Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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1 This invention relates to the polymerization of
2 olefins using a Ziegler catalyst system to produce large
3 particles of product having a narrow particle size distribu-
4 tion and only very small amounts of fines.
The polymeri~ation of olefins in the presence of
6 Ziegler polymerization catalyst systems is well known and it
7 is further known that the use of such catalyst particles pro-
8 vide "templates" for the formation of the polymer particles,
9 the size and size distribution of such polymer particles
being largaly dependent upon the size and particle size dis-
11 tribution (PSD) of the catalyst being used.
12 Catalysts of this type are difficult ~o handle and
13 techniques to modify them are limited. Agglomeration with
14 "binders" is unsuitable since "binders" normally poison the
catalyst sites and sieving the catalysts particles to remove
16 the ca~alyst "fines" is wasteful since large quantities of
17 useless fines are accumulated.
18 With certain olefin polymeriza~ion catalysts, the
19 growth of the catalyst itself ~rom the original catalyst seeds
can be controlled to yield products having a coarse structure
21 (20 microns or larger) which makes these catalysts more easily
22 handled. Thus, U.S. Patent 3,623,846 describes a process for
23 controlling particle size during condensation and/or desublima-
24 tion of a material such as titanium trichloride which may be
used in the polymerization oE alpha-olefins.
26 In another example, as described in British Patent
27 1,139~450, TiC13 catalysts are formed by controlled reduction
28 of titanium tetrachloride with aluminum alkyls. These mater-
29 ials have a narrow PSD, and have an average diameter greater
than 15 microns, and therefore are relatively easy to handle.
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1 However~ the latter two examples illustrating two
2 terhniques for improving the particle size of catalysts, spec-
3 ifically titanium trichloride defin polymerization catalysts,
4 have certain limitations. Thus, although the catalyst particle
size is greater than the 1 micron dimension which is normally
6 available, the 20 micron size still limits the usability of
7 these catalysts. Increase in catalyst growth to yield parti-
8 cles 100 microns or larger is more difficult. Furthermore,
9 control of particle size during catalyst synthesis is a prob-
lem common ~o every type of catalyst that might be employed.
11 What is needed, therefore, is a technique that is applicable
L2 to Ziegler-type catalysts in general~ a procedure that is
13 easy to employ~ and one that can yield catalysts with a narrow
14 PSD and large particle SizP; i.e., most of the particles having
a diameter of about 150 microns or greater
16 In U.S. Patent 3~990,993, a procedure is described
17 whereby olefin polymerizatlon catalysts, i.e., ~iegler TiC13-
18 nAlC13, can be mechanically treated with a fibrillatable poly-
19 tetrafluoroethylene (PTFE) in order to trap the cataly~ "fines"
in a web of PTFE microscopic fibers, ~hus producing a ca~alyst
21 of larger particle size having a more narrow particle-size dis-
22 tribution. Nevertheless, the catalyst is still limited in
23 size obtainable and in particle size distribution by the ran-
24 domizing technique of fracturing the catalyst-PTFE mixture
using shearing forces such as ballmilLing.
26 While it is pointed out ~hat the patentee is con-
27 cerned with the particle size range of various catalytic matPr-
28 ials and the desirability to form these materials into large,
29 uniform, easily handled shapes, U.S~ Patent 3,990,993 clearly
expresses concern for fines resulting from ballmilling o~
~ ~ 3~ ~ 4
1 polyolefin catalysts. Excessive ballmilling caused the PSD
2 to be widened since fines were again produced, even in the
3 presence of the ~ibrous web. Such concern is unnecessary in
4 the practice of this invention.
Further, as an expression of the prior art, U.S.
6 Patent 3,051,662 describes the use of polyolefins as binders
7 and lubricants for shaping solid materials. The disclosure
8 teaches the formation of simpLe mixtures which are extruded
9 through a die. In some instances where metal oxide catalysts
are involved, the lubricant-binder of the invention is removed,
11 usually by incineration or vaporization. This would destroy
12 the activity of many catalysts. PTFE is only casually men-
13 tioned, and the disclosure fails completely to recognize the
14 importance of the invention as disclosed and claimed herein.
Further, U.S. Patents 3,838,0h2, 3,838,~92, and
16 3,993,584 disclose the use o~ a fibrillatable PTFE to create
17 a weak agglomerate of dusts~ particularly toxic dusts.
