Note: Descriptions are shown in the official language in which they were submitted.
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POLYMERIZABLE COMPOSITIONS COMPRISING ALPHA-OLEFIN
S HYDROCARBON MONOMERS AND METHODS OF USE THEREFOR
Field of the Invention
This invention relates to polymerizable compositions comprising alpha-olefin
hydrocarbon monomers and a method for their pol~".,elizalion, wherein the method10 is tolerant of both oxygen and water. Catalysts for the polymerization include
organometallic complexes of Group VIII metals (CAS version of the Periodic
Table), preferably Pd or Ni. Methods for polymerizing the polymerizable
composition in open air and in the presence of water to provide novel polymers are
described.
Back~round of the lnvention
Non-free radical polymerizations of ethylenically-unsaturated monomers are
well known. Typically, these polymerizations use catalysts instead of initiators to
effect polymerizations. Examples of such catalyzed polymerizations include
20 Ziegler-Natta (ZN) polymerizations of alpha-olefins, ring-opening metathesis
polymerizations (ROMP) of cyclic olefins, group-tl;an~r~r polymerizations (GTP),and cationic and anionic polymerizations of activated olefins such as styrene oracrylate esters. More recently, metallocene catalysts have received considerableattention for polymerization of alpha-olefins. ZN and metallocene catalysts for
25 alpha-olefin polymerizations are susceptible to deactivation by adventitious oxygen
and water, requiring that such deactivating materials be rigorously excluded from all
reagents as well as the reaction vessel.
European Patent Application No. 454231 describes a polyrnerization
catalyst and a method of polymerizing ethylene, other olefins, and alkynes using a
30 polymerization catalyst whose cationic portion has the formula
LM_Rt
wherein M is a Group VIII metal, L is a ligand or ligands stabilizing the Group VIII
metal, and R is H, a hydrocarbyl radical or a substituted hydrocarbyl radical, and a
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substituted tetraphenylborate anion as the counterion. A preferred cationic portion
has the formula
(L')2M--R or ( > M--R
wherein L' is a two-electron donor ligand and L" L" are chelating ligands wherein
each L" is a neutral two-electron donor ligand, and M is nickel or p~llaflium All
olefin polymerizations were conducted with ethylene, were carried out under dry,oxygen-free nitrogen atmospheres and all solvents were thoroughly dried under
nitrogen by distillation from, e.g., sodium/benzophenone. High polymer (M
90,000) was not disclosed.
Johnson et al., (J. Am. Chem. Soc., l99S, 117, 6414-6415 and
supplementary material) describe Pd(II)- and Ni(II)-based catalysts for alpha-olefin
polymerizations wherein the catalysts are, for example, cationic metal methyl
complexes of the general formula
{(ArN=C(R~)C(R')=NAr)M(CH3)(0Et2)}+~ BAr'4}~
15 wherein M is Pd or Ni, Ar' is 3,5-C6H3(CF3)2, Ar is 2,6-C6H3(R') where R' is
isopropyl or methyl; Rl is H, methyl, or the two R' groups taken together are 1,8-
naphthalene-diyl. All polymerizations were carried out in inert atmospheres, andpolymers of ethylene, propene, and l-hexene are reported. The same authors and
S.J. McLain et al. reported that the same catalysts copolymerized ethylene and
20 methyl acrylate (see PMSE Abstracts, Vol. 73, p. 458, Fall 1995, Proceedingc of
the Arnerican Chemical Society, Fall 1995, Chicago, Illinois). A full publication
describing these findings and a catalyst {(ArN=C(R~)C(R')=NAr)M(CH2
CH2CH2C(OR2)(C=O))}+BAr'i are reported by Johnson et al. (J. Am. Chem. Soc.,
1996, 118, 267-268 and supplementary material), wherein R2 can be -CH3, t-butyl,25 or -CH2(CF2)6CF3, and Rl, Ar, and Ar' are as defined above. These findings also
appeared in M. Brookhart, L. K. Johnson, C. M. Killian, S. Mecking, D. J. Tempel,
PolymerPrepri~71s, 1996, 37, 254-255.
These catalysts were plepared in a multi-step sequence shown in Scheme I,
below. The ligand (ArN=C(R')C(R')=NAr) (III) was prepared from 2,6-
30 diisopropylaniline (II) and 1,2-dione O=C(R')C(R')=O (I), optionally in the
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presence of formic acid (H. T. Dieck, M. Svoboda, T. Greiser Z. Naturforsch. 36b,
1981, 823-832.). In a separate procedure, (1,5-cyclooctadiene)PdCl2 (IV) was
reacted with Me4Sn to give (1,5-cyclooctadiene)PdCl (Me) (V) (R. Rulke, J. M.
Ernsting, A. L. Spek, C. . Elsevier, P. W. N. M. van Meeuwen, K. Vrieze Inorg.
Chem., 1993, 32, 5769-5778). The ligand (ArN=C(R~)C(R')--NAr) (III) and (1,5-
cyclooctadiene)PdCI (Me) (V) were then reacted to give neutral organometallic
compound (ArN=C(R')C(R')=NAr)PdCl(Me) (Vl) (described in the previously
cited Johnson et al., J. Am. Chem. Soc., 1995, 117, 6414-6415 and supplementary
material ). This compound was further reacted with MgMe2 to give
(ArN=C(R')C(Rl)=NAr)Pd(Me)2 (VII). In a separate procedure, NaB{3,5-
C6H3(CF3)2}4 (IX) was synthesized by treating {Br-3,5-C6H3(CF3)2} (VIII) with
Mg, and reacting the product with NaBF4 (M. Brookhart, B. Grant, A. F. Volpe,
Jr. Organome~allics 1992, I l, 3929-3922). CAUTION: This preparation ofthis
salt is particularly hazardous in that trifluoromethyl aryl Grignards can explode (E.
I 5 Hauptman, R M. Waymouth, J. W. Ziller J. Am. Chem. Soc., 199~, 1 17, 11586-
11587). Then Na{B(3,5-C6H3(CF3)2)4) (IX) was converted to {H(OEt2)2)+{B(3,5-
C6H3(CF3)2)4}- (X). Finally, {H(OEt2)2)+{B(3,5-C6H3(CF3)2)4)- (X) and
(ArN=C(R')C(RI)=NAr)Pd(Me)2 (VlI) were reacted to give
{(ArN=C(R')C(R')=NAr)M(CH3)(0Et2)}+{B(3,5-C6H3(CF3)2)4)~ (XI).
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SCHEME I
~~ + 2 ~N~2 HC02,H ~/
11 RXN + 2H2O
Pd(COD)CI2 Mc4Sn Pd(COD)Cl(Me) m
IV V
m~v ~ ~) Me2M~ ~_2
Vl vn
CF3
j~ ~) Mg HCI/Et20
Br~ ) NaBF; NaB(C6H3(CF3k)4 ~ (Et2OkH {B(C6H3(CF3)2)4}
CF3
vm IX X
Vll + X ' X ,Pd(Me)(Et20)
R~ B(C6H3(CF3)2)4}
Xl
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In Scheme I, R' is H or methyl, or the two R's taken together are 1,8-
naphthalene-diyl, i.e.,
~'
the ligand made from acenaphthenequinone; and "COD" refers to 1,5-
cyclooctadiene .
U.S. Patent No. 5,296,566 describes certain organometallic catalysts for
ROMP of ring-strained cyclic olefins that are stable towards oxygen and water.
However, these catalysts are ineffective for polymerization of linear alpha-olefin
10 monomers.
Safir et al. (Macromolecules, 199S, 28, 5396-5398) describe bicyclic olefin
polymerizations catalyzed by Pd(II)-alkyl complexes such as, e.g.,
hexafluoroacetylacetonato -~ -(2-acetylbicyclo{2.2.1 }hepta-5-ene), related
dimers, and (bicyclo{2.2.1 }hepta-2,5-diene)PdCI2, wherein the catalysts are
15 reported to be stable to both air and moisture for extended periods, and are
reported to catalyze olefin insertion polymerization of bicyclic olefins such as, e.g,
norbornene. Polymerizations of alpha-olefins, even ethylene (the most reactive of
the alpha-olefins), are not reported.
Japanese Patent Application No. JP 0725932 describes Group VIII
20 catalysts (such as Ni) which polymerize ethylene. U.S. Patent No. 4,724,273
describes the use of nickel catalysts to polymerize alpha-olefins, yielding polymers
with methyl branching points. U.S. Patent No. 5,030,606 describes nickel-
cont~ining catalysts which are useful for producing copolymers of ethylene and
polar or non-polar comonomers.
European Patent Application No. 603,557 describes catalytic compositions
prepared by contacting an organonickel compound with a cyclicazacarbyl
compound which can be used to convert one or more olefins to oligomerization
and/or polymerization products. Only ethylene is exemplified.
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Summarv of the Invention
Briefly, the present invention describes a polymerizable composition
comprising one or more alpha-olefin hydrocarbon monomers, an effective amount
of an organometallic catalyst comprising a Group VIII metal (CAS version of the
5 Periodic Table), preferably Ni or Pd, and a polydentate ligand providing steric bulk
sufficient to permit formation of high polymer, and at least one of water and air.
In another aspect, the invention describes a method of polymerizing a
composition, the composition com~ ing at least one alpha-olefin monomer, as
catalyst an effective amount of the above-mentioned organometallic catalyst
10 comprising a Group VIII metal, preferably Ni or Pd, and at least one of water and
alr.
In a further aspect, the present invention provides an alpha-olefin polymer
comprising a plurality of C3 or larger alpha-olefin units wherein the polymer Mw is
greater than 90,000, preferably greater than 100,000, and the polymer has an
15 average number of branch points less than one per alpha-olefin unit.
In yet another aspect, the present invention provides a mixture comprising
an alpha-olefin polymer comprising at least one of 1) a plurality of C3 or larger
alpha-olefin units wherein the polymer has an average number of branch points less
than one per monomer unit, and 2) a plurality of C2 alpha-olefin units wherein the
20 polymer has an average number of branch points greater than 0.01, preferably
greater than 0.05, per alpha-olefin unit, the mixture further comprising water in an
amount sufficient to form a second phase. Preferably, the polymer Mw is greater
than 90,000, and most preferably greater than 100,000
In still another aspect, the present invention provides crosslinked alpha-
25 olefin polymers. In one embodiment, a method employing high-energy irradiation
of the polymer, preferably by electron beam irradiation, is used. In another
embodiment, a method employing ultraviolet (UV) irradiation is used, preferably
further comprising the addition of UV-activated crosslin~in~ agents.
In another aspect, the present invention provides improved one-part
30 catalysts which are organometallic salts useful for the polymerization of alpha-olefin
monomers in the presence of at least one of water and air.
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In a still further aspect, two-part catalysts comprising a neutral
organometallic compound and a cocatalyst, useful for the polymerization of alpha-
olefins, optionally in the presence of one or both of air and water, and methods of
preparation thereof, are also provided.
S In yet another aspect, the present invention provides an improved method of
preparing an organometallic catalyst wherein a neutral organomet~llic compound is
reacted with a salt of a non-coordin~ting counterion to give an organometallic salt
as catalyst and a halide salt as by-product. Variations of the method involve
different process conditions, to give one-part and two-part catalysts. Differentvariations may be preferred in specific applications.
In this invention:
"alpha-olefin" and "alpha-olefin hydrocarbon" are equivalent and mean a
hydrocarbon containing a double bond in the l-position, more particularly, ethylene
or a l-olefin containing three or more carbon atoms which can be acyclic or cyclic
and preferably is an acyclic alpha-olefin;
"alpha-olefin polymer" means a polymer formed from at least one alpha
olefin monomer which, not considering end groups, contains an average of two
bonds connecting each monomer unit to other monomer units;
"branch point" means a CH unit in the polymer, bonded to three other
carbon atoms, e.g.,
Cl --C----C--
C--C--C-- and C C C C
represent units with one and two branch points, respectively;
"steric bulk" means a size large enough and a location in the ligand sufficient
to physically block access to non-polymerizing sites on the metal;
"alpha-olefin unit" means a group of carbon atoms in a polymer derived by
polymerization from a single alpha-olefin molecule,
- "high polymer" means a polymer having a weight average molecular weight
(Mw) greater than 90,000, preferably greater than 100,000;
"poly" means two or more;
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"organometallic catalyst" means a catalyst comprising a Group VIII metal,
preferably one of Pd and Ni, a bidentate ligand having steric bulk sufficient topermit formation of high polymers, and a metal to R bond, wherein R is H, a
hydrocarbyl radical, or a hydrocarbyl radical substituted by at least one alkyl,5 haloalkyl or aryl group, each group having up to 20 carbon atoms;
"group" means a çhen-ic~l species that allows for substitution or which may
be substituted by conventional substitue~t~ that do not interfere with the desired
product;
"Me" means methyl (CH3-);
"Et" means ethyl (CH~CH2-);
"Bu" means butyl; "t-Bu" means tertiary butyl;
"i-Pr" means isopropyl; and
"gel fraction" means the fraction of polymer that is insoluble in an
appropriate solvent, e.g, toluene, particularly after crosslinking.
