Process for producing polydienes

Patent metadata

Field	Value
Publication number	US-2016108153-A1
Application number	US-201514978136-A
Country	US
Kind code	A1
Filing date	Dec 22, 2015
Priority date	Sep 23, 2010
Publication date	Apr 21, 2016
Grant date	—

Abstract

A method for producing a polydiene, the method comprising of combining a lanthanide compound, an alkylating agent, a halogen source, and optionally conjugated diene monomer to form an active preformed catalyst; independent of step (i), introducing an amine with conjugated diene monomer to be polymerized; independent of step (i), introducing the active preformed catalyst to the conjugated diene monomer to be polymerized to form an active polymerization mixture, where the active polymerization mixture includes less than 10% by weight, based on the total weight of the active polymerization mixture, of a solvent; and allowing the monomer to be polymerized to polymerize in the presence of the amine.

First claim

What is claimed is:

1 . A method for producing a polydiene, the method comprising:
(i) combining a lanthanide compound, an alkylating agent, a halogen source, and optionally conjugated diene monomer to form an active preformed catalyst; (ii) independent of step (i), introducing an amine with conjugated diene monomer to be polymerized; (iii) independent of step (i), introducing the active preformed catalyst to the conjugated diene monomer to be polymerized to form an active polymerization mixture, where the active polymerization mixture includes less than 10% by weight, based on the total weight of the active polymerization mixture, of a solvent; and (iv) allowing the monomer to be polymerized to polymerize in the presence of the amine.

2 . The method of claim 1 , where the amine is defined by the formula NR 3 , where each R, which may be the same or different, is a hydrocarbyl group or substituted hydrocarbyl group, or where two or more R groups combine to form a divalent or trivalent organic group, and where the hydrocarbyl group, including any hydrocarbyl group forming a substituted hydrocarbyl group, is selected from the group consisting of alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, aryl, and substituted aryl groups.

3 . The method of claim 1 , where the active polymerization mixture includes less than 5% by weight, based on the total weight of the active polymerization mixture, of a solvent.

4 . The method of claim 1 , where the active polymerization mixture is substantially devoid of a solvent.

5 . The method of claim 1 , where the lanthanide compound is a lanthanide carboxylate, lanthanide organophosphate, lanthanide organophosphonate, lanthanide organophosphinate, lanthanide carbamate, lanthanide dithiocarbamate, lanthanide xanthate, lanthanide β-diketonate, lanthanide alkoxide or aryloxide, or organolanthanide compound.

6 . The method of claim 1 , where the ratio of the amine to the lanthanide-containing compound is at least 20:1.

7 . The method of claim 1 , where said step of introducing an amine to conjugated diene monomer that is to be polymerized forms an amine/monomer blend, and where said step of polymerizing the conjugated diene monomer takes place within the amine/monomer blend.

8 . The method of claim 1 , where the amine and the preformed catalyst are introduced to the conjugated diene monomer to be polymerized simultaneously.

9 . The method of claim 1 , where at amine is a tertiary amine.

10 . The method of claim 9 , where the tertiary amine is selected from the group consisting of trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, triisopentylamine, tri-n-hexylamine, trioctylamine, tricetylamine, tridodecylamine, triheptylamine, tri-iso-heptylamine, trinonylamine, N-methyl-N,N-dioctylamine, N,N-dimethyl-N-ethylamine, N-methyl-N-ethyl-N-propylamine, N,N-dimethyl-Nhexylamine, tri-isoamylamine, and triamylamine.

11 . The method of claim 9 , where the tertiary amine is selected from the group consisting of tricyclopentylamine, tricyclohexylamine, and tricyclooctylamine.

12 . The method of claim 9 , where the tertiary amine is selected from the group consisting of N,N-dimethyl-1-naphthylamine, N,N-dimethylaniline, N,Ndiethylaniline, N,N-dimethylbenzylamine, and tribenzylamine.

13 . The method of claim 9 , where the tertiary amine is selected from the group consisting of N-methylpyrrolidine, 1,2-dimethylpyrrolidine, 1,3-dimethylpyrrolidine, 1,2,5-trimethylpyrrolidine, 2-methyl-2-pyrazoline, 1-methyl-2H-pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethyl-1-methyl pyrrole, 2,5-dimethyl-1-methyl pyrrole, N-methylpyrrole, 1,2,5-trimethylpyrrole, 3-pyrroline, 2-pyrroline, 2-methyl-1-pyrroline, 2-imidazoline, N-ethylpiperidine, 1-ethylpiperidine, N-cyclohexyl-N,N-dimethylamine, quinuclidine, 3-(biphenyl-4-yl)quinuclidine, and 1-methyl-carbozole.

