Patent US4124532A successfully refreshed from Google Patents.
US4124532A
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Catalysts for polymerizing olefins
Assignee: Montedison SpA
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Filing: 1976-03-26
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Granted: 1978-11-07
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Expires: 1996-03-26
Abstract
Abstract New catalysts for the polymerization and copolymerization of olefins are disclosed. The catalysts are prepared from (1) a new class of metal complexes of general formula MmM'X2mY.nE, in which M is Mg, Mn and/or Ca; m is a number from 0.5 to 2.0; M' is Ti, V and/or Zr; X is Cl, Br or I; Y is one or more atoms or groups of atoms of various kinds in an amount such as to satisfy the valence of M'; n is a number from 0.5m to 20m; and E is an electron-donor compound; and (2) organometallic compounds of metals belonging to one of Groups I to III of the Mendelyeev Periodic Table.
Inventors
- 👤 Umberto Giannini
- 👤 Enrico Albizzati
- 👤 Sandro Parodi
- 👤 Franco Pirinoli
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 05:39
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 48
Claim 1
Independent Claim
159 words
Components of catalysts useful to polymerize olefins having the general formula M.sub.m M'X.sub.2m Y.nE in which M is at least one metal selected from the group consisting of Mg, Mn and Ca; m is a number from 0.5 to 2; M' is at least one metal selected from the group consisting of Ti, V and Zr; X is Cl, Br or I; Y is a radical selected from the group consisting of halogen, --NR 2 , --OR, and ##STR7## in which R is a hydrocarbon radical, and mixtures thereof, said radicals R being present in an amount to satisfy the valence of the metal M'; n is a number from 0.5 m to 20 m; and E is a hydrocarbyl electron-donor compound selected from the group consisting of (a) esters of organic carboxylic acids, (b) amines, (c) esters of carbonic acid, (d) nitriles, (e) phosphoramides, (f) esters of phosphoric acid, (g) esters of phosphorus acid, and (h) phosphorus oxychloride.
Claim 2
Dependent Claim
159 words
Components of catalysts useful to polymerize olefins having the general formula M.sub.m M'X.sub.2m Y.nE in which M is at least one metal selected from the group consisting of Mg, Mn and Ca; m is a number from 0.5 to 2; M' is at least one metal selected from the group consisting of Ti, V and Zr; X is Cl, Br or I; Y is a radical selected from the group consisting of halogen, --NR 2 , --OR, and ##STR7## in which R is a hydrocarbon radical, and mixtures thereof, said radicals R being present in an amount to satisfy the valence of the metal M'; n is a number from 0.5 m to 20 m; and E is a hydrocarbyl electron-donor compound selected from the group consisting of (a) esters of organic carboxylic acids, (b) amines, (c) esters of carbonic acid, (d) nitriles, (e) phosphoramides, (f) esters of phosphoric acid, (g) esters of phosphorus acid, and (h) phosphorus oxychloride.
Claim 3
Dependent Claim
18 words
Catalytic component according to claim 1, having the formula MgTiCl 5 .2CH 3 COOC 2 H 5 .
Claim 4
Dependent Claim
22 words
Catalytic component according to claim 1, having the formula Mg 3 Ti 2 Cl 12 .7CH 3 COOC 2 H 5 .
Claim 5
Dependent Claim
22 words
Catalytic component according to claim 1, having the formula Mg 4 Ti 3 AlCl 20 .12CH 3 COOC 2 H 5 .
Claim 6
Dependent Claim
20 words
Catalytic component according to claim 1, having the formula Mg 3 Ti 2 Cl 12 .7C 6 H 5 CN.
Claim 7
Dependent Claim
24 words
Catalytic component according to claim 1, having the formula Mg 3 Ti 2 Cl 12 .6C 6 H 5 COOC 2 H 5 .
Claim 8
Dependent Claim
18 words
Catalytic component according to claim 1, having the formula MgTiCl 6 .2CH 3 COOC 2 H 5 .