Surprisingly, polymerization reactions of the invention proceed in the
presence of air and/or water at useful rat:es and produce in high yields high polymers
that have useful properties. Water may occur naturally in the monomer, especially
in liquid monomer. The polymerization reaction can even be carried out
successfully in systems in which water is present or added in amounts sufficient to
20 forrn a second (aqueous) phase. It is advantageous to be able to elimin~te the costs
and process steps associated with drying and deoxygenating monomers and
solvents. Neither ZN nor metallocene catalysts containing Periodic Groups IIIB,
IVB, or VB metals (CAS version of the Periodic Table) are active in the presenceof oxygen or water. Cocatalysts, such as alkylaluminum compounds,
25 methylaluminoxane, alkyl zinc compounds and the like, are also sensitive to air and
moisture and are not useful under the conditions in this invention and
organometallic catalysts employing these cocatalysts are outside the scope of this
invention.
As noted above, useful polymers are made from the polymerizable
30 compositions described herein. Depending on the process conditions, such as the
amount of air or water present, the amount and type of catalyst, and the monomer
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or monomer(s) selected, polymers having different properties can be produced.
Certain of these polymers may be prefel l ed for specific applications. The polymers
of the invention find use as functional and decorative co~tingc~ as molded or
extruded articles, and as binders.
In one embodiment, a distinct a~ueous phase is present in the polymerizable
composition such as in aqueous emulsion or suspension polymerizations and
provides processing advantages such as reduction or elimin~tion of organic
solvents. Also, it provides a therrnal sink to aid in process temperature control. In
another embodiment, after polymerization, a distinct aqueous phase is present in10 addition to the polymer and this mixture provides processing advantages such as
lower overall viscosity.
Polymerizable compositions comprising two or more monomers and
copolymers produced from such compositions are also within the scope of the
present invention.
Detailed Description of Preferred Embodiments of the Invention
The present invention describes a polymerizable composition comprising an
alpha-olefin hydrocarbon monomer, an effective amount of an organometallic
catalyst comprising a Group VIII metal (CAS version of the Periodic Table),
20 preferably Ni or Pd, and a polydentate ligand having steric bulk sufficient to perrnit
formation of high polymer, and at least one of water and air (oxygen).
Alpha-olefin hydrocarbon monomers useful in the invention include
substituted and unsubstituted, inclLl~ing acyclic, branched, and cyclic alpha-olefins,
wherein substituents on the olefin do not interfere with the polymerization process.
25 Such optional substituents include carboxylic acid and ester groups. Alpha-olefins
plefelled for polymerizations ofthe invention can have from 2 to about 30 carbonatoms, and include acyclic alpha-olefins such as ethylene, propene, l-butene, 1-pentene, I-hexene, I-heptene, I-octene, I-decene, I-dodecene, I-tetradecene, 1-
hexadecene, 1-octadecene, I-eicosene, and the like, and cyclic alpha-olefins such as
30 cyclopentene, and combinations thereof. Most preferably, alpha-olefins include
propene, I-butene, I-hexene, I-octene, and other alpha-olefins up to about C20. In
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some embodiments, liquid monomers are preferred, and higher boiling alpha-olefins,
e.g, 1-octene to about 1-hex~lecene~ are particularly plefe,led.
More than one monomer may be present in the polymerizable composition,
and copolymers of two or more di~rerenl monomers are within the scope of this
5 invention. Copolymers may be random or blocky (block copolymers), depending
on polymerization kinetics and processes. Useful comonomers can include other
alpha-olefins, alkyl acrylates and methacrylates, and acrylic and meth~crylic acids
and salts thereof.
Organometallic catalysts useful in the invention comprise metals of Periodic
Group VIII, ligands providing steric bulk sufficient to permit formation of highpolymers, and a metal to R bond, wherein R is H, a hydrocarbyl radical, or a
hydrocarbyl radical substituted by at least one of alkyl, haloalkyl or aryl groups.
Periodic Group VIII metals include Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt, and
preferred metals are Co, Ni and Pd. Ni and Pd are especially preferred, and Pd is
most preferred. Ligands (L) can be selected so that, when they are coordinated to
the metal atom, they are of sufficient size so as to block steric access to certain
coordination sites on the metal atom. Examples include ArN=C(R')C(R')=NAr,
wherein Ar is 2,6-C6H3(R3)2, where each R' independently can be H or methyl or
the two R' groups taken together can be 1,8-naphthalene-diyl, and each R3
independently can be methyl, ethyl, isopropyl, or tert-butyl. Without wishing to be
bound by theory, it is believed that blocking certain sites will reduce or elimin~e
processes which result in displacement of the polymer chain from the metal, which
prematurely terminates polymerization and results in lower polymer molecular
weights. Thus, steric bulk in the ligand permits the formation of high polymer.
Preferred catalysts comprise ligands that are chelating. Chel~ting means that
a ligand molecule contains two or more atoms or groups of atoms that are able toform coordinate links to a central metal atom. Preferred atoms or groups of atoms
are two-electron donors, preferably containing nitrogen, more preferably cot-~inil-g
an imine
( C--N--)
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I I
group. Most preferably a chelating ligand comprises two imine groups. Imine
groups bearing a substituted or unsubstituted group on the nitrogen are prerel~ ed,
more preferably such groups are polysubstituted aryl, and most preferably they are
2,6-disubstituted aryl. Substit~ltçnt~ on the aryl ring include alkyl, haloalkyl, and
S aryl, preferably alkyl, more preÇ~,~bly methyl or isopropyl, and most pre~l~bly
isopropyl. Catalysts also comprise an atom or group R, defined below, which
preferably is H or methyl, most preferably methyl.
Organometallic catalysts useful in the invention can be one-part or two-part.
One-part catalysts are organometallic salts of a Group VIIl metal and a polydentate
10 ligand having steric bulk sufficient to permit formation of high polymer, and an
anion selected from the group consisting of B(C6F5)4-, PF6-, SbF6-, AsF6-, BF4-,B{3,S-C6H~(CF3)3}~., (R,SO2)2CH-, (R,SO2)3C-, (RrSO2)2N, and RfSO3-, wherein
Rf is as defined below, which, when added to monomer, can immediately begin to
form polymer, such that no additional reagents or further reactions are necessary to
1 S generate an active polymerization catalyst. Such catalysts are advantageous in
certain processes, particularly when it is desired that a catalyst is to be added to the
reaction mixture immediately before polymerization is to begin. For example, such
catalysts can be useful in batch reactions used to prepare polymer. One-part
catalysts can be isolated and are essentially pure compounds. One-part catalysts are
20 preferably cationic complexes, and further comprise non-coordinating counterions.
Preparation of one-part Group VIII metal complexes useful as catalysts in
polymerizable compositions of the invention have been described in the previously-
mentioned European Patent Application No. 4S4,23 1, and the article by Johnson et
al. (J. Am. Chem. Soc., 1995, 117, 6414-641S), wherein these catalysts were
2S disclosed to be useful in inert atmospheres. The catalysts were characterized as
complexes having a cationic portion of the formula
LM-R+
wherein M is a Group VIII metal, L is a two-electron donor ligand or ligands, asdefined above, stabilizing the Group VIII metal, and R is H, a hydrocarbyl radical or
30 a substituted hydrocarbyl radical, wherein the substituting groups can be alkyl (1 to
10 carbon atoms), aryl (S to 20 carbon atoms), or halogen substituted alkyl. In
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European Patent Application No. 454,231, M is exemplified as cobalt and a
substituted tetraphenylborate anion is described as the counterion. Plefe"ed in the
reference is tetraarylborate with (CF3) substituents and B{3,5-C6H3(CF3)2}4-.is
exemplified A pl efel l ed cationic portion has the forrnula
(L )2M-R+
wherein the two L~ groups are joined through chemical bonds and each Ll is a two-
electron donor ligand as defined above, and M and R are as previously dçfined
Johnson et al. (J. Am. Chem. Soc., 1995, 117, 6414-6415) also describe
catalysts comprising nickel or p~ d jllrn and ligand groups chosen to provide steric
10 bulk sufficient to permit forrnation of high polymer. In particular, prefe, led Pd(II)-
and Ni(II)-based catalysts for olefin polymerizations are cationic metal methyl
complexes of the general formula
{(ArN=C(R')C(R')=NAr)M(CH3)(0Et2)} B{3,5-C6H3(CF3)2}4-
wherein M is Pd or Ni, Ar is 2,6-C6H3(R3)2 where R3 is isopropyl or methyl, and
15 each Rl independently is H or methyl, or the two Rl groups taken together are 1,8-
naphthalene-diyl .
A prer~"ed catalyst is
{ ((2~6-c6H3(i-pr)2)N=c(cH3)c(cH3)=N(2~6-c6H3(i-pr)2))pd(cH3)(Et2o) } {B(3, 5-
C6H3(CF3)2)43
Also useful in polymerizable compositions of the invention are compounds
of the formula
{(ArN=C(R')C(Rl)=NAr)Pd(CH2 CH2CH2CO2R2)}+BAr'4~
wherein R2 can be -CH3, t-butyl, or -CH2(CF2)6CF3 as reported by Johnson et al.
(J. Am. Chem. Soc., 1996, 1 18, 267-268 and supplementary material) to be useful25 in inert atmospheres.
Now, for the first time, it is recognized that alternative counterions can
provide improved catalysts. Thus, the present invention provides new compositions
of matter useful as one-part catalysts. One prere" ~d counterion is B(C6F5)4-, which
is safer to prepare than B(3,5-C6H3(CF3)2)4-, as judged by the number of reported
30 explosions, and is commercially available from Boulder Scientific Company, Mead,
CO, and provides better control over polymer molecular weight. Multiple reports
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have appeared concerning the hazards associated with the preparation of
trifluoromethyl-substituted tetraarylborate compounds, including the explosion of
intermediate aryl m~gnecium compounds (see I.C. Appleby, Chernistry and
IndlJstry, 1971, 120, and E. Hauptman, R. M. Waymouth, J. W. Ziller, J. Amer.
Chem. Soc., 199~, 1 17, 11586), and the explosive decomposition of solid lithiumsalt Li(C6H4(CF3)2) (M. Brookhart, B. Grant, A. F. Volpe, Jr., Organome~allics,
1992, 11, 1320). The counterion B(C6F5)4 is particularly prel~,~ed in
polymerizable compositions comprising a second (aqueous) phase. Other anions
useful as the anionic portion of the catalysts of the present invention may be
10 generally classified as fluorinated (including highly fluorinated and perfluorinated)
alkyl- or arylsulfonyl-containing compounds, as represented by Formulas XIIa
through XIId:
(Rf SO2)2CH (Rf SO2)3C (Rr SO2)2N RrSO3
(XIIa) (XIIb) (XIIc) (XIId)
wherein each R, is independently selected from the group consisting of
highly fluorinated or perfluorinated alkyl or fluorinated aryl radicals. Compounds of
Formulas XIIa, XIIb and XIIc may also be cyclic, when a combination of any two
20 Rf groups are linked to form a bridge.
The R~alkyl chains may contain from 1-20 carbon atoms, with 1-12 carbon
atoms preferred. The Rf alkyl chains may be straight, branched, or cyclic and
preferably are straight. Heteroatoms or radicals such as divalent non-peroxidic
oxygen, trivalent nitrogen or hexavalent sulfur may interrupt the skeletal chain.
