Silica-containing olefin polymerization catalysts and process

Method for making crystalline polymerization catalysts is disclosed which comprises contacting the soluble complex prepared from the combination of a metal dihalide and a transition metal compound with a particulate material comprising silica to produce a solid, and then reacting the solid with an organoaluminum halide. The resulting catalyst component can be further contacted with a halide ion exchanging source selected from halides of Groups IVA and VA. Novel catalysts prepared in accordance with the invention method, polymerization processes therewith and novel polymers, having high bulk density, low levels of polymer fines, and well defined particle size and shape are also disclosed.

This invention relates to a process for forming crystalline catalysts which 
can be used with a cocatalyst to form a catalyst system for the 
polymerization of .alpha.-olefins. In one aspect, the present invention 
relates to novel polymerization catalysts. In another aspect, the present 
invention relates to a process for polymerizing .alpha.-olefins. In yet 
another aspect, this invention relates to novel polymers of 
.alpha.-olefins. 
BACKGROUND OF THE INVENTION 
The polymerization of .alpha.-olefins and mixtures thereof at low pressures 
is known to be promoted by coordination catalysts prepared from mixtures 
of compounds of (a) transition elements, and (b) organometallic compounds 
of elements of Groups IA to IIIA of the Periodic Table. Such 
polymerizations can be carried out in suspension, in solution, in the gas 
phase, and the like. 
Because of favorable process economics, especially with low molecular 
weight olefins such as ethylene and propylene, it is frequently desirable 
to carry out olefin polymerization or copolymerization reactions in an 
inert diluent at a temperature at which the resulting polymer or copolymer 
does not go into solution; and where the polymer product is recovered 
without removing the polymerization catalyst. Thus, elaborate steps to 
remove catalyst from the polymer product are avoided. In order for this 
more economical method of polymer manufacture to be practical, the 
polymerization catalyst employed must be capable of producing polymer in 
high productivities in order to maintain the residual catalyst level in 
the final polymer at a very low level. Thus, the activity of an olefin 
polymerization catalyst is one important factor in the continuous search 
for catalysts useful for the polymerization of .alpha.-olefins. It is also 
desirable that (he process used in forming such catalysts allow for ease 
of preparation and ready control over the properties of the final catalyst 
formed. 
Another important aspect of a polymerization catalyst and polymerization 
process employing same is the properties of the polymer particles 
produced. It is desirable to produce polymer particles which are 
characterized by strength, uniformity of size, and a relatively low level 
of fine particulate matter. Although polymer fluff having relatively high 
percentages of polymer fines can be handled with plant modifications, the 
production of polymers in high productivity with low level of fines 
content is highly desirable so as to avoid the need for such plant 
modifications. Especially desirable are polymer particles having a high 
bulk density and relatively uniform shape as well as size. 
OBJECTS OF THE INVENTION 
It is an object of the present invention, therefore, to provide a novel and 
improved method for preparing catalyst compositions. 
Another object of the present invention is to provide a novel catalyst 
composition well adapted for the polymerization of .alpha.-olefins. 
A further object of the present invention is to provide an improved process 
for the polymerization of .alpha.-olefins. 
Yet another object of the present invention is to provide polymer 
compositions having high bulk densities, relatively low levels of polymer 
fines and relatively uniform shape and size. 
These and other objects of the present invention will become apparent from 
the disclosure, figures and claims herein provided. 
STATEMENT OF THE INVENTION 
In accordance with the present invention, we have discovered that polymer 
particles having low levels of polymer fines, high bulk density, and 
relatively uniform shape and size are obtained when prepared by 
polymerization of .alpha.-olefins with high activity, high 
stereospecificity heterogeneous olefin polymerization catalysts prepared 
by contacting a soluble complex (produced by contacting a metal dihalide 
with a transition metal compound) with a predominantly silica-containing 
particulate material prior to contacting the supported complex with an 
organoaluminum halide. After treatment with the organoaluminum halide the 
resulting catalyst component is activated for polymerization by treatment 
with an activating agent comprising Group IVA or IVB halides.

DETAILED DESCRIPTION OF THE INVENTION 
In accordance with the present invention, there is provided a method for 
the preparation oi a first olefin polymerization catalyst component which 
comprises: 
(a) contacting at least one metal dihalide selected from the group 
consisting of Group IIA and IIB dihalides with at least one transition 
metal compound in the presence of a diluent under conditions suitable for 
the formation of a soluble complex; 
(b) contacting the soluble complex produced in accordance with step (a) 
with 0.1 to 20 weight percent, based on the weight of the soluble complex, 
of a predominantly silica-containing particulate material to produce a 
first solid; 
(c) contacting said first solid with 0.1 to 10 mole of an organoaluminum 
halide per mole transition metal compound to produce said first catalyst 
component. 
Optionally, the first olefin polymerization catalyst component can be 
further contacted with a halide ion exchanging compound The first olefin 
polymerization catalyst component can also be further contacted with a 
cocatalyst, if desired. 
Further in accordance with the present invention, there are provided novel 
catalyst compositions produced as described hereinabove. 
Still further in accordance with the present invention there is provided a 
process for the polymerization of C.sub.2 up to C.sub.20 .alpha.-olefins 
which comprises contacting at least one of said .alpha.-olefins under 
polymerization conditions with catalyst prepared as described hereinabove. 
Still further in accordance with the present invention, there are provided 
novel polymer compositions produced by carrying out the above described 
polymerization process. The novel polymers oi the present invention have 
high bulk density, low levels of polymer fines, reactor soluble polymer 
which is less atactic and are composed of crystal-like appearing 
particles. 
Examples of Group IIA and IIB metal dihalides that can be used in forming 
the first component of the catalyst include, for example, the dihalides of 
beryllium, magnesium, calcium, and zinc. Dichlorides are preferred. 
Magnesium dichloride is presently preferred because it is readily 
available and relatively inexpensive and has provided excellent results. 
While the hydrous or anhydrous form of the metal dihalide can be employed 
as the starting material for the catalyst; it is desirable that the amount 
of water in the metal dihalide be from 0.5 to 1.5 moles/mole magnesium 
dihalide prior to contacting the dihalide with the transition metal 
compound. Any method known to those skilled in the art to limit the amount 
of water in the magnesium dihalide can be employed. It is preferred to 
admix the appropriate amount of water with the anhydrous metal dihalide to 
achieve the ratios set out above. 
The metal dihalide component is generally used in the form of a particulate 
solid to facilitate its reaction with the transition metal compound. It is 
also noted that various techniques for converting a metal halide compound 
to a fine particulate form, such as for example roll milling, 
reprecipitating, etc., can be used to prepare the metal halide compound 
for use according to the present invention. Such additional preparation of 
the metal halide compound promotes the reaction of the metal halide 
compound with the transition metal compound. It does not appear, however, 
to make any difference in a catalyst of the present invention prepared 
from a composition of matter of the present invention if the metal halide 
compound is in a fine particulate form, since catalyst productivity, for 
example, does not seem to be a function of the size of the particles of 
the metal halide compound employed. 
The transition metal compounds useful in this invention are those wherein 
the transition metal is selected from the Groups IVB and VB and the 
transition metal is bonded to at least one atom selected from the group 
consisting of oxygen, nitrogen, and sulfur; and said oxygen, nitrogen and 
sulfur atoms are in turn bonded to a carbon of a carbon-containing 
radical. 
The transition metal is preferably selected from titanium, zirconium and 
vanadium, although other transition metals can be employed. Excellent 
results have been obtained with titanium compounds and they are therefore 
preferred. Some of the titanium compounds that may be used in the instant 
invention include, for example, titanium tetrahydrocarbyloxides, titanium 
tetraimides, titanium tetraamides and titanium tetramercaptides. Other 
transition metal compounds includes, or example, zirconium 
tetrahydrocarbyloxides, zirconium tetraimides, zirconium tetraamides, 
zirconium tetramercaptides, vanadium tetrahydrocarbyloxides, vanadium 
tetraimides, vanadium tetraamides and vanadium tetramercaptides. 
The titanium tetrahydrocarbyloxides are presently preferred because they 
produce excellent results and are readily available. Preferred titanium 
tetrahydrocarbyloxide compounds include those expressed by the general 
formula Ti(OR).sub.4 wherein each R is individually selected from an 
alkyl, cycloalkyl, aryl, alkaryl, and aralkyl hydrocarbon radical 
containing from about 1 to about 20 carbon atoms per radical and each R 
can be the same or different. Titanium tetrahydrocarbyloxides in which the 
hydrocarbyl group contains from about 1 to about 10 carbon atoms per 
radical are more frequently employed because they are more readily 
available. Suitable titanium tetrahydrocarhyloxides include, for example, 
titanium tetramethoxide, titanium dimethoxidediethoxide, titanium 
tetraethoxide, titanium tetra-n-hutoxide, titanium tetrahexyloxide, 
titanium tetradecyloxide, titanium tetraeicosyloxide, titanium 
tetracyclohexyloxide, titanium tetrabenzyloxide, titanium 
tetra-p-tolyoxide and titanium tetraphenoxide. 
