The present invention provides an energy polymerizable composition comprising at least one epoxy monomer or at least one vinyl ether monomer and an initiation system therefor, the initiation system comprising at least one organometallic complex salt and at least one stabilizing additive. The cured composition provides useful articles or coated articles.

FIELD OF THE INVENTION 
This invention relates to energy-polymerizable compositions comprising a 
cationically curable monomer and, as two-component initiator, at least one 
organometallic complex salt and at least one stabilizing additive, and a 
method for curing the compositions. This invention also relates to 
preparing articles comprising the cured compositions. The compositions are 
useful as molded articles, as coating compositions including abrasion 
resistant coatings, as adhesives including structural adhesives, and as 
binders for abrasives and magnetic media. 
BACKGROUND OF THE INVENTION 
Epoxides, i.e., organic compounds having one or more terminal or pendant 
oxirane (epoxy) groups, have been widely used for many years in adhesive 
compositions. These compounds are commonly cured, or caused to harden, by 
the addition of a curing or hardening agent. Many epoxy compositions use 
curing agents that begin to act immediately, or after a short period of 
time, even at room temperature or lower. These two-part compositions 
require that the epoxide and the curing agent be stored separately and 
only mixed immediately before use. A one-part composition has inherent 
shelf-life stability problems. 
In many applications, it is desirable for a mixed two-part composition to 
be stable for a period of days, weeks, or months so that large batches can 
be prepared to be used as needed. Various attempts have been made to 
prolong "pot life" prior to cure of curable epoxy compositions. This 
allows the epoxide and curing agent to be mixed and stored before use as a 
one-part that is curable upon heating. Generally, it has been found that 
any increase in pot-life of epoxy compositions results in a corresponding 
sacrifice of cure speed. Additionally, achieving complete reaction, i.e., 
where all the epoxide functional groups are consumed, may require longer 
cure times and/or higher cure temperatures. 
Various publications disclosing the preparation and/or use of curing agents 
for epoxy resins and/or other curable compositions are discussed below. 
European Patent Application 0 511 405A1 teaches the use of onium salts 
having a nucleophilic pair anion, such as halogenide, perchlorate, 
alkylsulfate, arylsulfonate, as stabilizers for the polymerization of 
cationically polymerizable organic compositions, catalyzed by 
(n6-arene)(n.sup.5 -cyclopentadienyl)iron(+1) salt cationic 
photoinitiators. The pair anion of the onium salt attacks a growing 
terminal of the polymerization reaction during the curing of the 
composition leading to rapid termination. 
U.S. Pat. Nos. 5,130,406 and 5,179,179 disclose cationic initiators 
containing oxygenated sigma-donor ligands. Such initiators suffer from 
their high hygroscopicity (moisture sensitivity); additionally, these 
initiators provide very little work time because they must be mixed with 
the epoxide at low temperatures. 
Iron-arene salt cationic photoinitiators have been shown to effect the 
polymerization of pyrrole in the presence of oxygen. (Rabek, et al. 
Polymer 1992, 33, 4838-4844.) This polymerization proceeds through proton 
and hydrogen atom abstraction catalyzed by Fe(III). The polymerization was 
completely inhibited in the presence of 1,10-phenanthroline. 
U.S. Pat. No. 4,920,182 discloses the use of a photoactivated bis-arene Fe 
complex that initiates copolymerization of epoxy- and carboxyl-terminated 
polyesters after exposure to light and subsequent heating. There is, 
however, no indication of the degree of either pot-life before, or 
latency, after, photoactivation as well as the speed of cure and its 
relation to pot-life and latency. 
U.S. Pat. No. 4,846,905 describes the use of an acid/amine complex as a 
catalyst for copolymerizing epoxides and polyols. While excellent utility 
as a structural adhesive for bonding oily galvanized steel is shown, this 
particular catalyst system sacrifices pot-life to achieve rapid cure at 
low to moderate temperatures. 
U.S. Pat. No. 4,751,138 teaches a coated abrasive article prepared by 
polymerizing a combination of epoxy and acrylate monomers using a 
combination of photoinitiators which can be cationic organometallic salts, 
onium salts, or thermally active Lewis acids such as antimony 
pentafluoride. Stabilization of the Lewis acids by the addition of amines 
is taught. 
Australian Patent Application 38551/85 describes a hardenable composition 
consisting of a) a material polymerizable by cationic or free radical 
polymerization b) an iron (II)-.eta..sup.6 -benzene-.eta..sup.5 
-cyclopentadienyl complex salt, c) a sensitizer, and with certain monomers 
d) an electron acceptor. The electron acceptors are preferably an organic 
hydroperoxide, an organic peracid or a quinone. 
U.S. Pat. No. 5,073,476 teaches the combination of iron(II) aromatic 
complexes mixed with electron acceptors for the polymerization by 
irradiation of organic materials which can be polymerized cationically 
and/or by free radicals. Nonspecific reference is made to methods to 
increase the capacity of the compositions to be stored in the dark by the 
addition of weak organic bases which are broadly stated to be nitriles, 
amides, lactones or urea derivatives. 
U.S. Pat. No. 5,089,536 disclose curable compositions comprising an ionic 
salt of an organometallic complex cation and a cationically curable 
monomer. Novel compounds disclosed therein are claimed in U.S. Pat. No. 
5,191,101. There is no teaching as to how to increase the shelf life or 
pot-life of a cationically curable composition. 
Canadian Patent Application 2,040,010 relates to epoxy resin compositions 
comprising iron-arene complexes and specific primary amines or bipyridines 
as inhibitors. The epoxy containing compositions require light activation 
to cure. 
U.S. Pat. No. 4,503,211 teaches that a latently curable epoxy resin 
composition including a novel curing agent comprising the liquid salt of a 
substituted pentafluoroantimonic acid and an aromatic amine has long pot 
life yet cures rapidly when heated. 
U.S. Pat. No. 5,047,376 teaches the activation of organic cationically 
polymerizable materials through the use of a dispersion or a solution of 
an iron/arene salt and a polycarboxylic acid, an anhydride based on a 
polycarboxylic acid, or a polyisocyanate, by heating or with actinic 
irradiation. They teach increased shelf life using these compositions. 
A conductive metal-containing adhesive is disclosed in Canadian Patent No. 
1,277,070. Organic solvents useful to make coatable compositions are 
disclosed and include certain sulfoxides, sulfones, carboxylates, and 
lactones. 
SUMMARY OF THE INVENTION 
Briefly, in one aspect, this invention provides an energy polymerizable 
composition comprising: 
(a) at least one cationically curable monomer selected from the group 
consisting of epoxy monomers and vinyl ether-containing monomers; 
(b) a two-component initiator comprising: 
(1) at least one salt of an organometallic complex cation, and 
(2) at least one stabilizing additive; and 
(c) optionally, at least one of an alcohol containing material, an additive 
to increase the speed of cure, and additional adjuvants. 
In a further aspect, the invention provides a process for controlling the 
cure of a composition comprising the steps of: 
(a) providing the curable composition of the invention as described above, 
(b) adding sufficient energy to the composition in the form of at least one 
of heat and light in any combination and order to cure the composition, 
wherein energy preferably is heat only. 
In yet a further aspect, this invention provides an article comprising a 
substrate having on at least one surface thereof a layer of the 
composition of the invention. The article can be provided by a method 
comprising the steps: 
(a) providing a substrate, 
(b) coating the substrate with an energy polymerizable composition 
comprising at least one epoxy monomer or vinyl ether monomer, and a 
two-component initiator system comprising at least one salt of an 
organometallic complex cation and at least one stabilizing additive, and 
optionally adjuvants; preferably the coating is provided by methods such 
as bar, knife, reverse roll, extrusion die, knurled roll, or spin 
coatings, or by spraying, brushing, and 
(c) supplying sufficient energy to the composition in the form of at least 
one of heat and light in any combination and order to cure the 
composition, preferably heat only is used. 
As used in this application: 
"energy-induced curing" means curing or polymerization by means of heat or 
electromagnetic radiation (ultraviolet, visible, or electron beam), or 
electromagnetic radiation in combination with thermal (infrared and heat) 
means, such that heat and light are used simultaneously, or in any 
sequence, for example, heat followed by light, light followed by heat 
followed by light; preferably thermal energy only is used; 
"catalytically-effective amount" means a quantity sufficient to effect 
polymerization of the curable composition to a polymerized product at 
least to a degree to cause an increase in viscosity of the composition 
under the conditions specified; 
"organometallic salt" means an ionic salt of an organometallic complex 
cation, wherein the cation contains at least one carbon atom of an organic 
group that is bonded to a metal atom of the transition metal series of the 
Periodic Table of Elements ("Basic Inorganic Chemistry" F. A. Cotton, G. 
Wilkinson, Wiley, 1976, p 497); 
"initiator" and "catalyst" are used interchangeably and mean a substance 
that changes the speed of a chemical reaction; 
"cationically curable monomer" means at least one epoxide and/or at least 
one vinyl ether containing material; 
"polymerizable composition" as used herein means a mixture of the initiator 
system and the cationically curable monomer; alcohols, speed enhancers, 
and adjuvants optionally can be present; 
"polymerize or cure" means to supply sufficient energy to a composition in 
the form of at least one of heat and light in any order or combination to 
alter the physical state of the composition, to make it transform from a 
fluid to less fluid state, to go from a tacky to a non-tacky state, to go 
from a soluble to insoluble state, or to decrease the amount of 
cationically polymerizable material by its consumption in a reaction; 
"initiation system", "initiator system", or "two-component initiator" means 
at least one salt of an organometallic complex cation and at least one 
stabilizing additive, the system being capable of initiating cationic 
polymerization; 
"stabilizing additive" means at least one of specified classes of compounds 
that moderate the cure of a composition of the invention; 
"group" or "compound" or "ligand" means a chemical species that allows for 
substitution or which may be substituted by conventional substituents 
which do not interfere with the desired product, e.g., substituents can be 
alkyl, alkoxy, aryl, phenyl, halo (F, Cl, Br, I), cyano, nitro, etc., and 
"epoxy/polyol" and "catalyst/additive", etc., mean combinations of the 
substances on both sides of the slash ("/"). 
Applicants have recognized that the industry can benefit from a 
thermally-curable epoxy or vinyl ether-containing resin composition which 
has an extended pot life, preferably does not have to be activated by 
light, yet will cure rapidly over a broad temperature range 
(50.degree.-200.degree. C.) and will retain the desired physical 
properties as required by its intended use. 
Applicants believe there is no teaching in the art to polymerization of 
epoxy or vinyl ether monomers using as initiator system a combination of 
cationic organometallic salts combined with the classes of stabilizers 
disclosed herein.

DETAILED DISCLOSURE OF THE PREFERRED EMBODIMENTS OF THE INVENTION 
The present invention provides an energy polymerizable composition 
comprising at least one epoxy monomer or at least one vinyl ether monomer 
and an initiation system therefor, the initiation system comprising at 
least one organometallic complex salt and at least one stabilizing 
additive. The cured composition provides useful articles or coated 
articles. 
Epoxy compounds that can be cured or polymerized by the processes of this 
invention, using a catalytically effective amount of an initiator system 
comprising an organometallic cation salt and a stabilizing additive, are 
those known to undergo cationic polymerization and include 1,2-, 1,3-, and 
1,4-cyclic ethers (also designated as 1,2-, 1,3-, and 1,4-epoxides) and 
vinyl ethers. 
See the "Encyclopedia of Polymer Science and Technology", 6, (1986), 322, 
for a description of suitable epoxy resins. In particular, cyclic ethers 
that are useful include the cycloaliphatic epoxies such as cyclohexene 
oxide and the ERL.TM. series type of resins available from Union Carbide, 
New York, N.Y., such as vinylcyclohexene oxide, vinylcyclohexene dioxide, 
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 
bis-(3,4-epoxycyclohexyl) adipate and 
2-(3,4-epoxycylclohexyl-5,5-spiro-3,4-epoxy) cyclohexene-meta-dioxane; 
also included are the glycidyl ether type epoxy resins such as propylene 
oxide, epichlorohydrin, styrene oxide, glycidol, the Epon.TM. series type 
of epoxy resins available from Shell Chemical Co., Houston, Tex., 
including the diglycidyl either of bisphenol A and chain extended versions 
of this material such as Epon 828, Epon 1001, Epon 1004, Epon 1007, Epon 
1009 and Epon 2002 or their equivalent from other manufacturers, 
dicyclopentadiene dioxide, epoxidized polybutadienes such as the Poly 
bd.TM. resins from Elf Atochem, Philadelphia, Pa., 1,4-butanediol 
diglycidyl ether, polyglycidyl ether of phenolformaldehyde, cresol or 
novolac resin and resorcinol diglycidyl ether. 
The preferred epoxy resins include the ERL.TM. type of resins especially 
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 
bis-(3,4-epoxycyclohexyl) adipate and 
2-(3,4-epoxycylclohexyl-5,5-spiro-3,4-epoxy) cyclohexene-meta-dioxane and 
the bisphenol A Epon.TM. type resins including 
2,2-bis-[p-(2,3-epoxypropoxy)phenylpropane and chain extended versions of 
this material. It is also within the scope of this invention to use a 
blend of more than one epoxy resin. 
