US4298718A — Catalysts for the polymerization of olefins

Claim 1

Independent Claim 67 words

A catalyst-forming component for use in preparing catalysts for the polymerization of olefins and which is the product obtained by contacting a titanium tetrahalide with an anhydrous magnesium dihalide in an active form characterized in that, in its X-rays powder spectrum, the diffraction line which is most intense in the spectrum of the normal, non-active magnesium dihalide is less intense and, in its place, a halo appears.

Claim 2

Dependent Claim 67 words

A catalyst-forming component for use in preparing catalysts for the polymerization of olefins and which is the product obtained by contacting a titanium tetrahalide with an anhydrous magnesium dihalide in an active form characterized in that, in its X-rays powder spectrum, the diffraction line which is most intense in the spectrum of the normal, non-active magnesium dihalide is less intense and, in its place, a halo appears.

Claim 3

Dependent Claim 16 words

A catalyst-forming component according to claim 1, in which the titanium tetrahalide is TiCl 4 .

Claim 4

Dependent Claim 16 words

A catalyst-forming component according to claim 1, in which the magnesium dihalide is MgCl 2 .

Claim 5

Dependent Claim 16 words

A catalyst-forming component according to claim 1, in which the magnesium dihalide is MgBr 2 .

Claim 6

Dependent Claim 23 words

A catalyst-forming component according to claim 1, in which the titanium tetrahalide is TiCl 4 and the magnesium dihalide is MgCl 2 .

Claim 7

Dependent Claim 23 words

A catalyst-forming component according to claim 1, in which the titanium tetrahalide is TiCl 4 and the magnesium dihalide is MgBr 2 .

Claim 8

Dependent Claim 120 words

A catalyst-forming component for use in preparing catalysts for the polymerization of olefins, and which is the product obtained by cogrinding a titanium tetrahalide with an active form of a Mg dihalide selected from the group consisting of MgCl 2 and MgBr 2 said active forms being characterized in that in the X-rays powder spectrum of the active MgCl 2 a halo appears in a range of lattice distances (d) comprised from d=2.56 A to d-2.95 A, and in that in the X-rays powder spectrum of the active MgBr 2 a halo appears in a range of lattice distances (d) comprised from d=2.80 A to d=3.25 A, or in that the surface area is greater than 3 m 2 /g.

Claim 9

Dependent Claim 120 words

A catalyst-forming component for use in preparing catalysts for the polymerization of olefins, and which is the product obtained by cogrinding a titanium tetrahalide with an active form of a Mg dihalide selected from the group consisting of MgCl 2 and MgBr 2 said active forms being characterized in that in the X-rays powder spectrum of the active MgCl 2 a halo appears in a range of lattice distances (d) comprised from d=2.56 A to d-2.95 A, and in that in the X-rays powder spectrum of the active MgBr 2 a halo appears in a range of lattice distances (d) comprised from d=2.80 A to d=3.25 A, or in that the surface area is greater than 3 m 2 /g.

Claim 10

Dependent Claim 18 words

A catalyst-forming component according to claim 7 and the active Mg dihalide of which is MgCl 2 .

Claim 11

Dependent Claim 18 words

A catalyst-forming component according to claim 7 and the active Mg dihalide of which is MgBr 2 .

Claim 12

Dependent Claim 114 words

A catalyst-forming component prepared by cogrinding TiCl 4 with a support, the essential support material of which is an active magnesium dihalide selected from the group consisting of MgCl 2 and MgBr 2 and characterized in that, in the X-rays powder spectrum of the active MgCl 2 , a halo appears in a range of lattice distances (d) comprised from d=2.56 A to d=2.95 A, and in that, in the X-rays powder spectrum of the active MgBr 2 , a halo appears in a range of lattice distances (d) comprised from d=2.80 A to d=3.25 A; or in that the surface area of said active Mg dihalide is greater than 3 m 2 /g.

Claim 13

Dependent Claim 114 words

A catalyst-forming component prepared by cogrinding TiCl 4 with a support, the essential support material of which is an active magnesium dihalide selected from the group consisting of MgCl 2 and MgBr 2 and characterized in that, in the X-rays powder spectrum of the active MgCl 2 , a halo appears in a range of lattice distances (d) comprised from d=2.56 A to d=2.95 A, and in that, in the X-rays powder spectrum of the active MgBr 2 , a halo appears in a range of lattice distances (d) comprised from d=2.80 A to d=3.25 A; or in that the surface area of said active Mg dihalide is greater than 3 m 2 /g.