Claim 9
Dependent Claim
10 words
Catalytic component according to claim 1, having the formula ##STR8##
Claim 10
Dependent Claim
16 words
Catalytic component according to claim 1, having the formula MgTiCl 6 .6C 5 H 5 N.
Claim 11
Dependent Claim
14 words
Catalytic component according to claim 1, having the formula MgTiCl 6 .5POCl 3 .
Claim 12
Dependent Claim
20 words
Catalytic component according to claim 1, having the formula MgTiCl 5 (OCH 3 ).2CH 3 COOC 2 H 5 .
Claim 13
Dependent Claim
22 words
Catalytic component according to claim 1, having the formula MgTiCl 5 (OOC--C 6 H 5 ).2CH 3 COOC 2 H 5 .
Claim 14
Dependent Claim
24 words
Catalytic component according to claim 1, having the formula MgTiCl 5 [N(C 6 H 5 ) 2 ].3CH 3 COOC 2 H 5 .
Claim 15
Dependent Claim
24 words
Catalytic component according to claim 1, having the formula MgTiCl 2 (O--C 4 H 9 ) 4 .2CH 3 COOC 4 H 9 .
Claim 16
Dependent Claim
22 words
Catalytic component according to claim 1, having the formula Mg 3 V 2 Cl 12 .7CH 3 COOC 2 H 5 .
Claim 17
Dependent Claim
20 words
Catalytic component according to claim 1, having the formula MgTiCl 6 .3CH 2 (COOC 2 H 5 ) 2 .
Claim 18
Dependent Claim
18 words
Catalytic component according to claim 1, having the formula MgTiCl 6 .4[(CH 3 ) 2 N] 3 PO.
Claim 19
Dependent Claim
19 words
Catalytic component according to claim 1, having the formula MgTiCl 6 .2P (OC 6 H 5 ) 3 .
Claim 20
Dependent Claim
18 words
Catalytic component according to claim 1, having the formula MgTiCl 4 .2CH 3 COOC 2 H 5 .
Claim 21
Dependent Claim
23 words
Catalytic component according to claim 1, having the formula Mg 4 TiSn 1 .5 Cl 18 .14CH 3 COOC 2 H 5 .
Claim 22
Dependent Claim
74 words
Component of catalysts for the polymerization of olefins, consisting of a mixture of 99% to 1% by weight of a metal complex according to claim 1 and correspondingly 1% to 99% by weight of an anhydrous magnesium dihalide, the X-ray spectrum of said mixture showing a halo having an intensity peak shifted with respect to the interplanar distance of the most intense line appearing in the spectrum of the magnesium dihalide of normal type.
Claim 23
Dependent Claim
57 words
Components of catalysts according to claim 1, in which a portion of the Ti, V and/or Zr is replaced by metals selected from the group consisting of Zn, Al, Sn, Fe, Co, Ni, Cr and Mo, in such an amount that the atomic ratio between such metals and Ti, V and/or Zr ranges from 0.1 to 2:1.
Claim 24
Dependent Claim
22 words
Catalysts for (co)polymerizing olefins, prepared by mixing: (1) a catalytic component as defined in claim 21, and (2) an alkyl Al compound.
Claim 25
Dependent Claim
156 words
Catalysts for (co)polymerizing olefins, prepared by mixing (1) a catalyst component having the formula M.sub.m M'X.sub.2m Y.nE in which M is at least one metal selected from the group consisting of Mg, Mn and Ca; m is a number from 0.5 to 2; M' is at least one metal selected from the group consisting of Ti, V and Zr; X is Cl, Br or I; Y is halogen or one of the groups ##STR9## or mixtures thereof, in which R is a hydrocarbon radical, Y being present in an amount corresponding to the valence of M'; n is a number from 0.5 m to 20 m; and E is a hydrocarbyl electron-donor compound selected from the group consisting of (a) esters of organic carboxylic acids; (b) amines; (c) esters of carbonic acid; (d) nitriles; (e) phosphoramides; (f) esters of phosphoric acid; (g) esters of phosphorus acid; and (h) phosphorus oxychloride with (2) an alkyl Al compound.
