Catalyst component dispersion comprising an ionic compound and solid addition polymerization catalysts containing the same

A non-supported solid catalyst comprising (a) an ionic compound comprising a.1) a cation and a.2) an anion having up to 100 nonhydrogen atoms and said anion containing at least one substituent comprising an active hydrogen moiety, (b) a transition metal compound, and (c) an organometal compound wherein the metal is selected from the Groups 1-14 of the Periodic Table of the Elements; a supported solid catalyst comprising (a), (b), (c), and (d) a support material, obtainable by combining components (a), (b), (c), and (d) in any order, and wherein during at least one step in the preparation of the solid catalyst, component (a) dissolved in a diluent in which (a) is soluble, is converted into solid form; a method for preparing the solid catalysts; and a process of polymerization using these solid catalysts.

FIELD OF THE INVENTION 
This invention relates to a catalyst component dispersion comprising an 
ionic compound in solid form, to a non-supported solid catalyst comprising 
a transition metal compound, an ionic compound, and an organometal 
compound, to a supported solid catalyst comprising a transition metal 
compound, an ionic compound, an organometal compound, and a support 
material, to a method for preparing the catalyst component dispersion, to 
a method for preparing the solid catalysts, to a method for activating a 
catalyst suitable for addition polymerization, and to an addition 
polymerization process using the solid catalysts. 
BACKGROUND OF THE INVENTION 
Homogeneous ionic transition metal catalysts are known for their high 
catalytic activity in addition polymerizations, especially those of 
olefins and diolefins, and are capable of providing olefinic polymers of 
narrow molecular weight distributions and, for example when ethylene is 
copolymerized with a further alpha-olefin, narrow comonomer distributions. 
Under polymerization conditions where polymer is formed as solid 
particles, e.g. in gas phase or slurry phase polymerizations, these 
homogeneous (soluble) catalysts form polymer deposits on reactor walls and 
stirrers which deposits should be removed frequently as they prevent an 
efficient heat-exchange necessary for cooling the reactor contents, 
prevent the regular or continuous removal of polymer from the reactor, and 
cause excessive wear of the moving parts in the reactor. The polymers 
produced by these soluble catalysts further have undesirable particle 
characteristics such as a low bulk density which limits the commercial 
utility of both the polymer and the process. Therefore, there is a need to 
provide catalysts that would overcome such problems. 
Several supported catalysts have been proposed for use in particle forming 
polymerization processes. Support materials in the prior art are typically 
employed in combination with catalytic components to obtain the formation 
of polymer particles of desirable particle size and morphology. Secondly, 
support materials are used to increase catalytic activity per unit of 
active components by depositing such components on a support material 
having a relatively high surface area. Furthermore, support materials are 
employed for anchoring thereon the catalytic components to avoid the 
presence of significant amounts of catalyst which under particle forming 
polymerization conditions becomes solubilized and gives rise to particles 
of undesired size and morphology, said particles contributing to the 
formation of polymer deposits at reactor walls and other moving parts in 
the reactor. 
EP-327649 and EP-725086 describe solid catalysts using alumoxanes as 
cocatalyst. EP-327649 relates to a non-supported olefin polymerization 
catalyst composed of a transition metal compound and an alumoxane having 
an average particle size of 5 to 200 micrometers and a specific surface 
area of 20 to 1,000 m.sup.2 /g. EP-725086 describes a solid component of a 
catalyst for ethylene and alpha-olefins (co)polymerization comprising a 
metallocene supported on an inorganic solid carrier, where a carbon atom 
of one of the .eta..sup.5 -cyclopentadienyl rings coordinated to the 
transition metal is covalently bonded to a metal atom of the inorganic 
solid carrier. This solid component is typically used with an organic 
aluminum oxy-derivative which is usually alumoxane. 
Supported non-alumoxane catalysts are disclosed, for example, in EP-418044, 
EP-522581, WO-91/09882, WO-94/03506, WO-9403509, and WO-9407927. These 
describe supported catalysts obtained by combining a transition metal 
compound, an activator component comprising a cation capable of reacting 
with a transition metal compound and a bulky, labile anion capable of 
stabilizing the metal cation formed as a result of reaction between the 
metal compound and the activator component, and a catalyst support 
material. In EP-522581 and WO-9407927 additionally an organometal 
compound, typically an organoaluminum compound is employed. 
EP-727443 describes an olefin polymerization catalyst obtainable by 
contacting a transition metal compound, an organometallic compound, and a 
solid catalyst component comprising a carrier and an ionized ionic 
compound capable of forming a stable anion on reaction with said 
transition metal compound, wherein said ionized ionic compound comprises a 
cationic component and an anionic component and said cationic component is 
fixed on the surface of the carrier. 
WO-96/04319 describes a catalyst composition comprising a metal oxide 
support having covalently bound to the surface thereof directly through 
the oxygen atom of the metal oxide, an activator anion that is also 
ionically bound to a catalytically active transition metal compound. 
WO-93/11172 relates to polyanionic moieties comprising a plurality of 
non-coordinating anionic groups pendant from and chemically bonded to a 
core component. The core component may be a cross-linked polystyrene or 
polydivinylbenzene polymeric core or a polyanionic Lewis basic core 
substrate reactable with a Lewis acid. The polyanionic moieties are used 
in a non-coordinating association with cationic transition metal 
compounds. 
Copending application Ser. No. 08/610,647, filed Mar. 4, 1996, 
corresponding to WO-96/28480, describes supported catalyst components 
comprising a support material, an organometal compound, an activator 
compound comprising a cation which is capable of reacting with a 
transition metal compound to form a catalytically active transition metal 
complex and a compatible anion having up to 100 nonhydrogen atoms and 
containing at least one substituent comprising an active hydrogen moiety. 
When combined with a transition metal compound, the resulting supported 
catalysts are very useful addition polymerization catalysts. 
It would be desirable to provide a solid catalyst and solid catalyst 
dispersions, and components or precursors therefor, which do not require 
an alumoxane component and which can be used in particle formation 
polymerization processes without requiring a support material. 
It would also be desirable to provide a solid catalyst, including 
precursors therefor, which when used in a polymerization process are 
capable of producing polymers at good catalyst efficiencies. 
It is a further object to provide a solid catalyst, including precursors 
therefor, which when used in a particle forming polymerization process 
give reduced amounts of particles of undesired size and morphology. It is 
yet a further object to provide a solid catalyst, including precursors 
therefor, which when used in a particle forming polymerization process 
prevents or largely removes the problem of formation of polymer deposits 
at reactor walls and other moving parts in the reactor. 
It is yet a further object to provide a solid catalyst and polymerization 
process that is capable of forming polymers in the form of free flowing 
powder or particles. 
It is another object to provide a method for making a solid catalyst 
without requiring recovery or purification steps. 
It is a further object to provide a solid catalyst which further comprises 
a support material. 
One or several of these objects are accomplished by the embodiments of the 
present invention described hereinafter. 
SUMMARY OF THE INVENTION 
In one aspect of the present invention there is provided a catalyst 
component dispersion comprising (a) an ionic compound comprising a.1) a 
cation and a.2) an anion having up to 100 nonhydrogen atoms and said anion 
containing at least one substituent comprising an active hydrogen moiety, 
wherein (a) is in solid form dispersed in a diluent in which (a) is 
insoluble or sparingly soluble. 
In a further aspect the invention provides a non-supported solid catalyst 
comprising (a) an ionic compound comprising a.1) a cation and a.2) an 
anion having up to 100 nonhydrogen atoms and containing at least one 
substituent comprising an active hydrogen moiety, (b) a transition metal 
compound, and (c) an organometal compound wherein the metal is selected 
from the Groups 1-14 of the Periodic Table of the Elements 
In another aspect of the invention there is provided a supported solid 
catalyst comprising (a) an ionic compound comprising a.1) a cation and 
a.2) an anion having up to 100 nonhydrogen atoms and said anion containing 
at least one substituent comprising an active hydrogen moiety, (b) a 
transition metal compound, (c) an organometal compound wherein the metal 
is selected from the Groups 1-14 of the Periodic Table of the Elements, 
and (d) a support material, wherein the solid catalyst is obtained by 
combining components (a), (b), (c), and (d) in any order, and wherein 
during at least one step in the preparation of the solid catalyst, 
component (a) dissolved in a diluent in which (a) is soluble, optionally 
in the presence of one or more of components (b), (c), and (d) or the 
contact product of (a) with such one or more of (b), (c), and (d), is 
converted into solid form. 
In yet a further aspect there is provided a method for preparing a catalyst 
component dispersion comprising converting a solution of an ionic compound 
(a) comprising a.1) a cation and a.2) an anion having up to 100 
nonhydrogen atoms and said anion containing at least one substituent 
comprising an active hydrogen moiety, in a diluent in which (a) is soluble 
into a dispersion comprising component (a) in solid form dispersed in a 
diluent in which (a) is insoluble or sparingly soluble. 
In a further aspect the present invention provides a method for preparing a 
solid catalyst comprising combining, in any order, (a) an ionic compound 
comprising a.1) a cation and a.2) an anion having up to 100 nonhydrogen 
atoms and said anion containing at least one substituent comprising an 
active hydrogen moiety, (a) a transition metal compound, (c) an 
organometal compound wherein the metal is selected from the Groups 1-14 of 
the Periodic Table of the Elements, and optionally (d) a support material, 
wherein during at least one step in the preparation of the solid catalyst, 
component (a) dissolved in a diluent in which (a) is soluble, optionally 
in the presence of one or more of components (b), (c), and (d) or the 
contact product of (a) with such one or more of (b), (c), and (d), is 
converted into solid form, optionally followed by recovering the solid 
catalyst. 
In yet another aspect the invention provides a method for activating a 
catalyst suitable for addition polymerization wherein a substantially 
inactive catalyst precursor comprising (a) an ionic compound comprising 
a.1) a cation and a.2) an anion having up to 100 nonhydrogen atoms and 
said anion containing at least one substituent comprising an active 
hydrogen moiety, (b) a transition metal compound, and optionally (d) a 
support material, is contacted with (c) an organometal compound wherein 
the metal is selected from the Groups 1-14 of the Periodic Table of the 
Elements, to form an active catalyst. 
