Polymerization catalysts

Polymerization catalyst preparation comprising milling magnesium metal, an organic halide and titanium tetrahalide in the presence of a triaryl phosphite and an aluminum trihalide but in the absence of a complexing diluent. The titanium catalyst component is activated with an organoaluminum activator producing a catalyst for olefin polymerization. In one embodiment, the titanium catalyst component is milled in the presence of magnesium oxide. In another embodiment, the milled titanium catalyst component is subjected to heat treatment.

This invention relates to polymerization, polymerization catalysts, and to 
the preparation of polymerization catalysts. In accordance with one 
aspect, this invention relates to the preparation of improved 
polymerization catalysts comprising magnesium alkyl reduced titanium 
tetrahalide wherein at least a portion of the milling of the basic 
titanium catalyst is carried out in the presence of a triaryl phosphite 
and an aluminum trihalide. In accordance with another aspect, solventless 
magnesium alkyl reduced titanium tetrahalide catalysts are prepared by 
milling in the presence of magnesium oxide and at least one of a triaryl 
phosphite and an aluminum trihalide. In accordance with a further aspect, 
milled titanium-containing catalysts are subjected to heat treatment 
following milling. In accordance with another aspect, catalysts are 
prepared by milling magnesium metal, an organic halide, and a titanium 
tetrahalide, with or without magnesium oxide present during milling, 
followed by subsequent milling in the presence of a triaryl phosphite and 
an aluminum trihalide prior to activation with an organoaluminum 
activator. In a further aspect, the above catalysts are useful for the 
polymerization of olefins, especially propylene. 
It is known to reduce titanium tetrahalide with a true Grignard reagent, 
that is, a compound or mixture of compounds produced by reacting magnesium 
and an organic halide in the presence of an ether. Such a compound is 
conventionally expressed as RMgX. It is also known to produce what is 
termed in the art a "solventless" Grignard, which is produced by reacting 
magnesium metal with an organic halide in the presence of a solvent which 
is designated as a non-solvating solvent (i.e., an inert or non-complexing 
diluent) such as a hydrocarbon as distinguished from an ether. 
True Grignard reagents as a practical matter present serious problems as 
reducing agents in the production of high activity catalysts in view of 
the difficulty in removing the large amounts of remaining ether which can 
reduce the effectiveness of such Grignard reagents used in preparing 
olefin polymerization catalyst systems. 
In certain olefin polymerizations, it is necessary to tailor the catalyst 
to give the type of polymer desired. Particularly in the polymerization of 
propylene, it is desirable to cause the polymerization to take place in 
such a manner as to give a stereospecific polymer. 
Accordingly, an object of this invention is to provide a process for the 
production of an improved catalyst component. 
A further object of this invention is to provide a polymerization catalyst 
component exhibiting significant improvement in catalyst activity and/or 
decreased soluble polymer formation. 
Another object of this invention is to provide a stereospecific catalyst 
system. 
A further object of this invention is to provide simplified methods of 
producing a titanium catalyst component for olefin polymerization. 
A further object of this invention is to provide for the stereospecific 
polymerization of propylene. 
Other objects, aspects, and the several advantages of this invention will 
become apparent to those skilled in the art upon a study of the 
specification and appended claims. 
In accordance with the invention, a titanium catalyst component is prepared 
by milling magnesium metal, an organic halide and a titanium tetrahalide 
in the presence of a triaryl phosphite and an aluminum trihalide. 
In accordance with one embodiment of the invention, a titanium catalyst 
component is prepared by intensive milling of magnesium metal, an organic 
halide and a titanium tetrahalide under conditions to obtain a milled 
titanium catalyst component which is then further milled in the presence 
of a triaryl phosphite and an aluminum trihalide. 
In accordance with a further embodiment of the invention, a titanium 
catalyst component is prepared by first milling titanium tetrahalide with 
magnesium metal, an organic halide and magnesium oxide in the absence of a 
complexing diluent and then additional milling in the presence of a 
triaryl phosphite and an aluminum trihalide. 
In accordance with an additional embodiment, the milled products described 
above can be subjected to heat treatment to further reduce the formation 
of soluble polymers during polymerization. 
The catalysts prepared according to this invention represent an improvement 
of the solventless magnesium alkyl reduced titanium tetrachloride (SMART) 
catalysts disclosed in Ser. No. 958,870, filed Nov. 8, 1978. A SMART 
catalyst can be prepared, for example, by ball milling about equal 
quantities (molar) of magnesium powder, n-pentyl chloride, and titanium 
tetrachloride for sufficient time, e.g., 3 hours, to produce a catalyst 
active for propylene polymerization when used with an organoaluminum 
compound as cocatalyst. 
The improvement of the basic SMART catalyst, according to the invention, is 
accomplished by milling it in the presence of at least one of magnesium 
oxide, a triaryl phosphite, and an anhydrous trihalide of aluminum as 
adjuvants for the catalyst. The SMART catalyst can be milled first, with 
or without magnesium oxide being present, and then further milled in the 
presence of the other adjuvants or all of the components can be milled 
simultaneously. The milled catalyst component can be heat treated prior to 
combining with an organoaluminum activator. The resulting product is 
formed to exhibit a significant improvement in catalyst activity and/or 
decreased soluble polymer formation in propylene polymerization compared 
to the results obtained with the basic (unmodified) SMART catalyst. 
