Catalyst and method for production of polymers and copolymers of 1-alkenes

The supported catalyst for the polymerization of 1-alkenes is obtained by a consecutive depositing on the insert inorganic oxide of silicium and/or aluminium at least one organic compound of aluminium, at least one compound of titanium and vanadium and at least one organic compound of aluminium and/or magnesium. It can be phlegmatized by 0.5-50% w/w of the paraffinic hydrocarbon having melting point 25-150.degree. C., which is coated either together with active components of the catalyst or separately. The catalyst polymerize and copolymerize ethylene without any additional activation.

FIELD OF THE INVENTION 
Ziegler catalysts for polymerization and copolymerization of 1-olefines may 
be divided into unsupported and supported ones. Supported catalysts are 
divided again into classes of catalysts where the support is formed either 
by chlorides of magnesium or aluminium and/or by metal oxides, especially 
by silica and alumina. 
This invention deals with catalysts based on compounds of transition metals 
(titanium and vanadium) with silica and/or alumina as the support. 
such catalyst are described in many patent publications, for example--U.S. 
Pat. No. 3,787,384; U.S. Pat. No. 4,063,009; U.S. Pat. No. 4,148,754; U.S. 
Pat. No. 4,173,547; and U.S. Pat. No. 4,302,566. 
A disadvantage of this group of catalyst is that they need an additional 
activation by an organoaluminium compound immediately before 
polymerization or directly in the polymerization apparatus itself. 
Recently, there is a tendency to develop supported catalysts which do not 
require additional activation. 
such catalysts are described in patent publications U.S. Pat. No. 
4,426,317; U.S. Pat. No. 4,435,520; 
Another direction in development of the catalysts is a method for 
passivation of catalysts with a layer of paraffinic hydrocarbons with 
higher melting points. This modification of catalyst is described, for 
example, in patent applications: U.S. Pat. No. 4,200,715; FR 2,529,211; EP 
102,895; and EP 159,736. 
The catalyst according to this invention differs from known catalysts in 
that the layer of transition metal compounds is sandwiched on the support 
between two layers of organometallic compounds. The top layer of organic 
compounds of aluminium and/or magnesium modifies properties of transition 
metal compounds anchored on support impregnated by organoaluminium 
compounds in such a way that the catalyst is stable during storage and 
does not require additional activation in the polymerization. 
DESCRIPTION OF THE PRIOR ART 
Coordination catalysts for polymerization of 1-alkenes, known as Ziegler 
catalysts, are well established. Starting from the middle of the fifties, 
a great effort has been devoted to synthesis of the best catalysts, making 
possible a preparation of poly (1-alkenes) with defined structure and 
properties, a high yield and a good economy. Besides empirical search for 
new catalyst formulations, theoretical aspects of the polymerization 
reactions were studied, including their kinetics and mechanism. Despite of 
a great effort, the theory is not able to provide a procedure to 
synthesize suitable catalysts. It makes only possible to rationalize the 
information and catalysts of this type must be searched for, studied and 
developed empirically. 
Many physical and chemical parameters affect directly preparation of the 
catalysts and the actual polymerization. Due to a great number of demanded 
polymer types and an enormous number of combinations of components used, 
it is very difficult to find an optimum catalyst for a given purpose. 
During a routine catalyst preparation, it is necessary to keep qualities 
of raw materials, prescribed ratios and concentrations, reaction 
conditions, sequence of components, reaction times and temperatures, and 
all these parameters must be found at first experimentally and then they 
must be compiled. Due to an unsatisfactory theoretical background, the 
volume of necessary experiments is immense and the progress is rather 
slow. 
Effective catalytical systems capable to polymerize 1-alkenes at low 
temperatures and pressures have been developed, making possible to control 
molecular weights, the width of the molecular weight distributions and 
densities of polymers. In the case of polyethylene it is possible to 
produce, for example, by copolymerization at relatively low pressures, 
even low density types, produced until recently by a radical high pressure 
polymerization only. A procedure for production of some specific linear 
low density polyethylenes by polymerization in a reactor with a fluidized 
bed has been described by Karol et al in patent publication U.S. Pat. No. 
4,302,566. 
Catalytical systems based on transition metals of 4a and 5a groups of the 
periodic system of elements known until now polymerize ethylene readily, 
and due to suitable copolymerization parameters (comparing with previously 
used chromium-based catalysts), give copolymers of alkenes with a low 
unsaturation in the chain and a narrower molecular weight distribution, 
which is advantageous for some applications. Catalysts based on transition 
metals of 4a and 5a groups of the periodic system of elements demand an 
activation with an organometallic compound, which is mostly carried out 
additionally, either immediately before the polymerization or even in the 
polymerization reactor itself. The activation consists in alkylation of 
the transition metal and sometimes in its reduction. Disadvantages of 
these methods for production of the catalyst are: (1) a difficult control 
of a reduction degree of the transition metal (usually a deeper reduction 
takes place than desirable, and thus its activity decreases) and (2) a low 
stability of the catalysts (the activity decreases during storage 
spontaneously or by an action of impurities). 
An activation of the catalyst in a polymerization reactor causes 
technological complications, as for example, the necessity to feed the 
components separately and proportionally. One of them is pyrophoric and 
this is hazardous considering the presence of large amounts of 
combustibles. In addition to this, a free organometallic compound 
catalyses oligomerization of 1-alkenes to low molecular weight oligomers. 
They form undesirable coatings on inner walls of an apparatus, especially 
in the case of solvent-free processes as it is the case of the gas-phase 
polymerization. 
Catalytical systems of this type are described by Karol et al U.S. Pat. No. 
4,302,566; Stevens et al in U.S. Pat. No. 3,787,384; Strobel et al U.S. 
Pat. No. 4,148,754; Zielgler et al U.S. Pat. No. 4,063,009; and 
particularly by Graff U.S. Pat. No. 4,173,547. 
In recent years, there is a tendency to develop one-phase catalytical 
systems based on transition metals of 4a and 5a groups of the periodic 
system of elements. Using these catalysts for polymerization of 1-alkenes, 
complications with feeding of catalysts are eliminated, the coatings on 
walls of a polymerization apparatus are not formed and the obtained 
polymer has desired particle morphology. One-phase catalytical systems 
based on titanium and vanadium compounds were described, for example, in 
U.S. Pat. No.4,426,317 and U.S. Pat. No. 4,435,520. Rogers in U.S. Pat. 
No. 4,426,317 Aylward in U.S. Pat. No. 4,435,520 described supported 
catalysts obtained by a reaction of an inorganic oxide with organometals 
of the 3rd group of the periodic system of elements and then with some 
vanadium compounds. 