According to a final aspect, the present invention provides an addition 
polymerization process wherein one or more addition polymerizable monomers 
are contacted with a solid catalyst according to the invention under 
addition polymerization conditions. 
Surprisingly, it has been found that the ionic compound (a) can be 
advantageously used in a solid form dispersed in a diluent in which (a) is 
insoluble or sparingly soluble (the diluent in which (a) is insoluble or 
sparingly soluble is also referred to as "non-solvent"; the diluent in 
which (a) is soluble is also referred to as "solvent"). By use of the 
dispersed solid ionic compound (a) in association with transition metal 
compound (b) and organometal compound (c) an active solid particulate 
addition polymerization catalyst results, preferably in dispersed form. 
Such a solid dispersed catalyst advantageously can be used in a particle 
forming polymerization process, such as a slurry or gas phase 
polymerization process, without requiring an additional support material 
to produce polymer of the desired particle size and morphology. The solid 
dispersed catalysts of the present invention can produce polymers in the 
form of free flowing powder or particles, without causing substantial 
polymer deposits at reactor walls and other moving parts in the reactor. 
Free flowing ethylene based polymers and interpolymers preferably have 
bulk densities of at least about 0.20 g/cm.sup.3, and more preferably of 
at least about 0.25 g/cm.sup.3. 
When the catalyst of the present invention includes a support material (d) 
the versatility of the catalyst is improved. Employing a support material 
allows the particle size of the solid catalyst to be varied between wider 
ranges. 
DETAILED DESCRIPTION OF THE INVENTION 
All references herein to elements or metals belonging to a certain Group 
refer to the Periodic Table of the Elements published and copyrighted by 
CRC Press, Inc., 1989. Also any reference to the Group or Groups shall be 
to the Group or Groups as reflected in this Periodic Table of the Elements 
using the IU system for numbering groups. 
The term "non-supported" as used in the present application means in the 
absence of a material which typically may be used as support or carrier in 
addition polymerization catalyst, more in particular as olefin addition 
polymerization catalyst. Conversely, the term "supported" as used in the 
present application means in the presence of a material which typically 
may be used as support or carrier in addition polymerization catalyst, 
more in particular as olefin addition polymerization catalyst. Where in 
the present application the term "solid catalyst" is used, it embraces 
both non-supported and supported solid catalysts, unless it follows 
differently from the context. 
Where in the present invention a composition is defined by its starting 
components or starting compounds optionally in combination with certain 
process steps, such as for example contacting and combining steps, it is 
meant that the composition encompasses starting components or starting 
compounds but also the reaction product or reaction products of the 
starting components or starting compounds to the extent a reaction has 
taken place. 
The dispersion of (a) of the present invention is preferably characterized 
by an average particle size of (a), as measured by laser diffraction, in 
the range of from 0.1 to 200 .mu.m, more preferably in the range of from 
0.5 to 50 .mu.m. The dispersion of (a) preferably contains from 0.00001 to 
10 mole of solid compound (a)/l, more preferably from 0.0001 to 1 mole/l. 
The particle size of the dispersion of (a) was measured using a Malvern 
Mastersizer particle size analyser. 
Ionic compounds (a) to be used in the present invention and their methods 
of preparation are described in U.S. patent application Ser. No. 
08/610,647, filed Mar. 4, 1996 (corresponding to WO-96/28480) which is 
incorporated herein by reference. The term used in the anion a.2) of the 
ionic compound "at least one substituent comprising an active hydrogen 
moiety" means in the present application a substituent comprising a 
hydrogen atom bonded to an oxygen, sulphur, nitrogen or phosphorous atom. 
In the anion a.2), the at least one substituent comprising an active 
hydrogen moiety preferably corresponds to the formula 
EQU G.sub.q (T--H).sub.r (I) 
wherein G is a polyvalent hydrocarbon radical, the group (T--H) is a 
radical wherein T comprises O, S, NR, or PR, the O, S, N, or P atom of 
which is bonded to hydrogen atom H, wherein R is a hydrocarbyl radical, a 
trihydrocarbyl silyl radical, a trihydrocarbyl germyl radical, or 
hydrogen, H is hydrogen, q is 0 or 1, and preferably 1, and r is an 
integer from 1 to 3, preferably 1. Polyvalent hydrocarbon radical G has 
r+1 valencies, one valency being associated with a metal or metalloid of 
the Groups 5-15 of the Periodic Table of the Elements in the anion, the 
other r valencies of G being attached to r groups (T--H). Preferred 
examples of G include di- or trivalent hydrocarbon radicals such as: 
alkylene, arylene, aralkylene, or alkarylene radicals containing from 1 to 
20 carbon atoms, more preferably from 2 to 12 carbon atoms. Suitable 
examples of divalent hydrocarbon radicals G include phenylene, 
biphenylene, naphthylene, methylene, ethylene, 1,3-propylene, 
1,4-butylene, phenylmethylene (--C.sub.6 H.sub.4 --CH.sub.2 --). The 
polyvalent hydrocarbyl portion G may be further substituted with radicals 
that do not negatively impact the effect to be achieved by the present 
invention. Preferred examples of such non-interfering substituents are 
alkyl, aryl, alkyl- or aryl-substituted silyl and germyl radicals, and 
fluoro substituents. 
The group (T--H) in the previous formula may be an --OH, --SH, --NRH, or 
--PRH group, wherein R preferably is a C.sub.1-18, preferably a 
C.sub.1-12, hydrocarbyl radical or hydrogen, and H is hydrogen. Preferred 
R groups are alkyls, cycloalkyls, aryls, arylalkyls, or alkylaryls of 1 to 
18 carbon atoms, more preferably those of 1 to 12 carbon atoms. 
Alternatively, the group (T--H) comprises an --OH, --SH, --NRH, or --PRH 
group which are part of a larger functional moiety such as, for example, 
C(O)--OH, C(S)--OH, C(S)--SH, C(O)--SH, C(O)--NRH, C(S)--NRH, and 
C(O)--PRH, and C(S)--PRH. Most preferably, the group (T--H) is a hydroxy 
group, --OH, or an amino group, --NRH. 
Very preferred substituents G.sub.q (T--H) in anion a.2) include hydroxy- 
and amino-substituted aryl, aralkyl, alkaryl or alkyl groups, and most 
preferred are the hydroxyphenyls, especially the 3- and 4-hydroxyphenyl 
groups and 2,4-dihydroxyphenyl, hydroxytolyls, hydroxybenzyls 
(hydroxymethylphenyl), hydroxybiphenyls, hydroxynaphthyls, 
hydroxycyclohexyls, hydroxymethyls, and hydroxypropyls, and the 
corresponding amino-substituted groups, especially those substituted with 
--NRH wherein R is an alkyl or aryl radical having from 1 to 10 carbon 
atoms, such as for example methyl, ethyl, propyl, i-propyl, n-, i-, or 
t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl, phenyl, benzyl, 
tolyl, xylyl, naphthyl, and biphenyl. 
The anion a.2) may further comprise a single Group 5-15 element or a 
plurality of Group 5-15 elements but is preferably a single coordination 
complex comprising a charge-bearing metal or metalloid core. Preferred 
anions a.2) are those containing a single coordination complex comprising 
a charge-bearing metal or metalloid core carrying the at least one 
substituent containing an active hydrogen moiety. Suitable metals for the 
anions of ionic compounds (a) include, but are not limited to, aluminum, 
gold, platinum and the like. Suitable metalloids include, but are not 
limited to elements of groups 13, 14, and 15, of the periodic table of 
elements, preferably are, boron, phosphorus, and silicon. Ionic compounds 
which contain anions comprising a coordination complex containing a single 
boron atom and one or more substituents comprising an active hydrogen 
moiety are preferred. Examples of suitable anions comprising a single 
Group 5-15 element are disclosed in EP 277 004 and examples of those 
having a plurality of Group 5-15 elements are disclosed in EP 0 277 003, 
with the proviso that at least one of the subsituents in the anions 
described therein is substituted by a substituent comprising an active 
hydrogen moiety, preferably G.sub.q (T--H).sub.r. 
Preferably, anions a.2) may be represented by a single coordination complex 
of the following general Formula (II): 
EQU M'.sup.m+ Q.sub.n (G.sub.q (T--H).sub.r).sub.z !.sup.d- (II) 
wherein: 
M' is a metal or metalloid selected from Groups 5-15 of the Periodic Table 
of the Elements; 
Q independently in each occurrence is selected from the group consisting of 
hydride, dihydrocarbylamido, preferably dialkylamido, halide, 
hydrocarbyloxide, preferably alkoxide and aryloxide, hydrocarbyl, and 
substituted-hydrocarbyl radicals, including halo-substituted hydrocarbyl 
radicals, and hydrocarbyl- and halohydrocarbyl-substituted 
organo-metalloid radicals, the hydrocarbyl portion in each of these groups 
preferably having from 1 to 20 carbons, with the proviso that in not more 
than one occurrence is Q halide; 
G is a polyvalent hydrocarbon radical having r+1 valencies, and preferably 
a divalent hydrocarbon radical, bonded to M' and r groups (T--H); 
the group (T--H) is a radical wherein T comprises O, S, NR, or PR, the O, 
S, N, or P atom of which is bonded to hydrogen atom H, wherein R is a 
hydrocarbon radical, a trihydrocarbyl silyl radical, a trihydrocarbyl 
germyl radical, or hydrogen; 
m is an integer from 1 to 7, preferably 3; 
n is an integer from 0 to 7, preferably 3; 
q is an integer 0 or 1, preferably 1; 
r is an integer from 1 to 3, preferably 1; 
z is an integer from 1 to 8, preferably 1 or 2; 
d is an integer from 1 to 7, preferably 1; and 
n+z-m=d. 