The vinyl ether containing monomers can be methyl vinyl ether, ethyl vinyl 
ether, tert-butyl vinyl ether, isobutyl vinyl ether, triethylene glycol 
divinyl ether (Rapicure.TM. DVE-3, available from GAF, Wayne, N.J.), 
1,4-cyclohexanedimethanol divinyl ether (Rapicure.TM. CHVE, GAF), and the 
VEctomer.TM. resins from Allied Signal, such as VEctomer 2010, VEctomer 
2020, VEctomer 4010, and VEctomer 4020, or their equivalent from other 
manufacturers. It is within the scope of this invention to use a blend of 
more than one vinyl ether resin. 
It is also possible within the scope of this invention to use one or more 
epoxy resins blended with one or more vinyl ether resins. The different 
kinds of resins can be present in any proportion. 
Suitable salts of organometallic complex cations include, but are not 
limited to, those salts disclosed in U.S. Pat. No. 5,089,536, col. 2, line 
48, to col. 16, line 10, which is incorporated herein by reference. 
In the most preferred compositions of the invention, the organometallic 
complex salt of the initiator system is represented by the following 
formula: 
EQU [(L.sup.1).sub.y (L.sup.2).sub.z M].sup.+q X.sub.n (I) 
wherein 
M is selected from the group containing Cr, Ni, Mo, W, Mn, Tc, Re, Fe, Ru, 
Os, Co, Rh and Ir; 
L.sup.1 represents the same or different ligands contributing pi-electrons 
that can be selected from aromatic compounds and heterocyclic aromatic 
compounds, and capable of contributing six pi-electrons to the valence 
shell of M; 
L.sup.2 represents the same or different ligands contributing pi-electrons 
that can be selected from cyclopentadienyl and indenyl anion groups, and 
capable of contributing six pi-electrons to the valence shell of M; 
q is an integer having a value of 1 or 2, the residual charge of the 
complex cation; 
X is an anion selected from organic sulfonate anions and halogen-containing 
complex anions of a metal or metalloid; 
y and z are integers having a value of zero, one, or two, provided that the 
sum of y and z is equal to 2; and 
n is an integer having a value of 1 or 2, the number of complex anions 
required to neutralize the charge q on the complex cation. 
Ligands L.sup.1 and L.sup.2 are well known in the art of transition metal 
organometallic compounds. 
Ligand L.sup.1 is provided by any monomeric or polymeric compound having an 
accessible aromatic group regardless of the total molecular weight of the 
compound. By "accessible", it is meant that the compound (or precursor 
compound from which the accessible compound is prepared) bearing the 
unsaturated group is soluble in a reaction medium, such as an alcohol, 
e.g., methanol; a ketone, e.g., methyl ethyl ketone; an ester, e.g., amyl 
acetate; a halocarbon, e.g., trichloroethylene; an alkane, e.g., decalin; 
an aromatic hydrocarbon, e.g., anisole; an ether, e.g., tetrahydrofuran; 
or that the compound is divisible into very fine particles of high surface 
area so that the unsaturated group (that is, the aromatic group) is 
sufficiently close to the metal to form a pi-bond between that unsaturated 
group and M. By polymeric compound, is meant, as explained below, that the 
ligand can be a group on a Polymeric chain. 
Illustrative of ligand L.sup.1 are substituted and unsubstituted 
carbocyclic and heterocyclic aromatic ligands having up to 25 rings and up 
to 100 carbon atoms and up to 10 heteroatoms selected from nitrogen, 
sulfur, non-peroxidic oxygen, phosphorus, arsenic, selenium, boron, 
antimony, tellurium, silicon, germanium, and tin, such as, for example, 
eta.sup.6 -benzene, eta.sup.6 -mesitylene, eta.sup.6 -toluene, eta.sup.6 
-p-xylene, eta.sup.6 -o-xylene, eta.sup.6 -m-xylene, eta.sup.6 -cumene, 
eta.sup.6 -durene, eta.sup.6 -pentamethylbenzene, eta.sup.6 
-hexamethylbenzene, eta.sup.6 -fluorene, eta.sup.6 -naphthalene, eta.sup.6 
-anthracene, eta.sup.6 -perylene, eta.sup.6 -chrysene, eta.sup.6 -pyrene, 
eta.sup.6 -triphenylmethane, eta.sup.6 -paracyclophane, and eta.sup.6 
-carbazole. Other suitable aromatic compounds can be found by consulting 
any of many chemical handbooks. 
Illustrative of ligand L.sup.2 are ligands derived from the substituted and 
unsubstituted eta.sup.5 -cyclopentadienyl anion, for example, eta.sup.5 
-cyclopentadienyl anion, eta.sup.5 -methylcyclopentadienyl anion, 
eta.sup.5 -pentamethylcyclopentadienyl anion, eta.sup.5 
-trimethylsilylcyclopentadienyl anion, eta.sup.5 
-trimethyltincyclopentadienyl anion, eta.sup.5 
-triphenyltincyclopentadienyl anion, eta.sup.5 
-triphenylsilylcyclopentadienyl anion, and eta.sup.5 -indenyl anion. 
Each of the ligands L.sup.1 and L.sup.2 can be substituted by groups that 
do not interfere with the complexing action of the ligand to the metal 
atom or that do not reduce the solubility of the ligand to the extent that 
competing with the metal atom does not take place. Examples of 
substituting groups, all of which preferably have less than 30 carbon 
atoms and up to 10 hetero atoms selected from nitrogen, sulfur, 
non-peroxidic oxygen, phosphorus, arsenic, selenium, antimony, tellurium, 
silicon, germanium, tin, and boron, include hydrocarbyl groups such as 
methyl, ethyl, butyl, dodecyl, tetracosanyl, phenyl, benzyl, allyl, 
benzylidene, ethenyl, and ethynyl; cyclohydrocarbyl such as cyclohexyl; 
hydrocarbyloxy groups such as methoxy, butoxy, and phenoxy; 
hydrocarbylmercapto groups such as methylmercapto (thiomethoxy), 
phenylmercapto (thiophenoxy); hydrocarbyloxycarbonyl such as 
methoxycarbonyl and phenoxycarbonyl; hydrocarbylcarbonyl such as formyl, 
acetyl, and benzoyl; hydrocarbylcarbonyloxy such as acetoxy, and 
cyclohexanecarbonyloxy; hydrocarbylcarbonamido, for example, acetamido, 
benzamido; azo; boryl; halo, for example, chloro, iodo, bromo, and fluoro; 
hydroxy; cyano; nitro; nitroso; oxo; dimethylamino; diphenylphosphino; 
diphenylarsino; diphenylstibine; trimethylgermane; tributyltin; 
methylseleno; ethyltelluro; and trimethylsiloxy. 
Ligands L.sup.1 and L.sup.2 independently can be a unit of a polymer. 
L.sup.1 for example, can be the phenyl group in polystyrene, 
poly(.alpha.methylstyrene) or polymethylphenylsiloxane; or the carbazole 
group in polyvinylcarbazole L.sup.2 for example, can be the 
cyclopentadiene group in poly(vinylcyclopentadiene). Polymers having a 
weight average molecular weight up to 1,000,000 or more can be used. It is 
preferable that 5 to 50% of the aromatic groups present in the polymer be 
complexed with metallic cations. 
Suitable anions, X, in formula I, for use as the counterion in the ionic 
salts of the organometallic complex cation in the coating compositions are 
those in which X can be represented by the formula 
EQU DQ.sub.r (II) 
wherein 
D is a metal from Groups IB to VIIB and VIII or a metal or metalloid from 
Groups IIIA to VA of the Periodic Table of Elements (CAS notation), 
Q is a halogen atom, hydroxyl group, a phenyl group, or an alkyl group, and 
r is an integer having a value of 1 to 6. 
Preferably, the metals are copper, zinc, titanium, vanadium, chromium, 
manganese, iron, cobalt, or nickel and the metalloids preferably are 
boron, aluminum, antimony, tin, arsenic, and phosphorus. Preferably, the 
halogen atom, Q, is chlorine or fluorine. Illustrative of suitable anions 
are B(phenyl).sub.4.sup.-, B(phenyl).sub.3 (alkyl).sup.-, where alkyl can 
be ethyl, propyl, butyl, hexyl and the like, BF.sub.4 .sup.-, 
PF.sub.6.sup.-, AsF.sub.6.sup.-, SbF.sub.6.sup.-, FeCl.sub.4.sup.-, 
SnCl.sub.5.sup.-, SbF.sub.5 OH.sup.-, AlCl.sub.4.sup.-, AlF.sub.6.sup.-, 
GaCl.sub.4.sup.-, InF.sub.4.sup.-, TiF.sub.6.sup.-, ZrF.sub.6.sup.-, etc. 
Additional suitable anions, X, in formula I, of use as the counterion in 
the ionic salts of the organometallic complex cations include those in 
which X is an organic sulfonate. Illustrative of suitable 
sulfonate-containing anions are CH.sub.3 SO.sub.3.sup.-, CF.sub.3 
SO.sub.3.sup.-, C.sub.6 H.sub.5 SO.sub.3.sup.-, p-toluenesulfonate, 
p-chlorobenzenesulfonate and related isomers. Preferably, the anions are 
BF.sub.4.sup.-, PF.sub.6.sup.-, SbF.sub.6.sup.-, SbF.sub.5 OH.sup.-, 
AsF.sub.6.sup.-, SbCl.sub.6.sup.-, and CF.sub.3 SO.sub.3.sup.-. 
Organometallic salts are known in the art and can be prepared as disclosed 
in, for example, EPO Nos. 094,914, 094,915, 126,712, and U.S. Pat. Nos. 
5,089,536, 5,059,701, 5,191,101, which are incorporated herein by 
reference for the disclosure of organometallic salts and their 
preparation. Also, disubstituted ferrocene derivatives can be prepared by 
the general procedure described in J. Amer. Chem, Soc., 1978, 100, 7264. 
Ferrocene derivatives can be oxidized to prepare the corresponding 
ferrocenium salts by the procedure described in Inorg. Chem., 1971, 10, 
1559. 
The preferred salts of organometallic complex cations useful in the 
compositions of the invention are derived from formula I where L.sup.1 is 
chosen from the class of aromatic compounds, preferably based on benzene, 
and L.sup.2 is chosen from the class of compounds containing a 
cyclopentadienyl anion group, M is Fe and X is selected from the group 
consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, 
hexafluoroantimonate, hydroxypentafluoroantimonate or 
trifluoromethanesulfonate. The most preferred salts of the organometallic 
complex cations useful in the invention are included in formula I where 
only L.sup.1 or only L.sup.2 is present, M is Fe and X is selected from 
the group consisting of tetrafluoroborate, hexafluorophosphate, 
hexafluoroarsenate, hexafluoroantimonate, hydroxypentafluoroantimonate, or 
trifluoromethanesulfonate. The organometallic complex cations can be used 
as mixtures and isomeric mixtures. 
In the preferred compositions of the invention, salts of the organometallic 
complex cation include those disclosed in U.S. Pat. No. 5,089,536. 
Examples of the preferred salts of organometallic complex cations useful in 
preparing the compositions of the invention include the following: 
bis-(eta.sup.6 -benzene)iron(2+) hexafluoroantimonate 
bis-(eta.sup.6 -cumene)iron(2+) hexafluoroantimonate 
bis-(eta.sup.6 -durene)iron(2 +) hexafluoroantimonate 
bis-(eta.sup.6 -p-xylene)iron(2 +) hexafluoroantimonate 
bis-(eta.sup.6 -mesitylene)iron, (2 +) trifluoromethanesulfonate 
bis-(eta.sup.6 -mesitylene)iron (2+) hexafluoroantimonate 
bis-(eta.sup.6 -hexamethylbenzene)iron (2+) hexafluoroantimonate 
bis-(eta.sup.6 -pentamethylbenzene)iron (2+) hexafluoroantimonate 
bis-(eta.sup.6 -naphthalene)iron (2+) hexafluoroantimonate 
bis-(eta.sup.6 -pyrene)iron (2+) hexafluoroantimonate 
(eta.sup.6 -naphthalene) (eta.sup.5 -cyclopentadienyl) iron(1+) 
hexafluoroantimonate 
(eta.sup.6 -pyrene)(eta.sup.5 -cyclopentadienyl)iron (1+) 
hexafluoroantimonate 
(eta.sup.6 -chrysene)(eta.sup.5 -cyclopentadienyl)iron (1+) 
hexafluoroantimonate 
(eta.sup.6 -perylene) (eta.sup.5 -cyclopentadienyl) iron(1+) 
hexafluoroantimonate 
(eta.sup.6 -naphthalene)(eta.sup.5 -cyclopentadienyl)iron (1+) 
trifluoromethanesulfonate 
(eta.sup.6 -pyrene) (eta.sup.5 -cyclopentadienyl) iron(1+) 
trifluoromethanesulfonate 
bis-(eta.sup.5 -pentamethylcyclopentadienyl)iron (1+) hexafluoroantimonate 
bis-(eta.sup.5 -methylcyclopentadienyl)iron (1+) hexafluoroantimonate 
bis-(eta.sup.5 -trimethylsilylcyclopentadienyl)iron (1+) 
hexafluoroantimonate 
bis-(eta.sup.5 -triphenyltincyclopentadienyl)iron (1+) hexafluoroantimonate 
bis-(eta.sup.5 -indenyl)iron(1+) hexafluoroantimonate 
(eta.sup.5 -cyclopentadienyl)(eta.sup.5 -methylcyclopentadienyl)iron (1+) 
hexafluoroantimonate 
bis-(eta.sup.5 -cyclopentadienyl)iron(1+) trifluoromethanesulfonate 
bis-(eta.sup.5 -trimethylsilylcyclopentadienyl)iron(1+) 
trifluoromethanesulfonate 
bis-(eta.sup.5 -triphenyltincyclopentadienyl)iron(1+) 
trifluoromethanesulfonate 
bis-(eta.sup.5 -cyclopentadienyl)iron(1+) hexafluoroantimonate. 
