# US 2019/0169321 A1 · Methods for Terminating Olefin Polymerizations

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- Number: US 2019/0169321 A1
- Document ID: US20190169321A1
- Status: Published application
- Kind: A1
- Application number: 16/271,935
- Filed: 2019-02-11
- Published: 2019-06-06
- Earliest claimed: 2012-06-20
- Assignees: Chevron Phillips Chemical Company LP
- Inventors: Max P. McDaniel; Qing Yang; Kathy S. Clear; Tony R. Crain; Timothy O. Odi
- Web page: https://patentgrep.com/patent/US20190169321A1

## CPC

- C08F 2/40: using retarding agents
- C08F 2/38: Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation}
- C08F 2/42: using short-stopping agents
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- C08F 2410/05: Transitioning, i.e. transition from one catalyst to another with use of a deactivating agent
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Catalyst deactivating agents and compositions containing catalyst deactivating agents are disclosed. These catalyst deactivating agents can be used in methods of controlling polymerization reactions, methods of terminating polymerization reactions, methods of operating polymerization reactors, and methods of transitioning between catalyst systems.

## Claims

### Claim 1

A method of controlling a polymerization reaction in a polymerization reactor system, the method comprising:
(i) introducing a transition metal-based catalyst system, an olefin monomer, and optionally an olefin comonomer into a polymerization reactor within the polymerization reactor system;
(ii) contacting the transition metal-based catalyst system with the olefin monomer and the optional olefin comonomer under polymerization conditions to produce an olefin polymer; and
(iii) introducing a catalyst deactivating agent into the polymerization reactor to partially or completely terminate the polymerization reaction in the polymerization reactor;
wherein the catalyst deactivating agent comprises a natural source oil, a siloxane, or a combination thereof.

### Claim 2 (depends on 1)

The method of claim 1, wherein the catalyst deactivating agent comprises a natural source oil, and wherein the natural source oil comprises a tallow oil, an olive oil, a peanut oil, a castor bean oil, a sunflower oil, a sesame oil, a poppy seed oil, a palm oil, an almond seed oil, a hazelnut oil, a rapeseed oil, a canola oil, a soybean oil, a corn oil, a safflower oil, a cottonseed oil, a camelina oil, a flaxseed oil, a walnut oil, or any combination thereof.

### Claim 3 (depends on 2)

The method of claim 2, wherein the natural source oil comprises a soybean oil, a corn oil, a canola oil, a castor bean oil, or a combination thereof.

### Claim 4 (depends on 3)

The method of claim 3, wherein the natural source oil is a corn oil.

### Claim 5 (depends on 1)

The method of claim 1, wherein the catalyst deactivating agent comprises a siloxane, and wherein the siloxane has the formula:
wherein:
each R independently is a C1 to C18 hydrocarbyl group; and
n is an integer greater than or equal to 2.

### Claim 6 (depends on 5)

The method of claim 5, wherein:
each R independently is methyl, ethyl, propyl, butyl, phenyl, or benzyl; and
the siloxane has a viscosity of less than 10,000 cSt at 25° C.

### Claim 7 (depends on 6)

The method of claim 6, wherein:
the catalyst deactivating agent comprises a polydimethylsiloxane; and
the polydimethylsiloxane has a viscosity in a range from about 10 to about 1,000 cSt at 25° C.

### Claim 8 (depends on 1)

The method of claim 1, wherein the catalyst deactivating agent:
has a boiling point of at least 100° C.;
is miscible with a C3 to C10 hydrocarbon solvent; and
is a liquid throughout a temperature range of 20° C. to 80° C.

### Claim 9 (depends on 1)

The method of claim 1, wherein the catalyst deactivating agent:
has a boiling point of at least 120° C.;
is miscible with propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, n-hexane, or benzene, or a mixture thereof; and
is a liquid throughout a temperature range of −20° C. to 100° C.