The triaryl phosphites contemplated can be expressed as (RO).sub.3 P where 
R is aryl, alkyl-substituted aryl, cycloalkyl-substituted aryl and 
aryl-substituted aryl wherein the basic unsubstituted aryl has from 6 to 
14 carbon atoms and the alkyl, cycloalkyl and aryl substituents have 1 to 
about 10 carbon atoms. 
Exemplary triaryl phosphite compounds that can be used include triphenyl 
phosphite, tri-1-naphthyl phosphite, tri-9-anthryl phosphite, 
tri-4-phenanthryl phosphite, tri-o-tolyl phosphite, tri-p-cumenyl 
phosphite, tris(4-pentyl-1-naphthyl) phosphite, tris(3-heptyl-1-anthryl) 
phosphite, tris(5-decyl-2-phenanthryl) phosphite, tris(3-cyclobutylphenyl) 
phosphite, tris(6-cycloheptyl-2-naphthyl) phosphite, 
tris(10-cyclodecyl-9-anthryl) phosphite, tris(3-cyclopentylphenyl) 
phosphite, tris[4-(2-naphthyl)phenyl] phosphite, tris(7-phenyl-1-naphthyl) 
phosphite, tris(6-phenyl-2-anthryl) phosphite, 
tris(7-phenyl-1-phenanthryl) phosphite and the like. A presently preferred 
compound because of ready availability and relatively low cost is 
triphenyl phosphite. 
The anhydrous aluminum trihalide can be expressed as AlX.sub.3 where X is 
bromide, chloride, fluoride, iodide and mixtures. Presently preferred 
because of availability and relative low cost is aluminum trichloride. 
The organic halide can be a saturated or unsaturated hydrocarbyl halide 
having the formula R'X in which X represents a halogen, preferably 
chlorine or bromine, and R' is selected from an alkynyl, alkenyl, alkyl, 
aryl, cycloalkenyl or cycloalkyl radical and combinations thereof such as 
arylalkyl, and the like containing from 1 to about 12 carbon atoms per 
molecule. The organic halide can also be a polyhalogenated hydrocarbyl 
halide of the formula R"X.sub.2 where X is a halogen atom as before and R" 
is a saturated divalent aliphatic hydrocarbyl radical, containing from 2 
to about 10 carbon atoms per molecule. Exemplary compounds include 
1,2-dibromoethane, 1,4-dichlorobutane, cyclohexyl chloride, bromobenzene, 
1,10-dibromodecane and the like. An alkyl halide is presently preferred, 
however, containing from 1 to about 12 carbon atoms. Representative alkyl 
halides include methyl chloride, n-butyl bromide, n-pentyl chloride, 
n-dodecyl chloride and the like. A primary alkyl halide such as n-pentyl 
chloride is most preferred. 
The magnesium is in the form of the free metal, preferably in the form of a 
powder. 
The magnesium metal and organic halide are preferably reacted in 
stoichiometric amounts, although this can vary from 0.25:1 to 1:0.25 
preferably from 0.75:1 to 1:1 gram atoms Mg:moles of organic halide. 
The titanium tetrahalide is titanium tetrachloride, titanium tetrabromide, 
or titanium tetraiodide, preferably titanium tetrachloride. 
The weight ratio of SMART catalyst to magnesium oxide when used can range 
from about 1.5 to 1 to 10 to 1. Based on the calculated amount of 
TiCl.sub.3 present in the SMART catalyst the calculated mole ratio of 
TiCl.sub.3 :MgO can range from about 0.2:1 to 1.3:1. 
The weight ratio of SMART catalyst to triaryl phosphite and to aluminum 
trihalide can range from about 2 to 1 to 200 to 1. Based on the calculated 
content of TiCl.sub.3 present in the SMART catalyst, the calculated mole 
ratio of TiCl.sub.3 :triaryl phosphite can range from about 4:1 to 100:1, 
and the calculated mole ratio of TiCl.sub.3 :AlX.sub.3 can range from 
about 1.5:1 to 40:1. 
The organoaluminum compound activator component of this invention consists 
of trialkylaluminum compounds of formula AlR"'.sub.3, dialkylaluminum 
compounds of formula R"'.sub.2 AlZ, alkyl aluminum compounds of the 
formula R"'AlZ.sub.2 and dialkylaluminum alkoxides of formula R"'.sub.2 
AlOR"' wherein each R"' may be the same or different and represents an 
alkyl group containing from 1 to about 12 carbon atoms per molecule. 
However, a trialkylaluminum compound is preferred, which can be admixed 
with one or more of the other activator compounds listed. Z represents 
either a hydrogen atom or a halogen atom, preferably chlorine or bromine. 
Preferably the R"'AlZ.sub.2 compounds are dichlorides or dibromides. 
