Solution polymerization process

Patent metadata

Field	Value
Publication number	US-2016108221-A1
Application number	US-201514918686-A
Country	US
Kind code	A1
Filing date	Oct 21, 2015
Priority date	Oct 21, 2014
Publication date	Apr 21, 2016
Grant date	—

Abstract

This disclosure relates to a continuous solution polymerization process wherein production rate is increased. Process solvent, ethylene, optional comonomers, optional hydrogen and a single site catalyst formulation are injected into a first reactor forming a first ethylene interpolymer. Process solvent, ethylene, optional comonomers, optional hydrogen and a heterogeneous catalyst formulation are injected into a second reactor forming a second ethylene interpolymer. The first and second reactors may be configured in series or parallel modes of operation. Optionally, a third ethylene interpolymer is formed in an optional third reactor, wherein an optional heterogeneous catalyst formulation may be employed. In a solution phase, the first, second and optional third ethylene interpolymers are combined, the catalyst is deactivated, the solution is passivated and following a phase separation process an ethylene interpolymer product is recovered.

First claim

What we claim is:

1 . A continuous solution polymerization process comprising:
i) injecting ethylene, a process solvent, a single site catalyst formulation, optionally one or more α-olefins and optionally hydrogen into a first reactor to produce a first exit stream containing a first ethylene interpolymer in said process solvent; ii) passing said first exit stream into a second reactor and injecting into said second reactor, ethylene, said process solvent, a first heterogeneous catalyst formulation, optionally one or more α-olefins and optionally hydrogen to produce a second exit stream containing a second ethylene interpolymer and said first ethylene interpolymer in said process solvent; iii) passing said second exit stream into a third reactor and optionally injecting into said third reactor, ethylene, process solvent, one or more α-olefins, hydrogen and a second heterogeneous catalyst formulation to produce a third exit stream containing an optional third ethylene interpolymer, said second ethylene interpolymer and said first ethylene interpolymer in said process solvent; iv) phase separating said third exit stream to recover an ethylene interpolymer product comprising said first ethylene interpolymer, said second ethylene interpolymer and said optional third ethylene interpolymer; wherein, the production rate is increased at least about 9% relative to a continuous solution polymerization process wherein said first heterogeneous catalyst formulation and said optional second heterogeneous catalyst formulation are replaced with said single site catalyst formulation; wherein production rate is measured in kilograms of said ethylene interpolymer product produced per hour.

2 . A continuous solution polymerization process comprising:
i) injecting ethylene, a process solvent, a single site catalyst formulation, optionally one or more α-olefins and optionally hydrogen into a first reactor to produce a first exit stream containing a first ethylene interpolymer in said process solvent; ii) injecting ethylene, said process solvent, a first heterogeneous catalyst formulation, optionally one or more α-olefins and optionally hydrogen into a second reactor to produce a second exit stream containing a second ethylene interpolymer in said process solvent; iii) combining said first and said second exit streams to form a third exit stream; iv) passing said third exit stream into a third reactor and optionally injecting into said third reactor, ethylene, said process solvent, one or more α-olefins, hydrogen and a second heterogeneous catalyst formulation to produce a fourth exit stream containing an optional third ethylene interpolymer, said second ethylene interpolymer and said first ethylene interpolymer in said process solvent; v) phase separating said fourth exit stream to recover an ethylene interpolymer product comprising said first ethylene interpolymer, said second ethylene interpolymer and said optional third ethylene interpolymer; wherein, the production rate is increased at least about 9% relative to a continuous solution polymerization process wherein said first heterogeneous catalyst formulation and said optional second heterogeneous catalyst formulation are replaced with said single site catalyst formulation; wherein production rate is measured in kilograms of said ethylene interpolymer product produced per hour.