Of the titanium tetrahydrocarbyloxides, titanium tetraalkoxides are 
generally preferred and titanium tetra-n-butoxide is particularly 
preferred because of the excellent results obtained employing this 
material. Titanium tetra-n-butoxide is also generally available at a 
reasonable cost. 
The molar ratio of the transition metal compound to the metal halide 
compounds can be selected over a relatively broad range. Generally the 
molar ratio is within the range of about 10:1 to about 1:10, however, the 
most common molar ratios are within the range of about 2:1 to about 1:2. 
When titanium tetrahydrocarbyloxide and magnesium dichloride are employed 
to form a composition of matter of the invention, a molar ratio of 
titanium to magnesium oi about 1:2 is recommended. 
The metal halide compound and the transition metal compound employed in the 
present invention are normally mixed together by heating, e.g. refluxing, 
in a suitable dry (essential absence of water) solvent or diluent that is 
essentially inert to these components and the product. The term "inert" is 
used to mean that the solvent does not chemically react with the dissolved 
components. Such inert solvents or diluents for the purpose o: the instant 
invention include, for example, n-pentane, n-heptane, methylcyclohexane, 
toluene, xylenes and the like. It is emphasized that aromatic solvents are 
preferred, such as xylene, for example, because the solubilities of the 
metal halide compound and the transition metal compound are higher in 
aromatic solvents by comparison to aliphatic solvents, particularly at low 
mixing temperatures. Such mixing temperatures are generally within the 
range of from about 0.degree. C. to about 50.degree. C and preferably from 
about 10.degree. C to about 30.degree. C. 
Mixtures of two or more of the above solvents to dissolve the reagents of 
the first catalyst component can of course also be used and can be readily 
determined by one of ordinary skill in the art. 
Generally the amount of solvent or diluent employed can be selected over a 
broad range. Usually the amount of solvent or diluent is within the range 
of about 20 to about 100 cc per gram of metal dihalide. The temperature 
employed during the heating step can also be selected over a broad range. 
Normally the heating temperature is within the range of about 15.degree. 
C. to about 150.degree. C. when the heating step is carried out at 
atmospheric pressure. Higher heating temperatures can be employed if the 
pressure employed is above atmospheric pressure. 
Generally, the time required for heating these two components together is 
within the range of about 5 minutes to about 0 hours, although in most 
instances a time within the range of about 15 minutes to about 3 hours is 
sufficient. Following the heating operation, the resulting solution can be 
filtered if desired to remove any undissolved material or extraneous 
solid. 
In one embodiment of the present invention, it has been found that very 
useful catalyst components result if a third component or set of 
components is included during the reaction of the dihalide compound and 
the transition metal compound. Many combinations of third components and 
specific transition metal compounds provide significant improvements in 
either productivity or selectivity. 
Examples of compounds that may be used as third components include electron 
donors such as ammonia, hydroxylamine, alcohols, ethers, carboxylic acids, 
esters, acid chlorides, amides, nitriles, amines, and substituted and 
unsubstituted phenols, naphthols and their sulfur-containing analogs, i.e. 
thiophenols. The preferred compounds are aromatic compounds selected from 
the group consisting of phenols, thiophenols, naphthols, aralkyl alcohols, 
aromatic acids, and aromatic esters. 
The mole ratio of third component compound employed in step (1) relative to 
the transition metal compound can vary from about 5:1 to about 1:5, 
preferably about 1:1 to 2:1. 
In accordance with an especially preferred embodiment a phenol and an 
aromatic ester are employed in the reaction between the transition metal 
compound and the dihalide compound. 
The dihalides and the transition metal compounds, as well as optional 
election donors, as above described, can be reacted in the presence of a 
liquid diluent or solvent, or when at least one of the reagents is in the 
liquid state during the reaction the of diluent can be omitted. 
In accordance with the present invention, the soluble complex prepared as 
described above is then contacted with a particulate material consisting 
essentially of silica. The silica particulate material employed in this 
invention has a particle size in the range of about 50 up to 200 microns. 
The silica employed can be either substantially amorphous, substantially 
crystalline, or material which is a mixture of the two forms, i.e., 
partially crystalline material. When substantially amorphous silica is 
employed, such materials are preferably subjected to heat pretreatment 
before contacting with the soluble complex. Such heat treatment is 
generally carried out within the range of about 100 up to 900.degree. C., 
preferably 700.degree.-800.degree. C. In general, it has been found that 
polymer having a higher bulk density and a higher percentage of 
crystalline polymer particles is obtained when higher silica pretreatment 
temperatures are employed, up to a temperature of 800.degree. C., at which 
temperature the crystalline percentage is maximized. 
Substantially crystalline silica (known as silicalite), can alternatively 
be contacted with the soluble complex in this invention. Silicalites can 
be prepared in any manner known to those skilled in the art or can be 
obtained commercially. 
In addition to the silicalites used in this invention certain dealuminated 
zeolites such as dealuminated faujasite can also be employed. 
The use of silicalites and the dealuminated zeolites in the preparation of 
the invention catalyst leads to the production of smaller, less distinct 
catalyst crystals, and therefore smaller less distinct polymer particles. 
The polymer particles, however, still resemble crystals and are of high 
bulk density. The catalyst crystals formed when silica is used and when 
silicalites are used are depicted in FIGS. 1 and 3, respectively. The 
quantity of particulate material employed in the practice of the present 
invention, based on the weight of soluble complex employed, can vary over 
a wide range. Generally, the weight of silica employed can range from 
about 0.1 to 30 weight percent, with about 20 weight percent preferred. 
The desired quantity oi silica-containing material can be added to the 
soluble complex once preparation of the soluble complex is complete. The 
combination of silica and soluble complex can then be stirred at any 
suitable temperature for any suitable period of time. Generally, such 
contacting takes place from in the range of about 5 minutes up to 2 hours 
at a temperature in the range of about 20 up to 100.degree. C., before 
further treatment of the silica supported soluble complex with an 
organoaluminum halide as described below. 
The organoaluminum halide is selected from compounds having the general 
formula AlR.sub.n X.sub.3.sub.-n wherein each R is individually selected 
from saturated and unsaturated hydrocarbyl radicals containing 1 to 20 
carbon atoms per radical, X is a halogen and n is any number such that 
1.ltoreq.n.ltoreq.2. Typical examples include methylaluminum dibromide, 
ethylaluminum dichloride, ethylaluminum diiodide, isobutylaluminum 
dichloride, dodecylaluminum dibromide, dimethylaluminum bromide, 
diethylaluminum chloride, diisopropylaluminum chloride, 
methyl-p-propylaluminum bromide, di-n-octylaluminum bromide, 
diphenylaluminum chloride, triethylaluminum, dicyclohexylaluminum bromide, 
dieicosylaluminum chloride, methylaluminum sesquibromide, ethylaluminum 
sesquichloride, ethylaluminum sesquiiodide, and the like, and mixtures 
thereof. Ethylaluminum sesquichloride, ethylaluminum dichloride, and 
diethylaluminum chloride have been employed with good results and are 
preferred. The most preferred organoaluminum halide is ethylaluminum 
sesquichloride. 
The reaction with the organoaluminum halide can also be carried out either 
in the presence of a liquid diluent or in the absence of such diluent. 
Preferably, the product oi the reaction of the dihalide and the transition 
metal compound which has been adsorbed on the silica-containing material 
is contacted with a hydrocarbon solution of the aluminum halide. 
The temperature employed while mixing the first solid and organoaluminum 
halide as above described can be selected over a broad range. Generally 
the temperature employed is within a range of about 0.degree. C. to about 
50.degree. C. or higher, while temperatures within the range of 20.degree. 
C. to about 30.degree. C. were most often employed. Since heat is evolved 
when the first catalyst component and the second catalyst component are 
mixed, the mixing rate is adjusted as required and additional cooling is 
employed if necessary in order to maintain a relatively constant mixing 
temperature. After completing the mixing, the resulting slurry is stirred 
or agitated for a sufficient time, generally within a range of about 15 
minutes to about 5 hours to insure that mixing of the components is 
complete. Thereafter, stirring is discontinued and the solid product 
recovered by filtration, decantation, and the like. The product is then 
washed with a suitable material such as a hydrocarbon, e.g., n-pentane, 
n-heptane, cyclohexane, enxene, xylenes and the like, to remove any 
soluble material which may be present. The product is reactive and if it 
is to be stored before use, it must be protected against unwanted 
reactions and contamination of the catalyst preparation; this requirement 
is easily met by one possessing ordinary skill in the art. 