When q is 0 and polyvalent hydrocarbon radical G is not present, T is bound 
to M'. Preferred boron-containing anions a.2) which are particularly 
useful in this invention may be represented by the following general 
Formula (III): 
EQU BQ.sub.4-z' (G.sub.q (T--H).sub.r).sub.z' !.sup.d- (III) 
wherein: 
B is boron in a valence state of 3; 
z' is an integer from 1-4, preferably 1 or 2, most preferably 1; 
d is 1; and 
Q, G, T, H, q, and r are as defined for Formula (II). Preferably, z' is 1 
or 2, q is 1, and r is 1. 
Illustrative, but not limiting, examples of anions a.2) of ionic compounds 
to be used in the present invention are boron-containing anions such as: 
triphenyl(hydroxyphenyl)borate, triphenyl(2,4-dihydroxyphenyl)borate, 
tri(p-tolyl)(hydroxyphenyl)borate, 
tris-(pentafluorophenyl)(hydroxyphenyl)borate, 
tris-(2,4-dimethylphenyl)(hydroxyphenyl)borate, 
tris-(3,5-dimethylphenyl)(hydroxyphenyl)borate, 
tris-(3,5-di-trifluoromethyl-phenyl)(hydroxyphenyl)borate, 
tris(pentafluorophenyl)(2-hydroxyethyl)borate, 
tris(pentafluorophenyl)(4-hydroxybutyl)borate, 
tris(pentafluorophenyl)(4-hydroxycyclohexyl)borate, 
tris(pentafluorophenyl)(4-(4'-hydroxyphenyl)phenyl)borate, 
tris(pentafluorophenyl)(6-hydroxy-2-naphthyl)borate, and the like. 
Further preferred anions a.2) include those containing two substituents 
containing an active hydrogen moiety, for example: 
diphenyldi(hydroxyphenyl)borate, diphenyldi(2,4-dihydroxyphenyl)borate, 
di(p-tolyl) di(hydroxyphenyl)borate, 
di(pentafluorophenyl)di-(hydroxyphenyl)borate, di(2,4-dimethylphenyl) 
di(hydroxyphenyl)borate, di (3,5-dimethylphenyl) di(hydroxyphenyl)borate, 
di (3,5-di-trifluoromethylphenyl) di(hydroxyphenyl)borate, 
di(pentafluorophenyl) di(2-hydroxyethyl)borate, di(pentafluorophenyl) 
di(4-hydroxybutyl)borate, di(pentafluorophenyl) 
di(4-hydroxycyclohexyl)borate, di(pentafluorophenyl) 
di(4-(4'-hydroxyphenyl)phenyl)borate, di(pentafluorophenyl) 
di(6-hydroxy-2-naphthyl)borate, and the like. 
Other preferred anions are those above mentioned borates wherein the 
hydroxy functionality is replaced by an amino NHR functionality wherein R 
preferably is methyl, ethyl, or t-butyl. A highly preferred anion a.2) is 
tris(pentafluorophenyl)(4-hydroxyphenyl) borate. 
The cationic portion a.1) of the ionic compound is preferably selected from 
the group consisting of Bronsted acidic cations, especially ammnonium and 
phosphonium cations or sulfonium cations, carbonium cations, silylium 
cations, oxonium cations, and cationic oxidizing agents. The cations a.1) 
and the anions a.2) are used in such ratios as to give a neutral ionic 
compound. 
Bronsted acidic cations may be represented by the following general formula 
: 
EQU (L--H).sup.+ 
wherein: 
L is a neutral Lewis base, preferably a nitrogen, phosphorus, oxygen, or 
sulfur containing Lewis base; and (L--H).sup.+ is a Bronsted acid. 
Illustrative, but not limiting, examples of Bronsted acidic cations are 
trihydrocarbyl- and preferably trialkyl-substituted ammonium cations such 
as triethylammonium, tripropylammonium, tri(n-butyl)ammonium, 
trimethylammonium, tri(i-butyl)ammonium, and tri(n-octyl)ammonium. Also 
suitable are N,N-dialkyl anilinium cations such as N,N-dimethylanilinium, 
N,N-diethyl-anilinium, N,N-2,4,6-pentamethylanilinium, 
N,N-dimethylbenzylammonium and the like; dialkylammonium cations such as 
di-(i-propyl)ammonium, dicyclohexylammonium and the like; and 
triarylphosphonium cations such as triphenylphosphonium, 
tri(methylphenyl)phosphonium, tri(dimethylphenyl)phosphonium, 
dimethylsulphonium, diethylsulphonium, and diphenylsulphonium. 
In a highly preferred embodiment, the Bronsted acidic cation a.1) may be 
represented by the following general formula: 
EQU L*--H!.sup.+, 
wherein: 
L* is a nitrogen, oxygen, sulfur or phosphorus containing Lewis base which 
comprises at least one relatively long chain alkyl group. Preferably such 
L* groups contain from one to three C.sub.10-40 alkyl groups with a total 
of from 12 to 100 carbons, more preferably two C.sub.10-40 alkyl groups 
and from 21 to 90 total carbons. It is understood that the cation may 
comprise a mixture of alkyl groups of differing lengths. For example, one 
suitable cation is the protonated ammonium salt derived from the 
commercially available long chain amine comprising a mixture of two 
C.sub.14, C.sub.16 or C.sub.18 alkyl groups and one methyl group. Such 
amines are available from Witco Corp., under the trade name Kemamine.TM. 
T9701, and from Akzo-Nobel under the trade name Armeen.TM. M2HT. These 
preferred cations are described in U.S. provisional application Ser. No. 
60/014,284, filed Mar. 27, 1996, which is incorporated herein by 
reference. Ionic compounds (a) comprising the cation L*--H!.sup.+ can be 
easily prepared by subjecting an ionic compound comprising the cation 
L--H!.sup.+ and the anion a.2), as prepared in U.S. patent application 
Ser. No. 08/610,647, filed Mar.4, 1996 (corresponding to WO-96/28480), to 
a cation exchange reaction with a L*--H!.sup.+ salt. 
Illustrative, but not limiting examples of the highly preferred cations 
a.1) are tri-substituted ammonium salts such as: decyldi(methyl)ammonium, 
dodecyldi(methyl)ammonium, tetradecyldi(methyl)ammonium, 
hexaadecyldi(methyl)ammonium, octadecyldi(methyl)ammonium, 
eicosyldi(methyl)ammonium, methyldi(decyl)ammonium, 
methyldi(dodecyl)ammonium, methyldi(tetradecyl)ammonium, 
methyldi(hexadecyl)ammonium, methyldi(octadecyl)ammonium, 
methyldi(eicosyl)ammonium, tridecylammonium, tridodecylammonium, 
tritetradecylammonium, trihexadecylammonium, trioctadecylammonium, 
trieicosylammonium, decyldi(n-butyl)ammonium, dodecyldi(n-butyl)ammonium, 
octadecyldi(n-butyl)ammonium, N,N-didodecylanilinium, 
N-methyl-N-dodecylanilinium, N,N-di(octadecyl)(2,4,6-trimethylanilinium), 
cyclohexyldi(dodecyl)ammonium, and methyldi(dodecyl)ammonium. 
Suitable similarly substituted sulfonium or phosphonium cations such as, 
di(decyl)sulfonium, (n-butyl)dodecylsulfonium, tridecylphosphonium, 
di(octadecyl)methylphosphonium, and tri(tetradecyl)phosphonium, may also 
be named. 
Preferred ionic compounds (b) are di(octadecyl)methylammonium 
tris(pentafluorophenyl) (hydroxyphenyl)borate, octadecyl dimethylammonium 
tris(pentafluorophenyl)borate and di(octadecyl)(n-butyl)ammonium 
tris(pentafluorophenyl)(hydroxyphenyl)-borate, as well as the amino 
(--NHR) analogues of these compounds wherein the hydroxyphenyl group is 
replaced by the aminophenyl group. 
A second type of suitable cation corresponds to the formula: c.sup.+, 
wherein c.sup.+ is a stable carbonium or silylium ion containing up to 30 
nonhydrogen atoms. Suitable examples of cations include tropyllium, 
triphenylmethylium, benzene(diazonium). Silylium salts have been 
previously generically disclosed in J. Chem. Soc. Chem. Comm., 1993, 
383-384, as well as Lambert, J. B., et. al., Organometallics, 1994, 13, 
2430-2443. Preferred silylium cations are triethylsilylium, and 
trimethylsilylium and ether substituted adducts thereof. 
Another suitable type of cation comprises a cationic oxidizing agent 
represented by the formula: 
EQU Ox.sup.e+ 
wherein Ox.sup.e+ is a cationic oxidizing agent having a charge of e+, and 
e is an integer from 1 to 3. 
Examples of cationic oxidizing agents include: ferrocenium, 
hydrocarbyl-substituted ferrocenium, Ag.sup.+, and Pb.sup.2+. 
According to a further aspect of the present invention there is provided a 
non-supported solid catalyst comprising the ionic compound (a), (b) a 
transition metal compound, and (c) an organometal compound wherein the 
metal is selected from the Groups 1-14 of the Periodic Table of the 
Elements. The present invention furthermore provides a supported solid 
catalyst comprising ionic compound (b), transition metal compound (b), 
organometal compound (c), and a support material (do. Suitable ionic 
compounds (a) have been described hereinabove. The non-supported solid 
catalyst are preferably dispersed in a diluent in which the solid catalyst 
is insoluble or sparingly soluble. 
Suitable transition metal compounds (b) for use in the present invention 
include any compound or complex of a metal of Groups 3-10 of the Periodic 
Table of the Elements capable of being activated to olefin insertion and 
polymerization when combined with components (a) and (c) and optionally 
(d) of the present invention. Examples include Group 10 transition metal 
diimine derivatives which are described in WO96/23010. 
Additional catalysts include derivatives of Group 3, 4, 5, or 6 or 
Lanthanide metals which are in the +2, +3, or +4 formal oxidation state. 