25 When Rf is or contains a cyclic structure, such structure preferably has 5 or 6 ring
members, 1 or 2 of which can be heteroatoms. The alkyl radical Rf is also free of
ethylenic or other carbon-carbon unsaturation: e.g., it is a saturated aliphatic,
cycloaliphatic or heterocyclic radical. By "highly fluorinated" is meant that the
degree of fluorination on the chain is sufficient to provide the chain with properties
30 similar to those of a perfluorinated chain. More particularly, a highly fluorinated
alkyl group will have more than half the total number of hydrogen atoms on the
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chain replaced with fluorine atoms. Although hydrogen atoms may remain on the
chain, it is preferred that all hydrogen atoms be replaced with fluorine to form a
perfluoroalkyl group, and that any hydrogen atoms beyond the at least half
replaced with fluorine that are not replaced with fluorine be replaced with bromine
5 and/or chlorine. It is more pl C:Ç~I I ed that at least two out of three hydrogens on the
alkyl group be replaced with fluorine, still more pr~r~ d that at least three of four
hydrogen atoms be replaced with fluorine and most pr~re" ed that all hydrogen
atoms be replaced with fluorine to form a perfluorinated alkyl group.
The fluorinated aryl radicals of Formulas XIIa through XIId may contain
10 from 6 to 22 ring carbon atoms, preferably 6 ring carbon atoms, where at least one,
and preferably at least two, ring carbon atoms of each aryl radical is substituted
with a fluorine atom or a highly fluorinated or perfluorinated alkyl radical as defined
above, e.g, CF3.
Examples of anions useful in the practice of the present invention include:
(C2FsS02)2N, (C4FgS02)2N, (CgF~7S02)3C, (CF3S02)3C, (CF3S02)2N,
(C4FgS02)~C, (CF~S02)2(C4FgS02)C, (CF3S02)(C4FgS02)N,
{(CF3)2NC2F4S02}2N, (CF3)2NC2F4S02C (S02CF3)2, (3,5-bis(CF3)C6H3)S02N
S02CF3, C6FsS02C (S02CF3)2, C6FsS02N S02CF3, CF3S03, C8FI7SO3,
F2C~ C---SO2CF3
~ /~
O ~N--C2F4SO2N SO2CF3 0 F N--C2F4SO2C (SO2CF3)2
F2C_SO2
F2C so2
wherein F in the ring means the ring carbon atoms are perfluorinated, and the like.
More preferred anions are those described by Formulas XIIb and XIIc wherein Rf is
a perfluoroalkyl radical having 1-4 carbon atoms.
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Anions ofthis type, and representative syntheses, are described in, e.g, U.S.
PatentNos 4,505,997, 5,021,308, 4,387,222, 5,072,040, 5,162,177, and
5,273,840, incorporated herein by leference, and in Turowsky and Seppelt, Inorg
Chem.,1988, 27, 2135-2137. {C(S02CF3)3}-, {N(SO2CF3)2} and {N(SO2C2F5)2}-
are pr~r~l-ed, and {N(SO2CF3)2}- and ~N(SO2C2F5)2}- are particularly pref~.. ed.
Such counterions may be prer~.,ed with certain metals and ligands, or in some
processes. Other useful fluorinated non-coold~l~aling counterions include PF6,
SbF6-, AsF6-, and BF4-.
In the preparation of one-part catalysts of the invention, diethyl ether can be
useful but it is preferable to avoid its use because it can be dangerous to store and
handle due to its extreme flammability and tendency to form explosive peroxides.Alternative useful ethers are organic compounds containing one ether-type oxygenatom and include tetrahydrofuran and methyl t-butyl ether. Methyl t-butyl ether is
particularly preferred.
Thus, the present invention provides improved one-part catalysts useful for
the polymerization of alpha-olefin monomers. These catalysts are designed with the
advantages of improved counterions and ethers, and are new compositions of
matter. Preferred compositions can be of the formula
{(ArN=C(R')C(R')=NAr)Pd(Me)(ether)}+ Q~
wherein Ar and R' are as previously defined and ether can be
tetrahydrofuran, diethyl ether, or methyl t-butyl ether, and
Q can be selected from B(C6F5)4, anions as shown in Formulas XIIa through
XIId, PF6, SbF6, AsF6, and BF4. Particularly preferred are compounds wherein
ether is methyl t-butyl ether and Q is selected from B(C6Fs)4 and anions as shown
in Formulas XIIa through XIId.
Examples of prefelled novel one-part catalysts include:
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl
ether) } + { B(C6Fs)4 } ~,
{ ((2~6-c6H3(i-pr)2)N=c(cH3)c(cH3)=N(2~6-c6H3(i-pr)2))
Pd(CH3)(Et20)}+{B(C6F5)4}-,
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{ ((2, 6-c6H3(i-pr)2)N=c(cH3)c(cH3)=N(2~6-c6H3(i-pr)2))pd(cH3)
(tetrahydrofuran)}+{B(C6F5)4}',
{ ((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N (2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl
ether)} {N(S02CF3)2},
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-
(Et20)} {N(S02CF3)2},
{ ((2, 6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-
(tetrahydrofuran) } {N(S02CF3)2 },
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl
ether) } + { C (S02CF3)3 }~,
{ ((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-
(Et2O) } + { C(SO2CF3)3 } -,
{ ((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-
(tetrahydrofuran) } + { C(S02CF3)3 ) ~,
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl
ether)} {N(S02C2Fs)2},
{ ((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-
(Et20)} {N(S02C2Fs)2},
{ ((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-
(tetrahydrofilran)} {N(S02C2F5)2},
{((2,6-C6H3(Me)2)N=C(CH3)C(CH3)=N(2,6-C6H3(Me)2))Pd(CH3)(Me t-butyl
ether) } + { B(C6Fs)4 } ~,
{ ((2,6-C6H3(Me)2)N=C(CH3)C(CH3)=N(2,6-C6H3(Me)2))Pd(CH3)-
(Et20)} {B(C6Fs)4},
{((2,6-C6H3(Me)2)N=C(CH3)C(CH3)=N(2,6-C6H3(Me)2))Pd(CH3)-
(tetrahydrofuran)}+{B(C6F5)4}~,
{((2,6-C6H3(Me)2)N=C(CH3)C(CH3)=N(2,6-C6H3(Me)2))Pd(CH3)(Me t-butyl
ether) } + {N(S02CF3)2 } ~,
{ ((2~6-c6H3(Mek)N=c(cH3)c(cH3)=N(2~6-c6H3(Me)2))pd(cH3)
(Et20)} {N(S02CF3)2},
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((2,6-C6H3(Me)2)N=C(CH3)C(CH3)=N(2,6-
C6H3(Me)2))Pd(CH3)(tetrahydroiùran)} {N(S02CF3)2},
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl
ether) } + { N(S02CF3)(S02C4Fg) },
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-
(Et20) } + {N(S02CF3)(S02C4Fs) },
{ ((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-
(tetrahydrofuran)} {N(S02CF3)(S02C4Fg)~-,
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl
I 0 ether))+{BF4}~,
{ ((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Et20) }+{BF4}-,
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl
ether) } { CH(S02CF3)2 },
{ ((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-
(Et20)} {CH(S02CF3)2},
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl
ether)} {PF6},
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Et20)} {PF6},
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl
ether)} {SbF6}-,
{ ((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Et20)} { SbF6}-,
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl
ether) } + { S03CF3 }~,
{ ((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N~2,6-C6H3(i-Pr)2))Pd(CH3)-
(Et20) } + { S03CF3 } ~,
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N~2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl
ether)}+{ S03CJFg},
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-
(Et20)}+{ S03C4Fg}-,
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl
ether)}+{NS02(CF2)2S02}~, and
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{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-
Pr)2))Pd(CH3)(Et20)} {NS02(CF2)2S02}-.
Two-part catalysts comprise two reagents, a neutral organometallic
compound and a cocatalyst salt, that react upon mixing optionally in the presence of
5 monomer to yield an active catalyst. Two-part catalysts are particularly
advantageous when partial mixing of monomer and an organometallic compound is
desired (such as to achieve good solubility or suspension) but when it is also desired
to initiate polymerization at a later time, for inst~nce, when the second reagent is
added. Process advantages resulting from the ability to control the time at which
10 polymerization begins are significant. Two-part catalysts may also allow for the in
situ generation of active catalytic compounds which cannot be isolated, and may
also be preferred for those situations where the added time and expense of isolating
a one-part catalyst are not warranted.
Two-part catalysts preferably comprise a neutral organometallic Pd or Ni
15 compound which includes a ligand or ligands as previously defined, a moiety Rwhich is H, hydrocarbyl radical, or substituted hydrocarbyl radical, and a halogen
atom (preferably chlorine), and a cocatalyst. Preferred neutral compounds can be of
the general formula
{ ArN=C(R')C(R')=NAr}M(R)X
20 where Ar, R and R' are as defined above, and X represents a halogen atom,
preferably chlorine or bromine, most preferably chlorine.
Examples of p~efe,.ed neutral compounds include:
(2,6-dimethylphenyl)N=C(Me)C(Me)=N(2,6-dimethylphenyl)Pd(Me)CI,
(2,6-diisopropylphenyl)N=C(Me)C(Me)=N(2,6-diisopropylphenyl)Pd(Me)CI,
25 (2,6-dimethylphenyl)N=C(H)C(H)=N(2,6-dimethylphenyl)Pd(Me)CI,
(2,6-diisopropylphenyl)N=C(H)C(H)=N(2,6-diisopropylphenyl)Pd(Me)CI,
(2,6-dimethylphenyl)N=(1 ,2-acenaphthylene-diyl)=N(2,6-
dimethylphenyl)Pd(Me)CI, wherein 1,2-acenaphthylene-diyl is represented
by the structure
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~C C"
~'
(2,6-diisopropylphenyl)N=( 1 ,2-acenaphthylene-diyl)=N(2,6-
diisopropylphenyl)Pd(Me)Cl,
(2,6-dimethylphenyl)N=C(Me)C(Me)=N(2,6-dimethylphenyl)Ni(Me)CI,
5 (2,6-diisopropylphenyl)N=C(Me)C(Me)=N(2,6-diisopropylphenyl)Ni(Me)Cl,
(2,6-dimethylphenyl)N=C(H)C(H)=N(2,6-dimethylphenyl)Ni(Me)Cl,
(2,6-diisopropylphenyl)N=C(H)C(H)=N(2,6-diisopropylphenyl)Ni(Me)Cl,
(2,6-dimethylphenyl)N=( l ,2-acenaphthylene-diyl)=N(2,6-dimethylphenyl)Ni(Me)Cl,and
(2,6-diisopropylphenyl)N=(1,2-acenaphthylene-diyl)=N(2,6-
diisopropylphenyl)Ni(Me)Cl .
Especially preferred neutral compounds include
(2,6-dimethylphenyl)N=C(Me)C(Me)=N(2,6-dimethylphenyl)Pd(Me)Cl and
(2,6-diisopropylphenyl)N=C(Me)C(Me)=N(2,6-diisopropylphenyl)Pd(Me)Cl.
Useful cocatalyst salts are of the general formula
A+ Q-
wherein A is selected from silver, thallium, and metals of Periodic Group IA, and Q
is selected from B(3,5-C6H3(CF3)2)4, B(C6F5)4, anions as shown in Formulas XIIa
through XIId, PF6, SbF6, AsF6, and BF4, and solvates and hydrates thereof. For
20 some applications, silver salts are prefelled and can have the formulae
Ag{B(C6Fs)4}(arene)p and Ag{B(C6H3(CF3)2)4}(arene)p wherein arene can be an
aromatic hydrocarbon group having 6 to 18 carbon atoms that can be substituted by
up to 6 alkyl or aryl groups each having up to 12 carbon atoms, preferably arenecan be benzene, toluene, ortho-, meta-, or para-xylene, and mesitylene, and p can be
25 an integer 1, 2, or 3. However, in some applications the less expensive alkali metal
salts (Periodic Group IA) are prefe" ed. Particular counterions may be p~ ere" ed
under specific reaction conditions. For example, in two-part systems comprising a
second aqueous phase, B(C6F5)4 is prere"ed.
