Polymerizable compositions containing highly fluorinated aliphatic sulfonyl protonic acid catalyst

Two-part polymerizable compositions are described which contain (a) organic material having epoxide functionality, (b) organic material having hydroxyl functionality, and (c) a catalyst comprising highly fluorinated aliphatic sulfonyl protonic acid or a compound capable of liberating such acid. The compositions polymerize essentially completely at room temperature (or at slightly elevated temperatures). The polymerized compositions have desirable dielectric properties and are therefore especially useful for potting electrical components.

BACKGROUND OF THE INVENTION 
This invention relates to polymerizable compositions and, more 
particularly, to compositions containing organic material having epoxide 
functionality and organic material having hydroxyl functionality. 
Compositions based on the reaction of an organic material having epoxide 
functionality with an organic material containing hydroxyl functionality 
have previously been disclosed. For example, U.S. Pat. Nos. 2,914,490, 
2,990,396, 3,242,104, 3,244,754, 3,281,491, 3,379,791 and 3,424,817 
disclose such compositions containing one of a variety of acid catalysts 
or basic catalysts. These compositions are polymerized to thermoset resins 
by heating them at 50.degree. C. to 250.degree. C. from 1 to several 
hundred hours and accordingly they do not polymerize to a tack-free state 
in less than 30 minutes. Because of the need for use of thermal energy, 
and extended reaction times, in order to cure these compositions, they are 
not suitable or convenient for many applications. 
U.S. Pat. Nos. 3,080,341, and 3,281,491 disclose compositions based on the 
reaction of an organic material having epoxide functionality with an 
organic material having hydroxyl functionality in the presence of a Lewis 
acid. Although such compositions polymerize to a tack-free state in less 
than about 15 minutes, the polymerization is inhibited by the presence of 
moisture. Consequently, erratic results can be obtained when curing the 
compositions under various conditions of humidity. 
Furthermore, the rate of polymerization of epoxide-containing material with 
hydroxyl-containing material varies drastically with small changes in 
concentration of Lewis acid catalysts. Consequently, the rate of 
polymerization of such compositions can be difficult to control when using 
such catalysts. Also, Lewis acid catalysts may decompose with aging at 
elevated temperatures resulting in compositions whose cure times change 
significantly with time. This has been particularly noted with Lewis acid 
catalysts of the phosphorus family, e.g. PF.sub.5. 
U.S. Pat. No. 2,897,163 discloses the polymerization of butadiene dioxide 
and a polyoxyalkylene polyol, in the presence of an alkali metal 
alcoholate, to polyhydric oxyhydrocarbon products. Such compositions 
require 2 to 20 hours at 90.degree. C. to 100.degree. C. to assure 
complete reaction and are therefore not rapidly polymerizable 
compositions. 
SUMMARY OF THE INVENTION 
In accordance with the present invention there is provided a two-part 
polymerizable composition comprising: 
(a) a first organic material having epoxide functionality greater than 1; 
(b) a second organic material having hydroxyl functionality of at least 1; 
and 
(c) a catalyst comprising highly fluorinated aliphatic sulfonyl protonic 
acid or a compound capable of liberating such acid, said catalyst being 
present in an amount of at least about 0.01% by weight of said first 
organic material. 
These compositions polymerize rapidly at room temperature (or at slightly 
elevated temperatures). Also, the cured product exhibits very desirable 
dielectric properties. Accordingly, these compositions are very useful as, 
for example, potting compounds, adhesives, coatings, binders, etc. 
Because the compositions cure at or near room temperature they may be used 
in applications where elevated temperatures must be avoided. Also, since 
the compositions polymerize to essential completion rapidly their use 
results in a considerable saving of time. 
Furthermore, polymerization of the compositions is not significantly 
inhibited in the presence of moisture. Moreover, the rate of 
polymerization of the compositions is not as sensitive to change in 
catalyst concentration as is the case with prior compositions.