Preferred compounds include metal complexes containing from 1 to 3 
.pi.-bonded anionic or neutral ligand groups, which may be cyclic or 
non-cyclic delocalized n-bonded ligand groups. Exemplary of such 
.pi.-bonded ligand groups are conjugated or nonconjugated, cyclic or 
non-cyclic dienyl groups, allyl groups, boratabenzene groups, and arene 
groups. By the term ".pi.-bonded" is meant that the ligand group is bonded 
to the transition metal by means of delocalized .pi. electrons thereof. 
Each atom in the delocalized .pi.-bonded group may independently be 
substituted with a radical selected from the group consisting of hydrogen, 
halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl substituted metalloids, 
hdyrocarbyloxy, dihydrocarbylamino, wherein the metalloid is selected from 
Group 14 of the Periodic Table of the Elements and hydrocarbyl radicals or 
hydrocarbyl-substituted metalloid radicals further substituted with a 
Group 15 or 16 hetero atom containing moiety. Included within the term 
"hydrocarbyl" are C.sub.1-20 straight, branched and cyclic alkyl radicals, 
C.sub.6-20 aromatic radicals, C.sub.7-20 alkyl-substituted aromatic 
radicals, and C.sub.7-20 aryl-substituted alkyl radicals. In addition two 
or more such radicals may together form a fused ring system, a 
hydrogenated fused ring system, or a metallocycle with the metal. Suitable 
hydrocarbyl-substituted organometalloid radicals include mono-, di- and 
tri-substituted organometalloid radicals of Group 14 elements wherein each 
of the hydrocarbyl groups contains from 1 to 20 carbon atoms. Examples of 
suitable hydrocarbyl-substituted organometalloid radicals include 
trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, 
triphenylgermyl, and trimethylgermyl groups. Such hydrocarbyl and 
hydrocarbyl-substituted organometalloid radicals may be further 
substituted with a Group 15 or 16 hetero-atom containing moiety. Examples 
of Group 15 or 16 hetero atom containing moieties include amine, 
phosphine, ether or thioether moieties (see for example the compounds 
disclosed in WO-96/13529) or divalent derivatives thereof, e.g. amide, 
phosphide, ether or thioether groups bonded to the transition metal or 
Lanthanide metal, and bonded to the hydrocarbyl group or to the 
hydrocarbyl substituted metalloid containing group. 
Examples of suitable anionic, delocalized .pi.-bonded groups include 
cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, 
tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, 
dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups, and 
boratabenzene groups, as well as C.sub.1-10 hydrocarbyl-substituted, 
C.sub.1-10 hydrocarbyl-substituted silyl substituted, C.sub.1-10 
hydrocarbyl substituted germyl derivatives thereof, and divalent 
derivatives of the foregoing substituents Preferred anionic delocalized 
.pi.-bonded groups are cyclopentadienyl, pentamethylcyclopentadienyl, 
tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, indenyl, 
2,3-dimethylindenyl, fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, 
tetrahydrofluorenyl, octahydrofluorenyl, and tetrahydroindenyl. 
The boratabenzenes are anionic ligands which are boron containing analogues 
to benzene. They are previously known in the art having been described by 
G. Herberich, et al., in Organometallics, 14,1, 471-480 (1995). Preferred 
boratabenzenes correspond to the formula: 
##STR1## 
wherein R" is selected from the group consisting of hydrocarbyl, silyl, or 
germyl, said R" having up to 20 non-hydrogen atoms. 
A suitable class of transition metal compounds useful in the present 
invention corresponds to the formula (V): 
EQU L.sub.l MX.sub.m X'.sub.n X".sub.p, or a dimer thereof (V) 
wherein: 
L is an anionic, delocalized, .pi.-bonded group that is bound to M, 
containing up to 50 non-hydrogen atoms, optionally two L groups may be 
joined together forming a bridged structure, and further optionally one L 
may be bound to X; 
M is a metal of Group 4 of the Periodic Table of the Elements in the +2, +3 
or +4 formal oxidation state; 
X is an optional, divalent substituent of up to 50 non-hydrogen atoms that 
together with L forms a metallocycle with M; 
X' is an optional neutral ligand base having up to 20 non-hydrogen atoms; 
X" each occurrence is a monovalent, anionic moiety having up to 40 
non-hydrogen atoms, optionally, two X" groups may be covalently bound 
together forming a divalent dianionic moiety having both valences bound to 
M, or, optionally two X" groups may be covalently bound together to form a 
neutral, conjugated or nonconjugated diene that is .pi.-bonded to M, or 
further optionally one or more X" and one or more X' groups may be bonded 
together thereby forming a moiety that is both covalently bound to M and 
coordinated thereto by means of Lewis base functionality; 
l is 0, 1 or 2; 
m is 0 or 1; 
n is a number from 0 to 3; 
p is an integer from 0 to 3; and 
the sum, l+m+p, is equal to the formal oxidation state of M, except when 2 
X" groups together form a neutral conjugated or non-conjugated diene that 
is .pi.-bonded to M, in which case the sum l+m is equal to the formal 
oxidation state of M. 
Preferred complexes include those containing either one or two L groups. 
The latter complexes include those containing a bridging group linking the 
two L groups. Preferred bridging groups are those corresponding to the 
formula (ER*.sub.2).sub.x wherein E is silicon, germanium, tin, or carbon, 
R* independently each occurrence is hydrogen or a group selected from 
silyl, hydrocarbyl, hydrocarbyloxy, and combinations thereof, said R* 
having up to 30 carbon or silicon atoms, and x is 1 to 8. Preferably, R* 
independently each occurrence is methyl, ethyl, propyl, benzyl, 
tert-butyl, phenyl, methoxy, ethoxy or phenoxy. 
Examples of the complexes containing two L groups are compounds 
corresponding to the formula (VI) and (VII): 
##STR2## 
wherein: M is titanium, zirconium or hafnium, preferably zirconium or 
hafnium, in the +2 or +4 formal oxidation state; 
R.sup.3 in each occurrence independently is selected from the group 
consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and 
combinations thereof, said R.sup.3 having up to 20 non-hydrogen atoms, or 
adjacent R.sup.3 groups together form a divalent derivative (i.e., a 
hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring 
system, and 
X" independently each occurrence is an anionic ligand group of up to 40 
non-hydrogen atoms, or two X" groups together form a divalent anionic 
ligand group of up to 40 non-hydrogen atoms or together are a conjugated 
diene having from 4 to 30 non-hydrogen atoms forming a .pi.-complex with 
M, whereupon M is in the +2 formal oxidation state, and 
R*, E and x are as previously defined for bridging groups 
(ER*.sub.2).sub.x. 
The foregoing metal complexes are especially suited for the preparation of 
polymers having stereoregular molecular structure. In such capacity it is 
preferred that the complex possesses C.sub.s symmetry or possesses a 
chiral, stereorigid structure. Examples of the first type are compounds 
possessing different delocalized .pi.-bonded systems, such as one 
cyclopentadienyl group and one fluorenyl group. Similar systems based on 
Ti(IV) or Zr(IV) were disclosed for preparation of syndiotactic olefin 
polymers in Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256 (1980). 
Examples of chiral structures include rac bis-indenyl complexes. Similar 
systems based on Ti(IV) or Zr(IV) were disclosed for preparation of 
isotactic olefin polymers in Wild et al., J. Organomet. Chem., 232, 
233-47, (1982). 
Exemplary bridged ligands containing two .pi.-bonded groups are: 
(dimethylsilyl-bis(cyclopentadienyl)), 
(dimethylsilyl-bis(methylcyclopentadienyl)), 
(dimethylsilyl-bis(ethylcyclopentadienyl)), 
(dimethylsilyl-bis(t-butylcyclopentadienyl)), 
(dimethylsilyl-bis(tetramethylcyclopentadienyl)), 
(dimethylsilyl-bis(indenyl)), (dimethylsilyl-bis(tetrahydroindenyl)), 
(dimethylsilyl-bis(fluorenyl)), (dimethylsilyl-bis(tetrahydrofluorenyl)), 
(dimethylsilyl-bis(2-methyl-4-phenylindenyl)), 
(dimethylsilyl-bis(2-methylindenyl)), 
(dimethylsilyl-cyclopentadienylfluorenyl), 
(dimethylsilyl-cyclopentadienyloctahydrofluorenyl), 
(dimethylsilyl-cyclopentadienyltetrahydrofluorenyl), 
(1,1,2,2-tetramethyl-1,2-disilyl-bis-cyclopentadienyl), 
(1,2-bis(cyclopentadienyl)ethane, and 
(isopropylidene-cyclopentadienyl-fluorenyl). 
Preferred X" groups in formula (VI) and (VII) are selected from hydride, 
hydrocarbyl, silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl 
and aminohydrocarbyl groups, or two X" groups together form a divalent 
derivative of a conjugated diene or else together they form a neutral, 
.pi.-bonded, conjugated diene. Most preferred X" groups are C.sub.1-20 
hydrocarbyl groups. 
A further class of metal complexes utilized in the present invention 
corresponds to the preceding formula (V) L.sub.l MX.sub.m X'.sub.n 
X".sub.p, or a dimer thereof, wherein X is a divalent substituent of up to 
50 non-hydrogen atoms that together with L forms a metallocycle with M. 
Preferred divalent X substituents include groups containing up to 30 
non-hydrogen atoms comprising at least one atom that is oxygen, sulfur, 
boron or a member of Group 14 of the Periodic Table of the Elements 
directly attached to the delocalized .pi.-bonded group, and a different 
atom, selected from the group consisting of nitrogen, phosphorus, oxygen 
or sulfur that is covalently bonded to M. 
A preferred class of such Group 4 metal coordination complexes used 
according to the present invention corresponds to the formula (VIII): 
##STR3## 
wherein: M is titanium or zirconium, preferably titanium in the +2, +3, or 
+4 formal oxidation state; 
R.sup.3 in each occurrence independently is selected from the group 
consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo, 
hydrocarbyloxy, dihydrocarbylamino, and combinations thereof, said R.sup.3 
having up to 20 non-hydrogen atoms, or adjacent R.sup.3 groups together 
form a divalent derivative (i.e., a hydrocarbadiyl, siladiyl or germadiyl 
group) thereby forming a fused ring system, 
each X' in formula (VIII) is a hydride, halide, hydrocarbyl, hydrocarbyloxy 
or silyl group, said group having up to 20 non-hydrogen atoms, or two X" 
groups together form a neutral C.sub.5-30 conjugated diene or a divalent 
derivative thereof; 
Y is --O--, --S--, --NR*--, --PR*--, --NR*.sub.2 or --PR*.sub.2 ; and 
Z is SiR*.sub.2, CR*.sub.2, SiR*.sub.2 SiR*.sub.2, CR*.sub.2 CR*.sub.2, 
CR*.dbd.CR*, CR*.sub.2 SiR*.sub.2, or GeR*.sub.2, wherein R* is as 
previously defined. 