18 Surprisingly it has now been discovered that th
19 PSD can be held within a narrow range producing large cat-
alyst particles by U5iIlg one aspect of ~his invention. Once
21 such particles are produced a polymerization process can be
22 conducted which results in the production of polyolefins, par-
23 ticularly polye~hylene and polypropylene which have large
24 particles and a narrow PSD.
~n its broadest aspects this invention is an improve-
26 men~ in the process for polymerizing or copolymerizing olefins,
27 particularly ethylene or propylene, wherein the olefin is con-
28 tacted with the Ziegler catalyst system of a titanium halide
29 component and an organic aluminum cocatalyst component under
polymerization conditions. The improvement involves using,
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in the Ziegler catalyst system, titanium halide containing
catalyst component particles which have been mixed with both
fibrillatable component, polytetrafluoroethylene (PTFE) and a
non-fibrillatable polyolefin such as polyethylene, polypropylene,
ethylene/propylene copolymers or polyvinylchloride. The mixture
is then subjected to shearing forces such that the fibrillatable
polyolefin forms a fibrous web which traps the catalyst particles
and further which fibrous web becomes attached to particles of
the non-f ibrillatable polyolefin such that further degradation of
particle size is prohibited if milling is continued.
The polyolefin particles, particularly polypropylene or
polyethylene, resulting from a polymerization process using the
foregoing catalyst component results in large particle size with
a narrow particle size distribution, such that about ninety-eight
percent of the particles resulting from the polymerization
process will fail to pass a 100 mesh screen. This is equivalent
to saying that about 9B% or more of the particles have a diameter
of about 150 microns or greater.
The polyolefin product resulting from this process will be
largely particles which will fail ~o pass a 10~ mesh screen. At
least about ninety-eight percent of the polyolefin produced will
be retained thereon. Stated differently, at least about ninety-
eight percent of the polymer particles will be about 150 microns
in diameter or larger.
- Polymerization according to this invention and recovery of
polymer are suitably carried out according to methods and
conditions known to be suitable for low-pressure olefin
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polymerization processes of the prior art. This includes batch,
semibatch or continuous operations under conditions that exclude
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1 air and other atmospheric impurities~ particularly moisture
2 The reaction is typically conducted at temperatures
3 between 0 and 150F. with temperatures between 40 and 70
4 generally preferred. The reaction pressure is not critical.
It is usually only sufficiently high to maintain liquid phase
6 reaction conditions. It may be autogenous pressure, which
7 will vary depending upon the components of the reaction mix-
8 tu~e and the temperature, or it may be higher, e.g., up to
9 1000 psi. High pressures are suitably obtained by pressuring
with monomer gas ~ with an inert gas.
11 In batch operations the polymerization time can be
12 varied as desired; it may vary, for example, from a few min-
13 utes to several hours. Polymerizatiun in batch processes may
14 be terminated when monomer is no longer absorbed, or earlier,
if desired, e.g , if the reaction mixture becomes too viscous.
16 In continuous opexations the polymerization mixture passes
17 through a reactor of any suitable design well known to those
18 skilled in the art. The polymerization reactions in such
19 cases are suitably adjusted by varying the residence time.
Residence t~mes vary with the type of reac~or system and
21 range, for axample, from 10 to 15 minutes to two hours or
22 m~re.
23 In a suitable continuous operation, fresh feed~
24 diluent and the Ziegler catalyst system are con~inuously intro-
duced into an agitated reaction zone and reaction mixture is
26 withdrawn frDm the zone for removal and polymer recovery. Heat
27 of reaction may be withdrawn by indirect heat exchange or by
28 evapor~ion of diluent and/or monomer in the reaction zone.
29 After the polymerization is completel polymer is
recovered from a slurry or solution of the polymer in reaction
V4
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1 diluent. A simple filtration may be adequate to separate
2 polymer ~rom diluent but other means for separating polymer
3 from diluent may be satisfactorily employed. The polymer
4 may be treated separately or while slurried in the reaction
mixture~ in order to separate catalyst residues. Such treat-
6 ment may be with alcohols, such as methanol, ethanol, or iso-
7 propanol; with acidified alcohols; or with other similar polar
8 liquids. In many cases the polymers are produced in hydrocar-
g bon solutions and can be recovered by coagulation with acidi-
fied alcohol, e.g., rapidly stirred methanol orisopropanol
11 containing 2 wt. % hydrochloric acid. Following this initial
12 coagulation the polymers are pre~erably washed several more
13 times in methanol.