DETAILED DESCRIPTION OF THE INVENTION 
Epoxy-containing materials useful in the compositions of the invention are 
any organic compounds having an oxirane ring 
##STR1## 
polymerizable by ring opening. Such materials, broadly called epoxides, 
include monomeric epoxy compounds and epoxides of the polymeric type and 
can be aliphatic, cycloaliphatic, aromatic or heterocyclic. These 
materials generally have, on the average, at least one polymerizable epoxy 
group per molecule (preferably two or more epoxy groups per molecule). The 
polymeric epoxides include linear polymers having terminal epoxy groups 
(e.g., a diglycidyl ether of a polyoxyalkylene glycol), polymers having 
skeletal oxirane units (e.g. polybutadiene polyepoxide), and polymers 
having pendent epoxy groups (e.g., a glycidyl methacrylate polymer or 
copolymer). The epoxides may be pure compounds but are generally mixtures 
containing one, two or more epoxy groups per molecule. The "average" 
number of epoxy groups per molecule is determined by dividing the total 
number of epoxy groups in the epoxy-containing material by the total 
number of epoxy molecules present. It is preferred that no more than about 
25% of the epoxy equivalents in the compositions are in the form of a 
compound containing only one epoxy group. 
These epoxy-containing materials may vary from low molecular weight 
monomeric materials to high molecular weight polymers and may vary greatly 
in the nature of their backbone and substituent groups. For example, the 
backbone may be of any type and substituent groups thereon can be any 
group free of an active hydrogen atom which is reactive with an oxirane 
ring at room temperature. Illustrative of permissible substituent groups 
include halogens, ester groups, ethers, sulfonate groups, siloxane groups, 
nitro groups, amide groups, nitrile groups, phosphate groups, etc. The 
molecular weight of the epoxy-containing materials may vary from 58 to 
about 100,000 or more. Mixtures of various epoxy-containing materials can 
also be used in the compositions of this invention. 
Useful epoxy-containing materials include those which contain cyclohexene 
oxide groups such as the epoxycyclohexanecarboxylates, typified by 
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 
3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexane 
carboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate. For a 
more detailed list of useful epoxides of this nature, reference is made to 
the U.S. Pat. No. 3,117,099, incorporated herein by reference. 
Further epoxy-containing materials which are particularly useful in the 
practice of this invention include glycidyl ether monomers of the formula 
##STR2## 
where R' is alkyl or aryl and n is an integer of 1 to 6. Examples are the 
glycidyl ethers of polyhydric phenols obtained by reacting a polyhydric 
phenol with an excess of chlorohydrin such as epichlorohydrin (e.g., the 
diglycidyl ether of 2,2-bis-(2,3-epoxypropoxyphenol)propane). Further 
examples of epoxides of this type which can be used in the practice of 
this invention are described in U.S. Pat. No. 3,018,262, incorporated 
herein by reference, and in "Handbook of Epoxy Resins" by Lee and Neville, 
McGraw-Hill Book Co., New York (1967). 
There are a host of commercially available epoxycontaining materials which 
can be used in this invention. In particular, epoxides which are readily 
available include propylene oxide, octadecylene oxide, epichlorohydrin, 
styrene oxide, vinyl cyclohexene oxide, glycidol, glycidylmethacrylate, 
diglycidyl ether of Bisphenol A (e.g., those available under the trade 
designations "Epon 828," "Epon 1004" and "Epon 1010" from Shell Chemical 
Co., "DER-331," "DER-332," and "DER-334," from Dow Chemical Co.), 
vinylcyclohexene dioxide (e.g., "ERL-4206" from Union Carbide Corp.), 
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexene carboxylate (e.g., 
"ERL-4221" from Union Carbide Corp.), 
3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexene 
carboxylate (e.g. "ERL-4201" from Union Carbide Corp.), 
bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate (e.g. "ERL-4289" from 
Union Carbide Corp.), bis(2,3-epoxycyclopentyl) ether (e.g., "ERL-0400" 
from Union Carbide Corp.), aliphatic epoxy modified with polypropylene 
glycol (e.g., "ERL-4050" and "ERL-4052" from Union Carbide Corp.), 
dipentene dioxide (e.g. "ERL-4269" from Union Carbide Corp.), epoxidized 
polybutadiene (e.g. "Oxiron 2001" from FMC Corp.), silicone resin 
containing epoxy functionality (e.g. 2,4,6,8,10-pentakis 
[3-(2,3-epoxypropoxy)propyl]-2,4,6,8,10-pentamethylcyclopentasiloxane and 
the diglycidyl ether of 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane), 
flame retardant epoxy resins (e.g. "DER-580," a brominated bisphenol type 
epoxy resin available from Dow Chemical Co.), 1,4-butanediol diglycidyl 
ether (e.g. "Araldite RD-2" from Ciga-Geigy), polyglycidyl ether of 
phenolformaldehyde novolak (e.g. "DEN-431" and "DEN-438" from Dow Chemical 
Co.), and resorcinol diglycidyl ether (e.g. "Kopoxite" from Koppers 
Company, Inc.). 