Specific examples of the transition metal compounds of the types described 
above can be found in EP 0 129 368, EP 0 277 004, EP 0 416 815, 
WO-93/19104, WO-95/00526, WO-96/00734, WO-96/04290, WO-96/08498. 
Suitable organometal compounds (c) for use in the present invention are 
those comprising metals of Groups 1-14. Component (c) contains at least 
one substituent selected from hydride, hydrocarbyl radicals, 
trihydrocarbyl silyl radicals, and trihydrocarbyl germyl radicals. 
Additional substituents preferably comprise one or more substituents 
selected from hydride, halide, hydrocarbyloxide, dihydrocarbylamide 
hydrocarbyl radicals, trihydrocarbyl substituted silyl radicals, 
trihydrocarbyl substituted germyl radicals, and hydrocarbyl-, 
trihydrocarbyl silyl- or trihydrocarbyl germyl-substituted metalloid 
radicals. 
Examples of organometal compounds (c) include organo lithium, 
organomagnesium, organozinc, organoboron, organoaluminum, organosilicon, 
organogermanium, organotin, and organolead compounds, and mixtures 
thereof. Preferred examples are compounds represented by the following 
formulae: MgR.sup.1.sub.2, ZnR.sup.1.sub.2, BR.sup.1.sub.X R.sup.2 y, 
AlR.sup.1.sub.x R.sup.2 Y, wherein R.sup.1 independently each occurrence 
is hydride, a hydrocarbyl radical, a trihydrocarbyl silyl radical, a 
trihydrocarbyl germyl radical, or a trihydrocarbyl-, trihydrocarbyl 
silyl-, or trihydrocarbyl germyl-substituted metalloid radical, R.sup.2 
independently is the same as R.sup.1, x is 2 or 3, y is 0 or 1 and the sum 
of x and y is 3, and mixtures thereof. Examples of suitable hydrocarbyl 
moieties are those having from 1 to 20 carbon atoms in the hydrocarbyl 
portion thereof, such as alkyl, aryl, alkaryl, or aralkyl. Preferred 
radicals include methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, phenyl, 
and benzyl. Preferred components (c) are the aluminum compounds. 
Preferably, the aluminum component is an aluminum compounds of the formula 
AlR.sup.1.sub.x, wherein R.sup.1 in each occurrence independently is 
hydride or a hydrocarbyl radical having from 1 to 20 carbon atoms, and x 
is 3. Suitable trihydrocarbyl aluminum compounds are trialkyl or triaryl 
aluminum compounds wherein each alkyl or aryl group has from 1 to 10 
carbon atoms, or mixtures thereof, and preferably trialkyl aluminum 
compounds such as trimethyl, triethyl, tri-isobutyl aluminum. 
Alumoxanes (also referred to as aluminoxanes) may also be used as component 
(c). Alumoxanes are oligomeric or polymeric aluminum oxy compounds 
containing chains of alternating aluminum and oxygen atoms, whereby the 
aluminum carries a substituent, preferably an alkyl group. The structure 
of alumoxane is believed to be represented by the following general 
formulae (--Al(R)--O).sub.m, for a cyclic alumoxane, and R.sub.2 
Al--O(--Al(R)--O).sub.m --AlR.sub.2, for a linear compound, wherein R 
independently in each occurrence is a C.sub.1 -C.sub.10 hydrocarbyl, 
preferably alkyl, or halide and m is an integer ranging from 1 to about 
50, preferably at least about 4. Alumoxanes are typically the reaction 
products of water and an aluminum alkyl, which in addition to an alkyl 
group may contain halide or alkoxide groups. Reacting several different 
aluminum alkyl compounds, such as, for example, trimethyl aluminum and 
tri-isobutyl aluminum, with water yields so-called modified or mixed 
alumoxanes. Preferred alumoxanes are methylalumoxane and methylalumoxane 
modified with minor amounts of other lower alkyl groups such as isobutyl. 
Alumoxanes generally contain minor to substantial amounts of starting 
aluminum alkyl compound. 
The way in which the alumoxane is prepared is not critical. When prepared 
by the reaction between water and aluminum alkyl, the water may be 
combined with the aluminum alkyl in various forms, such as liquid, vapor, 
or solid, for example in the form of crystallization water. Particular 
techniques for the preparation of alumoxane type compounds by contacting 
an aluminum alkyl compound with an inorganic salt containing water of 
crystallization are disclosed in U.S. Pat. No. 4,542,199. In a particular 
preferred embodiment an aluminum alkyl compound is contacted with a 
regeneratable water-containing substance such as hydrated alumina, silica 
or other substance. This is disclosed in European Patent Application No. 
338,044. 
According to a further aspect the invention provides a supported solid 
catalyst comprising (a), (b), and (c) as described hereinbefore, as well 
as (d) a support material. 
Suitable support materials (d), also referred to as carriers or carrier 
materials, which may optionally be used in the present invention include 
those support materials which are typically used in the art of supported 
catalysts, and more in particular the art of supported olefin addition 
polymerization supported catalysts. Examples include porous resinous 
materials, for example, polyolefins such as polyethylenes and 
polypropylenes or copolymers of styrene-divinylbenzene, and solid 
inorganic oxides including oxides of Group 2, 3, 4, 13, or 14 metals, such 
as silica, alumina, magnesium oxide, titanium oxide, thorium oxide, as 
well as mixed oxides of silica. Suitable mixed oxides of silica include 
those of silica and one or more Group 2 or 13 metal oxides, such as 
silica-magnesia or silica-alumina mixed oxides. Silica, alumina, and mixed 
oxides of silica and one or more Group 2 or 13 metal oxides are preferred 
support materials. Preferred examples of such mixed oxides are the 
silica-aluminas. The most preferred support material is silica. The shape 
of the silica particles is not critical and the silica may be in granular, 
spherical, agglomerated, fumed or other form. 
Support materials suitable for the present invention preferably have a 
surface area as determined by nitrogen porosimetry using the B.E.T. method 
from 10 to about 1000 m.sup.2 /g, and preferably from about 100 to 600 
m.sup.2 /g. The pore volume of the support, as determined by nitrogen 
adsorption, is typically up to 5 cm.sup.3 /g, advantageously between 0.1 
and 3 cm.sup.3 /g, preferably from about 0.2 to 2 cm.sup.3 /g. The average 
particle size is not critical but typically is from 0.5 to 500 .mu.m, 
preferably from 1 to 200 .mu.m, more preferably to 100 .mu.m. 
The support material may be subjected to a heat treatment and/or chemical 
treatment to reduce the water content or the hydroxyl content of the 
support material. Both dehydrated support materials and support materials 
containing small amounts of water can be used. Typical, chemical 
dehydration or dehydroxylation agents are reactive metal hydrides, alkyls 
and halides such as aluminum alkyls, alkyl silicon halides and the like. 
Prior to its use, the support material can be subjected to a thermal 
treatment at 100.degree. C. to 100.degree. C., preferably at about 
200.degree. C. to about 850.degree. C. in an inert atmosphere or under 
reduced pressure. Typically, this treatment is carried out for about 10 
minutes to about 72 hours, preferably from about 0.5 hours to 24 hours. 
The support material, optionally thermally treated, may preferably be 
combined with a further organometal compound, more preferably an 
organoaluminum compound, most preferably a trialkylaluminum compound in a 
suitable diluent or solvent, preferably one in which the organometal 
compound is soluble. Typical solvents are hydrocarbon solvents having from 
5 to 12 carbon atoms, preferably aromatic solvents such as toluene and 
xylenes, or aliphatic solvents of 6 to 10 carbon atoms, such as hexane, 
heptane, octane, nonane, decane, and isomers thereof, cycloaliphatic 
solvents of 6 to 12 carbon atoms such as cyclohexane, or mixtures of any 
of these. 
The support material is combined with the organometal compound at a 
temperature of -20.degree. C. to 150.degree. C., preferably at 20.degree. 
C. to 100.degree. C. The contact time is not critical and can vary from 5 
minutes to 72 hours, and is preferably from 0.5 hours to 36 hours. 
Agitation is preferably applied. 
An alternative pretreatment of the support material involves a treatment 
with alumoxane. The alumoxane may be contacted with the support material 
in the manner described above or the alumoxane may be generated in situ on 
the support material by contacting an alkylaluminum, preferably 
trialkylaluminum compound, with a support material containing water. 
The pretreated support material is preferably recovered prior to its 
further use. 
According to the present invention, the ionic compound (a) can be formed 
into a dispersion of solid particles (a) by a controlled precipitation. 
This dispersion can be used as such in the preparation of a solid catalyst 
suitable for addition polymerization processes, thereby maintaining the 
dispersed nature. A range of suitable particle sizes for the solid 
dispersed catalyst can be obtained by selecting the solvents and 
non-solvents, temperature conditions and the specific catalyst components. 
No intermediate recovery or separation steps are required and the final 
solid catalyst, preferably still in dispersed form, may be employed as 
such in an addition polymerization process. Alternatively, the particulate 
solid (a) and the solid catalyst, and any solid intermediate product, can 
be recovered from the diluent in which it is dispersed by removing the 
liquid or non-solvent employing techniques such as filtration, vacuum 
drying, spray drying, and combinations thereof. Prior to its use, the 
particulate solid (a), the solid catalyst, and any solid intermediate 
product, may be redispersed in a suitable liquid diluent. 