The molar ratio of the transition metal compound in the first solid 
catalyst component to the organoaluminum halide can be selected over a 
relatively broad range. Generally, the molar ratio of the transition metal 
of the first catalyst component to the organoaluminum halide is within a 
range of 10:1 to 1:10, and more preferably within a range of about 2:1 to 
about 1:3 since a molar ratio within the latter range usually produces an 
especially active olefin polymerization catalyst. 
In accordance with one embodiment of this invention, the first catalyst 
component resulting from the reaction of the dihalide, the transition 
metal compound, the silica-containing material and the organoaluminum 
halide is then reacted with a halide ion exchanging source comprising a 
halogen-containing compound of Groups IVA and VA. 
The particularly preferred halide ion exchanging compounds of Groups IVA 
and VA are chlorine-containing compounds of Si, Ge, Sn, P, and C. Typical 
examples include COCl.sub.2, PCL.sub.2, SiCl.sub.4, SnCl.sub.4, CCL.sub.4, 
and acid chlorides of the formula R'COCl where R' is an aliphatic or 
aromatic radical, preferably containing 1 to 20 carbon atoms. 
Other halogen-containing compounds suitable in this embodiment include 
chlorosiloxanes of the formula Si.sub.n O.sub.n Cl.sub.2.sub.n+2 wherein n 
is a number in the range of 2 to 7, for example Si.sub.2 OCl.sub.6 ; 
chlorinated polysilanes having the formula Si.sub.n Cl.sub.2.sub.n+ where 
n is a number in the range of 2 to 6, such as Si.sub.4 Cl.sub.10 ; 
chlorinated silanes having the formula SiH.sub.4.sub.31 n Cl.sub.n wherein 
n is a number in the range of 1 to 3, such as SiHCl.sub.3 ; silanes having 
the formula R'SiH.sub.x Cl.sub.y wherein R' is an aromatic or aliphatic 
radical containing 1 to 20 carbon atoms, x a number in the range of 0 to 
2, and y is a number in the range of 1 to 3, such as C.sub.2 H.sub.5 
SiCl.sub.3, CH.sub.3 SiCl.sub.2 H, and (CH.sub.3).sub.2 SiCl.sub.2 ; 
alkoxy-halogensilanes of the formula Si(OR).sub.4.sub.- n Cl.sub.n wherein 
R is an alkyl or aryl radical having 1 to 20 carbon atoms and n is a 
number in the range of 1 to 3, such as Si(OC.sub.2 H.sub.5)Cl.sub.3. 
ln a particularly preferred embodiment, a chlorine-containing silicon 
compound or an organosilane is employed in combination with TiCl.sub.4. 
Examples of the preferred silicon compounds for this embodiment include 
SiCl.sub.4, HSiCl.sub.3, .phi.SiHCl.sub.2 and .phi.SiCl.sub.2, wherein 
.phi. is a phenyl radical. In this embodiment, the ratio of silicon 
compound to TiCl.sub.4 can vary considerably, generally however, best 
results are obtained if the molar ratio of silicon compound to TiCl.sub.4 
in the range of about 1/1. 
Generally the reaction of the first catalyst component with the halogen 
containing source can be carried out neat or in a liquid medium in which 
the halide ion exchanging source is soluble. Accordingly, the first 
catalyst component is generally contacted with an inert liquid diluent in 
the process containing the halide ion exchanging source. Any suitable 
inert diluent can be employed. Examples include normally liquid 
hydrocarbon such as n-pentane, n-heptane, cyclohexane, benzene, and 
xylene. 
The temperature employed in the reaction of the first catalyst component 
and halide ion exchanging source can be selected over a relatively broad 
range, generally in the range of -25.degree. C. to +250.degree. C., 
preferably 0.degree. C. to 200.degree. C., with a temperature of about 
100.degree. C. being most preferred. 
The treating time can also be selected over a broad range and generally is 
within the range of about 10 minutes to about 10 hours. While the weight 
ratio of the halide ion exchanging source to the first catalyst component 
can be selected over a relatively broad range, the weight ratio oi the 
halide ion exchanging source to the first catalyst component is generally 
within a range of about 10:1 to about 1:10 and more generally from about 
7:1 to about 1:4. Following the treatment of the first catalyst component 
with the halide ion exchanging source, the surplus halide ion exchanging 
source is removed by washing the solid catalyst with a dry (essential 
absence of water) liquid such as a hydrocarbon of the type previously 
discussed, n-hexane, or xylene for example. The resulting catalyst can be 
stored in the diluent, or after drying, stored under dry nitrogen. 
While it may not be necessary in all instances to employ a cocatalyst with 
the catalyst of the present invention, the use of cocatalysts is 
recommended for best results. The organometallic cocatalysts suitable for 
use in accordance with the invention can be selected from among the 
hydrides and organometallic compounds of metals of Groups IA, II, and IIIA 
of the periodic Table. Of the organometallic cocatalysts, organoaluminum 
compounds are preferred with the most preferred organoaluminum cocatalysts 
being compounds of the formula R.sub.3 Al which include, for example, 
trimethylaluminum, triethylaluminum, triisopropylaluminum, 
tridecylaluminum, triecosylaluminum, tricyclohexylaluminum, 
triphenylaluminum, 2-methylpentyldiethylaluminum, and 
triisoprenylaluminum. Triethylaluminia is preferred since this compound 
produced excellent results in the runs hereafter described. 
The molar ratio of the organometallic compounds of the cocatalyst to the 
transition metal compound of the first catalyst component is not 
particularly critical and can be selected over a relatively broad range. 
Generally, the molar ratio of the organometallic compounds of the 
cocatalyst to the transition metal compound of the first catalyst 
component is within a range of about 1:1 to about 1500:1. For catalyst 
systems wherein the cocatalyst comprises at least one organoaluminum 
compound typically there is employed about 0.25 to 15 milligrams of the 
titanium-containing component per mmole of organoaluminum cocatalyst. 
Generally it has also been found desirable to include a Lewis base when a 
triaalkyl aluminum is employed as the cocatalyst. Among Lewis bases 
capable of appropriate addition are amines, amides, ethers, esters, 
ketones, arsines, phosphoramides, thioethers, aldehydes, alcoholates, 
amides and salts of organic acids of metals of the first four groups of 
the Periodic Table. Preferred Lewis bases are an aromatic ester or an 
amine. Typical examples of aromatic esters are ethyl benzoate, ethyl 
p-methoxybenzoate (ethyl anisate), ethyl o-chlorobenzoate, ethyl 
naphthenate, ethyl toluate, and ethyl p-butoxybenzoate. A suitable amine 
is 2,2,6,6-tetramethylpiperidine. The preferred Lewis base:aluminum alkyl 
ratio is lower than 0.8:1, in the case of an aromatic ester or amine, the 
preferred ratio is from 0.1:1 to 0.6:1. The catalyst activity and 
stereospecifity seem to be related to the Lewis base:aluminum alkyl molar 
ratio. 
A variety of polymerizable compounds are suitable for use in the process oi 
the present invention. Olefins which can be homopolymerized or 
copolymerized with the invention catalysts include aliphatic mono-olefins. 
While the invention would appear to be suitable for use with any aliphatic 
mono-1-olefin, those olefins having 2 to 20 carbon atoms are most often 
used. The mono-2-olefins can be polymerized according to the present 
invention employing either a particle form process, a gas phase process, 
or a solution form process. Aliphatic mono-1-olefins can be copolymerized 
with other 1-olefins and/or with other smaller amounts of other such as 
1,3-butadiene, isoprene, 1,3-pentadiene, styrene, alpha-methylstyrene, and 
similar ethylenically unsaturated monomers which do not impair the 
catalyst. 
The catalysts of the invention are well suited for producing stereoregular 
polypropylene, offering potential for high rates as well as low soluble 
polymer formation. Moreover, catalyst activity remains constant for very 
long periods of time allowing productivities near 20 kg/g in 8 hours (FIG. 
5). This catalyst system is also unusual in that as productivity 
increases, the size of the polymer particles increase (FIG. 6). 
Polymerization may be conducted in a liquid phase, in liquid monomer in the 
presence or absence of an inert hydrocarbon diluent, or in a gas phase. In 
the polymerization of propylene, particularly satisfactory results have 
been attained operating in the presence of an aliphatic or aromatic 
hydrocarbon diluent, liquid under the polymerization conditions, such as 
propylene, toluene, gasoline, and the like. 