Claim 26
Dependent Claim
156 words
Catalysts for (co)polymerizing olefins, prepared by mixing (1) a catalyst component having the formula M.sub.m M'X.sub.2m Y.nE in which M is at least one metal selected from the group consisting of Mg, Mn and Ca; m is a number from 0.5 to 2; M' is at least one metal selected from the group consisting of Ti, V and Zr; X is Cl, Br or I; Y is halogen or one of the groups ##STR9## or mixtures thereof, in which R is a hydrocarbon radical, Y being present in an amount corresponding to the valence of M'; n is a number from 0.5 m to 20 m; and E is a hydrocarbyl electron-donor compound selected from the group consisting of (a) esters of organic carboxylic acids; (b) amines; (c) esters of carbonic acid; (d) nitriles; (e) phosphoramides; (f) esters of phosphoric acid; (g) esters of phosphorus acid; and (h) phosphorus oxychloride with (2) an alkyl Al compound.
Claim 27
Dependent Claim
22 words
Catalysts for (co)polymerizing olefins, prepared by mixing: (1) a catalytic component as defined in claim 22, and (2) an alkyl Al compound.
Claim 28
Dependent Claim
120 words
Components of catalysts useful to polymerize olefins, having the general formula M.sub.m M'X.sub.2m Y.nE wherein: M is at least one metal selected from the group consisting of Mg, Mn and Ca; m is a number from 0.5 to 2; M' is at least one metal selected from the group consisting of V, Zr, and trivalent Ti; X is Cl, Br or I; Y is halogen or one of the groups --NR 2 , --OR, and ##STR10## in which R is a hydrocarbon radical, or mixtures thereof, Y being present in an amount to satisfy the valence of M'; n is a number from 0.5 m to 20 m; and E is a hydrocarbyl electron donor compound which is an alcohol.
Claim 29
Dependent Claim
120 words
Components of catalysts useful to polymerize olefins, having the general formula M.sub.m M'X.sub.2m Y.nE wherein: M is at least one metal selected from the group consisting of Mg, Mn and Ca; m is a number from 0.5 to 2; M' is at least one metal selected from the group consisting of V, Zr, and trivalent Ti; X is Cl, Br or I; Y is halogen or one of the groups --NR 2 , --OR, and ##STR10## in which R is a hydrocarbon radical, or mixtures thereof, Y being present in an amount to satisfy the valence of M'; n is a number from 0.5 m to 20 m; and E is a hydrocarbyl electron donor compound which is an alcohol.
Claim 30
Dependent Claim
16 words
Catalytic component according to claim 26, having the formula MgTiCl 5 .6C 2 H 5 OH.
Claim 31
Dependent Claim
14 words
Catalytic component according to claim 26, having the formula MgTiCl 5 .10CH 3 OH.
Claim 32
Dependent Claim
16 words
Catalytic component according to claim 26, having the formula MnTiCl 5 .4C 2 H 5 OH.
Claim 33
Dependent Claim
16 words
Catalytic component according to claim 26, having the formula CaTiCl 5 .4C 2 H 5 OH.
Claim 34
Dependent Claim
18 words
Catalytic component according to claim 26, having the formula CaTiCl 3 I 2 .5C 2 H 5 OH.
Claim 35
Dependent Claim
162 words
Catalysts for (co)polymerizing olefins, prepared by mixing (1) a catalyst component having the formula M.sub.m M'X.sub.2m Y.nE in which M is at least one metal selected from the group consisting of Mg, Mn and Ca; m is a number from 0.5 to 2; M' is at least one metal selected from the group consisting of V, Zr and trivalent Ti; X is Cl, Br or I; Y is halogen or one of the groups --NR 2 , --OR, and ##STR11## in which R is a hydrocarbon radical, or mixtures thereof, Y being present in an amount corresponding to the valence of M'; n is a number from 0.5 m to 20 m; and E is a hydrocarbyl electron-donor compound selected from the group consisting of (a) esters of organic carboxylic acids; (b) amines; (c) esters of carbonic acid; (d) nitriles; (e) phosphoramides, (f) esters of phosphoric acid; (g) esters of phosphorus acid; and (h) phosphorus oxychloride; with (2) an alkyl Al compound.