Examples of preferred cocatalyst salts include:
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Ag+{B(C6F5)4}~(toluene)~, Ag {B(C6F5)4}~(xylene)3, Ag {B(3,S-C6H3(CF3)2)4}
(toluene), Li+{B(C6F5)4}-, Na {B(3,5-ChH3(CF3)2)4}-, Li {N(S02CF3)2},
Li+{B(C6F5)4}-(Et20)2, Lit{N(SO2CF3)(SO2C4Fg)}-, Li+{N(SO2C2F5)2}-, Li
+{N(SO2C2F5)2}~(hydrate), Li {N(S02C4Fg)2}, Li { NS02(CF2)2S02},
Ag+{C(SO2CF3)~}-, Li {C(S02CF3)3}-, Ag {CH(S02CF3)2}-, Li {CH(S02CF3)2},
Ag+{BF4}-, Na {BF4}-, Na {PF6}-, Ag {PF6}-, Na {SbF6}-, Ag ~SbF6}-,
Na+{AsF6}~, Agt{AsF6}~, Ag+{SO3CF3}-, Na+{SO3CF3}~, Na+{SO3C4Fg}~, and
Ag+ { SO3C4Fg} ~.
One- and two-part catalysts can be present in the invention mixture in the
10 range of 0 0001 to about 3 weight percent, preferably 0.001 to I weight percent.
The present invention provides an improved method of preparation of
organometallic catalyst. In this method, a neutral organometallic compound is
reacted with a salt of a non-coordinating counterion preferably comprising fluorine
(F) to give an organometallic catalyst and a halide salt as by-product. Preferably,
15 there is at least one mole of A+Q- per mole of neutral organometallic compound. In
some cases, excess A+Q- may be pre~, . ed since A+Q- may function as a surfactant
in the reaction mixture.
Variations of the method involve different process conditions, to give one-
part and two-part catalysts. Different variations may be preferred in specific
20 applications. However, in each of the variations, the improved method provides
significant advantages over the method of Johnson et al. As described therein,
referring to Scheme I, the neutral organometallic compound
{(Ar)N=C(R')C(R')=N(Ar)}PdCl(CH3) (Compound V) is treated with Me2Mg, an
air- and water-sensitive material which is hazardous to handle. This step results in
25 {(Ar)N=C(R')C(R')=N(Ar)}Pd(CH3)2 (Compound VI) in poor yields of 25 to 34
percent. In a separate step, the salt of a non-coordinating counterion Na+{B(3,5-
C6H3(CF3)2)4}- (Compound IX) is converted to (Et20)2H {B(3,5-C6H3(CF3)2)4}
(Compound X) in a procedure requiring the use of corrosive materials. Compounds
VII and X are then reacted, under carefully controlled conditions, to give one-part
30 catalyst {{(Ar)N=C(R')C(R')=N(Ar)}Pd(CH3)(Et20)} {B(3,5-C6H3(CF3)2)4}
(Compound XI). In contrast, the method of this invention uses one step instead of
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three, requires only simple and inexpensive process conditions, and provides
catalyst in good yield, typically greater than 75 percent.
The first variation of the method provides a one-part catalyst by reacting the
silver salt of a non-coor~in~ting counterion Ag+Q, wherein Q is as defined above,
5 or solvate thereof with a neutral organometallic compound of the formula
{ (Ar)N=C(RI)C(R')=N(Ar) }Pd(CH3)(halogen)
wherein Ar and R~ are as previously described, and halogen is Cl, Br, or I,
preferably Cl or Br, most p~ ably Cl. The reaction is conducted in an ether
solvent, or mixture of solvents containing an ether at or near room temperature (20~
l0 to 25~C). The one-part catalyst is isolated from the reaction mixture by removal of
solvent. Optionally, filtration to remove and recover AgCI by-product and further
purification by methods such as solvent extraction (for example, dissolution of
catalyst in an organic solvent such as CH2CI2, optional filtration, washing of this
solution with a portion of water, and removal of organic solvent) or recryst~11i7~tion
15 are apparent to those skilled in the art and are within the scope of this invention.
One-part Pd catalysts have been prepared according to this method with various
counterions, including {N(SO2C4F9)2}-, ~CH(S02CF3)2}-, (S03CF3)-, (SbF6)-,
(BF4)-, and (PF6)-. This method is particularly preferred for counterions wherein the
corresponding silver salt is readily available. It is also a useful method for rapid
20 synthesis when water-sensitive counterions are used.
In the second variation of the method, an alkali metal salt of a non-
coorflin~ting anion is dissolved in water and treated with a molar equivalent ofAgNO~ at or near room temperature (20~ to 25~C). Within minutes, a reaction
occurs. While not wishing to be bound by theory, the reaction product is believed
25 to be the silver salt of the non-coordinating anion, stabilized by one or more water
(solvent) molecules. This aqueous solution is then mixed with an organic ether
solution of {(Ar)N=C(R')C(R')=N(Ar)}Pd(CH3)(halogen) wherein halogen is as
defined above, and reaction occurs rapidly, essçnti~lly as fast as reagents in this
two-phase system can mix across phase boundaries. The organic layer is separated30 from solid AgCI (which may be recovered and recycled) and the aqueous layer, and
removal of solvent produces clean one-part Pd catalyst in good yield. This method
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is preferred because it provides for rapid synthesis of one-part catalyst in good
yield, and does not require the nreparation and isolation of the silver salt of a non-
coordin~tin~ counterion. This procedure has been used to prepare one-part Pd
catalysts cont~ininE the following counterions: {C(S02CF3)3}-, {B(C6H5)4}-,
{B{3,5-C6H3(CF3)2}4}, (SO3C4F9), N(S02CF3)2, N(SO2C2F5)2, and
NS02(CF2)2S02 .
A third variation of the method involves reaction of an alkali metal salt of a
non-coordinating counterion with {(Ar)N=C(R')C(R')=N(Ar)}Pd(CH3)(halide).
With this variation there is no need to use expensive silver compounds, but longer
10 reaction times are required. This method is pl erel I ed because it provides a safe,
easy and inexpensive synthesis of one-part catalyst. This variation has been used
with Li{B(C6F5)4}.
A fourth variation of the method provides two-part catalysts. In this
variation, a neutral organometallic compound as defined in the third variation is
15 used in combination with a cocatalyst comprising a silver salt of a non-coor-lin~ting
counterion. The advantages of two-part catalysts have been previously described.A fifth variation of this method provides two-part catalysts useful in two-
phase systems. This variation of a two-part catalyst comprises a neutral
organometallic compound as described above and a cocatalyst of a Group IA metal
20 in a two phase system. Such a catalyst system may be preferred because the second
(preferably aqueous) phase provides a heat sink which moderates polymerization
exotherms. This variation also avoids the expense of silver-cont~ining reagents. In
the presence of an aqueous phase, these two-part catalysts rapidly initiate
polymerization. Adjuvants optionally useful in any of the methods of catalyst
25 synthesis of the invention include solvents such as methylene chloride, and the like.
Additives, adjuvants and fillers as are known in the art can be added to the
polymerizable composition of the invention, providing they do not interfere with the
intended polymerization process or adversely affect the chemical and physical
pl Opt;l lies of the resultant polymers. Additives, adjuvants and fillers can include,
30 but are not limited to, glass or ceramic microspheres or microbubbles, pigments,
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dyes, or other polymers. Adjuvants may be present in the composition in the range
of 0.1 to 90 weight percent.
Surprisingly, it has been demonstrated that relatively acidic organic
compounds such as, e.g, phenols and carboxylic acids, can be present in the
polymerizable compositions of the invention without deleterious effect on the
subsequent polymerization reaction. Thus, polyme~ization of l-octene in the
presence of Irganox lOIOTM, a hindered phenol-type stabilizer commercially
available from Ciba-Geigy Corp., has been demonstrated to proceed to completion
in the same time period and with the same yield as polymerization of l-octene in the
10 absence of the stabilizer. Hindered phenol-type stabilizers useful in the invention
are well known to those skilled in the art, and are described in Jesse Edenbaum,Plastics Additives and Modifiers Handbook, Van Nostrand Reinhold, New York
( 1992) pp. 193-207. It is advantageous to add hindered phenol-type stabilizers to
polymers to improve polymer performance and aging. It is particularly
15 advantageous to add the stabilizer to liquid monomer. Mixing is easier in monomer
than in viscous polymer, and certain processes or product constructions may not
allow for addition of stabilizer at a later stage in the process. Other acidic additives,
such as carboxylic acids, may be advantageous to modify process conditions.
Other stabilizers containing phosphorus, for example, as phosphine or
20 phosphite, are also known as additives in polymers. These secondary antioxidants
halt polymerization. They can therefore be useful for stopping polymerization as,
for example, when it is desired to prevent formation of very viscous solutions, and
they may also provide other benefits, for example, lighter color, but they are not
usefully added to monomer prior to polymerization. Sulfur containing compounds
25 such as thiols are also useful in halting polymerization, as are strong oxidants such
as bleach (sodium hypochlorite).
Monomers or comonomers cont~ining organic functional groups, such as
carboxylic acids, and carboxylic acid salts and carboxylic esters, can also be useful
in the invention. Such monomers may be useful to modify polymer properties.
When water is present in major amounts above the solubility limit ofthe
organic phase, it forms a second (aqueous) phase which can provide process
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advantages such as lower overall viscosity, higher polymer molecular weight or
yield, temperature control, reduction or elimination of organic solvents, and isprere-led in certain applications. The aqueous phase may be contin~ous,
discontinuous, or cocontinuous with the organic phase.
Polymerizable compositions may further compl ise surfAct~nts Surf~ct~nts
are prere..ed when a second ;~u~o~.c phase is present. Ionic surf~ct~ntc are
pl efel I ed. Suitable surfact~nt~ include sodium and ammonium sulfonates. Specific
examples of suitable surfactants include sodium heptadecyl sulfate, sodium lauryl
sulfate, and ammonium lauryl sulfate. Certain surfactants contain groups which
10 reduce catalyst activity, and these should be avoided in the practice of thisinvention. In particular, polyether groups and halides, such as are found in
polyether sulfonate or tetraalkylammonium halide surfactants~ should be avoided.Surfactants can be present in the composition in the range of about 0.01 to 5 weight
percent.
The present invention also is directed toward a method of polymerizing a
composition comprising at least one alpha-olefin monomer, an effective amount ofan organometallic complex of a Group VIII metal, p~ eretably Ni or Pd, as a
catalyst, and at least one of water and air.
Polymerizations of the invention have been demonstrated to take place both
in open air and in the presence of water. In a typical open-air polymerization, the
above-mentioned one- or two-part palladium catalyst is mixed with the alpha-olefin
monomer (for example, l-octene) in a container and polymerization is allowed to
proceed. Optionally, organic solvents may be used to dissolve or disperse catalysts
and may be present in amounts from about 0.5 to 99 percent by weight.
For two-part systems, several variations in polymerizations of the invention
have been demonstrated: in method (A), the neutral organometallic compound and
cocatalyst salt can be mixed together and added to the monomer; in method (B), the
monomer can be mixed with neutral organometallic compound and the cocatalyst
salt subsequently added to that mixture; in method (C), two separate monomer
streams, one containing neutral organometallic compound and one contAi~ing
cocatalyst salt can be mixed. Such process variability allows for the control of the
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onset of polymerization. Other process advantages such as solubilizing the
organometallic compound or cocatalyst salt may also be achieved. Advantages of
further variations in the order of mixing are apparent to those skilled in the art, and
are within the scope of this invention.
Polymerizations can be conducted at various temperatures. Prere.~bly, the
reaction te-"~ lre is -78~ to +35~ C, more prer~ bly -40~ to +25~ C, and most
preferably -10~ to +20~ C. Te."peldlures above about 40~ C may deactivate the
catalyst, and good thermal control may be pl ef~,-ed since the polymerization ofalpha-olefin monomers is exothermic. It may be particularly advantageous to
employ a sec~nd aqueous phase as a heat sink to aid in the control of reaction
temperature.
Polymerizations can be conducted at pressures greater than atmospheric,
particularly in cases where one or more of the monomers is a gas. However, to
avoid the expense of pressurized reaction vessels, liquid monomers may be
pl ere~ed
In another embodiment, catalyst and monomer can be mixed and coated
onto a substrate, and the mixture allowed to polymerize without protection from the
ambient atmosphere. Particularly p-e~lled are monomers with boiling points
greater than about 1 00~C., such as I -octene and higher alpha-olefin monomers.
Variations in temperature, concentration and the like may be employed. See:
European Patent Application No. 694,575.
Water can be present in the polymerizable composition and during
pol~ on in the range of 0.001 up to 99 weight percent ofthe total
composition.