The catalyst component dispersion of the present invention can be prepared 
by converting a solution of the ionic compound (a), in a diluent (solvent) 
in which (a) is soluble, into a dispersion comprising component (a) in 
solid form. 
A solution of ionic compound (a) in a diluent can be obtained by using an 
appropriate solvent in which (a) is soluble. The diluent in which (a) is 
dissolved is not critical. Preferably, the diluent is compatible with the 
other catalyst components and under polymerization conditions, so that it 
does not need to be removed prior to its further use. Suitable solvents 
for (a) include aromatic hydrocarbons, such as toluene, benzene, 
ethylbenzene, propylbenzene, butylbenzene, xylenes, chlorobenzene, and the 
like. 
When a solvent is used in which (a) is not sufficiently soluble, or in 
order to assist in or speed up dissolution of (a), heating may be applied 
or solubilizing agents may be used, or a combination of both. The 
solubilizing agent to be used is compatible with the catalyst components, 
in a sense that it does not adversely affect the beneficial properties of 
the catalyst. Heating is preferably done at temperatures not higher than 
the decomposition temperature of (a). During the dissolution of (a) 
stirring is advantageously applied. 
Preferably, the solution of (a) contains from 0.0001 to 100 mole of (a) per 
liter, more preferably from 0.001 to 10 mole per liter. Any non-dissolved 
(a) is preferably removed by, for example, filtration techniques, prior to 
further using the solution of (a). 
The solution of (a) is then converted into a dispersion comprising (a) in 
solid form. The conversion of the solution of (a) to a dispersion of (a) 
can be carried out, for example, by cooling the solution, by contacting 
the solution with a diluent (non-solvent) in which (a) is insoluble or 
sparingly soluble, by evaporating part of the solvent, by adding 
precipitating agents, or a combination of any of these techniques, to 
achieve a controlled precipitation or solidification such that a 
dispersion of (a) is formed. It will be clear to a person skilled in the 
art that the distinction between a solvent and a non-solvent for a 
particular ionic compound (a) will primarily depend on the nature of the 
particular compound (a), on the temperature, and relative amount of (a) to 
be dissolved. For a given ionic compound (a), the skilled person can 
easily determine what solvent and temperature conditions are to be used to 
obtain a solution of the desired concentration. On the other hand, given 
the solution of (a), the skilled person can easily determine the 
conditions and means to obtain the dispersion of (a) having the desired 
solids concentration. 
When precipitating agents are used, they are preferably compatible with the 
catalyst components, such that the beneficial properties of the catalyst 
are not adversely affected. 
The non-solvent employed for generating the dispersion of (a) is not 
critical. Preferably, the non-solvent is compatible with the other 
catalyst components and under polymerization conditions, so that it does 
not need to be removed prior to further use. Preferred non-solvents are, 
for example, pentane, hexane, heptane, decane, dodecane, kerosene, and 
higher aliphatic hydrocarbons of up to 30 carbon atoms. 
The dispersion comprising component (a) is preferably generated by 
contacting a solution of (a) in a diluent in which (a) is soluble with a 
diluent in which (a) is insoluble or sparingly soluble. The diluent in 
which (a) is soluble is preferably selected from the group consisting of 
toluene, benzene, and xylenes, and the diluent in which (a) is insoluble 
or sparingly soluble is preferably selected from the group consisting of 
pentane, hexane, heptane, and octane. 
In contacting the solution of (a) with the non-solvent, the amount of 
non-solvent is usually 10 to 10,000 parts by weight, preferably 100 to 
1,000 parts by weight per 100 parts by weight of the solution of (a). The 
contacting temperature is usually from -100.degree. to 300.degree. C., 
preferably from -50.degree. to 130.degree.0C., and most preferably from 
10.degree. to 100.degree. C. 
When the solvent, in which (a) is dissolved, needs to be removed after 
contacting with the non-solvent, the solvent is preferably selected so 
that it has a lower boiling point than that of the non-solvent. The 
solvent can then be easily removed by heating the dispersion or by 
applying reduced pressure. 
The solid catalysts, either supported or non-supported, according to the 
present invention can be prepared by combining, in any order, components 
(a), (b), (c), and optionally (d) in case of a supported catalyst, wherein 
during at least one step in the preparation of the solid catalyst, 
component (a) dissolved in a diluent in which (a) is soluble, optionally 
in the presence of one or more of components (b), (c), and (d) or the 
contact product of (a) with one or more of (b), (c), and (d), is converted 
into solid form, optionally followed by recovering the solid catalyst. 
After this step the other components (b), (c) and optionally (d), to the 
extent they have not been added before, are contacted with (a) in solid 
form, preferably dispersed in solid form. 
According to a preferred embodiment for the preparation of the 
non-supported or supported solid catalyst, during the at least one step in 
the preparation of the solid catalyst, a dispersion comprising component 
(a) in solid form is generated by contacting a solution of (a) in a 
diluent in which (a) is soluble, optionally in the presence of one or more 
of components (b), (c), and (d) or the contact product of (a) with one or 
more of (b), (c), and (d), with a diluent in which (a) is insoluble or 
sparingly soluble. 
In all the process steps subsequent to the dispersion formation step, it is 
preferred not to use temperature conditions or types or quantities of 
solvents that would redissolve compound (a). The methods that can be used 
to generate the dispersion of (a) are essentially those which have been 
described above in relation to the formation of the catalyst component 
dispersion. 
In the method for preparing the non-supported or supported solid catalyst, 
the dispersion comprising component (a) can be formed first whereupon the 
other components (b), (c), and optionally (d) can be combined in arbitrary 
order. Further, the dispersion comprising component (a) can be formed in 
the presence of one or more of the other components (b), (c) and 
optionally (d). Exemplary embodiments are given below. 
In one embodiment for preparing the non-supported or supported solid 
catalyst, the dispersion comprising component (a) is first contacted with 
component (b) and the resulting product is subsequently contacted with 
component (c). Component (b) is preferably employed dissolved in a 
suitable solvent, such as a hydrocarbon solvent, advantageously a 
C.sub.5-10 aliphatic or cycloaliphatic hydrocarbon or a C.sub.6-10 
aromatic hydrocarbon. The contact temperature is not critical provided it 
is below the decomposition temperature of the transition metal. Component 
(c) can be used in a neat form, i.e. as is, or dissolved in a hydrocarbon 
solvent, which may be similar to the one used for dissolving component 
(b). 
In a further embodiment for preparing the non-supported or supported solid 
catalyst, components (b) and (c) are first contacted, preferably in a 
suitable solvent, and then contacting the resulting product with the 
dispersion comprising component (a). The solvent or solvents used for 
contacting (b) and (c) are of such nature or are used in such quantities, 
or a combination thereof, that when the resulting product is contacted 
with the dispersion comprising (a), component (a) is not substantially 
redissolved. 
In the method of preparing a supported solid catalyst, the manner in which 
component (d) is added is not critical. Component (d) can be added during 
one of the steps in the preparation of the solid catalyst. The support 
material (d) can be added after the components (a), (b), and (c) have been 
combined with each other, or (d) can be combined with at least one of the 
components prior to combining the resulting product with the remaining 
component or components. 
According to a preferred embodiment for the preparation of a supported 
solid catalyst, component (a) dissolved in a solvent is first combined 
with component (d), whereupon a dispersion of (a) is generated in the 
manner as described above in relation to the generation of the dispersion 
of (a). The combining of component (d) with the solution of component (a) 
may be carried out while forming a slurry, i.e. using an excess amount of 
liquid, or alternatively, only so much of the solution of component (a) is 
used that no slurry is formed. Advantageously in the latter situation, the 
volume of the solution of component (a) does not exceed substantially, and 
is preferably about equal to, the pore volume of component (d). After this 
contacting step, component (a) is converted into solid form, preferably by 
combining the contact product of (a) and (d) with a diluent in which (a) 
is insoluble or sparingly soluble. The amount of solids relative to the 
amount of non-solvent is not critical but typically is from 0.001 to 50 
wt. %. 
When component (d) is contacted with a solution of (a), (d) is preferably 
used after it has been pretreated to remove substantially all water and 
surface hydroxyl groups, and especially by treatment with an 
aluminumalkyl, more preferably with an aluminumtrialkyl compound. It is 
advantageous to contact the solution of (a) with component (c), preferably 
with one molar equivalent of (c), prior to contacting the same with 
component (d). A highly preferred support material for use in these 
embodiments is pretreated silica. 
Typical, yet not critical, temperatures for any of the steps except the 
dispersion formation step are -50.degree. to 150.degree. C. Preferably, 
each of the contacting steps is carried out while stirring or agitating. 
All steps in the present process should be conducted in the absence of 
oxygen and moisture. 
The non-supported or supported solid catalyst may be stored or shipped in 
free flowing form under inert conditions after removal of the solvent. 
The combining of components (a) and (b) in equimolar amounts does not 
result in a catalyst composition that has substantial activity in addition 
polymerization processes. Upon combining this composition with component 
(c) an active catalyst composition is surprisingly formed. Therefore, a 
further embodiment provides a method for activating a catalyst suitable 
for addition polymerization wherein a substantially inactive catalyst 
precursor comprising an ionic compound (a) and a transition metal compound 
(b) and optionally component (d), is contacted with organometal compound 
(c) to form an active catalyst. Preferably, the substantially inactive 
catalyst precursor is in a solid form, more preferably dispersed in a 
diluent. 
Preferably, according to this activating method, a dispersion of a 
non-supported or supported solid substantially inactive catalyst 
precursor, comprising (a),(b) and optionally (d), and the organometal 
compound (c) are each separately added, preferably directly, into an 
addition polymerization reactor containing addition polymerizable monomer 
or monomers, preferably under addition polymerizable conditions. The 
catalyst components can be added separately to the reactor or to specific 
locations in the reactor which enables the catalyst to be activated only 
in the reactor or in a specific location in the reactor, which offers a 
more controllable polymerization reaction. This is especially advantageous 
where the addition polymerization reactor is operated under slurry phase 
or gas phase polymerization conditions. 