14 The concentration of monomer in the reaction mix-
ture may vary upward from 5 percent by weight of the reaction
16 mixture, depending on the conditions employed; a range of
17 from 20 to 80 percent by weight is preferred.
18 It ls preferred to carry out the reactions accord-
19 ing to this invention in a suitable diLuent which is liquid
and inert under the conditions of reaction. The diluent may
21 have the same number of carbon ~oms per molecule as the
22 olefin reactant or it may be in a different boiling range.
23 Preferred diluents are alkane and cycloalkane hydrocarbons.
24 Suitable diluents are, for example, propene, propane, but~ne,
isobutane, n-heptane, cyclohexane, methylcyclohexane, Tetra-
26 lin, Decalin, or saturated hydrocarbon mixtures in the gaso-
27 line boiling range or diesel oil boiling range. Aromatic
28 hydrocarbons such as benzene, toluene, isopropylbenzene,
29 xylene, or the like, or halogenated aromatic compounds such
as chlorobenzene, or
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ortho-dichlorobenzene and the like may also be employed, if
desired.
The Ziegler catalyst systems employed are suitably used in a
concentration ranging from about 0.1 to about 2% by weight of
catalytically active material based on weight of the reaction
mixture.
Preferred catalytically active materials for use in this
invention are components for use in Ziegler-type titanium halide
catalyst systems, eOg., titanium halide containing catalyst com-
ponents obtained by reduction of the tetrahalide or titanium to atitanium compound with a lower oxidation state, such as
TiC13 XAlC13 where x is between 0O01 to 1.5; Ziegler-~ype
catalyst systems e.g. TlClmoxAlRnC13_n where x is between 0.01
to 1.5, m is between 2 to 3.5, n is between 0.01 to 3, and R is
an organic radical such as an organic hydrocarbon radical,
preferably alkyl radicals having from one to about five carbon
atoms such as CH3, C2Hs, etc., or other organic radical that
normally is known as described by Mole and Jeffrey, "Organo-
aluminum Compounds", Elsevier, (1972); and catalyst systems
represented by MX'm~xM'RnS3_n where metals, M and M~ are
selected from groups IIIB, IVB and VB of the periodic table of
Mendeleef as published inside the front cover of the Handbook of
Chemistry and Physics, 56th Edition, CRC Press Cleveland Ohio
1975, X and X' are elements of groups VIA and VIIA of the
periodic table~ and m, x and n vary as described above. It is
well known that the compounds induced are mixtures and that the
ranges of values of m, x and n herein are average values.
In preparing the catalyst of this invention used in the
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practice of the polymerization reaction of this invention the
non-fibrillatable polyolefin is an inert malleable material which
does not fracture on impact, preferably selected from polyethy-
lene, polypropylene, ethylene/propylene copolymers and polyvinyl-
chloride (PVC) and the like. In the overall mixture the non-
fibrillatable polyolefin is from about 20 to about 70 wt. % of
the catalyst with the amounts being preferably from about 40 to
about 60 wt. %. It would be selected from material which,
itself r has a narrow particle size distribution and be
substantially free o particIes having a diameter of less than
about 20 microns.
In the practice of this invention, a mixture of the solid
catalyst component particles, the non-fibrillatable polyolefin,
and the fibrillatable polytetrafluoroethylene is made such that
the fibrillatable PTFE is present in an amount from about 1 wt. %
to about 5 wt. % of the mix and, preferably, from about 1.5 wt. %
to 2~5 wt. %. Even though greater amounts than 5 wt. % can be
used, little advantage, if anyl is obtained~ It is best to use
the minimum amount necessary to entrap the active catalyst
particles, which, under the practice of the present invention,
even in the case of the Ziegler-type catalyst is being used,
remain remarkably active even though the non-fibrillatable
polyolefin is present with the active catalyst.
A fibrillatable polytetrafluoroethylene (PTFE) is one which,
on being subjected to shearing stresses, forms a fibrous network
of small ~ibers, often microscopically sized fibers, which entrap
the solid active catalyst particles. There are two types. One
is a colloidal aqueous dispersion concentrated to about 60% by
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weight of polymer, having particles from about 0.05 to about 0.5
microns in size, with average diameters of about 0.2 microns.