The polymerization process according to the present invention employing the 
catalysts and cocatalysts as above described can be performed either 
batchwise or continuously. In a batch process, for example, a stirred 
autoclave is prepared by first purging with nitrogen and then with a 
suitable compound, such as isobutane for example. When the catalyst and 
cocatalyst are employed either can be adapted to the reactor first or they 
can be charged simultaneously through an entry port under an isobutane 
purge. After closing the entry port, hydrogen; if used, is added, and then 
a diluent such as isobutane is added to the reactor. The reactor is heated 
to the desired reaction temperature, which for polymerizing ethylene, for 
example, is, for best results, generally within a range of about 
50.degree. C. to about 102.degree. C. and the monomer is then admitted and 
maintained at a partial pressure within a range of about 0.5 MPa to about 
5.0 MPa (70-725 psig) for best results. At the end of the designated 
reaction period, the polymerization reaction is terminated and the 
unreacted olefin and isobutane are vented. The reactor is opened and the 
polymer, such as polyethylene, is collected as a free-flowing white solid 
and is dried to obtain the product. 
In a continuous process, for example, a suitable reactor such as a loop 
reactor is continuously charged with suitable quantities of solvent or 
diluent, catalyst, cocatalyst, polymerizable compounds and hydrogen, if 
any, and in any desirable order. The reactor product is continuously 
withdrawn and the polymer recovered as appropriate, generally by flashing 
the diluent (solvent) and unreacted monomers and drying the resulting 
polymer. 
For optimum productivity of polymer of low solubility in the continuous 
polymerization of propylene, it is preferable to contact the cocatalyst 
comprising the trialkylaluminum-Lewis Base with the titanium-containing 
catalyst for a short period immediately prior to its being exposed to 
liquid propylene. It is preferable under these circumstances that the 
molar ratio of trialkylaluminum to Lewis base in the cocatalyst be greater 
than 2:1, generally 3-4:1. 
The olefin polymers made with the catalysts of this invention are useful in 
preparing articles by conventional polyolefin processing techniques such 
as injection molding, rotational molding, extrusion of film, and the like. 
A further understanding of the present invention and its advantages will be 
provided by the following examples illustrating a few embodiments of the 
invention. 
EXAMPLES 
All catalysts were prepared in 1 qt. (0.95 L) glass, capped, beverage 
bottles in dry, air-free environments as described below. 
A commercial, particulate, "anhydrous" MgCl.sub.2 was the MgCl.sub.2 source 
material, which analysis disclosed contained about 1.5 weight percent 
water. Magnesium chloride hydrates were general-y prepared by slurrying 
0.04 mol "anhydrous" MgCl.sub.2 in 300 ml xylene, then adding 0.04 mol 
H.sub.2 O and stirring the mixture at room temperature overnight 
(approximately 20 hours, 20-60 hours). 
Generally, about 0.04 mole of the "hydrated" MgCl.sub.2, about 0.02 mole of 
titanium titra-butoxide (Ti(OBu).sub.4,) 0.02 mole of phenol PH or 
H-phenyl phenol (4-PP) if employed, about 0.01 mole of ethyl benzoate 
(EB), if employed, and 300 mL of the xylene in a 1 qt. beverage bottle 
were heated for 1 hour at 100.degree. C. in an oil bath while stirring the 
contents to obtain a solution. Heating was discontinued and the 
predominantly silica-containing material was added. The mixture was 
stirred to evenly distribute the particles and the resulting admixture was 
diluted to about 500 mL with additional xylenes (at a temperature of about 
23.degree. C). With continued stirring, 25 mL of ethylaluminum 
sesquichloride (EASC) as a 25 weight percent solution in n-heptane (0.02 
mole EASC) was added dropwise. The product was isolated by centrifugation 
and washed several times by slurrying in n-hexane followed by 
centrifugation until the supernatant liquid was colorless. The washed 
material was then isolated by vacuum filtration and the cake allowed to 
dry in the glove box overnight. 
Each resulting composition was activated for polymerization by heating a 
weighed portion thereof, generally 20 g unless specified otherwise, with 
20-30 mL of a solution consisting of 50 volume percent TiCl.sub.4 (55.6 
weight percent), 37.5-40 volume percent HSiCl.sub.3 (32.4-34.5 weight 
percent) and 10-12.5 volume percent SiCl.sub.4 (9.6-12.0 weight percent), 
with stirring for 1 hour at 100.degree. C. In one series, 5 g of the 
isolated, purified, dry composition was treated for 1 hour at 100.degree. 
C. with 20 mL of a solution consisting of equal volumes of TiCl.sub.4 and 
SiCl.sub.4. 
The activated compositions were recovered by filtration, washed with 
n-hexane to remove unreacted halides and dried as before to obtain the 
catalysts. Each catalyst was stored in a stoppered container in a dry, 
inert atmosphere such as argon or nitrogen until ready for testing. The 
resulting invention catalysts, the crystal shaped particles, were isolated 
along with the particulate silica material; the total mixture was added to 
the polymerization reactor. 
Propylene polymerization was conducted in a 1 L stirred stainless steel 
reactor in liquid propylene for 1 hour at 70.degree. C. in the presence of 
10 psi hydrogen with a weighed portion oi the catalyst. Catalyst weights 
ranged from about 25 to about 100 mg. In each run, unless otherwise 
specified, a cocatalyst consisting of 2.0 mmoles of triethylaluminum (TEA) 
and 1.1 mmoles of ethyl anisate (EA), premixed, and 2.0 mmoles of 
diethylaluminum chloride (DEAC) were employed. The organometal solutions 
were each about 0.6 mole in n-heptane. 
Following polymerization, the polypropylene was recovered, stabilized and 
dried. 
Ethylene polymerizations was conducted in a 2 L stirred, stainless steel 
reactor containing 1.25 lbs. (567 g) of isobutane diluent at the specified 
temperatures, times and in the presence of hydrogen, if used, to control 
polymer melt index. In each run unless otherwise specified, 1 mL of TEA (1 
mmole TEA) as a solution in n-heptane, was used as cocatalyst. Total 
reactor pressure in each run was about 565 psia (3.89 MPa). Polymerization 
was terminated by discontinuing heating, venting gaseous reactants and 
recovering and drying the polyethylene produced. 
The xylene and propylene solubles test was performed as follows. A gram 
sample of polymer was placed in a 100 ml centrifuge tube containing 100 ml 
of xylene or propylene. The tube was then placed in a Heater-Evaporator 
and maintained at 140.degree. C. for 15 minutes while stirring 
occasionally. After the 15 minute heating was completed, the tube was 
removed from the heater and allowed to cool at room temperature for 15 
minutes, following by cooling in an ice bath for 30 minutes. The tube was 
then placed in an International Model V Centrifuge and centrifuged at 
approximately 1900 rpm for 15 minutes. The tube was removed from the 
centrifuge and 25 ml of the supernatant liquid was removed to an aluminum 
dish which had been previously weighted while empty. The dish containing 
the liquid was heated for 30 minutes, then was allowed to cool, and 
subsequently was reweighed. 
The weight percent solubles was calculated according to the equation: 
##EQU1## 
A=grams of polymer in aluminum dish, and S=grams of original polymer 
sample. 
EXAMPLE I 
A series of catalysts was prepared in a multi-step process comprising: (1) 
stirring a mixture consisting of 0.04 mole particulate MgCl.sub.2.0.008 
H.sub.2 O, 0.04 mole H.sub.2 O and 300 mL mixed xylenes (hereafter called 
xylene) for about 3 days at 23.degree. C., (2) admixing (1) with 0.02 mole 
Ti(OBu).sub.4 and 0.02 mole phenol and heating the stirred mixture at 
100.degree. C. for 1 hour to obtain a solution, (3) adding with stirring 
the silicas employed and diluting the resulting mixture to about 500 mL 
with room temperature (about 23.degree. C.) xylene, (4) reacting (3) with 
0.0% mole EASC as a 25 weight percent solution in n-heptane to form 
catalyst precursor A which is isolated by centrifugation, washed with 
n-hexane and dried, as described before. 
Each catalyst precursor A composition weighing 20 g was activated for 
polymerization by treatment with 20-30 mL of a 3-component halide mixture 
consisting of 50 volume percent TiCl.sub.4, 37.5 volume percent 
HSiCl.sub.3 and 12.5 volume percent SiCl.sub.4 at 100.degree. C. for 1 
hour. The corresponding weight ratio oi halides to initial MgCl.sub.2 
ranged from about 8:1 to about 10:1. The resulting compositions were 
isolated by suction filtration, then washed with n-hexane and dried to 
obtain the catalysts. 
The color of the dried precursor compositions A ranged from yellow to 
orange. The colors of the dried catalysts obtained were generally orange 
to reddish-brown. The silicas employed were conditioned for use in the 
catalyst preparations by calcining each in dry air under fluidizing 
conditions at the specified temperature for 3 hours. The conditioned 
supports were flushed with nitrogen, cooled, then recovered and stored 
under nitrogen. The silica used was Davison Chemical Company grade 952. 
The weights of the silica employed and the catalyst precursor and the 
activated catalyst were all measured. The weight of the active catalyst 
component (other than the silica) was then calculated for each catalyst, 
based on the ratio of silica in precursor to silica in activated catalyst. 