The relative amounts of the components to be used in the compositions and 
processes of the present invention will now be described. The relative 
amount of ionic compound (a) to gramatoms of transition metal in compound 
(b), is not critical but generally is in the range from 0.1 to 500 mole of 
(a) per gramatoms of (b). Preferably, 0.5 to 100 mole of (a) per gramatoms 
of (b) is used, most preferably from about 1 to 3 mole of (a) per 
gramatoms of (b). 
The ratio between organometal compound (c) and the ionic compound (a) is 
not critical, but generally lies within the range of 0.05 to 1,000 mole of 
(c) per mole of (a). Preferably, the ratio is from 0.5 to 100 mole (c) per 
mole (a), most preferably from about 1 to 50 mole (c) per mole (a). 
The amount of optional component (d) to be used in the present invention is 
also not critical, however, typical values range from 0.1 .mu.mol to 2 
mmol of ionic compound (a) per gram of support material. Preferably, from 
10 to 1,000 .mu.mol of ionic compound (a) is used per gram of support 
material. 
The solid catalyst can be used as such or after being subjected to 
prepolymerization. The prepolymerization can be carried out by any known 
methods such as by bringing a small amount of one or more polymerizable 
monomers into contact with the solid catalyst. The monomers which can be 
used in the prepolymerization are not particularly limited and include the 
olefins and diolefins mentioned hereinafter. It is preferable to use for 
the prepolymerization the same monomer as used in the subsequent 
polymerization. The prepolymerization temperature may usually range from 
-20.degree. C. to 100.degree. C., preferably from -10.degree. to 
70.degree. C., more preferably from 0.degree. to 50.degree. C., 
The prepolymerization may be carried out batchwise or continuously under 
atmospheric pressure or elevated pressures. The prepolymerization may be 
carried out in the presence of a molecular weight controlling agent such 
as hydrogen. The prepolymerization is carried out in the absence or 
presence of a solvent or diluent. When a solvent or diluent is used it is 
preferably an inert hydrocarbon, such as the ones described hereinafter 
with respect to the polymerization process. Preferably the solvent or 
diluent used does not substantially redissolve the solid catalyst 
comprising ionic compound (a). The prepolymerization is typically carried 
out to form a prepolymerized catalyst, i.e. polymer is formed on the solid 
catalyst particles, having from 0.1 to 100 g of polymer per 1 g of solid 
catalyst, preferably from 1 to 10 g of polymer per g of solid catalyst. 
Typical particle sizes of prepolymerized catalysts are in the range of 1 
to 200 .mu.m, preferably in the range from 10 to 100 .mu.m. 
The solid catalysts of the present invention, optionally prepolymerized, 
may be used in an addition polymerization process wherein one or more 
addition polymerizable monomers are contacted with the solid catalyst of 
the invention under addition polymerization conditions. 
Suitable addition polymerizable monomers include ethylenically unsaturated 
monomers, acetylenic compounds, conjugated or non-conjugated dienes, 
polyenes, and carbon monoxide. Preferred monomers include olefins, for 
examples alpha-olefins having from 2 to about 20, preferably from about 2 
to about 12, more preferably from about 2 to about 8 carbon atoms and 
combinations of two or more of such alpha-olefins. Particularly suitable 
alpha-olefins include, for example, ethylene, propylene, 1-butene, 
1-pentene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 
1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 
1-pentadecene, or combinations thereof. Preferably, the alpha-olefins are 
ethylene, propene, 1-butene, 4-methyl-pentene-1, 1-pentene, 1-hexene, 
1-octene, and combinations of ethylene and/or propene with one or more of 
such other alpha-olefins. Most preferably, ethylene or propylene is used 
as one of the addition polymerizable monomers. Suitable dienes include 
those having from 4 to 30 carbon atoms, especially those having 5 to 18 
carbon atoms. Typical of these are .alpha.,.omega.-dienes, 
.alpha.-internal dienes, including those dienes which are typically used 
for preparing EPDM type elastomers. Typical examples include 
1,3-butadiene, 1,3- and 1,4-pentadiene, 1,3-, 1,4-, and 1,5-hexadiene, 
1,7-octadiene, 1,9-decadiene, and lower alkyl substituted analogues of any 
of these. Other preferred monomers include styrene, halo- or alkyl 
substituted styrenes, tetrafluoroethylene, vinylcyclobutene, 
dicyclopentadiene, and ethylidene norbornenes. Suitable addition 
polymerizable monomers include also any mixtures of the above-mentioned 
monomers. 
The solid catalyst can be formed in situ in the polymerization mixture by 
introducing into said mixture the catalyst components (a), (b), (c), and 
optionally (d). 
The catalyst may be used in the polymerization reaction in a concentration 
of 10.sup.-9 to 10.sup.-3 moles, based on transition metal, per liter 
diluent or reaction volume, but is preferably used in a concentration of 
less than 10.sup.-5, preferably from 10.sup.-8 to 9.times.10.sup.-6 moles 
per liter diluent or reaction volume. 
The solid catalysts can be advantageously employed in a high pressure, 
solution, slurry, or gas phase polymerization process. A high pressure 
process is usually carried out at temperatures from 100.degree. C. to 
400.degree. C. and at pressures above 500 bar. A slurry process typically 
uses an inert hydrocarbon diluent and temperatures of from about 0.degree. 
C. up to a temperature just below the temperature at which the resulting 
polymer becomes substantially soluble in the inert polymerization to 
medium. Preferred temperatures are from about 30.degree. C., preferably 
from about 60.degree. C. to about 115.degree. C., preferably to about 
100.degree. C. The solution process is carried out at temperatures from 
the temperature at which the resulting polymer is soluble in an inert 
solvent up to about 275.degree. C. Generally, solubility of the polymer 
depends on its density. For ethylene copolymers having densities of 0.86 
g/cm.sup.3, solution polymerization may be achieved at temperatures as low 
as about 60.degree. C. Preferably, solution polymerization temperatures 
range from about 75.degree. C., more preferably from about 80.degree. C., 
and typically from about 130.degree. C. to about 260.degree. C., more 
preferably to about 170.degree. C. Most preferably, temperatures in a 
solution process are between about 80.degree. C. and 150.degree.0 C. As 
inert solvents typically hydrocarbons and preferably aliphatic 
hydrocarbons are used. The solution and slurry processes are usually 
carried out at pressures between about 1 to 100 bar. Typical operating 
conditions for gas phase polymerizations are from 20.degree. C. to 
100.degree. C., more preferably from 40.degree. C. to 80.degree. C. In gas 
phase processes the pressure is typically from subatmospheric to 100 bar. 
Preferably for use in gas phase polymerization processes, the solid 
catalyst has a median particle diameter from about 20 to about 200 .mu.m, 
more preferably from about 30 .mu.m to about 150 .mu.m, and most 
preferably from about 50 .mu.m to about 100 .mu.m. Preferably for use in 
slurry polymerization processes, the support has a median particle 
diameter from about 1 .mu.m to about 200 .mu.m, more preferably from about 
5 .mu.m to about 100 .mu.m, and most preferably from about 10 .mu.m to 
about 80 .mu.m. Preferably for use in solution or high pressure 
polymerization processes, the support has a median particle diameter from 
about 1 .mu.m to about 40 .mu.m, more preferably from about 2 .mu.m to 
about 30 .mu.m, and most preferably from about 3 .mu.m to about 20 .mu.m. 
Further details for polymerization conditions in a gas phase polymerization 
process can be found in U.S. Pat. Nos. 4,588,790, 4,543,399, 5,352,749, 
5,405,922, U.S. application Ser. No. 926,009, filed Aug. 5, 1992, now 
abandoned (corresponding to WO-94/03509), and U.S. application Ser. No. 
122,852, filed Sep. 17, 1993, now abandoned (corresponding to 
WO-95/07942), which are incorporated herein by reference. Gas phase 
processes wherein condensed monomer or inert diluent is present are 
preferred. 
In the polymerization process of the present invention impurity scavengers 
may be used which serve to protect the solid catalyst from catalyst 
poisons such as water, oxygen, and polar compounds. These scavengers can 
generally be used in amounts depending on the amounts of impurities. 
Typical scavengers include organometal compounds, and preferably 
trialkylaluminum or boron compounds and alumoxanes. Further, antistatic 
agents may be introduced into the reactor to prevent agglomeration or 
sticking of polymer or catalyst to the reactor walls. 
In the present polymerization process also molecular weight control agents 
can be used, such as hydrogen or other chain transfer agents. The polymers 
that are prepared according to such polymerization process may be combined 
with any conventional additives, such as UV stabilizers, antioxidants, 
anti-slip or anti-blocking agents, which may be added in conventional 
ways, for example, downstream of the polymerization reactor, or in an 
extrusion or molding step. 
Upon or after removal of the polymerization mixture or product of from the 
polymerization reactor, the supported catalyst may be deactivated by 
exposure to air or water, or through any other catalyst deactivating agent 
or procedure. 
The solid catalysts of the present invention, also when used in a slurry 
process or gas phase process, not only are able to produce ethylene 
copolymers of densities typical for high density polyethylene, in the 
range of 0.970 to 0.940 g/cm.sup.3, but surprisingly, also enable the 
production of copolymers having substantially lower densities. Copolymers 
of densities lower than 0.940 g/cm.sup.3 and especially lower than 0.930 
g/cm.sup.3 down to 0.880 g/cm.sup.3 or lower can be made while providing 
free flowing polymers, retaining good bulk density properties and while 
preventing or substantially eliminating reactor fouling. The present 
invention is capable of producing olefin polymers and copolymers having 
weight average molecular weights of more than 30,000, preferably more than 
50,000, most preferably more than 100,000 up to 1,000,000 and even higher. 
Typical molecular weight distributions M.sub.w /M.sub.n range from 1.5 to 
15, or even higher, preferably between 2.0 and 8.0. 
The solid catalysts of the present invention also can be used in a process 
using multiple reactors in parallel or in sequence, in combination with 
other catalysts, or a combination thereof.

Having described the invention the following examples are provided as 
further illustration thereof and are not to be construed as limiting. 
