Vapor phase synthesis of rubbery polymers

A method for vapor phase polymerizing isoprene into cis-1,4-polyisoprene in a process comprising the steps of:

• (1) charging into a reaction zone said isoprene and a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrachloride in the presence of at least one ether;
• wherein the isoprene is maintained in the vapor phase in said reaction zone by a suitable combination of temperature and pressure and wherein said reaction zone is in a fluidized bed reactor;
• (2) allowing said isoprene to polymerize into cis-1,4-polyisoprene at a temperature within the range of about 35.degree. C. to about 70.degree. C.;
• and
• (3) withdrawing said cis-1,4-polyisoprene from said reaction zone.

A method for vapor phase polymerizing isoprene into cis-1,4-polyisoprene in a process comprising the steps of:

• (1) charging into a reaction zone said isoprene and a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrachloride in the presence of at least one ether;
• wherein the isoprene is maintained in the vapor phase in said reaction zone by a suitable combination of temperature and pressure, wherein said ether contains from about 4 to about 20 carbon atoms, wherein said organoaluminum compound is a trialkylaluminum compound, and wherein the polymerization is conducted in the presence of a para-styrenated diphenylamine;
• (2) allowing said isoprene to polymerize into cis-1,4-polyisoprene at a temperature within the range of about 35.degree. C. to about 70.degree. C.;
• and
• (3) withdrawing said cis-1,4-polyisoprene from said reaction zone.

A method for vapor phase polymerizing isoprene into cis-1,4-polyisoprene in a process comprising the steps of:

• (1) charging into a reaction zone said isoprene and a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrachloride in the presence of at least one ether;
• wherein the isoprene is maintained in the vapor phase in said reaction zone by a suitable combination of temperature and pressure and wherein the polymerization is conducted in the presence of a diarylamine;
• (2) allowing said isoprene to polymerize into cis-1,4-polyisoprene at a temperature within the range of about 35.degree. C. to about 70.degree. C.;
• and
• (3) withdrawing said cis-1,4-polyisoprene from said reaction zone.

A method for vapor phase polymerizing 1,3-butadiene into high cis-1,4-polybutadiene in a process comprising the steps of:

• (1) charging said 1,3-butadiene and a catalyst system comprising (a) an organoaluminum compound, (b) a soluble organonickel compound and (c) hydrogen fluoride or a hydrogen fluoride complex into a reaction zone;
• wherein the 1,3-butadiene is maintained in the vapor phase in said reaction zone by a suitable combination of temperature and pressure;
• (2) allowing said 1,3-butadiene to polymerize into high cis-1,4-polybutadiene at a temperature within the age of 10.degree. C. to 130.degree. C.;
• and
• (3) withdrawing said high cis-1,4-polybutadiene from said reaction zone.

A method for vapor phase polymerizing isoprene into cis-1,4-polyisoprene in a process comprising the steps of:

• (1) charging into a reaction zone said isoprene and a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrachloride in the presence of at least one ether;
• wherein the isoprene is maintained in the vapor phase in said reaction zone by a suitable combination of temperature and pressure and wherein said reaction zone is in a stirred bed reactor;
• (2) allowing said isoprene to polymerize into cis-1,4-polyisoprene at a temperature within the range of about 35.degree. C. to about 70.degree. C.;
• and
• (3) withdrawing said cis-1,4-polyisoprene from said reaction zone.