This aqueous dispersion, of course, could be used in the instance
where the solid catalytic particles are insensitive to the
presence of water. of course, where there is a water sensitiv-
ity, such colloidal aqueous dispersion could not be used. In
such a case, the PTFE consists of solid agglomerates with average
diameters of 450 microns, made up of primary particles ranging in
size from 0.05 to 0O5 microns in diameter. Specific surface
areas of PTFE powders are o~ the order of 1 to about 12 m2/g with
an average apparent powder density of 475 g/liter. The foregoing
types of PTFE are more fully described in U.S. Patent 2,559,752.
PTFE, sold as "Teflon* K" by the DuPont Company, is preferred.
The light powder known as Teflon* K, Type 10, is worked at a
temperature of from about 20C. to abou~ 120C., and preferably,
of course, at ambient conditions. The common working temperature
in order to produce a fibrous mat, is about 100C. or below.
Once mixed, the catalyst component particles, the non-
fibrillatable polyolefin and the fibrillatable PTFE are subjected
Z0 to mechanical shearing forces such that the latter polyolefin be-
comes fibrillated and the catalyst particles are entrapped in a
fibrous network.
The non~fibrillatable polyolefin appears to collect this
network of catalyst on its surface such that what would have been
previously excessive shearing forces no longer serve to randomize
the size of the catalyst particles trapped in the network. While
the fibrous network is known, it was also known that there was
danger in subjecting it to excessive
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1 shearing forces which are ~nown to cause a randomization of
2 particle size and hence a widening of the particle size range
3 The presence of the non-fibrillatable polyolefin r~moves this
4 danger and surprisingly produces particles having a narrow PS~
and a large particle size. The presence of the non-fibrillat-
6 able polyolefin having a narrow PSD appears to stabilize the
7 catalyst particle size.
8 The shearing action is done mechanically under an
9 inert atmosphere, preferably nitrogen, in any one of a number
of well-known commercially available pieces of equipment such
11 as a ballmiLl, pugg mill, blender, or the like. This mechani-
12 cal shearing is performed for a time sufficient ~o form a
13 fibrous mat and to cause the mat to adhere to the non-fibril-
14 latable polyolefin, usually from about one to about sixty
minutes, with the preferable period from five to about forty
16 minutes. Of course, longer times can be used, but serve no
17 u5eful purpose once the shapable fi~rous mat is formed and
18 becomes protected by the non-fibrillatable olefin.
19 The shearing action time, of course, is easily
determined within the above parameter and is dependent upon
21 temperature and the concentration of the components in the
22 mix. When at higher temperatures 9 the shearing time is re-
23 duced, as is the shearing time when a higher concentration
24 of the fibrillatab1e polyolefin is used.
Thus it can be seen tha~; following the catalyst
26 preparation discussed above, polyolefins can be produ~ed which
27 hav~ generally larger particles, at least about 98% of them
28 being about 150 microns in diameter, and a more narrow PSD.
29 The specific aspects of this invention and further advantages
will be illustrated by the following examples which are offered
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1 for the purposes of illustration only and should not be con-
2 sidered to be limiting of the invention.
3 In the fo~Dwing examples the amounts are stated as
4 parts by weight. When the tabular data is reviewed which
relates to flow, homogeneity, fines, settling rate and parti-
6 cle size distribution, ratings are made on a scale of 1 to 5
7 where 5 is excellent and 1 is the lowest rating given. For
8 instance, with respect to fines, a rating of 5 indicates that
9 there are little or no fines present and would be an excellent
rating. With respect to a settling rate in heptane a 5 rating
11 is indicative of a fast settling rate while a 1 is a low rate.
12 A 5 in particle size distribution is an indication that there
13 is a narrow PSD. All of the observa~ions and ratings are made
14 by skilled personnel who are familiar with making such deter-
minations such that they are objective rather than subje~tive
16 in nature.
17 In determining visual spectra a 5 wt. % slurry of
18 catalyst, or polymer, is mixed in normal h~ptane in a 7/8
19 inch ~utside diameter glass cyLinder. The time required for
90% and 100% transmission o~ visual light ~650M~ through the
21 agitated slurry is measured and recorded~
22 Unless otherwise indicated, the transition metal
ata~st ~ompo~2r-~s
~ 23 ~1~l}~ PTFE, and the non-fibrillatable polyolefin are
B 24 mixed in a vibramill (Spex~mixer/mill, catalog number 8,000,
Spex Industry, Inc., Scotch Plains, New Jersey~ containing
26 three to four 5/8" diameter chromium/molybdenum steel balls.