Examples of suitable compounds include trimethylaluminum, 
triethylaluminum, tri-n-dodecylaluminum, dimethylethylaluminum, 
demethylaluminum bromide, diethylaluminum chloride, ethylaluminum 
dichloride, ethylaluminum dihydride, diisobutylaluminum bromide, 
di-n-dodecylaluminum chloride, ethyl-t-butylaluminum chloride, 
diisobutylaluminum hydride, dimethylaluminum butoxide, diethylaluminum 
ethoxide, di-n-dodecylaluminum n-propoxide, and ethylmethylaluminum 
ethoxide and mixtures thereof. Triethylaluminum is preferred. It is also 
within the scope of this invention to use an organoaluminum monohalide 
(previously described) in combination with additional magnesium reducing 
agent (previously described) as the activator component of the 
polymerization catalyst system. For ethylene polymerization, the 
organoaluminum activator preferably consists essentially of 
triethylaluminum. 
It is preferred to use one or more adjuvants which are polar organic 
compounds, i.e., electron donor compounds (Lewis bases) in addition to the 
magnesium reduced titanium catalyst component and activator in propylene 
polymerization. 
These may be precontacted with the activator or titanium tetrahalide or 
introduced at the same time the titanium tetrahalide is introduced into 
contact with the magnesium reducing agent or both. Preferably the 
activator is precontacted with an aromatic ester adjuvant as described in 
detail hereinbelow. 
Suitable compounds for this purpose are described in U.S. Pat. No. 
3,642,746 for the disclosure of which is hereby incorporated by reference. 
They include amides, amines, aldehydes, arsines, alcoholates, esters, 
ethers, ketones, nitriles, phosphines, phosphites, phosphoramides, 
stibines, sulfones and sulfoxides. Examplary compounds include 
triethylamine, acetamide, benzaldehyde, sodium ethoxide, ethyl acetate, 
diethyl ether, acetone, benzonitrile, triphenyl phosphine, triphenyl 
phosphite (TPP), hexamethyl phosphoric triamide, triethyl stibine, 
trioctyl arsine, dimethyl sulfone and dibutyl sulfoxide. 
Presently preferred adjuvants, when premixed with the organoaluminum 
compounds, are the lower alkyl esters (i.e., 1 to 4 carbon atoms per 
molecule) of benzoic acid which may be additionally substituted in the 
para position to the carboxyl group with a monovalent radical selected 
from the group consisting of --F, --Cl, --Br, --I, --OH, --OR"", --COCR"", 
--SH, --NH, --NR"".sub.2, --NHCOR"", --NO.sub.2, --CN, --CHO, --COOR"", 
--CONH.sub.2, --CONR.sub.2 "", --SO.sub.2 R"", and --CF.sub.3. The R"" 
group is a 1-4 carbon atom alkyl radical. Examples of suitable compounds 
include ethyl anisate (p-methoxybenzoate), ethyl benzoate, methyl 
benzoate, ethyl p-dimethylaminobenzoate, ethyl p-fluorobenzoate, isopropyl 
p-diethylaminobenzoate, butyl p-fluorobenzoate, n-propyl p-cyanobenzoate, 
ethyl p-trifluoromethylbenzoate, methyl p-hydroxybenzoate, methyl 
p-acetylbenzoate, methyl p-nitrobenzoate, ethyl p-mercaptobenzoate and 
mixtures thereof. Particularly preferred esters are ethyl anisate and 
ethyl benzoate. Triphenyl phosphite, triethylamine and dimethylaniline are 
preferred for mixing with the other components as they are contacted. As 
noted hereinabove another adjuvant such as ethyl anisate or ethyl benzoate 
may already be mixed with the organoaluminum compound. 
If one or more adjuvants are used with the titanium tetrahalide component, 
the molar ratio of titanium tetrahalide compound to adjuvant (or 
adjuvants) is generally in the range of about 1:1 to about 200:1. 
If one or more adjuvants are used with the organoaluminum compound or 
compounds in the activator component, the molar ratio of organoaluminum 
compound(s) component to adjuvant (or adjuvants) is generally in the range 
of about 1:1 to about 350:1. However, in no instance should the total 
adjuvant from all sources exceed a 1:1 mole ratio of adjuvant to aluminum. 
In propylene polymerization, it is preferred to employ about equal molar 
amounts of each type of organoaluminum compounds, e.g., triethyalaluminum 
and diethylaluminum chloride since good catalyst productivity is promoted. 
However, the mole ratios can vary from about 1:3 to 3:1. Generally, the 
total amount of organoaluminum compounds employed in a 1 liter reactor 
containing from about 0.06 to 0.2 g of catalyst calculated as TiCl.sub.3 
can range from about 4-12 mmoles and more preferably from about 8 to 10 
mmoles. The calculated mole ratio of total organoaluminum compounds to 
TiCl.sub.3 can range from about 25:1 to 200:1 and more preferably from 
about 35:1 to 165:1 since highest productivity is favored in this range. 
The calculated mole ratio of total organoaluminum compounds to ester, 
e.g., ethyl anisate, in the cocatalyst can range from about 2.4:1 to 
3.2:1, preferably 2.6:1 to 3.0:1, since good productivity coupled with 
good stereospecificity are found in these ranges. 
Generally, the mole ratio of triaryl phosphite to aluminum trihalide 
employed in the modified SMART catalysts is about 0.4:1. However, it can 
range from about 0.03:1 to about 6:1. 
