Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Plural component system comprising a - group i to iv metal...
Reexamination Certificate
1994-10-04
2004-05-04
Choi, Ling-Siu (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S104000, C502S113000, C502S117000, C502S134000
Reexamination Certificate
active
06730627
ABSTRACT:
The present invention relates to a solid component of catalyst, the procedure for its preparation and its use in procedures for the (co)polymerization of ethylene and &agr;-olefins.
It is well-known that ethylene, or &agr;-olefins in general, can be polymerized by means of a procedure at low pressure on Ziegler-Natta catalysts. These catalysts are generally composed of a compound of elements from sub-group IV to VI of the periodic table (compounds of transition metals), mixed with an organometallic compound, or hydride, of the elements belonging to group I to III of the periodic table.
Solid components of Ziegler-Natta catalysts are also known, containing a transition metal (generally titanium), a bivalent metal (generally magnesium), a halogen (generally chlorine) and also possibly an electron donor. These solid components, used in combination with an organometallic compound of aluminium, form active catalysts for the (co)polymerization of ethylene in procedures carried out at low temperature and pressure. U.S. Pat. No. 3,642,746, for example, describes a solid component of catalyst obtained by the contact of a compound of a transition metal with a halide of a bivalent metal treated with an electron donor. According to U.S. Pat. No. 4,421,674 a solid component of catalyst is obtained by the contact of a compound of a transition metal with the product of a solution of magnesium chloride in ethanol which has been spray-dried.
According to U.K. Patent 1.401.708 a solid component of catalyst is obtained by the interaction of a magnesium halide, a non-halogenated compound of a transition metal and an aluminium halide. U.S. Pat. Nos. 3,901,863 and 4,292,200 describe solid components of catalyst obtained by putting a non-halogenated compound of magnesium in contact with a non-halogenated compound of a transition metal and an aluminium halide.
U.S. Pat. No. 4,843,049 and European Patent Application publication 243.327 describe solid components of catalyst which contain titanium, magnesium, aluminium, chlorine and alkoxy groups, highly active in procedures for the (co)polymerization of ethylene carried out at low pressure and temperature, using the technique of suspension, and at high pressure and temperature respectively, in vessels or tubular reactors. These solid components are generally obtained by spray-drying an ethanol solution of magnesium chloride to obtain an active support, which is subsequently reacted with a titanium tetraalkoxide or with titanium tetrachloride and an alkyl aluminium chloride respectively.
It has now been found, according to the present invention, that by introducing magnesium-carboxylate bonds and a transition metal-carboxylate, generally improved solid components of catalyst are obtained, compared to those of the known art, with respect to their highly developed activity in procedures for the (co)polymerization of ethylene and &agr;-olefins carried out at low pressure and temperature, at high pressure and temperature and in solution and also to the nature of the polymers thus obtained.
In accordance with this, the first aspect of the present invention relates to a solid component of catalyst for the (co)polymerization of ethylene and &agr;-olefins which contains magnesium-carboxylate bonds and a transition metal-carboxylate and which can be represented by the formula:
M
1
Mg
(0.3-20)
X
(2-60)
Al
(0-6)
(R—COO)
(0.1-3)
(I)
wherein:
M is at least one metal selected from titanium, vanadium, zirconium and hafnium,
X is a halogen excluding iodine, and
R is an aliphatic, cycloaliphatic or aromatic hydrocarbon radical, containing at least 4 carbon atoms.
According to one embodiment, the metal M in formula (I), represents titanium, or titanium and another metal selected from zirconium and hafnium in an atomic ratio between titanium and the other metal of 0.25:1 to 2.0:1 and preferably 0.33:1 to 1:1.
In another preferred embodiment, the halogen X, in formula (I), represents chlorine or bromine and in the more preferred form chlorine.
The maximum number of carbon atoms of the radical R, in formula (I) is not particularly critical, however it is generally not advisable to exceed a value of 25.
