Retreating comminuted olefin polymerization catalyst with a titanium (IV) compound and an ester

Claim 2

A polymerization catalyst for alpha-olefins comprising (A) an organoaluminum compound and (B) a solid, titanium-containing component formed by: (1) comminuting a solid reaction product comprising: (a) at least one halogen-containing compound of titanium(IV); (b) at least one electron donor containing at least one atom of oxygen, nitrogen, sulfur, or phosphorus; and (c) at least one hydrocarbon-insoluble, magnesium-containing compound; and (2) retreating such comminuted product with (a) at least one halogen-containing compound of titanium(IV); and (b) at least one carboxylic organic acid ester.

Claim 3

The catalyst of claim 1 wherein retreatment component (2)(a) is titanium tetrachloride.

Claim 4

The catalyst of claim 1 wherein retreatment component (2)(b) is an alkyl, haloalkyl, aryl or haloaryl ester of an aliphatic or aryl organic acid.

Claim 5

The catalyst of claim 2 or 3 wherein the retreatment component (2)(b) is ethyl benzoate, ethyl anisate or methyl-p-toluate.

Claim 6

The catalyst of claim 1 wherein the solid titanium component is comminuted by ball-milling.

Claim 7

The catalyst of claim 1 wherein the magnesium-containing compound (1)(c) is a pretreatment product of components comprising (i) at least one magnesium alcoholate; and (ii) at least one Group II or Group IIIA metal alkyl.

Claim 8

The catalyst of claim 1 wherein the magnesium-containing component (1)(c) is (i) a magnesium halide or (ii) a reaction product of a magnesium halide with an organometallic compound of Groups I-III metals.

Claim 9

The catalyst of claim 1 wherein the molar ratio of electron donor (1)(b) to titanium(IV) compound (1)(a) is about 0.001:1 to about 1:1 and the atomic ratio of titanium in (1)(a) to magnesium in (1)(c) is at least about 0.5:1.

Claim 10

The catalyst of claim 1 wherein component (1)(a) comprises titanium tetrachloride.

Claim 11

The catalyst of claim 1 wherein component (1)(b) comprises a C 1 -C 6 alkyl ester of an aromatic monocarboxylic acid or of an aromatic monocarboxylic acid substituted with at least one halogen, hydroxyl, oxo, alkyl, alkoxy, aryl or aryloxy substituent.

Claim 12

The catalyst of claim 1 wherein the atomic ratio of retreatment titanium(IV) (2)(a) to titanium contained in the comminuted product is about 50:1 to about 500:1 and the ratio of moles of organic acid ester to gram-atom of titanium contained in the comminuted product is about 0.5:1 to about 10:1.

Claim 13

A polymerization catalyst for alpha-olefins comprising (A) an organoaluminum compound and (B) a solid, titanium-containing component formed by: (1) comminuting a solid reaction product comprising: (a) at least one halogen-containing compound of titanium(IV); (b) at least one electron donor containing at least one atom of oxygen, nitrogen, sulfur or phosphorus; and (c) at least one hydrocarbon-insoluble, magnesium-containing pretreatment product comprising (i) at least one magnesium alcoholate; and (ii) at least one Group II or Group IIIA metal alkyl; and (2) retreating such comminuted product with (a) at least one halogen-containing compound of titanium(IV); and (b) at least one carboxylic acid ester.

Claim 14

A polymerization catalyst for alpha-olefins comprising (A) an organoaluminum compound and (B) a solid, titanium-containing component formed by: (1) comminuting a solid reaction product comprising: (a) at least one halogen-containing compound of titanium(IV); (b) at least one electron donor containing at least one atom of oxygen, nitrogen, sulfur or phosphorus; and (c) at least one hydrocarbon-insoluble, magnesium-containing pretreatment product comprising (i) at least one magnesium alcoholate; and (ii) at least one Group II or Group IIIA metal alkyl; and (2) retreating such comminuted product with (a) at least one halogen-containing compound of titanium(IV); and (b) at least one carboxylic acid ester.

Claim 15

The catalyst of claim 12 wherein the retreatment titanium(IV) compound (2)(a) comprises titanium tetrachloride.

Claim 16

The catalyst of claim 12 wherein the retreatment organic acid ester (2)(b) is an alkyl, haloalkyl, aryl or haloaryl ester of an aliphatic or aryl organic acid.

Claim 17

The catalyst of claim 13 wherein the retreatment organic acid ester (2)(b) is ethyl benzoate, ethyl anisate or methyl-p-toluate.