Other epoxy-containing materials are copolymers of acrylic acid esters of 
glycidol such as glycidylacrylate and glycidylmethacrylate with one or 
more copolymerizable vinyl compounds. Examples of such copolymers are 1:1 
styrene-glycidylmethacrylate, 1:1 methylmethacrylate-glycidylacrylate and 
a 62.5:24:13.5 methylmethacrylate-ethyl acrylate-glycidylmethacrylate. 
Still other epoxy-containing materials, albeit less preferable, are the 
polyurethane polyepoxides which are obtained by reacting an organic 
polyisocyanate with a triol or a mixture of a triol and diol to form an 
isocyanate-terminated polyurethane prepolymer and reacting the prepolymer 
with a hydroxy aliphatic epoxide compound. Further examples of 
epoxy-containing material of this type which can be used in the practice 
of this invention are described in U.S. Pat. No. 3,445,436, incorporated 
herein by reference. 
The hydroxyl-containing material which is used in the present invention may 
be any liquid or solid organic material having hydroxyl functionality of 
at least 1, and preferably at least 2. Also, the hydroxyl-containing 
organic material is free of other "active hydrogens." The term "active 
hydrogen" is well known and commonly used in the art, and as used herein 
it means active hydrogen as determined by the method described by 
Zerewitinoff in J. Am. Chem. Soc., Vol. 49, 3181 (1927), incorporated 
herein by reference. Of course, the hydroxyl-containing material is also 
substantially free of groups which may be thermally unstable. 
Preferably the organic material contains two or more primary or secondary 
aliphatic hydroxyl groups (i.e. the hydroxyl group is bonded directly to a 
non-aromatic carbon atom). The hydroxyl groups may be terminally situated, 
or they may be pendent from a polymer or copolymer. The molecular weight 
(i.e. number average molecular weight) of the hydroxyl-containing organic 
material may vary from very low (e.g. 62) to very high (e.g. one million 
or more). The equivalent weight (i.e. number average equivalent weight) of 
the hydroxyl-containing material is preferably in the range of about 31 to 
5000. When materials of higher equivalent weight are used they tend to 
reduce the rate and extent of copolymerization. 
Representative examples of suitable organic materials having a hydroxyl 
functionality of 1 include alkanols, monoalkyl esters of 
polyoxyalkyleneglycols, monoalkyl ethers of alkyleneglycols, and others 
known to the art. 
Representative examples of useful monomeric polyhydroxy organic materials 
include alkylene glycols (e.g. 1,2-ethanediol, 1,3-propanediol, 
1,4-butanediol, 2-ethyl-1,6-hexanediol, bis(hydroxymethyl)cyclohexane, 
1,18-dihydroxyoctadecane, 3-chloro-1,2-propanediol), polyhydroxyalkanes 
(e.g., glycerine, trimethylolethane, pentaerythritol, sorbitol) and other 
polyhydroxy compounds such as N,N-bis(hydroxyethyl)benzamide, 
2-butyne-1,4-diol, 4,4'-bis(hydroxymethyl)diphenylsulfone, castor oil, 
etc. 
Representative examples of useful polymeric hydroxycontaining materials 
include polyoxyethylene and polyoxypropylene glycols and triols of 
molecular weights from about 200 to about 10,000, corresponding to 
equivalent weights of 100 to 5000 for the diols or 70 to 3300 for triols; 
polytetramethylene glycols of varying molecular weight; copolymers of 
hydroxypropyl and hydroxyethyl acrylates and methacrylates with other free 
radical-polymerizable monomers such as acrylate esters, vinyl halides, or 
styrene; copolymers containing pendent hydroxy groups formed by hydrolysis 
or partial hydrolysis of vinyl acetate copolymers, polyvinylacetal resins 
containing pendent hydroxyl groups; modified cellulose polymers such as 
hydroxyethylated and hydroxypropylated cellulose; hydroxy-terminated 
polyesters and hydroxyterminated polylactones; and hydroxy-terminated 
polyalkadienes. 