Stabilizing additives of the present invention can be selected from five 
classes of materials. The active portions of these materials (see formulae 
III to VIII which can be converted to an active portion by replacement, 
for example, of a hydrogen atom by a bonding site), can be part of a 
polymer or included as part of any component in the compositions of the 
invention. 
Class 1 is described by the formula III 
EQU R.sup.1 --Z.sup.1 --R.sup.1 (III) 
where Z.sup.1 is a diradical moiety selected from the group consisting of 
##STR1## 
and each R.sup.1 is a radical moiety which can be independently selected 
from C.sub.1 to C.sub.10 substituted and unsubstituted alkyl groups, and 
groups of one to four substituted or unsubstituted aromatic rings wherein 
two to four rings can be fused or unfused, and the R.sup.1 s taken 
together can form a heterocyclic ring having 5 to 7 ring atoms. Examples 
of substituting groups which can be present in any R.sup.1 group, all of 
which preferably have less than 30 carbon atoms and up to 10 hetero atoms 
wherein heteroatoms can interrupt carbon chains to form, for example, 
ether, thio, or amino linkages selected from nitrogen, sulfur, 
non-peroxidic oxygen, phosphorus, arsenic, selenium, antimony, tellurium, 
silicon, germanium, tin, and boron, include hydrocarbyl groups such as 
methyl, ethyl, butyl, dodecyl, tetracosanyl, phenyl, benzyl, allyl, 
benzylidene, ethenyl, and ethynyl; cyclohydrocarbyl groups such as 
cyclohexyl; hydrocarbyloxy groups such as methoxy, butoxy, and phenoxy; 
hydrocarbylmercapto groups such as methylmercapto (thiomethoxy), 
phenylmercapto (thiophenoxy); hydrocarbyloxycarbonyl such as 
methoxycarbonyl and phenoxycarbonyl; hydrocarbylcarbonyl such as formyl, 
acetyl, and benzoyl; hydrocarbylcarbonyloxy such as acetoxy, and 
cyclohexanecarbonyloxy; hydrocarbylcarbonamido, for example, acetamido, 
benzamido; azo; boryl; halo, for example, chloro, iodo, bromo, and fluoro; 
hydroxy; cyano; nitro; nitroso; oxo; dimethylamino; diphenylphosphino; 
diphenylarsino; diphenylstibine; trimethylgermane; tributyltin; 
methylseleno; ethyltelluro; trimethylsiloxy; and aromatic groups such as 
cyclopentadienyl, phenyl, naphthyl and indenyl. 
Class 1 stabilizers are particularly useful with bis-eta.sup.6 -arene type 
organometallic salts and can be present in an amount in the range of 0.1 
to 5.0 weight percent, preferably 0.1 to 3.0 weight percent of the total 
composition. 
Class 2 comprises macrocyclic compounds described by formula IV 
##STR2## 
wherein Z.sup.2 is a diradical and can be --O--, --S--, or --NH--; wherein 
each R.sup.2 independently can be hydrogen or it can be R.sup.1 as 
previously defined, or two R.sup.2 s together can form at least one ring 
which is saturated or unsaturated and the ring can be substituted or 
unsubstituted with alkyl, alkenyl or alkynyl groups containing from 1 to 
30 carbon atoms; the carbon atoms can be interrupted with up to 10 
individual, non-catenated heteroatoms selected from O, S, and N; x can be 
1 or 2, and bis an integer from 3 to 10. 
Included in formula IV are macrocyclic complexes containing oxygen, 
generally known as crown ethers (De Jong, F. et al. Adv. Org. Chem. 1980, 
17, 279-433; Gokel, G. W. et al. Aldrichimica Acta, 1976, 9, 3-12.). In 
addition to oxygen, these macrocyles may also contain any combination of 
nitrogen or sulfur atoms. Cryptands, which are bicyclic and cycles of 
higher order may also be used. Examples of suitable crown ethers and 
cryptands are 15-crown-5, 12-crown-4, 18-crown-6, 21-crown-7, 
dibenzo-18-crown-6, dicyclohexyl-18-crown-6, benzo-15-crown-5, 
Kryptofix.TM. 21, Kryptofix 211, Kryptofix 222, Kryptofix 222B, all 
available from Aldrich Chemical Company, Milwaukee, Wis. The preferred 
crown ether of this invention is 15-crown-5 
(1,4,7,10,13-pentaoxacyclopentadecane). 
Class 3 is represented by formulae V and VI: 
##STR3## 
wherein each R.sup.2 has the same definition as in formula IV. Examples of 
this class of stabilizer include unsubstituted and substituted 
phenanthroline compounds, the most common substituents being alkyl groups 
having 1 to 20 carbon atoms, the preferred phenanthroline being 
1,10-phenanthroline; oxygen is not required in this stabilization; and 
##STR4## 
a class of tripyridyltriazines, wherein each R.sup.2 has the same 
definition as in formula IV, with the preferred being 
2,4,6-tripyridyltriazine. 
Class 4 is described by formula VII: 
##STR5## 
wherein Z.sup.3 is nitrogen, phosphorus, arsenic or antimony; c can be 1 
or 2; 
wherein R.sup.1 has the same definition as in formula I and R.sup.3 can be 
R.sup.1 or a difunctional group (as when c=2) selected from alkylene 
(having 3 to 10 carbon atoms) and phenylene groups. 
Examples of suitable stabilizing additives include, but are not limited to 
trialkyl, tricycloalkyl, tri(alkylcycloalkyl), triaryl, and trialkaryl 
amines, phosphines, phosphine oxides, phosphites, arsines, and stibines, 
including triphenylphosphine, triphenylstibene, triphenylarsine, 
tricyclohexylphosphine, tributylphosphine, tripropylphosphine, 
triethylphosphine, trimethylphosphine, triisopropylphosphine, 
triisopropylphosphite, tributylphosphite, triphenylphosphite, 
triethylamine, tripropylamine, tributylamine, and chelating phosphines 
such as diphenylphosphinomethane, diphenylphosphinoethane, 
diphenylphosphinopropane. Other suitable tertiary amines are listed in 
U.S. Pat. No. 4,503,211 and incorporated by reference especially 
diethyl-o-toluidine. The preferred stabilizers from Class 4 include 
compounds such as triarylphosphines, triarylstibines and substituted and 
unsubstittued dialkylaryl tertiary amines. 
Class 5 is described by formula VIII: 
##STR6## 
wherein R.sup.3 and each R.sup.2 are as previously defined; and wherein d 
is 1 or 2. These stabilizers are chosen from the general type of compounds 
known as Schiff base derivatives and are generally made by the 
condensation of a ketone or aldehyde with a primary amine. They can be 
prepared by the general methods described in U.S. Pat. No. 4,909,954, 
which methods are incorporated herein by reference. In preferred compounds 
d is 1, one R.sup.2 is a substituted or unsubstituted phenyl group and the 
other R.sup.2 is hydrogen, R.sup.3 is a substituted or unsubstituted 
alkyl, phenyl or alkoxy group; or when d is 2, one R.sup.2 is a phenyl 
group and the other R.sup.2 is hydrogen, and R.sup.3 is a diradical 
bridging alkylene or phenylene group. 
The initiator system is present in a catalytically effective amount. 
Typically, the initiator system (two components) can be present in the 
range of 0.01 to 20% by weight, preferably 0.1 to 5% by weight of the 
total polymerizable composition. When a class 1 stabilizing additive is 
used, the mole ratio of the organometallic complex salt to the stabilizing 
additive is generally in the range of 1:5 to 1:30, preferably 1:6 to 1:25. 
For classes 2 to 5 of stabilizing additive, the mole ratio of the 
organometallic complex salt to the stabilizing additive is generally in 
the range of 1:10 to 10:1, preferably 1:5 to 5:1. 
When it is desired to increase the rate of cure of the compositions of the 
invention, it can be useful to additionally include a cure rate enhancer 
such as a peroxide group, hydroperoxide (--OOH group), or acid-generating 
esters. 
A description of useful peroxides can be found in the "Encyclopedia of 
Chemical Technology" 17, 1982, 1-90. Many useful peroxides are 
commercially available such as di-tert-butyl peroxide, di-tert-amyl 
peroxide, tert-butyl cumyl peroxide, tert-butyl perbenzoate, tert-amyl 
perbenzoate, 1,1-di-(tert-butylperoxy)-3,5,5,-trimethylcyclohexane, 
dibenzoyl peroxide, dilauroyl peroxide, and 
n-butyl-4,4-di-(tert-butylperoxy)-valerate. 
Commercially available hydroperoxides include tertiary butyl hydroperoxide, 
cumene hydroperoxide, triphenylmethyl hydroperoxide, tetralin 
hydroperoxide, .alpha.-methyl tetralin hydroperoxide, tert-amyl 
hydroperoxide, decalin hydroperoxide, 
2,5-dihydroperoxy-2,5-dimethylhexane, p-methane hydroperoxide, 
diisopropylbenzene hydroperoxide. Ketone peroxides containing the 
hydroperoxy group are also useful and may include methyl ethyl ketone 
peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, and 
2,4-pentanedione peroxide. 
Acid-generating esters are described in U.S. Pat. No. 3,907,706 which is 
incorporated herein by reference for disclosure of these esters and their 
preparation. 
Preferred esters can be prepared by an esterification reaction between 
oxalic acid and tertiary alkyl alcohols such as: t-butanol, 
1,1-dimethylpropanol, 1-methyl-2-ethylpropanol, 1,1-dimethyl-n-butanol, 
1,1-dimethyl-n-pentanol, 1,1-dimethylisobutanol, 
1,1,2,2-tetramethylpropanol, 1-methylcyclopentanol, 1-methylcyclohexanol, 
1,1-dimethyl-n-hexanol, 1,1-dimethyl-n-octanol, 1,1-diphenylethanol, and 
1,1-dibenzyl ethanol. 
Typically the cure rate enhancers can be present in the range of 0.01 to 20 
percent by weight, preferably 0.1 to 5 percent by weight of the total 
polymerizable composition. 
When the resin contains an epoxy, it can also be preferred and within the 
scope of this invention to add mono- or poly-alcohols as tougheners to the 
epoxy curable composition. The alcohol or polyol aids in chain extension 
and preventing over-crosslinking of the epoxide during curing. 
Representative mono-alcohols can include methanol, ethanol, 1-propanol, 
2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 1-pentanol, 
neopentyl alcohol, 3-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 
2-phenoxythanol, cyclopentanol, cyclohexanol, cyclohexylmethanol, 
3-cyclohexyl-1-propanol, 2-norbornanemethanol, and tetrahydrofurfuryl 
alcohol. 
The polyols useful in the present invention have two to five, preferably 
two to four, hydroxyl groups. Examples of useful polyols include, but are 
not limited to, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 
1,4-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 
2,2-dimethyl-1,3-propanediol, and 2-ethyl-1,6-hexanediol, 1,5-pentanediol, 
1,6-hexanediol, 1,8-octanediol, neopentyl glycol, glycerol, 
trimethylolpropane, 1,2,6-hexanetriol, trimethylolethane, pentaerythritol, 
quinitol, mannitol, diethylene glycol, triethylene glycol, tetraethylene 
glycol, glycerine, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, 
2-ethyl-2-methyl-1,3-propanediol, pentaerythritol, 
2-ethyl-1,3-pentanediol, and 2,2-oxydiethanol, sorbitol, 1,4-cyclohexane 
dimethanol, 1,4-benzene dimethanol, 2-butene-1,4-diol, and polyalkoxylated 
bis-phenol A derivatives. Other examples of useful polyols are disclosed 
in U.S. Pat. No. 4,503,211. 
Higher molecular weight polyols include the polyethylene and polypropylene 
oxide polymers in the molecular weight range of 200 to 20,000 such as the 
Carbowax.TM. polyethyleneoxide materials supplied by Union Carbide, 
caprolactone polyols in the molecular weight range of 200 to 5,000, such 
as the Tone.TM. polyol materials supplied by Union Carbide, 
polytetramethylene ether glycol in the molecular weight range of 200 to 
4,000, such as the Terathane.TM. materials supplied by Dupont (Wilmington, 
Del.), hydroxyl terminated polybutadiene resins such as the Poly bd.TM. 
supplied by Elf Atochem, or equivalent materials supplied by other 
manufacturers. 
The alcohol functional component can be present as a mixture of materials 
and can contain mono- and poly-hydroxyl containing materials. The alcohol 
is preferably present in an amount sufficient to provide an epoxy to 
hydroxy ratio in the composition between about 1:0.1 and 1:1, more 
preferably between about 1:0.2 and 1:0.8, and most preferably between 
about 1:0.3 and 1:0.6. 