The SMART catalyst and the adjuvants are intensively milled together for 
about 0.5 to 100 hours at ambient conditions by means of a ball mill, rod 
mill, vibrating mill, and the like. Cooling of the mill can be employed, 
if desired, to keep the temperature of milling material within a specified 
temperature range, e.g., 25.degree.-75.degree. C., if desired. An 
atmosphere, inert in the process such as nitrogen, argon, etc., can be 
employed in the milling vessel. 
It is within the scope of the invention to subject the milled titanium 
catalyst component to a suitable heat treatment to reduce the production 
of polymer solubles. The milled catalysts can be subjected to heat 
treatment at a temperature of about 50.degree. to 250.degree. C. under a 
pressure of about 0.5 psia to 5 psia (51-510 kPa) for a period of time 
ranging from about 10 minutes to about 5 hours. 
The catalysts of this invention are suitable for the polymerization of at 
least one aliphatic mono-1-olefin containing 2 to 8 carbon atoms per 
molecule. The catalysts are particularly suitable for the stereospecific 
polymerization of propylene. 
The conditions suitable for carrying out the polymerization reaction are 
similar to other related processes in which a catalyst system comprising 
reduced titanium is employed. The process is conveniently carried out in 
liquid phase in the presence or absence of an inert hydrocarbon diluent, 
e.g., n-heptane, n-pentane, isobutane, cyclohexane, etc., but it is not 
limited to liquid phase conditions. If no added diluent is used, the 
process can be carried out in liquid monomer which is preferred. 
The polymerization temperature employed depends on the monomer employed and 
the mode of reaction selected but generally falls within the range of 
60.degree.-212.degree. F. (15.5.degree.-100.degree. C.). In the liquid 
phase polymerization of propylene, for example, a temperature in the range 
of about 75.degree. to about 200.degree. F. (24.degree.-93.degree. C.) can 
be employed. Any convenient pressure is used. However, in liquid phase 
operation, sufficient pressure is employed to maintain the reactants in 
liquid phase within the reaction zone. 
Gram atom ratios of Ti/Mg used in the catalyst preparation are preferably 
from 0.5:1 to 5:1, more preferably 0.75:1 to 1.25:1. Ratios below 0.5:1 
are operable but give lower productivities. The actual ratio in the 
catalyst itself will be slightly lower than that used in its preparation. 
As is known in the art, control of the molecular weight of the polymer is 
readily achieved by the presence of small amounts of hydrogen during the 
polymerization. 
The polymers prepared with the catalysts of this invention are normally 
solid resinous materials which can be extruded, molded, etc., into useful 
articles including film, fibers, containers and the like.

EXAMPLE I 
PREATION OF BASIC SMART CATALYST A 
A 1 liter, spherical steel vessel containing 1400 g of 0.5 inch (1.3 cm) 
steel balls was charged, in order, with 12 g (0.5 mole) of 50 mesh (U.S. 
Sieve Series) magnesium powder, 61 ml (0.5 mole, 53.3 g) of n-pentyl 
chloride and 55 ml (0.5 mole, 94.8 g) of titanium tetrachloride. The 
vessel was placed on a Vibratom mill and a 3.1 hour milling time at 
ambient conditions was employed. The vessel was transferred to a dry box 
where its contents were washed with 4-800 ml portions of dry n-hexane, the 
milled product was washed into a fritted funnel with additional dry 
n-hexane and the material was washed with 3-800 ml portions of dry 
n-hexane. The washed material was then vacuum dried about 6 hours and 
sieved through a 50 mesh screen yielding 63 g of a purple colored solid as 
the basic SMART catalyst. 
CATALYST B (CONTROL) 
A 10 g sample of the base SMART Catalyst A was milled for 1.3 hours in a 
250 ml steel vessel with 300 g of 1/4 inch (0.64 cm) steel balls on the 
Vibratom. Cooling tap water (about 70.degree. F., 21.degree. C.) was run 
over the vessel during the milling. The milled sample was recovered by 
passage through a 100 mesh screen. 
CATALYST C (INVENTION) 
A 10 g sample of base SMART Catalyst A, already milled, 1.6 g AlCl.sub.3 
(12 mmoles) and 1.6 g TPP (5.2 mmoles) was milled 2.9 hours on the 
Vibratom in the manner described under Catalyst B. The deep purple product 
was recovered from the milling vessel through a 100 mesh screen. The 
weight ratio of base SMARt catalyst to each adjuvant is about 6:1. Since 
the base SMART catalyst is calculated to contain about 50 wt. % 
TiCl.sub.3, a 10 g portion of it contains about 5 g (32.4 mmoles) 
TiCl.sub.3. In Catalyst C, therefore, the calculated mole ratios are: 
TiCl.sub.3 :AlCl.sub.3 of 2.7:1, TiCl.sub.3 :TPP of 6.2:1 and 
TPP:AlCl.sub.3 of 0.4:1. 
CATALYST A.sup.1 
This is a repeat preparation of base SMART Catalyst A employing the same 
quantities of reagents and same procedure recited before. The milling time 
used was 3.8 hours. The recovered product weighed 68 g. 
CATALYST D (CONTROL) 
A 10 g sample of Catalyst base A.sup.1 was milled for 1.2 hours on the 
Vibratom in a 250 ml steel vessel containing 300 g of 1/4 inch steel balls 
employing cooling as described for Catalyst B. The milled sample was 
recovered by passage through a 50 mesh screen. 