Unless stated to the contrary all parts and percentages are expressed on a 
weight basis. 
EXAMPLES 
The bulk density of the polymers produced in the present examples was 
determined according to ASTM 1895. All experiments were carried out under 
the exclusion of oxygen and water under a nitrogen atmosphere, unless 
indicated otherwise. 
Preparation of the hydrochloride of Kemamine.TM. T9701 
Kemamine.TM. T9701, (NMe(C.sub.18 H.sub.37).sub.2 (13.4 gram, 25 mmol), 
available from Witco Corp. (Kemamine is a trademark of Witco Corp.) was 
dissolved in diethylether (300 ml). Hydrogen chloride gas was bubbled 
through the solution for 5 minutes, until the pH was acidic as shown by pH 
paper. The mixture was stirred for 15 minutes and the white precipitate 
was collected by filtration, washed with three 50 ml portions of 
diethylether and dried under vacuum. The yield of the NHClMe(C.sub.18 
H.sub.37).sub.2 was 12.6 gram. 
Preparation of (p-HOC.sub.6 H.sub.4)B(C.sub.6 F.sub.5).sub.3 
!NHMe(C.sub.18 H.sub.37).sub.2 ! 
NHClMe(C.sub.18 H.sub.37).sub.2 (4.58 gram, 8 mmol) was dissolved in 
dichloromethane (50 ml). Triethylammonium 
tris(pentafluorophenyl)(4-hydroxyphenyl) borate (p-HOC.sub.6 
H.sub.4)B(C.sub.6 F.sub.5).sub.3 !NHEt.sub.3 ! (5.66 gram, 8 mmol, 
prepared as substantially described in Example 1B of U.S. patent 
application Ser. No. 08/610,647, filed Mar. 4, 1996 (corresponding to 
WO-96/28480)) was added followed by 40 ml distilled water. The mixture was 
rapidly agitated for 4 hours and then the water layer was removed by 
syringe. The dichloromethane layer was washed three times with 40 ml 
portions of distilled water. The dichloromethane layer was then dried over 
sodium sulphate, filtered and vacuum dried to yield an oil. The oil was 
extracted into toluene (200 ml), the resulting solution was filtered and 
the filtrate was vacuum dried to yield 8.84 gram of a colorless oil. 
Preparation of catalyst 
1 ml of a 0.031M solution of (p-HOC.sub.6 H.sub.4)B(C.sub.6 F.sub.5).sub.3 
!NHMe(C.sub.18 H.sub.37).sub.2 ! in toluene was treated with 18 ml of 
n-hexane by adding the n-hexane yielding a cloudy suspension which was 
stirred for 5 minutes A solution of titanium, 
(N-1,1-dimethylethyl)dimethyl(1-(1,2,3,4,5-eta)-2,3,4,5-tetramethyl-2,4-cy 
clopentadien-1-yl)silanaminato))(2-)N)-(.eta..sup.4 -1,3-pentadiene) 
C.sub.5 Me.sub.4 SiMe.sub.2 N.sup.t Bu)Ti(.eta..sup.4 -1,3-pentadiene 
(0.33 ml of a 0.0925M solution in Isopar.TM. E; Isopar E, a trademark of 
Exxon Chemical Company, is a mixture of C.sub.8 saturated hydrocarbons) 
was added to generate a red-brown colored suspension. After 5 minutes 
while stirring a 6 ml aliquot of this mixture was treated with 0.2 mmol of 
triethylaluminum (2 ml of a 0.1M solution in n-hexane) and the mixture was 
stirred for a further 15 minutes before using as such in a polymerization 
reaction. 
Slurry phase polymerization 
A stirred 5 l reactor was charged with 100 .mu.mol of triisobutylaluminum, 
3 1 of hexane and 0.5 normal liter of hydrogen before heating to 
60.degree. C. Ethylene was then added to the reactor in an amount 
sufficient to bring the total pressure to 10 bar. An aliquot of the 
catalyst prepared as described above containing 10 .mu.mol of titanium was 
then added to initiate the polymerization. The reactor pressure was kept 
essentially constant by continually feeding ethylene on demand during the 
polymerization reaction. The temperature was kept substantially constant 
by cooling the reactor as required. After 49 minutes the ethylene feed was 
shut off and the contents of the reactor were transferred to a sample pan. 
After drying, 925 g of a free flowing polyethylene powder was obtained. 
The efficiency was calculated to be 2,003,200 g polyethylene PE/g Ti and 
the bulk density 0.29 g/cm.sup.3. Scanning electron micrographs of the 
polymer powder indicated the presence of spherical particles having a 
smooth surface morphology. 
Example 2 
(comparative) 
The slurry polymerization procedure of Example 1 was repeated, yet without 
using triethylaluminum in the catalyst preparation step, without adding 
triisobutylaluminum to the reactor, and while using an amount of 30 
.mu.mol of titanium for the polymerization reaction. No polyethylene 
product was obtained. 
Example 3 
1 ml of a 0.031M solution of (p-HOC.sub.6 H.sub.4)B(C.sub.6 F.sub.5).sub.3 
!NHMe(C.sub.18 H.sub.37).sub.2 ! in toluene was treated with 10 ml of 
n-hexane yielding a cloudy suspension and the mixture was stirred for 5 
minutes. A mixture of a solution of (C.sub.5 Me.sub.4 SiMe.sub.2 N.sup.t 
Bu)Ti(.eta..sup.4 -1,3-pentadiene) (0.33 ml of a 0.0925M solution in 
Isopar.TM. E) and 0.3 mmol of triethylaluminum (3 ml of a 0.1M solution in 
n-hexane) was added and the mixture was stirred for 15 minutes. An aliquot 
of this mixture containing 10 micromol of titanium was used as such in a 
polymerization reaction. 
The polymerization conditions were identical to those of Example 1 except 
that the duration was 48 minutes. After drying, 850 gram of a free flowing 
polyethylene powder was obtained. The efficiency was calculated to be 
1,774,530 g PE/g Ti. 
Example 4 
0.5 ml of a 0.031M solution of (p-HOC.sub.6 H.sub.4)B(C.sub.6 
F.sub.5).sub.3 !NHMe(C.sub.18 H.sub.37).sub.2 ! in toluene was treated 
with 5 ml of n-hexane yielding a cloudy suspension and the mixture was 
stirred for 5 minutes. 0.075 mmol of triethylaluminum (0.75 ml of a 0.1M 
solution in n-hexane) was added and the mixture was stirred for 5 minutes. 
A solution of (C.sub.5 Me.sub.4 SiMe.sub.2 N.sup.t Bu)Ti(.eta..sup.4 
-1,3-pentadiene) (0.16 ml of a 0.0925M solution in Isopar.TM. E) was added 
and the mixture stirred for 5 minutes. This mixture was used as such in a 
polymerization reaction. 
The polymerization conditions were identical to those of Example 1 except 
that the duration was 30 minutes. After drying, 630 gram of a free flowing 
polyethylene powder was obtained. The efficiency was calculated to be 
888,675 g PE/g Ti. 
Example 5 
40 gram of silica SP12 (Grace Davison) which had been heated at 250.degree. 
C. for 3 hours under vacuum was slurried in toluene (400 ml) and then 
treated with 40 ml of triethylaluminum in 250 ml toluene. The mixture was 
stirred for 1 hour, filtered and the treated silica was washed with 
toluene (100 ml, of about 100.degree. C.) and dried under high vacuum. 
10 ml of a 0.031M solution of (p-HOC.sub.6 H.sub.4)B(C.sub.6 
F.sub.5).sub.3 !NHMe(C.sub.18 H.sub.37).sub.2 ! in toluene was treated 
with 40 ml of n-hexane yielding a cloudy suspension. The mixture was 
stirred for 5 minutes. 3.1 mmol of triethylaluminum (15.5 ml of a 0.2M 
solution in n-hexane) was added and the mixture was stirred for 5 minutes. 
An aliquot of this suspension containing 40 .mu.mole of the borate was 
treated with 40 .mu.mole of a solution of (C.sub.5 Me.sub.4 SiMe.sub.2 
N.sup.t Bu)Ti(.eta..sup.4 -1,3-pentadiene) (0.43 ml of a 0.0925M solution 
in Isopar E). The resulting suspension was added to a slurry of 1 gram of 
the silica treated as described above, in 20 ml of hexane. The mixture was 
stirred for 5 minutes and then an aliquot of the mixture containing 15 
.mu.mole of titanium was used as such in a slurry polymerization. 
The polymerization conditions were identical to those of Example 1 except 
that the polymerization time was 30 minutes. 600 grams of a free flowing 
polyethylene powder was isolated of bulk density 0.31 g/cm.sup.3. The 
efficiency was calculated to be 835,070 g PE/g Ti. 
Example 6 
2 gram of triethylaluminum treated silica (prepared as in Example 5) were 
placed in a 20 ml flask. In a separate vessel 1.23 ml of a solution of 
(p-HOC.sub.6 H.sub.4)B(C.sub.6 F.sub.5).sub.3 !NHMe(C.sub.18 
H.sub.37).sub.2 ! (0.065M) in toluene containing 80 micromol of the borate 
was diluted with a further 1 ml of toluene. 0.13 ml of a 0.6M solution of 
triethylaluminum in hexane was added and the mixture stirred for 10 
minutes. 
The borate/TEA solution, the volume of which about corresponded to the pore 
volume of the support material, was added to the treated support material 
and the mixture agitated. 8 ml of hexane was added to the dry powder to 
give a slurry followed by a solution of (C.sub.5 Me.sub.5 SiMe.sub.2 
N.sup.t Bu)Ti(.eta..sup.4 -1,3-pentadiene) (0.86 ml of a 0.0925M solution 
in Isopar.TM. E) to yield a green colored supported catalyst. 
The polymerization conditions were identical to those of Example 1 except 
that the polymerization time was 36 minutes and an aliquot of catalyst 
containing 15 micromol Ti was used. 260 gram of free flowing polymer 
powder of bulk density 0.25 g/cm.sup.3 was obtained. The efficiency was 
361,860 g PE/g Ti.