Stereoregular diblock polybutadienes having a 1,4-cis/syndiotactic 1,2 structure from stereospecific polymerization

Patent metadata

Field	Value
Publication number	US-10066044-B2
Application number	US-201415032207-A
Country	US
Kind code	B2
Filing date	Nov 3, 2014
Priority date	Nov 5, 2013
Publication date	Sep 4, 2018
Grant date	Sep 4, 2018

Abstract

Stereoregular diblock polybutadiene composed of a polybutadiene block having a 1,4-cis structure and a polybutadiene block having a syndiotactic 1,2 structure. Said stereoregular diblock polybutadiene can be advantageously used in both the footwear industry (for example, in the production of soles for shoes) and in the production of tires for motor vehicles and/or trucks.

First claim

The invention claimed is:

1. A process for the preparation of a stereoregular diblock polybutadiene composed of a polybutadiene block having a 1,4-cis structure and a polybutadiene block having a 1,2 syndiotactic structure, and having the following formula (I):
PB 1 —PB 2   (I)

wherein:
PB 1 corresponds to the polybutadiene block having a 1,4-cis structure; and
PB 2 corresponds to the polybutadiene block having a 1,2 syndiotactic structure;

wherein said stereoregular diblock polybutadiene has a content of 1,4-trans units of less than 3 mol %, with respect to a total molar quantity of butadiene units present in said stereoregular diblock polybutadiene,

the process comprising:
subjecting 1,3-butadiene to total or partial stereospecific polymerization in the presence of a catalytic system comprising at least one complex of cobalt including at least one imine nitrogen, in order to obtain polybutadiene with a 1,4-cis living structure;
adding at least one monodentate aromatic phosphine and optionally 1,3-butadiene, and continuing said stereospecific polymerization, in order to obtain said stereoregular diblock polybutadiene composed of a polybutadiene block having a 1,4-cis structure and a polybutadiene block having a 1,2 syndiotactic structure.

2. The process according to claim 1 , wherein said cobalt complex including at least one imine nitrogen is selected from bis-imine complexes of cobalt having general formula (I):

wherein:
n is 0 or 1;
Y represents a group —CR′R″ wherein R′ and R″, the same or different, represent a hydrogen atom; or a linear or branched C 1 -C 20 alkyl group; or a divalent aromatic group optionally substituted;
R 1 and R 2 , the same or different, represent a hydrogen atom; or they are selected from a linear or branched C 1 -C 20 alkyl group, optionally halogenated, cycloalkyl groups optionally substituted; or R 1 and R 2 can be optionally bound to each other to form, together with the other atoms to which they are bound, a cycle containing from 4 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C 1 -C 20 , said cycle optionally containing a heteroatom selected from the group consisting of oxygen, sulfur, nitrogen, silicon, phosphorous, and selenium;
R 3 and R 4 , the same or different, represent a hydrogen atom; or they are selected from a linear or branched C 1 -C 20 alkyl group optionally halogenated, cycloalkyl groups optionally substituted; aryl groups optionally substituted;
or R 2 and R 4 can be optionally bound to each other to form, together with the other atoms to which they are bound, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C 1 -C 20 alkyl groups, said cycle optionally containing a heteroatom selected from the group consisting of oxygen, sulfur, nitrogen, silicon, phosphorous, and selenium;
or R 1 and R 3 can be optionally bound to each other to form, together with the other atoms to which they are bound, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C 1 -C 20 alkyl groups, said cycle optionally containing a heteroatom selected from the group consisting of oxygen, sulfur, nitrogen, silicon, phosphorous, and selenium;
X 1 and X 2 , the same or different, represent a halogen atom selected from the group consisting of chlorine, bromine, and iodine; or they are selected from linear or branched C 1 -C 20 alkyl groups, —OCOR 5 groups or —OR 5 groups wherein R 5 is selected from linear or branched C 1 -C 20 alkyl groups.

3. The process according to claim 1 , wherein said cobalt complex including at least one imine nitrogen is selected from oxo-nitrogenated complexes of cobalt having general formula (Ia):

wherein:
R 1 and R 2 , the same or different, represent a hydrogen atom; or they are selected from linear or branched C 1 -C 10 alkyl groups, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted;
R 3 represents a hydrogen atom, or it is selected from linear or branched C 1 -C 20 , alkyl groups optionally halogenated, cycloalkyl groups optionally substituted; aryl groups optionally substituted; or R 3 represents a ketoimine group having formula:

wherein R′ and R″, the same or different, represent a hydrogen atom, or they are selected from linear or branched C 1 -C 20 alkyl groups, cycloalkyl groups optionally substituted, aryl groups optionally substituted;
X 1 and X 2 , the same or different, represent a halogen atom selected from the group consisting of chlorine, bromine, and iodine; or they are selected from linear or branched C 1 -C 20 alkyl groups, —OCOR 4 groups or —OR 4 groups wherein R 4 is selected from linear or branched C 1 -C 20 alkyl groups.

4. The process according to claim 1 , wherein said cobalt complex including at least one imine nitrogen is selected from oxo-nitrogenated complexes of cobalt having general formula (Ib):

wherein
R 1 and R 2 , the same or different, represent a hydrogen atom; or they are selected from linear or branched C 1 -C 20 alkyl groups, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted;
Y represents an oxygen atom; or a —N—R 3 group wherein R 3 represents a hydrogen atom, or it is selected from linear or branched C 1 -C 20 alkyl groups, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted;
or, when Y represents a group —N—R 3 , R 2 and R 3 can be optionally bound to each other to form, together with the other atoms to which they are bound, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C 1 -C 20 alkyl groups, said cycle optionally containing a heteroatom selected from the group consisting of oxygen, sulfur, nitrogen, silicon, phosphorous, and selenium;
X 1 and X 2 , the same or different, represent a halogen atom selected from the group consisting of chlorine, bromine, and iodine; or they are selected from linear or branched C 1 -C 20 alkyl groups, —OCOR 4 groups or —OR 4 groups wherein R 4 is selected from linear or branched C 1 -C 20 alkyl groups.

5. The process according to claim 1 , wherein said cobalt complex including at least one imine nitrogen is selected from bis-imine-pyridine complexes of cobalt having general formula (Ic):

wherein:
R 2 and R 3 , the same or different, represent a hydrogen atom; or they are selected from linear or branched C 1 -C 20 alkyl groups, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted;
R 1 and R 4 , different from each other, represent a hydrogen atom, or they are selected from linear or branched C 1 -C 20 alkyl groups, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted, arylalkyl groups;
or R 1 and R 2 can be optionally bound to each other to form, together with the other atoms to which they are bound, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C 1 -C 20 a

Assignees

• Versalis Spa

Inventors

• Masi Francesco
• Sommazzi Anna
• Ricci Giovanni
• Leone Giuseppe
• Coppola Salvatore

Classifications

• C08F4/7006

  NN · CPC title

• C08F4/7044

  NNO · CPC title

• C08F295/00 Primary

  Macromolecular compounds obtained by polymerisation using successively different catalyst types without deactivating the intermediate polymer · CPC title

• C08F4/7008

  NO · CPC title

• C08F4/7042

  NNN · CPC title