CATALYST E (INVENTION) 
A 10 g sample of Catalyst A.sup.1, 1.1 g AlCl.sub.3 (8.2 mmoles) and 1.1 g 
TPP (3.5 mmoles) was milled 2.8 hours in the manner described for Catalyst 
C. The product was recovered through a 50 mesh screen. The weight ratio of 
base SMART catalyst to each adjuvant is about 9:1. The calculated mole 
ratios are: TiCl.sub.3 :AlCl.sub.3 of 4.0:1, TiCl.sub.3 :TPP of 9.3:1 and 
TPP:AlCl.sub.3 of 0.4:1. 
CATALYST F (INVENTION) 
A 10 g sample of catalyst base A.sup.1, 1.6 g AlCl.sub.3 and 1.6 g TPP was 
milled for 2.8 hours in the manner described under Catalyst A. The product 
was recovered through a 50 mesh screen. The weight and calculated mole 
ratios for this catalyst are the same reported for Catalyst B. 
CATALYST G (INVENTION) 
A 6.7 g sample of Catalyst base A.sup.1, 1.65 g AlCl.sub.3 (12.4 mmoles) 
and 1.65 g TPP (5.32 mmoles) was charged to a 250 ml steel vessel 
containing 350 g of 1/4 inch steel balls and milled for 2.5 hours. The 
red-brown product was recovered through a 50 mesh screen. The weight ratio 
of base SMART catalyst to each adjuvant is about 4:1. In 6.7 g of catalyst 
base A.sup.1 is calculated TiCl.sub.3 content of about 3.35 g (21.7 
mmoles). The calculated mole ratios are: TiCl.sub.3 :AlCl.sub.3 of 1.7:1, 
TiCl.sub.3 :TPP of 4.1:1 and TPP:AlCl.sub.3 of 0.4:1. 
CATALYST H (INVENTION) 
A 3.0 g sample of catalyst base A.sup.1, 0.75 g AlCl.sub.3 (5.6 mmoles) and 
0.75 g TPP (2.4 mmoles) was milled for 2.3 hours on the Vibratom in the 
manner described under Catalyst F. The red-brown product was recovered 
through a 50 mesh screen. The weight and molar ratios of the components 
are the same reported for Catalyst F. 
CATALYST A.sup.2 
This is another repeat preparation of base SMART Catalyst A employing the 
same quantities of reagents and same procedure recited before. The milling 
time used was 3.5 hours. The recovered product weight 67 g. 
CATALYST I (CONTROL) 
A 10 g sample of catalyst base A.sup.2 was milled for 2 hours in a 250 ml 
steel vessel containing 350 g of 1/4 inch steel balls on the Vibratom. The 
milled sample was recovered by passage through a 50 mesh screen. 
CATALYST J (INVENTION) 
A 4.2 g sample of Catalyst base A.sup.2, 0.65 g AlCl.sub.3 (4.8 mmoles), 
and 0.65 g TPP (2.1 mmoles) was milled for 13/4 hours in a 250 ml steel 
vessel containing 350 g of 1/4 inch steel balls on the Vibratom with no 
cooling employed. The product was recovered through a 50 mesh screen. The 
weight ratio of base SMART Catalyst A.sup.2 to each adjuvant is about 
6.5:1. The calculated mole ratios are TiCl.sub.3 :AlCl.sub.3 of 2.8:1, 
TiCl.sub.3 :TPP of 6.5:1 and TPP:AlCl.sub.3 of 0.4:1. 
CATALYST A.sup.3 
Three separate batches were prepared, each employing twice the quantities 
of reagents used in preparing the base SMART Catalyst A. Each batch was 
ball milled at ambient conditions in a 2 liter Norton grinding jar 
containing 5000 g of 0.5 inch steel balls by means of a roll mill. Batch 1 
was milled for 751/4 hours, batch 2 for 721/2 hours and batch 3 for 701/4 
hours. Each product was recovered as described in part (A), combined and 
blended together to yield 484 g of total product. 
CATALYST K (CONTROL) 
A 10 g sample of Catalyst base A.sup.3 and 0.4 g AlCL.sub.3 (3.0 mmoles) 
was charged to a Norton size 000 jar mill containing 500 g of 1/4 inch 
steel balls and the mixture was milled for 16 hours at ambient conditions 
on a roll mill. The product was recovered through a 50 mesh screen. In 10 
g of catalyst base A.sup.3 is a calculated TiCl.sub.3 content of about 5 g 
(32.4 mmoles). Therefore, the calculated mole ratio of TiCl.sub.3 
:AlCl.sub.3 is 10.8:1. The weight ratio of the base SMART catalyst to 
AlCl.sub.3 is about 25:1. 
EXAMPLE II 
Propylene was polymerized in a 1 l stirred, reactor employing the 
designated catalyst and the process described in the basic SMART catalyst. 
Each run was conducted at about 175.degree. F. (80.degree. C.) for 1 hour 
in the presence of molecular hydrogen as a polymer molecular weight 
modifier. Initial partial pressure of hydrogen was about 24.7 psia (0.17 
MPa). The polymers were isolated and the yields of crystalline power and 
xylene-soluble polymer determined as in the cited case. The calculated 
productivity is expressed as g polymer per g catalyst per hour. The 
abbreviations have the following meanings: 
TPP--triphenyl phosphite 
DEAC--diethylaluminum chloride 
TEA--triethylaluminum 
EA--ethyl anisate 
The quantities of compounds employed and the results obtained are presented 
in Table 1. 