27 The materials are loaded in a "dry box" containing an inert
28 atmosphere and are subjected to shearing forces for the time
29 shown below.
Unless other~7ise stated, the catalys~s were evalu-
~ ~r~Q ~/l~
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1 ated for polymerization in an inert atmosphere by subjecting
2 1 to 3 grams of catalyst to the action of an et~yl aluminum
3 halide cocatalyst followed by treatment with propylene or
4 ethylene purified gas for a period of 2 hours at 65C. The
reaction mixture is worked up by adding to it two volumes of
6 isopropyl alcohol per volume of heptane reaction solvent. The
7 polymeric product was filtered with the quality of the dry poly-
8 meric product being determined by the amount of polymer that
9 was insoluble in boiling heptane. The percent heptane insol-
ubles recorded included the soluble polymer in the reaction
11 filtrateO Comparative examples 1~4 show representative 2xper-
12 imental results of polymerization tests using, i.e., prior art
13 catalysts.
14 Comparative Example 1
A TiC13-0.33 AlC13 catalyst obtained from Stauffer
16 Chemical Company (TiC13 M), representative of the type of
17 material commercially available and frequently used in the
18 polymerization industry, was tested to determine properties
19 before applications of the method of this invention. Micro-
scopic examination of the sample showed a wide particle size
21 distribution and many catalys~s fines. The material3 when
22 suspended in hep~an~, does not permit light transmittance
23 even after it has been allowed to settle f~r more than 100
24 seco~ds. (See Table 1)
Comparative Exa_E~
26 This example illustrates that the ballmilling, as
27 described, is essential for making a good catalyst. A cat-
28 alyst mixture was prepared as described above using 7.35 gms.
29 of polypropylene, 7.35 gms. of TiC13AA catalyst, and 0.3 gms.
PTFE (Teflon K, type 10, DuPont~ manually mixed without sig-
20~
1 nificant agitation. It was not ballmilled. The catalyst has
2 properties as indicated in Table 1 and is shown to have a wide
3 particla size distribution including many catalyst fines.
4 Com~arative Example 3
This example illustrates the necessity for having
6 fibrillatable PTFE present during the ballmilling. Ten gms.
7 of polypropylene and five gms. of TiC13AA were ballmilled for
8 60 minutes. The properties show that the catalyst has a wide
9 particle size distribution containing many catalyst fines.
See Table 1.
11 Comparative_Exam~e 4
12 This example illustrates the necessity for having
13 non-fibrillatable polyolefin present during ballmilling to
14 obtain a narrow particle size distribution product. 14.7 gms.
of TiCl3M and 0.3 gms. of Teflon were mixed and ballmilled
16 for 60 minutes. The product containing no fines, but had,
17 however, a wide particle size distribution.
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1 TABLE 1
2 CONTROL CATALYST SAMPLES
3 Comparative
4 Example No. 1 2 3 4
COMPOSITION
6 Polymer ~~ PP PP
7 Wt. % -- 49 67 0
8 TiC13M , Wt. %100 49 33 98
9 PTFE, Wt~ % -- 2 0 2
10 BALLMILLED~ MIN 0 0 60 60
11 APPEARANCE
12 Flow 1 1 2 3
L3 Homogeneity l 1 1 2
14 Fines 1 1 1 5
15 Color purple purple purple dk.purple
16 dull dull shiny
17 BULK DENSITY
18 IN FLASK
19 Settling rate
20 in heptane 1 1 1 5
21 Visual Spectra
22 90% sec ~100 >100 >100 ~ 5
23 100% sec ~10~ ~100 ~100 10
24 MICROSCOPE
25 P.S.D. 1 1 1 3
26 Colorpurple Wh.particles, purple black
27 purple cat.
28 Fines (at 31x) 1 1 1 5
29 ShapeIrreg. Spherical PP, Irreg. Irreg.
Irreg. cat. V.large
31 ~ es 1~3
32 These ~xampLes illustrate the effect of concentra-
33 tion of the non-fibrillatable polyolefin on catalyst proper-
34 ties. In these cases, as illustrated by the results in Table
2, the wt. % o~ PTFE was being held constant ~ile the wt. %
36 of polypropylene and TiC13AA catalyst was varied. As the con-
37 centration of pol~propyLene is increased the particle size
38 distribution of the final catalysts is made more narrow.