Useful commercially available hydroxyl-containing materials include the 
"Polymeg" .RTM. series (available from Quaker Oats Company) of 
polytetramethylene ether glycols such as "Polymeg" 650, 1000 and 2000; 
"PeP" series (available from Wyandotte Chemicals Corporation) of 
polyoxyalkylene tetrols having secondary hydroxyl groups such as "PeP" 
450, 550 and 650; "Butvar" series (available from Monsanto Chemical 
Company) of polyvinylacetal resins such as "Butvar" B-72A, B-73, B-76, 
B-90 and B-98; and "Formvar" 7/70, 12/85, 7/95S, 7/95E, 15/95S and 15/95E; 
"PCP" series (available from Union Carbide) of polycaprolactone polyols 
such as "PCP" 0200, 0210, 0230, 0240, 0300; "Paraplex U-148" (available 
from Rohm and Haas), an aliphatic polyester diol; "Multron" &gt; series 
(available from Mobay Chemical Co.) of saturated polyester polyols such as 
"Multron" R-2, R-12A, R-16, R-18, R-38, R-68 and R-74; "Klucel E" 
(available from Hercules Inc.) a hydroxypropylated cellulose having an 
equivalent weight of approximately 100; and "Alcohol Soluble Butyrate" 
(available from Eastman Kodak) a cellulose acetate butyrate ester having a 
hydroxyl equivalent weight of approximately 400. 
The amount of hydroxyl-containing organic material used in the compositions 
of the invention may vary over broad ranges, depending upon factors such 
as the compatibility of the hydroxyl-containing material with the epoxide, 
the equivalent weight and functionality of the hydroxyl-containing 
material, the physical properties desired in the final cured composition, 
etc. 
Generally speaking, with increasing amounts of hydroxyl-containing material 
in the composition the cured product exhibits improved impact resistance, 
adhesion to substrates, flexibility, and decreased shrinkage during 
curing, and correspondingly there is a gradual decrease in hardness, 
tensile strength and solvent-resistance. 
Although both mono-functional and poly-functional hydroxyl-containing 
materials provide desirable results in the compositions of the invention, 
use of the poly-functional hydroxyl-containing materials is highly 
preferred for a majority of applications, although the mono-functional 
hydroxyl-containing materials are particularly effective in providing low 
viscosity, solvent-free coating compositions. When using 
hydroxyl-containing organic materials having a functionality significantly 
less than 2 (e.g. 1 to 1.5), amounts greater than about 0.2 equivalent of 
hydroxyl per equivalent of epoxy tend to provide cured compositions which 
are generally low in internal strength and tensile strength and are 
susceptible to solvent attack, and consequently may be unsuitable for many 
applications. This tendency becomes increasingly more apparent with 
increasing equivalent weight of the hydroxyl-containing material. 
Accordingly, when using mono-functional hydroxy materials it is preferred 
that the equivalent weight thereof be no greater than about 250. When 
using mixtures of mono- and poly-functional hydroxyl-containing materials, 
up to about 25% of the total hydroxyl equivalents in the mixture may be in 
the form of the mono-functional hydroxyl-containing material. 
In the polymerizable compositions of the invention the ratio of equivalents 
of hydroxyl-containing material to equivalents of epoxide may vary from 
about 0.001/1 to 3.1, preferably from about 0.3/1 to 1.5/1, depending upon 
the properties desired in the cured composition. For applications where 
one primarily desires flexibilization of an epoxy resin (e.g., for 
protective coatings on metal) ratios as low as 0.001/1 provide improved 
results. For applications where the epoxide is present primarily as an 
insolubilizing agent for a polyhydroxyl-containing film-forming 
thermoplastic organic material (e.g. coatings for printing plates), ratios 
of hydroxyl equivalents to epoxide equivalents may be as high as 3/1. 
Generally speaking, the higher the hydroxyl equivalent weight the more 
effective such material is in imparting a given degree of toughness and 
flexibility to the cured composition. 
Mixtures of hydroxyl-containing materials may be used, when desired. For 
example, one may use mixtures of two or more poly-functional hydroxy 
materials, one or more mono-functional hydroxy materials with 
poly-functional hydroxy materials, etc. 
Catalysts which are useful in the compositions of the invention for 
effecting substantially complete reaction between the first and second 
organic materials are bis(highly fluorinated aliphatic sulfonyl) alkanes 
(preferably C.sub.1 -C.sub.5) and compounds which liberate such catalysts 
in the presence of, e.g. heat or moisture. For example, bis(highly 
fluorinated alkyl sulfonyl)alkenes, upon hydrolysis, will yield 
bis-(highly fluorinated alkyl sulfonyl) alkanes. 
