3,308,094

United States Patent Office Patented Mar. 7, 1967

1. 2
3,308,094 positions, and particularly epoxy resinous compositionis;
CATALYST FOR CURING POLYEPOXDES which have been cured in the presence of a 1,1,3,3-tetra
Alan E. Sherr, Norwalk, Conn., assignor to American alkylguanidine or a 1,1,2,3,3-pentaalkylguanidine.
Cyanamid Company, Stamford, Conn., a corporation These and other objects of my invention will be dis
of Maine cussed more fully hereinbelow.
No Drawing. Filed Nov. 8, 1962, Ser. No. 236,430 The tetra- and pentaalkylguanidines employed in the
16 Claims. (C. 269-47) practice of the present invention, as well as methods for
This invention relates to novel curable polyepoxide their preparation, are so well known in the art that a de
containing compositions. This invention further relates tailed discussion of said methods herein is considered un
to curable polyepoxide-containing compositions, and par O necessary. An illustrative but by no means exhaustive
ticularly thermosetting epoxy resinous compositions, listing of 1,1,3,3-tetraalkylguanidines and 1,1,2,3,3-penta
which contain a novel curing catalyst. alkylguanidines coming within the scope of Formula I
The widespread commercial importance achieved in above includes:
recent years by polyepoxide-containing compositions, and 1,1,3,3-tetramethylguanidine,
particularly thermosetting epoxy resinous compositions, 5 1,1,3,3-tetraethylguanidine,
has led to considerable experimentation in this field. 1,1,3,3-tetrapropylguanidine,
This is especially true with respect to attempts to provide 1,1-diethyl-3,3-dimethylguanidine.
better methods of curing these compositions. 1,1-dimethyl-3,3-dipropylguanidine,
Among the catalytic materials most commonly used at 1,1-dibutyl-3,3-dimethylguanidine,
present to cure polyepoxide-containing compositions are 20 1,3-diethyl-1,3-dimethylguanidine,
sodium hydroxide, sodium alkoxides and phenoxides, pri 1-ethyl-1,3,3-trimethylguanidine,
mary, secondary and tertiary amines, Friedel-Crafts 1-amyl-1,3,3-trimethylguanidine,
catalysts and various inorganic and organic acids and an 1-hexyl-1,3,3-triethylguanidine,
hydrides. However, one disadvantage shared by most 1,1,2,3,3-pentamethylguanidine,
of these catalysts is that they will convert polyepoxide 25 1,1,2,3,3-pentaethylguanidine,
containing compositions to a substantially insoluble and 2-ethyl-1,1,3,3-tetramethylguanidine,
infusible state fairly rapidly either at room temperature 2-propyl-1,1,3,3-tetramethylguanidine,
or at only slightly elevated temperatures, thus giving 2-butyl-1,1,3,3-tetramethylguanidine,
catalyzed compositions which exhibit marked increases in 2-hexyl-1,1,3,3-tetramethylguanidine,
room temperature viscosity shortly after the addition of 30 1,1-diethyl-2,3,3-trimethylguanidine,
the catalyst. This makes it necessary to use these cata 1,1-dipropyl-2,3,3-trimethylguanidine,
lyzed compositions within a relatively short time after 1,1-dibutyl-2,3,3-trimethylguanidine,
the catalyst has been added. - 1,3-dimethyl-1,2,3-triethylguanidine,
A further and perhaps more serious disadvantage in 1,2-diethyl-1,3,3-trimethylguanidine,
herent in many of these commonly used catalysts is the 35 1-hexyl-1,2,3,3-tetramethylguanidine,
fact that they must be used in relatively large amounts and the like. The tetramethyl- and pentamethylguani
to achieve the degree of cure necessary to obtain good
physical properties, e.g., flexural strength, high deflection dines, due to their relative ease of preparation, are pre
temperature, and the like, in the final cured composition. ferred. The above-described tetraalkyl- and pentaalkyl
I have now discovered that relatively small amounts 40 guanidines are either liquids at room temperature or will
of the 1,1,3,3-tetraalkylguanidines and 1,1,2,3,3-penta melt at temperatures below those at which the poly
alkylguanidines represented by the general formula: epoxide compositions containing them will be cured and,
in the liquid state, will dissolve in the polyepoxide.
