IP Library Granted Patent US 9,266,980
Granted Patent B2
US 9,266,980 · App. 14/565,577 · Granted Feb 23, 2016

Polyisobutylene prepared at high velocity and circulation rate

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Quick Facts
Patent No.
US 9,266,980
App. No.
14/565,577
Granted
Feb 23, 2016
Kind
B2
Abstract

A method of making a polyisobutylene polymer in a recirculating loop reactor with one or more reaction tubes in contact with a heat transfer medium includes controlling the delta P and polymerization reaction to provide a linear velocity of the reaction mixture of at least 11 ft/sec in the one or more tubes of the loop reactor and/or controlling the delta P and polymerization reaction of steps (b) and (c) to provide a recirculation ratio of the recirculation rate to the feed rate of at least 30:1. Typically, the process utilizes a recirculating pump operating at a pressure differential of from 35 psi to 70 psi.

Claims (35)

1. A method of making a polyisobutylene polymer in a recirculating loop reactor with one or more reaction tubes in contact with a heat transfer medium comprising:

(a) feeding isobutylene, catalyst and optionally other feed components to a residual reactor stream at a feed rate to form a reaction mixture;

(b) recirculating the reaction mixture in the one or more reaction tubes of the loop reactor at a recirculation rate utilizing a recirculating pump operating at a pressure differential, delta P, of from 35 psi to 70 psi;

(c) polymerizing the reaction mixture in the one or more tubes of the loop reactor to convert isobutylene to polyisobutylene polymer at a conversion rate expressed in %, w/w, while cooling the one or more tubes of the loop reactor with the heat transfer medium;

(d) controlling the recirculation rate, the delta P and polymerization reaction of steps (b) and (c) to provide polyisobutylene polymer at a particular molecular weight having a lower polydispersity as compared to polyisobutylene polymer produced in the reactor operated with a Delta P lower than 35 psi at substantially the same reactor temperature and diluent level, wherein substantially the same reactor temperature means the reactor temperatures are within 5° F. and substantially the same diluent level means within 1 wt %; and

(e) withdrawing polyisobutylene polymer from the loop reactor.

2. The method according to claim 1 , wherein the conversion of isobutylene to polymer is from 50% to 80%.

3. The method according to claim 2 , wherein the conversion of isobutylene to polymer is at least 55%.

4. The method according to claim 2 , wherein the conversion of isobutylene to polymer is at least 65%.

5. The method according to claim 2 , wherein the conversion of isobutylene to polymer is at least 75%.

6. The method according to claim 1 , wherein the delta P of the recirculating pump is at least 40 psi.

7. The method according to claim 1 , wherein the delta P of the recirculating pump is at least 50 psi.

8. The method according to claim 1 , operated at a recirculation ratio of from 30:1 to 50:1.

9. The method according to claim 8 , operated at a recirculation ratio of at least 35:1.

10. The method according to claim 9 , operated at a recirculation ratio of at least 45:1.

11. A method of making a polyisobutylene polymer in a recirculating loop reactor with one or more reaction tubes in contact with a heat transfer medium comprising:

(a) feeding isobutylene, catalyst and optionally other feed components to a residual reactor stream at a feed rate to form a reaction mixture;

(b) recirculating the reaction mixture in the one or more reaction tubes of the loop reactor at a recirculation rate greater than the feed rate utilizing a recirculating pump operating at a pressure differential, delta P, of from 35 psi to 70 psi;

(c) polymerizing the reaction mixture in the one or more tubes of the loop reactor to convert isobutylene to polyisobutylene polymer at a conversion rate expressed in %, w/w, while cooling the one or more tubes of the loop reactor with the heat transfer medium;

(d) controlling the recirculation rate, the delta P and polymerization reaction of steps (b) and (c) to provide a linear velocity of the reaction mixture of at least 11 ft/sec in the one or more tubes of the loop reactor with the proviso that if the conversion of isobutylene is less than 55%, the recirculation rate, the delta P and the polymerization reaction of steps (b) and (c) are controlled to provide a linear velocity of the reaction mixture in the one or more reaction tubes of at least 13.5 ft/sec; and

(e) withdrawing polyisobutylene polymer from the loop reactor.

12. The method according to claim 11 , wherein the delta P of the recirculating pump is at least 40 psi.

13. The method according to claim 11 , wherein the delta P of the recirculating pump is at least 50 psi.

14. A method of making a polyisobutylene polymer in a recirculating loop reactor with one or more reaction tubes in contact with a heat transfer medium comprising:

(a) feeding isobutylene, catalyst and optionally other feed components to a residual reactor stream at a feed rate to form a reaction mixture;

(b) recirculating the reaction mixture in the one or more reaction tubes of the loop reactor at a recirculation rate greater than the feed rate utilizing a recirculating pump operating at a pressure differential, delta P, of from 35 psi to 70 psi;

(c) polymerizing the reaction mixture in the one or more tubes of the loop reactor to convert isobutylene to polyisobutylene polymer at a conversion rate expressed in %, w/w, while cooling the one or more tubes of the loop reactor with the heat transfer medium;

(d) controlling the recirculation rate, the delta P and polymerization reaction of steps (b) and (c) to provide a linear velocity of the reaction mixture of at least 11 ft/sec in the one or more tubes of the loop reactor with the proviso that if the conversion of isobutylene is less than 55%, the recirculation rate, the delta P and the polymerization reaction of steps (b) and (c) are controlled to provide a linear velocity of the reaction mixture in the one or more reaction tubes of at least 13.5 ft/sec and wherein further, there is provided a recirculation ratio of the recirculation rate to the feed rate of at least 30:1; and

(e) withdrawing polyisobutylene polymer from the loop reactor.