The catalysts useful in this invention are generally called highly 
fluorinated aliphatic sulfonyl protonic acids. Preferably, the catalysts 
are bis(perfluoroalkylsulfonyl)methanes. 
In the practice of this invention, the term highly fluorinated aliphatic 
radical encompasses fluorinated, saturated, monovalent, aliphatic radicals 
having 1 to 20 carbon atoms. The skeletal chain of the radical may be 
straight, branched or, if sufficiently large (e.g. at least 3 or 4 atoms) 
cycloaliphatic, and may be interrupted by divalent oxygen atoms or 
trivalent nitrogen atoms bonded only to carbon atoms. Preferably the chain 
of the fluorinated aliphatic radical does not contain more than one hetero 
atom, i.e. nitrogen or oxygen, for every two carbon atoms in the skeletal 
chain. A fully fluorinated group is preferred, but hydrogen or chlorine 
atoms may be present as substituents in the fluorinated aliphatic radical 
provided that not more than one atom of either is present in the radical 
for each carbon atom. Preferably, the fluoroaliphatic radical is a 
saturated perfluoroalkyl radical having a skeletal chain that is straight 
or branched and has the formula 
EQU C.sub.x F.sub.2x+1 
wherein x has a value from 1 to 18. 
The preferred catalysts of this invention are those compounds having the 
formula 
##STR3## 
where R.sub.f ' and R.sub.f are independently a highly fluorinated or 
perfluorinated alkyl and R is selected from H, Br, Cl, I, alkyl having 1 
to 20 or preferably 1 to 4 carbon atoms, alkenyl of 3 to 4 carbon atoms, 
aryl (e.g. phenyl, pyridyl naphthyl, thienyl, benzthienyl) or alkaryl (of 
up to 10 carbon atoms); the alkyl, aryl and alkaryl may, if desired, be 
substituted by one or more halogens, highly fluorinated alkylsulfonyl, 
carboxyl, alkoxycarbonyl, nitro, alkoxy, or acyloxy. 
By fluorinated alkyl, it is meant herein a fluorinated, saturated 
monovalent, non-aromatic, aliphatic radical that is straight, branched, or 
cyclic. A fully fluorinated group is preferred, but hydrogen or chlorine 
atoms may be present as substituents in the fluorinated aliphatic radical 
provided that not more than one atom of either is present in the radical 
for every two atoms. The fluorinated aliphatic radical generally contains 
not more than 20 carbon atoms, preferably less than 8 carbon atoms, and 
more preferably contains up to 4 carbon atoms. Illustrative 
bis(perfluoroalkyl sulfonyl) protonic acids are: 
Bis(trifluoromethylsulfonyl)methane 
Tris(trifluoromethylsulfonyl)methane 
Bis(trifluoromethylsulfonyl)-4-bromophenylmethane 
Bis(trifluoromethylsulfonyl)-2-thienylmethane 
Bis(trifluoromethylsulfonyl)chloromethane 
Bis(trifluoromethylsulfonyl)benzylmethane 
Bis(trifluoromethylsulfonyl)phenylmethane 
Bis(trifluoromethylsulfonyl)-1-naphthylmethane 
Bis(perfluorobutylsulfonyl)methane 
Perfluorobutyltrifluoromethylmethane 
Ethyl, 6, 6-Bis(perfluoromethylsulfonyl)-4-bromohexanoate 
Methyl 4,4-Bis(perfluoromethylsulfonyl)-2-carbomethoxy-2-bromobutanoate 
Ethyl 4,4-Bis(perfluoromethylsulfonyl)-2-carboethoxy-2-nitrobutanoate 
1,1,3,3-Tetra(trifluoromethylsulfonyl)propane 
1,1-Bis(trifluoromethylsulfonyl)octadecane 
Representative examples of suitable fluoroalkyl protonic acids useful as 
catalysts herein are described in U.S. Pat. Nos. 3,632,843, 3,704,311, 
3,704,408, 3,776,960, 3,794,687, and assignee's copending application, 
Ser. No. 556,494, filed Mar. 7, 1975, incorporated herein by reference. 
The compositions of the invention are typically provided as two-part 
compositions in which Part A contains organic material having epoxide 
functionality greater than 1 and Part B contains organic material having a 
hydroxyl functionality of at least 1 and also contains the desired 
catalyst. 
