Catalyst and method for preparation of drag reducing substances

Claim 2

An improved Ziegler/Natta catalyst for the polymerization of α-olefins containing from 2 to 30 carbon atoms, to form non-crystalline, hydrocarbon-soluble polymers said catalyst containing a titanium halide, wherein titanium has a valence less than maximum, and an organoaluminum compound, the improvement comprising modifying the catalyst by adding (1) cyclic or acyclic ketone(s) of the general formula ##STR2## wherein R 1 and R 2 are, independently, aryl, alkyl, cycloalkyl, alkaryl, and aralkyl, each containing from 1 to 20 carbon atoms, and wherein R 1 and R 2 can be joined through a covalent bond, and (2) a monoether of the formula R 3 OR 4 wherein R 3 and R 4 are, independently, aryl, alkyl, aralkyl, cycloalkyl, alkaryl, each containing from 1 to 20 carbon atoms.

Claim 3

A catalyst as described in claim 1 wherein the ether is selected from the group consisting of benzyl ether n-butyl ether tert-butyl methyl ether diethyl ether isopropyl ether n-propyl ether m-phenoxyl toluene phenyl ether anisole butyl phenyl ether 2,3-dimethylanisole 2,4-dimethylanisole 2,5-dimethylanisole 2,6-dimethylanisole 3,5-dimethyanisole 1-ethoxynaphthalene 1-methoxynaphthalene 2-methoxynaphthalene 1,4-benzodioxan 2,3-benzofuran cyclododecane epoxide cyclohexane oxide cyclooctene oxide cyclopentene oxide 2,5-dimethylfuran 2,5-dimethyltetrahydrofuran p-dioxane 1,2-epoxybutane furan 2-methylfuran 2-methyl tetrahydrofuran 3-methyl tetrahydrofuran styrene oxide tetrahydrofuran tetrahydropyran.

Claim 4

A catalyst as described in claim 1 wherein the ketone is selected from the group consisting of acetone benzylacetone 2-butanone di-n-hexyl ketone 2,6-dimethyl-4-heptanone 3,5-dimethyl-4-heptanone 2,4-dimethyl-3-pentanone 4,4-dimethyl-2-pentanone 1,1-diphenylacetone 1,3-diphenylacetone 9-heptadecanone 2-heptanone 3-heptanone 4-heptanone 2-hexanone 3-hexanone 2-methyl-3-hexanone 5-methyl-2-hexanone 3-methyl-2-pentanone 4-methyl-2-pentanone 10-nonadecanone 2-nonanone 5-nonanone 2-octanone 3-octanone 4-octanone 8-pentadecanone 2-pentanone 3-pentanone phenylacetone 1-phenyl-2-butanone 2-undecanone 6-undecanone benzophenone 4-benzyolbiphenyl 2-methylbenzophenone 4-methylbenzophenone 4-acetylbiphenyl 2-acetylfluorene 2-acetylphenanthrene 3-acetylphenanthrene 9-acetylphenanthrene deoxybenzoin hexanophenone o-methylacetophenone m-methylacetophenone p-methylacetophenone propiophenone undecanophenone valerophenone 2-adamantanone anthrone benzathrone bicyclo[3.3.1]nonan-9-one bicyclo[3.2.1]octan-2-one 4-tert-butylcyclohexanone (+)-camphor dl-camphor (-)-camphor carone carbomenthone cyclobutanone cyclodecanone cyclododecanone cycloheptanone cyclohexanone cyclononanone cyclooctanone cyclopentadecanone cyclopentanone cycloundecanone 2,5-dimethylcyclopentanone 4-ethylcyclohexanone fenchone 9-fluorenone 1-indanone 2-indanone menthone 2-methylcyclohexanone (+)-3-methylcyclohexanone 3-methylcyclohexanone (+)-3-methylcyclopentanone dl-3-methylcyclopentanone 1-methyl-2-decalone 1-methyl-2-tetralone 2-methyl-1-tetralone 4-methyl-1-tetralone norcamphor α-tetralone β-tetralone 3,3,5,5-tetramethylcyclohexanone thujone 2,2,6-trimethylcyclohexanone verbanone verbenone.

