US4367321A — Preparation of homopolymers and copolymers of α-m…

Claim 1

Independent Claim 504 words

A process for the preparation of homopolymers and copolymers of C 2 -C 6 -α-monoolefins by polymerizing the monomer or monomers at from 30° to 200° C., under a pressure of from 0.1 to 200 bar, by means of a Ziegler catalyst system comprising (1) a titanium-containing catalyst component and (2) an aluminum compound of the formula AlA.sub.3-n X.sub.n where A is a C 1 -C 18 -hydrocarbon radical, X is chlorine, bromine or hydrogen, and n is from 0 to 2, with the provisos that the atomic ratio of titanium from catalyst component (1) to aluminum from catalyst component (2) is from 1:0.1 to 1:500, and that (1.1) to prepare the catalyst component (1) (1.1.1) a titanium compound (I) of the formula TiCl.sub.3.z(AlCl.sub.3) or Cl.sub.m Ti(OB).sub.4-m where z is from 0 to 0.5, m is from 0 to 3, and B is C 1 -C 18 -alkyl, and (1.1.2) a magnesium alcoholate (II) of the formula Mg(OD).sub.2 where D is a monovalent C 1 -C 18 saturated-aliphatic and/or aromatic hydrocarbon radical, (1.1.3) with or without a metal chloride (III) of the formula AlCl 3 , ZnCl 2 or MnCl 2 , in the weight ratio of titanium compound (I) to magnesium alcoholate (II) of from 1:200 to 1:0.2, and in the weight ratio of titanium compound (I) to metal chloride (III) of from 1:0 to 1:20, are milled with one another for from 1 to 200 hours, under a milling acceleration of from 30 to 70 m/s 2 , to form a milled product (IV), in which process, when preparing the catalyst component (1) (1.2) in an additional stage (1.2.1) the milled product (IV) obtained according to (1.1), (1.2.2) a C 1 -C 12 -alkanol (V), and (1.2.3) a C 5 -C 12 -alkane (VI) are brought together in the weight ratios of milled product (IV):alkanol (V)=from 1:0.01 to 1:1, and milled product (IV):alkane (VI)=from 1:1 to 1:1,000, to form a suspension (VII), and the batch is kept, with continuous mixing, at from 0° to 195° C., for a period of from 0.5 to 60 minutes, after which (1.3) in a further additional stage (1.3.1) there is added, to the suspension (VII) obtained according to (1.2), (1.3.2) a metal compound (VIII) of the general formula MtG.sub.s-t E.sub.t where Mt is aluminum, silicon or titanium, G is a C 1 -C 12 -hydrocarbon radical, E is chlorine, bromine, hydrogen or --OR, R is a C 1 -C 12 -hydrocarbon radical, s is the maximum valency of the metal Mt and t is (a) from 0 to s-1 if Mt is aluminum, (b) from 0 to 4 if Mt is silicon, and (c) 4 if Mt is titanium, whilst maintaining a suspension state, addition being continued until the atomic ratio of magnesium from the solid contained in suspension (VII) to metal from the metal compound (VIII) is from 1:0.1 to 1:20, the product (IX), which results from stage (1.3) and is present as a solid phase in the suspension, constituting the titanium-containing catalyst component (1).

Claim 2

Dependent Claim 504 words

A process for the preparation of homopolymers and copolymers of C 2 -C 6 -α-monoolefins by polymerizing the monomer or monomers at from 30° to 200° C., under a pressure of from 0.1 to 200 bar, by means of a Ziegler catalyst system comprising (1) a titanium-containing catalyst component and (2) an aluminum compound of the formula AlA.sub.3-n X.sub.n where A is a C 1 -C 18 -hydrocarbon radical, X is chlorine, bromine or hydrogen, and n is from 0 to 2, with the provisos that the atomic ratio of titanium from catalyst component (1) to aluminum from catalyst component (2) is from 1:0.1 to 1:500, and that (1.1) to prepare the catalyst component (1) (1.1.1) a titanium compound (I) of the formula TiCl.sub.3.z(AlCl.sub.3) or Cl.sub.m Ti(OB).sub.4-m where z is from 0 to 0.5, m is from 0 to 3, and B is C 1 -C 18 -alkyl, and (1.1.2) a magnesium alcoholate (II) of the formula Mg(OD).sub.2 where D is a monovalent C 1 -C 18 saturated-aliphatic and/or aromatic hydrocarbon radical, (1.1.3) with or without a metal chloride (III) of the formula AlCl 3 , ZnCl 2 or MnCl 2 , in the weight ratio of titanium compound (I) to magnesium alcoholate (II) of from 1:200 to 1:0.2, and in the weight ratio of titanium compound (I) to metal chloride (III) of from 1:0 to 1:20, are milled with one another for from 1 to 200 hours, under a milling acceleration of from 30 to 70 m/s 2 , to form a milled product (IV), in which process, when preparing the catalyst component (1) (1.2) in an additional stage (1.2.1) the milled product (IV) obtained according to (1.1), (1.2.2) a C 1 -C 12 -alkanol (V), and (1.2.3) a C 5 -C 12 -alkane (VI) are brought together in the weight ratios of milled product (IV):alkanol (V)=from 1:0.01 to 1:1, and milled product (IV):alkane (VI)=from 1:1 to 1:1,000, to form a suspension (VII), and the batch is kept, with continuous mixing, at from 0° to 195° C., for a period of from 0.5 to 60 minutes, after which (1.3) in a further additional stage (1.3.1) there is added, to the suspension (VII) obtained according to (1.2), (1.3.2) a metal compound (VIII) of the general formula MtG.sub.s-t E.sub.t where Mt is aluminum, silicon or titanium, G is a C 1 -C 12 -hydrocarbon radical, E is chlorine, bromine, hydrogen or --OR, R is a C 1 -C 12 -hydrocarbon radical, s is the maximum valency of the metal Mt and t is (a) from 0 to s-1 if Mt is aluminum, (b) from 0 to 4 if Mt is silicon, and (c) 4 if Mt is titanium, whilst maintaining a suspension state, addition being continued until the atomic ratio of magnesium from the solid contained in suspension (VII) to metal from the metal compound (VIII) is from 1:0.1 to 1:20, the product (IX), which results from stage (1.3) and is present as a solid phase in the suspension, constituting the titanium-containing catalyst component (1).

