Process to prepare procatalyst for polymerization of olefins

Patent metadata

Field	Value
Publication number	US-11192962-B2
Application number	US-201716336993-A
Country	US
Kind code	B2
Filing date	Jun 19, 2017
Priority date	Sep 29, 2016
Publication date	Dec 7, 2021
Grant date	Dec 7, 2021

Abstract

The present invention relates to a process for the preparation of a procatalyst suitable for preparing a catalyst composition for olefin polymerization, said process comprising the steps of: Step A) providing or preparing a Grignard compound; Step B) contacting the Grignard compound an alkoxy- or aryloxy silane compound, to give a solid support; Step C) optionally contacting the solid support obtained with at least one activating compound; and Step D) reacting the (activated) support with a halogen-containing Ti-compound as catalytic species, an activator and at least one internal electron donor in several sub steps wherein the internal donor is added in portions during at least two of said stages to obtain a procatalyst. The invention moreover relates to a procatalyst, a catalytic system comprising said procatalyst and to a process to prepare polyolefins using said catalyst system and the polyolefins obtained therewith.

First claim

The invention claimed is:

1. A process for the preparation of a procatalyst suitable for preparing a catalyst composition for olefin polymerization, said process comprising the steps of
Step A) providing or preparing a compound having the formula R 4 z MgX 4 2-z wherein
R 4 is independently a linear, branched or cyclic hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyl, alkylaryl groups, and one or more combinations thereof;
wherein said hydrocarbyl group is substituted or unsubstituted, and optionally contains one or more heteroatoms;
X 4 is independently fluoride (F—), chloride (Cl—), bromide (Br—) or iodide (I—);
z is in a range of larger than 0 and smaller than 2, being 0<z<2;

Step B) contacting the compound R 4 z MgX 4 2-z obtained in step A) with a silane compound Si(OR 5 ) 4-n (R 6 ) n to give a first intermediate reaction product, being a solid Mg(OR 1 ) x X 1 2-x , wherein:
R 1 , R 5 and R 6 are each independently a linear, branched or cyclic hydrocarbyl group selected from 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;
X 1 is independently fluoride (F—), chloride (Cl—), bromide (Br—) or iodide (I—);
n is in range of 0 to 4;
x is in a range of larger than 0 and smaller than 2, being 0<x<2;

Step C) optionally contacting the first intermediate reaction product obtained in step B) with at least one activating compound formed by an activating electron donor and a metal alkoxide compounds of the formula M 1 (OR 2 ) v-w (OR 3 ) w or M 2 (OR 2 ) v-w (R 3 ) w , to obtain a second intermediate reaction product; wherein: M 1 is a metal of Ti, Zr, Hf, Al or Si; M 2 is a metal being Si; v is the valency of M 1 or M 2 and w<v; R 2 and R 3 are each a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be is substituted or unsubstituted, and optionally contains one or more heteroatoms;
Step D) reacting the first or second intermediate reaction product, obtained respectively in step B) or C), with a halogen-containing Ti-compound, an activator and at least one internal electron donor in several sub steps:
D-I) in a first stage: contacting the first or second intermediate reaction product, obtained respectively in step B) or C), with the halogen-containing Ti-compound, the activator and optionally a portion of the internal electron donor;
D-II) in a second stage: contacting the product obtained in step D-I) with the halogen-containing Ti-compound, and optionally a portion of the internal electron donor;
D-III) in a third stage: contacting the product obtained in step D-II) with the halogen-containing Ti-compound, and optionally a portion of the internal electron donor;
D-IV) optionally in a fourth stage: contacting the product obtained in step D-III) with the halogen-containing Ti-compound, and optionally a portion of the internal electron donor;

wherein said internal electron donor is added in at least two portions during at least two of the stages D-I, D-II, D-III, and D-IV to obtain said procatalyst.

2. The process according to claim 1 , wherein the internal electron donor is added in two portions wherein the amount of the internal electron donor is split between these two portions in a weight ratio of from 80%:20% to 20%:80%.

3. The process according to claim 1 , wherein the internal electron donor is added in three portions wherein the amount of the internal electron donor is split between these three portions in a weight ratio of from 20% to 40% for each portion, wherein the total of the three portions is 100%.

4. The process according to claim 1 , wherein the activator is one of the following: i) a monoester, or ii) a benzamide according to formula X:

wherein R 70 and R 71 are each independently hydrogen or an alkyl, and R 72 , R 73 , R 74 , R 75 , and R 76 are each independently hydrogen, a heteroatom, or a hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, alkylaryl groups, and one or more combinations thereof.

5. The process according to claim 1 , wherein the internal electron donor is one of the following: i) a carbonate-carbamate compound according to formula A:

wherein: R 81 , R 82 , R 83 , R 84 , R 85 , and R 86 are the same or different and are independently hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl, alkylaryl groups, and one or more combinations thereof; R 87 is a hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, alkylaryl groups, and one or more combinations thereof each R 80 group is independently a linear, branched or cyclic hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyl, alkylaryl groups, and one or more combinations thereof; R 80 is an alkyl having 1 to 30 carbon atoms; N is a nitrogen atom; 0 is an oxygen atom; and C is a carbon atom;
or ii) an aminobenzoate compound according to Formula B

wherein each R 90 group is independently a substituted or unsubstituted aromatic group; R 91 , R 92 , R 93 , R 94 , R 95 , R 96 and R 97 are the same or different and are independently hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl, alkylaryl groups, and one or more combinations thereof; N is nitrogen atom; O is oxygen atom; and C is carbon atom; or
iii) a 1,3-diether represented by the Formula C,

wherein R 51 and R 52 are each independently a hydrogen or a hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, alkylaryl groups, and one or more combinations thereof, and wherein R 53 and R 54 are each independently a hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, alkylaryl groups, and one or more combinations thereof; said hydrocarbyl group of R 53 -R 54 is linear, branched or cyclic; and said hydrocarbyl group is substituted or unsubstituted, and optionally contains one or more heteroatoms.

6. The process according to claim 1 , wherein during stage I of step D) N,N-dimethyl benzamide is added as activator and wherein during stages I and II bis(methoxymethyl)fluorene is added as internal electron donor in two portions, each portion having a weight ratio of from 60%:40% to 40%:60% wherein the total of the two portions equals 100%.

7. The process according to claim 1 , wherein during stage I of step D) ethyl benzoate is added as the activator and wherein during stages II and III 4-[(ethoxycarbonyl)(methyl)amino]pentan-2-yl ethyl carbamate is added as the internal electron donor in two portions, each portion having a weight ratio of from 60%:40% to 40%:60% wherein the total of the two portions equals 100% or wherein during stage I of step D) ethyl benzoate is added as the activator and wherein during stages II, III and IV, 4-[(ethoxycarbonyl)(methyl)amino]pentan-2-yl ethyl carbamate is added as the internal electron donor in three portions, each portion having a weight ratio of from 20% to 40%, wherein the total of the three portions equals 100%.

8.

Assignees

• Sabic Global Technologies Bv

Inventors

• Moman Akhlaq
• Siddiqui Inaamul Haq
• Padmanabhan Sudhakar R
• Al-Humaidan Osamah
• Al-Enazi Haitham

Classifications

• C08F210/06

  Propene · CPC title

• C08F4/6565

  and magnesium or compounds thereof · CPC title

• C08F110/06 Primary

  Propene · CPC title

• C08F2410/06

  Catalyst characterized by its size · CPC title

• C08F4/651 Primary

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