Claim 36
Dependent Claim
162 words
Catalysts for (co)polymerizing olefins, prepared by mixing (1) a catalyst component having the formula M.sub.m M'X.sub.2m Y.nE in which M is at least one metal selected from the group consisting of Mg, Mn and Ca; m is a number from 0.5 to 2; M' is at least one metal selected from the group consisting of V, Zr and trivalent Ti; X is Cl, Br or I; Y is halogen or one of the groups --NR 2 , --OR, and ##STR11## in which R is a hydrocarbon radical, or mixtures thereof, Y being present in an amount corresponding to the valence of M'; n is a number from 0.5 m to 20 m; and E is a hydrocarbyl electron-donor compound selected from the group consisting of (a) esters of organic carboxylic acids; (b) amines; (c) esters of carbonic acid; (d) nitriles; (e) phosphoramides, (f) esters of phosphoric acid; (g) esters of phosphorus acid; and (h) phosphorus oxychloride; with (2) an alkyl Al compound.
Claim 37
Dependent Claim
189 words
Process for preparing the catalytic components M m M'X 2m Y.nE, comprising reacting a compound of formula MX 2 in which M represents at least one metal selected from the group consisting of Mg, Mn and Ca and X is chlorine, bromine or iodine, at a temperature ranging from room temperature to about 150° C., with a compound of formula M'Y in which M' represents at least one metal selected from the group consisting of Ti, V and Zr and Y represents a radical selected from the group consisting of halogen, --NR 2 , --OR, and ##STR12## and mixtures thereof, said radicals being present in an amount to satisfy the valence of M', in a solvent which is a hydrocarbyl compound selected from the group consisting of the electron-donor compounds: (a) esters of organic carboxylic acids, (b) amines, (c) esters of carbonic acid, (d) nitriles, (e) phosphoramides, (f) esters of phosphoric acid, (g) esters of phosphorus acid, and (h) phosphorus oxychloride, and isolating the complex thus formed by crystallization from the solvent, by evaporation of the solvent, or by precipitation with a solvent in which the complex is insoluble.
Claim 38
Dependent Claim
189 words
Process for preparing the catalytic components M m M'X 2m Y.nE, comprising reacting a compound of formula MX 2 in which M represents at least one metal selected from the group consisting of Mg, Mn and Ca and X is chlorine, bromine or iodine, at a temperature ranging from room temperature to about 150° C., with a compound of formula M'Y in which M' represents at least one metal selected from the group consisting of Ti, V and Zr and Y represents a radical selected from the group consisting of halogen, --NR 2 , --OR, and ##STR12## and mixtures thereof, said radicals being present in an amount to satisfy the valence of M', in a solvent which is a hydrocarbyl compound selected from the group consisting of the electron-donor compounds: (a) esters of organic carboxylic acids, (b) amines, (c) esters of carbonic acid, (d) nitriles, (e) phosphoramides, (f) esters of phosphoric acid, (g) esters of phosphorus acid, and (h) phosphorus oxychloride, and isolating the complex thus formed by crystallization from the solvent, by evaporation of the solvent, or by precipitation with a solvent in which the complex is insoluble.
Claim 39
Dependent Claim
71 words
The process according to claim 33, in which the halide MX 2 is reacted, at a temperature comprised between room temperature and 150° C., with the compound M'Y in an electron-donor solvent in which the halide MX 2 and the compound M'Y are soluble, to form a complex in solution, and the selected electron-donor solvent is then added to the solution of the complex or to the complex after isolation thereof.