Claim 14

Dependent Claim 146 words

Polymerization catalysts prepared by mixing (a) a supported catalyst-forming component the essential support material of which is an active magnesium dihalide, said component being obtained by cogrinding a titanium tetrahalide with a normal, non-active anhydrous magnesium dihalide to obtain a component (a) the magnesium dihalide support material of which is activated and characterized in that it has one or both of the following properties (1) its X-rays powder spectrum does not show the most intense diffraction lines as they appear in the X-rays powder spectrum of normal, non-active magnesium dihalide, the spectrum of the activated magnesium dihalide showing a broadening of said most intense diffraction lines; (2) the surface area of the activated magnesium dihalide is greater than 3 m 2 /g; with (b) a hydride or organometallic compound of a metal belonging to one of Groups I to III inclusive of the Mendelyeev Periodic Table.

Claim 15

Dependent Claim 146 words

Polymerization catalysts prepared by mixing (a) a supported catalyst-forming component the essential support material of which is an active magnesium dihalide, said component being obtained by cogrinding a titanium tetrahalide with a normal, non-active anhydrous magnesium dihalide to obtain a component (a) the magnesium dihalide support material of which is activated and characterized in that it has one or both of the following properties (1) its X-rays powder spectrum does not show the most intense diffraction lines as they appear in the X-rays powder spectrum of normal, non-active magnesium dihalide, the spectrum of the activated magnesium dihalide showing a broadening of said most intense diffraction lines; (2) the surface area of the activated magnesium dihalide is greater than 3 m 2 /g; with (b) a hydride or organometallic compound of a metal belonging to one of Groups I to III inclusive of the Mendelyeev Periodic Table.

Claim 16

Dependent Claim 74 words

A polymerization catalyst according to claim 11, in which the activated magnesium dihalide is characterized in that it has a surface area greater than 3 m 2 /g and in that its X-rays powder spectrum does not show the most intense diffraction lines as they appear in the X-rays powder spectrum of normal, non-active magnesium dihalide, the X-rays powder spectrum of the activated magnesium dihalide showing a broadening of said most intense diffraction lines.

Claim 17

Dependent Claim 25 words

Catalysts according to claim 11, characterized in that the amount of titanium tetrahalide used is less than about 10%, with respect to the magnesium dihalide.

Claim 18

Dependent Claim 29 words

Catalysts according to claim 11, characterized in that the total amount of titanium compound present on the support, expressed as tetrahalide, is comprised between 0.01 and 20% by weight.

Claim 19

Dependent Claim 25 words

Catalysts according to claim 11, characterized in that the total amount of titanium compound on the support, expressed as tetrahalide, is between 0.1% and 5%.

Claim 20

Dependent Claim 32 words

Process for the polymerization of ethylene and mixtures thereof with higher alpha-olefins and/or diolefins, characterized in that the polymerization is conducted in the presence of a catalyst as defined in claim 11.

Claim 21

Dependent Claim 49 words

The process according to claim 16, further characterized in that the polymerization is conducted at temperatures comprised between -80° C. and +200° C., in the presence of an inert liquid, and that the polymer thus obtained does not require any purification treatment for the removal of catalyst residues therefrom.

Claim 22

Dependent Claim 14 words

Catalysts according to claim 11, in which the titanium tetrahalide is TiCl 4 .

Claim 23

Dependent Claim 14 words

Catalysts according to claim 11, in which the magnesium dihalide is MgCl 2 .

Claim 24

Dependent Claim 14 words

Catalysts according to claim 11, in which the magnesium dihalide is MgBr 2 .

Claim 25

Dependent Claim 14 words

Catalysts according to claim 11, in which component (b) is an alkyl aluminum compound.

Claim 26

Dependent Claim 31 words

Catalysts according to claim 11, in which the titanium tetrahalide is TiCl 4 , the magnesium dihalide is MgCl 2 or MgBr 2 and component (b) is an alkyl aluminum compound.