A suitable initiation system that includes organometallic complex ionic 
salts described by formula I, and at least one stabilizing additive taken 
from Classes 1 through 5 contains those combinations that, upon 
application of sufficient energy generally in the form of heat and/or 
light will catalyze the polymerization of the compositions of the 
invention. The level of catalytic activity depends on various factors such 
as the choice of ligands and counterions in the organometallic salt and 
the selection of the at least one stabilizing additive. 
Temperature of polymerization and amount of initiator system used will vary 
depending on the particular polymerizable composition used and the desired 
application of the polymerized product. 
Solvents, preferably organic, can be used to assist in dissolution of the 
initiator system in the cationically polymerizable monomers, and as a 
processing aid. It may be advantageous to prepare a concentrated solution 
of the organometallic complex salt in a small amount solvent to simplify 
the preparation of the polymerizable composition. Useful solvents are 
lactones, such as gamma-butyrolactone, gamma-valerolactone; ketones such 
as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone 
and cyclohexanone; sulfones, such as tetramethylene sulfone, 
3-methylsulfolane, 2,4-dimethylsulfolane, butadiene sulfone, methyl 
sulfone, ethyl sulfone, propyl sulfone, butyl sulfone, methyl vinyl 
sulfone, 2-(methylsulfonyl)ethanol, 2,2'-sulfonyldiethanol; sulfoxides, 
such as dimethyl sulfoxide; cyclic carbonates such as propylene carbonate, 
ethylene carbonate and vinylene carbonate; carboxylic acid esters such as 
ethyl acetate, methyl cellosolve acetate, methyl formate; and other 
solvents such as methylene chloride, nitromethane, acetonitrile, glycol 
sulfite and 1,2-dimethoxyethane (glyme). In some applications, it may be 
advantageous to adsorb the initiator onto an inert support such as silica, 
alumina, clays, as described in U.S. Pat. No. 4,677,137, which is 
incorporated herein by reference. 
Suitable sources of heat to cure the compositions of the invention include 
induction heating coils, ovens, hot plates, heat guns, IR sources 
including lasers, microwave sources, etc. 
Suitable substrates useful to provide articles of the invention include, 
for example, metals (for example, aluminum, copper, cadmium, zinc, nickel, 
steel, iron, silver), glass, paper, wood, various thermoplastic or 
thermoset films (for example, polyethylene terephthalate, plasticized 
polyvinyl chloride, polypropylene, polyethylene), cloth, ceramics and 
cellulosics, such as cellulose acetate. 
Adjuvants may optionally be added to the compositions such as colorants, 
abrasive granules, stabilizers, light stabilizers, antioxidants, flow 
agents, bodying agents, flatting agents, inert fillers, binders, blowing 
agents, fungicides, bactericides, surfactants, plasticizers, rubber 
tougheners and other additives known to those skilled in the art. They 
also can be substantially unreactive, such as fillers both inorganic and 
organic. These adjuvants, if present are added in an amount effective for 
their intended purpose. 
Compositions of this invention are useful to provide abrasion-resistant or 
protective coatings to articles, as molded articles, as adhesives, 
including hot melt and structural adhesives, and as binders for abrasives. 
In general, a composition's physical properties, i.e., hardness, stiffness, 
modulus, elongation, strength, etc., is determined by the choice of the 
epoxy resin, and if an alcohol containing material is used, the ratio of 
epoxy to alcohol and the nature of the alcohol. Depending on the 
particular use, each one of these physical properties of the system will 
have a particular optimum value. Generally, the cured material from a 
higher epoxy/alcohol ratio is stiffer than from a lower epoxy/alcohol 
ratio. Generally, for an epoxy/alcohol composition, a shorter chain polyol 
yields a cured composition that is stiffer than when using a longer chain 
polyol. The stiffness of a composition can also be increased by using a 
shorter chain monofunctional alcohol to replace a polyol. The speed of 
cure can be controlled by the choice of initiator system, its level, and 
the particular curable materials. Epoxy/alcohol mixtures generally cure 
faster than epoxy only compositions. Cycloaliphatic epoxies cure more 
rapidly than glycidyl ether epoxies. Mixtures of these two types of 
epoxies can be used adjust the cure rate to a desired level. 
To prepare a coated abrasive article using the materials of the subject 
invention, abrasive particles must be added to the curable composition. 
The general procedure is to select a suitable substrate such as paper, 
cloth, polyester, etc., coat this substrate with the make coat which 
consists of the curable composition containing the abrasive particles, and 
then curing by the application of a source of energy. A size coat, which 
cures to a harder material than the make coat, is then coated over the 
make coat and cured. The size coat serves to lock the abrasive particles 
in place. 
To prepare a structural/semi-structural adhesive, the curable composition 
could contain additional adjuvants such as silica fillers, glass bubbles 
and tougheners. These adjuvants add toughness to and reduce the density of 
the cured composition. Generally shorter chain polyols would be used to 
give toughness through chain extension of the cured epoxy. Too long a 
chain diol generally would produce too soft a cured composition that would 
not have the strength needed for structural/semi-structural applications. 
Using polyols having high hydroxyl functionality greater than three could 
produce an overcrosslinked material resulting in a brittle adhesive. 
To prepare magnetic media using the materials of the subject invention, 
magnetic particles must be added to the curable composition. Magnetic 
media need to be coated onto a suitable substrate, generally a polymeric 
substrate like polyester. Generally the coatings are very thin so that 
sufficient carrier solvent must be added to allow the production of a 
suitably thin, even coating. The coating must cure rapidly so a fast 
initiator system and curable materials must be chosen. The cured 
composition must have a moderately high modulus so the curable materials 
must be selected appropriately. 
To prepare a clear abrasion resistant coating from the materials of the 
subject invention, two important criteria for selecting the composition 
are clarity and toughness of the cured composition. Generally, particulant 
adjuvants would not be added since they would reduce the gloss and clarity 
of the cured composition. Optionally, pigments could be added to produce a 
colored film. 
Molded articles are made by means known to those skilled in the art, as, 
for example, by reaction injection molding, casting, etc. 
Objects and advantages of this invention are further illustrated by the 
following examples, but they should not be construed as limiting the 
invention; the scope of which is defined by the claims. 
EXAMPLES 
In the examples, all parts, ratios, and percents are by weight unless 
specifically indicated otherwise. All materials used are either known or 
commercially available unless otherwise indicated or apparent. All 
examples were prepared in ambient atmosphere (in the presence of usual 
amounts of oxygen and water vapor) unless indicated otherwise. 
The general sample preparation procedure was as follows: the desired amount 
of stabilizing additive was mixed with the epoxy or vinyl ether containing 
composition; the composition was warmed if necessary to insure complete 
mixing of the components; the mixture was allowed to cool to room 
temperature (23.degree. C.) before use. Curable mixtures were prepared by 
measuring out the desired amount of the cationic organometallic catalyst, 
and, if needed, adding the desired amount of solvent to dissolve the 
catalyst, then adding the epoxy or vinyl ether containing mixture and 
mixing thoroughly. 
TEST METHODS 
TENSILE TEST SAMPLE PREATION 
Tensile test samples were prepared by using an ASTM 628-87 Type IV die to 
cut a mold out of 0.91 millimeter (mm) thick silicone rubber mold. A 
sandwich construction was prepared by first laying down on an aluminum 
panel a 0.025 micrometer (.mu.m) polyester sheet coated with a 
conventional silicone release layer, release side up. The silicone rubber 
mold was placed on this layer. The polymerizable composition to be cured 
was applied to the mold. A second piece of release layer coated polyester, 
release side down, was placed over the mold and a rubber roller was used 
to smooth out the sample and eliminate air bubbles. The samples were cured 
with various temperature cycles as stated in the particular example. Using 
this procedure, reproducible samples were made for tensile tests. 
TENSILE TESTING PROCEDURE 
Tensile tests were conducted following the method described in ASTM 628-87 
Tensile Testing Methods standard. The samples were tested at a strain rate 
of 5 mm/min. An Instron Model 1122 tensile tester was used for the tests. 
Ultimate tensile strength is reported in MPa and is the strength at break, 
percent elongation is reported in % using the crosshead movement as a 
measure of elongation, energy at break is reported in Newton-meters (N-m) 
and is the area under the stress-strain curve and modulus is reported in 
MPa and is the modulus at 3% elongation. 
OVERLAP SHEAR TEST 
Sheets of 0.76 mm thick G60 hot-dipped extra smooth galvanized steel, 
obtained from National Steel Corporation, Livonia, MI, were cut into 25.4 
mm by 76.2 mm test coupons and degreased with acetone. Both coupons are 
allowed to dry for 30 minutes at about 22.degree. C. The adhesive 
composition was spread over one end of the first coupon. The spacing 
distance, 0.254 mm, was maintained by the presence of glass microbeads in 
the adhesive mix. The other coupon was placed over the adhesive such that 
there was a 12.7 mm overlap of the coupons and with the uncoated ends of 
the coupons aligned in opposite directions from each other. The coupons 
were clamped together and cured at 170.degree. C. for 30 minutes. The 
prepared samples were cooled for at least 1 hour at about 22.degree. C. 
before testing. The lap shear was determined using a tensile tester 
according to ASTM Test Method D1002-72 with a crosshead speed of 5 cm/min. 
The lap shear strength was reported in megaPascals (MPa). 
Differential Scanning Calorimetry (DSC) 
Differential Scanning Calorimetry was used to measure the exothermic heat 
of reaction associated with the cure of the cationically polymerizable 
monomer. This energy is measured in Joule/gram (J/g). The exotherm 
profile, i.e. peak temperature, onset temperature, etc., of the exotherm 
provided information on conditions that are needed to cure the material. 
The integrated energy under an exothermic peak is related to the extent of 
cure. For a stable composition, more of that exotherm energy should remain 
with time indicating that the composition is not curing prematurely. For 
an unstable composition, the exotherm energy will decrease more rapidly 
with time indicating that the composition has undergone some degree of 
cure prematurely. 
______________________________________ 
GLOSSARY 
IDENTIFICATION OF COMPONENTS USED 
IN THE EXAMPLES 
______________________________________ 
4221.TM. 3,4-epoxycyclohexylmethyl-3,4-epoxy 
cyclohexanecarboxylate (ERL-4221 
available from Union Carbide) 
Epon .TM. 828 
diglycidyl ether of bisphenol A 
(EPON 828 available from Shell 
Chemical Co.) 
CHDM 1,4-cyclohexanedimethanol 
Paraloid .TM. BTA 
methyl methacrylate/butadiene/ 
IIIN2 brand styrene copolymer available from 
copolymer Rohm & Haas Company 
Reactive diglycidyl ether of neopentyl glycol 
Diluent WC68 .TM. 
having an epoxy equivalent weight of 
about 135 available from Rhone- 
Poulenc 
GP7I .TM. silica 
silicon dioxide having a particle 
size range from 20-30 micrometers 
available from Haribson Walker Corp. 
Cab-O-Sil .TM. 
fumed silica available from Cabot 
TS720 .TM. brand 
Corp. 
silica 
B37/2000 .TM. 
glass bubbles, available from 
Minnesota Mining and Manufacturing 
Company 
Catalysts 
Cp.sub.2 FeSbF.sub.6 
bis-(.eta..sup.5 -cyclopentadienyl)iron(+1) 
hexafluoroantimonate 
(MeCp).sub.2 FeSbF.sub.6 
bis-(.eta..sup.5 -methylcyclopentadienyl)- 
iron(+1) hexafluoroantimonate 
(Me.sub.3 SiCP).sub.2 FeSbF.sub.6 
bis-(.eta..sup.5 -trimethylsilylcyclopenta- 
dienyl)iron(+1)hexafluoro 
antimonate 
(Ph.sub.3 SnCp).sub.2 FeSbF.sub.6 
bis-(.eta..sup.5 -triphenyltincyclopenta- 
dienyl)iron(+1) 
hexafluoroantimonate 
CpFeXylSbF.sub.6 
(.eta..sup.6 -xylenes)(.eta..sup.5 -cyclopentadienyl)- 
iron(+1) hexafluoroantimonate 
Cp cyclopentadienyl 
Me methyl 
Ph phenyl 
Mes mesitylene 
______________________________________ 
______________________________________ 
Stabilizing Additives (SA) 
______________________________________ 
SA1 
##STR7## 
SA2 
##STR8## 
SA3 
##STR9## 
SA4 
##STR10## 
SA5 
##STR11## 
SA6 
##STR12## 
SA7 
##STR13## 
SA8 
##STR14## 
SA9 
##STR15## 
SA10 
##STR16## 
SA11 
##STR17## 
SA12 
##STR18## 
SA13 
##STR19## 
SA14 
##STR20## 
SA15 
##STR21## 
SA16 
##STR22## 
SA17 
##STR23## 
SA18 
##STR24## 
SA19 
##STR25## 
SA20 
##STR26## 
SA21 
##STR27## 
SA22 
##STR28## 
______________________________________ 
Comparative Example C1 
To determine the gel time for an unstabilized epoxy composition, 0.01g of 
Cp.sub.2 FeSbF.sub.6 was weighed into an aluminum dish and 0.025g of 
gamma-butyrolactone added to completely dissolve the catalyst. To this was 
added 2.00g of ERL-4221, mixed thoroughly and then placed on a hot plate 
at 50.degree. C. and the time to produce a gel was recorded. The presence 
of gel was indicated by the formation of insoluble material, or an 
increase in viscosity. In this example gel was formed after 90 sec at 
50.degree. C. 
