US4429085A — Microencapsulated aqueous polymerization catalyst

Claim 1

Independent Claim 149 words

A process for producing polybutadiene composed essentially of syndiotactic 1,2-polybutadiene in an aqueous medium comprising polymerizing 1,3-butadiene in said aqueous medium in the presence of (1) a catalyst composition which contains (a) at least one cobalt compound selected from the group consisting of (i) β-diketone complexes of cobalt, (ii) β-keto acid ester complexes of cobalt, (iii) cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms, and (iv) complexes of halogenated cobalt compounds of the formula CoX n , wherein X represents a halogen atom and n represents 2 or 3, with an organic compound selected from the group consisting of tertiary amine alcohols, tertiary phosphines, ketones and N,N-dialkylamides, and (b) at least one organoaluminum compound of the formula AlR 3 wherein R represents a hydrocarbon radical of 1 to 6 carbon atoms, wherein said catalyst composition is microencapsulated in a polyene product; and (2) carbon disulfide.

Claim 2

Dependent Claim 149 words

A process for producing polybutadiene composed essentially of syndiotactic 1,2-polybutadiene in an aqueous medium comprising polymerizing 1,3-butadiene in said aqueous medium in the presence of (1) a catalyst composition which contains (a) at least one cobalt compound selected from the group consisting of (i) β-diketone complexes of cobalt, (ii) β-keto acid ester complexes of cobalt, (iii) cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms, and (iv) complexes of halogenated cobalt compounds of the formula CoX n , wherein X represents a halogen atom and n represents 2 or 3, with an organic compound selected from the group consisting of tertiary amine alcohols, tertiary phosphines, ketones and N,N-dialkylamides, and (b) at least one organoaluminum compound of the formula AlR 3 wherein R represents a hydrocarbon radical of 1 to 6 carbon atoms, wherein said catalyst composition is microencapsulated in a polyene product; and (2) carbon disulfide.

Claim 3

Dependent Claim 153 words

A process for producing polybutadiene composed essentially of syndiotactic 1,2-polybutadiene in an aqueous medium comprising polymerizing 1,3-butadiene in said aqueous medium in the presence of (1) a catalyst component solution which is prepared by dissolving in an inert organic solvent containing at least one polyene (a) at least one cobalt compound selected from the group consisting of (i) β-diketone complexes of cobalt, (ii) β-keto acid ester complexes of cobalt, (iii) cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms, and (iv) complexes of halogenated cobalt compounds of the formula CoX n , wherein X represents a halogen atom and n represents 2 or 3, with an organic compound selected from the group consisting of tertiary amine alcohols, tertiary phosphines, ketones and N,N-dialkylamides, and (b) at least one organoaluminum compound of the formula AlR 3 wherein R represents a hydrocarbon radical of 1 to 6 carbon atoms; and (2) carbon disulfide.

Claim 4

Dependent Claim 153 words

A process for producing polybutadiene composed essentially of syndiotactic 1,2-polybutadiene in an aqueous medium comprising polymerizing 1,3-butadiene in said aqueous medium in the presence of (1) a catalyst component solution which is prepared by dissolving in an inert organic solvent containing at least one polyene (a) at least one cobalt compound selected from the group consisting of (i) β-diketone complexes of cobalt, (ii) β-keto acid ester complexes of cobalt, (iii) cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms, and (iv) complexes of halogenated cobalt compounds of the formula CoX n , wherein X represents a halogen atom and n represents 2 or 3, with an organic compound selected from the group consisting of tertiary amine alcohols, tertiary phosphines, ketones and N,N-dialkylamides, and (b) at least one organoaluminum compound of the formula AlR 3 wherein R represents a hydrocarbon radical of 1 to 6 carbon atoms; and (2) carbon disulfide.