Water may be present in minor amounts when care is not taken to dry the
monomer or optional organic solvents. Preferably it is present in naturally-
occurring amc~unts, in monomers as supplied and handled in air. For example,
water is soluble in l-hexene to the extent of approximately 480 parts per million at
room temperature, and such concentration is within the scope of the present
30 invention, since water at that concentration is known to deactivate ZN and
metallocene catalysts. Monomers are often supplied with varying amounts of
CA 02236817 1998-0~-0~
~VO 97/17380 PCT/US96/05227
- 26 -
water, from 0.001 weight percent up to the maximum solubility of water in the
monomer, depending on te,l")el~ re, specific monomer, ambient humidity, storage
conditions, and the like. Optional solvents similarly contain varying amounts ofwater. Oxygen can be present in an amount of 0.001 to about 2 weight percent or
more of the total composition. Monomers and solvents may contain varying
amounts of oxygen from the atmosphere depending on tenlpel alure~ specific
monomer or solvent, storage conditions, and the like. Oxygen can also be presentin atmospheric amounts in environments surrounding the polymerizable mixture,
such as headspace in a reaction vessel. It is advantageous to avoid the expense and
1~ process steps of drying and deoxygenating monomer and solvent.
In other catalyzed alpha-olefin polymerizations, such as Ziegler-Natta and
metallocene catalyzed polymerizations, it is necessary to remove water and oxygen
from monomers, especially liquid monomers, by procedures including, but not
limited to, sparging with inert gas such as nitrogen or argon, treating with molecular
15 sieves, and scrubbing with highly water-reactive reagents such as sodium, alkyl-
substituted aluminum or zinc compounds, and the like, then m~int~ining rigorously
dry and oxygen-free conditions during addition of catalyst and polymerization ofmonomer. Such purified monomers and methods of purification and polymerization
are outside the scope of this invention.
2~ Surprisingly, polymerization of the present invention monomers can take
place when water is present in sufficient amount to form a second aqueous phase.Surfactants can be added to the aqueous phase prior to or after addition of a
mixture of monomer and catalyst, or in any other useful sequence. Depending on
process conditions, such as stirring rate, amount of surfactant, and other additives,
2~ polymer particles of different properties, inclu~ing particle size, may be formed.
Agglomeration of polymer may occur, again depending on variables such as
monomer, reaction temperature, and additives, and is desirable in some processes(for example, where polymer is to be separated from the water) and undesirable in
others (for example, where polymer is to be coated from the aqueous mixture).
The present invention provides alpha-olefin polymers comprising a plurality
of C~ or larger alpha-olefin units wherein the polymer Mw is greater than 90,000,
CA 02236817 1998-0=,-0=,
W O 97/17380 PCTAUS96/05227
-27-
preferably greater than 100,000, and the polymer has an average number of branchpoints less than one per alpha-olefin unit. Without wishing to be bound by theory
and recognizing that state-of-the-art analytical techniques are inadequate to
deterrnine all structural features, particularly minor ones, it is believed that polymers
5 obtained using catalysts of the invention consist ess~nti~lly of two types of repeating
units: { -CH2-CHR4- }x and {-(CH2)n-}y wherein n is the number of carbon atoms in
the alpha-olefin monomer used to make the polymer and R4 is {CH3(CH2)(n 3)- }.
The number of branched units {-CH2-CHR4-} is less than the total number of
monomer units in the polymer, that is x has a value from 0.01 to 0.99, preferably
0.20 to 0.95, more preferably 0.40 to 0.90, and (x + y) has a value of 0.90 to 1.00.
The polymer structure will vary as the monomer or monomers used in the
polymerizable composition vary. For example, a polymer made from l-octene, that
is, n is 8, has a structure consisting essentially of {-CH2-CH(n-hexyl)-}x and
{-(CH2)8-}y, wherein x is in the range 0.45 to 0.70, and (x + y) is in the range 0.90
1~ to 0.98. In another example, a polymer made from l-hexene, that is, n is 6, has a
structure consisting essensi~lly of {-CH2-CH(n-butyl)-}x and {-(CH2)6-}y, wherein
x is in the range 0.50 to 0.7S, and (x + y) is in the range 0.90 to 0.98. Those
skilled in the art will recognize that variations in polymerizable composition, such as
the kind and amount of optional solvent or aqueous phase or the catalyst selected
20 and polymerization method can affect the polymer structure. Polymer structure can affect polymer properties, such as crystallinity or modulus.
For many applications, a high polymer (Mw over 90,000, preferably over
100,000, up to about 10,000,000, preferably up to about 2,000,000) is highly
desirable, resulting in improved product performance. High polymers can be
25 obtained by, for instance, an appropriate choice of catalyst-to-monomer ratio. In
addition, high polymers can be obtained by continuing the polymerization reaction
essenti~lly to completion, that is, consumption of substantially all available
monomer.
In some applications, a crosslinked polymer provides better product
30 performance. Crosslinking may be accomplished during the poly.n~.i,a~ion reaction
by copolymerization with a polyfunctional monomer, or may be effected by
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WO 97/17380 PCT/US96/05227
- 28 -
chemical reactions brought about by thermal means or actinic radiation, including
high energy sources such as electron beams, gamma radiation, or ultraviolet
irradiation, occurring after polymerization. Cro~.clin'-~d polymers are within the
scope of this invention.
Polyolefins prepared using organometallic catalysts described above,
especially those comprising Ni or Pd, can be crosslin~ed via irradiation with
electron beams at dosages preferably in the range of 20 MRad or less, more
preferably 10 MRad or less. It is known that polyethylene can be cros~lin~.~d toproduce a useful material upon irradiation without significant polyrner degradation
whereas polypropylene degrades much faster than it crosslinks, and polyolefins
prepared via traditional Ziegler-Natta polymerizations are only modestly affected by
irradiation. However, treatment of polyolefins of the present invention with
electron beams produces crosslinked polymers as indicated by the presence of a
polymer gel fraction. Advantageously, the crosslinked polyolefins are free of added
chemical crosslinking agents that might otherwise impair the chemical or physical
properties of the polymer or be disadvantageous in subsequent use, for example,
due to color or leaching. Further, electron-beam crosslinking can be carried outafter fabrication or other processing of the polyolefin by, e.g., extrusion, solvent
casting, coating, molding, and the like, to give crosslinked shaped articles such as
fibers, tubes, blocks, profiles, films, and the like. Other useful high-energy sources
are known, and are within the scope of the present invention.
Polymers of the present invention can also be crosslinked by ultraviolet
irradiation. Preferably, and without wishing to be bound by theory, additives that
absorb ultraviolet light and subsequently react to give radicals by homolytic
cleavage and/or hydrogen abstraction are mixed with the polymer prior to
irradiation. Typical additives include trihalomethyl-substituted s-triazines (such as
2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine), aryl alkyl ketones(such as acetophenone, benzoin ethers, and ketals of benzil), and diaryl ketones(such as benzophenone and anthraquinone). Other useful additives will be apparent
30 to those skilled in the art and are within the scope of this invention. CrosslinL-ing by
ultraviolet irradiation is plefelled in certain processes and product constructions,
CA 02236817 1998-05-05
PCT/US96/05227 ; ~ , PA ~Ei~lT~ ",L'-~
Minnesota Mining & Mfg. Co. , . EU~GPEA~ PAI E~T AT-~,~
Our Ref: B 1686 PCT - 29 ~ eser~str. 4 - ~ ,C -c~n~
wherein it is necessal y to process an uncrosslinked polymer, as in a solution or an
extrusion process, prior to cro~clinl~ing
Alpha-olefin polymers of the present invention are useful as molded or
extruded articles, as functional or decorative co~ingS~ and as binders.
s ~l~s~ h~ p~gc~ ~qQ 1~ >
Objects and advantages of this invention are further illustrated by the
following examples, but the particular materials and amounts thereof recited in
these examples, as well as other conditions and details, should not be construed to
unduly limit this invention.
EXAMPLES
For all trials described as occurring in air, reagents were used as supplied
and were handled in air, with no attempt to reduce or remove oxygen or water in
reagents, solvents or glassware. Solvents used were typical reagent grade, not
anhydrous grade. "Ambient te.,,~.,.atlJre~ is approxi"~d~ely 23~ C. Throughout
these examples, the shorthand notation C~ is used to refer to an alpha-olefin
containing z carbons. Thus, C2 is ethylene, C3 iS propylene, C6 is l-hexene, C8 is 1-
octene, and so on. All chemicals can be obtained from Aldrich Chemical Company
(Milwaukee, Wisconsin) unless otherwise noted.
Molecular weights were determined by gel-permeation chromatography,
rererenced to polystyrene standards.
Preparation of Catalysts
Throughout these e~mp'~, the material referred to as Pd-A was {(2,6-
diisopropylphenyl)N=C(Me)-C(Me)=N(2,6-diisopropylphenyl)~PdMeCI, prcpar~d
according to known procedures:
A. Synthesis of ligand (2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-
Prh)
The ligand was preparct according to the procedure des~, ;bct in H. t.
Dieclc, M. Svoboda, T. Greiser Z. N~u~.ror~ . 36b, 823-832. A mixture of 625
mL methanol, 41.7 g 2,3-butanedione, 171.75 g 2,6-diisopropylaniline and 6.75 g
A~,IEND'0 SH~
CA 02236817 1998-05-05
'ZqA. '
S~c ~ s o9~ ~hc prc~ c~ bc~l
vc cl~ by ~c ~ i~5:
1. A polymerizable composition comprising:
a) an alpha-olefin hydrocarbon l,.ono.,.~-,
b) one or both of water and air, and
c) an effective amount of an organol.l.,lallic catalyst colnl.. ;sl~lg a
Group V III metal and a pol~d~,n~le ligand having steric bulk
sufficient to pennit formation of high polymer.
2. The polymerizable composition according to ~ I wherein said
10 compos;lion further CGIllpliSeS a copolymerizable monomer.
~ >
3. The polymerizable composition according to ~1 wherein said
alpha-olefin compl;ses one or more of l-octene, I-pentene, I-hexene, and l-decene, 1-
dodecene, I-tetradecene, I-he~decenç, I-oct~decene, l-eicosene, and cyclopentene.
4. The polymerizable composition according to ~ I further comprising
one or both of a stabilizer and a surfactant.
5. The polymerizable composition according to ~4 wherein said
20 stabilizer is a hindcred phenol-type st;~bi~ r
6. The polymerizable composition according to ~1 I wherein air is
present.
7. The polymerizable composition accord;ng to,~ I wherein water is
present in the range of 0.001 to 99 weight percent.
8. The pol~ e. i~ble composition according to ~ I wherein said
catalyst is a one-part catalyst comprising an organometallic salt or a two-part catalyst
comprising a neutral organometallic compound and a cocatalyst.
> AMEND.D
,, . CA 02236817 1998-05-05
9. The polyrnenzable col..pos;tion according to ~t 8 wherein said one-
part catalyst co".l,l;ses a cationic portion having the formula LM-R wherein M is a
Group V~II metal, L is a two electto.~ donor ligand or ligands, as defined above,
stabilizing the Group VIII metal, and R is H, a hydrocarbyl radical or a substituted
5 hydrocarbyl radical wherein the s~bstit~ting groups can be alkyl having 1 to 10 carbon
atoms, aryl having 5 to 20 carbon atoms, or halogen substituted alkyl.
10. The pol~...c~ i~able co.l.pos;lion according to hai~ 8 wherein said one-
part catalyst comprises an anionic counterion sele~!led from the group con,;.l;~g of
(RfSO2)2C~, (R,SO2hC~ SO2)2~, RrSO3~, B(C6F,)~-, PF6-, SbF6-, AsF6-, BF4-,
and B(3,5-C6H3(CF3k)~-, wherein each Rf is independently sel~cle~ from the groupconsisting of highly fluorinated or perfluorinated alkyl groups having I to 20 carbon
atoms, or fluorinated aryl groups having 6 to 22 ring carbon atoms.
C ~
11. The polymerizable composition according to ~ 8 wherein said one-
part catalyst has the forrnula
{ (ArN=C(R')C(R')=NAr)Pd(Me)(ether) } ~ Q
wherein
Ar is 2,6-C6H3(R3)2 wherein R3 is isopropyl or methyl, and each R'
independently is H or methyl, or the two Rl groups taken together are 1,8-
naphth~lene-diyl,
ether is tetrahydrofuran or methyl t-butyl ether, Me is methyl, and
Q is sclec~cd from B(C6F5)4, PF6, SbF6, AsF6, BF4, B(3,5-C6H3(CF3h)4,
(Rr SO2)2CH, (Rf SO2)3C, (R~ SO2)2N, and RrSO3, wherein Rf is as previously
define~
12. The polymerizable con~position according to ~ 8 wherein said one-
part catalyst comprises {(ArN=C(R~)C(RI)=NAr)M(CH3)(0Et2)}~B(C6F5); wherein
M = Ni or Pd, Et = ethyl, Ar is 2,6-C6H3(R3)2 where each R3 independently is
30 isopropyl or methyl, and each Rl independently is H or methyl, or the two R~ groups
taken together are 1,8-naphthalene-diyl.