Examples 1-6 
Stock solutions of Schiff base stabilizing additive and epoxy were prepared 
by first mixing 0.1 g of the Schiff base with 10 g of ERL-4221. The 
mixtures were heated to 50.degree. C. and stirred to complete dissolution 
of the additive in the epoxy. This produced a 1% w/w solution of additive 
in the epoxy. Lower concentrations of additive were obtained by successive 
dilution. Gel times were determined following the procedure described in 
Comparative Example C1. 
The standard procedure was to weigh out 0.01 g of Cp.sub.2 FeSbF.sub.6 into 
an aluminum pan, add 0.025 g gamma-butyrolactone then 2.0 g of the 
additive/epoxy solution. After thorough mixing, the composition was placed 
on a series of hot plates set at successively higher temperatures. If a 
composition did not form a gel at a lower temperature it was then moved to 
a higher temperature until a gel was formed. The time to form a gel was 
recorded. 
The data of Examples 1-6 (see Table 1, below) show that the Schiff base 
stabilizing additives can be used to control the temperature of 
polymerization of an initiation system/epoxy composition. These additives 
can be used to increase the gel temperature of a composition when compared 
to Comparative Example C1. This stabilizing effect can be controlled by 
the identity and concentration of the additive. The ability to move the 
temperature of polymerization is the ability to control the shelf life of 
a composition at lower temperatures but still obtain rapid cure at a 
higher temperature. 
TABLE 1 
______________________________________ 
Gel Time Experiments 
Exs. Additive 50.degree. C. 
100.degree. C. 
150.degree. C. 
______________________________________ 
1 1.0% SA1 600 ng 40 g -- 
2 1.0% SA2 600 ng 720 ng 45 g 
3 0.25% SA3 600 ng 600 ng 30 g 
4 0.125% SA3 600 ng 30 g -- 
5 0.25% SA4 600 ng 180 g -- 
6 0.125% SA4 600 ng 30 g -- 
______________________________________ 
Gel times are in seconds 
ng means no gel formed after the specified time 
g means gel formed after the specified time 
-- means no test was carried out for that combination 
Comparative Example C2 
To determine the gel time for an unstabilized epoxy composition, 0.01 g of 
Cp.sub.2 FeSbF.sub.6, was weighed into an aluminum dish and 0.025 g of 
gamma-butyrolactone added, then 2.00 g of Epon 828 was added, mixed 
thoroughly and then placed on a hot plate at 100.degree. C. and the time 
to produce a gel was recorded. The presence of gel was indicated by the 
presence of insoluble material. Gel was formed after 15 minutes at 
100.degree. C. 
Examples 7-15 
Stock solutions of Schiff base stabilizing additive and epoxy were prepared 
by first mixing 0.1 g of the Schiff base with 10 g of Epon 828. The 
mixtures were heated to 100.degree. C. and stirred to complete dissolution 
of the additive in the epoxy. The solutions were then cooled to room 
temperature. This produced a 1% w/w solution of additive in the epoxy. 
Lower concentrations of additive were obtained by successive dilution. Gel 
times were determined following the procedure described in Examples 1-6 
and are shown in Table 2. 
The data of Examples 7-15 show that the Schiff base stabilizing additives 
can be used to control the temperature of polymerization of an initiation 
system/epoxy composition. These additives can be used to increase the gel 
temperature of a composition when compared to Comparative Example C2. This 
stabilizing effect can be controlled by the identity and concentration of 
the additive. The ability to move the temperature of polymerization is the 
ability to control the shelf life of a composition at lower temperatures. 
Relative to Comparative Example C2, Examples 7-15 show that a range of 
stability can be obtained when the stabilizing additives are used with the 
cationic organometallic compounds of the subject invention. 
TABLE 2 
______________________________________ 
Gel Time Experiments 
Exs. Additive 100.degree. C. 
150.degree. C. 
______________________________________ 
7 0.5% SA1 45 ng 2 g 
8 0.125% SA2 45 ng 11 g 
9 0.5% SA5 45 ng 5 g 
10 0.125% SA3 45 ng 3 g 
11 0.25% SA4 45 ng 4 g 
12 0.25% SA6 45 ng 20 g 
13 0.5% SA7 45 ng 1 g 
14 0.125% SA8 45 ng 15 g 
15 0.25% SA9 45 ng 15 g 
______________________________________ 
Gel times are in minutes. 
ng means no gel formed after the specified time. 
g means gel formed after the specified time. 
Comparative Examples C3-C6 
To test the effect of catalyst concentration on gel time, a series of 
catalyst/epoxy compositions were prepared and evaluated following the 
procedure and using the same materials described in Comparative Example 
C2. The results of these evaluations are shown in Table 3. 
TABLE 3 
______________________________________ 
Effect of Catalyst Concentration on Gel Time 
Comparative Catalyst 
Example Concentration 
100.degree. C. 
______________________________________ 
C3 2.0% 8 g 
C4 1.0% 13 g 
C5 0.5% 16 g 
C6 0.25% 25 g 
______________________________________ 
Gel times are in minutes 
g means gel formed after the specified time 
Examples 16-19 
To test the effect of catalyst concentration on gel time, a series of 
catalyst/additive/epoxy compositions were prepared and evaluated following 
the procedure and using the same epoxy and catalyst described in Examples 
7-15. The additive, SA5, was kept at a constant level of 0.5% w/w. The 
results of these evaluations are shown in Table 4. 
These trials show that a combination of catalyst concentration and additive 
can be used to control the gel time and temperature for a 
catalyst/additive/epoxy composition. The increase in time and temperature 
to produce a gel for Examples 16-19 over comparative Examples C3-C6 show 
the utility of the stabilizing additives of the disclosure in controlling 
cure of epoxy compositions. 
TABLE 4 
______________________________________ 
Effect of Catalyst Concentration on Gel Time 
Catalyst 
Examples Concentration 100.degree. C. 
150.degree. C. 
______________________________________ 
16 2% 20 g -- 
17 1% 45 ng 1 g 
18 0.5% 45 ng 4 g 
19 0.25% 45 ng 7 g 
______________________________________ 
Gel times are in minutes 
ng means no gel formed after the specified time 
g means gel formed after the specified time 
-- means test not performed. 
Comparative Examples C7-C10 
To test the effect of catalyst concentration on gel time, a series of 
catalyst/epoxy/polyol compositions were prepared and evaluated following 
the procedure described in Comparative Example C2. The ratio of epoxy 
functionality to hydroxyl functionality was selected as 1/0.4. The amount 
of materials to mix to obtain this ratio was determined by using an epoxy 
equivalent weight of 188 for the epoxy, Epon 828, and a hydroxyl 
equivalent weight of 45.06 for the polyol, 1,4-butanediol. The results of 
these evaluations are shown in Table 5. 
Compared to the results in Comparative Examples C3-C6, the gel times with a 
polyol present are in general shorter than without the polyol. This makes 
these compositions more difficult to stabilize. 
TABLE 5 
______________________________________ 
Effect of Catalyst Concentration on Gel Time 
Comparative Catalyst 
Example Concentration 100.degree. C. 
150.degree. C. 
______________________________________ 
C7 2.0% 1.5 g -- 
C8 1.0% 5 g -- 
C9 0.5% 7 g -- 
C10 0.25% 20 g -- 
______________________________________ 
Gel times are in minutes 
g means gel formed after the specified time 
Examples 20-23 
To evaluate the effect of catalyst concentration on gel time, a series of 
catalyst/additive/epoxy/polyol compositions were prepared using the same 
catalyst/epoxy/polyol materials and evaluated following the procedure 
described in Comparative Examples C7-C10. The additive, SA11, was kept at 
a constant level of 0.5% w/w. The results of these evaluations are shown 
in Table 6. 
These trials show that a combination of catalyst concentration and additive 
can be used to control the gel time and temperature for a 
catalyst/additive/epoxy/polyol composition. The increase in time and 
temperature to produce a gel for Examples 20-23 over Comparative Examples 
C7-C10 show the utility of the stabilizing additives of the disclosure in 
controlling cure of epoxy/polyol compositions. While inhibiting gel 
formation of the compositions at lower temperatures, the stabilizing 
additives still allowed rapid cure at a slightly higher temperature. 
TABLE 6 
______________________________________ 
Effect of Catalyst Concentration on Gel Times 
Catalyst 
Example Concentration 100.degree. C. 
150.degree. C. 
______________________________________ 
20 2% 40 g -- 
21 1% 45 ng 1.5 g 
22 0.5% 45 ng 2 g 
23 0.25% 45 ng 4 g 
______________________________________ 
Gel times are in minutes 
ng means no gel formed after the specified time 
g means gel formed after the specified time 
-- means test not performed. 
Examples 24-26 and Comparative Example C11 
To evaluate the effect of the polyol and epoxy/hydroxyl ratio on the gel 
time and temperature of a catalyst/epoxy/polyol composition, a series of 
evaluations were performed varying the polyol and its amount. Stock 
solution was prepared by mixing 100 g Epon 828 and 25.14 g of 
1,2-hexanediol to produce a composition of 1/0.8 epoxy/hydroxyl ratio. A 
1% solution of stabilizing additive SA16 was prepared by mixing 0.1 g of 
SA16 and 10 g of the stock solution. Lower concentrations of SA16 were 
obtained by successive dilution. 
Trial samples were prepared by mixing adding 0.025 g propylene carbonate to 
0.01 g Cp.sub.2 FeSbF.sub.6 in an aluminum dish, dissolving the catalyst, 
then adding either the stock solution or a solution containing additive 
SA16. Gel times were obtained by the method described in Comparative 
Example C1. 
The data in Table 7 demonstrate the stabilizing effect of the additives by 
increasing the cure temperature to a higher but still accessible 
temperature or a longer but still reasonable time. The gel time and 
temperature can be adjusted by the level of the stabilizing additive. 
TABLE 7 
______________________________________ 
Effect of Concentration of Stabilizing Additive on 
Gel Times 
Exs. Additive 100.degree. C. 
150.degree. C. 
180.degree. C. 
______________________________________ 
C11 None 45 ng 2 g -- 
24 0.5% SA16 45 ng 30 ng 5 g 
25 0.25% SA16 45 ng 6 g -- 
26 0.125% SA16 45 ng 3 g -- 
______________________________________ 
Gel times are in minutes 
ng means no gel formed after the specified time 
g means gel formed after the specified time 
-- means no test was carried out for that combination. 
Examples 27-30 and Comparative Examples C12-14 
A series of curable compositions using different catalysts were prepared to 
evaluate the effect of the stabilizing additives in an epoxy/polyol 
composition. The epoxy/polyol composition was the same as used in 
Comparative Examples C7-C10 and the stabilized compositions used SA3 as 
the stabilizing additive in the amount listed in Table 8. The curable 
compositions were prepared by placing 0.01 g of the selected catalyst in a 
dish, adding 0.025 g of propylene carbonate to dissolve the catalyst then 
adding 2.0 g of the epoxy/polyol composition with or without stabilizing 
additive. Gel times were determined as described in Comparative Example 
C1. 
The data in Table 8 show that the stabilizing additive/catalyst combination 
can be varied to obtain a wide range of gel times and temperatures. The 
data also show that one additive can be effective with a wide range of 
catalysts. 
TABLE 8 
______________________________________ 
Effect of Catalyst on Gel Times 
Exs. Catalyst Additive 100.degree. C. 
150.degree. C. 
180.degree. C. 
______________________________________ 
Comp. #2 No additive 
13 g -- -- 
Ex. C12 
27 #2 0.125% SA3 45 ng 9 g -- 
Comp. #3 No additive 
45 ng 2 g -- 
Ex. C13 
28 #3 0.125% SA3 45 ng 18 g -- 
Comp. #4 No additive 
18 g -- -- 
Ex. C14 
29 #4 0.125% SA3 45 ng 30 ng 30 ng 
30 #4 0.0625% SA3 
45 ng 7 g -- 
______________________________________ 
Gel times are in minutes 
ng means no gel formed after the specified time 
g means gel formed after the specified time 
-- means no test was carried out for that combination. 
Catalysts #2 Cp.sub.2 FeSbF.sub.6, #3 (MeCP).sub.2 FeSbF.sub.6, #4 
(Ph.sub.3 SnCp).sub.2 FeSbF.sub.6. 
Examples 31-33 and Comparative Example C15 
A curable composition's viscosity can be used to measure its useful work 
life. Maintaining a stable viscosity over a set time period, typically 
hours or days, while still having a reasonable curing time, can make a 
composition more useful. Cure times at easily accessible temperatures has 
been demonstrated in previous examples. This example uses viscosity to 
demonstrate the increased useful work time for a curable composition when 
the catalyst/additive combinations of the present invention are utilized. 
Viscosity measurements were made using a Brookfield Model DV-1 viscosimeter 
at room temperature, 22.degree.-23.degree. C. Samples were placed in 100 
ml plastic beakers for measurements. Viscosity measurements were recorded 
over a specified time period. 
