High activity catalyst for the polymerization of alpha-olefins

Claim 2

An alpha-olefin polymerization catalyst comprising (A) an organometallic promoter selected from the group consisting of Group IA, IIA, IIB, IIIA, and IVA metal alkyls, hydrides, alkylhydrides, and alkylhalides; and (B) a solid, hydrocarbon insoluble component which is the reaction product of components comprising (1) at least one compound of a Group IVB, VB or VIB metal, (2) at least one divalent metal salt of a phosphorus acid ester, said salt containing the structure ##STR2## wherein M is a divalent Group IIA, IIB, IVA, VIIB, or VIII metal, each Y is independently oxygen or sulfur, A is hydrogen, --YH, R, or --YR, and each R is independently an organic radical or a halo- or amino-substituted organic radical, said organic radical being an alkyl radical of 1 to about 12 carbon atoms, an aryl radical of 6 to about 10 carbon atoms, or an alkaryl or aralkyl radical of 7 to about 12 carbon atoms, and (3) at least one alkylaluminum halide, wherein the atomic ratio of metal contained in (1) to metal contained in (2) ranges from about 0.05:1 to about 10:1 and the amount of (3) employed is at least effective to halide the metal contained in (1) and (2); said reaction being carried out under substantially anhydrous conditions.

Claim 3

The catalyst of claim 1 wherein the at least one compound of a Group IVB, VB, or VIB metal comprises a halide, oxohalide, alkoxide, oxoalkoxide, alkoxyhalide or oxoalkoxyhalide of titanium(IV), zirconium(IV), or vanadium(III), (IV), or (V).

Claim 4

The catalyst of claim 2 wherein the organometallic promoter is a Group IIIA metal alkyl or dialkylhydride having 1 to about 20 carbon atoms per alkyl radical.

Claim 5

The catalyst of claim 3 wherein (2) comprises a compound of the formula ##STR3## wherein M is magnesium, manganese(II) or iron(II).

Claim 6

The catalyst of claim 4 wherein the at least one compound of a Group IVB, VB, or VIB metal comprises a titanium(IV) chloride, bromide, alkoxide, alkoxychloride, or alkoxybromide having 1 to about 10 carbon atoms per alkoxy radical; a zirconium(IV) chloride, bromide, alkoxide, alkoxychloride or alkoxybromide having 1 to about 10 carbon atoms per alkoxy radical; a vanadium(III) or (IV) chloride, bromide, alkoxide, alkoxychloride or alkoxybromide having 1 to about 10 carbon atoms per alkoxy radical; a vanadium(IV) or (V) oxochloride, oxobromide, oxoalkoxide, oxoalkoxychloride, or oxoalkoxybromide having 1 to about 10 carbon atoms per alkoxy radical; or a mixture thereof.

Claim 7

The catalyst of claim 5 wherein each organic radical in the formula ##STR4## is independently an alkyl radical of 1 to about 6 carbon atoms.

Claim 8

The catalyst of claim 6 wherein the phosphorus acid ester salt is the reaction product of an anhydrous, divalent metal salt of an alkanoic acid of 2 to about 6 carbon atoms with a phosphorus acid ester of the formula Y═P(YR) 2 A wherein each Y is independently oxygen or sulfur, A is hydrogen, --YH, R, or --YR, and each R is an alkyl group of 1 to about 6 carbon atoms; the anhydrous, divalent metal salt and phosphorus acid ester being employed in amounts such that the equivalent ratio of phosphorus acid ester to metal-carboxylate bonds in the anhydrous divalent metal salt ranges from about 1:1 to about 10:1, said reaction being carried out at a temperature ranging from about 0° to about 150° C.

Claim 9

The catalyst of claim 6 wherein the alkylaluminum halide is an alkylaluminum dichloride wherein the alkyl radical contains 1 to about 6 carbon atoms.

Claim 10

The catalyst of claim 8 wherein the phosphorus acid ester salt is an alkyl phosphite, mono- or dialkyl orthophosphate, or alkyl alkylphosphonate salt containing 1 to about 6 carbon atoms per alkyl radical.

Claim 11

The catalyst of claim 9 wherein the phosphorus acid ester salt is the reaction product of an anhydrous, divalent metal acetate with a dialkyl phosphite, di- or trialkyl orthophosphate, or dialkyl alkylphosphonate having 1 to about 5 carbon atoms per alkyl radical in amounts such that the equivalent ratio of phosphorus acid ester to metal-acetate bonds in the metal acetate ranges from about 1.1:1 to about 6:1, said reaction being carried out at a temperature ranging from that which is effective to distill organic acid ester by-products to about 150° C.