The weights oi silica employed, precursor made, catalyst produced, 
calculated percentages, etc. are presented in Table 1A. 
TABLE 1A 
__________________________________________________________________________ 
Precursors and Isolated Catalysts Thereof 
Silica Isolated Catalyst.sup.(a) 
Catalyst Calcining 
Precursor 
Total.sup.(b) 
Wt..sup.(c) 
Calc. Wt. %.sup.(d) 
No. Wt. g 
Temp. .degree.C. 
Wt. g Wt. g 
Calc., g 
Silica 
Active Catalyst 
__________________________________________________________________________ 
1 20.8 
150 30.2 19.3 
13.8 71.5 
28.5 
2 23.2 
200 33.3 19.1 
14.0 73.3 
26.7 
3 22.2 
500 32.7 19.0 
13.6 71.6 
28.4 
4 26.5 
700 34.1 18.6 
15.5 83.3 
16.7 
5 22.8 
800 32.9 18.1 
13.8 76.2 
23.8 
6 27.2 
900 35.2 18.7 
15.5 82.9 
17.1 
__________________________________________________________________________ 
.sup.(a) Catalyst prepared from 20 g of corresponding precursor and 
activated with the previously described TiCl.sub.4 --HSiCl.sub.3 
--SiCl.sub.4 mixture. 
.sup.(b) Silica + active catalyst component. 
.sup.(c) Calculated weight of the silica in the final catalyst was 
obtained by multiplying the percentage of silica in the catalyst precurso 
by the 20 g of precursor used. 
.sup.(d) Calculated weight percentages for the silica in the final 
catalyst was obtained by dividing the calculated weight of the silica in 
the final catalyst by the measured total weight of the final catalyst, 
then multiplying by 100. The weight precentage for the active catalyst wa 
then calculated as the remaining percentage. 
A portion of each catalyst in Table 1A was tested for propylene 
polymerization under the conditions previously described. The results are 
set forth in Table 1B. 
TABLE 1B 
__________________________________________________________________________ 
Propylene Polymerization 
Calc. Activity 
Weight, mg kg/g/hr.sup.(a) Melt Flex 
Cat. 
Total 
Active 
Total 
Active 
Wt. % Solubles.sup.(b) 
Flow.sup.(c) 
Density.sup.(d), g/cc 
Mod..sup.(e) 
No. 
Cat. 
Cat. 
Cat. 
Cat. 
Propylene 
Xylene 
g/10 min. 
Molded 
Bulk 
MPa 
__________________________________________________________________________ 
1 39.9 
11.4 
1.44 
5.04 
3.1 3.7 6.0 0.9075 
0.378 
1509 
2 66.8 
17.8 
1.76 
6.59 
1.8 4.5 4.4 0.9055 
0.381 
1392 
3 64.2 
18.2 
1.84 
6.39 
1.3 3.9 4.0 0.9063 
0.413 
1398 
4 57.0 
9.52 
1.08 
6.45 
2.4 3.7 5.2 0.9067 
.about.0.44 
1567 
5 60.8 
14.5 
1.87 
7.83 
1.3 3.8 3.4 0.9058 
0.452 
1411 
6 56.1 
9.59 
0.822 
4.81 
3.1 2.8 3.8 0.9074 
.about.0.44 
1396 
__________________________________________________________________________ 
.sup.(a) Calculated activity is based on polymer recovered from the 
reactor but does not include propylene soluble polymer. It is in terms of 
kilograms polypropylene per g solid catalyst per hour 
.sup.(b) Solubles test described herein. 
.sup.(c) ASTM D 1238, condition L 
.sup.(d) ASTM D 1505 
The results in Table 1B show that the suPported catalysts are all active in 
propylene polymerization under the conditions employed and that the 
polymers made with them are in the commercially useful range based on the 
melt flows ranging from about 3 to 6, with molded densities in the 0.906 
to 0.907 g/cc range and flexural modulus values ranging from about 1400 to 
about 1560 MPa. The catalysts are all effective in suppressing 
propylene-soluble and xylene-soluble polymer levels based on the values 
shown. In considering the contribution made by the active catalyst only 
(neglecting the silica weight), calculated results show productivities 
ranging from about 4.8 to 7.8 kg polypropylene per g active catalyst per 
hour at 70.degree. C. 
The recovered polymers were all in the form of granules, generally 
containing some crystal-like appearing particles, see FIG. 2A, which 
depicts a SEM photograph of the polymer produced with catalyst 5. The bulk 
density of the nascent polymer increased from about 0.38 g/cc with 
catalyst 1, prepared in the presence oi silica which had been calcined at 
150.degree. C., to about 0.45 g/cc with catalysts 4, 5, 6, prepared in the 
presence of silica which had been calcined at 700.degree., 800.degree., 
and 900.degree. C., respectively. Individual crystal shaped polymer 
particles had densities of 0.88 g/cc, about 97% of the density of the 
molded material. When good catalyst activity and high bulk density of as 
nascent polymer are both desired, the overall results obtained with 
catalysts 4, 5 suggest that the optimum silica calcining temperature is in 
the 700.degree. -800.degree. C. with the catalyst system of the invention. 
EXAMPLE II 
A series of catalysts was prepared from 5 g portions of the precursor A 
compositions used in producing catalysts 1, 2, 3, 5 of Example I by 
contacting each precursor portion with about 20 mL of a halide mixture 
consisting of equal volumes of TiCl.sub.4 and SiCl.sub.4 at 100.degree. C. 
for 1 hour. The corresponding weight ratio of halides to initial 
MgCl.sub.2 was about 6:1 The resulting compositions were purified and 
recovered as before to obtain the orange-colored catalysts. 
The weights of catalysts produced, the calculated weight of silica 
contained in each catalysts, and calculated weight percent of silica and 
active catalyst of each catalyst are given in Table 2A. 
TABLE 2A 
______________________________________ 
Silica-Containing Catalysts 
Catalyst Wt. Silica Calculated Weight Percent 
No. Wt. g Calc., g.sup.(a) 
Silica.sup.(b) 
Active Catalyst 
______________________________________ 
7 4.7 3.45 73.4 26.6 
8 4.7 3.5 74.5 25.5 
9 4.5 3.4 75.6 24.4 
10 4.4 3.5 79.5 20.5 
______________________________________ 
.sup.(a) See footnote (c) in Table 1A. 
.sup.(b) See footnote (d) in Table 1A. 
A portion of each catalyst in Table 2A was tested in propylene 
polymerization under the conditions previously described. The results are 
given in Table 2B. 
TABLE 2B 
__________________________________________________________________________ 
Propylene Polymerization 
Calc. Activity 
Weight, mg kg/g/hr.sup.(a) Melt Flex 
Cat. 
Total 
Active 
Total 
Active 
Wt. % Solubles.sup.(b) 
Flow.sup.(c) 
Density.sup.(d), g/cc 
Mod..sup.(e) 
No. 
Cat. 
Cat. 
Cat. 
Cat. 
Propylene 
Xylene 
g/10 min. 
Molded 
Bulk 
MPa 
__________________________________________________________________________ 
7 51.6 
13.7 
1.81 
6.83 
2.0 3.3 7.4 0.9077 
0.306 
1479 
8 54.7 
13.9 
1.46 
5.76 
2.9 3.7 5.4 0.9073 
0.352 
1467 
9 54.6 
13.3 
1.18 
4.83 
2.3 3.9 6.0 0.9076 
0.404 
1506 
10 55.5 
11.4 
1.12 
5.43 
3.1 4.2 4.9 0.9074 
0.420 
1396 
__________________________________________________________________________ 
.sup.(a) Calculated activity is based on polymer recovered from the 
reactor but does not include propylene soluble polymer. It is in terms of 
kilograms polypropylene per g solid catalyst per hour. 
.sup.(b) Solubles test described herein. 
.sup.(c) ASTM D 1238, condition L 
.sup.(d) ASTM D 1505 
.sup.(e) ASTM D 790 
The TiCl.sub.4 -SiCl.sub.4 mixture was used in Example II to activate a 
portion of the precursor A compositions whereas in Example I, the 
corresponding precursor A compositions were activated with the TiCl.sub.4 
-HSiCl.sub.3 -SiCl.sub.4 mixture. 
The polymerization results in Table 2B indicate that catalyst activity 
declines somewhat as the calcining temperature of the silica increases 
from 150.degree. to 800.degree. C. The results shown in Table 1B are just 
the reverse. The soluble levels, flexural modulus results, molded density 
results and melt :low values are approximately the same suggesting that 
similar polymers are made with each activated catalyst regardless of the 
activating halide mixture employed. However, the bulk density results, 
compared with those in Table 1B, suggest that polymers made with catalyst 
activated with the 2-component halide mixture may have slightly lower bulk 
densities. The nascent polymer was in the form of granules containing 
crystal-like particles obtained with catalyst 7 to mostly crystal-like 
particles obtained with catalyst 10. Generally, as the amount of 
crystal-like particles increased, the bulk density of the polymer also 
increased. 