Claim 5

Dependent Claim 157 words

A process for producing polybutadiene composed essentially of syndiotactic 1,2-polybutadiene in an aqueous medium comprising polymerizing 1,3-butadiene in said aqueous medium, distributing throughout said aqueous medium containing 1,3-butadiene, a catalyst composition which contains (a) at least one cobalt compound selected from the group consisting of (i) β-diketone complexes of cobalt, (ii) β-keto acid ester complexes of cobalt, (iii) cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms, and (iv) complexes of halogenated cobalt compounds of the formula CoX n , wherein X represents a halogen atom and n represents 2 or 3, with an organic compound selected from the group consisting of tertiary amine alcohols, tertiary phosphines, ketones and N,N-dialkylamides, and (b) at least one organoaluminum compound of the formula AlR 3 wherein R represents a hydrocarbon radical of 1 to 6 carbon atoms wherein said catalyst composition is microencapsulated in a polyene product; followed by the distribution of carbon disulfide throughout said medium.

Claim 6

Dependent Claim 157 words

A process for producing polybutadiene composed essentially of syndiotactic 1,2-polybutadiene in an aqueous medium comprising polymerizing 1,3-butadiene in said aqueous medium, distributing throughout said aqueous medium containing 1,3-butadiene, a catalyst composition which contains (a) at least one cobalt compound selected from the group consisting of (i) β-diketone complexes of cobalt, (ii) β-keto acid ester complexes of cobalt, (iii) cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms, and (iv) complexes of halogenated cobalt compounds of the formula CoX n , wherein X represents a halogen atom and n represents 2 or 3, with an organic compound selected from the group consisting of tertiary amine alcohols, tertiary phosphines, ketones and N,N-dialkylamides, and (b) at least one organoaluminum compound of the formula AlR 3 wherein R represents a hydrocarbon radical of 1 to 6 carbon atoms wherein said catalyst composition is microencapsulated in a polyene product; followed by the distribution of carbon disulfide throughout said medium.

Claim 7

Dependent Claim 163 words

A process for producing polybutadiene composed essentially of syndiotactic 1,2-polybutadiene in an aqueous medium comprising polymerizing 1,3-butadiene in said aqueous medium by distributing throughout said aqueous medium containing said 1,3-butadiene, a catalyst component solution which is prepared by dissolving in an inert organic solvent containing at least one polyene (a) at least one cobalt compound selected from the group consisting of (i) β-diketone complexes of cobalt, (ii) β-keto acid ester complexes of cobalt, (iii) cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms, and (iv) complexes of halogenated cobalt compounds of the formula CoX n , wherein X represents a halogen atom and n represents 2 or 3, with an organic compound selected from the group consisting of tertiary amine alcohols, tertiary phosphines, ketones and N,N-dialkylamides, and (b) at least one organoaluminum compound of the formula AlR 3 wherein R represents a hydrocarbon radical of 1 to 6 carbon atoms; followed by the distribution of carbon disulfide throughout said medium.

Claim 8

Dependent Claim 163 words

A process for producing polybutadiene composed essentially of syndiotactic 1,2-polybutadiene in an aqueous medium comprising polymerizing 1,3-butadiene in said aqueous medium by distributing throughout said aqueous medium containing said 1,3-butadiene, a catalyst component solution which is prepared by dissolving in an inert organic solvent containing at least one polyene (a) at least one cobalt compound selected from the group consisting of (i) β-diketone complexes of cobalt, (ii) β-keto acid ester complexes of cobalt, (iii) cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms, and (iv) complexes of halogenated cobalt compounds of the formula CoX n , wherein X represents a halogen atom and n represents 2 or 3, with an organic compound selected from the group consisting of tertiary amine alcohols, tertiary phosphines, ketones and N,N-dialkylamides, and (b) at least one organoaluminum compound of the formula AlR 3 wherein R represents a hydrocarbon radical of 1 to 6 carbon atoms; followed by the distribution of carbon disulfide throughout said medium.

