IP Library Granted Patent US 11,370,854
Granted Patent B2
US 11,370,854 · App. 16/837,667 · Granted Jun 28, 2022

Non-phthalate donor for polyolefin catalysts

Inventors: Binh Thanh Nguyen (League City, TX); Jonas Alves Fernandes (Pittsburgh, PA); Vladimir P. Marin (Houston, TX); Mushtaq Ahmed Patel (Maharashtra, IN)
Assignees: Braskem America, Inc.; W.R. Grace & Co.-CONN.
C08F10/06B01J31/12B01J31/26B01J31/38C08F4/654C08F110/06
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Quick Facts
Patent No.
US 11,370,854
App. No.
16/837,667
Granted
Jun 28, 2022
Kind
B2
Abstract

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

Claims (74)

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

titanium;

magnesium;

a halogen; and

an internal electron donor compound;

wherein:

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

R 1 is a group of formula:

E is —CR 6 R 7 —, O, S, —OS(═O) 2 O—, —OS(═O)O—, —S(═O)O—, —N(R 4 )—, S, —P(R 4 )—, —Si(R 5 ) 2 —;

R 2 and R 3 are individually H, OR 4 , SR 8 , NR 4 2 , PR 4 2 , Si(R 5 ) 2 , alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, or heteroaryl;

each R 4 is individually H, alkyl, or aryl;

each R 5 is individually H, OR 4 , alkyl, or aryl;

R 6 is H, alkyl, or cycloalkyl;

R 7 is H, alkyl, or cycloalkyl;

R 8 is haloaryl, haloheteroaryl, or haloheterocyclyl;

R 17 , R 18 , R 19 , R 20 , R 21 , and R 22 are independently H, F, Cl, Br, I, CN, NO 2 , OR 4 , SR 4 , NR 4 2 , PR 4 2 , SiR 5 3 , alkyl, aryl, or where any two adjacent members of R 17 , R 18 , R 19 , R 20 , R 21 , and R 22 may join together to form a fused ring structure; and

X is C, S, P, O, or NR Y , wherein R Y is H, alkyl, alkenyl, or alkynyl;

with the provisos that:

where E is O, R 2 and R 3 are not both OR 4 ; and

where R 2 is OR 4 , R 3 is not phenyl.

2. The solid catalyst component of claim 1 which is dibenzo[b,d]furan-4,6-diyl bis(furan-2-carboxylate); dibenzo[b,d]furan-4,6-diyl diheptanoate; dibenzo[b,d]furan-4,6-diyl bis(2-methoxybenzoate); [6-(2-methylbenzoyl)oxydibenzofuran-4-yl]-2-methylbenzoate; [6-(4-ethoxybenzoyl)oxydibenzofuran-4-yl]-4-ethoxybenzoate; [6-(4-methoxybenzoyl)oxydibenzofuran-4-yl]-4-methoxybenzoate; (6-benzoyloxydibenzofuran-4-yl) benzoate; or [6-(cyclohexanecarbonyloxy)dibenzofuran-4-yl] benzoate.

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

4. The solid catalyst component of claim 1 , wherein the solid catalyst component further comprises at least one secondary internal donor compound selected from the group consisting of mono-or poly-carboxylic esters, ethers, ketones, organic compounds containing carboxylic and ether groups, organic compounds containing carboxylic groups and carbonyl groups, and organic compounds containing carboxylic groups, ether groups, and carbonyl groups.

5. The solid catalyst component of claim 4 , wherein the at least one secondary internal donor compound is selected from the group consisting of:

a compound represented by general formula (II):

a compound represented by general formula (III):

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):

and

combinations of any two or more 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 nonsaturated 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.

6. A solid catalyst component for use in olefinic polymerization, comprising a reaction product of a titanium compound, a magnesium compound, and an internal electron donor compound, wherein the internal electron donor compound is at least one compound represented by Formula (I):

R 1 is a group of formula:

E is CH 2 , O, S, —OS(═O) 2 O—, —OS(═O)O—, —S(═O)O—, NR 4 , PR 4 , or Si(R 15 )(R 16 );

R 2 and R 3 are individually H, OR 4 , SR 8 , NR 4 2 , PR 4 2 , Si(R 5 ) 2 , alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, or heteroaryl;

R 4 is H, alkyl, or aryl;