AMcNDr-D S~IEET
. CA 02236817 1998-05-05
,~a '
13. The pol~"le,izable co,.~pos;~;on according to ~ 8 wherein the
neutral o~g.mo",e~allic compound of said two-part catalyst has the forrnula
{ArN=C(Rl)C(RI)=NAr}M(R)X
5 wherein Ar, Rl, M, and R are as previously define~ and X is a halogen atom.
14. The pol~"le~;~ble coml-osi~ion according to ~ 8 wherein said
cocatalyst of said two-part catalyst has the formula
A~Q-
f- 10 wherein A is a metal selected ~om the group cons;alh~g of silver, and Group ~A metals,
and Q is selected from the group con~is~i, g of B(C6H3(CF3)2)4, B(C6F~)4, PF6, SbF6,
AsF6, BF4, (Rr SO2)2CH, (Rr SO2)3C, (Rf SO2)2N, and R,SO3, wherein R~ is as
previously dçfined
15. The polymerizable composition accor.ling to ~1 13 wherein R is
methyl.
16. The polymerizable composition according to ~1 wherein said
Group VIII metal of said catalyst is one or both of Pd and Ni.
17. A compound having a formula sçlected from the group consisting of
Ag{B(C6~5)4}(arene)p and Ag{B(C6H3(CF3)2)~}(arene)p where;n arene is an aromatich~.lrocarl.on group having 6 to 18 carbon atoms that can be substituted by up to 6
alkyl or aryl groups each having up to 12 carbon atoms.
18. The compound according to ~ 17 wherein arene is sçlected from ~he
group consisting of benzene, tcl~sçne, ortho-, meta-, or para-xylene, and mesitylene,
andp= 1,2,or3.
Ar~ J S~
CA 022 36817 1998 - 05 - 05
~ , , ~
,~f ' ' ' . ' ~
19. The compound according to ,61~f 17 having the formula
Ag~{B(C6F~)"} (toluene)3, Ag {B(C6F5),~ (xylene)3, and Ag {B(3,5-C6H3(CF3)2)~}
(toluene).
20. The polyrnerized compocition acco~in~, to ~ 1.
21. The pol~ e.iLed composition accoldin~ to ~ 20 which co~llplises a
plurality of C3 or higher alpha-olefin units wllelc.ll the polymer M~,, is greater than
90,000 and the polymer has an average number of branch points less than one per
alpha-olefin unit.
22. The pol~",e.i,ct composition according to ,6~120 which co."p,ises
one or more of 1) a plurality of C3 or larger alpha-olefin units wherein the polymer has
an average number of branch points less than one per monomer unit, and 2) a plurality
of C2 alpha-olefin units wherein the polymer has an average number of branch points
greater than 0.01, and water in an amount sufflcient to form a second phase.
23. The pol~",e.;zed composition according to ~id 20 which comprises a
crosslin~ed alpha-olefin polymer.
~_~
24. The pol~",e~ ized composition according to 61~ 23 which has been
cro~sl;nl~ed by one or more of ele~.on beam irradiation, ultraviolet irradiation, and
optionally W-activated crosCl~nl ;nB agents.
25. The polyme~ izet composition according to ,~ 22 wherein said
polymer M~ is greater than 90,000.
26. A co..lpo~ilion of matter comprising a compound having the formula
{(ArN=C(R')C(R')=NAr)Pd(Me)(ether)}~ Q XIII
30 wherein
AN~NO~:~ S~
r - CA 02236817 1998-05-05
-5~- ' . . '
Ar is 2,6-C6H3(R3)2 wherein each R3 independently is isopropyl or
methyl, and each R~ independently is H or methyl, or the two Rl groups taken together
are 1,8-napthalene-diyl,
ether is diethyl ether, tetrahydrofuran, diethyl ether, or methyl t-butyl ether, and
Q is selected from the group co~lc;sl;ng of B(C6F5)~, PF6, SbF6, AsF6, BF~,
(R~ S02)2CH, (Rf S02~3C, (Rf S02)2N, and RfS03, ~I.e~in Rf is as previously define~1,
and X is a halogen atom.
27. The CQ~ o~ ;on according to ~ 26 wherein compounds of formula
. ~ 10 X~II are sPIect~ from the group consisting of
{((2,6-C6H3(i-Pr)2)N=;C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl
ether) } ~ {B(C6F5)~
((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))-
Pd(CH3)(Et20) } ~ ~ B(C6Fs)~ ) ',
1 S { ((2,6-C6H3(i-Prh)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl
ether)} {N(S02CF3)2}',
{ ((2,6-GH3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)
(Et20)} {N(S02CF3)2}',
{((2,6-GH3(i-Prh)N=C(CH3)C(CH3)--N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl
ether)}~{N(S02C2F5)2}', and
{ ((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-
(Et2O)} {N(SO2C2F5)2}.
28. A process comprising the step of
2S ad~ n8 an alpha-olefin hydrocarbon monomer, optionally a
copolymerizable .,.onG...cr, with an ol~anolllclallic catalyst Colll~l;S;A8 a Group VIII
metal and a polydentate ligand having steric bulk sufficient to permit formation of high
polymer, in the prcsence of one or both of air and water to provide a poly...e~ i ed
alpha-olefin.
.~ r ~ t Er
, . CA 02236817 1998-05-05
2~
,~
>
29. The process according to ~ 28 further comprising the step of
crosclinking the resulting polymer.
30. The process according to ~ 29 wherein said crosclin~ing step is
5 effected by one or more of elecl, on beam irradiation, ultraviolet irradiation, and
optionally W-activated c~ossl;n~;ng agents.
31. The process accordin~ to ~ 28 wherein said catalyst is a one-part
catalyst col.lp..s;ng an org~no..,ct~llic salt or a two-part catalyst cor..p.ising a neutral
10 o,~,ano.~ c con~po~nd and a cocatalyst
32. The process according to ~ 2B wherein said alpha-olefin monomer
is l-octene, I-pentene, l-hexene, I-decene, I-tetradecene, 1-11eY~deC
octadecene, I-eicosene, and cyclopentene.
33. The process according to ~28 wherein said admixture further
comprises one or both of a stabilizer and a surfactant.
34. The process according to ~ 28 wherein said water is present in
20 sufficient quantity to provide a second phase.
3 5. A process for prepa~ ing a one-part or two-part organomet~llic catalyst
comprising the step of admixing a neutral organometallic compound of the formula
{(Ar)N=C(R')C(R')=N(Ar)~Pd(CH3)(halogen)
25 wherein Ar and Rl are as previously defined, and a salt of a non-coordin~tingcounterion of the formula A Q wherein A and Q are as previously define~l
36. The process according to ~135 wherein said admixture further
comprises one or more of AgNO3, an alpha-olefin hydrocarbon ,nGno..,cr, diethyl
30 ether, tetrahydrofuran, methyl t-butyl ether, water, and air.
AM~ 5
CA 02236817 1998-05-05
,Z~ " ;
~-->
~ 37. A process according to ~ 3 5 wherein A is silver.
c_~
38. A process acco~ding to ~t 35 wherein A is a Group IA metal, and
A~03, water and one or more of diethyl ether, tetrahydrofuran and methyl t-butyl5 ether are present.
C ~
39. A process accor.iing to ~id 36 wherein A is a Group IA metal and
one of diethyl ether, tetrahydrofuran and methyl t-butyl ether are present.
C--~
,~ 10 40. A process according to ~ 3 5 wherein A is a Group IA metal and
water is present in an amount suffi~ient to form a second phase.
A~,~N~EO S~,cET
CA 02236817 1998-0~-0~
WO 97/17380 PCT/US96/05227
- 30 -
formic acid was prepared in air, then stirred under nitrogen atmosphere at ambient
temperature for approximately 18 hr. A yellow preçipit~te formed, and was
collected by filtration. The precipitate was recryst~lli7ed from hot ethanol to yield
152.6 gm of {2,6-C6H3(iPr)2}N=C(CH3)C(CH3)=N{2,6-C6H3(i-Pr)2}. This ligand
can be handled and stored in air.
B . Synthesis of (1,5-cyclooctadiene)Pd(Me)CI
The compound was prepared according to the procedure described in R.
Rulke, J. M. Ernsting, A. L. Spek, C. . Elsevier, P. W. N. M van Meeuwen, K.
10 Vrieze/~70rg. Chem., 1993, 32, 5769-5778. All procedures were conducted in a
dry nitrogen atmosphere. The bright yellow solid (1,5-cyclooctadiene)PdCI2,
49.97 g, was placed in 1 L of dry, deoxygenated CH2C12. While stirring, 37.46 g
Me4Sn was added, and the reaction was stirred at ambient temperature for a total of
about 4 days. Black solids (presumably Pd metal) formed, and were removed
15 occasionally during this time by filtration through a pad of Fuller's Earth (filter aid).
When the reaction solution was a pale yellow, it was filtered once more, and solvent
was removed. There was obtained 63.94 g white (l,S-cyclooctadiene)Pd(Me)CI.
This compound is preferably handled in an inert atmosphere.
C. Synthesis of { { 2,6-C6H3(i-Pr)2}N=C(CH3)C(CH3)=N{2,6-C6H3(i-
Pr)2) }Pd(CH3)Cl.
This neutral organometallic compound was prepared according to the
procedure described in L. K.Johnson, C. M. Killian, M Brookhart J. Am. Chem.
Soc., 1995, 117, 6414-6415 and supplementary material. ln an inert atmosphere
25 (nitrogen), 31.64 g (1,5-cyclooctadiene)Pd(Me)CI (synthesis B, above) was placed
in 375 mL of dry deoxygenated diethyl ether. The (1,5-cyclooctadiene)Pd(Me)CI
was not completely dissolved. To this mixture was added 48.31 g {2,6-C6H3(i-
Pr)2}N=C(CH3)C(CH3)=N{2,6-C6H3(i-Pr)2} (synthesis A, above). An orange
precipitate soon formed. The reaction mixture was stirred for about 18 hr, after30 which44.11 g {{2,6-C6H3(i-Pr)2}N=C(CH3)C(CH3)=N{2,6-C6H3(i-
CA 02236817 1998-0~-0~
WO 97/17380 PCTAJS96/05227
- 31 -
Pr)2} }Pd(CH3)CI was collected by filtration. This compound can be handled and
stored in air.
Example 1. Ag(toluene)3B(C6Fs)4~ referred to as Ag-A
Ag(toluene)3B(C6F5)4 was prepared as follows, and is referred to as Ag-A
throughout these examples. Under a nitrogen atmosphere, using dry, oxygen-free
solvents, a solution of 200 mL hexane, 50 mL diethyl ether, and 17.29 g BrC6F5
was cooled to -78~C. Thirty mL of 2.5 M n-BuLi in hexane was added all at once
with stirring. The reaction was stirred for 30 minutes, during which time an orange
precipitate formed. (CAUTION! If it is necessary to discontinue the reaction at
this point and deactivate reagents, it is reported that the reaction of LiC6F5 with
water can result in an explosion; see E. Kinsella et al., Chemis~ry in Bri~ain, 1971,
7, 457. In the practice ofthis invention, however, water is not added at this time.)
Then 17.5 mL of BCI3 (1.0 M in hexane) was added dropwise. The reaction was
allowed to slowly warm to room temperature, and allowed to stir for about 60
hours. The reaction mixture was filtered and solvent removed to give white, solid
Li{B(C6F5)4}(Et20)2. Thirteen g ofthis product were placed in 250 mL CH2C12
and 60 mL toluene and filtered. AgBF4 (3.14 g dissolved in 10.4 mL toluene) was
added dropwise, and the reaction was allowed to stir for 30 minutes. The mixturewas filtered again, and solvent removed from the filtrate under vacuum to give
white to pink solid Ag-A. Spectroscopic data confirrned the structure. This
compound was only stable as the toluene solvate, so care had to be taken not to use
high temperatures or prolonged drying times.
