# US 10,246,529 B2 · Procatalyst for polymerization of olefins

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- Number: US 10,246,529 B2
- Document ID: US10246529B2
- Status: Granted
- Kind: B2
- Application number: 15/541,088
- Filed: 2016-01-20
- Published: 2018-01-04
- Granted: 2019-04-02
- Earliest claimed: 2015-01-21
- Assignees: Sabic Global Technologies B.V.
- Applicants: Sabic Global Technologies B.V.
- Inventors: Sudhakar R. Padmanabhan; Khalid Abdullah Al-Bahily
- Web page: https://patentgrep.com/patent/US10246529B2

## CPC

- C08F 10/06: Propene
- C07F 7/28: Titanium compounds
- C08F 2410/06: Catalyst characterized by its size
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

The invention relates to a procatalyst for polymerization of olefins. The invention also relates to a process for preparing said procatalyst. Furthermore, the invention is directed to a catalyst system for polymerization of olefins comprising the said procatalyst, a co-catalyst and optionally an external electron donor; a process of preparing polyolefins by contacting an olefin with said catalyst system and to polyolefins obtained or obtainable by said process. The invention also relates to the use of said procatalyst in the polymerization of olefins.

## Claims

### Claim 1

A process for preparing a procatalyst for preparing a catalyst composition for olefin polymerization, said process comprising the steps of:
ia) contacting a Grignard reagent comprising R4zMgX42-z and an alkyl magnesium compound MgR4′2 with an alkoxy- or aryloxy-containing silane compound to give a first intermediate reaction product, being a solid Mg(OR1)xX12-x, wherein:
R4 and R4′ are the same as R1 being a linear, branched or cyclic hydrocarbyl group independently selected from the group consisting of alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group is substituted or unsubstituted, and optionally contains one or more heteroatoms;
X4 and X1 are each independently selected from the group consisting of fluoride (F—), chloride (Cl—), bromide (Br—) or iodide (I—);
x is in a range of larger than 0 and smaller than 2, being 0<x<2; and
z is in a range of larger than 0 and smaller than 2, being 0<z<2;
ib) precipitating the solid Mg(OR1)xX12-x obtained in step ia) by contacting it with an tetrahalogensilane, SiX4′4, wherein X4′ is each independently selected from the group consisting of fluoride (F—), chloride (Cl—), bromide (Br—) or iodide (I—), to obtain a solid support;
ii) optionally contacting the solid support obtained in step ib) with at least one activating compound selected from the group consisting of activating electron donors and metal alkoxide compounds of formula M1(OR2)v-w(OR3)w and M2(OR2)v-w(R3)w, to obtain a second intermediate reaction product; wherein:
M1 is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si;
M2 is a metal being Si;
v is the valency of M1 or M2;
w is smaller than v;
R2 and R3 are each a linear, branched or cyclic hydrocarbyl group independently selected from the group consisting of alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group is substituted or unsubstituted, and optionally contains one or more heteroatoms;
iii) contacting the first or second intermediate reaction product obtained in step ib) or ii) respectively, with a halogen-containing titanium compound and either an activator or an internal electron donor to obtain a third intermediate reaction product;
iv) optionally modifying the third intermediate reaction product obtained in step iii) with a modifier having the formula MX3, wherein M is a metal selected from the Group 13 metals and transition metals of the IUPAC periodic table of elements, and wherein X is a halide, to yield a modified intermediate reaction product; and
v) contacting said third intermediate reaction product obtained in step iii) or said modified intermediate reaction product obtained in step iv) with a halogen-containing titanium compound and in the case that in step iii) an activator was used an internal donor to obtain the procatalyst.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the activator added during step iii) is selected from the group consisting of alkyl benzoate, benzamide, and monoester.

### Claim 3 (depends on 1)

The process according to claim 1, wherein the alkyl magnesium compound used in step ia) is dibutylmagnesium.

### Claim 4 (depends on 1)

The process according to claim 1, wherein the Grignard reagent used in step ia) is butyl magnesium chloride.

### Claim 5 (depends on 1)

The process according to claim 1, wherein the Grignard reagent used in step ia), and the halogen-containing titanium compound used in step iii) and step v) are used in such amounts that the resulting procatalyst comprises in wt. % based on the total weight of the procatalyst:magnesium: from 15 to 24; titanium: from 1 to 4.