It is known from the patent literature that highly reactive catalysts 
exist, being passivated against effects of water or oxygen by coating 
their surface with a layer of an inert solid substance, forming an 
effective diffusion barrier. These catalysts, however, must be in its 
active form during polymerization, the monomer diffusion to active sites 
must not be hindered. Therefore, the protective layer should be formed 
from a material with melting point between environmental temperature and 
polymerization temperature. In reality, higher saturated hydrocarbons and 
their mixtures can be used. 
U.S. Pat. No. 4,200,715 describes a dispergation of a supported catalyst in 
a solid phase, obtained by mixing a paraffinic wax with a liquid, low 
molecular weight hydrocarbon. The catalyst modified in such a way is 
resistant against diffusion of impurities during its transport and 
storage. The dispergation is carried out with the finished catalyst only, 
the possibility to change chemical parameters of the catalyst during the 
stage of depositing catalytical constituents is not utilized. patent 
publication EP 159,736 describes a modification of an one-phase 
unsupported catalyst by coating it with a layer of a viscous mineral oil. 
In this case, however, the particle size distribution of the catalyst and 
also of the polymer formed is too broad in this particular unsupported 
catalyst and it is not possible to utilize it in the gas-phase 
polymerization. 
It is also known that a protective layer can be formed on the catalyst 
surface by a prepolymerization of 1-alkenes. The prepolymerization with an 
aim of improving the activity of a catalyst was the subject matter of 
patent publication FR 2,529,211. An elimination of particle sticking was 
described in patent publication EP 102,895. The disadvantage of these 
catalysts is the use of MgCl.sub.2 and AlCl.sub.3 as a support, which 
contains an abundance of chloride ions and has an unsuitable particle size 
distribution. Now we have found a simple method for preparation of a new 
one-phase catalyst and a method for polymerization and copolymerization of 
ethylene using this catalyst. 
SUMMARY OF THE INVENTION 
The subject matter of this invention is a one-phase supported catalyst for 
polymerization of ethylene and its copolymerization with 1-alkenes having 
3-10 carbon atoms, obtained by a consecutive deposition of at least one 
aluminium compound of general formula (I) R.sub.m AlX.sub.3-m where m is 
1-3, at least one compound of titanium of general formula (IIa) R.sub.n 
TiX.sub.4-n where n is 0-4, and/or vanadium of general formula (IIb) 
R.sub.p VX.sub.5-p or R.sub.q VX.sub.4-q where p is 0-5, q is 0-4, and at 
least one organometallic compound of general formula III, which compound 
can be an organoaluminium compound identical with the compound of general 
formula I, and/or organomagnesium compound of general formula (IIIb) 
R.sub.r Mg X.sub.2-r where r is 1-2 and R in all compounds I, II, III 
means alkyl, aryl, alkoxide with 1-20 carbon atoms, X means halogen or in 
compounds II one X.sub.2 can be oxygen and the substituents R and X in 
compounds I, II, and III may be but need not be identical, on the support 
formed by silica and/or alumina with the specific surface 50-500 m.sup.2 
/g, with 0.3-3 mmole of hydroxyl groups per one gram of the carrier and 
with the inner porosity 0.5-3 ml/g, with the particle sizes in the range 
of 1-200 um. The supported one-phase catalyst has the ratio of 
organoaluminium compounds I to the hydroxyl groups of the support in the 
range of 0.1-10, the mole ratio of transition metal compounds II to 
organoaluminium compounds I in the range 0.01-10 and the mole ratio of 
organometallic compounds III to transition metal compounds II 0.1-20. An 
advantageous execution of this invention is the supported one-phase 
catalyst in which the organoaluminium compounds I have alkyls with 1-8 
carbons atoms, the transition metal compounds II are titanium 
tetrachloride, titanium tetraalkoxide, vanadium tetrachloride, vanadium 
tetraalkoxide and vanadium oxytrichloride, and the organomagnesium 
compounds III are dialkylmagnesium with 1-10 carbon atoms in alkyl groups. 
A further subject matter of this invention is the method for production of 
this supported one-phase catalyst, in which depositions of compounds I, 
II, and III on the support are performed in a gas phase or a hydrocarbon 
solvent, and the supported one-phase catalyst as described before, which 
is coated with a paraffinic hydrocarbon having melting point in the range 
of 25.degree.-150.degree. C. in the amount of 0.5-100% w/w of the uncoated 
catalyst either separately or together with compound III, or on which 
linear and/or branched 1-alkenes with 2-10 carbon atoms are prepolymerized 
in the amount of 0.5-100% w/w of the uncoated catalyst. According to this 
invention, ethylene is polymerized or copolymerized with 1-alkenes having 
3-10 carbon atoms using these catalysts at temperature 
30.degree.-300.degree. C. and pressure of 0.1-250 MPa in slurry, gas phase 
or in fluidized bed containing 50-100 volume per cent of 1-alkenes and 
0-50 volume per cent of hydrogen in the monomer mixture. Finally, the 
subject matter of this invention are the polymers of ethylene and its 
copolymers with 1-alkenes having 3-10 carbon atoms, produced using the 
catalysts and the method described above. 
For the catalyst suitable to produce polymers and copolymers of ethylene 
according to this invention, an appropriate support is silica and/or 
alumina with specific surface 50-500 m.sup.2 /g, pore volume 0.5-3.0 ml/g, 
which has been dehydrated at temperatures 200.degree.-950.degree. C. by a 
stream of air or nitrogen in a fluidized bed for at least 4 hours. Silica 
and/or alumina treated in such a way contain 0.3-3.0 mmole of hydroxyl 
groups per one gram of support according to dehydration temperature. 
Organoaluminium compounds I are chosen from compounds, such as 
trialkylaluminium, dialkylaluminiumhalogenide, alkylaluminiumdihalogenide, 
dialkylalkoxyaluminium, alkyldialkoxyaluminium, where alkyls are 
hydrocarbon groups with 1-20 carbon atoms and may be different within one 
compound. These organic compounds of aluminium have general formula (I) 
R.sub.m AlX.sub.3-m, where m is 1-3, R is branched or linear alkyl or 
alkoxide with 1-20 carbons, and all R groups can be (but not necessarily) 
identical, X is halogenide, preferentially chloride. These organometals 
are usually used as hydrocarbon solution at a concentration 5-25% w/w. For 
example, it is possible to use ethylaluminium dichloride, 
triethylaluminium, triisobutylaluminium, diethylaluminium ethoxide, 
tri-n-hexlaluminium and/or their mixtures. Using these compounds is 
economically advantageous, because they are produced on mass scale. 