Also prepared was Ag+~B(3,5-C6H3(CF3)2)4}~(toluene). The compound
Na+tB(3,5-C6H3(CF3)2)4}- was prepared as described in M. Brookhart, B. Grant,
A.F. Volpe, Jr., Organome~allics 1992, l 1, 3929-3922. To remove associated
water (two molecules of water per Na+{13(3,5-C6H3(CF3)2)4}~) a solution of 0.92 g
Na+{B(3,5-C6H3(CF3)2)4}~ in 20 mL toluene was stirred with 5 g 4A molecular
sieves for 20 hours. The solution was filtered and to the filtrate was added with
stirringasolutionofO.19gAgBF4in 5 mLtoluene. After 15 minlltesagranular
pl eci~ ate had formed, which was collected on a filter and, while still damp,
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WO 97/17380 PCT/US96/05227
- 32 -
extracted with 20 mL dichloromethane. The extract was clarified by filtration
through CeliteTM Filter Agent, and then dried under vacuum. Upon sufficient drying
there was obtained 0.64 g of white powder. Analytical data confirmed the structure
as Ag+{B(3,5-C6H3(CF3)2)4}-(toluene).
Example 2. Polymerization of Alpha-Olefin Monomer in Air
This example illustrates the poly~ izalion of 1-octene (C8) in air.
Catalyst was prepared from 121 mg Pd-A and 190 mg Ag-A in 10.14 g
tetrahydrofuran. For Sample 2-A (comparative), a 1.4 g portion ofthe catalyst
solution was mixed with 4.70 g of dry, oxygen-free C8 in inert atmosphere. For
Sample 2-B, 0.75 g of catalyst solution was mixed with 4.8 g C8 in air. For Sample
2-C, 1.5 g of catalyst solution was placed in a vial, and solvent was removed. The
resulting solids were mixed with 5.0 g C8 in air. Samples 2-A and 2-B became
viscous within 15 minutes, forming polymer at similar rates. Sample 2-C became
viscous and hot (due to the polymerization exotherm) within ten minutes.
Comparison of Samples 2-A and 2-B showed that polymerization was occurring at
comparable rates in air and inert atmosphere; note that 2-B contained less catalyst
than 2-A. Sample 2-C showed a 100 percent solids (no solvent) formulation, whichpolymerized at a faster rate.
Sample 2-B, Polymer Analyses: Mw 9.15 x 104, Mn 6.05 x 104.
Sample 2-C, Polymer Analyses: Mw 1.60 x ]o5, Mn 3.71 x 104.
Example ~. Polymerization of Alpha-Olefin Monomer in Air
This example illustrates the polymerization of propylene (C3) in air. The
monomer is a gas at ambient temperature and pressure, so the polymerization was
conducted in a high pressure reactor.
Catalyst was prepared from 260 mg Pd-A and 441 mg Ag-A in 6.49 g
diethyl ether. Ether was removed, and the resulting solids were mixed with 26 g
CH2CI2 in air. The catalyst solution was placed in the reactor, which was then
cooled to below -24~C, evacuated (so as to maximize the amount of C3 that could
be charged to the reactor) and filled with 150 g C3. The reactor was shaken and
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allowed to warm at room temperature over a period of about four hours, then leftfor an additional 20 hours. Excess C3 was vented, and 30 g of polymer was
recovered from the reactor.
Sample 3, Polymer Analyses: Mw S.49 x 10S, Mn 1.54 x 10
s
Example 4. Polymerization in the Presence of an Aqueous Phase
This example illustrates a polymerizable composition comprising alpha-
olefin monomer, catalysts, and water in an amount suffirient to form a second,
aqueous phase.
Catalyst was prepared from 84 mg Pd-A and 132 mg Ag-A in 5 mL diethyl
ether. Ether was removed, and the resulting solids mixed with 3.66 g CH2C12 in air.
271 g deionized water, 121 g l-octene and 1.32 g sodium heptadecyl sulfate
(Tergitol 7TM, Union Carbide, New York, New York) were placed in a flask, and
stirred with a magnetic stir bar. A milky mixture resulted. The catalyst solution
15 was added as the mixture was stirred. Polymer could be observed within five
minutes (by adding a small aliquot of the reaction mixture to methanol, which
dissolved water and C8, but from which polymer plecipiL~ted), and over the next 36
minutes, the temperature of the mixture rose from 23 to 25~C due to the
polymerization exotherm. Soon after, polymer (designated Sample 4) began to
20 collect on glass surfaces in the reaction vessel. The reaction was stopped at 41
minutes, and the large agglomerates of polymer which had formed were collected
by filtration, washed with methanol, and dried in vacuum. Yield: 12.4 g.
Sample 4, Polymer Analyses: Mw 1.27 x 105, Mn 7.16 x 1 o4.
Similar trials were conducted with comparable amounts of water and C8, but
25 using a blender (high shear stirring) or shaking to form the two-phase mixture
Polymer again formed, but did not agglomerate, instead remaining as an
organic/aqueous foam occupying about half of the volume of the reaction mixture,with a mostly aqueous phase occupying the other half.
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Example 5. Polymerization in the Presence of Various Additives, and
Employing Variations in Method
Polymerizations were generally performed as described in the previous
examples. In Samples 5-A, 5-B, and 5-C (Table 1), Pd-A and Ag-A were mixed in
5 diethyl ether, ether was removed, solvent (CH2CI2 unless otherwise indicated) was
used to dissolve the resl-ltin~ solids in air, and this solution was mixed with
monomer and other additives, as indicated. Samples 5-D, 5-E, and 5-I employed
one part catalyst Pd-B, dissolved in CH2CI2 and added to monomer. Sample 5-F
also employed a one-part catalyst dissolved in CH2CI2 except that a second,
10 aqueous phase, was present.
Samples 5-G and 5-H were prepared in a manner similar to 5-D, using a
one-part catalyst and, instead of solvent, vigorous mixing, with phosphite additives
added afler polymerization had occurred. A temperature "r.t." indicates room
temperature (about 23~C).
Table 1
Pd-A, Pd-B, Ag-A, Monomer rxntemp
Sample mg mg mg Solvent (g) ~C. Other
5-A 11 0 18 1.33 g C8, 4.67 r.t.
5B 11 0 18 1.33 g Cg, 4.52 r.t.Irganox
1010,
42 mg
5-C 198 0 358 6.53 g C6, 176 r.t.
5-D 0 500 0 100g Cg, 100 0
S-E 0 500 0 100g C6, 100 0
5-F 0 250 0 2.5 g C6, 50 10H2O, 150
g Tergitol
7, 1.00g
5-G 0 5 0 0g Cl0, 5.0 r.t.P(OMe)3,
0.4g
5-H 0 8 0 0 g C,0, 5.0 r.t.W618F*
0.2g
5-I 0 100 0 1.47 g Cg, 39 r.t.acetic
acid, 3 g
* W618F is Weston 618F (distearylpenterythritol diphosphite)
Observations were made as follows:
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Sample 5-B contained Irganox IOIOTM (Ciba Geigy Corp., Ardsley, NY), a
hindered-phenol-type stabilizer throughout the polymerization. This sample was
compared to 5-A, and no significant differences in polymerization rate were
observed. Polymer yields at about 2 days were 62% for 5-A and 63% for 5-B.
Sample 5-C, Polymer Analyses: Mw 1.04 x 105, Mn 4.23 x 104.
Sample 5-D, Polymer Analyses: Mw 3.27 x 105, Mn 1.76 x 105.
Sample 5-E, Polymer Analyses: Mw 2.37 x 105, Mn 1.50 x 104.
NMR analyses of Samples 5-D and 5-E were con~lucted. Integration of the
'H spectra showed only 69 and 54%, respectively, of the number of CH3 groups
10 that would be expected if there were one CH3 group per monomer unit in the
polymer.
High polymer was formed in Samples 5-C, 5-D, and 5-E. Mw was not
obtained for Samples 5-A and 5-B.
For Sample 5-F, C6 and Tergitol 7 surfactant (sodium heptadecyl sulfate,
15 Union Carbide) were mixed, catalyst was added to this, and then water was
immediately added. Weight yield of polymer was 31% at I hour 35 minutes
reaction time. Mw was not determined.
In Sample 5-G, P(OMe)3 was added after 1.5 hours of polymerization. The
yellow reaction mixture became clear and colorless, and no further polymerization
20 occurred. In Sample 5-H, distearylpenterythritol diphosphite (Weston 618FTM, GE
Specialty Chemicals, Morgantown, WV) was added after 20 minutes
polymerization. Dissolution of this phosphite was slower than in 5-G, but a nearly
colorless solution was formed and polymerization was halted. Mw was not
determined. In sample 5-I, acetic acid was present throughout the polymerization.
Sample 5-I, Polymer Analyses: Mw 2.23 x 105, Mn I.19 x 105.
Example 6. Two-Part Catalyst.
This example illustrates one method of preparing a two-part catalyst. In this
variation, a neutral organometallic compound was used in combination with a
30 cocatalyst comprising a silver salt of a non-coordinating counterion.
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In multiple runs, two-part catalysts were prepared by weighing equimolar
amounts of Pd-A and Ag-A into a container and adding a solvent, typically an ether
such as diethyl ether or THF. This was pe~ ~o- Illed either under inert atmosphere to
prevent adsorption of water by the silver salt (which might result in inaccuracies in
weighing), or in air. Within mimltes, the color of the mixture changed, and a
precipitate (presumably AgCI) formed. The solution could be h~nrlled in air and
added to monomer at this point, or ether or THF solvent (which affect
polymerization rates) could be substantially removed to yield a yellow-brown solid
which could be suspended in monomer or used in a different solvent. Variations in
l 0 order of addition, stoichiometry, amounts and kinds of solvent, atmosphere (e.g.,
pure oxygen or air of high or low humidity) and the like are within the scope of this
invention. ln particular, it may be desired to mix Pd-A and Ag-A after dissolution
in the monomer, or after cooling, or to add each reagent to different portions or
different phases of a polymerizable composition. In particular, two-part catalysts
may be pl ~fe, I ed to control the onset of polymerization.
Example 7. Preparation and Isolation of One-Part Catalyst
In this example, a one-part catalyst was prepared by reacting the silver salt
of a non-coordinating counterion with a neutral organometallic compound.
One part catalyst Pd-B was prepared from equimolar amounts of Pd-A and
Ag-A, which were mixed in diethyl ether in dry, oxygen-free conditions. Filtration
and removal of solvent from the filtrate yielded a small amount of red-orange
catalytically active material. However, the ether-insoluble solids when extracted
with CH2C12 gave a larger yield of yellow-orange solids, of greater catalyst activity
and presumably greater purity (free of excess ether and silver chloride), and this
fraction was used and is referred to as Pd-B throughout these examples.
Example 8. Preparation and Isolation of One-Part Catalyst
A solution of 12.44 g LiN(SO2CF3)2 (HQI l5TM, commercially available
from 3M, St. Paul, MN) and 7.36 g AgNO3 in 350 mL deionized water was stirred
with a solution of 22.13 g Pd-A in 350 rnL methyl t-butyl ether. A color change
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was evident within minutes. The ether layer was separated from the water and
solids that formed, and washed with a second portion of water, then taken to
dryness in vacuo to produce 30.79 g {(2,6-diisopropylphenyl)N=C(Me)-
C(Me)=N(2,6-diisopropylphenyl)PdMe(methyl t-butyl ether)} {N(SO2CF3)2},
5 86 % of theoretical yield. NMR spectroscopy confirmed the identity of this
compound.
Similarly, Pd catalysts co~ -g the following counterions were prepared:
{C(SO2CF3)3}-, {B(C6Hs)4}~, {B{3,5-C6H3(CF3)2}4}-, (SO3C4Fs), {N(SO2C2Fs)2},
and ~NSO2(CF2)2S02} .
10This example shows that a neutral organometallic catalyst can be prepared
without the necessity of isolating an intermediate silver salt of the counterion.
Example 9. Preparation and Isolation of One-Part Catalyst
This trial was conducted in dry solvent under an inert atmosphere. A
15solution of 0.214 g Pd-A and 0.304 g Li{B(C6F5)4}(Et2O)2 (Example 1) in 10 mL
previously-dried diethyl ether was stirred under a nitrogen atmosphere for one
week, then filtered to produce a red-orange solution. Removal of solvent from the
filtrate under vacuum yielded 0.365 g of {(2,6-diisopropylphenyl)N=C(Me)-
C(Me)=N(2,6-diisopropylphenyl)PdMe(diethyl ether)n}+ {B(C6F5)4}, where n is I
20 to about 10 (depending on drying conditions), preferably about 1.