15. The method according to claim 14 , wherein the ratio of the recirculation rate to the feed rate is from 30:1 to 50:1.

16. The method according to claim 14 , wherein the delta P of the recirculating pump is at least 40 psi.

17. The method according to claim 14 , wherein the delta P of the recirculating pump is at least 50 psi.

18. The method according to claim 14 , wherein the delta P of the recirculating pump is at least 55 psi.

19. The method according to claim 14 , operated continuously at a residence time of from 1 to 10 minutes.

20. The method according to claim 14 , operated continuously at a residence time of from 3 to 6 minutes.

Assignments (14)
RELEASE OF SECURITY INTEREST Recorded Dec 16, 2024
From: GLAS TRUST COMPANY LLC
To: TPC GROUP LLC
Reel/Frame 069602/0182 →
SECURITY INTEREST Recorded Dec 16, 2024
From: TPC GROUP LLC
To: JEFFERIES FINANCE LLC, AS AGENT
Reel/Frame 069594/0055 →
TERMINATION AND RELEASE OF GRANT OF SECURITY INTEREST IN UNITED STATES PATENTS AT REEL/FRAME 060287/0820 Recorded Dec 20, 2022
From: GLAS AMERICAS LLC, AS COLLATERAL AGENT
To: TPC GROUP LLC
Reel/Frame 062171/0674 →
TERMINATION AND RELEASE OF SUPPLEMENTAL GRANT OF SECURITY INTEREST IN UNITED STATES PATENTS AT REEL/FRAME 055119/0158 Recorded Dec 20, 2022
From: U.S. BANK TRUST COMPANY, NATIONAL ASSOCIATION, AS SUCCESSOR COLLATERAL AGENT TO U.S. BANK NATIONAL ASSOCIATION
To: TPC GROUP LLC
Reel/Frame 062171/0666 →
TERMINATION AND RELEASE OF SUPPLEMENTAL GRANT OF SECURITY INTEREST IN UNITED STATES PATENTS AT REEL/FRAME 049949/0024 Recorded Dec 20, 2022
From: U.S. BANK TRUST COMPANY, NATIONAL ASSOCIATION, AS SUCCESSOR COLLATERAL AGENT TO U.S. BANK NATIONAL ASSOCIATION
To: TPC GROUP LLC
Reel/Frame 062171/0658 →
RELEASE OF SECURITY INTEREST AT REEL/FRAME 60113/0169 Recorded Dec 16, 2022
From: ECLIPSE BUSINESS CAPITAL LLC, AS AGENT
To: TPC GROUP LLC
Reel/Frame 062142/0523 →
SECURITY INTEREST Recorded Dec 16, 2022
From: TPC GROUP LLC
To: ECLIPSE BUSINESS CAPITAL LLC, AS COLLATERAL AGENT
Reel/Frame 062130/0001 →
SECURITY INTEREST Recorded Dec 16, 2022
From: TPC GROUP LLC
To: GLAS TRUST COMPANY LLC, AS COLLATERAL AGENT
Reel/Frame 062130/0137 →
RELEASE OF SECURITY INTEREST AT REEL/FRAME 49942/0467 Recorded Jun 8, 2022
From: BANK OF AMERICA, N.A., AS AGENT
To: TPC GROUP LLC
Reel/Frame 060392/0673 →
GRANT OF SECURITY INTEREST IN UNITED STATES PATENTS Recorded Jun 6, 2022
From: TPC GROUP LLC
To: GLAS AMERICAS LLC, AS COLLATERAL AGENT
Reel/Frame 060287/0820 →
SECURITY INTEREST Recorded Jun 6, 2022
From: TPC GROUP LLC
To: ECLIPSE BUSINESS CAPITAL LLC, AS AGENT
Reel/Frame 060113/0169 →
SECURITY INTEREST Recorded Feb 2, 2021
From: TPC GROUP LLC
To: U.S. BANK NATIONAL ASSOCIATION, AS AGENT
Reel/Frame 055119/0158 →
SECURITY INTEREST Recorded Aug 2, 2019
From: TPC GROUP LLC
To: BANK OF AMERICA, N.A.
Reel/Frame 049942/0467 →
SECURITY AGREEMENT Recorded Aug 2, 2019
From: TPC GROUP LLC
To: U.S. BANK NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 049949/0024 →