These examples use viscosity measurements to demonstrate the increased 
useful work time for a curable epoxy composition when the 
catalyst/additive combinations of the present invention are utilized. 
For Example 31, a 0.125% additive in epoxy mixture was prepared by adding 
together 0.24 g of additive SA17 and 200 g of Epon 828. For Example 32, a 
0.5% additive in epoxy mixture was prepared by adding together 1.0 g of 
additive SA1 and 200 g of Epon 828. For Example 33, a 0,125% additive in 
epoxy mixture was prepared by adding together 0.240 g of additive SA12 and 
200 g of Epon 828. These compositions were heated, mixed thoroughly and 
allowed to cool to room temperature before use. 
A curable composition was prepared from 0.75 g of Cp.sub.2 FeSbF.sub.6, 1.0 
g gamma-butyrolactone and 150 g of the each of the preceding 
additive/epoxy mixtures. 
For Comparative Example C15, a curable composition was prepared from 0.75 g 
of Cp.sub.2 FeSbF.sub.6, 1.0 g gamma-butyrolactone and 150 g of Epon 828. 
The data in Table 9 show that without the stabilizing additive, the curable 
composition increased by about a factor of ten over the first eight hours 
and by a factor of about 300 to 400 over 24 hours. With the stabilizing 
additive, the viscosity underwent little change over the total time of the 
measurements. 
TABLE 9 
______________________________________ 
Viscosity Measurements over Time 
Time, Comparative 
in Example Example Example Example 
hours 31* 32* 33* C15* 
______________________________________ 
0 19000 15800 17000 17800 
1 17000 16200 17200 18200 
2 17000 16400 17200 21600 
3 17000 16600 17400 28200 
4 15800 15800 17400 49000 
5 16000 15400 16600 77200 
6 15600 15400 16200 119800 
7 15400 15200 15600 180400 
24 17000 17600 16600 4136000 
48 18000 21200 18800 cured hard 
126 17000 25400 19200 cured hard 
______________________________________ 
*viscosity in centipoise 
Examples 34-35 and Comparative Examples C16-17 
These examples use viscosity measurements to demonstrate the increased 
useful work time for a curable epoxy/polyol composition when the 
catalyst/additive combinations of the present invention are utilized. 
A mixture of 95.12 g of polyethylene glycol 400 and g of Epon 828 was 
prepared to give an epoxy/hydroxyl functionality ratio of 1/0.2. For 
Example 34, a 0.125% additive composition was prepared by adding together 
0.25 g of additive SA17 and 200 g of polyethylene glycol Epon 828 mixture. 
A mixture of 46.88 g of 2-butene-1,4-diol in 400 g Epon 828 was prepared to 
give an epoxy/hydroxyl ratio of 1/0.5. For Example 35, a 0.125% additive 
composition was prepared by adding together 0.25 g of additive SA18 and 
200 g of the 2-butene-1,2-diol/Epon 828 mixture. These compositions were 
heated, mixed thoroughly and allowed to cool to room temperature before 
use. 
A curable composition was prepared from 0.75 g of Cp.sub.2 FeSbF.sub.6, 1.0 
g gamma-butyrolactone and 150 g of the each of the preceding 
additive/epoxy/polyol mixtures. 
For Comparative Example C16, a curable composition was prepared from 0.75 g 
of Cp.sub.2 FeSbF.sub.6, 1.0 g gamma-butyrolactone and 150 g of the 
polyethylene glycol 400 Epon 828 mixture. For Comparative Example C17, a 
curable composition was prepared from 0.75 g of Cp.sub.2 FeSbF.sub.6, 1.0 
g gamma-butyrolactone and 150 g of the 2-butene-1,2-diol/Epon 828 mixture. 
Viscosity measurements were made as described in Examples 31-33. The data 
in Table 10 show that without the stabilizing additive, the viscosity of 
the curable composition increases over the time period of the 
measurements. With the stabilizing additive, the viscosity remained 
essentially unchanged over the total time of the measurements. 
TABLE 10 
______________________________________ 
Viscosity Measurements over Time 
Time, Comparative Comparative 
in Example Example Example Example 
hours 34* C16* 35* C17* 
______________________________________ 
0 2480 2520 6560 6240 
1 2480 2600 6480 4960 
2 2560 2960 7040 6240 
3.5 2400 4080 6480 6400 
4.5 2320 5520 6480 6160 
5.5 2280 7240 6240 5360 
6.5 2120 9160 6080 5440 
7.5 2200 11760 5760 6240 
8.5 2200 16280 6080 10960 
72 2440 cured 7120 cured 
______________________________________ 
*viscosity in centipoise 
Examples 36-39 and Comparative Example C18 
DSC tests were rum on unstabilized and stabilized catalyst/epoxy/polyol 
compositions to test the effect of varying the stabilizing additive level. 
A stock solution was prepared from 40 g ERL-4221 and 10 g of 
1,2-propanediol, heating mixing well and allowing to cool before 
proceeding. A stock solution of stabilizing additive/epoxy/polyol was 
prepared by mixing 0.32 g of additive SA21 and 10 g of ERL-4221/polyol to 
produce a 4% SA21/ERL-4221/polyol, w/w, mixture. Successive dilution was 
used to prepare mixtures of 2%, 1% and 0.5% SA21/ERL-4221/polyol, w/w. For 
each Example, a test solution was prepared by mixing 0.01 g of 
(Me3SiCp)2FeSbF.sub.6 and 2.5 g of the appropriate additive/epoxy/polyol 
stock solution. 
For Comparative Example C18, a curable composition was prepared by mixing 
0.01 g (Me.sub.3 SiCp).sub.2 FeSbF.sub.6 and 2.5 g of ERL-4221. 
After each composition was thoroughly mixed, DSC samples were prepared in 
sealed liquid sample pans, sample size 8-13 mg. The area under the 
exotherm and the peak temperature were recorded for each run. The results 
of these tests are presented in Table 11. 
The data in Table 11 show how dramatically catalyst/epoxy/alcohol 
compositions were stabilized when the appropriate stabilizing additive was 
used. Without the stabilizing additive, Comparative Example C18 lost 90% 
of its cure energy in 6 days while all the Examples retained 90-100% of 
their activity. The Examples also demonstrated that the stability can be 
adjusted by the concentration of the stabilizing additive. 
TABLE 11 
______________________________________ 
DSC Measurements 
Energy (J/g)/Peak Temperature (.degree.C.) 
Exs. Day 1 Day 6 Day 15 Day 22 
______________________________________ 
Comp. Ex. 
426/87 45/98 27/97 17/100 
C18 
36 487/168 482/165 481/164 473/164 
37 507/161 484/160 500/157 464/158 
38 496/147 503/154 457/153 419/153 
39 491/138 469/139 448/139 201/142 
______________________________________ 
Examples 40 and 41 and Comparative Example C19 
Besides maintaining thermal stability it was important that physical 
properties of the cured composition were not affected adversely by the use 
of a stabilizing additive. The previous examples have shown that the 
stabilizing additives when combined with the catalyst/curable materials 
mixtures do produce compositions of controllable thermal stability. This 
set of Examples demonstrates that the physical properties of the final 
cured composition were not substantially altered by the use of the 
stabilizing additives. 
For Comparative Example C19, 0.5 g of Cp.sub.2 FeSbF.sub.6 was dissolved in 
0.5 g of gamma-butyrolactone then 50 g of Epon 828 was added mixed 
thoroughly and heated briefly to 40.degree. C. to eliminate bubbles from 
the sample. For Examples 40 and 41 were made by first preparing a 1% 
solution of SA1 and SA20, respectively, in Epon 828 by mixing together the 
components, heating them to 40.degree. C., mixing thoroughly and allowing 
the mixture to cool before proceeding. Curable compositions were prepared 
by dissolving 0.5 g Cp.sub.2 FeSbF.sub.6 in 0.5 g of gamma-butyrolactone 
then adding 50 g 1% stabilizing additive/Epon 828 mixture, mixing 
thoroughly and heating briefly to 40.degree. C. to eliminate bubbles from 
the sample. 
The tensile test samples were prepared as described in the testing section 
and the curing cycle was 15 minutes at 100.degree. C., 15 minutes at 
110.degree. C., 15 minutes at 130.degree. C. and 30 minutes at 140.degree. 
C. Tensile tests were performed as described in the testing section. The 
results of the tensile tests are shown in Table 12. As can be seen from 
the data presented in Table 12, the presence of the stabilizing additive 
had little effect on the physical properties of the cured compositions. 
Other examples have shown the presence of these stabilizing additives 
increased the work time of compositions and these examples demonstrated 
that physical properties were not sacrificed. 
TABLE 12 
______________________________________ 
Tensile Tests 
Tensile Elonga- 
Strength tion at Energy in 
Modulus 
Exs. in MPa Break in % N-m in MPa 
______________________________________ 
Comp. Ex. 
75.3 9.5 0.69 1149 
C19 
40 73.1 8.5 0.67 1194 
41 71.1 8.1 0.54 1175 
______________________________________ 
Comparative Example C20 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish and 0.03 g of gamma-butyrolactone was added to completely dissolve 
the catalyst. One g of Epon 828 was added and mixed in thoroughly. Several 
DSC sample pans were prepared, hermetically sealed, and stored at room 
temperature. Shelf life analysis of the mixture was performed by DSC on 
the day of preparation (0 weeks), and over time. The data of Table 13 
illustrate that the composition used had poor shelf-life with only 26% of 
the maximum cure energy retained. This means that 74% of the monomer has 
polymerized. 
TABLE 13 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Exotherm 
Time Energy T.sub.onset 
T.sub.max 
T.sub.end 
(weeks) (Joules/gram) (.degree.C.) 
(.degree.C.) 
(.degree.C.) 
______________________________________ 
0 518 45 98 167 
1 278 55 103 120 
2 184 &gt;50* 106 122 
3 167 &gt;50* 109 129 
4 175 &gt;50* 111 124 
6 137 &gt;60** 111 123 
______________________________________ 
T.sub.onset = point of initial exothermicity; T.sub.max = maximum exother 
temperature; T.sub.end = point at which 90% of the material has cured. 
*endothermic transition between 35-50.degree. C. **endothermic transition 
between 40-60.degree. C. 
Example 42 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish and 0.04 g of 3-methylsulfolane was added to completely dissolve the 
catalyst. Epon 828 (1 g) was added and mixed in thoroughly. Several DSC 
sample pans were prepared and analyzed as in Example C20. As can be seen 
from the data of Table 14, when 3-methylsulfolane was used as a solvent, 
the formulation had greater work time, as evidenced by the higher onset 
temperatures; additionally, shelf like was improved as evidenced by a 
decrease in exotherm energy slower than that observed in Example C20. 
TABLE 14 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Exotherm 
Time Energy T.sub.onset 
T.sub.max 
T.sub.end 
(weeks) (Joules/gram) (.degree.C.) 
(.degree.C.) 
(.degree.C.) 
______________________________________ 
0 503 75 118 175 
1 425 75 109 153 
2 318 65 111 155 
3 271 70 114 126 
4 242 70 116 122 
6 206 75 118 122 
______________________________________ 
Comparative Example C21 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish and 0.04 g of propylene carbonate was added to completely dissolve 
the catalyst. Epon 828 (1 g) was added and mixed in thoroughly. Analysis 
of the cure by DSC showed T.sub.onset =75.degree. C., T.sub.max 
=117.degree. C., and T.sub.end =162.degree. C. When compared to the data 
of Example C20, it can be seen that the use of propylene carbonate as 
solvent provided greater stability as evidenced by the higher onset 
temperature. 
Example 43 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish and 0.04 g of 3-methylsulfolane was added to completely dissolve the 
catalyst. Epon 828 (2 g) was added and mixed in thoroughly. Several DSC 
sample pans were prepared and analyzed as in Example C20. As can be seen 
from the data of Table 15, after 6 weeks of the maximum cure energy was 
retained. 
TABLE 15 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/gram) 
(.degree.C.) 
______________________________________ 
0 480 113 
1 524 111 
2 479 108 
3 437 110 
4 395 115 
5 361 114 
6 258 116 
______________________________________ 
Example 44 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish and 0.04 g of 3-methylsulfolane was added to completely dissolve the 
catalyst. One g of an Epon 1,6-hexanediol/CHDM (78:11:11 w/w) mixture was 
added and mixed in thoroughly. Several DSC sample pans were prepared and 
analyzed as in Example C20. As can be seen from the data of Table 16, this 
composition retained 19% of the maximum cure energy after five weeks. 
TABLE 16 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/gram) 
(.degree.C.) 
______________________________________ 
0 426 116 
1 396 111 
2 333 111 
3 258 115 
4 105 113 
5 82 124 
______________________________________ 
Comparative Example C22 
Finely powdered (mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was 
dispersed in 1 g of an Epon 828/1,6-hexanediol/CHDM (78:11:11 w/w) 
mixture. Several DSC sample pans were prepared and analyzed as in Example 
C20, with the results listed in Table 17. 
TABLE 17 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/gram) 
(.degree.C.) 