### Claim 6 (depends on 1)

The process according to claim 1, wherein step ii) is carried out using a combination of an alcohol and a tetra alkoxy titanium compound as the activating compounds.

### Claim 7 (depends on 1)

The process according to claim 1, wherein the ratio between the alkyl magnesium and Grignard reagent is between 1:1 and 1:4.

### Claim 8 (depends on 1)

The process according to claim 1, wherein a ratio of an amount of said tetrahalogensilane compound to the combined amount of magnesium of the Grignard reagent and the compound MgR4′2 is 0.2 to 5.

### Claim 9 (depends on 1)

A procatalyst obtained by the process according to claim 1, said procatalyst comprising a titanium catalyst supported on a solid magnesium-containing support characterized in that the procatalyst comprises in wt. % based on the total weight of the procatalyst:magnesium: from 15 to 24; and titanium: from 1 to 4.

### Claim 10 (depends on 9)

The procatalyst according to claim 9, wherein the procatalyst comprises in wt. % based on the total weight of the procatalyst:magnesium: from 19.0 to 19.5; and/or titanium: from 1.5 to 3.5.

### Claim 11 (depends on 9)

A catalyst system for olefin polymerization comprising the procatalyst according to claim 9, a co-catalyst, and optionally an external electron donor.

### Claim 12 (depends on 11)

The catalyst system according to claim 11, wherein the co-catalyst is an organometallic compound containing a metal from group 1, 2, 12 or 13 of the Periodic System of the Elements.

### Claim 13 (depends on 11)

A process of preparing a polyolefin, the process comprising contacting at least one olefin with a polymerization catalyst system according to claim 11.

### Claim 14 (depends on 1)

The process according to claim 1, wherein
the activator added during step iii) is selected from the group consisting of alkyl benzoate, benzamide, and monoester;
the alkyl magnesium compound used in step ia) is dibutylmagnesium;
the Grignard reagent used in step ia) is butyl magnesium chloride;
the Grignard reagent used in step ia), and the halogen-containing titanium compound used in step iii) and step v) are used in such amounts that the resulting procatalyst comprises in wt. % based on the total weight of the procatalyst:magnesium: from 15 to 24; titanium: from 1 to 4;
step ii) is carried out using a combination of an alcohol and a tetra alkoxy titanium compound as the activating compounds;
the ratio between the alkyl magnesium compound and Grignard reagent is between 1:1 and 1:4;
a ratio of an amount of said tetrahalogensilane compound to the combined amount of magnesium of the Grignard reagent and the compound MgR4′2 is 0.2 to 5.

### Claim 15 (depends on 14)

The process according to claim 14, wherein
X4 and X1 have from 1 to 20 carbon atoms;
X4, X1, and X4′ are each chloride;
R2 and R3 each have from 1 to 20 carbon atoms;
step v) is carried out at least two times;
the activator is ethyl benzoate;
the Grignard reagent used in step ia), and the halogen-containing titanium compound used in step iii) and step v) are used in such amounts that the resulting procatalyst comprises in wt. % based on the total weight of the procatalyst:magnesium: from 18.0 to 19.5; titanium: from 1.5 to 3.5;
step ii) is carried out using an combination of ethyl alcohol and tetraethoxy titanium as the activating compounds; and
said tetrahalogensilane compound is present in respect of the amount of magnesium of the Grignard reagent and the compound MgR4′2 in a ratio of 0.5 to 1.

### Claim 16 (depends on 14)

A catalyst system for polymerization of ethylene or a mixture of ethylene and propylene, the method comprising:
a procatalyst obtained by the method of claim 14, said procatalyst comprising a titanium catalyst supported on a solid magnesium-containing support characterized in that the procatalyst comprises in wt. % based on the total weight of the procatalyst:magnesium: from 15 to 24; and titanium: from 1 to 4;
a co-catalyst, wherein the co-catalyst is an organometallic compound containing a metal from group 1, 2, 12 or 13 of the Periodic System of the Elements, and
optionally an external electron donor.

### Claim 17 (depends on 16)

A process of preparing a polyolefin, the process comprising contacting of ethylene or a mixture of ethylene and propylene with a polymerization catalyst system according to claim 16.