This example shows that a neutral organometallic catalyst can be prepared
directly from a lithium salt of a noncoordinating anion without the need to use a
silver salt. Although reaction time is longer, the method requires few steps and uses
less expensive and less hazardous reagents.
2~
Example 10. Preparation, Isolation, and Use of Two-Part Catalyst
A solution of 0.036 g Pd-A in 2.210 g CH2C12 was stirred with 8.032 g
1 -octene. A red solution resulted. Next., 12.131 g deionized water was added,
resulting in a second, aqueous phase. Finally, 112 mg Li{B(C6H5)4}(Et2O)2 was
30 added, and the reaction mixture was shaken. A milky yellow mixture resulted.
Within 6 minutes the mixture was warm to the touch, indicating a polymerization
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exotherm, and at 7 minutes the weight yield of isolated polymer was 33% of
theoretical. Af~er 24 hours, the weight yield of isolated polymer was 59% of
theoretical.
5 Example 11. Preparation, lsolation, and Use of Two-Part Catalyst
A mixture of 1351 g water, 900 g l-octene, and a solution of 1.44 g Pd-A
in 67 gm CH2Cl2 was placed into a large jar. The mixture was cooled to about
0~C, 3.23 g Li{B(C6H5)4} (Example 1) was added, and the mixture was ~ ed
at 0~ to 4~ C with shaking. After about 18 hr, a solid plug of polymer filled the
10 container, and the weight yield of polymer after drying in a vacuum oven at ~0~C
for two days was determined to be 65%.
Examples 10 and l l show that alpha-olefin polymerization can take place in
a simple, rapid, one-pot procedure without the need to isolate the catalyst or to use
relatively expensive silver salts. In this Example, a large volume of water was used
1~ as a sink for the heat of polymerization, and the reaction was carried out at a
sufficiently low temperature that good polymer yield and molecular weight were
achieved
Polymer Analysis: Mw 3.99 x 105, Mn 2.24 x 105.
20 Example 12: Polymerization of Monomers to give Polymers, Employing
Variations in Monomer and Catalyst
In this example, catalyst was mixed with monomer and optional solvent as
indicated. Polymerization was conducted at the temperature and for the time
indicated. All procedures were conducted in air and with no attempt to remove
2~ water from monomer or solvent.
In these examples, one-part catalysts had the forrnula { {(2,6-
C6H~(isopropyl)2)N=c(Me)c(Me)=N(2~6-c6H3(isopropyl)2)}pd(Me)(ether)}+Q-
~wherein ether and Q are as specified in Table 2, below.
In Table 2, in the column "Rxn Cond," reactions conditions are indicated as
30 follows: A general procedure (indicated by A through D)/reaction temperature in
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degrees Centigrade/reaction time in hours. Specifics of the procedures are as
indicated below.
A: contained one-part catalyst, and varying amounts of liquid monomer and
CH2CI2 solvent. In specific procedures, the amounts by weight of monomer to
CH2CI2 are: A-l, I to l; A-2, 3 to 1; A-4, 7.7 to 1; A-5, 1 to 2; A-6, 3.8 to 1;A-7, 5 portions of each comonomer to 1 portion of CH2CI2; and A-8, 5 to 1.
Reaction mixture was homogeneous initially, and polymer precipilated in some
cases depending on monomer, temperature and extent of reaction. In A-3, one-partcatalyst was dissolved in CH2CI2 in a pressure vessel and gaseous monomer was
10 added, but the exact amount of monomer charged was not recorded. For the
samples where reaction times are shown as unknown, reaction progress was not
carefully monitored and reaction times were greater than 100 hours, but not known
with certainty.
B: contained one-part catalyst, 4 portions by weight of ethyl acetate, and
15 1 portion by weight of monomer. Reaction mixture was initially homogeneous, but
polymer soon began to precipitate from solution.
C: contained two phase (monomer and water) mixture with two-part
catalyst, as described in Example 11.
D: contained one-part catalyst and monomer, with no solvent. Reaction
20 mixture formed a solution and polymer precipitated from the solution as it formed.
Reaction progress was not carefully monitored and reaction times were greater than
100 hours, but not known with certainty. D* contained one-part catalyst and 1
portion by weight of each of two comonomers.
In the column "Mono/Pd" is indicated the amount of monomer in grams,
25 divided by the amount of Pd in moles.
For the last two samples in Table 2, copolymerizations were conducted by
mixing the two or more comonomers listed with one-part catalyst in the amounts
indicated.
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Example 13. Post-Polymerization Crosslinking by E-Beam Irradiation
Solutions of polyhexene and polyoctene prepared according to the invention
(Samples 13A, 13B, and 13C) as well as polyhexene and polyoctene prepared by
means of known Ziegler-Natta polymerization methods (Comparative Samples 13D,
5 13E, and 13F) were coated onto a polymeric liner and subjected to electron beam
irradiation, as shown in Table 3.
Samples in solvent were coated at the weight shown onto 0.025 mm
poly(ethyleneterephthalate) liner, the solvent was removed by brief air drying followed
by drying in an oven at 93~ C for about 5 min. The dried samples were exposed to 175
10 kV electron beam irradiation on a moving web at 7.62 m/min. In Table 3, "Gel
Fraction" refers to the amount, by weight percent, of polymer that was insoluble in
toluene after irradiation.
Table 3
Coating
Wt %Weight, Mol. WtxGel Fractionst
Sample Monomer Solvent solidsglcm2 x 1~-4 10-5 Do~ e (MRad)
Mn Mw ~ S 10
13A C8 Toluene 25 41.4 1.763.27 4.3 77.8 90.4
13B C8 Xylene 16.727.2 2.897.02 5.3 79.6 88.7
13C C6 Toluene 25 41.0 1.502.37 2.2 62.1 82.5
13D~ C8 He.Yane 26 38.9 ' ' 3.0 30.1 49.9
(Comp)
13Eb C8 Hexane 20 30.5 2.6614.7 3.1 45.4 57.9
(Comp)
13Fb C6 Toluene 25 43.9 NA 7.35d 4.4 2.9 2.6
(Comp)
1~
a Prepared as described in U. S. Patent No. 5,298,708, "Polymers A"
b Sample obtained from Eastman Chemical Co., Kingsport, TN
c Not available; Inherent Viscosity = 2.67
d Extrapolated from Inherent Viscosity
21~
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The data in Table 3 show that polyhexene and polyoctene prepared according
to the invention was readily crosslin~ed by moderate doses of electron beam
irradiation, whereas the polyhexene and polyoctene obtained by standard Ziegler-Natta
polymerization could not be effectively crosslinked under similar conditions. Polymers
5 that could be crosslinked after co~ting~ casting, molding or extruding can show
significant advantages in, e.g., wearability, solvent resist~nce, creep resistance,
weatherability, tensile strength, etc., over similar non-crosslinked polymers.
Example 14. Post-Polymerization Crosslirl~ g by UV Irradiation
Polyhexene was prepared by adding 100.0 gm of l-hexene (cooled to 0~C) to
0.50 g of { {(2,6-diisopropyl-C6H3)N=C(Me)C(Me)=N(2,6-diisopropyl-
C6H3)}Pd(Me)(Et2O)}+{B(C6F5)4}~ (Example 9) in 100.0 g CH2CI2 at 0~C. The
reaction was kept at 0~C for about 42 hr. Volatiles were removed in a vacuum oven.
The polymer produced had Mn = 1.50 x 105, Mw 2.37 x 105 (by gel permeation
chromatography, as compared to polystyrene standards) Polyoctene was prepared inan identical manner, to give a polymer with Mn = 1.76 x 105, Mw 3.27 x 105.
The polymers were dissolved in toluene (25% polymer by weight), 2-(4-
methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine (the preparation of which is
described in German Patent No. 1,200,314), was added in the amount of 0.15% by
weight of polymer, and the solutions were coated onto 1 mil (0.025 mm) polyester film
and dried as described in Example I 0 to give a dry film coating weight of 40.13 x 10-4
g/cm2 (9.6 +/- 0.2 grains per 24 square inches). The films were irradiated undernitrogen with two medium pressure mercury lamps (high intensity, 200 watt/2.54 cm)
made by Aetek International, Division of GEO, Plainfield, Illinois. Calibration for the
UV energy indicated in Table 4 is according to MIL-STD-45662A (0 means the
sample was not irradiated). Gel fractions, which are the percent by weight of polymer
that is insoluble in toluene, measure the amount of crosslinked polymer that wasformed. The data is shown in Table 4, below.
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Table 4
PolymerUV Energy, mJ/cm2 % Gel
Polyoctene 0 0
Polyoctene 306 63.6
Polyoctene 614 70.8
Polyhexene 0 0
Polyhexene 306 51 7
Polyhexene 614 64.9
The data presented in Table 4 indicate that crosslinking of alpha-olefin
polymers of the invention was accomplished upon ultraviolet irradiation of the polymer
5 in the presence of a crosslinking additive.
Example 15. Preparation of a molded article.
Polyoctene was prepared according to the procedure of Example 12, Mw =
3.15 x 105, Mn = 1.39 x 105. 4.83 g ofthis polymer was placed in a 10 mL round-
10 bottom flask. The polymer and glass container (which was used in this example as amold) were heated to 70~C. The polymer melted and flowed to fill the bottom of the
container. Additional portions of polymer were added over a total time of 80 minutes,
over a temperature range of 70~ to 90~C. The polymer sample was cooled, and
removed from the mold by breaking the glass to give a sphere of polymer of diameter
2.7 cm, weight 11.43 g ~inclut1ing a small neck). This sphere bounced when dropped
onto the floor.
Another sphere was prepared in a similar manner from polydodecene, Mw =
4.84 x 105, Mn = 1.93 x 105, using 9.42 g of polymer heated to 120~C over a period of
2.5 hours. Again, removal from the mold yielded a sphere of diameter 2.7 cm, which
20 bounced when dropped onto the floor.
Example 16. Varying Non-coordinating Counterions
This example shows the use of one-part catalysts with varying non-
coor-lin~ -g counterions.
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In each ofthe samples shown in Table 5, one-part catalyst {(2,6-
C6H3(isopropyl)2)N=C(CH3)C(CH3)=N(2,6-C6H3(isopropyl)2)Pd(Me)(ether) } +Q~
wherein ether and Q are as specified in Table 5, was employed. The catalyst was
mixed in the amount specified with 10 g CH2CI2 and 10 g l-octene. Mixing and
5 polymerization occurred at 0~C. No attempt was made to remove or exclude water or
air. Reaction progress was monitored by removing an aliquot from each sample at the
times indicated, and drying each aliquot to determine the amount of non-volatilepolymer present, from which the weight yield of polymer at that time was calculated.
The molecular weight of the polymers formed after 24 hr of reaction time was
I O measured.
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-41i-
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Reaction rates for all three samples were nearly identical. However, the
polymer molecular weight data showed that polymer of broader polydispersity, that is,
greater ratio MWlMn was formed in sample 16C. Narrow polymer polydispe~ es are
generally preferred.
In another set of trials, the samples were repeated in what was believed to be
an identical manner, but a dillere.ll lot of catalyst was used for the catalyst wherein Q
was B(3,5-C6H3(CF3)2)4. In these trials, the catalyst containing counterion B(3,5-
C6H3(CF3)2)4 produced polymer at a significantly lower rate (about one-half that of the
other two samples) and yielded polymer of lower Mw and Mn and greater Mw/Mn ratio
I O than the other two samples. In these trials, the different lot of catalyst wherein Q was
B(3,5-C6H3(CF3)2)4 was suspected to contain low levels of impurities which had
proved difficult to remove.
In all of these trials, it was observed that catalysts wherein Q is N(S02CF3) orB(C6F5)4 provided better control of poly,l.eri,alion outcomes such as polymer
molecular weight distribution than catalyst wherein Q is B(3,5-C6H3(CF3)2)4 in
polymerizable compositions of this invention., that is, in the presence of water and air.
Various modifications and alterations of this invention will become apparent to
those skilled in the art without departing from the scope and spirit of this invention,
2() and it should be understood that this invention is not to be unduly limited to the
illustrative embodiments set forth herein.