Additionally, the compositions may contain conventional fillers to modify 
or impart desirable properties thereto. The fillers may be either organic 
or inorganic, e.g. finely divided silica, clays, flake mica, titanium 
dioxide, gypsum, refractories, colloidal carbon, glass fibers, and 
powders, flakes and fibers of organic polymers such as nylon and 
phenolformaldehyde resin. The compositions may also contain dyes, 
pigments, plasticizers, and the like. 
The invention is further illustrated by means of the following non-limiting 
examples wherein the term "parts" refers to parts by weight unless 
otherwise indicated. 
EXAMPLES 1-6 
Several two-part curable compositions were prepared using various 
catalysts. In each example, Part A of the composition comprised 80 parts 
by weight diglycidyl ether of Bisphenol A ("Epon 828," commercially 
available from Shell Development Co.), and Part B comprised 20 parts by 
weight diethyleneglycol. The catalyst to be tested was also present in 
Part B, and the amount of catalyst used was sufficient to bring about 
gelling of the mixture of Part A and Part B in about 15 minutes. 
Table I below shows, for each example, the catalyst tested, the amount of 
catalyst present, and the surface condition (i.e. tack-free or tacky) of 
the product attained by reaction of Part A and Part B after 0.5 hour in an 
atmosphere having a relatively humidity of about 40% (further curing by 
heating the products at 60.degree. C. for 0.5 hour did not change the 
surface conditions listed). 
TABLE I 
______________________________________ 
Surface 
Ex. No. Catalyst (Parts) Condition 
______________________________________ 
1 (CF.sub.3 SO.sub.2).sub.2 CH.sub.2 
(0.12) Tack-free 
2 (CF.sub.3 SO.sub.2).sub.2 CH(C.sub.6 H.sub.5) 
(0.19) " 
3 DSMe* (0.06) " 
4 DSBrMe** (0.08) " 
5 BF.sub.3 (0.05) Tacky 
6 PF.sub.5 (0.15) " 
______________________________________ 
*methyl 4,4-bis(trifluoromethylsulfonyl)-2-carbomethoxybutanoate 
**methyl 4,4-bis(trifluoromethylsulfonyl)-2-carbomethoxy-2-bromobutanoate 
These examples show that highly fluorinated aliphatic sulfonyl protonic 
acid catalysts are effective in curing the compositions to a tack-free 
state even in atmospheres having a considerable relative humidity, whereas 
compositions containing conventional Lewis Acid catalysts remain tacky 
under the same conditions. 
EXAMPLES 7-11 
To illustrate the curing characteristics of various compositions in the 
presence of water, in addition to atmospheric humidity, several two-part 
compositions were prepared. Part A of each composition was as described in 
Examples 1-6; Part B comprised 20 parts by weight of diethyleneglycol and, 
for each example, sufficient catalyst to bring about gelling of the 
mixture of Part A and Part B in 1-2 minutes. Additionally, water (1% based 
on total weight of Part A and Part B) was added during the mixing of Part 
A and Part B. 
Table II below shows, for each example, the catalyst tested, the amount of 
catalyst present, the gel time in the presence of 1% water, and the 
surface condition (i.e. tack-free or tacky) of the product attained by 
reaction of Part A and Part B after 0.5 hour in an atmosphere having a 
relative humidity of about 40%. 
TABLE II 
______________________________________ 
Gel Time 
(Minutes) 
Ex. O% 1% Surface 
No. Catalyst (Parts) Water Water Condition 
______________________________________ 
7 BF.sub.3 (0.02) 1-2 20 Tacky 
8 (CF.sub.3 SO.sub.2)CH.sub. 2 
(1.2) " 6 Tack-free 
9 (CF.sub.3 SO.sub.2)CH(C.sub. 6 H.sub.5) 
(1.2) " 8 " 
10 DSMe* (1.0) " 13 " 
11 DSBrMe** (0.6) " 14 " 
______________________________________ 
*methyl 4,4-bis(trifluoromethylsulfonyl)-2-carbomethoxybutanoate 
**methyl 
4,4-bis(trifluoromethylsulfonyl)-2-carbomethoxy-2-bromobutantanoate 
These examples show that the curing of compositions containing highly 
fluorinated aliphatic sulfonyl protonic acid catalysts is not appreciably 
retarded by the presence of 1% water, whereas the curing of compositions 
containing BF.sub.3 is significantly retarded under the same conditions. 