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l TABLE 2
2 CONCENTRATION OF POLYPROPYLENE VS. CATALYST PROPE~TIES
3 EXAMPLE NO. 1 2 3
4 COMPOSITION
5 Polymer PP PP PP
6 Wt. %, Polymer 66 49 20
7 TiC13AA, Wt. % 32 49 78
8 PTFE, Wt. % 2 2 2
9 BALLMILLED, MIN 60 60 60
APPEARANCE
11 Flow 3
12 Homogeneity S 5 3
13 Fines 5 5 5
14 Color purple, purple purple
shiny
16 BULK DENSITY
17 IN FLASK
18 Settling rate
19 in heptane 3 4 5
20 Visual Spectra
21 90%, sec. ~5 10 ~5
22 (dk. colored
23 soln.)
24 100%, sec. 40 90 15
MICROSCOPE
26 P.S.D. ~ 3
27 Color purple white & purple
2,3 Fines (at 31x) 3 purple . 5 (2)
29 Shape Irreg,(l) Spherical
W ~b~e-~ lys~ concentrated in specific agglomerates
31 (2~ Regular or spherical and homogeneously covered with catalyst
32
33 A catalyst is prepared with amounts of polypropylene
34 TiC13AA, and PTFE (Teflon K, type 10) adjusted so that the con-
,~ .
centrati~n of the fibrillatable PTFE is O.7 wt. %. The proper-
36 ties of this catalyst can be compared with the properties of
37 the catalysts prepared according to Example 2. See Table 3.
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l TABLE 3
2CONCENTRATION OF PTFE VS. CATALYST PROPERTIES
3 EXAMPLE NO. 2 4
4 COMPOSITION
Polymer PP PP
6 W~. % 49 49-7
7 TiC13AA, Wt. %49 49.7
8 PTFE, Wt. % 2 0.7
g BALLMILLED, MIN 60 60
APPEARANCE
11 Flow 4 4
12 Homogeneity 5 - 4
13 Fines 5 5
14 Color purple purple
8ULK DEN5ITY - ~
16 IN FLASK~
17 Settling rate
18 in hep~ane 4 3
19 Vis. Spectra
90%, sec. 10 40
21 (dk. colored
22 soln.)
23 190%, sec. 90 100
24 MICROSCOPE
P.S.D. 3 2
26 Color Wh. & purple purple
27 Fines (at 31x3 2
28 Shape Irreg.
29 ~
A series of cat~lysts were prepared as in the prep-
31 aration of Example 2 excep~ that the non-fibrilla~able poly-
32 olefin u~ed was changed, The comparative properties of these
33 examples, tabulated in Table 4~ illustrate that the superaor
34 ca~alyst properties result regardless of polyolefin used.
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2 Samples of the non-fibrillatable polyolefin used in
3 examples of this invention are identified in Examples 5-11.
4 Properties of these polyolefins are tabulated in Table 5.
Examples 10-18
6 The necessity of including the PTFE with the non-
7 fibrillatable polyolefin and catalyst is illustrated by Exam-
8 ples 17-25, the data from which is shown in Table 6. Ball-
9 milling of TiC13AA cataLyst with polypropylene, polyethylene,
or polyvinylchloride without the pres~nce of PTFE leads to
11 catalysts with wide particle size distribution having many
12 catalyst fines. Catalysts ballmilled with PTFE, non-fibril-
13 latable polyolefin and catalyst particles lead to materials
14 having a narrow particle distribution as shown in other Exam-
ples.
16 Examples l9-26
17 Catalysts prepared according to previous Examples
18 were tested by polymerizing the indicated olein. The prop-
19 erties of the finished polymer are as shown on Table 7.
Comparative Example 12
21 This example illustrates one advantage of this in-
22 vention by demonstrating the probl~m when the catalyst and
23 flbrillatable PTFE are excessively ballmilled absent the non-
24 ~ibrillatable polymer. In accordance with procedures prev-
iously described, 9~95 grams of TiC13 0.33AlC13 having particle
26 size diameters varying from 0.1 to 100 microns was mixed~ and
27 ballmilled for 15 minutes with 0.05 gms of a fibrillatable
28 PTFE resulting in a catalytic material having large particle
29 size diameters from 20 to 2000 microns.
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-23-
Ballmilling for an addition21 four hours produced small cat-
2 alyst particles having diameters from O.1 co 50 microns.
