IP Library Granted Patent US 11,168,158
Granted Patent B2
US 11,168,158 · App. 16/491,098 · Granted Nov 9, 2021

Electron donors for ziegler-natta precatalyst preparation and catalyst system for olefin polymerization

Inventors: Binh Thanh Nguyen (League City, TX); Jonas Alves Fernandes (Pittsburgh, PA); Zhenxing Xi (Sugar Land, TX)
Assignees: BRASKEM AMERICA, INC.; W.R. GRACE & CO.-CONN.
C08F10/06C07F7/0816C07F7/30
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 11,168,158
App. No.
16/491,098
Granted
Nov 9, 2021
Kind
B2
Abstract

A solid precatalyst component for use in olefinic polymerization, includes titanium, magnesium, and an electron donor compound; wherein: the electron donor compound is at least one compound represented by Formula (I).

Claims (95)

1. A solid precatalyst component for use in olefinic polymerization, the solid precatalyst component comprising:

titanium;

magnesium; and

an electron donor compound;

wherein:

the electron donor compound comprises at least one compound represented by Formula (I):

wherein:

E is Si or Ge;

when E is Si:

R 1 and R 2 are independently a moiety represented by formula IIA, IIB, IIC, or IID;

a is 0;

b is 1 or 2;

c is 0, 1 or 2;

R 5 is a C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, aryl or heteroaryl group, optionally interrupted or substituted by one or more functional groups selected from the group consisting of ether, ester, amide, carbonate, halogens, phosphate, sulfate, sulfide, sulfoxide, sulfone, carbamate, and a combination of any two or more thereof; and

R 3 and R 4 together with E are cyclized to form a hydrocarbyl ring structure;

when E is Ge:

R 1 and R 2 are independently a moiety represented by formula IIA, IIB, IIC, IID, IIIA, or IIIB;

a is 0, 1, 2, 3, or 4;

b is 1 or 2; and

c is 0 , 1 , 2 , 3 , 4 , or 5 ;

R 5 is a C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, aryl or heteroaryl group, optionally interrupted or substituted by one or more functional groups selected from the group consisting of ether, ester, amide, carbonate, halogens, phosphate, sulfate, sulfide, sulfoxide, sulfone, carbamate, and a combination of any two or more thereof; and

R 3 and R 4 are independently alkyl, aryl, or heteroaryl; and

formula IIA, IIB, IIC, IID, IIIA, and IIIB are:

wherein:

L comprises a heteroaryl group.

2. The solid precatalyst component of claim 1 , wherein:

E is Si;

R 1 and R 2 are independently a moiety represented by formula IIA, IIB, IIC, or IID;

a is 0,

b is 1 or 2;

c is 0, 1 or 2;

R 5 is a C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 4 -C 6 aryl, or C 4 -C 6 heteroaryl group, optionally interrupted or substituted by one or more functional groups selected from the group consisting of ether, ester, amide, carbonate, halogens, phosphate, sulfate, sulfide, sulfoxide, sulfone, carbamate, and a combination of any two or more thereof; and

R 3 and R 4 together with E are cyclized to form a hydrocarbyl ring structure.

3. The solid precatalyst component of claim 1 , wherein:

E is Ge;

R 1 and R 2 are independently a moiety represented by formula IIIA or IIIB;

a is 0, 1, 2, 3, or 4;

b is 1 or 2;

c is 0, 1, or 2; and

R 3 and R 4 are independently C 1 -C 20 alkyl, C 4 -C 6 aryl, or C 4 -C 6 heteroaryl.

4. The solid precatalyst component of claim 1 , wherein: R 1 and R 2 are the same.

5. The solid precatalyst component of claim 1 , wherein: R 3 and R 4 are the same.

6. The solid precatalyst component of claim 1 , wherein the compound represented by Formula (I) comprises:

silolane-1,1-diylbis(methylene) dibenzoate;

silinane-1,1-diylbis(methylene) bis(4-methylbenzoate);

silinane-1,1-diylbis(methylene) dibenzoate;

(diphenylgermanediyl)bis(methylene) dibenzoate;

(diphenylgermanediyl)bis(methylene) bis(4-methylbenzoate);

dibutyl 2,2′-(diphenylgermanediyl)diacetate;

(dibutylgermanediyl)bis(methylene) dibenzoate;

siletane-1,1-diylbis(methylene) dibenzoate; or

silinane-1,1-diylbis(methylene) bis(furan-2-carboxylate).