Claim 9

Dependent Claim 183 words

A process for producing polybutadiene composed essentially of syndiotactic 1,2-polybutadiene, comprising the steps of: (A) preparing a catalyst component solution by dissolving, in an inert organic solvent containing 1,3-butadiene, (a) at least one cobalt compound selected from the group consisting of (i) β-diketone complexes of cobalt, (ii) β-keto acid ester complexes of cobalt, (iii) cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms, and (iv) complexes of halogenated cobalt compounds of the formula CoX n , wherein X represents a halogen atom and n represents 2 or 3, with an organic compound selected from the group consisting of tertiary amine alcohols, tertiary phosphines, ketones and N,N-dialkylamides, and (b) at least one organoaluminum compound of the formula AlR 3 wherein R represents a hydrocarbon radical of 1 to 6 carbon atoms; (B) preparing a reaction mixture by mixing said catalyst component solution with a 1,3-butadiene/water mixture containing desired amounts of said 1,3-butadiene; (C) preparing a polymerization mixture by mixing carbon disulfide throughout said reaction mixture; and (D) polymerizing said 1,3-butadiene in said polymerization mixture into polybutadiene while agitating said polymerization mixture.

Claim 10

Dependent Claim 183 words

A process for producing polybutadiene composed essentially of syndiotactic 1,2-polybutadiene, comprising the steps of: (A) preparing a catalyst component solution by dissolving, in an inert organic solvent containing 1,3-butadiene, (a) at least one cobalt compound selected from the group consisting of (i) β-diketone complexes of cobalt, (ii) β-keto acid ester complexes of cobalt, (iii) cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms, and (iv) complexes of halogenated cobalt compounds of the formula CoX n , wherein X represents a halogen atom and n represents 2 or 3, with an organic compound selected from the group consisting of tertiary amine alcohols, tertiary phosphines, ketones and N,N-dialkylamides, and (b) at least one organoaluminum compound of the formula AlR 3 wherein R represents a hydrocarbon radical of 1 to 6 carbon atoms; (B) preparing a reaction mixture by mixing said catalyst component solution with a 1,3-butadiene/water mixture containing desired amounts of said 1,3-butadiene; (C) preparing a polymerization mixture by mixing carbon disulfide throughout said reaction mixture; and (D) polymerizing said 1,3-butadiene in said polymerization mixture into polybutadiene while agitating said polymerization mixture.

Claim 11

Dependent Claim 29 words

A process as specified in claim 5 wherein the process of polymerizing said 1,3-butadiene is carried out at a temperature of from about -20° C. to about 90° C.

Claim 12

Dependent Claim 27 words

A process as specified in claim 6 wherein the process of polymerizing said 1,3-butadiene is carried out at a temperature of from 0° C. to 40° C.

Claim 13

Dependent Claim 24 words

A process as specified in claim 7 wherein the process of polymerizing said 1,3-butadiene is carried out at a temperature of about 10° C.

Claim 14

Dependent Claim 38 words

A process as specified in claim 5 wherein said inert organic solvent is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, halogenated aromatic hydrocarbons, and mixtures of two or more of the above-mentioned compounds.

Claim 15

Dependent Claim 45 words

A process as specified in claim 5 wherein said catalyst component solution is prepared by first dissolving said cobalt compound into said inert organic solvent containing 1,3-butadiene and secondly, dissolving said organoaluminum compound into said inert organic solvent containing said 1,3-butadiene and said cobalt compound.

Claim 16

Dependent Claim 48 words

A process as specified in claim 5 wherein said catalyst component solution contains 0.0005 to 1.0% by mole of said cobalt compound and 0.001 to 10% by mole of said organoaluminum compound, based on the amount by mole of said 1,3-butadiene to be polymerized in said polymerization mixture.

Claim 17

Dependent Claim 48 words

A process as specified in claim 11 wherein said catalyst component solution contains 0.001 to 0.5% by mole of said cobalt compound and 0.03 to 5% by mole of said organoaluminum compound, based on the amount by mole of said 1,3-butadiene to be polymerized in said polymerization mixture.

Claim 18

Dependent Claim 36 words

A process as specified in claim 5 wherein said polymerization mixture contains from 0.005 to 2 mole percent carbon disulfide, based on the amount by mole of said 1,3-butadiene to be polymerized in said polymerization mixture.

Claim 19

Dependent Claim 36 words

A process as specified in claim 13 wherein said polymerization mixture contains from 0.001 to 1 mole percent carbon disulfide, based on the amount by mole of said 1,3-butadiene to be polymerized in said polymerization mixture.

Claim 20

Dependent Claim 22 words

A process as specified in claim 5 wherein said catalyst component solution is prepared at a temperature of 10° to 50° C.

