NOVEL Ti-Aryl COMPLEXES AS INTERNAL OR EXTERNAL MODIFIERS,

IMPROVING PERFORMANCE OF MgCl2 SUPPORTED POLYPROPYLENE CATALYSTS

Gregory G. Arzoumanidis
Oakwood Consulting, Inc.
Wheaton, Illinois 60!"
arzoumandis#gmail.com
oakwoodconsulting.com

Abstrat

$he recently announced multi%site &eha'ior
o( some )( organometallic com*le+es in ole(in
*olymerizations ,- may &e attri&uted in *art to
ole(in insertion into the )(%aryl &ond. We ha'e
now a**lied (or the (irst time a num&er o( no'el
hindered aromatic com*le+es, (eaturing a $i%aryl
&ond and one or more heteroatoms, to
demonstrate su&stantial im*ro'ements in
catalytic *er(ormance o( .gCl2 su**orted
/oly*ro*ylene ,//- catalysts. Com*le+es with
other metals, such as 0r, showing identical
structures, ha'e also &een *re*ared.
$hese com*le+es may &e used either as
internal or e+ternal modi(iers o( .gCl2
su**orted // catalysts. As internal modi(iers,
they may not re*lace entirely the *hthalates or
other well known internal modi(iers. Instead, &y
an o*timum *artial re*lacement o( the e+isting
modi(iers, they may im*art mainly acti'ity
enhancements u* to !01.
As e+ternal modi(iers that could &e deli'ered
mi+ed with the aluminum alkyl, they may
re*lace "0%001 o( the silane commonly used.
2esides the acti'ity enhancement, they are
e+*ected to im*art su&stantial im*ro'ements to
// *roduct *ro*erties, due to their multi%site
&eha'ior. $o take ad'antage o( this technology in
a // *rocess, there is no need (or changes in the
use and o*eration o( an e+isting .gCl2
su**orted catalyst, e+ce*t (or the addition o( the
com*le+es as e+ternal modi(iers.
$he com*le+es were *re*ared in a one%*ot,
single ste* reaction in toluene o( $iCl3 or 0rCl3
with com*ounds o( the general (ormula Ar+%4%5,
where Ar6Aryl attached to 4, +6%3, 46 a
*olycyclic or monocyclic heteroaromatic ligand,
containing one or more heteroatoms,
56heteroatom a'aila&le (or coordination7&ond
(ormation with the metal. $he reaction in'ol'es
an orthometallation and (ormation o( a 8% or 6%
mem&er metallocyclic ring. $hese com*le+es
(urther undergo chemical trans(ormation and
metal reduction with aluminum alkyls, such as
triethylaluminum ,$5A-. $he resulting *roducts
may acce*t a great 'ariety o( a*rotic electron
donors.
Although we *re*ared only a (ew
orthometalated com*le+es, we ha'e identi(ied
dozens o( ligands that ha'e the *otential to (orm
such com*ounds. I( one counts one or more
su&stituents on these ligands, it a**ears that this
new technology o((ers endless *ossi&ilities.
$he com*le+es are e+*ected to &e utilized as
inde*endent catalysts as well, in se'eral other
al*ha%ole(in *olymerizations and
co*olymerizations such as ethylene, &utene, etc,
and *articularly in high tem*erature solution
*rocesses. $heir great ad'antage is their
acti'ation with aluminum alkyls such as $5A,
not .AO or other non%coordinating anions.

I!tr"#$ti"!