______________________________________ 
0 429 118 
1 425 114 
2 421 113 
3 394 114 
4 210 110 
5 165 110 
6 154 108 
______________________________________ 
Example 45 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish and 0.04 g of 3-methylsulfolane was added to completely dissolve the 
catalyst. Two g of an Epon 828/1,6-hexanediol/CHDM (78:11:11 w/w) mixture 
was added and mixed in thoroughly. Several DSC sample pans were prepared 
and analyzed as in Example C20. As can be seen from the data of Table 18, 
at the end of a six-week period this composition retained 28% of the 
maximum cure energy. 
TABLE 18 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/gram) 
(.degree.C.) 
______________________________________ 
0 426 115 
1 429 112 
2 414 113 
3 372 112 
4 228 115 
5 148 112 
6 122 116 
______________________________________ 
Example 46 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish and 0.04 g of 3-methylsulfolane was added to completely dissolve the 
catalyst. Two g of an Epon 828/15-crown-5 (100:0.29 w/w) mixture was added 
and mixed in thoroughly. Several DSC sample pans were prepared and 
analyzed as in Example C20. When compared to Table 15, the data of Table 
19 illustrate that addition of 15-crown-5 to the composition resulted in 
nearly complete stabilization over six weeks, with 95% of the maximum cure 
energy being retained. 
TABLE 19 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/gram) 
(.degree.C.) 
______________________________________ 
0 467 152 
1 471 148 
2 497 147 
3 500 135 
4 489 138 
5 475 133 
6 476 138 
______________________________________ 
Example 47 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish and 0.04 g of 3-methylsulfolane was added to completely dissolve the 
catalyst. Two g of an Epon 828/15-crown-5 (100:0.14 w/w) mixture was added 
and mixed in thoroughly. Several DSC sample pans were prepared and 
analyzed as in Example C20. The data of Table 20 illustrate the 
stabilizing effect the addition of 15-crown-5 had on the room temperature 
cure of the composition; 96% of the maximum cure energy was retained after 
a six-week period with the formulation of this example, whereas the data 
from Example 43 show that in an analogous formulation without added 
15-crown-5, 49% of the maximum cure energy was retained. 
TABLE 20 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/Gram) 
(.degree.C.) 
______________________________________ 
0 462 147 
1 429 143 
2 453 132 
3 485 124 
4 485 120 
5 469 117 
6 467 123 
______________________________________ 
Example 48 
Evaluations were carried out to examine the effect of 15-crown-5 on the 
shelf-life of epoxy-alcohol mixtures. A stock solution of 
epoxide/alcohol/additive was prepared by adding 0.29 g of 15-crown-5 to a 
100 g mixture of Epon 828/1,6-hexanediol/CHDM (78:11:11 w/w). 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish. 3-methylsulfolane (0.04 g) was added to completely dissolve the 
catalyst, after which 2 g of the stock solution was added and mixed 
thoroughly. Several DSC sample pans were prepared and analyzed as in 
Example C20. When compared to Table 18, the data of Table 21 illustrate 
the stabilizing effect the addition of 15-crown-5 had on the room 
temperature cure of the composition. 
TABLE 21 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/gram) 
(.degree.C.) 
______________________________________ 
0 367 146 
1 406 130 
2 316 123 
3 361 125 
4 412 127 
5 261 121 
6 157 116 
______________________________________ 
Example 49 
Finely powdered (mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was 
dispersed in 2 g of the stock solution prepared in Example 48, and mixed 
thoroughly. Several DSC sample pans were prepared and analyzed as in 
Example C20, with the results listed in Table 22. The data of Table 22 
illustrate the stabilizing effect the addition of 15-crown-5 had on the 
room temperature cure of the composition; 87% of the maximum cure energy 
was retained after a six-week period. 
TABLE 22 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/gram) 
(.degree.C.) 
______________________________________ 
0 455 154 
1 441 145 
2 421 143 
3 429 140 
4 402 131 
5 411 135 
6 398 135 
______________________________________ 
Example 50 
Further evaluations to examine the effect of 15-crown-5 on the shelf-life 
of epoxy-alcohol mixtures. A stock solution of epoxide/alcohol/additive 
was prepared by adding 0.14 g of 15-crown-5 to a 100 g mixture of Epon 
828/1,6-hexanediol/CHDM (78:11:11 w/w). 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish. 3-methylsulfolane (0.04 g) was added to completely dissolve the 
catalyst, after which 2 g of the stock solution was added and mixed 
thoroughly. Several DSC sample pans were prepared and analyzed as in 
Example C20. When compared to Table 18 (Example 45), the data in Table 23 
illustrate the stabilizing effect the addition of 15-crown-5 had on the 
room temperature cure of the composition; with the formulation of this 
example, 46% of the maximum cure energy was retained after a six-week 
period, while only was retained in the analogous formulation without the 
15-crown-5. 
TABLE 23 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/gram) 
(.degree.C.) 
______________________________________ 
0 429 126 
1 409 122 
2 419 121 
3 394 119 
4 387 116 
5 344 116 
6 282 114 
______________________________________ 
Example 51 
Finely powdered (mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g), was 
dispersed in 2 g of the stock solution prepared in Example 50, and mixed 
thoroughly. Several DSC sample pans were prepared and analyzed as in 
Example C20. When compared to data of Table 17, the data of Table 24 
illustrate the stabilizing effect the addition of 15-crown-5 had on the 
room temperature cure of the composition. 
TABLE 24 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/gram) 
(.degree.C.) 
______________________________________ 
0 407 139 
1 431 137 
2 418 136 
3 406 135 
4 431 129 
5 426 131 
6 398 122 
______________________________________ 
Examples 52A and 52B 
Trials were run to examine the affect of a second additive to a stabilized 
composition of the invention. 
52A: Trials were run to examine the effect of 2-2'-bipyridyl on the 
shelf-life of epoxy resins. A stock solution of epoxide/additive was 
prepared by adding 0.10 g of finely dispersed bipyridyl to 100 g of Epon 
828. This mixture was heated to 80.degree. C. for approximately 20 minutes 
with vigorous shaking to ensure complete dissolution of the additive in 
the epoxide. 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish and 0.04 g of 3-methylsulfolane was added to completely dissolve the 
catalyst. Two g of the stock solution was added and mixed in thoroughly. 
Several DSC sample pans were prepared and analyzed as in Example C20. The 
data in Table 25 illustrate that after a six-week period at room 
temperature, 59% of the maximum exotherm energy was retained, and little 
change was observed upon longer aging. 
TABLE 25 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/gram) 
(.degree.C.) 
______________________________________ 
0 452 116 
1 495 116 
2 468 115 
3 493 112 
5 424 115 
6 290 113 
13 312 122 
______________________________________ 
52B: Trials were run to examine the effect of 1,10-phenanthroline on the 
shelf-life of epoxy resins. A stock solution of epoxide/additive was 
prepared by adding 0.12 g of finely dispersed 1,10-phenanthroline to 100 g 
of Epon 828. This mixture was heated to 80.degree. C. for approximately 20 
minutes with vigorous shaking to ensure complete dissolution of the 
additive in the epoxide. 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish and 0.04 g of 3-methylsulfolane was added to completely dissolve the 
catalyst. Two g of the stock solution was added and mixed in thoroughly. 
Several DSC sample pans were prepared and analyzed as in Example C20. When 
compared to the data in Table 15, the data of Table 26 illustrate the 
stabilizing effect the addition of 1,10-phenanthroline had on the room 
temperature cure of the composition. The data in Table 26 show that for 
this formulation 95% of the maximum cure energy was retained after a 
six-week period at room temperature; whereas, with only a class 1 
stabilizing additive present (Example 43), 49% of the cure was retained. 
Additionally, when compared to the data in Table 25 it can be seen that 
the formulation containing 1,10-phenanthroline had a longer shelf life 
than did the formulation containing 2,2'-bipyridyl as was shown in Example 
52A. 
TABLE 26 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/gram) 
(.degree.C.) 
______________________________________ 
0 501 116 
1 495 118 
2 454 118 
3 506 116 
4 486 116 
5 504 115 
6 481 115 
______________________________________ 
Example 53 
Evaluations were carried out to determine if lower levels of 
1,10-phenanthroline would provide the same stabilization of the 
epoxy/catalyst mixture. A stock solution of epoxide/additive was prepared 
as in Example 52, using 0.06 g of finely dispersed 1,10-phenanthroline. 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish and 0.04 g of 3-methylsulfolane was added to completely dissolve the 
catalyst. Two g of the stock solution was added and mixed in thoroughly. 
Several DSC sample pans were prepared and analyzed as in Example C20. The 
data in Table 27 illustrate that the lower level of 1,10-phenanthroline 
was effective at stabilizing the cure, as 85% of the maximum exotherm 
energy was retained after a six-week period at room temperature, whereas, 
49% of the cure was retained when only a class 1 stabilizing additive was 
present as was shown in Example 43. 
TABLE 27 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/gram) 
(.degree.C.) 
______________________________________ 
0 500 115 
1 499 115 
2 499 115 
3 512 113 
4 488 115 
5 487 113 
6 427 114 
______________________________________ 
Example 54 
Trials were run to examine the effect of 1,10-phenanthroline on the 
shelf-life of epoxy-alcohol resins. A stock solution of epoxide,alcohol, 
and additive was prepared by adding 0.06 g of finely dispersed 
1,10-phenanthroline to a 100 g mixture of Epon 828/1,6-hexanediol/CHDM 
(78:11:11 w/w). This mixture was heated to 80.degree. C. for approximately 
20 minutes with vigorous shaking to ensure complete dissolution of the 
additive in the epoxide. 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish and 0.04 g of 3-methylsulfolane was added to completely dissolve the 
catalyst. Two g of the stock solution was added and mixed in thoroughly. 
Several DSC sample pans were prepared and analyzed as in Example C20. When 
compared to data of Table 18, the data of Table 28 illustrate the 
stabilizing effect the addition of 1,10-phenanthroline had on the room 
temperature cure of the composition. 
TABLE 28 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/gram) 
(.degree.C.) 
______________________________________ 
0 438 117 
1 436 114 
2 436 116 
3 430 116 
4 435 115 
5 429 114 
6 322 117 
______________________________________ 
Example 55 
Evaluations were performed to examine the effect of 
2,4,6-tripyridyltriazine (TPTZ) on the shelf-life of epoxy resins. A stock 
solution of epoxide/additive was prepared by adding 0.10 g of finely 
dispersed TPTZ to g of Epon 828. This mixture was heated to 80.degree. C. 
for approximately 20 minutes with vigorous shaking to ensure complete 
dissolution of the additive in the epoxide. 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish and 0.04 g of 3-methylsulfolane was added to completely dissolve the 
catalyst. Two g of the stock solution was added and mixed in thoroughly. 
Several DSC sample pans were prepared and analyzed as in Example C20. When 
compared to data of Table 15, the data of Table 29 illustrate the 
stabilizing effect the addition of TPTZ had on the room temperature cure 
of the composition. 
TABLE 29 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/gram) 
(.degree.C.) 
______________________________________ 
0 482 112 
1 512 115 
2 499 114 
3 433 115 
5 409 115 
6 405 116 
12 279 125 
______________________________________ 
Example 56 
Evaluations were performed to examine the effect of triphenylphosphine on 
the shelf-life of epoxy resins. A stock solution of epoxide/additive was 
prepared by adding 0.34 g of finely dispersed triphenylphosphine (SA14) to 
100 g of Epon 828. This mixture was heated to 80.degree. C. for 
approximately 20 minutes with vigorous shaking to ensure complete 
dissolution of the additive in the epoxide. 
(Mesitylene).sub.2 Fe(SbF.sub.6).sub.2 (0.01 g) was added to an aluminum 
dish and 0.04 g of 3-methylsulfolane was added to completely dissolve the 
catalyst. Two g of the stock solution was added and mixed in thoroughly. 
Several DSC sample pans were prepared and analyzed as in Example C20. When 
compared to the data of Table 15, the data of Table 30 illustrate the 
stabilizing effect the addition of triphenylphosphine had on the room 
temperature cure of the composition. 
TABLE 30 
______________________________________ 
Polymerization Exotherm Profile over Time 
Reaction Time Exotherm Energy 
T.sub.max 
(weeks) (Joules/gram) 
(.degree.C.) 
______________________________________ 
0 396 127 
1 477 121 
2 445 116 
3 474 120 
4 489 118 
6 469 113 
7 488 119 
9 408 124 
______________________________________ 
Preparation of Adhesive Premix 
The epoxy based composition was prepared by combining 59.40 parts Epon 828, 
5.87 parts WC68.TM., 8.88 parts Paraloid BTA IIIN2 copolymer. The mixture 
was stirred with a high shear mixer at about 115.degree. C. for two hours, 
then cooled to room temperature. To this cooled mixture was added 20.59 
parts GP-7I, 1.38 parts B37/2000, 2.58 parts TS-720, and 1.30 parts 0,254 
mm (0.01 inch) glass beads (Cataphote, Inc., Jackson, Miss.) to make 100 
parts of composition. High shear mixing was continued for 30 minutes at 
room temperature (23.degree. C.), followed by vacuum degassing at room 
temperature. This mixture constituted the adhesive premix used in Examples 
C24-C25 and Examples 57-60. 