The examples further show that tack-free surfaces are obtained even when 
curing the foregoing compositions of this invention in the presence of 1% 
water. 
EXAMPLE 12 
To show the effect of increasing amounts of hydroxyl-containing material in 
the compositions of the invention, two series of experiments were run in 
which the amount of hydroxyl-containing material was incrementally 
increased from 0 to 30% by weight of total composition. In one series 
bis(trifluoromethylsulfonyl)methane was used as catalyst and in the other 
boron trifluoride was the catalyst. Part A comprised "Epon 828;" Part B 
comprised diethyleneglycol (DEG). The results are shown in Table III. 
TABLE III 
__________________________________________________________________________ 
Composition: 
"Epon 828"/DEG 
100/0 
95/5 
90/10 
85/15 
80/20 
75/25 
70/30 
__________________________________________________________________________ 
Catalyst-0.6 
part (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
Gel Time (sec.) 
.infin. 
190 120 120 90 100 110 
Surface After 
60 mins. NT.sup.(1) 
NT NT NT NT NT 
Catalyst-0.2 
part BF.sub.3 
Gel Time (sec.) 
15 45 60 70 90 120 130 
Surface After 
60 mins. T.sup.(2) 
T T T T T T 
__________________________________________________________________________ 
(1)NT signifies non-tacky surface after 60 minutes at relative humidity o 
about 40&. 
(2)T signifies tacky surface after 60 minutes at relative humidity of 
about 40%. 
In Table III, it may be seen that when using a highly fluorinated aliphatic 
sulfonyl protonic acid catalyst, as the concentration of diethylene glycol 
(DEG) is increased, the gel time drops remarkably from infinity (i.e. no 
curing) to 190 seconds with only 5% DEG and continues to drop with 
concentrations of DEG up to 20%. Above 20% DEG, the gel time rises slowly. 
On the other hand, when using BF.sub.3 as the catalyst, the gel time of 
the composition increases linearly with increased DEG concentration. 
EXAMPLES 13-26 
To illustrate the effect of catalyst concentration on the rate of curing of 
compositions containing both (a) material having epoxide functionality, 
and (b) material having hydroxyl functionality, there were run a series of 
examples, each having a Part A and a Part B. Part A in each example 
comprised 50 grams of a mixture of 80 parts "Epon 828" and 20 parts "ERL 
4206" (vinyl cyclohexene dioxide commercially available from Union Carbide 
Corp.). Part B in each example comprised 50 grams of a mixture of 50 parts 
"NIAX" HEXOL LS-490 (a hexahydroxyl alkyleneoxide derivative commercially 
available from Union Carbide Corp.), 35 parts "Polycine 99F" (a castor oil 
polyol commercially available from Baher Castor Oil Co.), and 15 parts of 
"Piccolastic A-5" (a thermoplastic polystyrene resin commercially 
available from Pennsylvania Industrial Chemical Corp.). 
For Examples 13-21 a sufficient amount of a solution of 20 parts 
bis(trifluoromethylsulfonyl)methane in 20 parts of diethylene glycol was 
added to Part B of each example to provide the catalyst concentration 
shown in Table IV (based on total weight of Part A plus Part B). For 
Examples 22-26 a sufficient amount of a solution of 20 parts boron 
trifluoride in 80 parts of glycerol was added to Part B of each example to 
provide the catalyst concentration shown in the table. Parts A and B were 
then mixed and the gel time shown in Table IV measured. 
TABLE IV 
______________________________________ 
Gel Time 
Ex. No. Catalyst Concentration Wt. % 
Minutes 
______________________________________ 
13 0.60 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
6.5 
14 0.50 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
7.9 
15 0.45 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
8.8 
16 0.40 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
12.1 
17 0.35 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
13.25 
18 0.30 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
14.0 
19 0.25 (CF.sub.3 SO.sub. 2).sub. 2 CH.sub.2 
23.6 
20 0.20 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
45.0 
21 0.15 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
70.0 
22 0.10 BF.sub.3 1.8 
23 0.08 BF.sub.3 2.9 
24 0.06 BF.sub.3 5.0 
25 0.05 BF.sub.3 
20.0 
26 0.04 BF.sub.3 &gt;90.0 
______________________________________ 
Thus, the data shows that a four-fold change in concentration of the highly 
fluorinated aliphatic sulfonyl protonic acid catalyst produces less than 
an eleven-fold change in the gel time of the composition. However, a 2.5 
fold change in concentration of boron trifluoride catalyst produces more 
than a 50 fold change in gel time of the composition. 
