US 4,366,298 AGranted

Process and heavy metal catalyst for the polymerization of .alpha.-olefins, particularly polyethylene

AssigneeWacker Chemie AG

InventorDieter Kurz

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Abstract

Poly-.alpha.-olefins, particularly polyethylene, having a broad molecular-weight distribution, can be prepared in the presence of a catalyst solid which is manufactured in two reaction steps, from a primary solid containing magnesium and chlorine which has been reacted, in a reaction stage A, with secondary and/or tertiary alcohols and with halogen-containing metal compounds of elements of IV and/or V sub-group(s) of the Mendeleev Periodic Table, and, in a reaction stage B, with halogen-containing metal compounds of elements of IV and/or V sub-group(s) of the Mendeleev Periodic Table and metal organyl compounds of metals of the II and/or III main group(s) of the Mendeleev Periodic Table. The sequence of the reaction stages A and B is not critical for the success of the process according to the invention.

Claims12

Dependent claims

An improvement in the process for the polymerization of an at least one .alpha.-olefin comprising reacting said .alpha.-olefin under elevated temperatures and pressures in the presence of a solid polymerization catalyst consisting essentially of a solid compound containing (1) element(s) of the IV and/or V sub-group(s) of the Mendeleev Periodic Table, (2) magnesium, (3) halogen, (4) oxygen, and possibly (5) element(s) of the II and/or III main group(s) of the Mendeleev Periodic Table, which solid compound is activated with at least one organometallic compound where said metal is from the II and/or III main group(s) of the Mendeleev Periodic Table, and recovering a polymerizate, the improvement consisting of preparing said solid compound prior to activation, by reacting a primary solid containing magnesium and halogen prepared from at least one hydrocarbon-soluble magnesium compound and at least one halogen compound selected from the group consisting of a chloroalkane having from 1 to 6 carbon atoms of which at least one carbon atom has at least two directly bonded chlorine atoms, a carbon chloride compound having from 1 to 6 carbon atoms, and mixtures thereof, in two successive and separate reacting stages A and B, in either order,

where a solid based on magnesium compound(s) is reacted in reaction stage A in suspension in at least one liquid hydrocarbon with
(i) an alcohol selected from the group consisting of tert.-butanol, isopropanol and mixtures thereof, and
(ii) at least one halogen-containing titanium compound of the formula:
X.sub.a Ti(OR.sup.6).sub.4-a
wherein X represents halogen, R.sup.6 is a substituent selected from the group consisting of alkyl having from 1 to 8 carbon atoms and hydrocarbon aryl having from 6 to 8 carbon atoms, and a is 2, 3 or 4,
and, in reaction stage B, a solid based on magnesium compound(s) in suspension in at least one liquid hydrocarbon is reacted with
(i) at least one halogen-containing metal titanium compound of the formula:
X'.sub.b Ti(OR.sup.7).sub.4-b
wherein X' represents halogen, R.sup.7 represents a substituent selected from the group consisting of alkyl having from 1 to 8 carbon atoms and hydrocarbon aryl having from 6 to 8 carbon atoms, and b is 2, 3, or 4, and
(ii) at least one organoaluminum compound,
whereby a polymerizate is recovered having a broad molecular-weight distribution.

8 more elements

An improvement in the process for the polymerization of an at least one .alpha.-olefin comprising reacting an .alpha.-olefin selected from the group consisting of ethylene and mixtures of ethylene with up to 10 mol percent of .alpha.-alkenes having from 3 to 6 carbon atoms under elevated temperatures and pressures in the presence of a solid polymerization catalyst consisting essentially of a solid compound containing (1) element(s) of the IV and/or V sub-group(s) of the Mendeleev Periodic Table, (2) magnesium, (3) halogen, (4) oxygen, and possibly (5) element(s) of the II and/or III main group(s) of the Mendeleev Periodic Table, which solid compound is activated with at least one organometallic compound where said metal is from the II and/or III main group(s) of the Mendeleev Periodic Table, and recovering a polymerizate, the improvement consisting of preparing said solid compound prior to activation, by reacting a primary solid containing magnesium and halogen prepared from at least one hydrocarbon-soluble magnesium compound and at least one halogen compound selected from the group consisting of a chlorohydrocarbon having from 1 to 6 carbon atoms of which at least one carbon atom has at least two directly bonded chlorine atoms, a carbon chloride compound having from 1 to 6 carbon atoms, and mixtures thereof, in two successive and separate reacting stages A and B, in either order,

where a solid based on magnesium compound(s) is reacted in reaction stage A in suspension in at least one liquid hydrocarbon with
(i) an alcohol selected from the group consisting of tert.-butanol, isopropanol and mixtures thereof, and
(ii) at least one halogen-containing titanium compound of the formula:
X.sub.a Ti(OR.sup.6).sub.4-a
wherein X represents halogen, R.sup.6 is a substituent selected from the group consisting of alkyl having from 1 to 8 carbon atoms and hydrocarbon aryl having from 6 to 8 carbon atoms, and a is 2, 3 or 4,
and, in reaction stage B, a solid based on magnesium compound(s) in suspension in at least one liquid hydrocarbon is reacted with
(i) at least one halogen-containing metal titanium compound of the formula:
X'.sub.b Ti(OR.sup.7).sub.4-b
wherein X' represents halogen, R.sup.7 represents a substituent selected from the group consisting of alkyl having from 1 to 8 carbon atoms and hydrocarbon aryl having from 6 to 8 carbon atoms, and b is 2, 3, or 4, and
(ii) at least one organoaluminum compound,
whereby a polymerizate is recovered having a broad molecular-weight distribution.

8 more elements

Dependencies are inferred from the claim text.