Claim 27

Dependent Claim 50 words

Catalysts according to claim 11, in which the active anhydrous magnesium dihalide is characterized in that, in its X-rays powder spectrum, the diffraction line which is most intense in the X-rays powder spectrum of the normal, non-activated magnesium dihalide is less intense and, in its place, a broadened halo appears.

Claim 28

Dependent Claim 14 words

Catalysts according to claim 23, in which the titanium tetrahalide is TiCl 4 .

Claim 29

Dependent Claim 14 words

Catalysts according to claim 23 in which the magnesium dihalide is MgCl 2 .

Claim 30

Dependent Claim 14 words

Catalysts according to claim 23, in which the magnesium dihalide is MgBr 2 .

Claim 31

Dependent Claim 21 words

Catalysts according to claim 23, in which the titanium tetrahalide is TiCl 4 and the magnesium dihalide is MgCl 2 .

Claim 32

Dependent Claim 34 words

Catalysts according to claim 23, in which the titanium tetrahalide is TiCl 4 , the magnesium dihalide is MgCl 2 or MgBr 2 and component (b) of the catalyst is an alkyl aluminum compound.

Claim 33

Dependent Claim 89 words

A catalyst useful for polymerizing olefins and prepared by mixing (a) a catalyst-forming component obtained by contacting a titanium tetrahalide with an anhydrous magnesium dihalide in an active form characterized in that, in its X-rays powder spectrum, the diffraction line which is most intense in the spectrum of the normal, non-active magnesium dihalide is less intense and, in its place, a halo appears; with (b) a catalyst-forming component which is a hydride or organometallic compound of a metal belonging to Groups I to III of the Mendelyeev Periodic Table.

Claim 34

Dependent Claim 89 words

A catalyst useful for polymerizing olefins and prepared by mixing (a) a catalyst-forming component obtained by contacting a titanium tetrahalide with an anhydrous magnesium dihalide in an active form characterized in that, in its X-rays powder spectrum, the diffraction line which is most intense in the spectrum of the normal, non-active magnesium dihalide is less intense and, in its place, a halo appears; with (b) a catalyst-forming component which is a hydride or organometallic compound of a metal belonging to Groups I to III of the Mendelyeev Periodic Table.

Claim 35

Dependent Claim 15 words

A catalyst according to claim 29, in which the titanium tetrahalide is TiCl 4 .

Claim 36

Dependent Claim 15 words

A catalyst according to claim 29, in which the magnesium dihalide is MgCl 2 .

Claim 37

Dependent Claim 15 words

A catalyst according to claim 29, in which the magnesium dihalide is MgBr 2 ,

Claim 38

Dependent Claim 22 words

A catalyst according to claim 29, in which the titanium tetrahalide is TiCl 4 and the magnesium dihalide is MgCl 2 .

Claim 39

Dependent Claim 22 words

A catalyst according to claim 29, in which the titanium tetrahalide is TiCl 4 and the magnesium dihalide is MgBr 2 .

Claim 40

Dependent Claim 15 words

A catalyst according to claim 29, in which component (b) is an alkyl aluminum compound.

Claim 41

Dependent Claim 31 words

A catalyst according to claim 29, in which the titanium tetrahalide is TiCl 4 , the magnesium dihalide is MgCl 2 , and the component (b) is an alkyl aluminum compound.

Claim 42

Dependent Claim 30 words

A catalyst according to claim 29, in which the titanium tetrahalide is TiCl 4 , the magnesium dihalide is MgBr 2 , and component (b) is an alkyl aluminum compound.

Claim 43

Dependent Claim 73 words

A catalyst for polymerizing olefins and prepared by mixing (a) a catalyst-forming component which is a hydride or organometallic compound of a metal belonging to Groups I to III of the Mendelyeev Periodic Table with (b) a catalyst-forming component obtained by cocomminuting a titanium tetrahalide with an anhydrous magnesium dihalide for one hour in a ball mill loaded with balls until the mixture has a surface area higher than 3 m 2 /g.

Claim 44

Dependent Claim 73 words

A catalyst for polymerizing olefins and prepared by mixing (a) a catalyst-forming component which is a hydride or organometallic compound of a metal belonging to Groups I to III of the Mendelyeev Periodic Table with (b) a catalyst-forming component obtained by cocomminuting a titanium tetrahalide with an anhydrous magnesium dihalide for one hour in a ball mill loaded with balls until the mixture has a surface area higher than 3 m 2 /g.