TABLE I 
______________________________________ 
PROPYLENE POLYMERIZATION 
2 
RUN NO. 1 (Inv.) 3 4 5 6 
______________________________________ 
Catalyst 
Parts by weight 
per 100 parts 
unmodified base 
Number B C C C A.sup.3 
K 
TPP 0 12 12 12 0 0 
AlCl.sub.3 0 12 12 12 0 25 
Charged mg 51.0 55.5 43.4 40.1 47.9 67.4 
Calc. TiCl.sub.3 
mg 25.5 21.0 16.4 15.2 24.0 32.4 
mmoles 0.17 0.14 0.11 0.10 0.16 0.21 
Cocatalyst 
Calc. mmoles 
DEAC 4.95 4.95 0 4.12 0 0 
TEA 4.95 4.95 9.80 0 9.80 9.80 
EA 3.25 3.25 3.25 0 3.25 3.25 
Total Al/TiCl.sub.3.sup.(d) 
58 71 89 41 61 47 
EA/TiCl.sub.3.sup.(d) 
19 23 30 0 20 15 
Total Al Cpds/EA.sup.(c) 
3 3 3 na.sup.(b) 
3 3 
Polymer Yield, g 
94.5 138.4 68.3 25.0 66.6 135.7 
Wt. % Xylene 
Soluble Polymer 
13 5.7 8.5 nd.sup.(a) 
12 11 
Calc. Productivity 
1850 2490 1570 623 1390 2010 
g/g/hr. 
______________________________________ 
Note: 
.sup.(a) nd is not determined 
.sup.(b) na is not applicable 
.sup.(c) Al compounds in the cocatlyst system (calculated mole ratio) 
.sup.(d) Calculated mole ratio 
.sup.(e) Runs 1 and 3-6 are controls 
In inspecting the data given in Table 1 it is noted that the base SMART 
catalysts employed in control runs 1 and 5 are of different preparations 
hence runs 1-4 are to be compared directly and runs 5-6 are to be compared 
directly. The productivity and soluble polymer results shown in run 1 are 
typical of an unmodified (base) SMART catalyst. Invention run 2 shows that 
milling 12 parts by weight each of AlCl.sub.3 and TPP with the base 
catalyst yields a composite, a sample of which gives about 600 g polymer 
per g catalyst per hour more than the base catalyst and the soluble 
polymer formed has decreased from 13 wt. % to 5.7 wt. %. Control run 3 
shows at about the same level of total organoaluminum compound in the 
cocatalyst as in run 2 that the absence of DEAC in the cocatalyst system 
results in significantly lower productivity. Control run 4 shows that DEAC 
alone is not an effective cocatalyst with the catalysts of this invention. 
(Although only about 1/2 the amount of organoaluminum compound is employed 
as in runs 2 and 3 it is believed based on previous work that doubling the 
DEAC level would have little effect on the productivity results). 
In comparing the results of control runs 5 and 6, it can be seen that 
incorporating AlCl.sub.3 in the base catalyst yields a composite, a sample 
of which is more active in propylene polymerization than the unmodified 
catalyst. However, the level of soluble polymer produced is essentially 
the same as that produced with the base catalyst, hence, improvement in 
decreasing soluble polymer is not realized. 
EXAMPLE III 
Propylene was polymerized as described previously by contact with the 
designated catalyst. The effect of varying the amounts of TPP and 
AlCl.sub.3 employed in preparing the catalysts was determined. Unless 
otherwise indicated, each run was 1 hour in length conducted at 80.degree. 
C. in the presence of molecular hydrogen as before. The polymers were 
isolated and the results determined as described before. The abbreviations 
have the same meaning as in the previous example. 
The quantities of compounds employed and the results obtained are given in 
Table 2. 
TABLE 2 
__________________________________________________________________________ 
PROPYLENE POLYMERIZATION 
8 9 10 11 12 
RUN NO. 7 (Inv.) 
(Inv.) 
(Inv.) 
(Inv.) 
(Inv.) 
__________________________________________________________________________ 
Catalyst 
Parts by weight per 100 
parts unmodified base 
Number D E F G H H 
TPP 0 9 12 16.5 
16.5 
16.5 
AlCl.sub.3 0 9 12 16.5 
16.5 
16.5 
Charged mg 34.9 
41.5 
45.7 
47.5 
28.6 
41.4 
Calc. TiCl.sub.3 
mg 17.4 
17.0 
17.3 
15.9 
4.58 
13.9 
mmoles 0.11 
0.11 
0.11 
0.10 
0.062 
0.090 
Cocatalyst 
Calc. mmoles 
DEAC 4.95 
4.95 
4.95 
4.95 
4.95 
2.48 
TEA 4.95 
4.95 
4.95 
4.95 
4.95 
2.48 
EA 3.25 
3.25 
3.25 
3.25 
3.25 
1.63 
Total Al/TiCl.sub.3.sup. (d) 
89 89 89 98 158 55 
EA/TiCl.sub.3.sup. (c) 
30 30 30 32 52 18 
Total Al Cpds/EA.sup.(a) 
3 3 3 3 3 3 
Polymer Yield, g 
73.8 
110.6 
83.9 
107.4 
91.2 
95.6 
Wt. % Xylene Soluble 
Polymer 10.6 
8.0 6.7 7.2 7.6 9.7 
Calc. Productivity g/g/hr. 