The reaction of organic compounds of aluminium R.sub.m AlX.sub.3-m (I) with 
the surface of silica can be expressed by equations: 
##STR1## 
New chemical bonds Si--O--Al or Al--O--Al, if alumina is used, are formed, 
which assure a strong fixing of organoaluminium compound I on the surface. 
An ability of these structures to bond other compounds and to form active 
polymerization sites depends on density and type of these bonds and on 
specificities of substitutes of the anchored aluminium. 
The mole ratio of the sum of all organic compounds of aluminium I to 
hydroxyl groups of the support is in a range of 0.1-10, advantageously 
0.5-1.0. For a uniform deposition of organometals i, it is necessary to 
stir intensively a slurry of the support or a layer of the support. 
Temperature during the reaction can fluctuate in a broad range, depending 
on the vapor pressure of organometallic compound I and on boiling point of 
a hydrocarbon used as a solvent; the reaction can be carried out at 
10.degree.-70.degree. C., advantageously at room temperature. Reaction 
time depends on the reactivity of organometals I, on their concentration 
and temperature; in reality, several tens of minutes are sufficient. 
In a next step, at least one compound II of titanium and/or vanadium is 
deposited on the support with anchored organoaluminium compound I. they 
are selected from a group of halogenides, halogenalkoxides, alkyls, aryls, 
alkoxides, oxihalogenides of titanium and vanadium. For example, titanium 
tetrachloride, vanadium tetrachloride, vanadium oxytrichloride, 
tetraalkoxides of titanium and vanadium and mixtures of these compounds. 
The use of titanium and vanadium compounds in their highest oxidation 
state is preferred, vanadium compounds also in oxidation state +4. A small 
amount of compounds in a lower oxidation state (e.g. Ti.sup.+3) is not 
detrimental. The most advantageous halogenide is chloride, but it is 
possible to use also other halogenides, e.g. bromides or iodides. It is 
possible to use, for example, ethoxide, isobutoxide etc. as alkoxides. The 
use of alkyl- and especially arylderivates of titanium and vanadium, e.g. 
methyl-titanium trichloride, tetrabenzyl titanium, benzyl-titanium 
trichloride, tetraphenyl-titanium, is possible, but it is economically 
less advantageous and a possible shortening of preparation time does not 
improve economy. 
The reaction of compounds II with the modified support is advantageously 
made in a hydrocarbon medium or by a direct contact of titanium of 
vanadium compound II vapors with the solid phase of the intermediate 
product, preferentially at laboratory temperature. A strong anchoring of 
titanium or vanadium compounds on the support is achieved and they react 
with the fixed reaction products from the preceding step. Again, it is 
necessary to secure perfect stirring of the slurry to obtain a homogeneous 
product. The mole ratio of the sum of transition metal compounds II to sum 
of organoaluminium compounds I is kept in a range of 0.02-10, 
advantageously 0.05-1. 
By chemical bonding of organometals I to the free hydroxyl groups of the 
support, a modification of their reduction capabilities and simultaneously 
their immobilization on the support surface are achieved. By the choice of 
ratio of organoaluminium compounds I to hydroxyl groups and ratio of 
organoaluminium compounds I to compounds of titanium and/or vanadium II, a 
formation of active sites on the support surface takes place, which are 
capable to polymerize 1-alkenes, either immediately, or after a reaction 
with another organometal compound. 
Properties of an intermediate of the one-phase catalysts obtained in such a 
way are improved by depositing at least one further organoaluminium 
compound IIIa and/or organomagnesium compound IIIb chosen from 
trialkylaluminium, dialkylaluminium halogenide, 
alkylaluminiumdihalogenide, dialkylaluminium alkoxide, alkylaluminium 
dialkoxide, dialkylmagnesium or alkylmagnesium chloride, or their mixtures 
(III). Organoaluminium compounds IIIa used in this third step of 
preparation are chosen from the same group of organoaluminium compounds I, 
used in the first step of catalyst preparation. For example, it is 
possible to use ethylaluminium dichloride, diethylaluminium chloride, 
triisobutylaluminium, tri-n-hexylaluminium, diethylaluminium ethoxide, 
di-isobutylaluminium n-butoxide and their mixtures and the mixtures with 
organomagnesium compounds IIIb. 
Organic compounds of magnesium IIIb for preparation of the catalyst have 
general formula (IIIb) R.sub.r Mg X.sub.2-r where X is chloride, bromide 
or iodide and R is a hydrocarbon group containing 1-20 carbon atoms. Both 
R groups may be (but not necessarily) identical, they can be alkyls, 
cycloalkyls, aryls, alkenyls. Examples of suitable compounds IIIb are 
diisopropylmagnesium, dibutylmagnesium, diisobutylmagnesium, 
dihexylmagnesium, dioctylmagnesium, butyloctylmagnesium, 
dicyclohexylmagnesium, difenylmagnesium, ditolylmagnesium, ethylmagnesium 
chloride, butylmagnesiumm chloride. Organic magnesium compounds IIIb 
should not contain appreciable amounts of ethers. For choice of type of 
organic compounds of magnesium IIIb and aluminium IIIa and their ratios in 
mixtures (III), economic considerations applied (organomagnesium compounds 
are rather expensive and therefore it is advantageous to use only a 
necessary amount of these compounds). The mole ratios of organometallic 
compounds III to transition metal compounds II is kept in a range of 
0.5-20, advantageously 1-8. Conditions and a depositing method for 
organometallic compounds III are similar as are those for deposition or 
the preceding components; again, it is necessary to secure a slow 
deposition and an intensive mixing. 
During research and development of supported one-phase catalysts it was 
discovered surprisingly, that by depositing organoaluminium compound IIIa 
on the product of reactions of the support with constituents I and II, the 
polymerization activity of the obtained sandwiched catalyst is increased 
to values comparable with catalysts activated immediately before 
polymerization or in a polymerization reactor itself, and in some cases 
even better. Moreover, the mole ratio of organoaluminium compounds IIIa to 
transition metal compounds II is many times lower than that for two-phase 
catalysts. The supported one-phase catalysts with organoaluminium 
compounds IIIa as their third active constituent produce polymers with a 
high bulk density. 
Similarly, it was found surprisingly, that an analogical effect can be 
obtained, using organomagnesium compounds IIIb. By their anchoring on the 
product of reactions of the support with constituents I and II, the 
supported one-phase catalysts are obtained, capable to polymerize 
1-alkenes with a higher rate than two-phase catalysts activated 
immediately by an organometal before polymerization or in the 
polymerization reactor itself. Moreover, needed amounts of organomagnesium 
compounds IIIb as their third active constituents produce polymers with 
lower bulk densities than the comparable supported one-phase catalysts 
with organoaluminium compounds IIIa, but they polymerize with higher 
rates. 