Claim 45

Dependent Claim 15 words

A catalyst according to claim 38, in which the titanium tetrahalide is TiCL 4 .

Claim 46

Dependent Claim 15 words

A catalyst according to claim 38, in which the magnesium dihalide is MgCl 2 .

Claim 47

Dependent Claim 71 words

A catalyst for polymerizing olefins and prepared by mixing (a) a catalyst-forming component which is a hydride or organometallic compound of a metal belonging to Groups I to III of the Mendelyeev Periodic Table with (b) a catalyst-forming component obtained by cocomminuting a titanium tetrahalide with an anhydrous magnesium dihalide in a ball mill loaded with balls until the magnesium dihalide has a surface area higher than 3 m 2 /g.

Claim 48

Dependent Claim 71 words

A catalyst for polymerizing olefins and prepared by mixing (a) a catalyst-forming component which is a hydride or organometallic compound of a metal belonging to Groups I to III of the Mendelyeev Periodic Table with (b) a catalyst-forming component obtained by cocomminuting a titanium tetrahalide with an anhydrous magnesium dihalide in a ball mill loaded with balls until the magnesium dihalide has a surface area higher than 3 m 2 /g.

Claim 49

Dependent Claim 15 words

A catalyst according to claim 41, in which the titanium tetrahalide is TiCl 4 .

Claim 50

Dependent Claim 15 words

A catalyst according to claim 41, in which the magnesium dihalide is MgCl 2 .

Claim 51

Dependent Claim 112 words

A catalyst for polymerizing olefins and prepared by mixing (a) a catalyst-forming component which is a hydride or organometallic compound of a metal belonging to Groups I to III of the Mendelyeev Periodic Table with (b) a catalyst-forming component which is the product obtained by co-comminuting a titanium tetrahalide with an anhydrous magnesium dihalide in a ball mill loaded with balls until the magnesium dihalide has one or both of the following properties (1) its surface area is higher than 3 m 2 /g; (2) it shows, in its X-rays spectrum, a halo in place of the most intense diffraction line appearing in the X-rays spectrum of the normal, non-active magnesium dihalide.

Claim 52

Dependent Claim 112 words

A catalyst for polymerizing olefins and prepared by mixing (a) a catalyst-forming component which is a hydride or organometallic compound of a metal belonging to Groups I to III of the Mendelyeev Periodic Table with (b) a catalyst-forming component which is the product obtained by co-comminuting a titanium tetrahalide with an anhydrous magnesium dihalide in a ball mill loaded with balls until the magnesium dihalide has one or both of the following properties (1) its surface area is higher than 3 m 2 /g; (2) it shows, in its X-rays spectrum, a halo in place of the most intense diffraction line appearing in the X-rays spectrum of the normal, non-active magnesium dihalide.

Claim 53

Dependent Claim 15 words

A catalyst according to claim 44, in which the titanium tetrahalide is TiCl 4 .

Claim 54

Dependent Claim 15 words

A catalyst according to claim 44, in which the magnesium dihalide is MgCl 2 .

Claim 55

Dependent Claim 96 words

A process for the polymerization of olefins comprising polymerizing at least one olefin in an inert hydrocarbon solvent and in contact with a catalyst prepared by mixing (a) a catalyst-forming component which is a hydride or organometallic compound of a metal belonging to Groups I to III of the Mendelyeev Periodic Table with (b) a catalyst-forming component which is the product obtained by co-comminuting a titanium tetrahalide with an anhydrous magnesium dihalide for one hour in a ball mill loaded with balls and until the mixture has a surface area higher than 3 m 2 /g.

Claim 56

Dependent Claim 96 words

A process for the polymerization of olefins comprising polymerizing at least one olefin in an inert hydrocarbon solvent and in contact with a catalyst prepared by mixing (a) a catalyst-forming component which is a hydride or organometallic compound of a metal belonging to Groups I to III of the Mendelyeev Periodic Table with (b) a catalyst-forming component which is the product obtained by co-comminuting a titanium tetrahalide with an anhydrous magnesium dihalide for one hour in a ball mill loaded with balls and until the mixture has a surface area higher than 3 m 2 /g.