The polyepoxide-containing compositions which can be
45 cured using my novel catalysts comprise organic materials
having a plurality of reactive 1,2-epoxy groups, i.e.,
wherein each R represents the same or a different lower ---
alkyl group having from 1 to 6 carbon atoms, inclusive, Yo^
Such as methyl, ethyl, propyl, n-butyl, sec-butyl, amyl, 50
groups. These polyepoxide materials can be monomeric
hexyl and the like, and R can represent hydrogen (in or polymeric, saturated or unsaturated, aliphatic, cyclo
the case of the tetra-substituted guanidines) or can also aliphatic, aromatic or heterocyclic, and they may be sub
represent a lower alkyl group (in the case of the penta Stituted, if desired, with other substituents besides the
substituted guanidines), preferably one having from 1 epoxy groups, e.g., hydroxyl groups, ether radicals, halo
to 6 carbon atoms, inclusive, as described above for R, gen atoms, and the like.
are efficient curing catalysts for polyepoxides in general A. Widely used class of polyepoxides which can be
and epoxy resins in particular. More particularly, the catalyzed according to the practice of the present in
practice of the present invention permits the preparation vention encompasses the resinous epoxy polyethers ob
of polyepoxide-containing compositions which have a long tained by reacting an epihalodyrin, such as epichlorohy
pot life and yet can be cured at moderately elevated 60 drin, epibromohydrin, epiiodohydrin, and the like, with
temperatures to provide substantially insoluble and in either a polyhydric phenol or a polyhydric alcohol.
fusible products having good physical properties. Among the polyhydric phenols which can be used in
It is, therefore, an object of my invention to provide preparing these resinous epoxy polyethers are dihydric
novel curable polyepoxide-containing compositions. phenols represented by the general formula:
It is also an object of my invention to provide novel 65
R3
curable polyepoxide-containing compositions, and par
ticularly thermosetting epoxy resinous compositions, con
taining, as a curing catalyst, a 1,1,3,3-tetraalkylguanidine,
e.g., 1,1,3,3-tetramethylguanidine, or a 1,1,2,3,3-pentaal
HO
& X--KY R - or (II
kylguanidine, e.g., 1,1,2,3,3-pentamethylguanidine. 70 wherein the phenolic hydroxy groups may be in any of
A further object of my invention is to provide substan the 2,2'; 2,3'; 2,4'; 3,3'; 3,4'; or 4,4' positions on the aro
tially insoluble and infusible polyepoxide-containing com matic nuclei, and each of R8 and R4 represent hydrogen,
an alkyl group, such as methyl, ethyl, propyl, isopropyl,
 3,308,094
3. 4.
butyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, iso The resulting resinous reaction products may contain
hexyl, and the like; a cyclo(lower) alkyl group, Such as free terminal hydroxyl groups or terminal hydroxyl
a cyclohexyl or substituted cyclohexyl group, e.g., meth groups and terminal epoxy groups, and will vary in molec
yl-, ethyl-, propyl-, butyl-, pentyl- and hexyl-substituted ular weight depending on the reactants employed, the
cyclohexyl, or an aromatic group, such as phenyl, tolyl, 5 relative amounts thereof, and the extent to which the
xyly, and the like. In addition, the phenolic rings may reaction is carried out. These thermosetting epoxy res
have other substituents besides the hydroxyl groups, for inous materials are generally soluble in solvents Such as
example lower alkyl groups containing from 1 to 4 carbon acetone, methyl ethyl ketones, methyl isobutyl ketone,
atoms, i.e., methyl, ethyl, propyl, isopropyl, butyl, Sec cyclohexanone, and the like.