Therefore, it is advantageous to combine both organometals for obtaining 
desired properties of the catalyst and to deposit organoaluminium and 
organomagnesium compounds on the product of reactions of the support with 
constituents I and II in mixtures. 
A majority of organomagnesium compounds IIIb and/or a part of 
organoaluminium compound IIIa are anchored on the surface of support 
particles and they do not diffuse inside the particles during the 
preparation and storage of the catalyst. This accumulation organomagnesium 
compound IIIb or possibly of a part of organoaluminium compound IIIa, on a 
periphery of the support particles influences positively stability of 
active sites against deactivating reactions of strong electron-donor 
compounds, which are usually contained in raw materials or can contact the 
catalyst during its preparation, storage and transport. During the 
polymerization, especially at higher temperatures, these organometals 
diffuse to transition metals compounds II and activate precursors of 
active sites. 
Organoaluminium compound IIIa on one hand alkylates and/or reduces titanium 
and/or vanadium compounds II, and on the other hand it decreases the 
oligomerization ability of organomagnesium compound IIIb, increasing its 
mobility and its diffusion rate inside the catalyst particles to the fixed 
transition metals II. Formation of a transition metal species active in 
the polymerization is divided into two steps, i.e.: (i) a reaction of 
organometal I of the modified support with transition metal compound II 
and (ii) a product of this reaction reacts with organometallic compound 
III. Both reactions proceed under very mild, easily controllable 
conditions. Application of organometallic compounds II make possible to 
choose organometals I with low alkylating and reducing power, and to use 
them in necessary amounts. Thus, all compounds are exploited fully for 
formation of active polymerization sites and their protection against 
common amounts of impurities. Organometals III can be used in some surplus 
and can be exploited during polymerization, affecting positively its 
kinetics and maximum polymerization rate. 
During all stages of preparation of the supported one-phase catalyst 
according to this invention, it is necessary to avoid an excess of 
compounds, such as water and oxygen, decomposing organometallic compounds. 
It is necessary to work in an inert atmosphere, e.g. under blanket of 
highly pure nitrogen or argon, containing less than 1 ppm of impurities. 
Hydrocarbon solvents used for preparation of the catalyst must be dried 
thoroughly, e.g. by distillation or rectification employing a principle of 
a higher volatility of water dissolved in hydrocarbons. Contents of 
impurities in media used for preparation of the supported one-phase 
catalyst must be checked systematically as well as purity of used vessels 
and fittings. The catalyst is stable and active in polymerization for a 
very long time, if vessels are perfectly tight during its preparation, 
storage, transport and feeding. 
When a limited access of impurities can not be prevented, it is preferred 
for a long-term storage of the catalyst to coat its surface with a 
paraffinic hydrocarbon, and to blow the catalyst by highly pure nitrogen 
immediately before feeding it into the reactor. 
Some properties of the catalyst are improved by coating a paraffinic 
hydrocarbon on the surface of catalyst particles. The paraffinic 
hydrocarbon must have its melting point between maximum usual environment 
temperature, at which the catalyst is produced, stored and transported, 
and polymerization temperature. 
Advantageously, a paraffin with melting point 50.degree.-70.degree. C., an 
atactic polypropylene or other saturated hydrocarbons with suitable 
melting points can be used. The presence of multiple bonds and heteroatoms 
(i.e. elements other than carbon, hydrogen, and fluorine) in chains of 
paraffinic hydrocarbons is undesirable, because it decreases activity of 
the catalyst. Low molecular weight impurities of the electron-donor type 
also exhibit a negative influence. The paraffinic hydrocarbon can be 
deposited on the ready-to-use catalyst suspended in a hydrocarbon solvent, 
or simultaneously with the last catalyst constituent, it means with 
organic compound of aluminium and/or magnesium III. the paraffinic 
hydrocarbon is deposited in such a way, that its content is 0.5-100% w/w 
per catalyst, preferably 1-10% w/w. Principle of the beneficial behavior 
of the paraffinic hydrocarbon is coating of catalyst particles and 
prevention of diffusion of impurities to active sites during isolation, 
storage, transport and feeding of the catalyst. A formation of a diffusion 
barrier on the catalyst surface stabilizes further the catalytic system in 
the absence of monomer. Reactivity of catalyst components is decreased 
substantially and a majority of active sites are formed only after 
melting-off paraffinic hydrocarbon in a reactor. 
Phlegmatization of catalyst particles according to this invention is not a 
necessary condition for obtaining an active catalyst. All aims of this 
invention can be also reached without deposition the paraffinic 
hydrocarbon. The paraffinic hydrocarbon confer a long-term storability and 
a resistance against impurities of the electron-donor type (water, oxygen) 
upon the catalyst and influences polymerization kinetics. Beside of 
methods for depositing the paraffinic hydrocarbon given above, it is 
possible to prepolymerize a low amount of 1-alkene, for example, ethylene, 
propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene or 
their mixture. 1-alkenes other than ethylene are prepolymerized 
preferentially, because more active sites are formed. Amount of the 
prepolymer obtained in such a way should be 0.5-50% w/w of the final 
catalyst, preferably 1-20% w/w. 
By depositing catalytical constituents on the support in the sequence and 
amounts given above, a highly active polymerization catalyst is obtained, 
capable to polymerize ethylene and to copolymerize it with other 1-alkenes 
in a solvent or in a gas phase. If polymerization in a gas phase is 
carried out, it is necessary to evaporate solvent for obtaining a loose, 
free-flowing powder. A thorough drying is not necessary, because the 
powder flows freely even when it contains a content up to several tens of 
percents (w/w) of a solvent. 
Size of the polymer particles is determined by the size of catalyst 
particles, but it is necessary to obey the procedure of depositing 
constituents according to this invention. 
The support for the catalyst according to this invention is a porous 
fine-grained oxide, silica and/or alumina. Nature and properties of the 
support influence the catalyst activity and properties of the polymer. 