A (lurry o( research acti'ity took *lace in the
*ast se'eral years &y // *roducers in de'elo*ing
new internal modi(iers (or commercial .gCl2
su**orted catalysts, &eyond the 9classical:
*hthalate, succinate, and other esters, and
diethers. $he incenti'e (or this acti'ity has &een
im*ro'ements in *rocess and *roduct, sa(ety
issues, and ac;uiring a *ro*rietary *osition.
5+am*les o( new commercial internal modi(iers
are car&onates ,2-, sul(onyl com*ounds ,<-, a
*air o( organosilicon com*ounds ,3-, ketone%
ether deri'ati'es ,8,6-, ali*hatic cyclic esters
,",!-, ,!%na*hthyl%diaryloates ,=-, and in%situ
(ormation o( di%octyl%*hthalate, using an
emulsion *rocess to control *article mor*hology
,0-.
As *art o( a similar e((ort, we screened
se'eral *otential candidates as modi(iers o( a
widely used commercial // catalyst, originally
de'elo*ed &y us in the =!0s ,-. In order to
e+*edite the screening *rocess, we tested the
*otential modi(iers as e+ternal modi(iers (irst,
using a la&oratory &atch gas *hase unit ,-, and
monitored *ossi&le changes in the o'erall
catalyst system *er(ormance. $he (irst Ar+%4%5
ty*e material tested ga'e us an a'erage o( <81
increase in // yield, im*ro'ed e+tracta&les and
*owder &ulk density.
>ollowing u* on this de'elo*ment, and a(ter
a series o( e+*eriments discussed &elow, we
gradually recognized that, whereas the known
internal modi(iers coordinate with the .gCl2
,2-, the Ar+-L-E interact primarily with the
TiCl4 on the catalyst. $his is a key *oint in
understanding all the de'elo*ments and
*ro*osals we outline in this *a*er, and may
re*resent a new conce*t in .gCl2 su**orted //
catalysts.
$he Ar+%4%5 materials are unrelated to
e+isting internal modi(iers o( .gCl2 su**orted
// catalysts. In (act, they may not e'en act as
modi(iers, &ut com&ined with $iCl3, constitute
inde*endent catalytic s*ecies. We &elie'e they
re*resent a new class o( $i ,and other transition
metals- organometallic com*le+es, (eaturing
metal%aryl &onds, disco'ered &y mere
serendi*ity. $hey are e+*ected to ha'e
interesting and widely ranging a**lications in
*olyole(in catalysis.
R%s$lts a!# Dis$ssi"!
A .gCl2 su**orted // catalyst was
*re*ared using an Ar+%4%5 com*ound ,I-, with
+62, and a ligand ,4- with a single heteroatom,
as the internal modi(ier. $his was the same
material which ga'e us earlier the <81 acti'ity
increase as an e+teral modi(ier. $he catalyst
*re*aration *rocedure has &een descri&ed
elsewhere ,-. $he *olymerization test results
(rom this catalyst were une+*ectedly in(erior to
the control catalyst, *re*ared similarly with di%n%
&utyl *hthalate ,?@2/- as the internal modi(ier.
We then *roceeded to *re*are catalysts with
mi+tures o( ?@2/7,I- at molar ratios o( =070,
!878, "8728, and 80780. $he &est
*olymerization test results were o&tained (rom
the (irst two catalysts, with an acti'ity
im*ro'ement o( u* to 681 o'er the control, and
signi(icant im*ro'ements in e+tracta&les and
*owder &ulk density. We also determined that i(
we reduce the amount o( silane in the
*olymerization test &y a&out "01, we get an
additional acti'ity &oost u* to 201, retaining the
e+tracta&les similar to the control. $he last two
catalysts at "8728 and 80780 ga'e results similar
to the control, in terms o( acti'ity and
stereos*eci(icity, &ut there were *ro&lems with
lower *owder &ulk density.
We then a**lied cross%*olarization with
magic angle s*inning ,C/.AA- solid state
<
C
@.B techni;ue to two o( the (our catalyst
sam*les, =070 and 80780. $he sam*les were
*acked into .AA rotors in dry &o+ under
nitrogen. $he s*ectra o( the =070 had only
*eaks that could &e assigned to 'arious car&ons
o( ?@2/. All maCor @.B *eaks (or ,I- were
com*letely o&scured &y the more intense *eaks
o( ?@2/.
$he 80780 catalyst s*ectrum was similar to
the a&o'e, e+ce*t (or an additional small *eak at
!< **m, &arely distinguisha&le at the &ase o( the
more intense *eak due to car&onyl car&ons o(
?@2/. $he *eak at !< **m could not &e
assigned to any car&on o( *ure ,I-.
$o clearly identi(y the origin o( this
unusually shi(ted
<
C @.B *eak, we attem*ted
to *re*are a *ure D$iCl3
&
,I-E com*le+. We
reacted ,I- with $iCl3 in toluene at ele'ated
tem*eratures at a molar ratio o( 27. A semi
crystalline *roduct was isolated, which
crystallized a(ter se'eral washings and dried
under 'acuum. 5lemental analysis indicated a
D2,I-
&
<$iCl3E stoichiometry.
In the solid state
<
C @.B o( the com*le+,
the !< **m *eak is clearly e'ident, along with
all the other *eaks that could &e assigned to ,I-.
$he !< **m *eack was now assigned to an
aromatic car&on atom directly &onded to $i. $he
(ormation o( the $i%Aryl &ond was also *redicted
&y com*utational calculations. On the &asis o(
analytical, solid state
<
C @.B, IB ,discussed
&elow- and modeling data, we assign the
(ollowing structure to the com*le+F
Com*le+ ,II-
$he )Cl *roduced &y the metallation o( the
*henyl grou* is &eing retained in the structure.
$he Cl (rom each o( the two )Cl molecules is
coordinating with the middle $i, and each ) is
&ridging with another Cl &elonging to an end $i.
$hus we ha'e the creation o( an D)Cl2E moiety,
which has &een demonstrated in se'eral other
crystal structures ,<-.
$he >$IB s*ectrum o( )Cl on ice *articles
at 80
o