3 . The process of claim 1 further comprising:
a) optionally adding a catalyst deactivator A to said second exit stream, downstream of said second reactor, forming a deactivated solution A;
b) adding a catalyst deactivator B to said third exit stream, downstream of said third reactor, forming a deactivated solution B; with the proviso that step b) is skipped if said catalyst deactivator A is added in step a);
c) phase separating said deactivated solution A or B to recover said ethylene interpolymer product;
wherein, the production rate is increased at least about 9% relative to a continuous solution polymerization process wherein said first heterogeneous catalyst formulation and said optional second heterogeneous catalyst formulation are replaced with said single site catalyst formulation.

4 . The process of claim 2 further comprising:
a) optionally adding a catalyst deactivator A to said third exit stream, downstream of said first and said second reactor, forming a deactivated solution A;
b) adding a catalyst deactivator B to said fourth exit stream, downstream of said third reactor, forming a deactivated solution B; with the proviso that step b) is skipped if said catalyst deactivator A is added in step a);
c) phase separating said deactivated solution A or B to recover said ethylene interpolymer product;
wherein, the production rate is increased at least about 9% relative to a continuous solution polymerization process wherein said first heterogeneous catalyst formulation and said optional second heterogeneous catalyst formulation are replaced with said single site catalyst formulation.

5 . The process of claim 3 further comprising:
a) adding a passivator to said deactivated solution A or B forming a passivated solution, and;
b) phase separating said passivated solution to recover said ethylene interpolymer product;
wherein, the production rate is increased at least about 9% relative to a continuous solution polymerization process wherein said first heterogeneous catalyst formulation and said optional second heterogeneous catalyst formulation are replaced with said single site catalyst formulation.

6 . The process of claim 4 further comprising:
a) adding a passivator to said deactivated solution A or B forming a passivated solution, and;
b) phase separating said passivated solution to recover said ethylene interpolymer product;
wherein, the production rate is increased at least about 9% relative to a continuous solution polymerization process wherein said first heterogeneous catalyst formulation and said optional second heterogeneous catalyst formulation are replaced with said single site catalyst formulation.

7 . The process of claim 5 wherein said single site catalyst formulation comprises:
a) a component (i) defined by the formula
(L A ) a M(PI) b (Q) n

wherein L A is selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl;
M is a metal selected from titanium, hafnium and zirconium;
PI is a phosphinimine ligand;
Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C 1-10 hydrocarbyl radical, a C 1-10 alkoxy radical and a C 5-10 aryl oxide radical; wherein each of said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted or further substituted by a halogen atom, a C 1-18 alkyl radical, a C 1-8 alkoxy radical, a C 6-10 aryl or aryloxy radical, an amido radical which is unsubstituted or substituted by up to two C 1-8 alkyl radicals or a phosphido radical which is unsubstituted or substituted by up to two C 1-8 alkyl radicals;
wherein a is 1; b is 1; n is 1 or 2; and (a+b+n) is equivalent to the valence of the metal M;
b) an alumoxane co-catalyst;
c) an boron ionic activator, and;
d) optionally, a hindered phenol.

8 . The process of claim 7 wherein a molar ratio of said boron ionic activator to said component (i) in said first reactor is from about 0.1:1 to about 10:1; a molar ratio of said alumoxane co-catalyst to said component (i) in said first reactor is from about 1:1 to about 1000:1, and; a molar ratio of said optional hindered phenol to said alumoxane co-catalyst in said first reactor is from 0.0:1 to about 10:1.

9 . The process of claim 7 wherein said al

Assignees

• Nova Chem Int Sa

Inventors

• Sibtain Fazle
• Dobbin Christopher John Brooke
• Hartlen Donald Gary
• Taylor Kenneth Edward
• Khakdaman Hamidreza

Classifications

• C08L2203/10

  used for bottles · CPC title

• C08L2205/025

  containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure · CPC title

• C08L23/0815 Primary

  with aliphatic 1-olefins containing one carbon-to-carbon double bond · CPC title

• C08F4/6555

  and magnesium or compounds thereof · CPC title

• C08F2/001

  Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer (C08F295/00, C08F297/00 take precedence) · CPC title