The size of the support particles should be in the range of 1-200 um. The 
optimum size of particles can be found experimentally. A content of 
particles with diameter less than 10 um is disadvantageous, because 
polymer fines are formed, and a danger exists that large flakes (or even 
chunks) may be formed in a reactor and thick, deposits may appear in 
on-stream parts of the polymerization apparatus, plugging e.g. coolers of 
the recirculating gas. Silica or alumina are well known materials and 
commonly used as supports of polymerization catalyst. For this purpose, 
materials with a high specific surface (50-500 m.sup.2 /g) and a high pore 
volume (0.5-3.0 ml/g) are preferable. The particle size distribution of 
the support determines the particle size distribution of the catalyst and 
influences rheological properties of the polymer, the bulk density of the 
powder and thus the economy of its processing. The specific surface and 
the pore volume of support particles can be determined using BET method, 
described in paper: S. Brunauer, P. Emmett, E. Teller, Journal of American 
Chemical Society 60, p. 209-319 (1938). 
Hydroxyl groups are present on the surface of silica or alumina and the 
groups can react with catalyst constituents. Water, absorbed physically, 
induces undesirable reactions and it is necessary to remove it. It is 
advantageous to remove water bonded physically by thermal activation of 
silica or alumina, with a slow removal of desorbed water. Activation 
temperature is chosen in a range of 200-950.degree. C., preferentially 
400-800.degree. C. It is necessary to secure perfect stirring, thus, it is 
advantageous to perform activation in a fluidized bed. Silica and/or 
alumina is placed in a cool activation apparatus, then temperature is 
increased slowly to 200.degree. C. while a stream of an inert gas is blown 
through the support or it is pumped-out. Thus, water vapors can leave 
without destroying structure of silica and/or alumina and condensing on 
cooler parts of the apparatus. Then it is possible to increase temperature 
quickly to a desired level without any problems. 
Dehydration of silica and alumina is performed at a chosen temperature 
usually for at least 4 hours. Silica and alumina are cooled by a stream of 
nitrogen containing less than 1 ppm of water and oxygen. Dehydration 
temperature of the support must be chosen below the sintering temperature 
to prevent a destruction of the porous structure, a decrease of the 
specific surface and the pore volume. The amount of hydroxyl groups on the 
oxide support may be determined by any common method, e.g. by the reaction 
of the inorganic oxide with surplus of triethylaluminium, determining the 
amount of ethane released. One mole of ethane is formed per each mole of 
reactive hydroxyl groups in this reaction. 
Due to high reactivity of compounds used and to a high heat effects of 
reactions, it is suitable to use organometallic compounds I and III and 
compounds of titanium and vanadium II in a diluted form, dissolved in 
suitable solvents. In general, it is possible to use aliphatic 
hydrocarbons with linear or branched chains, for example, butanes, 
pentanes, hexanes, oxtanes, and their mixtures, e.g. kerosene, gasoline as 
solvents. Usage of cyclic hydrocarbons, e.g. cyclopentane, 
methylcyclohexane, cyclohexane, as well as aromatic hydrocarbons, 
especially benzene, toluene, xylenes, is not excluded, but it is not 
economically advantageous. 
In the first reaction step, i.e. reaction of silica and/or alumina with 
organoaluminium compound I in a liquid phase, it is advantageous to use 
organometal I diluted in such a way, that the total amount of solvent at 
least doubles the pore volume of the support. The reaction of 
organoaluminium compound I with the support is carried out preferably at 
room temperature, reaction time is in a range of several minutes to 
several hours, depending on reaction conditions. After the reaction of 
organometal I is brought to completion, the solvent may be, but not 
necessarily, removed by decantation, evaporation or evacuation. It is 
recommended to remove the solvent and wash-out the support with the 
deposited organometal I in case that organometal I was used in a surplus, 
which could produce in the next step a new microheterogenous phase, 
containing no silica or alumina as a support. 
In the second step, compounds of titanium and/or vanadium or their mixture 
II are added slowly with stirring. Conditions are identical with those 
used in the first step, it is possible to use the same solvent and it is 
possible, though not necessary, to remove it after the reaction. 
In the third step, at least one organoaluminium compound IIIa and/or 
organomagnesium compound IIIb is added to the slurry, obtained in the 
second step, alternatively together with a paraffinic hydrocarbon. 
Reaction conditions are similar to those used in the first step; it is 
advantageous to remove the solvent after reaction, for example, by 
decantation, by evacuation, or by evaporation with stirring etc. If the 
paraffinic hydrocarbon is deposited in the third step together with 
organoaluminium and/or organomagnesium compound III it is advantageous to 
work at higher temperatures, or to increase temperature in the final stage 
of the solvent evaporation, to secure a uniform coating of support 
particles with the paraffinic hydrocarbon. 
The paraffinic hydrocarbon can be deposited also separately in the fourth 
preparation step, when the paraffinic hydrocarbon is added successively 
and evenly to the product of the third step, at temperature higher than 
melting point of the paraffinic hydrocarbon, as a melt or as a solution in 
a suitable hydrocarbon solvent. Alternatively, it is possible to mix a 
solid dispersed finely paraffinic hydrocarbon with the reaction product of 
the third step at a low temperature and then to increase the temperature 
slowly over the melting point of the paraffinic hydrocarbon. After cooling 
and possible drying of a surplus of the solvent, a loose, free-flowing 
powder of the supported one-phase catalyst can be obtained. All reactions 
leading to the catalyst can be carried out without a solvent in a gas 
phase, using a fluidized bed stirred mechanically or pneumatically. 
Organometals I and III and compounds of transition metal II can be 
deposited as vapors in a stream of an inert gas, for example, nitrogen or 
argon, or in a form of solutions in a hydrocarbon solvent; in the latter 
case it is necessary to keep conditions to prevent sticking of particles 
during the whole process of depositing the components. Particles remain 
unsticky even when they contain several tens of weight percents of a 
solvent; the exact value must be determined experimentally for particular 
conditions. Deposition of components I-III on silica and/or alumina from a 
gas phase is advantageous, but it is necessary to keep carefully suitable 
temperatures, concentrations, flow rates and reaction times, to prevent 
formation of undesirable large flakes and chunks. 
The supported one-phase catalyst prepared by the method according to this 
invention is effective in polymerization without a necessity to activate 
it additionally before a polymerization or in the reactor itself. The 
polymerization activity of the catalyst does not change in a pure medium 
during storage at common temperatures. If the catalyst contains the 
paraffinic hydrocarbon, it is resistant also against a mild access of 
impurities during storage, transport and feeding of the catalyst. Taking 
into account that some access of impurities of the electron-donor type 
cannot be excluded, the phlegmatization by a paraffinic hydrocarbon is 
advantageous. A paraffinic hydrocarbon with melting point between maximum 
temperature of surroundings and the polymerization temperature can be 
prepared also by a prepolymerization of a small amount of 1-alkenes, such 
as ethylene, propylene, 1-butene, 4-methyl-1-pantene, 1-hexene, and 
1-octene. These monomers are contacted with the product of the third step 
under an intensive stirring, advantageously at increased temperatures 
(50.degree.-100.degree. C.), either in the hydrocarbon solvent after the 
third reaction step, or in a gas phase. Reaction time is dependent on the 
required amount of the prepolymer. It is advantageous to remove the 
unreacted monomer before cooling and drying the catalyst. 