butyl and tert-butyl groups, halogen atoms, i.e., fluorine, O A related class of polymeric polyepoxides which can
chlorine, bromine or iodine, and the like. be catalyzed according to the practice of the present in
An illustrative but by no means exhaustive listing of vention comprises the polyepoxypolyhydroxy polyethers
dihydric phenols falling within this general formula in obtained by reacting, again preferably in alkaline medium,
cludes 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxy a polyhydric phenol such as bisphenol A, resorcinol,
diphenyldimethylmethane (bisphenol A), 2,4'-dihydroxy catechol and the like, or a polyhydric alcohol such as
diphenylethylmethane, 3,3' - dihydroxydiphenyldiethyl glycerol, sorbitol, pentaerythritol and the like, with a
methane, 3,4-dihydroxydiphenylmethylpropylmethane, polyepoxide such as bis(2,3-epoxypropyl)ether, bis(2,3-
2,3'-dihydroxydiphenylethylphenylmethane, 4,4'-dihy epoxy-2-methylpropyl)ether, 1,2-epoxy-4,5-epoxypentane
droxydiphenylpropylphenylmethane, 4,4' - dihydroxydi and the like.
phenylbutylphenyimethane, 2,2' - dihydroxydiphenyidi 20 Another class of polymeric polyepoxides which can be
tolylmethane, 4,4'-dihydroxydiphenyltolylmethylmethane, cured by means of the above-described tetra- and penta
and the like. alkylguanidines includes the epoxy novolac resins obtained
Other polyhydric phenols which may also be coreacted by reacting, preferably in the presence of a basic catalyst,
with an epihalohydrin to provide these resinous epoxy e.g., sodium or potassium hydroxide, an epihalohydrin
polyethers are such compounds, as resorcinol, hydroqui 25 such as epichlorohydrin with the resinous condensate of
none, substituted hydroquinones, e.g., p-tert-butylhydro an aldehyde, e.g., formaldehyde, and either a monohydric
quinone, and the like, indanols such as those disclosed phenol, e.g., phenol itself, or a polyhydric phenol, e.g.,
in U.S. Patent No. 2,754,285 to Petropoulos, and poly bisphenol A. A representative number of the epoxy
hydric phenols having two hydroxy aryl groups separated novolac resins obtained by reacting an epihalohydrin with
by an aliphatic chain of at least six carbon atoms in 30 a monohydric phenol-formaldehyde resinous condensate
length, said chain being attached by carbon-to-carbon can be represented by the general formula:
bonding to nuclear carbon atoms of the hydroxyaryl O O
groups. Members of this latter class of polyhydric phe / N / N.
nols can be conveniently obtained by condensing phenol QCH-CH-CH, g R6 OCH-C-CH
itself with a phenol substituted with an aliphatic side
chain having one or more olefinic double bonds positioned
therein, thus providing the required number of separating CH
atoms between the two hydroxyphenyl groups of the re
Sulting polyhydric phenol. Cardonal, obtainable in known RS
manner from cashew nut shell liquid, is a convenient 40
source of phenols containing Such side chains. wherein, for example, R5 represents either hydrogen or
Among the polyhydric alcohols which can be core a lower alkyl group, such as methyl, ethyl, and the like,
R represents hydrogen, a halohydrin group, e.g.,
acted with an epihalohydrin to provide these resinous
epoxy polyethers are such compounds as ethylene glycol, OH Gl
propylene glycols, butylene glycols, pentane diols, bis (4-
hydroxycyclohexyl) dimethylmethane, 1,4-dimethylolben
-OH,-bH-CH,
45 a glycol group, e.g.,
zene, glycerol, 1,2,6-hexanetriol, trimethylol propane, OE OEI
mannitol, sorbitol, erythritol, pentaerythritol, their dimers,