7. The solid precatalyst component of claim 1 , wherein the titanium comprises a titanium compound having at least one titanium-halogen bond and the electron donor compound is supported on a magnesium halide crystal lattice.

8. The solid precatalyst component of claim 1 , wherein the titanium comprises TiCl 4 .

9. A catalyst system for use in olefinic polymerization, the catalyst system comprising:

the pre catalyst component of claim 1 ; and

an organoaluminum compound represented by general formula (XII):

AlR n X 3-n (XII),

wherein

R independently represents a hydrocarbon group usually having 1 to about 20 carbon atoms, X represents a halogen atoms, and n is greater than 0, up to, and including, 3;

and optionally, further comprising an organosilicon compound represented by the formula (XIII):

R n Si(OR′) 4-n (XIII)

wherein

each R and R′ independently represent a hydrocarbon group, and n is from 0 to less than 4.

10. The catalyst system of claim 9 further comprising at least one additional electron donor compound selected from the group consisting of:

a compound represented by general formula (IV):

a compound represented by general formula (V):

a compound represented by general formula (VI):

a compound represented by general formula (VII):

a compound represented by general formula (VIII):

a compound represented by general formula (IX):

a compound represented by general formula (X):

and

combinations thereof, wherein

R 30 is selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cycylic or arcyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens;

R 31 is selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cyclic or acyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens;

R 32 , R 33 , R 34 , R 35 , R 36 , and R 37 are each independently selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cyclic or acyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens;

R 38 is selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cyclic or acyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens;

R 39 is selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cyclic or acyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens;

R 40 , R 41 , R 42 , and R 43 are each independently selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cyclic or acyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens;

R 44 , R 45 and R 46 are each independently selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cyclic or acyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens;

R 47 is selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cyclic or acyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens;

R 48 , R 49 , R 50 , and R 51 are each independently selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cyclic or acyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens;

R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , and R 59 are each independently selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cyclic or acyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens;

R 60 and R 61 are each independently selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cyclic or acyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens;

R 62 , R 63 , R 64 and R 65 are each independently selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cyclic or acyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens;

R 66 is selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cyclic or acyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens;

R 67 is selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cyclic or acyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens;

R 68 and R 69 are each independently selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cyclic or acyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens; and

R 70 , R 71 , R 72 , and R 73 are each independently selected from the group consisting of a hydrogen; a halogen; and a linear or branched, cyclic or acyclic, saturated or non-saturated C 1 to C 22 hydrocarbyl group, wherein the hydrocarbyl group optionally contains a —O—, —NH—, or —S— group in place of a —CH 2 — group or a —N═ group in place of a —C═ group, and wherein the hydrocarbyl group is optionally substituted by one or more halogens.

11. A process of polymerizing or copolymerizing one or more olefin monomers, the process comprising:

contacting the one or more olefin monomers with the catalyst system of claim 9 to form a polymer or a copolymer.

12. The solid precatalyst component of claim 1 , wherein:

E is Ge; and

R 1 and R 2 are independently a moiety represented by formula IIIA or IIIB.

Assignments (6)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 26, 2026
From: W.R. GRACE & CO.- CONN.
To: BRASKEM AMERICA, INC.
Reel/Frame 074192/0694 →
NOTES SECURITY INTEREST Recorded Jan 29, 2026
From: W. R. GRACE & CO.-CONN.; ADVANCED REFINING TECHNOLOGIES LLC
To: WILMINGTON TRUST, NATIONAL ASSOCIATION, AS NOTES COLLATERAL AGENT
Reel/Frame 074532/0229 →
SECURITY AGREEMENT (SUPPLEMENTAL NO. 2) Recorded Aug 19, 2025
From: W. R. GRACE & CO.-CONN.
To: JPMORGAN CHASE BANK, N.A., AS COLLATERAL AGENT
Reel/Frame 072497/0481 →
SECURITY INTEREST Recorded Aug 19, 2025
From: W. R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 072519/0240 →
SECURITY INTEREST Recorded Aug 19, 2025
From: W. R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 072519/0265 →
SECURITY AGREEMENT (NOTES) Recorded Aug 19, 2025
From: W. R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION, AS NOTES COLLATERAL AGENT
Reel/Frame 072520/0653 →