The catalyst prepared according to this invention can be used for 
homopolymerization of ethylene and for its copolymerization with 
propylene, 1-butene, 1-pentene, 4 methyl-1-pentene, 1-hexene, 1-octene and 
further 1-alkenes and their mixtures. 
A polymerization of 1-alkenes using the one-phase catalyst according to 
this invention can be carried out in a fluidized bed, in a mechanically 
stirred layer in gas phase, in a solvent or in a liquid 1-alkene. Any 
liquid, which does not react with the catalytical system, and does not 
decrease its polymerization activity, can be used as a solvent. It is 
suitable to use aliphatic hydrocarbons with linear or branched chains, 
liquid under conditions of the polymerization, e.g. butanes, pentanes, 
hexanes, heptanes, their mixtures, distillation fraction of oil, e.g. 
petrol kerosene, diesel oil, or aromatic and cyclic hydrocarbons (benzene, 
toluene, xylenes, cycloalkanes) or chlorinated aliphatic or aromatic 
hydrocarbons. It is advantageous to polymerize in a liquid monomer 
(1-alkene) thus increasing the productivity of the reactor due to the 
absence of an inert diluent. Preferably, cheap aliphatic hydrocarbons of 
their mixtures are used as solvents. On the large scale, it is 
advantageous to polymerize in a fluidized bed, because it is not necessary 
to remove the solvent from the polymer. 
The polymerization pressure may be atmospheric, or it can be higher, for 
example, up to 250 MPa. Preferably, it is polymerized at pressures 0.5-4 
MPa. In the gas phase polymerization, pressures in a range of 1-3 MPa are 
the most economical. Higher pressures are advantageous for obtaining 
polymers with a very low content of the catalyst residues. 
It is possible to polymerize discontinously or more preferably, 
continuously. Feeding of the catalyst can be in charges or continuously in 
such an amount, to keep the concentration of transition metal in a range 
of 0.001-10 mmole/l, preferably 0.01-0.5 mmole/l. 
Polymerizations may be carried out at 30.degree.-300.degree. C. At 
temperatures exceeding melting point of the polymer formed, it is possible 
to perform so-called solution polymerization in a solvent or the high 
pressure polymerization catalysed by the catalyst according to this 
invention. 
In the gas-phase polymerization it is necessary to keep the temperature 
5.degree.-10.degree. C. below the melting point of the polymer to prevent 
agglomerization of particles and formation of large flakes. 
The molecular weight of polymers can be controlled by the content of 
comonomers, by the polymerization temperature and by the hydrogen feed. 
The absence of hydrogen and comonomer leads to formation of 
ultra-high-molecular weight polymers (UHMW PE). 
The polymerization can be performed also in more stages, arranged in series 
or in parallel, where different conditions can be used: e.g. different 
catalyst compositions, temperatures, residence times, compositions of 
monomer mixtures, pressures, hydrogen concentrations etc. Thus, it is 
possible to prepare polymers with a broad molecular weight distribution, 
suitable for some applications. The polymers with a broad molecular weight 
distribution is advantageous to prepare in two or more stages, where 
different reaction conditions or different catalyst compositions are used, 
e.g. a different ratio titanium: vanadium or (aluminium and magnesium): 
(titanium and vanadium). By using a mixture of catalysts or a mixture of 
titanium and vanadium compounds within one catalyst, polymers with a broad 
molecular weight distribution can be obtained also in a single stage, 
because in this case active sites of different quality can coexist on the 
catalyst surface. 
Spherical particles of the polymer are formed during the polymerization, 
replicating the shape of original particles of the catalyst and thus also 
that the support. The enlargement factor is 10-50 times. Compact particles 
are formed by polymerization with the diameter several tenths of a 
millimeter up to several millimeters, depending on the polymerization time 
(in the discontinuous process) or on the residence time (in the continuous 
process). The usual polymerization time is 0.5-8 hours, preferably 2-6 
hours. At shorter polymerization times, the contents of ash and catalyst 
residues are higher, while the reactor productivity is high. On the 
contrary, at longer polymerization times the quality of the polymer 
improves and the reactor productivity decreases. 
The catalyst is deactivated upon the discharge from the reactor by air, 
water vapor, or by carbon monoxide. Due to a low content of the catalyst 
residues, it is not necessary to wash them from the polymer. 
The invention will be clarified by following examples, which do not limit 
the scope of the invention.

EXAMPLES 
EXAMPLES 1-7 
Into a reactor freed from water and oxygen, containing 50 ml of stripped 
n-heptane, 2.0 g of the support (silica and/or alumina) were poured under 
a blanket of pure nitrogen and organoaluminium compound I was added in the 
amounts according to Table 1. After 15 minutes of stirring at laboratory 
temperature, titanium and/or vanadium compound II was added (see Table 1), 
it was again stirred for 15 minutes and organic compound of aluminium 
and/or magnesium (III) according to Table 1 was added and it was stirred 
for further 15 minutes. 
The last step of the catalyst preparation was a solvent removal by a stream 
of dry nitrogen or by evacuation. The catalysts, prepared in such a way 
are obtainable as dry powders, containing at most about 50% w/w of a 
solvent. Over this limit, a sticky powder or a paste are obtained, which 
can not be transported pneumatically and fed into the reactor without 
difficulties. If the polymerization is carried out in liquid phase, a 
slurry of the catalyst in a hydrocarbon can be fed directly into the 
polymerization reactor. 
During preparation, storage, transport, and feeding of the catalyst, it is 
necessary to exclude an excess of catalytical poisons of the 
electron-donor type, for example oxygen, water, dienes, carbon oxides etc. 
All operations and manipulations with the catalyst must be carried out in 
an inert atmosphere, for example under blanket of pure nitrogen or argon, 
containing less then 10 ppm, preferably less than 1 ppm of impurities of 
the electron-donor type. 
Example 8 
Into a purified reactor containing 50 ml of stripped n-heptane, 2.0 g of 
the support (silica and/or alumina) were poured against the flow of pure 
nitrogen, and a measured amount of organoaluminium compound (I) according 
to Table 1 was added. After about 30 minutes of reaction at environmental 
temperature, an amount of compound of the transition metal II according to 
Table 1 was fed and the mixture was stirred for additional 30 minutes. 