EXAMPLE III 
A series of 5 catalyst precursors and comparison catalysts therefrom was 
produced as described in Example I. In this series, the precursor 
compositions were formed in the presence of alumina, or a modified silica, 
or a modified alumina-silica. 
Catalyst 11 was prepared in the presence of grade 952 silica, modified as 
follows: 10 mL of the silica was fluidized in nitrogen at 800.degree. C. 
and treated over about 30 minutes by slowly injecting 4.0 mL of toluene 
into the fluidizing gas. Heating in nitrogen at 800.degree. C. was 
continued for 11/2 hours. As before, the product, which was black in color 
due to carbon formed from the toluene, was cooled and stored under 
nitrogen. 
Catalyst 12 was prepared in the presence of grade 952 silica, modified by 
pretreatment with methanol at 300.degree. C. In this instance, 100 mL of 
the silica was fluidized in dry air at 300.degree. C., flushed with 
nitrogen and treated by slow injection of 5.0 mL of methanol over about 30 
minutes. Heating was continued another 30 minutes in nitrogen and the 
support was cooled and recovered in the presence of nitrogen. A volume 
ratio of silica:methanol of 20:1 was used. 
Catalyst 13 was prepared in the presence of grade 952 silica modified by 
pretreatment with carbon monoxide at 900.degree. C. A 100 mL sample of the 
silica was fluidized in dry air at 900.degree. C. for about 30 minutes, 
then flushed with nitrogen, then fluidized at 900.degree. C. for 1 hour 
with carbon monoxide The carbon monoxide was replaced with N.sub.2 and the 
support was cooled and stored in its presence. 
Catalyst 14 was prepared in the presence of Davison Chemical Co. grade SRS 
11 (93.4 wt. Al.sub.2 O.sub.3 and 6.6 wt. % SiO.sub.2) modified by 
phosphating. A 30 g sample of the support was slurried in 1 liter of water 
containing 3.8 mL of 85% H.sub.3 PO.sub.4 for about 15 hours. The product 
was washed once with water, once with isopropanol, dried in a vacuum oven 
at m 80.degree. C. and then fluidized in dry air at 600.degree. C. for 3 
hours. The air was replaced with N.sub.2 and the product was cooled and 
stored under N.sub.2 as before. The calculated atom ratio of P/AI was 
about 0.1:1. 
Catalyst 15 was prepared in the presence of Davison Chemical Co. grade SRA 
alumina spheres, previously heated under fluidizing conditions in dry air 
for 3 hours at 200.degree. C. The air was replaced with N.sub.2 and the 
support was cooled and stored in its presence. The weights of catalyst 
precursor A, catalyst produced therefrom and calculated quantities as 
noted before are presented in Table 3A. 
TABLE 3A 
__________________________________________________________________________ 
Isolated Catalyst.sup.(a) 
Solid Material Precursor Wt. Solid.sup.(b) 
Calc. Wt. %.sup.(c) 
No. 
Wt. g 
Type Wt. g Wt. g 
Calc., g 
Support 
Catalyst 
__________________________________________________________________________ 
11 16.05 
modified SiO.sub.2 
24.7 9.3 
5.5 59.1 40.9 
12 20.0 
modified SiO.sub.2 
29.9 18.5 
13.4 72.4 27.6 
13 20.0 
modified SiO.sub.2 
29.0 17.4 
13.8 79.3 20.7 
14 16.1 
modified Al.sub.2 O.sub.3 --SiO.sub.2 
25.1 19.6 
12.8 65.3 34.7 
15 17.2 
Al.sub.2 O.sub.3 
26.7 18.8 
12.9 68.6 31.4 
__________________________________________________________________________ 
.sup.(a) Catalyst prepared from 20 g (and for run No. 11 only, 10 g) of 
corresponding precursor and activated with the previously described 
TiCl.sub.4 --HSiCl.sub.3 --SiCl.sub.4 mixture. 
.sup.(b) See footnote (c) in Table 1A. 
.sup.(c) See footnote (d) in Table 1A. 
Catalyst 12-5 were activated by contact of 20 g of precursor with 20-30 mL 
of the 3-component halide mixture at 100.degree. C. as described in 
Example I. Catalyst 11 was activated hy contact of 10 g of its precursor 
with about 10 mL of the 3-component halide mixture at 100.degree. C. for 1 
hour. 
A portion of each catalyst in Table 3A was tested in propylene 
polymerization under the conditions previously described. The results are 
presented in Table 3B. 
TABLE 3B 
__________________________________________________________________________ 
Propylene Polymerization 
Calc. Activity 
Weight, mg kg/g/hr.sup.(a) Melt 
Cat. 
Total 
Active 
Total 
Active 
Wt. % Solubles.sup.(b) 
Flow.sup.(c) 
Density.sup.(d), g/cc 
Mod..sup.(e) 
No. 
Cat. 
Cat. 
Cat. 
Cat. 
Propylene 
Xylene 
g/10 min. 
Molded 
Bulk 
MPa 
__________________________________________________________________________ 
11 20.4 
8.34 
2.06 
5.04 
3.3 3.5 7.9 0.9069 
0.317 
1520 
12 59.71 
16.5 
1.74 
6.30 
2.9 4.4 6.1 0.9038 
0.332 
1208 
13 56.6 
11.7 
1.08 
5.25 
2.9 6.8 7.1 0.9062 
0.261 
1374 
14 56.2 
19.5 
1.60 
4.61 
3.3 7.5 6.9 0.9040 
.sup.(f) 
1214 
15 72.3 
22.7 
0.844 
2.69 
3.8 5.5 8.2 0.9060 
0.195 
1237 
__________________________________________________________________________ 
.sup.(a) Calculated activity is based on polymer recovered from the 
reactor but does not include propylene soluble polymer. It is in terms of 
kilograms polypropylene per g solid catalyst per hour. 
.sup.(b) Solubles test described herein. 
.sup.(c) ASTM D 1238, condition L 
.sup.(d) ASTM D 1505 
.sup.(e) ASTM D 790 
.sup.(f) A dash signified no determination was made. 
The results in Table 3B show that active propylene polymerization catalysts 
are made containing the alumina employed in catalyst 15, the phosphated 
alumina-silica used in catalyst 14 and the modified silica employed in 
catalysts 11-13. However, none of the catalysts produced crystal-like 
polymer particles as did invention catalysts 1-10. Catalyst 11, made with 
silica containing carbon, produced a light, gray-colored fluff having a 
bulk density of about 0.32 g/cc. Catalyst 12 made with methanol-treated 
silica produced polymer granules having a bulk density of about 0.33 and a 
relatively low flexural modulus value of 1208 MPa, the lowest value of the 
polypropylene samples made in the Examples. Catalyst 13, made with carbon 
monoxide-treated silica, produced polymer granules having a bulk density 
of only about 0.26 g/cc and an increased xylene-soluble level of 6.8 
weight percent. Catalyst 14, made with phosphated alumina-silica, produced 
relatively large but light solid spheres (bulk density not determined) and 
a relatively high xylene-soluble level of 7.5 weight percent, the highest 
value of any of the polypropylene samples made in the Examples. Catalyst 
15, made with alumina calcined at 200.degree. C., produced a light fluffy 
polymer having a bulk density of only about 0.2 g/cc, the lightest bulk 
density polypropylene produced in the Examples. 
EXAMPLE IV 
A series of 4 catalyst precursors and comparison catalysts therefrom was 
produced in the manner described in Example III except that 0.01 mole of 
4-phenylphenol was substituted for the phenol. 
Catalyst 16 was prepared in the presence oi grade 952 silica pretreated 
with methanol in the manner employed in catalyst 12 except that a volume 
ratio of silica:methanol of 10:1 was used. 
Catalyst 17 was prepared in the presence of grade 952 silica modified by 
pretreatment with CCl.sub.4 at 600.degree. C. in nitrogen. A 100 mL sample 
of the silica was fluidized in dry air at 600.degree. C. for 1 hour. The 
air was replaced with nitrogen, then the nitrogen was bubbled through 
CCl.sub.4 and passed into the fluidized bed for 1 hour at 600.degree. C. 
The bed was flushed with nitrogen alone and the support was cooled and 
stored in its presence. 
Catalyst 18 was prepared in the presence of grade SRS Il as in the manner 
described for catalyst 14 except that the phosphating was accomplished 
with 4.1 mL of H.sub.3 PO.sub.4 rather than 3.8 mL. The calculated atom 
ratio of P/Al remains about 0.1:1, however. 
