Process for producing polydienes

Patent metadata

Field	Value
Publication number	US-9249244-B2
Application number	US-201113825703-A
Country	US
Kind code	B2
Filing date	Sep 15, 2011
Priority date	Sep 23, 2010
Publication date	Feb 2, 2016
Grant date	Feb 2, 2016

Abstract

A method for producing a polydiene, the method comprising the steps of: (i) forming an active catalyst by combining a lanthanide-containing compound, an alkylating agent, and a halogen source in the substantial absence of an amine; and (ii) polymerizing conjugated diene monomer in the presence of the active catalyst and an amine.

First claim

What is claimed is:

1. A method for producing a polydiene, the method comprising the steps of:
(i) preparing an active preformed catalyst by introducing a lanthanide-containing compound, an alkylating agent, a halogen source, and optionally monomer;
(ii) independent of step (i), introducing the preformed catalyst to conjugated diene monomer that is to be polymerized;
(iii) independent of step (i), introducing an amine to the conjugated diene monomer that is to be polymerized, where the ratio of the amine to the lanthanide-containing compound is at least 20:1; and
(iv) polymerizing the conjugated diene monomer that is to be polymerized with the preformed catalyst in the presence of the amine to produce a polymer having a reactive end, where the amine and the preformed catalyst are introduced separately and individually to the conjugated diene monomer that is to be polymerized.

2. The method of claim 1 , where the polydiene is a cis-1,4-polybutadiene having a cis-1,4-linkage content of greater than 97%, a 1,2-linkage content of less than 2%, and a molecular weight distribution of less than 2.5; and where at least 90% of the polymer chains of the polydiene possess a reactive end.

3. 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.

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

5. The method of claim 1 , where at least one R is an alkyl group selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl, and n-decyl.

6. The method of claim 1 , where at least one R is a cycloalkyl group selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2-t-butylcyclohexyl and 4-t-butylcyclohexyl.

7. The method of claim 1 , where at least one R is an aryl group selected from the group consisting of phenyl, substituted phenyl, biphenyl, substituted biphenyl, bicyclic aryl, substituted bicyclic aryl, polycyclic aryl, and substituted polycyclic aryl groups.

8. The method of claim 1 , where at least one R is a substituted phenyl group selected from the group consisting of 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 3,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, and 2,4,6-trimethylphenyl (also called mesityl).

9. The method of claim 1 , where at least one R is a bicyclic or polycyclic aryl selected from the group consisting of 1-naphthyl, 2-napthyl, 9-anthryl, 9-phenanthryl, 2-benzo[b]thienyl, 3-benzo[b]thienyl, 2-naphtho[2,3-b]thienyl, 2-thianthrenyl, 1-isobenzofuranyl, 2-xanthenyl, 2-phenoxathiinyl, 2-indolizinyl, N-methyl-2-indolyl, N-methyl-indazol-3-yl, N-methyl-8-purinyl, 3-isoquinolyl, 2-quinolyl, 3-cinnolinyl, 2-pteridinyl, N-methyl-2-carbazolyl, N-methyl-β-carbolin-3-yl, 3-phenanthridinyl, 2-acridinyl, 1-phthalazinyl, 1,8-naphthyridin-2-yl, 2-quinoxalinyl, 2-quinazolinyl, 1,7-phenanthrolin-3-yl, and 1-phenazinyl, N-methyl-2-phenothiazinyl, 2-phenarsazinyl, and N-methyl-2-phenoxazinyl.

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

11. The method of claim 10 , 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-N-hexylamine, tri-isoamylamine, and triamylamine.

12. The method of claim 10 , where the tertiary amine is selected from the group consisting of tricyclopentylamine, tricyclohexylamine, and tricyclooctylamine.

13. The method of claim 10 , where the tertiary amine is selected from the group consisting of N,N-dimethyl-1-naphthylamine, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethylbenzylamine, and tribenzylamine.

14. The method of claim 10 , 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.

15. The method of claim 10 , 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.

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

17. 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.

18. The method of claim 1 , where the ratio of the amine to the lanthanide-containing compound is at least 30:1.

19. The method of claim 1 , where the ratio of the amine to the lanthanide-containing compound is from about 40:1 to about 80:1.

20. The method of claim 1 , further comprising the step of introducing a q

Assignees

• Mccauley Kevin M
• Luo Steven
• Bridgestone Corp

Inventors

• Mccauley Kevin M
• Luo Steven

Classifications

• C08C19/22

  Incorporating nitrogen atoms into the molecule · CPC title

• 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