R 15 is H, OR 4 , alkyl, or aryl;

R 16 is H, OR 4 , alkyl, or aryl;

R 8 is haloaryl, haloheteroaryl, or haloheterocyclyl;

R 17 , R 18 , R 19 , R 20 , R 21 , and R 22 are independently H, F, Cl, Br, I, CN, NO 2 , OR 4 , SR 4 , NR 4 2 , PR 4 2 , SiR 5 3 , alkyl, aryl, or where any two adjacent members of R 17 , R 18 , R 19 , R 20 , R 21 , and R 22 may join together to form a fused ring structure; and

X is C, S, P, O, or NR Y , wherein R Y is H, alkyl, alkenyl, or alkynyl;

with the provisos that:

where E is O, R 2 and R 3 are not both OR 4 ;

where R 2 is OR 4 , R 3 is not phenyl; and

where E is O and R 1 is naphthyl, R 2 and R 3 are not both phenyl.

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

the olefin polymerization catalyst component of claim 4 ; and

an organoaluminum compound.

8. The catalyst system of claim 7 further comprising an organosilicon compound.

9. The catalyst system of claim 8 , wherein the organosilicon compound is represented by chemical formula (III):

R n Si(OR′) 4-n   (III)

wherein each R and R′ independently represent a hydrocarbon group, and n is an integer from 0 to 3.

10. A process of polymerizing or copolymerizing an olefin monomer, the process comprising:

providing the catalyst system of claim 8 ;

polymerizing or copolymerizing the olefin monomer in the presence of the catalyst system to form a polymer or a copolymer; and

recovering the polymer or the copolymer.

Assignments (9)
CORRECTIVE ASSIGNMENT TO CORRECT THE PROPERTY TYPE TO U.S. PATENT NO. 11370854 PREVIOUSLY RECORDED ON REEL 69524 FRAME 44. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Apr 10, 2025
From: BASF CORPORATION
To: W. R. GRACE & CO. - CONN.
Reel/Frame 070808/0352 →
CORRECTIVE ASSIGNMENT TO CORRECT THE THE PROPERTY TYPE FROM APPLICATION NUMBER TO PATENT NUMBER PREVIOUSLY RECORDED AT REEL: 69501 FRAME: 56. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Apr 10, 2025
From: W. R. GRACE & CO.-CONN.
To: BRASKEM AMERICA, INC.; BRASKEM SA; BRASKEM EUROPE GMBH
Reel/Frame 070809/0359 →
CORRECTIVE ASSIGNMENT TO CORRECT THE PROPERTY TYPE TO U.S. PATENT NO. 11370854 PREVIOUSLY RECORDED ON REEL 69520 FRAME 672. ASSIGNOR(S) HEREBY CONFIRMS THE JOINT OWNERSHIP ACKNOWLEDGEMENT. Recorded Apr 10, 2025
From: W. R. GRACE & CO.-CONN.
To: BRASKEM AMERICA, INC.; BRASKEM SA; BRASKEM EUROPE GMBH
Reel/Frame 070809/0502 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 5, 2024
From: BRASKEM EUROPE GMBH
To: BRASKEM AMERICA, INC.
Reel/Frame 069503/0416 →
NUNC PRO TUNC ASSIGNMENT Recorded Dec 5, 2024
From: NGUYEN, BINH THANH; MARIN, VLADIMIR P.; PATEL, MUSHTAQ AHMED
To: BASF CORPORATION
Reel/Frame 069500/0418 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 5, 2024
From: BASF CORPORATION
To: W. R. GRACE & CO. - CONN.
Reel/Frame 069524/0044 →
JOINT OWNERSHIP ACKNOWLEDGEMENT Recorded Dec 5, 2024
From: W. R. GRACE & CO.-CONN.
To: BRASKEM AMERICA, INC.; BRASKEM SA; BRASKEM EUROPE GMBH
Reel/Frame 069520/0672 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 5, 2024
From: FERNANDES, JONAS ALVES
To: BRASKEM AMERICA, INC.
Reel/Frame 069500/0640 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 5, 2024
From: BRASKEM SA
To: BRASKEM AMERICA, INC.
Reel/Frame 069503/0391 →
Continuity (3)
Continuation 16303630
Provisional Application 62340347 · May 23, 2016
Related Publication 20200223958A1 · Jul 16, 2020