Anionic polymerization initiators and processes

Patent metadata

Field	Value
Publication number	US-9365660-B2
Application number	US-201013381311-A
Country	US
Kind code	B2
Filing date	Jun 28, 2010
Priority date	Jun 30, 2009
Publication date	Jun 14, 2016
Grant date	Jun 14, 2016

Abstract

A group of compounds defined by the general formula (I) can be used to anionically initiate polymerization of unsaturated monomers. In the formula, M is an alkali metal atom, R 1 is an aryl group having at least one OR 2 substituent group where each R 2 is a group that is nonreactive toward M, and R is a hydrocarbyl group. The subject initiators can be used in semi-batch and continuous polymerization processes, even those which are performed at elevated temperatures.

First claim

That which is claimed is:

1. A method of making a functionalized random interpolymer, said interpolymer comprising polyene and styrenic mer units, said method comprising (a) in a reaction vessel that contains ingredients which comprise a non-polar solvent, a polar coordinator compound, and unsaturated monomers that comprise one or more polyenes and a sufficient amount of one or more hydrocarbon styrenes so as to provide about 20 to about 40% of the constituent mer units of said interpolymer, initiating polymerization of said unsaturated monomers with an effective amount of an initiating compound having the general formula

where
M is an alkali metal atom,
R is a hydrocarbyl group,
each G p independently is a protecting group, and
m is an integer of from 2 to 5 inclusive,

and (b) hydrolyzing each of said protecting groups by reaction with tetrabutylammonium fluoride, thereby providing said functionalized random interpolymer.

2. The method of claim 1 wherein said one or more polyenes comprises at least one diene.

3. The method of claim 1 wherein said one or more polyenes comprises at least one conjugated diene.

4. The method of claim 1 wherein a portion of said unsaturated monomers is added to said reaction vessel after initiation of said polymerization.

5. The method of claim 4 wherein at least one of said initiating compound and said unsaturated monomers is added to said reaction vessel continuously.

6. The method of claim 1 wherein said reaction vessel is maintained at a temperature of at least 70° C.

7. The method of claim 1 wherein said initiating compound is provided by reacting equimolar amounts of a hydrocarbyl alkali metal compound with a styrenic compound having the general formula

where
each G p independently is a protecting group, and
m is an integer of from 2 to 5 inclusive.

8. The method of claim 3 wherein said random interpolymer has a number average molecular weight of from about 103,000 to about 165,000 g/mol.

9. A method of making a functionalized random interpolymer, said interpolymer comprising conjugated diene and styrenic mer units, said method comprising
(a) in a reaction vessel that contains ingredients which comprise a non-polar solvent, a polar coordinator compound, and unsaturated monomers that comprise one or more conjugated dienes and a sufficient amount of one or more hydrocarbon styrenes so as to provide about 20 to about 40% of the constituent mer units of said interpolymer, initiating polymerization of said unsaturated monomers with an effective amount of an initiating compound having the general formula

where
M is an alkali metal atom,
R is a hydrocarbyl group,
each G p independently is a protecting group, and
m is an integer of from 1 to 5 inclusive,

with the proviso that, when m=1, the (OG p ) substituent is para the M-containing substituent, thereby providing a random interpolymer having a number average molecular weight of from about 103,000 to about 165,000 g/mol, and

(b) hydrolyzing each of said protecting groups by reaction with tetrabutylammonium fluoride, thereby providing said functionalized random interpolymer.

10. The method of claim 9 wherein a portion of said unsaturated monomers is added to said reaction vessel after initiation of said polymerization.

11. The method of claim 10 wherein at least one of said initiating compound and said unsaturated monomers is added to said reaction vessel continuously.

12. The method of claim 9 wherein said reaction vessel is maintained at a temperature of at least 70° C.

13. The method of claim 9 wherein said initiating compound is provided by reacting equimolar amounts of a hydrocarbyl alkali metal compound with a styrenic compound having the general formula

where
each G p independently is a protecting group, and
m is an integer of from 1 to 5 inclusive, with the proviso that, when m=1, the (OG p ) substituent is para the vinyl group.

14. The method of claim 9 wherein m is 2.

Assignees

• Yan Yuan-Yong
• Qin Zengquan
• Pan Xiao-Dong
• Roggeman David M
• Bridgestone Corp

Inventors

• Yan Yuan-Yong
• Qin Zengquan
• Pan Xiao-Dong
• Roggeman David M

Classifications

• C08F4/484

  an alkali metal bound to a cyclic carbon · CPC title

• C08F236/10

  with vinyl-aromatic monomers · CPC title

• C08F2810/40

  taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains · CPC title

• C07F1/02

  Lithium compounds · CPC title

• C08F4/48 Primary

  selected from lithium, rubidium, caesium or francium {(C08F4/461 takes precedence)} · CPC title