14 . The method of claim 9 , where the tertiary amine includes pyridine, methylpyridine, 2,6-dimethylpyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, dimethylpyridine, trimethylpyridine, ethylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2,4-diethylpyridine, 2,6-diethylpyridine, 3,4-diethylpyridine, 2,3-,dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine, triethylpyridine, 1,4,5-triethylpyridine, 2,4,5-triethylpyridine, 2,3,4-trimethylpyridine, 2,3,5-trimethylpyridine, 2,3,6-trimethylpyridine, 2,4,6-trimethylpyridine, propylpyridine, 3-methyl-4-propyl-pyridine, butylpyridine, 4-(1-butylpentyl)pyridine, 4-tert-butylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, diphenylpyridine, 2-phenylpyridine, benzylpyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, 2,6-dimethyl-4-ethylpyridine, 3-ethyl-4-methylpyridine, 3,5-dimethyl-2-ethylpyridine, 2,3,4,5-tetramethylpyridine, pyrazine, pyridazine, pyrimidine, 4-methylpyrimidine, 1,2,3-triazole, 1,3,5-triazine, quinoline, 2-ethylquinoline, 3-ethylquinoline, 4-ethylquinoline, 2-methylquinoline, 3-methylquinoline, 4-methylquinoline, 5-methylquinoline, 6-methylquinoline, 8-methylquinoline, 2,4-dimethylquinoline, 4, 6-dimethylquinoline, 4, 7-dimethylquinoline, 5,8-dimethylquinoline, 6,8-dimethylquinoline, 2,4,7-trimethylquinoline, isoquinoline, 4-ethyl-isoquinoline, 1-ethylisoquinoline, 3-ethylisoquinoline, 4-methyl-2-phenylimidazole, 2-(4-methylphenyl)indolizine, indolizine, quinoxaline, 2-amino-8-methyl-quinoxaline, 1-methylindole, 1,8-naphthyridine, cinnoline, quinazoline, pteridine, acridine, phenazine, 1-methylpyrazole, 1,3-dimethylpyrazole, 1,3,4-trimethylpyrazole, 3,5-dimethyl-1-phenylpyrazole, and 3,4-dimethyl-1-phenylpyrazole.

15 . The method of claim 9 , where the tertiary amine is pyridine.

16 . A method for producing a polydiene, the method comprising:
(i) combining a lanthanide compound, an alkylating agent, a halogen source, and optionally conjugated diene monomer to form an active preformed catalyst; (ii) independent of step (i), introducing an amine with conjugated diene monomer to be polymerized; (iii) independent of step (i), introducing the active preformed catalyst to the conjugated diene monomer to be polymerized to form an active polymerization mixture; and (iv) allowing the monomer to be polymerized to polymerize in the presence of the amine, where the lanthanide compound is a lanthanide carboxylate, lanthanide organophosphate, lanthanide organophosphonate, lanthanide organophosphinate, lanthanide carbamate, lanthanide dithiocarbamate, lanthanide xanthate, lanthanide β-diketonate, lanthanide alkoxide or aryloxide, or organolanthanide compound.

17 . The method of claim 16 , where the lanthanide-containing compound is neodymium formate, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium valerate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate (a.k.a., neodymium versatate), neodymium naphthenate, neodymium stearate, neodymium oleate, neodymium benzoate, or neodymium picolinate.

18 . The method of claim 16 , where the lanthanide-containing compound is neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methylheptyl) phosphate, neodymium bis(2-ethylhexyl) phosphate, neodymium didecyl phosphate, neodymium didodecyl phosphate, neodymium dioctadecyl phos

Assignees

• Bridgestone Corp

Inventors

• Mccauley Kevin M
• Luo Steven

Classifications

• C08F4/04

  Azo-compounds · CPC title

• C08F36/04 Primary

  conjugated · CPC title

• C08F4/12

  of boron, aluminium, gallium, indium, thallium or rare earths · CPC title

• C08F136/06 Primary

  Butadiene · CPC title

• C08C19/22

  Incorporating nitrogen atoms into the molecule · CPC title