Comparative Example C23 and Examples 57-61 
Evaluations were performed to determine the initial overlap shear strength 
of an adhesive formulation, and to monitor the strength over time. Table 
31 shows the composition formulations. The adhesive compositions were 
prepared by dissolution of the cationic organometallic salt and any 
additional additives in a solvent, followed by addition of the premix and 
difunctional alcohols. The mixture was stirred until a uniform mixture was 
obtained. The overlap shear data are shown below in Table 32. 
TABLE 31 
______________________________________ 
Adhesive Formulation 
Parts by Weight 
Constituent 
Ex. 57 Ex. C23 Ex. 58 
Ex. 59 
Ex. 60 
Ex. 61 
______________________________________ 
Adhesive 
50.8 50.8 50.8 50.8 50.8 50.8 
premix 
1,6- 3.6 3.6 3.6 3.6 3.0 3.0 
hexanediol 
CHDM 3.6 3.6 3.6 3.6 3.6 3.6 
(Mes).sub.2 Fe- 
0.3 -- 0.3 0.3 -- -- 
(SbF.sub.6).sub.2 
Cp.sub.2 Fe- 
-- 0.3 -- -- 0.3 0.3 
(SbF.sub.6) 
1,10- -- -- 0.07 -- -- -- 
phenan- 
thro- 
line 
15-crown-5 
-- -- -- 0.17 -- -- 
SA1 -- -- -- -- 0.3 -- 
SA3 -- -- -- -- -- 0.08 
3-methyl- 
0.5 -- 0.5 0.5 -- -- 
sulfolane 
propylene 
-- 0.5 -- -- 0.5 0.5 
carbonate 
______________________________________ 
TABLE 32 
______________________________________ 
Overlap Shear Strength (MPa) over Time 
Ex. Initial 1 Week 3 Weeks 4 Weeks 
6 Weeks 
______________________________________ 
57 10.33 10.55 ** * * 
58 11.75 14.87 11.62 *** 14.24 
59 16.10 16.67 13.83 16.58 15.36 
C23 13.51 * * * * 
60 16.21 15.05 * * * 
61 13.90 13.00 ** * * 
______________________________________ 
* = Sample hardened; 
** = Sample too viscous to make good bonds; 
*** = Sample not hard; however, no data taken. 
Comparative Example C24 and Example 62 
Studies were conducted to test the stabilizing effect of 15-crown-5 on 
formulations containing Cp.sub.2 Fe(SbF.sub.6). Table 33 shows the 
composition formulation of Examples C24 and 62. Initial DSC analysis of 
Examples C24 and 62 gave exotherm energies of 297 J/g and 290 J/g, 
respectively. After one week Example 62 had become more viscous due to 
partial curing; DSC analysis gave an exotherm energy of 187 J/g. The 
formulation from Comparative Example C24 was hard, thus affirming the 
stabilizing effect of 15-crown-5 on formulations containing Cp.sub.2 
Fe(SbF.sub.6). 
TABLE 33 
______________________________________ 
Adhesive Formulation 
Comparative 
Constituent Example 24 Example 62 
______________________________________ 
Adhesive Premix 50.8 50.8 
1,6-hexanediol 3.6 3.6 
CHDM 3.6 3.6 
Cp.sub.2 Fe(SbF.sub.6) 
0.3 0.3 
15-Crown-5 -- 0.2 
______________________________________ 
Comparative Examples C25-C32 
Evaluations were carried out to show how the organometallic salts disclosed 
within this invention performed differently from conventional Lewis acid 
catalysts. U.S. Pat. No. 4,503,211 teaches that SbF.sub.5 
.multidot.diethylene glycol (DEG) is effective as a catalyst for epoxy 
polymerizations when added at approximately 3% by weight. Therefore, 
SbF.sub.5 .multidot.DEG was added in this amount to epoxy resins, and to 
epoxy/additive mixtures to determine the cure times as was performed in 
previous examples. 
Comparative Example C25 
In an aluminum dish, 0.06 g of SbF.sub.5 .multidot.DEG was added to 2.01 g 
of Epon 828 and mixed in thoroughly. As in Example C2 and Examples 7-15, 
planned gel time trials at 100.degree. C. gave surprising results in that 
this formulation gel particles formed immediately, and a rapid exotherm 
occurred within 1.5 minutes of mixing at room temperature. As was seen in 
Example C2, the analogous formulation containing Cp.sub.2 Fe(SbF.sub.6) 
took 15 minutes to cure at 100.degree. C. Additionally, the data of Table 
15 show that an analogous formulation containing (mesitylene).sub.2 
Fe(SbF.sub.6).sub.2 was stable at room temperature for at least two weeks 
before slow cure started. 
Comparative Example C26 
In an aluminum dish, 0.06 g of SbF.sub.5 .multidot.DEG was added to 2.01 g 
of an Epon 828/1,6-hexanediol/CHDM (78:11:11 w/w) mixture and mixed in 
thoroughly. Gel particles formed upon mixing and a rapid exotherm occurred 
within 2.5 minutes of mixing at room temperature. The data of Table 18 
show that an analogous formulation containing (mesitylene).sub.2 
Fe(SbF.sub.6).sub.2 was stable at room temperature for at least two weeks 
before slow cure started. 
Comparative Example C27 
A stock solution of Schiff base additive and epoxy was prepared by mixing 
0.05 g of Schiff base additive SA1 with 20 g of Epon 828. The mixture was 
heated to 60.degree. C. for 5 min and stirred to ensure uniform mixing of 
the additive in the epoxy. The mixture was cooled to room temperature 
before use. 
In an aluminum dish, 0.06 g of SbF.sub.5 .multidot.DEG was added to 2.01 g 
of the Epon 828/additive mixture and mixed in thoroughly. Gel particles 
formed upon mixing, along with an increase in viscosity. After 12 hours 
the mixture was very viscous, but not completely cured. 
Comparative Example C28 
A stock solution of Schiff base additive and epoxy was prepared by mixing 
0.10 g of Schiff base additive SA1 with 20 g of Epon 828. The mixture was 
heated to 60.degree. C. for 5 min and stirred to ensure uniform mixing of 
the additive in the epoxy. The mixture was cooled to room temperature 
before use. 
2.01 g of the Epon 828/additive mixture was weighed out in an aluminum dish 
and 0.06 g of SbF.sub.5 .multidot.DEG was added, mixed thoroughly. Gel 
particles formed upon mixing; when placed on a hot plate at 100.degree. 
C., the gel particles darkened immediately and the bulk of the material 
cured to a grannular solid within 1 minute. It is to be noted that in 
Example 7 an analogous composition containing Cp.sub.2 FeSbF.sub.6 did not 
cure after 45 minutes at 100.degree. C. 
Comparative Example C29 
A stock solution of Schiff base additive and epoxy was prepared by mixing 
0.025 g of Schiff base additive SA3 with 20 g of Epon 828. The mixture was 
heated to 60.degree. C. for 5 min and stirred to ensure uniform mixing of 
the additive in the epoxy. The mixture was cooled to room temperature 
before use. 
In an aluminum dish, 0.06 g of SbF.sub.5 .multidot.DEG was added to 2.01 g 
of Epon 828 and mixed in thoroughly. Gel particles formed upon mixing and 
a hard granular product was produce within 2 minutes of mixing at room 
temperature. As was seen in Example 10, the analogous resin mixture 
containing Cp.sub.2 Fe(SbF.sub.6) did not gel even after 45 minutes at 
100.degree. C. 
Comparative Example C30 
In an aluminum dish, 0.06 g of SbF.sub.5 .multidot.DEG was added to 2.01 g 
of an Epon 828/15-crown-5 (100:0.29 w/w) mixture and mixed in thoroughly. 
Gel particles formed upon mixing and a rapid exotherm occurred within 2.5 
minutes of mixing at room temperature. As can be seen from Example 46, an 
analogous resin mixture containing (mesitylene).sub.2 Fe(SbF.sub.6).sub.2 
was stable at room temperature for at least six weeks. 
Comparative Example C31 
A stock solution of 15-crown-5 and epoxy was prepared by mixing 0.29 g of 
15-crown-5 with 100 g of an Epon 828/1,6-hexanediol/CHDM (78:11:11 w/w) 
mixture and mixed in thoroughly. 
In an aluminum dish, 0.06 g of SbF.sub.5 .multidot.DEG was added to 2.01 g 
of the stock solution and mixed in thoroughly. Gel particles formed upon 
mixing and a rapid exotherm occurred within 2 minutes of mixing at room 
temperature. The data of Example 48 show that an analogous resin mixture 
containing (mesitylene).sub.2 Fe(SbF.sub.6).sub.2 was stable at room 
temperature for at least two weeks before slow cure started. 
Comparative Example C32 
A stock solution of 1,10-phenanthroline and epoxy was prepared by mixing 
0.12 g of 1,10-phenanthroline with 100 g of an Epon 
828/1,6-hexanediol/CHDM (78:11:11 w/w) mixture and mixed in thoroughly. 
In an aluminum dish, 0.06 g of SbF.sub.5 .multidot.DEG was added to 2.01 g 
of the stock solution and mixed in thoroughly at room temperature. Gel 
particles formed upon mixing and a rapid exotherm occurred within 2 
minutes. The data of Example 52B show that an analogous resin mixture 
containing (mesitylene).sub.2 Fe(SbF.sub.6).sub.2 was stable at room 
temperature for at least five weeks before slow cure started. 
The data of Comparative Examples C25-C32 show that conventional Lewis acid 
catalysts must be used in higher concentrations than the organometallic 
salts disclosed in this invention. Additionally, epoxy mixtures containing 
this conventional Lewis acid catalyst were not stabilized by the additives 
in this invention under equivalent conditions used for the cationic 
organometallic salts. 
Comparative Examples C33-C44 
To compare the physical properties produced by different Lewis acid 
catalysts the following evaluations were performed. Tensile test samples 
were prepared as described in the tensile test sample preparation section 
using Ph3SSbF.sub.6 (CAT1), a 
triphenylsulfonium/phenylthiophenyldiphenylsulfonium hexafluoroantimonate 
salt from 3M Company, St. Paul, Minn., CpFeXylSbF.sub.6 (CAT2), SbF.sub.5 
/DEG/SA21 (CAT3), a 1/1/2.93 w/w/w mixture, and Cp.sub.2 FeSbF.sub.6 
(CAT4) as catalysts. Stock solutions were prepared from 30 g of Epon 828 
and 0.035, 0.075 and 0.15 g of each catalyst. For CAT1 and CAT2, they were 
dissolved directly in the epoxy with heating in the dark. For formulations 
containing CAT3, the stabilized composition had to be used or the samples 
would cure before the tensile test samples could be prepared. For CAT4, an 
equivalent amount of gamma-butyrolactone was used to dissolve the catalyst 
before adding the epoxy. 
Compositions containing CAT1 and CAT2 were photosensitive and were 
activated using 3 passes through a PPG Industries Model QC1202 UV 
Processor at 15.24 m/min (50 ft/min) with two lamps set at normal power 
giving an exposure of 100 mj/cm.sup.2. The thermal cure cycle on all 
samples was one hour at 70.degree. C. then 16 hours at 100.degree. C. 
Tensile tests were preformed as described in the tensile test section. The 
results are presented in Table 34-36. 
TABLE 34 
__________________________________________________________________________ 
0.12% Catalyst 
Comparative Tensile, Energy at 
Tan Modulus 
Example 
Catalyst 
MPa % Elongation 
Break, N-m 
MPa 
__________________________________________________________________________ 
C33 CAT1 24.3 5.7 0.11 677 
C34 CAT2* 
2.1 203.4 0.22 2.4 
C35 CAT3** 
-- -- -- -- 
C36 CAT4 76 10 0.60 1342 
__________________________________________________________________________ 
*samples not fully cured. 
**samples did not cure, no test run. 
TABLE 35 
__________________________________________________________________________ 
0.25% catalyst 
Comparative Tensile, Energy at 
Tan Modulus 
Example 
Catalyst 
MPa % Elongation 
Break, N-m 
MPa 
__________________________________________________________________________ 
C37 CAT1 20.22 4 0.06 676 
C38 CAT2 45.6 5.3 0.18 1226 
C39 CAT3* 
-- -- -- -- 
C40 CAT4 81.2 9 0.63 1329 
__________________________________________________________________________ 
*samples did not cure, no test run. 
TABLE 36 
__________________________________________________________________________ 
0.5% catalyst 
Comparative Tensile, Energy at 
Tan Modulus 
Example 
Catalyst 
MPa Elongation % 
Break, N-m 
MPa 
__________________________________________________________________________ 
C41 CAT1 13 2.6 0.3 580 
C42 CAT2 50.6 4.4 0.17 1464 
C43 CAT3* 
36.1 19 0.57 836 
C44 CAT4 71.8 9 0.66 1283 
__________________________________________________________________________ 
*samples not fully cured. 
The data of Tables 34, 35, and 36 demonstrate that these Lewis acids 1) had 
different levels of activity when used at the same weight percentage, some 
were more effective than others at lower levels which would be more 
advantageous from a cost standpoint and 2) the same composition was useful 
to produce different physical properties when cured by these various Lewis 
acids. It has been shown that their activities were not the same and the 
cured composition exhibited different properties. 
In sum, all Lewis acids are not equivalent and one cannot predict the 
usefulness of the stabilizing addition without extensive experimentation. 
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, and it should be understood that this invention 
is not to be unduly limited to the illustrative embodiments set forth 
herein.