Claim 18

The catalyst of claim 14 wherein the retreatment organic acid ester (2)(b) is ethyl benzoate, ethyl anisate or methyl-p-toluate.

Claim 19

The catalyst of claims 13, 14, 15 or 16 wherein the solid titanium component is comminuted by ball-milling.

Claim 20

The catalyst of claims 13, 14, 15 or 16 wherein the titanium(IV) compound (1)(a) is titanium tetrachloride.

Claim 21

The catalyst of claims 13, 14, 15 or 16 wherein the electron donor (1)(b) comprises an alkyl ester of benzoic acid or an alkyl- or halo-substituted benzoic acid wherein the alkyl radicals contain one to about six carbon atoms.

Claim 22

The catalyst of claims 13, 14, 15 or 16 wherein the electron donor (1)(b) comprises ethyl benzoate.

Claim 23

The catalyst of claims 13, 14, 15 or 16 wherein component (1)(c)(ii) comprises a compound of the formula MR 3 m wherein M is aluminum, magnesium, or zinc, each R 3 is independently an alkyl radical of 1 to about 20 carbon atoms, and m corresponds to the valence of M.

Claim 24

The catalyst of claims 13, 14, 15 or 16 wherein component (1)(c)(i) comprises a compound of the formula Mg(OR 1 ) n (OR 2 ) 2-n wherein R 1 and R 2 are identical or different hydrocarbyl radicals of 1 to about 20 carbon atoms and n ranges from 0 to 2.

Claim 25

The catalyst of claims 13, 14, 15 or 16 wherein magnesium-containing compound (1)(c) further includes at least one pretreatment modifier selected from the group consisting of mineral acids and anhydrides of sulfur, organometallic chalcogenide derivatives of hydrogen sulfide in which each hydrogen is replaced by an organosilicon, organogermanium or organotin group wherein the organic radicals are selected from the group consisting of phenyl, alkyl-substituted phenyl, phenyl-substituted alkyl and alkyl radicals, said alkyl radicals containing 1 to about 6 carbon atoms, organic acids containing 1 to about 20 carbon atoms and 1 to about 4 carboxyl groups and C 1 to about C 12 alkyl and haloalkyl and C 6 to about C 10 aryl and haloaryl esters of said organic acids.

Claim 26

The catalyst of claim 23 wherein the pretreatment modifier comprises methyl benzoate, chlorosulfonic acid or a mixture thereof.

Claim 27

The catalyst of claim 23 wherein component (1)(b) comprises an alkyl ester of benzoic acid or a halobenzoic acid, said alkyl radical containing 1 to about 6 carbon atoms.

Claim 28

The catalyst of claim 23 wherein component (1)(c)(ii) comprises a compound of the formula MR 3 m wherein M is aluminum, magnesium, or zinc, each R 3 is independently an alkyl radical of 1 to about 20 carbon atoms, and m corresponds to the valence of M.

Claim 29

The catalyst of claim 23 wherein component (1)(c)(i) comprises a compound of the formula Mg(OR 1 ) n (OR 2 ) 2-n wherein R 1 and R 2 are identical or different hydrocarbyl radicals of 1 to about 20 carbon atoms and n ranges from 0 to 2.

Claim 30

The catalyst of claim 23 wherein the pretreatment modifier comprises sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, hydrogen sulfide, benzoic acid, a C 1 to about C 6 alkyl benzoate or halobenzoate, or a mixture thereof.

Claim 31

The catalyst of claims 1 and 12 wherein the organoaluminum compound (A) comprises a trialkylaluminum containing 2 to about 12 carbon atoms per alkyl radical.

Claim 32

The catalyst of claim 29 further characterized in that said catalyst comprises at least one crystallinity promoter.

Claim 33

The catalyst of claim 30 wherein the organoaluminum compound (A) comprises triethylaluminum.

Claim 34

A propylene polymerization catalyst comprising (A) triethylaluminum, triisobutylaluminum or mixture thereof and (B) a solid, titanium-containing component formed by: (1) ball-milling the solid reaction product comprising: (a) titanium tetrachloride (b) ethylbenozate (c) a hydrocarbon-insoluble, magnesium-containing pretreatment product comprising: (i) magnesium ethoxide; (ii) triethylaluminum; (iii) chlorosulfonic acid; and (iv) methyl benzoate; and (2) retreating such ball-milled product with (a) titanium tetrachloride; and (b) ethyl benzoate, ethyl anisate or methyl-p-toluate.