Another aspect of the present invention relates to a procedure for the preparation of the solid component of catalyst (I) which includes:
(i) the formation of a solution, in an inert organic solvent, of a magnesium carboxylate or halide of magnesium carboxylate:
MgX
n
(R—COO)
(2−n)
(II)
and at least one transition metal carboxylate or halide of at least one transition metal carboxylate:
MX
m
(R—COO)
(4−m)
(III)
wherein:
M is at least a metal selected from titanium, vanadium, zirconium and hafnium,
X is a halogen excluding iodine,
R is an aliphatic, cycloaliphatic or aromatic hydrocarbon radical, containing at least 4 carbon atoms, up to about 25 carbon atoms,
n varies from 0 to 1, and
m varies from 0 to 2, and wherein the atomic ratio between the magnesium in (II) and the transition metal (M) in (III) is within the range of 0.3:1 to 20:1;
(ii) the addition to the solution of step (i) of an alkyl aluminium halide having the formula:
AlR′
p
X
(3−p)
(IV)
wherein:
R′ is a linear or branched alkyl radical, containing from 1 to 20 carbon atoms, and
X is a halogen atom excluding iodine, and wherein the ratio between the halogen atoms in (IV) and the total carboxy groups in (II) and (III) varies from 0.3:1 to 10:1, to precipitate the solid component of catalyst (I) into a solid granular form, and
(iii) the recovery of the solid component of catalyst from the reaction products of step (ii).
The solvent used to prepare the solution in step (i) of the procedure, may be any inert (not reactive) organic solvent towards the other constituents. Preferred solvents for the purpose are aliphatic, cycloaliphatic or aromatic hydrocarbon solvents, liquid in the operating conditions, such as hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, benzene, toluene, xylenes and mesithylenes.
Examples of R—COO carboxylic groups, in formulae (II) and (III), are those wherein:
the radical R is a linear alkyl containing at least 9 carbon atoms; for example n-decanoate, n-undecanoate and n-dodecanoate groups;
the radical R is a branched alkyl product having a branching on the secondary carbon atom in &agr; with respect to the carboxyl carbon:
wherein the sum of carbon atoms in R
1
and R
2
is equal to at least 2; for example isobutyrate groups, 2-methylbutyrate groups and 2-ethylhexanoate groups;
the radical R is a branched alkyl having two branchings on the tertiary carbon atom in &agr; with respect to the carboxyl carbon
wherein the sum of the carbon atoms in R
3
, R
4
and R
5
is equal to at least 3; for example 2,2-dimethyl propanoate and versatate groups;
the radical R is an alkyl having a branching on the secondary carbon atom in &bgr; position with respect to the carboxyl carbon atom:
wherein the sum of the carbon atoms in R
6
and R
7
is equal to at least 4; for example 3-ethyl pentanoate and citronellate groups;
the radical R is a cycloalkyl, cycloaryl, alkylene cycloalkyl or alkylene cycloaryl:
R
a
—(CH
2
)
a
—COO
wherein R
8
represents the cycloalkyl or cycloaryl portion, either monocyclic or with several condensed or uncondensed cycles, and s varies from 0 to 10; for example the naphthenate group;
the radical R is an alkyl substituted with aryl in position &agr; with respect to the carboxyl carbon atom:
wherein R
9
is an aryl, for example a phenyl and R
10
is an alkyl containing at least 1 carbon atom; for example the 2-phenylbutyrate group.
In accordance with one embodiment, the metal M, in formula (III), represents titanium, or titanium and another metal selected from zirconium and hafnium, with an atomic ratio between the titanium and the other metal of 0.25:1 to 2.0:1 and preferably 0.33:1 to 1:1.
In another preferred embodiment, X, in formulae (II) and (III), represents chlorine or bromine and in the preferred form chlorine.
In accordance with a furth
Barazzoni Lia
Ferrero Cesare
Invernizzi Renzo
Masi Francesco
Masini Sergio
Choi Ling-Siu
ECP Enichem Polimeri S.r.l.
Kramer Levin Naftalis & Frankel LLP
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