Claim 21

Dependent Claim 27 words

A process as specified in claim 5 wherein the ratio by mole of said 1,3-butadiene to said cobalt compound in the catalyst component solution is about 25.

Claim 22

Dependent Claim 28 words

A process as specified in claim 16 wherein the ratio by mole of said 1,3-butadiene to said cobalt compound in the catalyst component solution is at least 5.

Claim 23

Dependent Claim 31 words

A process as specified in claim 5 wherein the ratio by mole of the amount of said organoaluminum compound to said cobalt compound is in the range from 0.5 to 50.

Claim 24

Dependent Claim 28 words

A process as specified in claim 18 wherein said ratio by mole of the amount of said organoaluminum compound to said cobalt compound is from 2 to 10.

Claim 25

Dependent Claim 21 words

A process as specified in claim 5 wherein the 1,3-butadiene/water mixture contains from about 2% of about 50% 1,3-butadiene by weight.

Claim 26

Dependent Claim 19 words

A process as specified in claim 20 wherein the 1,3-butadiene/water mixture contains from 15% to 35% 1,3-butadiene by weight.

Claim 27

Dependent Claim 19 words

A process as specified in claim 21 wherein the 1,3-butadiene/water mixture contains about 20% to 25% 1,3-butadiene by weight.

Claim 28

Dependent Claim 28 words

A process as specified in claim 5 wherein said inert organic solvent contains at most 500 ppm of water based on the weight of said inert organic solvent.

Claim 29

Dependent Claim 26 words

A process as specified in claim 23 wherein said amount of water is at most 200 ppm based on the weight of said inert organic solvent.

Claim 30

Dependent Claim 29 words

A process as specified in claim 5 wherein said β-diketone complex of cobalt is a member selected from the group consisting of cobalt (II) acetylacetone and cobalt (III) acetylacetonate.

Claim 31

Dependent Claim 80 words

A process specified in claim 5 wherein said β-diketone complex of cobalt has a diketone group of the formula: ##STR3## wherein R 1 and R 4 , which are the same as or different from one another, are each an alkyl radical of 1 to 6 carbon atoms and R 2 and R 3 , which are the same as or different from one another, are each a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms.

Claim 32

Dependent Claim 43 words

A process as specified in claim 5, wherein said β-keto acid ester complex of cobalt has a β-keto acid ester group of the formula: ##STR4## wherein R 1 , R 2 , R 3 and R 4 are the same as defined above.

Claim 33

Dependent Claim 22 words

A process as specified in claim 5 wherein said β-keto acid ester complex of cobalt is a cobalt-acetoacetic acid ethyl ester complex.

Claim 34

Dependent Claim 18 words

A process as specified in claim 5 wherein said cobalt salt is either cobalt octoate or cobalt napthenate.

Claim 35

Dependent Claim 23 words

A process as specified in claim 5 wherein said organoaluminum compound is selected from the group consisting of trimethylaluminum, triethylaluminum, tributylaluminum and triphenylaluminum.

Claim 36

Dependent Claim 32 words

A process as specified in claim 1 or 3 wherein said polyene product is a product of at least one polyene selected from the group consisting of butadiene, 1,3-pentadiene, isoprene, and myrcene.

Claim 37

Dependent Claim 24 words

A process as specified in claim 2 or 4 wherein said polyene is selected from the group consisting of butadiene, 1,3-pentadiene, isoprene and myrcene.

Claim 38

Dependent Claim 20 words

A process as specified in claim 1 or 3 wherein said polyene product is a product of a conjugated polyene.

Claim 39

Dependent Claim 16 words

A process as specified in claim 2 or 4 wherein said polyene is a conjugated polyene.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1987-01-30	1987-08-01	1988-01-31	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1991-01-30	1991-08-01	1992-01-31	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1995-01-30	1995-08-01	1996-01-31	$7700.00	Window Closed / Lapsed

Microencapsulated aqueous polymerization catalyst

Abstract

Inventors

Bibliographic Details

Claims Analysis

References Cited (Backward Citations)

USPTO Annuity & Maintenance Windows

Assigned Categories & Tags

Assign Category Tag