Then the temperature was increased to 60.degree.-80.degree. C. and the 
organometallic compound or their mixture III was added according to Table 
1. Finally, a paraffinic hydrocarbon with melting point 
48.degree.-50.degree. C. was added in the amount according to Table 1. 
After its dissolution, the solvent was removed by evacuation under steady 
stirring. A loose powder was obtained, exhibiting similar mechanical 
properties as those of the original support. 
Example 9 
It was proceeded according to Example 8 with the following difference: 
instead of the paraffinic hydrocarbon a mixture of ethylene with 40% vol. 
of hydrogen was introduced in such a way to polymerize 50 mmole of 
ethylene into oligomers solid at environmental temperature. After 
finishing this prepolymerization, a majority of the solvent was removed to 
obtain a loose, free-flowing powder. The catalyst is unsticky at 
environmental temperature, resistant against a diffusion of impurities and 
storable before a polymerization for a virtually unlimited period of time. 
Example 10 
The procedure is identical as in Example 8 with the following difference: 
instead of the paraffinic hydrocarbon, 30 mmole of 1-butene with 10 mmole 
of hydrogen was added and the stirring at 60.degree.-80.degree. C. 
continued until 1-butene was polymerized totally. After the 
prepolymerization period, a majority of n-heptane was removed by 
blowing-through nitrogen and the one-phase supported catalyst was 
isolated, capable to polymerize 1-alkenes without a necessity of an 
additional activation by any further component. 
Example 11 
A glass reactor (volume 1 dm.sup.3) was used equipped with a spiral stirrer 
making possible to mix powders thoroughly. It was dried by nitrogen and 
300 g of a support, dehydrated for at least 6 hours at temperatures 
200.degree.-950.degree. C. with a stream of nitrogen, was poured in and 
stirring was switched on. Nitrogen of a very high purity was introduced 
through a sintered glass to the bottom of a 80 cm.sup.3 evaporator and 
bubbled through a solution of organoaluminium compound I or their mixtures 
in a hydrocarbon (hexane). After saturating with vapors of organoaluminium 
compound I, the nitrogen was introduced through the bottom of the glass 
reactor into the layer of the activated support. After consecutive 
evaporation of all solution of organoaluminium compound I, at least one 
transition metal compound II is poured into the evaporator, neat or as a 
solution in a hydrocarbon, and nitrogen is again bubbled through. Finally, 
at least one organoaluminium compound IIIa and/or organomagnesium compound 
IIIb or their mixture is dosed into the emptied evaporator and let to 
evaporate to completion. Evaporation can be facilitated by heating the 
evaporator. In some cases, especially when organomagnesium compounds IIIb 
are used, heating is necessary. It is advantageous to cool the reactor at 
the beginning of introduction of organoaluminium compound I, to remove 
reaction heat. Small increase of temperature of the reactor to 
60.degree.-100.degree. C. is not detrimental. The reaction components I, 
II, and III can be fed as neat substances, but for safety reasons, their 
solutions in hydrocarbons are preferred. All handling of the activated 
support and constituent I-III must be carried out in a medium of a very 
high purity, advantageously under blanket of an inert gas (nitrogen, 
argon) containing less than 1 ppm of water, oxygen and other impurities. 
According to this procedure a white-to-beige free-flowing powder is 
obtained, which is suitable for polymerization in a gas phase without any 
additional activation. Data concerning the preparation are given in Table 
1. 
Example 12 
The process was identical with example 8 except that instead of 
organomagnesium compound III, its mixture with a paraffin having melting 
point 48.degree.-50.degree. C. in a hydrocarbon was added. After about 1 
hour of additional stirring, the solvent was evaporated by evacuation. A 
free-flowing powder was obtained. Data concerning its properties are given 
in Table 1. 
The catalysts prepared according to Examples 1-12 are obtainable as dry, 
loose powders, containing a small amount of a low molecular weight solvent 
or a paraffinic hydrocarbon. The maximum amount of a low molecular weight 
fraction depends on a composition of the catalyst and on temperature and 
it can be determined easily for particular conditions. 
The catalyst prepared according to Examples 8-12 are storable unlimitedly 
in common reservoir equipped with customary armatures. In case of an 
infiltration of impurities of the electron-donor type to the catalyst, it 
is necessary to blow a layer of the catalyst by highly pure nitrogen 
before polymerization, for preventing an access of impurities into the 
polymerization apparatus. 
Example 13 
A 1.5 dm.sup.3 laboratory reactor, making possible to prepare 300 g of a 
polymer, was purged by a stream of 0.5 dm.sup.3 /min of high purity 
nitrogen for 16 hours, then it was pressurized at the polymerization 
temperature (60.degree.-100.degree. C.) 10 times by nitrogen to 2.0 MPa 
and finally washed out twice by ethylene. The reactor was thermostated to 
the polymerization temperature using a jacket. A mixture of monomers with 
hydrogen was introduced into the reactor. The polymerization was started 
by breaking a glass vial with 50-150 mg of a catalyst, prepared according 
to Examples 1-12. 
The bed was fluidized by a mechanical stirring and the polymerization rate 
was measured from the consumption of the fed monomer mixture. After about 
4 hours, the reactor was depressurized, opened and the polymer processed. 
All conditions of the polymerization are given in Table 2. 
Example 14 
In a 1.5 dm.sup.3 laboratory reactor, n-hexane was stripped by a stream of 
nitrogen of very high purity in such a way, that more than 15% w/w of the 
hydrocarbon was evaporated. Then the reactor pressure was adjusted by 
feeding a monomer mixture at polymerization temperature (see Table 2). The 
polymerization was commenced by breaking a glass vial with the catalyst 
(as a powder or as a slurry in a hydrocarbon) and it was carried out 4 
hours at constant temperature, pressure was composition of the monomer 
mixture. After opening the reactor, the polymer was isolated by 
evaporating the solvent and dried in vacuum oven. 
Example 15 
The powdery catalyst was fed by a feeding device, using overpressure of 
nitrogen, into a bottom part of a continuous pilot plant reactor. The 
polymerization took place in a fluidized bed, composed from a mixture of 
the powdery polymer and the catalyst, is kept fluidized by a stream of the 
monomer mixture. The velocity of the stream of the mixture was 3-6 times 
higher than the minimum velocity needed for fluidization. A steady state 
was kept, defined by pressure 1.8-2.0 MPa, temperature in a range of 
70.degree.-110.degree. C. and mole ratios according to Table 2. The 
polymer produced was removed discontinously from the reactor depending on 
its production rate. Productivity of the reactor depends on residence time 
(between 2-8 hours), on efficiency of cooling of the recycling monomer 
mixture (given by design parameters) and on activity and concentration of 
the catalyst (direct proportionality). 
