Claims
- 1. A process for preparing low molecular weight poly-n-butene having an M.sub.n in the range of about 300 to about 900, having a molecular weight distribution less than about 1.4, and having less than about 10% by weight of light-end polymer of number average molecular weight less than or equal to about 250, said process comprising:
- (a) providing a monomer feedstream comprising
- from 10 to 50 wt. % isobutylene;
- 1-butene;
- and 2-butene;
- (b) selectively polymerizing the isobutylene to form a composition comprising polyisobutylene and unreacted monomers;
- (c) separating the unreacted monomers from the polyisobutylene as an unreacted monomer feedstream, the unreacted monomer feedstream comprising less than 5% by weight isobutylene and at least about 12% by weight normal-butenes;
- (d) injecting into the unreacted monomer feedstream derived in accordance with step (c), an amount of HCl of from about 0.01 to 0.6 parts by weight per 100 parts by weight of said unreacted monomer feedstream, in the substantial absence of aluminum trichloride catalyst and under conditions sufficient to substantially completely react the injected HCl and thereby form 2-chlorobutane cocatalyst, thereby producing a treated unreacted monomer feedstream which contains less than 1.0 ppm free HCl;
- (e) simultaneously introducing the treated unreacted monomer feedstream mixture and aluminum trichloride chloride catalyst as separate streams into a reaction zone;
- (f) contacting the introduced treated unreacted monomer feedstream mixture and the introduced catalyst in the reaction zone at from 10.degree. C. to 90.degree. C., for a time and under conditions sufficient to form a polymerization reaction mixture comprising the poly-n-butene;
- (g) withdrawing the polymerization reaction mixture from the reaction zone; and
- (h) recovering the poly-n-butene product from the withdrawn polymerization reaction mixture.
- 2. The process of claim 1 wherein the aluminum trichloride catalyst is introduced into said rection zone in an amount of from about 0.2 to 2 wt. % based on the weight of said introduced treated feedstream mixture.
- 3. The process of claim 1 wherein the poly-n-butene product has a molecular weight distribution of about 1.2 to 1.4.
- 4. The process of claim 1 wherein the poly-n-butene product has a viscosity of 5 to 30 centistokes at 100.degree. C.
- 5. The process of claim 1 wherein the polymerization temperature is from about 20.degree. C. to 60.degree. C.
- 6. The process of claim 1 wherein the poly-n-butene has an Mn of about 900 to about 2,500.
- 7. The process of claim 1 wherein the aluminum trichloride chloride is added in admixture with C.sub.4 hydrocarbons.
- 8. A continuous process for preparing low molecular weight poly-n-butene having an M.sub.n in the range of about 300 to about 900, having a molecular weight distribution of less than about 1.4, and having less than about 10% by weight of light-end polymer of number average molecular weight less than or equal to about 250, said process comprising:
- (a) providing a monomer feedstream comprising from 10 to 50 wt. % isobutylene; 1-butene, and 2-butene;
- (b) selectively polymerizing the isobutylene to form a composition comprising polyisobutylene and unreacted monomers;
- (c) separating the unreacted monomers from the polyisobutylene as an unreacted monomer feedstream, the unreacted monomer feedstream comprising less than 5% by weight isobutylene and at least about 12% by weight normal-buteness;
- (d) injecting into unreacted monomer feedstream derived in accordance with step (c), an amount of HCl of from about 0.01 to 0.6 parts by weight per 100 parts by weight of said unreacted monomer feedstream, in the substantial absence of aluminum trichloride catalyst and under conditions sufficient to substantially completely react the injected HCl and thereby form 2-chlorobutane cocatalyst, thereby producing a treated unreacted monomer feedstream which contains less than 1.0 ppm free HCl;
- (e) simultaneously continuously introducing the treated unreacted monomer feedstream mixture and aluminum trichloride chloride catalyst as separate streams into a reaction zone;
- (f) contacting the introduced treated unreacted monomer feedstream mixture and the introduced catalyst in the reaction zone at from 10.degree. C. to 90.degree. C., for a time and under conditions sufficient to form a polymerization reaction mixture comprising the poly-n-butene;
- (g) continuously withdrawing the polymerization reaction mixture from the reaction zone; and
- (h) recovering the poly-n-butene product from the
- 9. The process of claim 8 wherein said withdrawn polymerization reaction mixture is quenched with aqueous alkali and said poly-n-butene product is recovered from said quenched polymerization reaction mixture.