Claim 40
Dependent Claim
36 words
Process according to claim 33, in which the halide MX 2 and the compound M'Y are employed in a MX 2 /M'Y molar ratio equal to the value of m in the complex to be prepared.
Claim 41
Dependent Claim
27 words
Process according to claim 33, in which the halide MX 2 and the compound M'Y are employed in a MX 2 /M'Y molar ratio higher than 2.
Claim 42
Dependent Claim
26 words
Process according to claim 33, in which the halide MX 2 and the compound M'Y are employed in a M'Y/MX 2 molar ratio higher than 2.
Claim 43
Dependent Claim
71 words
The process according to claim 33, in which the halide MX 2 is reacted, at a temperature comprised between room temperature and 150° C., with the compound M'Y in an electron-donor solvent in which the halide MX 2 and the compound M'Y are soluble, to form a complex in solution, and the selected electron-donor solvent is then added to the solution of the complex or to the complex after isolation thereof.
Claim 44
Dependent Claim
36 words
Process according to claim 33, in which the halide MX 2 and the compound M'Y are employed in a MX 2 /M'Y molar ratio equal to the value of m in the complex to be prepared.
Claim 45
Dependent Claim
27 words
Process according to claim 33, in which the halide MX 2 and the compound M'Y are employed in a MX 2 /M'Y molar ratio higher than 2.
Claim 46
Dependent Claim
26 words
Process according to claim 33, in which the halide MX 2 and the compound M'Y are employed in a M'Y/MX 2 molar ratio higher than 2.
Claim 47
Dependent Claim
192 words
Process for preparing catalytic components of formula M m M'X 2m Y.nE, comprising reacting a compound of formula MX 2 in which M represents at least one metal selected from the group consisting of Mg, Mn and Ca and X is chlorine, bromine or iodine, at a temperature ranging from room temperature to about 150° C., with a compound of formula M'Y in which M' represents at least one metal selected from the group consisting of V, Zr and trivalent Ti and Y represents halogen or one of the groups --NR 2 , --OR, and ##STR13## in which R is a hydrocarbon radical, or mixtures thereof, Y being present in an amount to satisfy the valence of M', in a solvent which is a hydrocarbyl electron-donor compound selected from the group consisting of (a) esters of organic carboxylic acids, (b) amines, (c) esters of carbonic acid, (d) nitriles, (e) phosphoramides, (f) esters of phosphoric acid, (g) esters of phosphorus acid, and (h) phosphorus oxychloride, and isolating the complex thus formed by crystallization from the solvent, by evaporation of the solvent, or by precipitation with a solvent in which the complex is insoluble.
Claim 48
Dependent Claim
192 words
Process for preparing catalytic components of formula M m M'X 2m Y.nE, comprising reacting a compound of formula MX 2 in which M represents at least one metal selected from the group consisting of Mg, Mn and Ca and X is chlorine, bromine or iodine, at a temperature ranging from room temperature to about 150° C., with a compound of formula M'Y in which M' represents at least one metal selected from the group consisting of V, Zr and trivalent Ti and Y represents halogen or one of the groups --NR 2 , --OR, and ##STR13## in which R is a hydrocarbon radical, or mixtures thereof, Y being present in an amount to satisfy the valence of M', in a solvent which is a hydrocarbyl electron-donor compound selected from the group consisting of (a) esters of organic carboxylic acids, (b) amines, (c) esters of carbonic acid, (d) nitriles, (e) phosphoramides, (f) esters of phosphoric acid, (g) esters of phosphorus acid, and (h) phosphorus oxychloride, and isolating the complex thus formed by crystallization from the solvent, by evaporation of the solvent, or by precipitation with a solvent in which the complex is insoluble.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-11-06 | 1982-05-08 | 1982-11-07 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-11-06 | 1986-05-08 | 1986-11-07 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-11-06 | 1990-05-08 | 1990-11-07 | $7700.00 | Window Closed / Lapsed |