Claim 12

The catalyst of claim 9 wherein the at least one compound of a Group IVB, VB, or VIB metal comprises a titanium(IV) compound selected from the group consisting of titanium tetrachloride, tetraalkoxides, and alkoxychlorides having 1 to about 6 carbon atoms per alkoxy radical, or a mixture of said titanium(IV) compound with a zirconium(IV) compound selected from the group consisting of zirconium tetrachloride, tetraalkoxides, or alkoxychlorides having 1 to about 6 carbon atoms per alkoxy radical.

Claim 13

The catalyst of claim 11 wherein the phosphorus acid ester salt is a bis(dialkyl orthophosphate) salt wherein each alkyl radical contains 1 to about 6 carbon atoms.

Claim 14

The catalyst of claim 12 wherein the at least one compound of a Group IVB, VB, or VIB metal is a titanium tetraalkoxide.

Claim 15

The catalyst of claim 13 wherein the alkylaluminum dichloride is ethylaluminum dichloride.

Claim 16

The catalyst of claim 14 wherein the divalent metal salt of a phosphorus acid ester is magnesium bis(diethyl orthophosphate).

Claim 17

The catalyst of claim 15 wherein the magnesium bis(diethyl orthophosphate) is prepared by reacting anhydrous magnesium acetate with triethyl orthophosphate at about 70° to about 150° C. in amounts such that the equivalent ratio of triethyl orthophosphate to metalacetate bonds ranges from about 1.1:1 to about 3:1.

Claim 18

The catalyst of claim 15 wherein the organometallic promoter is a trialkylaluminum having 1 to about 6 carbon atoms per alkyl radical.

Claim 19

The catalyst of claim 15 wherein the titanium tetraalkoxide is titanium tetrabutoxide.

Claim 20

The catalyst of claim 18 wherein the trialkylaluminum is triethylaluminum.

Claim 21

The catalyst of claim 12 wherein the at least one compound of a Group IVB, VB, or VIB metal is a mixture of a titanium tetraalkoxide having 1 to about 6 carbon atoms per alkoxy radical and a zirconium tetraalkoxide having 1 to about 6 carbon atoms per alkoxy radical.

Claim 22

The catalyst of claim 20 wherein the alkylaluminum dichloride is ethylaluminum dichloride.

Claim 23

The catalyst of claim 21 wherein the divalent metal salt of a phosphorus acid ester is magnesium bis(diethyl orthophosphate).

Claim 24

The catalyst of claim 22 wherein the magnesium bis(diethyl orthophosphate) is prepared by reacting anhydrous magnesium acetate with triethyl orthophosphate at about 70° to about 150° C. in amounts such that the equivalent ratio of triethyl orthophosphate to metal-acetate bonds ranges from about 1.1:1 to about 3:1.

Claim 25

The catalyst of claim 22 wherein the organometallic promoter is a trialkylaluminum having 1 to about 6 carbon atoms per alkyl radical.

Claim 26

The catalyst of claim 24 wherein the titanium tetraalkoxide is titanium tetrabutoxide, the zirconium tetraalkoxide is zirconium tetrabutoxide, and the atomic ratio of zirconium to titanium ranges from about 0.1:1 to about 10:1.

Claim 27

The catalyst of claim 25 wherein the trialkylaluminum is triethylaluminum.

Claim 28

The catalyst of claim 1 wherein the solid, hydrocarbon insoluble component, (B), is contacted with an agent capable of temporarily and reversibly deactivating said component.

Claim 29

The catalyst of claim 27 wherein the agent is ethanol.

Claim 30

An alpha-olefin polymerization catalyst comprising (A) an organometallic promoter selected from the group consisting of Group IA, IIA, IIB, IIIA, and IVA metal alkyls, hydrides, alkylhydrides, and alkylhalides; and (B) and solid, hydrocarbon insoluble component which is the reaction product of components comprising (1) at least one compound of a Group IVB, VB, or VIB metal, (2) at least one divalent metal salt of a phosphorus acid ester prepared by reacting (a) at least one divalent Group IIA, IIB, IVA, VIIB, or VIII metal salt of an organic acid with (b) at least one phosphorus acid ester of the formula Y═P(YR).sub.2 A wherein each Y is independently oxygen or sulfur, A is hydrogen, --YH, --YR, or R, and each is R is independently an organic radical or an amino- or halo-substituted organic radical, said organic radical being an alkyl radical of 1 to about 12 carbon atoms, an aryl radical of 6 to about 10 carbon atoms or an alkaryl or aralkyl radical of 7 to about 12 carbon atoms, wherein said components (a) and (b) are reacted in amounts such that a phosphorus acid ester salt having at least one phosphorus acid ester group bonded to metal through oxygen or sulfur is produced and the reaction temperature is such that said components (a) and (b) will react without substantial decomposition of (b); and (3) at least one alkylaluminum halide; wherein the atomic ratio of metal contained in (1) to metal contained in (2) ranges from about 0.05:1 to about 10:1 and the amount of (3) employed is at least effective to halide the metal contained in (1) and (2); said reaction being carried out under substantially anhydrous conditions.