2110 
2670 
1840 
2260 
3190.sup.(b) 
2310 
__________________________________________________________________________ 
Notes:- 
.sup.(a) Al compounds in the cocatalyst system (calculated mole ratio) 
.sup.(b) Polymer produced in a 21/2 hr. run 
.sup.(c) Calculated mole ratio 
.sup.(d) Run 7 is control 
Inspection of the results presented in Table 2 shows that invention runs 
8-10 in which the incorporation of from 9 to 16.5 parts by weight each of 
AlCl.sub.3 and TPP with 100 parts by weight base SMART catalyst has been 
made yields active catalysts which exhibit increased polymer yields and/or 
decreased soluble polymer formation than the results shown in control run 
1. Invention run 11 demonstrates that the invention catalysts retain 
polymerization activity for at least 21/2 hours. The productivity and 
soluble polymer results shown in invention run 12 show that good polymer 
productivity is achieved even when the total organoaluminum compound level 
is cut about 50% from about 10 to about 5 mmoles. However, even though a 
favorable mole ratio of organoaluminum compounds to EA of 3 is used, the 
amount of soluble polymer formed has increased to about 10 wt. % from the 
7-8 wt. % level because the amount of EA employed is reduced from a 
desirable level of about 3.2 mmoles to about 1.6 mmoles. 
EXAMPLE IV 
Propylene was polymerized as described before by contact with the 
designated catalysts. The effect of various reactor temperatures employed 
during polymerization was determined as was the effect of varying the 
cocatalyst system. Each run was conducted for 1 hour at 80.degree. C. in 
the presence of molecular hydrogen. The polymers were isolated and the 
results determined in the manner described before. The abbreviations have 
the same meaning as before. 
The quantities of compounds employed and the results obtained are presented 
in Table 3. 
TABLE 3 
__________________________________________________________________________ 
PROPYLENE POLYMERIZATION 
14 15 17 
RUN NO. 13 (Inv.) 
(Inv.) 
16 (Inv.) 
18 
__________________________________________________________________________ 
Reactor Temp. .degree.C. 
80 80 80 80 71 60 
Catalyst 
Parts by weight per 100 
parts unmodified base 
Number I J J J J J 
TPP 0 12 12 12 12 12 
AlCl.sub.3 0 12 12 12 12 12 
Charged mg 49.2 
41.2 
37.6 
37.6 
36.5 
39.4 
Calc. TiCl.sub.3 
mg 24.6 
15.6 
14.3 
14.3 
13.8 
14.9 
mmoles 0.16 
0.10 
0.092 
0.092 
0.090 
0.097 
Cocatalyst 
Calc. mmoles 
DEAC 4.95 
4.95 
2.48 
2.48 
2.48 
2.48 
TEA 4.95 
4.95 
2.48 
2.48 
2.48 
2.48 
EA 3.25 
3.25 
1.63 
3.25 
1.63 
1.63 
Total Al/TiCl.sub.3 .sup.(b) 
61 98 54 54 55 51 
EA/TiCl.sub.3 .sup.(b) 
20 32 18 35 18 17 
Total Al cpds/EA.sup.(a) 
3 3 3 1.5 3 3 
Polymer Yield g 
87.0 
87.2 
116.0 
21.8 
110.0 
92.9 
Wt. % Xylene Soluble 
Polymer 10.1 
7.3 11.0 
7.8 7.7 14.2 
Calc. Productivity g/g/hr. 
1770 
2120 
3080 
580 3020 
2360 
__________________________________________________________________________ 
Notes: 
.sup.(a) Al compounds in the cocatalyst system (calculated mole ratio) 
.sup.(b) Calculated mole ratio 
.sup.(c) Runs 13, 16 and 18 are controls 
Inspection of the Table 3 data shows in control run 13 the typical results 
obtained with the unmodified base catalyst, e.g., soluble polymer about 10 
wt. % and a productivity of about 1800 g polymer per g catalyst per hour 
at about 80.degree. C. In the remaining runs each catalyst contained 12 
parts by weight each of AlCl.sub.3 and TPP per 100 parts by weight 
unmodified SMART catalyst. Invention runs 14, 15 and 17 demonstrate the 
increased productivity resulting even at several cocatalyst variations at 
reactor temperatures of 80.degree. C. and 71.degree. C. The results shown 
in runs 15 and 17 suggest that when the cocatalyst level is cut about 50% 
from that of run 14 it is desirable to also lower the reactor temperature 
from about 80.degree. C. to about 70.degree. C. Thus soluble polymer 
formation is reduced from about 11 wt. % at 80.degree. C. to about 8 wt. % 
at 70.degree. C. without affecting productivity. The results of control 
run 16 shows that when the total organoaluminum compound to EA ratio is 
decreased below the instant invention specified minimum of about 2.6:1, 
low soluble polymer formation is achieved but at the expense of lower 
productivity to an unacceptable low level of about 600 g polymer per g 
catalyst per hour. Control run 18 shows that a reactor temperature of 
about 60.degree. C. is too low in the instant process with the catalysts 
employed. Although good productivity results are shown, the soluble 
polymer formed has increased to an unacceptable level of about 14 wt. %. 