Catalyst 19 was prepared in the presence of grade SRA alumina beads, 
calcined in dry air for 3 hours at 200.degree. C. as described for 
Catalyst 15. 
The weights of catalyst precursor A made, catalyst produced therefrom and 
calculated quantities as noted before are set forth in Table 4A. 
TABLE 4A 
__________________________________________________________________________ 
Isolated Catalyst.sup.(a) 
Catalyst Solid Precursor 
Total 
Wt. Solid.sup.(b) 
Calc. Wt. %.sup.(c) 
No. 
Wt. g 
Type Wt. g Wt. g 
Calc., g 
Solid 
Active Catalyst 
__________________________________________________________________________ 
16 20 Modified SiO.sub.2 
27.6 18.9 
14.7 77.8 
22.2 
17 20 Modified SiO.sub.2 
26.6 18.6 
15.0 80.6 
19.4 
18 20 Modified Al.sub.2 O.sub.3 --SiO.sub.2 
30.8 20.3 
13.0 64.0 
36.0 
19 20 Al.sub.2 O.sub.3 
29.2 19.2 
13.7 71.4 
28.6 
__________________________________________________________________________ 
.sup.(a) Produced with 20 g of the corresponding precursor and activated 
with 20-30 mL of the 3component halide mixture at 100.degree. C. as 
described in Example I. 
.sup.(b) See footnote (c) in Table 1A. 
.sup.(c) See footnote (d) in Table 1A. 
A portion of each catalyst in Table 4A was tested in propylene 
polymerization under the conditions previously described. The results are 
given in Table 4B. 
TABLE 4B 
__________________________________________________________________________ 
Propylene Polymerization 
Calc. Activity 
Weight, mg kg/g/hr.sup.(a) 
Calc. Calc. Melt Flex 
Cat. 
Supported 
Active 
Total 
Active 
Wt. % Solubles.sup.(b) 
Flow.sup.(c) 
Density.sup.(d), g/cc 
Mod..sup.(e) 
No. 
Total Cat. 
Cat. 
Cat. 
Propylene 
Xylene 
g/10 min. 
Molded 
Bulk 
MPa 
__________________________________________________________________________ 
16 117.4 26.1 
0.702 
3.16 
2.4 3.2 10 0.9063 
.sup.(f) 
1368 
17 55.0 10.7 
1.91 
9.81 
1.7 3.6 3.9 0.9077 
0.205 
1426 
18 39.5 14.2 
0.603 
1.68 
6.1 3.4 -- -- -- -- 
19 60.6 17.3 
0.500 
1.75 
5.2 6.5 6.3 0.9065 
-- 1320 
__________________________________________________________________________ 
.sup.(a) Calculated activity is based on polymer recovered from the 
reactor but does not include propylene soluble polymer. It is in terms of 
kilograms polypropylene per g solid catalyst per hour. 
.sup.(b) Solubles test described herein. 
.sup.(c) ASTM D 1238, condition L 
.sup.(d) ASTM D 1505 
.sup.(e) ASTM D 790 
.sup.(f) A dash signifies no determination was made. 
Catalysts 16, 18, 19 of Table 4B differ primarily from the corresponding 
catalysts 12, 14, 15 of Table 3B in the type of phenol employed in their 
production. Table 3B catalysts were made with 0.02 mole phenol whereas 
those in Table 4B were made with 0.02 mole 4-phenylphenol. The polymer 
activity results obtained with each set of catalysts suggest that the 
catalysts of Table 4B are less active than the corresponding set of Table 
3B catalysts since lower activity values are listed, e.g. 0.72 kg/g solid 
cat.hr for catalysts 16 of Table 4B vs. 1.79 kg/g solid cat.hr for 
catalyst 12 of Table 3B. However, the catalysts of Table 4B are generally 
more selective than those of Table 3B, except for catalyst 19, since less 
xylene-soluble polymer is produced, e.g. 3.2 wt. % for catalysts 16 vs. 
4.4. wt. % for catalyst 12. Generally, both sets of catalysts produced 
similar nascent polymer. 
Catalyst 17 of Table 4B, prepared in the presence of chlorinated silica, 
was the most active and selective catalysts of this series. The support 
catalysts produced about 1.9 kg polypropylene per g catalyst per hour, 
only 1.7 wt. % propylene-soluble polymer and 3.6 wt. % xylene-soluble 
polymer. The calculated active portion of the supported catalyst, e.g. 
minus the support, has a calculated activity of about 9.8 kg polypropylene 
per g catalyst per hour. However, the catalyst produced fluffy nascent 
polymer having a bulk density of about 0.2 g/cc. 
EXAMPLE V 
A variation in catalyst preparation was employed in the production of this 
catalysts designated catalyst 20. A mixture of 0.02 mole of Ti(OBu).sub.4, 
0.02 mole of 4-PP, 0.04 mole of H.sub.2 O and 300 mL of xylene was stirred 
for 1/2 hour, then 0.04 mole of the "anhydrous" MgCl.sub.2 described in 
Example I was added. The stirred mixture was heated for 0.75 hour at 
100.degree. C., then 0.01 mole of ethyl benzoate was added and the 
resulting mixture was heated for 1/4 hour at 100.degree. C. Then 26.0 g of 
grade 952 silica, previously calcined in air for 3 hours at 800.degree. 
C., was added. The reaction mixture, after stirring 10 minutes, was 
diluted up to 500 mL with xylene, reacted with EASC and recovered as 
before to yield 35.9 g of a red-brown solid as precursor A. A 20 g sample 
of the precursor was activated with the 3-component halide mixture at 
100.degree. C. then washed and dried, all as before, to yield 20.95 g of a 
purple solid as the catalyst. 
The isolated supported dry catalyst was calculated to contain 14.5 g of the 
support corresponding to 69.1 weight percent silica and 30.9 weight 
percent active catalyst. 
A 56.7 mg portion of the supported catalysts, corresponding to a calculated 
17.5 mg of active catalyst, was employed in propylene polymerization under 
the conditions detailed before. Calculated activities of 0.61 kg 
polypropylene per g catalyst per hour for the supported catalyst 
corresponding to 5.22 kg polypropylene per g catalyst per hour for the 
active catalyst alone were obtained in the run. It was ascertained that 
2.2 weight percent propylene solubles and 3.0 weight percent xylene 
solubles were made. 
The polymer was found to have a melt flow of 8.7 g/10 min., a molded 
density of 0.9074 g/cc and a flexural modulus of 1548 MPa. These values 
are all in the range previously shown. The polymer, however, was in the 
form of a light, granular fluff, exhibiting a very low bulk density of 
14.7 lbs./ft..sup.3 (0.156 g/cc). 
EXAMPLE VI 
A series of 3 catalyst precursors containing crystalline silicas 
(silicalites) and 5 comparison catalysts containing various zeolite type 
materials (obtained from Linde Chemical Co.) were produced in the manner 
described in Example III, except that 5 gram samples were activated in the 
three component halide mixture. 
Invention catalyst 21 was prepared in the presence of a commercially 
obtained silicalite. Comparison catalyst 22 was prepared in the presence 
of an (NH.sub.4) Y zeolite; comparison catalyst 23 was prepared in the 
presence of a mordenite; comparison catalyst 24 was prepared in the 
presence of a (K) L zeolite; comparison catalyst 25 was prepared in the 
presence of an erionite; invention catalyst 26 was prepared in the 
presence of a silicalite (also obtained from Linde); and comparison 
catalyst 28 was prepared in the presence of a zeolite designated 
ELZ-.OMEGA.-6 (from Linde). 
Invention catalysts 27 was prepared in the presence of a dealuminated 
faujasite. A sample of faujasite was heated at 840.degree. C. in air for 4 
hours, then was slurried in a 3 molar solution of HCl, then was dried at 
140.degree. C. in order to prepare the dealuminated fajuasite. 
The weight of catalysts precursor made, catalyst produced therefrom and 
calculated quantities as noted before are set forth in Table 5A. 
TABLE 5A 
__________________________________________________________________________ 
Isolated Catalyst 
Catalyst Solid Precursor 
Total 
Wt. Solid.sup.(a) 
Calc. Wt. %.sup.(b) 
No Wt. % 
Type Wt. g Wt. g 
Calc., g 
Solid 
Active Catalyst 
__________________________________________________________________________ 
21 20.0 
Silicalite 
25.6 4.6 3.91 84.9 
15.1 
22 20 (NH.sub.4).sub.4 Zeolite 
22.4 6.2 4.47 72.1 
27.9 
23 20 Mordenite 
25.6 5.1 3.91 76.6 
23.4 
24 20 (K) L Zeolite 
29.7 5.4 3.37 62.5 
37.5 
25 20 Erionite 
26.4 5.3 3.79 63.8 
36.2 
26 20 Silicalite 
27.8 4.1 3.60 88.5 
11.5 
27 20 Dealuminated 
29.4 4.3 3.40 78.9 
21.1 
28 20 ELZ-.OMEGA.-6 
29.4 4.5 3.40 75.6 
24.4 
__________________________________________________________________________ 
.sup.(a) See footnote (c) in Table 1A. 