Claim 31

An alpha-olefin polymerization catalyst comprising (A) an organometallic promoter selected from the group consisting of Group IA, IIA, IIB, IIIA, and IVA metal alkyls, hydrides, alkylhydrides, and alkylhalides; and (B) and solid, hydrocarbon insoluble component which is the reaction product of components comprising (1) at least one compound of a Group IVB, VB, or VIB metal, (2) at least one divalent metal salt of a phosphorus acid ester prepared by reacting (a) at least one divalent Group IIA, IIB, IVA, VIIB, or VIII metal salt of an organic acid with (b) at least one phosphorus acid ester of the formula Y═P(YR).sub.2 A wherein each Y is independently oxygen or sulfur, A is hydrogen, --YH, --YR, or R, and each is R is independently an organic radical or an amino- or halo-substituted organic radical, said organic radical being an alkyl radical of 1 to about 12 carbon atoms, an aryl radical of 6 to about 10 carbon atoms or an alkaryl or aralkyl radical of 7 to about 12 carbon atoms, wherein said components (a) and (b) are reacted in amounts such that a phosphorus acid ester salt having at least one phosphorus acid ester group bonded to metal through oxygen or sulfur is produced and the reaction temperature is such that said components (a) and (b) will react without substantial decomposition of (b); and (3) at least one alkylaluminum halide; wherein the atomic ratio of metal contained in (1) to metal contained in (2) ranges from about 0.05:1 to about 10:1 and the amount of (3) employed is at least effective to halide the metal contained in (1) and (2); said reaction being carried out under substantially anhydrous conditions.

Claim 32

The catalyst of claim 29 wherein (1) comprises a halide, oxohalide, alkoxide, oxoalkoxide, alkoxyhalide, or oxoalkoxyhalide of titanium(IV), zirconium(IV), or vanadium(III), (IV) or (V).

Claim 33

The catalyst of claim 30 wherein the organometallic promoter is a Group IIIA metal alkyl or dialkylhydride having 1 to about 20 carbon atoms per alkyl radical.

Claim 34

The catalyst of claim 31 wherein (2) (a) comprises a divalent metal salt of an organic acid selected from the group consisting of aliphatic acids of 2 to about 20 carbon atoms, aromatic acids of 7 to about 12 carbon atoms, and aliphatically-substituted aromatic acids and aromatically-substituted aliphatic acids of 8 to about 20 carbon atoms.

Claim 35

The catalyst of claim 31 wherein (2) (a) comprises a salt of divalent magnesium, manganese, or iron and each R in the formula Y═P(YR) 2 A is independently an alkyl radical of 1 to about 6 carbon atoms.

Claim 36

The catalyst of claim 33 wherein (2) (a) comprises a salt of an alkanoic acid of 2 to about 6 carbon atoms.

Claim 37

The catalyst of claim 34 wherein the equivalent ratio of (2) (b) to (2) (a) ranges from about 1:1 to about 10:1 and the reaction temperature ranges from about 0° to about 150° C.

Claim 38

The catalyst of claim 35 wherein (3) comprises an alkylaluminum dichloride wherein the alkyl radical contains 1 to about 6 carbon atoms.

Claim 39

The catalyst of claim 36 wherein each Y in the formula Y═P(YR) 2 A is oxygen.

Claim 40

The catalyst of claim 37 wherein (2) (a) is a metal acetate and (2) (b) comprises a trialklyl orthophosphate having 1 to about 6 carbon atoms per alkyl radical.

Claim 41

The catalyst of claim 38 wherein (1) is a titanium(IV) compound selected from the group consisting of titanium tetrachloride, tetraalkoxides, and alkoxychlorides having 1 to about 6 carbon atoms per alkoxy radical, or a mixture of said titanium(VI) compound with a zirconium(IV) compound selected from the group consisting of zirconium tetrachloride, tetraalkoxides, and alkoxychlorides having 1 to about 6 carbon atoms per alkoxy radical.

Claim 42

The catalyst of claim 39 wherein (3) is ethylaluminum dichloride.

Claim 43

The catalyst of claim 40 wherein (2) (a) is magnesium acetate and (2) (b) is triethyl orthophosphate.

Claim 44

The catalyst of claim 41 wherein (1) is titanium tetrabutoxide.

Claim 45

The catalyst of claim 41 wherein (1) is a mixture of titanium tetrabutoxide and zirconium tetrabutoxide.

Claim 46

The catalyst of claim 41 wherein the organometallic promoter is triethylaluminum or triisobutylaluminum.

Claim 47

The catalyst of claim 29 wherein the solid, hydrocarbon soluble component, (B), is contacted with an agent capable of temporarily and reversibly deactivating said component.