EXAMPLE V 
CATALYST A.sup.4 (CONTROL) 
This is a repeat preparation of base SMART Catalyst A employing the same 
quantities of reagents and the same procedure recited before for Catalysts 
A, A.sup.1 and A.sup.2. The recovered purple-maroon colored product 
weighed 75 g. 
CATALYST L (CONTROL) 
In this example, the basic SMART Catalyst A was prepared in the presence of 
powdered MgO which had been previously heated for 16 hours at about 
1000.degree. F. (538.degree. C.) in air, then cooled. A 1 liter spherical 
steel vessel containing 1400 g of 0.5 inch steel balls was charged with 
the same quantity of reagents as described in Example I plus 36 g (0.89 
mole) of MgO. The weight ratio of base SMART catalyst to MgO is about 4.4 
to 1. The vessel was placed on the Vibraton and a 3.75 hour milling time 
was employed. The purple colored recovered product weighed 110 g. 
CATALYST M (INVENTION) 
A 5 g sample of control Catalyst L, 0.8 g AlCl.sub.3 (6 mmoles) and 0.77 g 
TPP (2.5 mmoles) was milled for 2 hours in a 250 ml steel vessel with 300 
g of 1/4 inch steel balls on the Vibraton at ambient conditions. After 
milling, the vessel and contents were heated for 1 hour at 95.degree. C. 
The brownish-violet solid product was recovered from the vessel through a 
50 mesh screen following the heat treatment. The calculated amount of MgO 
in 5 g of Catalyst L is 1.75 g (43 mmoles) and 3.25 g of base SMART 
catalyst. Thus, the calculated amount of TiCl.sub.3 in 5 g of Catalyst L 
is 1.625 g (11 mmoles). The calculated weight ratio of base SMART catalyst 
to each adjuvant is about: SMART:MgO of 1.8:1, SMART:AlCl.sub.3 of 4.1:1, 
and SMART:TPP of 4.2:1. The calculated mole ratios are TiCl.sub.3 :MgO of 
0.26:1, TiCl.sub.3 :AlCl.sub.3 of 1.8:1, TiCl.sub.3 :TPP of 4.4:1 and 
TPP:AlCl.sub.3 of 0.42:1. 
Propylene was polymerized as described previously by contact with the 
catalysts at 70.degree.-71.degree. C. The quantities of compounds employed 
and the results obtained are given in Table 4. The abbreviations have the 
same meanings as before. 
TABLE 4 
______________________________________ 
PROPYLENE POLYMERIZATION 
Run 19 20 21 22 
No. (Control) 
(Control) 
(Inv.) (Inv.) 
______________________________________ 
Catalyst 
Parts by weight per 
100 parts unmodified 
base 
Number A.sup.4 L M M 
TPP 0 0 4.2 4.2 
AlCl.sub.3 0 0 4.1 4.1 
MgO 0 4.4 1.8 1.8 
Charged mg 44.1 42.0 38.9 29.4 
Calculated TiCl.sub.3 
mg 22.05 13.6 9.6 7.3 
mmoles 0.14 0.088 0.062 0.047 
Cocatalyst 
Calc. mmoles 
DEAC 2.15 2.15 2.15 2.15 
TEA 2.15 2.15 2.15 2.15 
EA 1.63 1.63 1.63 1.63 
Total Al.sup.(a) /TiCl.sub.3 
31 49 69 91 
EA/TiCl.sub.3 
12 19 26 35 
Total Al Cpds./EA 
2.6 2.6 2.6 2.6 
Polymer Yield, g 
80.2 39.6 91.3 95.5 
Wt. % Xylene 
Soluble Polymer 
11.6 13.5 9.1 9.1 
Cal. Productivity, 
g/g/hr 1820 943 2350 3250/ 
(3640).sup.(b) 
(2910).sup.(b) 
(9510).sup.(b) 
2.5 hrs 
13080/ 
2.5 hrs.).sup.(b) 
______________________________________ 
.sup.(a) Total moles of Al compounds in cocatalyst 
.sup.(b) Calculated grams polymer per gram calculated TiCl.sub.3 
Control catalyst A.sup.4 used in Run 19 is the unmodified SMART catalyst 
for the other catalysts prepared in this time period. The results obtained 
with it are similar to those obtained previously in other time periods. 
The addition of only MgO to the SMART catalyst results in a low productive 
catalyst as the results of Run 20 demonstrate. Thus, productivity is about 
halved and somewhat more soluble polymer is formed. However, the 
combination of MgO, TPP, and AlCl.sub.3 as promoters (adjuvants) for the 
base SMART catalyst simultaneously improves catalyst productivity and 
lowers soluble polymer formation. A marked jump in productivity is more 
clearly seen when the catalysts are compared on the basis of grams polymer 
produced per gram calculated TiCl.sub.3 per hour. Part of the increase is 
attributed to the heat treatment afforded invention catalyst M.