.sup.(b) See footnote (d) in Table 1A. 
A portion of each catalyst in Table 5A was tested in propylene 
polymerization under the conditions previously described in Example I. The 
results are given in Table 5B. 
TABLE 5B 
__________________________________________________________________________ 
Propylene Polymerization 
Calc. Activity, 
Weight, mg kg/g/hr.sup.(a) 
Calc. Calc. Melt Flex 
Cat. 
Supported 
Active 
Total 
Active 
Wt. % Solubles.sup.(b) 
Flow.sup.(c) 
Density.sup.(d), g/cc 
Mod..sup.(e) 
No. 
Total Cat. 
Cat. 
Cat. 
Propylene 
Xylene 
g/10 min. 
Molded 
Bulk 
MPa 
__________________________________________________________________________ 
21 32.4 4.89 
0.861 
5.69 
3.29 3.29 
--.sup.(f) 
-- -- -- 
22 40.6 11.33 
0.079 
0.237 
15.6 -- -- -- -- -- 
23 61.9 14.48 
0.273 
1.12 
4.08 -- -- -- -- -- 
24 89.7 36.64 
0.011 
0.018 
39.0 -- -- -- -- -- 
25 116.3 42.10 
.186 
0.494 
3.75 -- -- -- -- 1487 
26 89.5 10.29 
2.12 
18.3 
.29 4.71 
3.3 -- -- 1528 
27 83.9 17.70 
.579 
2.67 
2.59 4.55 
6.8 -- -- -- 
28 29.0 7.08 
.234 
0.873 
9.12 -- -- -- -- -- 
__________________________________________________________________________ 
.sup.(a) Calculated activity is based on polymer recovered from the 
reactor but does not include propylene soluble polymer. It is in terms of 
kilograms polypropylene per g solid catalyst per hour. 
.sup.(b) Solubles test described herein. 
.sup.(c) ASTM D 1238, condition L 
.sup.(d) ASTM D 1505 
.sup.(e) ASTM D 790 
.sup.(f) A dash signifies no determination was made. 
The polymer results in Table 5B indicate that catalyst activity was higher 
for the silicalites, catalysts 21 and 26. The catalyst prepared from the 
dealuminated faujasite (catalyst 27) exhibited slightly lower activity. 
The remaining zeolite supported catalysts exhibited poor activity overall. 
The amount of solubles was also lower for the catalysts prepared with on 
the predominantly silica-containing materials. 
The flexural modulus for the polymers produced with the silica containing 
catalysts compares well with the previous invention runs, see Table 1B. 
As can be seen from FIG. 4, the polymer produced with the silicalite 
supported catalyst appears crystal-like, although the crystals are not as 
well defined as those of the polymer in FIG. 2 which was produced with a 
silica containing catalyst. 
EXAMPLE VII 
Propylene polymerization runs were conducted with individual portions of 
previous catalyst precursors, catalyst 5 precursor, catalyst 21 precursor, 
and catalyst 26 precursor, all using a cocatalyst mixture of 2 moles TEA, 
2 moles DEAC and 1 mole of 2,2,6,6-tetramethylpiperadine (TMP, obtained 
from Fluka AG of Switzerland. Polymerization was conducted in the 2 L 
reactor containing 1.25 lbs. of isobutane at a total reactor pressure of 
565 psia. The pressure was maintained during a run from the addition of 
ethylene, as needed, from a pressurized reservoir. Hydrogen was employed 
in all but one run for melt index control. 
The reactor temperatures employed, actual run times used, hydrogen pressure 
employed, productivity calculated for the actual run time and normalized 
to 60 minutes, when necessary, are given in Table 6. Also included is 
calculated productivity per 60 minutes based on active catalyst contained 
in the supported catalyst. 
TABLE 6 
__________________________________________________________________________ 
Calc. Activity 
Kg/g/hr. 
Run 
Cat. Weight, mg 
Calc. Reactor Calc. Wt. % Solubles 
No. 
No. 
Total Cat. 
Active Cat. 
Temp .degree.C. 
H.sub.2 Psi 
Total Cat. 
Active Cat. 
Propylene 
Xylene 
__________________________________________________________________________ 
1 5 6.2 1.48 70.degree. C. 
40 .970 4.06 -- -- 
2 5 133.3 31.73 80.degree. C. 
40 1.88 7.90 -- -- 
3 5 183.4 43.65 90.degree. C. 
40 .867 3.64 -- -- 
4 5 103.8 24.70 70.degree. C. 
40 2.02 8.49 -- -- 
5 21 34.9 5.27 70.degree. C. 
40 2.78 18.4 0.75 8.98 
6 26 30.5 3.51 70.degree. C. 
NO .138 1.20 11.4 -- 
7 27 85.0 17.95 70.degree. C. 
25 1.21 5.73 1.12 7.58 
__________________________________________________________________________ 
The activity results shown in Table 6 range from 1.2 to 18.4 kg/g/hr. when 
TMP was employed with TEA and DEAC as the cocatalyst. Note that Run 6 gave 
poor results when compared to the other runs, all of which use the 
invention catalyst. One possible explanation for this poor activity is the 
lack of hydrogen in the reaction. 
The use of TMP in the cocatalyst appears to enhance the activity of the 
catalyst under certain conditions, compare Run 4 with catalyst 5, Table 1B 
results. 
EXAMPLE VIII 
Ethylene polymerization runs were conducted with individual portions of 
catalyst 1 precursor, designated 1 P, catalyst 1 and catalyst 5, all 
described in Example 1, and 1 mmole of TEA as cocatalyst. Polymerization 
was conducted in the 2 L reactor containing 1.25 lbs. of isobutane at a 
total reactor pressure of 565 psia. The pressure was maintained during a 
run from the addition of ethylene, as needed, from a pressurized 
reservoir. Hydrogen was employed in several runs for melt index control. 
The reactor temperatures employed, actual run times used, hydrogen pressure 
employed, activity calculated for the actual run time and normalized to 60 
minutes, when necessary, are given in Table 7. Also included is calculated 
activity per 60 minutes based on active catalyst contained in the 
supported catalyst. 
TABLE 7 
__________________________________________________________________________ 
Ethylene Polymerization 
Activities, kg/g Solid Cat./hr. 
Calc. 60 Min., 
Run 
Catalyst 
Reactor 
H.sub.2 
Run Time 
Actual Norm. 
Calc. Active 
No. 
No. 
Wt. mg. 
Temp .degree.C. 
Psi 
Min. Per Run Time 
60 Min. 
Cat. 
__________________________________________________________________________ 
8 1P 
156.0 
90 0 45 1.60 2.13 7.07 
9 1 98.0 
90 50 17 1.79 6.30 22.1 
10 5 74.3 
90 0 30 3.90 7.81 32.8 
11 5 78.9 
85 50 20 2.46 7.38 31.0 
12 5 118.3 
75 150 
60 0.845 -- 3.55 
__________________________________________________________________________ 
The activity results obtained ranging from about 0.9 to about 7.8 kg 
polyethylene per g active catalyst per 60 minutes indicate that the 
catalysts are active for ethylene polymerization at a variety of reactor 
temperatures and in the absence and presence of hydrogen as a reactor 
adjuvant. Even catalyst lP, the precursor A composition itself is fairly 
active as an ethylene polymerization catalyst. 
The polymer made with catalyst lP in run 1 was in the form of granular 
fluff. Its melt index was not determined. 
The polymer made with catalyst I in run 2 was in the form of granules and 
porous crystal-like particles. It has a melt index (MI) of 3.0 and high 
load melt index (HLMI; ASTM D 1238-65T) of 108. The HLMI/MI ratio of 36 is 
typical of ethylene polymers made with Ti-based catalysts. 
The polymer made with catalyst 5 in run 4 was in the form of granules and 
large porous crystal-like particles. This polymer is depicted in the 
scanning electron microscope (SEM) photograph in FIG. 2B. Its melt index 
properties were not determined. 
The polymer made with catalyst 5 in run 4 was in the form of rough spheres 
admixed with a few crystal-like particles. It had a MI of 0.43 and HLMI of 
12.6. The HLMI/MI ratio of 29 is also typical of Ti-based catalyst. 
The polymer made with catalyst 5 in run 5 was in the form of granules and 
small, porous crystal-like particles. It had a melt index of 3.2. 
The examples have been provided merely to illustrate the practice of our 
invention and should not be read so as to limit the scope of our invention 
or the appended claims in any way. Reasonable variations and 
modifications, not departing from the essence and spirit of our invention, 
are contemplated to be within the scope of patent protection desired and 
sought.