Claim 57

Dependent Claim 37 words

The process of claim 47, in which the olefin is polymerized in contact with a catalyst prepared by mixing a component (a) with a component (b) obtained by co-comminuting TiCl 4 with an anhydrous MgCl 2 .

Claim 58

Dependent Claim 12 words

The process of claim 47, in which the olefin polymerized is ethylene.

Claim 59

Dependent Claim 12 words

The process of claim 48, in which the olefin polymerized is ethylene.

Claim 60

Dependent Claim 132 words

A process for the polymerization of olefins comprising polymerizing at least one olefin in an inert hydrocarbon solvent and in contact with a catalyst prepared by mixing (a) a catalyst-forming component which is a hydride or organometallic compound of a metal belonging to Groups I to III of the Mendelyeev Periodic Table with (b) a catalyst-forming component which is the product obtained by co-comminuting a titanium tetrahalide with an anhydrous magnesium dihalide in a ball mill loaded with balls until the magnesium dihalide is activated and has one or both of the following properties (1) its X-rays powder spectrum shows a halo in place of the most intense diffraction line appearing in the X-rays spectrum of normal, non-active magnesium dihalide; (2) it has a surface area higher than 3 m 2 /g.

Claim 61

Dependent Claim 132 words

A process for the polymerization of olefins comprising polymerizing at least one olefin in an inert hydrocarbon solvent and in contact with a catalyst prepared by mixing (a) a catalyst-forming component which is a hydride or organometallic compound of a metal belonging to Groups I to III of the Mendelyeev Periodic Table with (b) a catalyst-forming component which is the product obtained by co-comminuting a titanium tetrahalide with an anhydrous magnesium dihalide in a ball mill loaded with balls until the magnesium dihalide is activated and has one or both of the following properties (1) its X-rays powder spectrum shows a halo in place of the most intense diffraction line appearing in the X-rays spectrum of normal, non-active magnesium dihalide; (2) it has a surface area higher than 3 m 2 /g.

Claim 62

Dependent Claim 36 words

The process of claim 51, in which the olefin is polymerized in contact with a catalyst prepared by mixing a component (a) with a component (b) obtained by co-comminuting TiCl 4 with anhydrous MgCl 4 .

Claim 63

Dependent Claim 12 words

The process of claim 51, in which the olefin polymerized is ethylene.

Claim 64

Dependent Claim 12 words

The process of claim 52, in which the olefin polymerized is ethylene.

Claim 65

Dependent Claim 129 words

A process for the polymerization of olefins which comprises polymerizing at least one olefin in an inert hydrocarbon solvent and in contact with a catalyst prepared by mixing (a) a catalyst-forming component which is a hydride or organometallic compound of a metal belonging to Groups I to III of the Mendelyeev Periodic Table with (b) a catalyst-forming component which is the product obtained by co-comminuting titanium tetrachloride with an anhydrous magnesium dihalide in a ball mill loaded with balls until the magnesium dihalide has one or both of the following properties (1) a surface area higher than 3 m 2 /g; (2) it shows, in its X-rays spectrum, a halo in place of the most intense diffraction line appearing in the X-rays spectrum of the normal non-active magnesium dihalide.

Claim 66

Dependent Claim 129 words

A process for the polymerization of olefins which comprises polymerizing at least one olefin in an inert hydrocarbon solvent and in contact with a catalyst prepared by mixing (a) a catalyst-forming component which is a hydride or organometallic compound of a metal belonging to Groups I to III of the Mendelyeev Periodic Table with (b) a catalyst-forming component which is the product obtained by co-comminuting titanium tetrachloride with an anhydrous magnesium dihalide in a ball mill loaded with balls until the magnesium dihalide has one or both of the following properties (1) a surface area higher than 3 m 2 /g; (2) it shows, in its X-rays spectrum, a halo in place of the most intense diffraction line appearing in the X-rays spectrum of the normal non-active magnesium dihalide.

Claim 67

Dependent Claim 12 words

The process of claim 55, in which the olefin polymerized is ethylene.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1984-11-02	1985-05-04	1985-11-03	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1988-11-02	1989-05-04	1989-11-03	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1992-11-02	1993-05-04	1993-11-03	$7700.00	Window Closed / Lapsed

Catalysts for the polymerization of olefins

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