Claim 3

Dependent Claim 114 words

The process of claim 1 wherein A is a C 1-12 alkyl or a C 3-12 alkenyl, X is chlorine or hydrogen, n is 0 or 1, the titanium compound (I) is TiCl 3 .Z(AlCl 3 ), D is a monovalent C 1-10 saturated aliphatic hydrocarbon radical or phenyl and the metal compound (VIII) is selected from the group comprising Al(C 2 H 5 ) 2 Cl, Al(C 2 H 5 ) 1 .5 Cl 1 .5, Al(C 2 H 5 )Cl 2 , Al(C 2 H 5 ) 2 H, SiCl 4 , Si(CH 3 ) 3 Cl, Si(C 2 H 5 ) 3 Cl and Si(C 2 H 5 ) 3 H.

Claim 4

Dependent Claim 35 words

The process of claim 2 wherein A is a C 2-8 alkyl, D is a C 1-4 alkyl and the metal compound (VIII) is Al(C 2 H 5 ) 2 Cl or SiCl 4 .

Claim 5

Dependent Claim 9 words

The process of claim 3 wherein n is 0.

Claim 6

Dependent Claim 23 words

The process of claim 3 or 4 wherein compound (V) is a C 1-8 alkanol and compound (VI) is a C 6-8 alkane.

Claim 7

Dependent Claim 15 words

The process of claim 5 wherein the alkanol is ethanol and the alkane is n-heptane.

Claim 8

Dependent Claim 123 words

The process of claim 5 wherein the atomic ratio of titanium from catalyst component (1) to aluminum from catalyst component (2) is from 1:0.2 to 1:200, Z is from 0.31 to 0.35, no metal chloride (III) is present, the weight ratio of titanium compound (I) to magnesium alcoholate (II) is from 1:1 to 1:100, the weight ratio of milled product (IV) to alkanol (V) is from 1:0.03 to 1:0.75, the weight ratio of milled product (IV) to alkane (VI) is from 1:1 to 1:100, the mixing-in step (1.2.3) is at from 10° to 100° C. for from 1 to 30 minutes and the atomic ratio of magnesium from the solid contained in suspension (VII) to metal compound (VIII) is from 1:1 to 1:10.

Claim 9

Dependent Claim 123 words

The process of claim 6 wherein the atomic ratio of titanium from catalyst component (1) to aluminum from catalyst component (2) is from 1:0.2 to 1:200, Z is from 0.31 to 0.35, no metal chloride (III) is present, the weight ratio of titanium compound (I) to magnesium alcoholate (II) is from 1:1 to 1:100, the weight ratio of milled product (IV) to alkanol (V) is from 1:0.03 to 1:0.75, the weight ratio of milled product (IV) to alkane (VI) is from 1:1 to 1:100, the mixing-in step (1.2.3) is at from 10° to 100° C. for from 1 to 30 minutes and the atomic ratio of magnesium from the solid contained in suspension (VII) to metal compound (VIII) is from 1:1 to 1:10.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1986-01-03	1986-07-05	1987-01-04	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1990-01-03	1990-07-05	1991-01-04	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1994-01-03	1994-07-05	1995-01-04	$7700.00	Window Closed / Lapsed

Preparation of homopolymers and copolymers of α-mono-olefins by means of a Ziegler catalyst system

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