These examples show that the process according to this invention allows 
production of homopolymers and copolymers of ethylene with high bulk 
density and suitable properties. The process for preparation of the 
catalyst and the polymerization itself are simple, without necessity to 
activate the catalyst additionally before feeding it into a reactor or in 
the polymerization reactor itself. Deposits and large flakes are not 
formed on walls of the reactor during the polymerization and a high bulk 
density of the polymerization bed assures high productivity of the 
polymerization. It is possible to prepare a polymer with desired 
properties by changing the composition of the one-phase catalyst, the 
process of its preparation and conditions of the polymerization. There are 
very many combinations of these possibilities. 
The catalyst is stable and active in the polymerization for unlimited time 
when an access of impurities of the electron-donor type is prevented. In 
the case of paraffinic hydrocarbon deposited on the catalyst, its 
resistance against these impurities is increased extraordinarily. 
Although the invention is described and illustrated with reference to a 
plurality of embodiments thereof, it is to be expressly understood that it 
is in no way limited to the disclosure of such preferred embodiments but 
is capable of numerous modifications within the scope of the appended 
claims. 
TABLE 1 
__________________________________________________________________________ 
Composition of the catalysts 
Paraffinic 
OH-group content 
Organometal I 
Compound II Organometal III 
hydrocarbon 
Example 
mmole OH mmole I mmole II mmole III 
g IV 
No. g support 
g support g support g support 
g support 
__________________________________________________________________________ 
1 0.7 AlEt.sub.2 Cl (0.5) 
TiCl.sub.4 (0.1) 
BuMgOct (0.4) 
-- 
2 0.7 AliBu.sub.3 (0.5) 
TiCl.sub.4 (0.2) 
BuMgOct (0.2) 
-- 
3 0.7 AliBu.sub.3 (0.7), AlEtCl.sub.2 (0.3) 
TiCl.sub.4 (0.15) 
AliBu.sub.3 (0.2) 
-- 
4 0.8 AlEt.sub.2 Cl (0.3), AliBu.sub.3 (0.3) 
TiCl.sub.4 (0.1) 
BuMgOct (0.2) 
-- 
5 1.9 AlEt.sub.2 Cl (1.8) 
TiCl.sub.4 (0.1), VCl.sub.4 (0.1) 
AliBu.sub.3 (0.5) 
-- 
6 0.75 AlEt.sub.2 Cl (0.75) 
TiCl.sub.4 (0.03), VOCl.sub.3 
EtMgBu (0.1) 
-- 
7 0.8 AlEt.sub.2 Cl (0.67) 
TiCl.sub.4 (0.16) 
Et.sub.2 AlOEt (0.16) 
-- 
8 0.7 AlEt.sub.2 Cl (0.5) 
TiCl.sub.4 (0.1) 
BuMgOct (0.4) 
0.20 
9 0.7 AliBu.sub.3 (0.5) 
TiCl.sub.4 (0.2) 
BuMgOct (0.2) 
0.70 
10 0.7 AlEt.sub.2 Cl (0.5) 
TiCl.sub.4 (0.1) 
BuMgOct (0.4) 
0.84 
11 0.8 AlEt.sub.3 (0.4) 
TiCl.sub.4 (0.15) 
EtMgBu (0.15) 
-- 
AliBu.sub.3 (0.1) 
12 0.7 AlEt.sub.2 Cl (0.67) 
TiCl.sub.4 (0.1) 
BuMgOct (0.4) 
0.20 
__________________________________________________________________________ 
Notes: 
1. Symbols: Et = ethyl; Bu = nbutyl; iBu = isobutyl; Oct = octyl. 
2. Silica Davison 959 was used as a support with specific surface 250-300 
m.sup.2 /g, the pore volume 1.6 ml/g, with maximum pore radius 11 nm, 
dehydrated 4 hours at 800.degree. C. (Examples 1-3, 8 and 10), 600.degree 
C. (Examples 4 and 6) and 200.degree. C. (Example 5). Alumina with 
specific volume 150 m.sup.2 /g, pore volume 1.0 ml/g with maximum pore 
radius 25 nm, dehydrated at 800.degree. C. was used as a support in 
Example 7. 
TABLE 2 
__________________________________________________________________________ 
Conditions of polymerisation and properties polymers 
Ex- 
am- 
Temper- Productivity Bulk 
ple 
ature 
Partial pressure, MPa 
kg polym. 
Density 
density Particles size 
distribution, mm 
No. 
.degree.C. 
H.sub.2 
ethylene 
1-butene 
h .times. g Ti or V 
kg/m kg/m.sup.3 
MFI.sub.2.3 
MFR &gt;0.5 
&gt;0.2 to 
&gt;0.1 to 
__________________________________________________________________________ 
&lt;0.2 
1 90 0.02 
1.8 -- 80 960 340 0.06 
36 91.2 
8.5 0.3 
2 90 0.04 
1.8 -- 37 960 350 0.11 
50 92.6 
7.1 0.3 
3 80 0.05 
1.75 -- 19 960 360 0.26 
56 92.1 
7.7 0.2 
4 90 0.01 
1.85 0.03 120 935 300 0.22 
36 91.3 
8.6 0.1 
5 90 0.02 
1.7 0.08 23 925 310 0.15 
35 93.7 
6.2 0.2 
6 90 0.02 
1.75 0.025 
136 940 320 0.28 
36 94.3 
5.6 0.1 
7 100 0.015 
1.8 0.025 
30 940 300 0.30 
32 93.7 
6.0 0.3 
8 90 0.02 
1.8 -- 105 960 345 0.10 
35 91.8 
8.1 0.1 
9 90 0.04 
1.8 -- 45 960 360 0.15 
45 91.4 
8.0 0.5 
10 90 0.02 
1.8 -- 95 960 350 0.15 
38 92.3 
7.5 0.2 
11 90 0.02 
1.8 0.08 928 330 0.11 
35 94.1 
5.5 0.4 
12 90 0.02 
1.8 -- 110 960 350 0.12 
31 92.2 
7.1 0.7 
__________________________________________________________________________ 
Notes: 
MFI.sub.2.3 = melt flow index at 190.degree. C. and 2.3 kg load. 
MFR = melt flow ratio at loads 2.3 kg and 23 kg, respectively. 
Polymerizations with the catalyst prepared according to Examples 1-10 wer 
effected according to Example 13; catalyst 11 according to Example 14; 
catalyst 12 according to Example 15.