catalyst system used in the polymerization of ethylene for producing high molecular weight polyethylenes.

First claim

The invention claimed is:

1. Supported Ziegler-Natta procatalyst for ethylene polymerisation, comprising:
(i) a procatalyst that includes
a) a Group 1 to 3 metal of the periodic table, in the range of 6.5 to 18 wt. %,
b) a Group 13 or 14 metal of the periodic table, in the range of 0.3 to 3.5 wt. %,
c) an internal donor selected from bi-(oxygen containing ring)

compounds of formula (I):

X is C or Si,
each R 1 is the same or different and is hydrogen, a linear or branched C 1 to C 8 -alkyl group, or a C 3 -alkylene group,
and each R 2 to R 5 are the same or different and are hydrogen,
a linear or branched C 1 to C 8 -alkyl, or a C 3 -C 8 -alkylene group,
whereby two or more of R 1 to R 5 optionally form a ring,
n is the same for both oxygen-containing rings and is 1 or 2,
whereby the two oxygen-containing rings are individually saturated or unsaturated,
or an isomer mixture therefrom, and
d) a Group 4 to 6 metal of the periodic table, in the range of 2.0 to 7.0 wt %; and
(ii) an inorganic support.

2. Supported Ziegler-Natta procatalyst according to claim 1 , wherein in formula (I) X is C, both R 1 are the same and are a linear C 1 -C 4 -alkyl, each R 2 to R 5 are the same or different and are H or a C 1 to C 2 alkyl, n is for both oxygen-containing rings 1 and both oxygen-containing rings are saturated.

3. Supported Ziegler-Natta procatalyst according to claim 1 wherein in formula (I) X is C, both R 1 are the same and are methyl, up to four of the residues R 2 to R 5 are methyl and the remaining residues are H, n is for both oxygen-containing rings 1 and both oxygen-containing rings are saturated.

4. Supported Ziegler-Natta procatalyst according to claim 1 , wherein the procatalyst is deposited on the inorganic support.

5. Supported Ziegler-Natta procatalyst according to claim 1 , wherein the inorganic support is silica or magnesium chloride.

6. Supported Ziegler-Natta procatalyst according to claim 1 , wherein the inorganic support is silica or magnesium chloride.

7. Process for preparing a supported procatalyst according to claim 1 comprising depositing on a particulate inorganic support:
a) a metal compound of Group 1 to 3, comprising a magnesium compound of formula Mg(OR 7 ) 2-n (R 6 )n (II), wherein each R 7 and R 6 is independently a C 1-20 alkyl group which may optionally be substituted with halogen and 0≤n<2
b) a metal compound of Group 13 or 14, comprising an Al compound having the formula Al(alkyl) x X 3-x (111), where alkyl is an alkyl group with 1 to 12 carbon atoms, X is halogen and 0≤x≤3,
c) an internal donor selected from bi-(oxygen containing ring) compounds of formula (I):

X is C or Si,
each R 1 is the same or different and is hydrogen, a linear or branched C 1 to C 8 -alkyl group, or a C 3 -C 8 -alkylene group, and each R 3 to R 5 are the same or different and are hydrogen, a linear or branched C 1 to C 8 -alkyl, or a C 3 -C 8 -alkylene group,
whereby two or more of R 1 to R 5 can form a ring,
n is the same for both oxygen-containing rings and can be 0, 1 or 2, whereby the two oxygen-containing rings can be individually saturated or unsaturated, and
d) a transition metal compound of Group 4 to 6, comprising a halogen-containing titanium compound of the formula X y Ti(OR 8 ) 4-y (IV), wherein R 8 is a C 2 -C 20 alkyl group, X is halogen and y is 1, 2, 3 or 4.