G shows a strong D)Cl2E &and at "08
cm
%
and a weak &and at 28 cm
%
attri&uted to
Cl
...
)Cl , a strong &and at 23=8 cm
%
assigned to
)Cl, and a shoulder at 2"80 cm
%
attri&uted to
)Cl solid ,3-.
In the IB s*ectrum o( com*le+ ,II- there are
two weak &ands at 8=6 cm
%
and 86! cm
%

which we assign to the D)Cl2E moiety. $hese
&ands are shi(ted lower &ecause o( the
coordination o( the Cl with $i. Also, they are
two instead o( one &ecause the three atoms
Cl)Cl are *ro&a&ly at an angle and not in a
straight lineH 60
o
to!0
o
angles ha'e &een
o&ser'ed ,<-. $here are also corres*onding
a&sor*tions at 2<672<<" cm
%
and 2"2<726!0
cm
%
.
>urthermore, (our 'ery strong a&sor*tions at
3!, 30, <=!, <"8 cm
%
are assigned to I $i%Cl.
2y com*arison, $iCl3
&
?@2/ com*le+ which has
an octahedral con(iguration around $i,
synthesized &y us, showed ma+ima at 306, 300,
<!<, and <"3 cm
%
,8-. A strong &and o( ,I- at
6!8 cm% characteristic o( the (i'e consecuti'e )
atoms o( the *henyl grou* is not *resent in ,II-.
Instead, a new strong &and a**ears at "22 cm
%

assigned to a (our consecuti'e ) atoms in an
aromatic ring, a su**orting e'idence (or the
metallation o( the *henyl grou*. Other &ands
attri&uted to the heteroatom%car&on &ond, and to
the aromatic rings are also *resent.
In a similar (ashion we reacted 0rCl3 with ,I-
to o&tain a com*le+, which &y
<
C @.B, IB, and
elemental analysis has similar structure to ,II-.
Com*le+ ,II- was reacted with Al5t<, and a
new *roduct ,III- was isolated. $he )Cl reacts
with Al5t< to yield a chlorinated aluminum alkyl
Al5tzCl<%z with release o( ethane. A**arently,
the organometallic *ortion o( ,II- se*arates out,
com*le+ing with the Al ethyl chloride s*ecies
also (ormed &y the $i,IJ- to $i,III- reduction.
$he num&er o( Cl atoms and ethyl grou*s on Al
may 'ary, de*ending on reaction conditions. In
one case the 'alue o( z was calculated to &e 0.<.