Claim 35

A propylene polymerization catalyst comprising (A) triethylaluminum, triisobutylaluminum or mixture thereof and (B) a solid, titanium-containing component formed by: (1) ball-milling the solid reaction product comprising: (a) titanium tetrachloride (b) ethylbenozate (c) a hydrocarbon-insoluble, magnesium-containing pretreatment product comprising: (i) magnesium ethoxide; (ii) triethylaluminum; (iii) chlorosulfonic acid; and (iv) methyl benzoate; and (2) retreating such ball-milled product with (a) titanium tetrachloride; and (b) ethyl benzoate, ethyl anisate or methyl-p-toluate.

Claim 36

A process for preparing a catalyst component usful in polymerization of alpha-olefins comprising (A) contacting components comprising (1) at least one magnesium alcoholate, and (2) at least one Group II or IIIA metal alkyl in amounts such that the atomic ratio of metal in (2) to metal in (1) ranges from about 0.001:1 to about 1:1; (B) removing unreacted Group II or IIIA metal component from the product of (A) to form a solid, hydrocarbon-insoluble, magnesium-containing pretreatment product; (C) contacting said pretreatment product with components comprising at least one titanium(IV) halide or haloalcoholate and at least one organic electron donor containing at least one of oxygen, nitrogen, sulfur and phosphorus, in amounts such that the atomic ratio of titanium to metal in (A)(1) is at least about 0.5:1 and the ratio of organic electron donor to titanium ranges from about 0.001 to about 1 mole per gram-atom, to form a solid catalyst component; (D) comminuting the resulting product; and (E) retreating the comminuted product by contacting such product with components comprising at least one titanium(IV) halide or haloalcoholate and at least one organic acid ester in amounts such that the atomic ratio of retreatment titanium to titanium contained in the comminuted product is about 50:1 to about 500:1 and the ratio of moles of carboxylic organic acid ester to gram-atom of titanium contained in the comminuted product is about 0.5:1 to about 10:1.

Claim 37

A process for preparing a catalyst component usful in polymerization of alpha-olefins comprising (A) contacting components comprising (1) at least one magnesium alcoholate, and (2) at least one Group II or IIIA metal alkyl in amounts such that the atomic ratio of metal in (2) to metal in (1) ranges from about 0.001:1 to about 1:1; (B) removing unreacted Group II or IIIA metal component from the product of (A) to form a solid, hydrocarbon-insoluble, magnesium-containing pretreatment product; (C) contacting said pretreatment product with components comprising at least one titanium(IV) halide or haloalcoholate and at least one organic electron donor containing at least one of oxygen, nitrogen, sulfur and phosphorus, in amounts such that the atomic ratio of titanium to metal in (A)(1) is at least about 0.5:1 and the ratio of organic electron donor to titanium ranges from about 0.001 to about 1 mole per gram-atom, to form a solid catalyst component; (D) comminuting the resulting product; and (E) retreating the comminuted product by contacting such product with components comprising at least one titanium(IV) halide or haloalcoholate and at least one organic acid ester in amounts such that the atomic ratio of retreatment titanium to titanium contained in the comminuted product is about 50:1 to about 500:1 and the ratio of moles of carboxylic organic acid ester to gram-atom of titanium contained in the comminuted product is about 0.5:1 to about 10:1.

Claim 38

The process of claim 33 wherein the step of comminuting is by ball-milling.

Claim 39

The process of claim 34 wherein retreatment titanium compound is titanium tetrachloride.

Claim 40

The process of claim 35 wherein retreatment organic acid ester is ethyl benzoate, ethyl anisate or methyl-p-toluate.

Claim 41

The process of claims 35 or 36 wherein components in (A) further include at least one pretreatment modifier from the group consisting of mineral acids and anhydrides of sulfur, organometallic chalcogenide derivatives of hydrogen sulfide in which each hydrogen is replaced by an organosilicon, organogermanium or organotin group wherein the organic radicals are selected from the group consisting of phenyl, alkyl-substituted phenyl, phenyl-substituted alkyl and alkyl radicals, said alkyl radicals containing 1 to about 6 carbon atoms, organic acids containing 1 to about 20 carbon atoms and 1 to about 4 carboxyl groups and C 1 to about C 12 alkyl and haloalkyl and C 6 to about C 10 aryl and haloaryl esters of said organic acids.

Claim 42

The process of claim 37 wherein (A) is conducted in the presence of at least one alpha-olefin.

Claim 43

The process of claim 37 further characterized in that said solid catalyst component is contacted with at least one liquid Lewis acid having a high enough Lewis acidity to remove impurities from the surface of said solid.