IP Library Granted Patent US 8,946,361
Granted Patent B2
US 8,946,361 · App. 14/346,367 · Granted Feb 3, 2015

Polyisobutylene prepared at high velocity and circulation rate

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Quick Facts
Patent No.
US 8,946,361
App. No.
14/346,367
Granted
Feb 3, 2015
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 at a pressure differential of from 35 psi to 70 psi.

Claims (25)

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 greater than the feed rate utilizing a recirculating pump operating at a pressure differential, delta P, corresponding to a recirculating flow;

(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, 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.

2. The method according to claim 1 , wherein the delta P and polymerization reaction are controlled to provide a linear velocity of the reaction mixture of from 11 ft/sec to 20 ft/sec in the one or more reaction tubes of the loop reactor.

3. The method according to claim 2 , wherein the delta P and polymerization reaction are controlled to provide a linear velocity of the reaction mixture of at least 12 ft/sec in the one or more reaction tubes of the loop reactor.

4. The method according to claim 2 , wherein the delta P and polymerization reaction are controlled to provide a linear velocity of the reaction mixture of at least 13 ft/sec in the one or more reaction tubes of the loop reactor.

5. The method according to claim 2 , wherein the delta P and polymerization reaction are controlled to provide a linear velocity of the reaction mixture of at least 14 ft/sec in the one or more reaction tubes of the loop reactor.

6. The method according to claim 2 , wherein the delta P and polymerization reaction are controlled to provide a linear velocity of the reaction mixture of at least 15 ft/sec in the one or more reaction tubes of the loop reactor.

7. The method according to claim 1 , with the further proviso that if the conversion rate of isobutylene is less than 55%, the pressure delta and the polymerization of the reaction mixture in the one or more reaction tubes is at least 14 ft/sec.

8. The method according to claim 1 , with the further proviso that if the conversion rate of isobutylene is less than 55%, the delta P and the polymerization of the reaction mixture in the one or more reaction tubes is at least 15 ft/sec.

9. The method according to claim 1 , wherein the heat transfer coefficient between the reaction mixture and the heat transfer medium is from 50 BTU/hr ft 2 ° F. to 150 BTU/hr ft 2 ° F.

10. The method according to claim 9 , wherein the heat transfer coefficient between the reaction mixture and the heat transfer medium is at least 55 BTU/hr ft 2 ° F.

11. The method according to claim 9 , wherein the heat transfer coefficient between the reaction mixture and the heat transfer medium is at least 60 BTU/hr ft 2 ° F.

12. The method according to claim 9 , wherein the heat transfer coefficient between the reaction mixture and the heat transfer medium is at least 70 BTU/hr ft 2 ° F.

13. The method according to claim 1 , wherein the polyisobutylene withdrawn from the loop reactor is a highly reactive polyisobutylene with a number average molecular weight of from 500 to 4000 Daltons.

14. The method according to claim 13 , wherein the loop reactor is operated with a catalyst complex turnover number of from 650 to 1350 lbs. polymer/lbs. catalyst when the polyisobutylene withdrawn from the loop reactor is a highly reactive polyisobutylene with a number average molecular weight of from 1500 to 4000 Daltons.

15. The method according to claim 13 , wherein the loop reactor is operated with a catalyst complex turnover number of from 800 to 1500 lbs. polymer/lbs. catalyst complex when the polyisobutylene withdrawn from the loop reactor is a highly reactive polyisobutylene with a number average molecular weight of from 500 to 1500 Daltons.

16. The method according to claim 15 , wherein the loop reactor is operated with a catalyst complex turnover number of at least 900 lbs. polymer/lbs. catalyst complex.

17. The method according to claim 1 , wherein the polymer withdrawn from the loop reactor is a mid-range vinylidene polyisobutylene polymer with a number average molecular weight of from 500 Daltons to 4000 Daltons.

18. The method according to claim 17 , wherein the loop reactor is operated with a catalyst complex turnover number of from 1600 lbs. polymer/lbs. catalyst complex to 3000 lbs. polymer/lbs. catalyst complex.

19. The method according to claim 17 , wherein the loop reactor is operated with a catalyst complex turnover number of at least 1800 lbs. polymer/lbs. catalyst.

20. The method according to claim 1 , wherein the loop reactor has a plurality of reaction tubes.

Assignments (19)
SECURITY INTEREST Recorded Dec 16, 2024
From: TPC GROUP LLC
To: JEFFERIES FINANCE LLC, AS AGENT
Reel/Frame 069594/0055 →
RELEASE OF SECURITY INTEREST Recorded Dec 16, 2024
From: GLAS TRUST COMPANY LLC
To: TPC GROUP LLC
Reel/Frame 069602/0182 →
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 →
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 →
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 60113/0169 Recorded Dec 16, 2022
From: ECLIPSE BUSINESS CAPITAL LLC, AS AGENT
To: TPC GROUP LLC
Reel/Frame 062142/0523 →
RELEASE OF SECURITY INTEREST AT REEL/FRAME 37551/0742 Recorded Jun 8, 2022
From: BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT
To: TPC GROUP LLC
Reel/Frame 060392/0859 →
SECURITY INTEREST Recorded Jun 6, 2022
From: TPC GROUP LLC
To: ECLIPSE BUSINESS CAPITAL LLC, AS AGENT
Reel/Frame 060113/0169 →
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 Feb 2, 2021
From: TPC GROUP LLC
To: U.S. BANK NATIONAL ASSOCIATION, AS AGENT
Reel/Frame 055119/0158 →
TERMINATION AND RELEASE OF SECURITY INTEREST IN UNITED STATES TRADEMARKS AND PATENTS Recorded Aug 6, 2019
From: U.S. BANK NATIONAL ASSOCIATION, AS SUCCESSOR COLLATERAL AGENT TO WELLS FARGO BANK, NATIONAL ASSOCIATION
To: TPC GROUP LLC
Reel/Frame 049970/0219 →
CONFIRMATION OF SUCCESSION OF AGENCY Recorded Aug 5, 2019
From: WELLS FARGO BANK, NATIONAL ASSOCIATION
To: U.S. BANK NATIONAL ASSOCIATION
Reel/Frame 049963/0119 →
TERMINATION AND RELEASE OF SECURITY INTEREST IN INTELLECTUAL PROPERTY Recorded Aug 2, 2019
From: RIVERSTONE CREDIT PARTNERS, L.P.
To: TPC GROUP, LLC
Reel/Frame 049949/0259 →
SECURITY AGREEMENT Recorded Aug 2, 2019
From: TPC GROUP LLC
To: U.S. BANK NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 049949/0024 →
SECURITY INTEREST Recorded Jan 21, 2016
From: TPC GROUP LLC
To: BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 037551/0742 →
SECURITY INTEREST Recorded Jan 21, 2016
From: TPC GROUP LLC
To: WELLS FARGO BANK, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 037551/0867 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 25, 2014
From: SHAIKH, SOHEL K.; CHIU, ALFRED; BRADLEY, PATRICK L.; VALDEZ, GILBERT D.; MACATANGAY, PEGGY J.
To: TPC GROUP LLC
Reel/Frame 032514/0407 →