# US 10,370,470 B2 · Catalyst modification to control polymer architecture

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- Number: US 10,370,470 B2
- Document ID: US10370470B2
- Status: Granted
- Kind: B2
- Application number: 15/819,189
- Filed: 2017-11-21
- Published: 2018-03-22
- Granted: 2019-08-06
- Earliest claimed: 2015-08-06
- Assignees: NOVA Chemicals (International) S.A.
- Applicants: NOVA Chemicals (International) S.A.
- Inventors: Darryl J Morrison; Stephen Salomons; Isam Jaber
- Web page: https://patentgrep.com/patent/US10370470B2

## CPC

- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/6592: containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- C08F 2420/04: Cp or analog not bridged to a non-Cp X ancillary anionic donor
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

By controlling the ratio of catalyst components or the type of activator the homogeneity of a polymer produced using a single site catalyst may be improved.

## Claims

### Claim 1

A method to increase the homogeneity of an ethylene copolymer comprising one or more comonomers chosen from propylene, 1-butene, 1-hexene, and 1-octene by reducing the amount of the component eluting at a temperature of greater than 90° C. in the temperature rising elution fraction analysis wherein the copolymer is produced using a solution polymerization process at pressures from 6,000 kPa to 22,000 kPa, comprising two or more reactors in series in which the first reactor is operated at temperatures from 120° C. to 180° C. and the second and subsequent optional reactors are operated at higher temperatures up to 220° C. in the presence of a catalyst system comprising:
(I) transition metal catalyst of the formula:
(L)n-M-(X)p
wherein M is a transition metal, for example a transition metal chosen from Ti, Hf and Zr; L is a monoanionic ligand chosen from a cyclopentadienyl ligand, an indenyl ligand and a fluorenyl ligand which ligands are unsubstituted or up to fully substituted with one or more substituents chosen from chlorine atoms, fluorine atoms and C1-4 alkyl radicals which are optionally substituted with chlorine or fluorine atoms,
and
a phosphinimine ligand of the formula:
wherein each R3 is independently chosen from a hydrogen atom; a halogen atom; C1-10 hydrocarbyl radicals which are optionally substituted by a halogen atom; a C1-8 alkoxy radical; a C6-10 aryl or aryloxy radical; and an amido radical which is optionally substituted by up to two C1-10 hydrocarbyl radicals;
X is a monoanionic ligand chosen from C1-4 alkyl radicals and a chlorine atom;
n is an integer from 1 to 3, and
p is an integer from 1 to 3, provided that the sum of n+p equals the valence state of M, and
further provided that two L ligands are optionally bridged by a silyl radical or a C1-4 alkyl radical;
(II) a boron activator capable of ionizing the transition metal complex chosen from:
(i) compounds of the formula [R5]+[B(R7)4]− wherein B is a boron atom, R5 is a cyclic C5-7 aromatic cation or a triphenylcarbenium cation and each R7 is independently chosen from phenyl radicals which are unsubstituted or substituted with from 3 to 5 substituents chosen from a fluorine atom, a C1-4 alkyl or alkoxy radical which is unsubstituted or substituted by a fluorine atom; and a silyl radical of the formula —Si—(R9)3; wherein each R9 is independently chosen from a hydrogen atom and a C1-4 alkyl radical;
(ii) compounds of the formula [(R8)tZH]+[B(R7)4]− wherein B is a boron atom, H is a hydrogen atom, Z is a nitrogen atom or phosphorus atom, t is 2 or 3 and R8 is chosen from C1-8 alkyl radicals, a phenyl radical which is unsubstituted or substituted by up to three C1-4 alkyl radicals, or one R8 taken together with the nitrogen atom to optionally form an anilinium radical and R7 is as defined above; and
(iii) compounds of the formula B(R7)3 wherein R7 is as defined above;
(III) an aluminoxane of the formula (R4)2AlO(R4AlO)mAl(R4)2 wherein each R4 is independently chosen from C1-4 alkyl radicals, m is from 3 to 50:
and adjusting one or more of:
a) the ratio of components 2 and 3; or
b) changing component 2.

### Claim 2 (depends on 1)

The method according to claim 1, wherein in the catalyst n is 2.

### Claim 3 (depends on 2)

The method according to claim 2, where in one L is a phosphinimine ligand.

### Claim 4 (depends on 3)

The process according to claim 3, wherein the starting ratio of catalyst components aluminoxane:catalyst:ionic activator is 100:1:greater than 1.1 and is reduced to 50-100:1:0.3-1.05.

### Claim 5 (depends on 4)

The process according to claim 4, where in the ionic activator is chosen from triphenylcarbenium tetrakis(pentafluorophenyl)borate and tris(pentafluorophenyl)borane.

### Claim 6 (depends on 5)

The method according to claim 5, wherein the aluminoxane is methyl aluminoxane which is optionally used in conjunction with a hindered phenol to provide a molar ratio of hindered phenol:Al up to 0.6:1.

### Claim 7 (depends on 6)

The method according to claim 6, wherein the catalyst is cyclopentadienyl tri-tert-butylphosphinimine titanium dichloride.

### Claim 8 (depends on 7)

The method according to claim 7, wherein the catalyst is alkylated within ten minutes prior to use.