Low-fluoride, reactive polyisobutylene
View Patent ↗A method of making a low-fluoride reactive PIB composition includes (a) providing a modified C4 feedstock by way of blending a mixed C4 feedstock with a second feedstock having a lower LB/IsoB ratio; or providing a C4 feedstock with an LB/IsoB index of less than 10%; (b) feeding the modified C4 feedstock or the C4 feedstock with an LB/IsoB index of less than 10% to a CSTR with a homogeneous catalyst comprising BF 3 and a modifier selected from alcohols, ethers and mixtures thereof; (c) polymerizing the modified C4 feedstock or the C4 feedstock with an LB/IsoB index of less than 10% in the reactor while maintaining the reactor at a temperature above −15° C. and utilizing a residence time less than 45 minutes to produce a crude PIB composition in a polymerization mixture; and (d) recovering a purified PIB composition from the polymerization mixture having a molecular weight, Mn, from 250 to 5000 Daltons and an alpha vinylidene content of at least 50 mol %. The crude PIB composition suitably has a fluoride content of less than 100 ppm and the purified PIB composition has a fluoride content of less than 20 ppm in preferred embodiments. In the most preferred embodiments, ammonium salts are used to neutralize the catalyst and fluoride salts are sublimed from the product at elevated temperatures.
1. A method of making a low-fluoride reactive PIB composition comprising:
(a) providing a modified C4 feedstock by way of blending a mixed C4 feedstock with a second feedstock having a lower LB/IsoB ratio; or providing a C4 feedstock with an LB/IsoB index of less than 10%;
(b) feeding the modified C4 feedstock or the C4 feedstock with an LB/IsoB index of less than 10% to a CSTR provided with cooling together with a homogeneous catalyst comprising BF 3 and a modifier selected from alcohols, ethers and mixtures thereof;
(c) polymerizing the modified C4 feedstock or the C4 feedstock with an LB/IsoB index of less than 10% in the reactor while maintaining the reactor at a temperature above −15° C. and utilizing a residence time less than 45 minutes to produce a crude PIB composition in a polymerization mixture; and
(d) recovering a purified PIB composition from the polymerization mixture having a molecular weight, Mn, from 250 to 5000 Daltons and an alpha vinylidene content of at least 50 mol %.
2. The method according to claim 1 , wherein the residual fluoride content of the crude PIB composition is less than 200 ppm.
3. The method according to claim 1 , wherein the residual fluoride content of the purified PIB composition is less than 30 ppm.
4. The method according to claim 3 , wherein the residual fluoride content of the purified PIB composition is less than 20 ppm.
5. The method according to claim 1 , wherein the residual organic fluoride content of the purified PIB composition is less than 10 ppm.
6. The method according to claim 5 , wherein the residual organic fluoride content of the purified PIB composition is less than 5 ppm.
7. The method according to claim 1 , wherein the reactor is maintained at a temperature of −10° C. or above.
8. The method according to claim 1 , wherein the reactor is maintained at a temperature of 0° C. or above.
9. The method according to claim 1 , wherein the residence time is 20 minutes or less.
10. The method according to claim 1 , wherein the catalyst complex comprises a modifier selected from methanol, ethanol, tertiary butanol, isopropyl ether, diethyl ether and mixtures thereof.
11. The method according to claim 1 , further comprising:
(e) withdrawing the crude PIB composition from the reactor;
(f) neutralizing the crude PIB composition with a quenching agent; and
(g) treating the crude PIB composition at a temperature of from 150° C. to 300° C. to separate oligomers from the crude PIB composition.
12. The method according to claim 11 , further comprising washing the neutralized crude PIB composition with water and decanting the washed PIB composition to provide an aqueous phase and an organic phase containing PIB polymer.
13. The method according to claim 12 , comprising treating the organic phase containing PIB polymer at a temperature of from 150° C. to 300° C. and a pressure of from 0.25 psia to 10 psia to remove PIB oligomers from the composition.
14. The method according to claim 13 , wherein the purified PIB composition has less than 10% by weight C8 to 24 oligomers.
15. The method according to claim 1 , wherein step (a) includes providing the modified C4 feedstock by way of blending a mixed C4 feedstock with a second feedstock having a lower LB/IsoB ratio, step (b) includes feeding the modified C4 feedstock to a CSTR provided with cooling together with a homogeneous catalyst comprising BF 3 and a modifier selected from alcohols, ethers and mixtures thereof and step (c) includes polymerizing the modified C4 feedstock while maintaining the reactor at a temperature above −15° C. and utilizing a residence time less than 45 minutes to produce a crude PIB composition in a polymerization mixture.
16. The method according to claim 15 , wherein the first mixed C4 feedstock comprises raffinate or dehydro effluents.
17. The method according to claim 15 , wherein the second feedstock has an LB/IsoB index of less than 1%.
18. A method of making a low-fluoride reactive PIB composition comprising:
(a) providing a C4 feedstock with an LB/IsoB index of less than 10%;
(b) feeding the C4 feedstock with an LB/IsoB index of less than 10% to a CSTR provided with cooling together with a homogeneous catalyst comprising BF 3 and a modifier selected from alcohols, ethers and mixtures thereof;
(c) polymerizing the feedstock with an LB/IsoB index of less than 10% in the reactor while maintaining the reactor at a temperature above −15° C. and utilizing a residence time less than 45 minutes to produce a crude PIB composition in a polymerization mixture; and
(d) recovering a purified PIB composition from the polymerization mixture having a molecular weight, Mn, from 250 to 5000 Daltons and an alpha vinylidene content of at least 50 mol %.
19. A method of making a low-fluoride reactive PIB composition comprising:
(a) providing a modified C4 feedstock by way of blending a mixed C4 feedstock with a second feedstock having a lower LB/IsoB ratio; or providing a C4 feedstock with an LB/IsoB index of less than 10%;
(b) feeding the modified C4 feedstock or the C4 feedstock with an LB/IsoB index of less than 10% to a CSTR provided with cooling together with a homogeneous catalyst comprising BF 3 and a modifier selected from alcohols, ethers and mixtures thereof;
(c) polymerizing the modified C4 feedstock or the C4 feedstock with an LB/IsoB index of less than 10% in the reactor while maintaining the reactor at a temperature above −15° C. and utilizing a residence time less than 45 minutes to produce a crude PIB composition in a polymerization mixture; and
(d) recovering a purified PIB composition from the polymerization mixture having a molecular weight, Mn, from 250 to 5000 Daltons and an alpha vinylidene content of at least 50 mol %,
wherein the feed composition and reaction conditions are selected such that the residual fluoride content of the crude PIB composition is less than 200 ppm.
20. The method according to claim 19 , wherein the residual fluoride content of the crude PIB composition is less than 100 ppm.
21. The method according to claim 19 , wherein the residual fluoride content of the crude PIB composition is less than 50 ppm.
22. The method according to claim 19 , utilizing a residence time of 15 minutes or less.
23. The method according to claim 13 , wherein the quenching agent used to neutralize the crude PIB composition is an ammonium quenching agent.
24. The method according to claim 23 , wherein the quenching agent is ammonium hydroxide.