Claim 5

A catalyst as described in claim 1 comprising: (a) titanium trichloride of the general formula TiCl 3 .nAlCl 3 wherein n is from 0.00 to 0.50, which is selected from the group consisting of products produced by; (1) reducing titanium tetrachloride with aluminum, (2) reducing titanium tetrachloride with hydrogen, (3) reducing titanium tetrachloride with an organo-metallic compound, or (4) milling titanium tetrachloride with a Group III metal salt, in conjunction with (b) a saturated acyclic ketone, and/or a saturated cyclic ketone, (c) a compound selected from the group consisting of Group IA or IIA metal halides, transition metals, quanternary ammonium halide or sulfate salts, alkaline earth phosphates and alkyl alkali metal sulfates, (d) a catalyst modifier of the formula R 3 OR 4 wherein R 3 and R 4 are, independently, aryl, alkyl, aralkyl, or alkaryl containing up to 20 carbon atoms each.

Claim 6

A catalyst for the polymerization of α-olefins containing from 2 to 30 carbon atoms, comprising, (a) titanium trichloride of the general formula TiCl 3 .nAlCl 3 wherein n is from 0.00 to 0.50, which is selected from the group consisting of products produced by; (1) reducing titanium tetrachloride with aluminum, (2) reducing titanium tetrachloride with hydrogen, (3) reducing titanium tetrachloride with an organo-metallic compound, or (4) milling a titanium trichloride with the salt of a Group III metal salt in conjuction with (b) a saturated acyclic or cyclic ketone, (c) a compound selected from the group consisting of Group IA or IIA metal halides, transition metals, quaternary ammonium halide or sulfate salts, alkaline earth phosphates and alkyl alkali metal sulfates, (d) an organo-aluminum halide of the formula AlR n X 3-n where R is a hydrocarbon radical containing from 1 to 20 carbon atoms, X is hydrogen or halogen and n is 2 or 3, and (e) a catalyst modifier of the formula R 3 OR 4 wherein R 3 and R 4 are, independently, aryl, alkyl, aralkyl, cycloalkyl or alkaryl containing up to 20 carbon atoms.

Claim 7

A catalyst for the polymerization of α-olefins containing from 2 to 30 carbon atoms, comprising, (a) titanium trichloride of the general formula TiCl 3 .nAlCl 3 wherein n is from 0.00 to 0.50, which is selected from the group consisting of products produced by; (1) reducing titanium tetrachloride with aluminum, (2) reducing titanium tetrachloride with hydrogen, (3) reducing titanium tetrachloride with an organo-metallic compound, or (4) milling a titanium trichloride with the salt of a Group III metal salt in conjuction with (b) a saturated acyclic or cyclic ketone, (c) a compound selected from the group consisting of Group IA or IIA metal halides, transition metals, quaternary ammonium halide or sulfate salts, alkaline earth phosphates and alkyl alkali metal sulfates, (d) an organo-aluminum halide of the formula AlR n X 3-n where R is a hydrocarbon radical containing from 1 to 20 carbon atoms, X is hydrogen or halogen and n is 2 or 3, and (e) a catalyst modifier of the formula R 3 OR 4 wherein R 3 and R 4 are, independently, aryl, alkyl, aralkyl, cycloalkyl or alkaryl containing up to 20 carbon atoms.

Claim 8

A catalyst as described in claim 5 wherein the TiCl 3 contains 0.33AlCl 3 , the ketone is camphor, the ionic compound is sodium bromide, and the catalyst modifier is dibutyl ether.

Claim 9

A catalyst as described in claim 6 wherein (a) comprises TiCl 3 (b) ketone is present at from 2.5 to 10% by weight and (c) is present up to 1% by weight, all based on the weight of (a).

Claim 10

A catalyst as described in claim 7 wherein the aluminum/ether/titanium ratio ranges from 1/0.01/1 to 15/5/5, respectively.

Claim 11

A catalyst as described in claim 8 wherein the ether-to-aluminum ratio is from 0.01 to 1.0.

Claim 12

A catalyst as described in claim 9 wherein the aluminum/ether/titanium ratio is 3/0.5/1.0, respectively.

Claim 13

A catalyst as described in claim 10 wherein (a) has the formula TiCl 3 0.33AlCl 3 .

Claim 14

A catalyst as described in claim 11 wherein the polar compound is a Group IA or IIA metal halide.

Claim 15

A catalyst as described in claim 12 wherein the ether is dibutylether.