### Claim 10 (depends on 1)

The method of claim 1, wherein the transition metal-based catalyst system comprises chromium, vanadium, titanium, zirconium, hafnium, or a combination thereof.

### Claim 11 (depends on 1)

The method of claim 1, wherein the transition metal-based catalyst system is a chromium-based catalyst system, a Ziegler-Natta based catalyst system, a metallocene-based catalyst system, or a combination thereof.

### Claim 12 (depends on 1)

The method of claim 1, wherein the olefin monomer is a C2-C20 olefin.

### Claim 13 (depends on 1)

The method of claim 1, wherein the olefin monomer is ethylene and the olefin comonomer comprises propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.

### Claim 14 (depends on 1)

The method of claim 1, wherein the polymerization reactor system comprises a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof.

### Claim 15 (depends on 1)

The method of claim 1, wherein the catalyst deactivating agent is introduced into the polymerization reactor at a weight ratio of the catalyst deactivating agent to the transition metal in the transition metal-based catalyst system in a range from 0.001:1 to 1000:1.

### Claim 16 (depends on 1)

The method of claim 1, wherein the step of introducing the catalyst deactivating agent into the polymerization reactor:
reduces the catalyst activity of the transition metal-catalyst system by at least 50%;
reduces the production rate of the olefin polymer by at least 50%; or
both.

### Claim 17 (depends on 1)

The method of claim 1, further comprising:
a step of discontinuing the introducing of the transition metal-based catalyst system into the polymerization reactor before, during, or after the step of introducing the catalyst deactivating agent into the polymerization reactor;
a step of discontinuing the introducing of the olefin monomer into the polymerization reactor before, during, or after the step of introducing the catalyst deactivating agent into the polymerization reactor; or
both.

### Claim 18 (depends on 1)

The method of claim 1, wherein the step of introducing the catalyst deactivating agent into the polymerization reactor:
reduces the catalyst activity of the transition metal-catalyst system by at least 95% in a time period of less than 1 minute;
reduces the production rate of the olefin polymer by at least 95% in a time period of less than 1 minute; or
both.

### Claim at position 19

19-20. (canceled)

### Claim 21 (depends on 1)

The method of claim 1, wherein a process variable is monitored to detect an undesired condition in the polymerization reactor system, and when the undesired condition has reached a predetermined critical level, the catalyst deactivating agent is introduced into the polymerization reactor.

### Claim 22

A method of controlling a polymerization reaction in a polymerization reactor system, the method comprising:
(A) introducing a first transition metal-based catalyst system, a first olefin monomer, and optionally a first olefin comonomer into a polymerization reactor in the polymerization reactor system;
(B) contacting the first transition metal-based catalyst system with the first olefin monomer and the optional first olefin comonomer under polymerization conditions to produce a first olefin polymer;
(C) discontinuing the introducing of the first transition metal-based catalyst system into the polymerization reactor before, during, or after a step of introducing a catalyst deactivating agent into the polymerization reactor; and
(D) introducing a second transition metal-based catalyst system into the polymerization reactor and contacting the second transition metal-based catalyst system with a second olefin monomer and optionally a second olefin comonomer under polymerization conditions to produce a second olefin polymer;
wherein the catalyst deactivating agent comprises a natural source oil, a siloxane, or a combination thereof.

### Claim 23

A composition comprising:
a hydrocarbon solvent having from 3 to 18 carbon atoms; and
a catalyst deactivating agent comprising a natural source oil, a siloxane, or a combination thereof.

### Claim 24 (depends on 22)

The method of claim 22, wherein the catalyst deactivating agent is introduced into the polymerization reactor at a weight ratio of the catalyst deactivating agent to the transition metal in the first transition metal-based catalyst system in a range from 0.001:1 to 1000:1.

### Claim 25 (depends on 24)

The method of claim 24, wherein the step of introducing the catalyst deactivating agent into the polymerization reactor:
reduces the catalyst activity of the first transition metal-catalyst system by at least 50%;
reduces the production rate of the first olefin polymer by at least 50%; or
both.