EXAMPLES 27-40 
To illustrate the effect of catalyst concentration on the rate of curing of 
compositions containing both (a) aromatic compounds having epoxide 
functionality, and (b) compounds having hydroxyl functionality, there were 
run a series of examples, each having a Part A and a Part B. Part A in 
each example comprised 80 grams of "Epon 828" (an aromatic epoxide); Part 
B comprised 20 grams of diethylene glycol. 
For Examples 27-34 there was added to Part B the various amounts of 
bis(trifluoromethylsulfonyl)methane shown in Table V, and in Examples 
35-40 there was added to Part B the various amounts of boron trifluoride 
shown in the table. The weight % of catalyst shown is based on the total 
weight of Part A and Part B. Parts A and B were then mixed and the gel 
time obtained for each composition is shown in Table V. 
TABLE V 
______________________________________ 
Gel Time 
Ex. No. Catalyst Concentration Wt. % 
Minutes 
______________________________________ 
27 0.60 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
4.3 
28 0.50 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
5.2 
29 0.45 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
5.7 
30 0.40 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
6.3 
31 0.30 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
8.5 
32 0.25 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
10.25 
33 0.20 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
12 
34 0.15 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
17.8 
35 0.14 BF.sub.3 5 
36 0.10 BF.sub.3 7 
37 0.08 BF.sub.3 9 
38 0.06 BF.sub.3 16 
39 0.05 BF.sub.3 18 
40 0.04 BF.sub.3 23 
______________________________________ 
Upon standing for about 1/2 hour each of the compositions of Examples 27-34 
were cured to a tack-free state while those of Examples 35-40 remained 
tacky. 
The data of Table V shows that when the material having epoxy functionality 
is an aromatic compound, compositions having a gel time of 5 to 10 minutes 
are obtained when using 0.25 to 0.50 weight percent of a highly 
fluorinated aliphatic sulfonyl protonic acid catalyst. On the other hand, 
when using BF.sub.3 as the catalyst the concentration thereof must be 
maintained about 0.08 and 0.14 weight percent in order to obtain a 
composition having a gel time of 5 to 10 minutes. Thus, the catalyst 
concentration in the foregoing compositions of the invention is less 
critical and requires less control than when using BF.sub.3. 
EXAMPLES 41-47 
To illustrate the effect of catalyst concentration on the curing of 
compositions containing both (a) aliphatic compounds having epoxide 
functionality, and (b) compounds having hydroxyl functionality, a series 
of examples were run as in Examples 27-40 except that Part A comprised an 
aliphatic epoxy compound "ERL 4221" in place of "Epon 828." "ERL-4221" is 
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexene carboxylate, commercially 
available from Union Carbide Corp. The concentrations of catalyst used and 
the gel times obtained for the various compositions are shown below in 
Table VI. 
TABLE VI 
______________________________________ 
Ex. Gel Time 
No. Catalyst Concentration Wt. % 
Minutes 
______________________________________ 
41 0.05 (CF.sub.3 SO.sub.2).sub. 2 CH.sub.2 
&lt;1 
42 0.025 (CF.sub.3 SO.sub.2).sub.2 CH.sub.2 
2 
43 0.017 (CF.sub.3 SO.sub.2).sub.2 CH.sub.2 
3 
44 0.010 (CF.sub.3 SO.sub.2 ).sub.2 CH.sub.2 
8 
45 0.008 (CF.sub.3 SO.sub.2).sub.2 CH.sub.2 
13 
46 0.06 BF.sub.3 Localized gelling in 
&lt;10 sec. but no cure 
47 0.04 BF.sub.3 Exotherm but no 
gelling or cure 
______________________________________ 
The data in Table VI show that compositions in which the epoxy-containing 
material is aliphatic require much less highly fluorinated aliphatic 
sulfonyl protonic acic catalyst for curing than is necessary for curing 
compositions in which the epoxy-containing material is aromatic. Example 
47 shows that 0.04% BF.sub.3 causes the composition to exotherm but does 
not gel or cure, and Example 46 shows that 0.06% BF.sub.3 causes localized 
gelling but does not effect complete gelling or curing. 
After standing for about 1/2 hour the product of each of Examples 41-45 
were cured to a tack-free state while the compositions of Examples 46 and 
47 were not gelled.