Com*le+ ,III-
$he
<
C solid state @.B s*ectrum o( ,III-
shows a large *eak at ca. 8 **m (rom ethyl
grou* car&ons, indicating alkylation on $i and an
ethyl aluminum moiety &eing incor*orated in the
structure. $he *eak assigned to *henyl car&on
&onded to $i is shi(ted (urther to =6 **m. $hese
and other analytical data were used to su**ort the
*ro*osed structure ,III-.
/roduct ,III-, under *olymerizaton conditions
is e+*ected to yield *roduct ,IJ-, &y insertion o(
the ole(in to the $i%*henyl &ond.
,IJ-
?e*ending on the insertion mode ,,2% or 2,%
insertion-, eight stereoisomers, 0 in the case o(
ethylene co*olymerization, are e+*ected to &e
(ormed ,-. 5ach stereoisomer is e+*ected to
ha'e a di((erent im*act on the *olymer *roduced.
Com*le+ ,IJ- &elongs to the class o( multi%site
catalysts.
Catalyst ,IJ- will most likely &e use(ul in
ethylene and other ole(in co%*olymerizations.
$he im*ortant ad'antage o( ,III- o'er other
multi%site catalysts, is the (act that it is acti'ated
with Al alkyls rather than .AO or other non%
coordinating anions, such as *er(luoro&orates.
.i+tures o( ?@2/ with se'en di((erent Ar+%
4%5 com*ounds ha'e &een used at the o*timum
!878 molar ratio to *re*are .gCl2 su**orted //
catalysts. $hese Ar+%4%5 com*ounds 'aried &y
the num&er + ,(rom to 3-, &y the element o(
heteroatom ,5- *resent, and &y di((erent ligand
structures, (used aromatics or otherwise, that
may contain additional heteroatoms, the same or
di((erent (rom ,5-. In all catalyst *re*arations,
we ha'e assumed that the $i com*le+es are &eing
(ormed in situ.
$he control was a similarly *re*ared catalyst
with ?@2/ as the only internal modi(ier. In all
cases the o'erall yield ad'antage (or the catalysts
*re*ared with mi+ed modi(iers was &etween 201
and 681, and de*ended u*on the ligand structure
and the ty*e o( test ,slurry, gas *hase-.

In most cases, reduction o( the silane e+ternal
modi(ier used in the *olymerization test &y "01
increases the yield (urther &y &etween 0%201,
without a((ecting the e+tracta&les.
It is noteworthy that yield and other
ad'antages were o&tained (rom each one o( the
se'en ligands in'estigated. )owe'er, the data
were too limited to discern accurate structure and
*er(ormance relationshi*s.
We ha'e identi(ied o'er 80 ligand structures that
could *otentially yield *roducts similar to ,II-.
C"!l$si"!s
. @o'el orthometallated heteroaryl
com*le+es o( $i, 0r, and other transition
metals (or the stereos*eci(ic
*olymerization o( *ro*ylene and other
al*ha%ole(ins ha'e &een de'elo*ed. $hese
catalysts may &e acti'ated with aluminum
alkyls such as $5A and $I2A.
2. $he com*le+es may &e synthesized in a
one *ot7single ste* reaction, with o(( the
shel(, readily a'aila&le materials.
<. $he com*le+es enhance the *er(ormance
o( e+isting .gCl2 su**orted // catalysts,
and are e+*ected to im*ro'e *olymer
*roduct *ro*erties through their multi%site
catalytic &eha'ior.
3. $hey may &e used in ethylene and other
al*ha%ole(in *olymarizations, either
su**orted on silica, silica7alumina etc, or
unsu**orted in a high tem*erature
solution *rocess.
R%'%r%!%s
. ?. )ustad et al, K.A. /atent !,<62,62 ,20<-.
2. L. @. Coalter et al, K.A. /atent A**lication
2070<082=, and K.A. /atent !,26<,820 ,202-
<. L. Mi et al, K.A. /atent !,303,"!= ,20<-, and
K.A. /atent !,3"0,=3 ,20<-.
3. .. )osaka, K.A. /atent !,326,8<" ,20<-.
8. .. Chang, K.A. /atent !,00<,88! ,20-.
6. M. >uCiwara, K.A. /atent !.2!!,3!! ,202-.
". A. 5arnst, K.A. /atent A**lication
20070!00!< ,200-.
!. G. .atsunaga et al, K.A. /atent ",!!!,3<!
,20-.
=. .. Chang, !,00<,88! ,20-.
0. $. 4einonen et al, K.A. /atent !,26,=8"
,202-.
. G.G. Arzoumanidis et al, K.A. /atent
3,=!!,686 ,==-.
2. M.J. Gissin 9Isos*eci(ic /olymerization o(
Ole(ins with )eterogeneous 0iegler%@atta
Catalysts: A*ringer Jerlag, *. 23!.
<. 2.). Ward et al, Chem. .ater., ==!, 0 ,3-,
**. 02%0!. Also in NN/h3As
O
Cl
%&
)ClNN.
3. L./. ?a'lin et al, @ature, 3", 26= ,2002-
8. G.G. Arzoumanidis et al, 9Catalytic Ole(in
/olymerization: /roceedings o( International
Aym*osium, $okyo, =!=, Gadansha, 4td.