8. Process according to claim 7 , wherein the inorganic support is silica or magnesium chloride.

9. Process according to claim 7 , wherein procatalyst is prepared by:
contacting the inorganic support first with the Al compound having the formula Al(alkyl) x X 3-x (III), where alkyl is an alkyl group with 1 to 12 carbon atoms, X is halogen and 0≤x≤3 to give a first reaction product;
then the first reaction product is contacted with a magnesium compound of formula Mg(OR 7 ) 2-n (R 6 )n (II), wherein each R 7 and R 6 is independently a C 1-20 alkyl group which may optionally be substituted with halogen and 0≤n<2 to give a second reaction product;
the second reaction product is contacted with the halogencontaining titanium compound of the formula X y Ti(OR 8 ) 4-y (IV), wherein R 8 is a C 2 C 20 alkyl group, X is halogen and y is 1, 2, 3 or 4,
whereby the magnesium compound of formula Mg(OR 7 ) 2-n (R 6 ) n (II) is first contacted with the internal donor of the formula (I) or an isomer mixtures therefrom before contacting with the first reaction product.

10. Process according to claim 7 , wherein
procatalyst is prepared by:
contacting the inorganic support with the Al compound having the formula Al(alkyl) x X 3-x (III), where alkyl is an alkyl group with 1 to 12 carbon atoms, X is halogen and 0≤x≤3 and the magnesium compound of formula Mg(OR 7 ) 2-n (R 6 )n (II), wherein each R 7 and R 6 is independently a C 1-20 alkyl group which may optionally be substituted with halogen and 0≤n<2 in any order to form a first solid intermediate
and either contacting the first solid intermediate with the internal donor of the formula (I) or an isomer mixture therefrom and subsequently with the halogen-containing titanium compound of the formula X y Ti(OR 8 ) 4-y (IV), wherein R 8 is a C 2 -C 20 alkyl group, X is halogen and y is 1, 2, 3 or 4,
or contacting the first solid intermediate with the halogen-containing titanium compound of the formula X y Ti(OR 8 ) 4-y (IV), wherein R 8 is a C 2 -C 20 alkyl group, X is halogen and y is 1, 2, 3 or 4, and then with the internal donor of the formula (I) or an isomer mixture therefrom.

11. Process for preparing a supported procatalyst according to claim 1 comprising the steps of:
1) preparing a solid magnesium aluminium complex containing magnesium, halogen, aluminium and an internal donor of the formula (I) or an isomer
mixtures therefrom by
(a1) adding to a solution of a magnesium compound of the formula (II):
Mg(OR 7 ) 2-n (R 6 ) n , wherein each R 6 and R 7 independently represents a C 1 -C 20 alkyl group and 0≤n<2,
an internal donor of formula (I) or an isomer mixture therefrom and
(a2) contacting the solution of (a1) with a solution of a compound of formula (III):
Al(alkyl) x X 3-x , wherein each alkyl independently represents an alkyl of 1 to 6 carbon atoms; X is independently a halogen; 0≤x<3,
(a3) separating the solidified reaction product from the reaction mixture and optionally washing the product with a wash solution once up to 4 times,
2) subsequently treating said solid magnesium aluminium complex with a halogen-containing titanium compound of the formula X y Ti(OR 8 ) 4-y (IV), wherein R 8 is a C 2 -C 20 alkyl group, X is halogen and y is 1, 2, 3 or 4, and
3) optionally performing one to 4 washing steps and recovering the supported procatalyst.

12. Process for preparing a supported procatalyst according to claim 1 comprising the steps of:
1) preparing a solid magnesium aluminium complex containing magnesium, halogen, aluminium and an internal donor of the formula (I) or an isomer mixtures therefrom by
(b1) adding to a solution of a magnesium compound of the formula (II):
Mg(OR 7 ) 2-n (R 6 )n, wherein each R6 and R7 independently represents a C1-C20 alkyl group and 0≤n<2,
a solution of a compound of formula (Ill):
Al(alkyl) x X 3-x , wherein each alkyl independently represents an alkyl of 1 to 6 carbon atoms; X is independently a

Assignees

• Borealis Ag

Inventors

• Jayaratne Kumudini
• Hamalainen Elina
• Kallio Kalle

Classifications

• C08F210/16 Primary

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

• C08F210/02

  Ethene · CPC title

• C08F4/6555

  and magnesium or compounds thereof · CPC title

• C08F210/08

  Butenes · CPC title

• C08F4/651

  Pretreating with non-metals or metal-free compounds · CPC title