- 10. The process of claim 8 wherein the aluminum trichloride catalyst is introduced into said rection zone in an amount of from about 0.2 to 2 wt. % based on the weight of said introduced treated feedstream mixture.
- 11. The process of claim 8 wherein the poly-n-butene product has a molecular weight distribution of about 1.2 to 1.4.
- 12. The process of claim 8 wherein the poly-n-butene product has a viscosity of 5 to 30 centistokes at 100.degree. C.
- 13. The process of claim 8 wherein the polymerization temperature is from about 20.degree. C. to 60.degree. C.
- 14. The process of claim 8 wherein the poly-n-butene has an Mn of about 900 to about 2,500.
- 15. The process of claim 8 wherein the aluminum trichloride chloride is added in admixture with C.sub.4 hydrocarbons.
- 16. The process of claim 15 wherein the aluminum trichloride catalyst is introduced into said rection zone in an amount of from about 0.2 to 2 wt. % based on the weight of said introduced treated feedstream mixture.
- 17. The process of claim 16 wherein the poly-n-butene product has a molecular weight distribution of about 1.2 to 1.4.
- 18. The process of claim 17 wherein the poly-n-butene product has a viscosity of 5 to 30 centistokes at 100.degree. C.
- 19. The process of claim 18 wherein said withdrawn polymerization reaction mixture is quenched with aqueous alkali and said poly-n-butene product is recovered from said quenched polymerization reaction mixture.
- 20. A process for preparing poly-n-butene having a number average molecular weight of at least about 300, which process comprises:
- (a) providing an unreacted monomer feedstream comprising isobutylene and a greater amount of 1-butene;
- (b) injecting into said unreacted monomer feedstream an amount of HCl in the substantial absence of aluminum trichloride catalyst and under conditions sufficient to substantially completely react the injected HCl, thereby producing a treated unreacted monomer feedstream mixture which contains 2-chlorobutane and less than 1.0 ppm free HCl;
- (c) introducing the treated unreacted monomer feedstream mixture into a reaction zone; and
- (d) contacting the introduced treated unreacted monomer feedstream mixture with a quantity of AlCl.sub.3 catalyst in said reaction zone at a reaction temperature of no less than 10.degree. C., for a time and under conditions sufficient to form a polymerization reaction mixture comprising the poly-n-butene;
- (e) with the proviso that a substantial molar excess of said AlCl.sub.3 catalyst over said injected HCl-at a concentration of said AlCl.sub.3 catalyst of no greater than 2.0% by weight of said treated unreacted monomer feedstream mixture-be effective, under the reaction conditions and time employed, in converting at least about 80% of said 1-butene to polymer product.
- 21. The process of claim 20 wherein the mole ratio of said AlCl.sub.3 catalyst to said injected HCl is at least about 1.3.
- 22. The process of claim 21 wherein the mole ratio of said AlCl.sub.3 catalyst to said injected HCl is at least 2.
- 23. The process of claim 20 wherein the amount of HCl injected is no less than about 0.09 parts by weight per 100 parts by weight of said unreacted monomer feedstream.
- 24. The process of claim 20 wherein the amount of HCl injected is no less than about 2 parts per weight per 100 parts per weight of said isobutylene in said unreacted monomer feedstream.
- 25. The process of any of claims 1, 8 or 20 wherein said reaction of injected HCl is conducted to a temperature of no less than about 10.degree. C.
Parent Case Info
This is a continuation of application Ser. No. 823,120, filed Jan. 21, 1992 and now abandoned, which is a continuation of application Ser. No. 262,919, filed Oct. 26, 1988 and now abandoned.
US Referenced Citations (11)
Foreign Referenced Citations (3)
Number |
Date |
Country |
731006 |
Sep 1969 |
BEX |
1195760 |
Jun 1970 |
GBX |
1449840 |
Sep 1976 |
GBX |
Continuations (2)
|
Number |
Date |
Country |
Parent |
823120 |
Jan 1992 |
|
Parent |
262919 |
Oct 1988 |
|