trimers and higher polymers, e.g., polyethylene glycols, -CH-CH-CH,
polypropylene glycols, triglycerol, dipentaerythritol and or a glycidyl group, i.e.,
the like, polyallyl alcohol, polyvinyl alcohol, polyhydric 50
thioethers such as 2,2'-dihydroxydiethyl sulfide, 2,2',3,3'- /o
tetrahydroxydipropyl sulfide and the like, mercapto alco -CFI-CH-CH
hols such as o-monothioglycerol, c,C'-dithioglycerol, and and n is a number of 1 or greater. Similarly, a repre
the like, polyhydric alcohol partial esters such as mono Sentative number of the epoxy novolac resins obtained by
stearin, pentaerythritol monoacetate and the like, and hal reacting an epihalohydrin with a polyhydric phenol-form
ogenated polyhydric alcohols such as the monochlorohy aldehyde resinous condensate can be represented by the
drins of glycerol, sorbitol, pentaerythritol and the like. general formula:
When preparing these resinous epoxy polyethers from O O
an epihalohydrin and a polyhydric phenol, the reaction / N / N
will preferably be carried out in the presence of an 60 QCH-C H-CH g R6 QCH-CH-CH,
amount of an alkaline material, e.g., sodium hydroxide or
potassium hydroxide, sufficient to combine with the halo
gen released by the epihalohydrin during the course of the
reaction. The amount of epihalohydrin used is generally
in excess of the stoichiometric quantity required for re 65
CH G CH O
action with the epihalohydrin. In addition the reaction R3-C-R4 R-3-R. R-(-R
will preferably be carried out at a temperature ranging
from about 50° C. to about 150° C., usually for periods
of time ranging up to several hours.
When reacting in epihalohydrin, with a polyhydric al O O O
cohol, the reaction is preferably carried out in the pres OCH-CH-CH
/ N
OR8 Ari (CH-off So H
ence of an acid-acting material, e.g., hydrofluoric acid or
a boron trifluoride-ether complex, and the resulting halo (IV)
hydrin product is then dehydrohalogenated in the pres wherein R3 and R are as defined for Formula II above
ence of an alkaline material, . - 5 and R and n are as defined for Formula II above. Fur
 3,308,094
5 6
ther details concerning the nature and preparation of ate, bis(3,4-epoxycyclohexylmethyl)maleate, bis(3,4-
these epoxy novolac resins can be obtained in Carswell, epoxy-6-methylcyclohexylmethyl)succinate, ethylene gly
T. S., “Phenoplasts' (New York: Interscience Publishers, col bis(3,4-epoxycyclohexanecarboxylate), 2-ethyl-1,3-
1947), page 29 et seq. hexanediol bis(3,4-epoxy-6-methylcyclohexanecarboxyl
Still another class of polymeric polyepoxides which ate), tris(3,4-epoxycyclohexylmethyl) 1,2,4-hexanetricar
can be catalyzed with the above-described tetra- and penta boxylate, glyceryl tris(3,4-epoxy-6-methylcyclohexane
substituted guanidines includes polymers, i.e., homopoly carboxylate) and the like.
mers and copolymers, of epoxy-containing monomers Other monomeric polyepoxides which can be cured by
which also contain at least one polymerizable double bond. means of the above-described substituted guanidines in
Such monomers can be polymerized through their double 10 clude dicyclopentadiene dioxide, epoxidized triglycerides
bonds in known manner, e.g., in bulk or in solution in such as epoxidized glycerol trioleate, epoxidized glycerol
an inert organic solvent such as benzene and the like, pref trilinoleate, the diacetate of epoxidized glycerol trilinole
erably by heating in the presence of oxygen or a per ate and the like, 1,8-bis(2,3-epoxypropoxy) octane, 1,4-
oxide catalyst but in the absence of alkaline or acidic cat bis(2,3-epoxypropoxy) cyclohexane, 1,4-bis(3,4-epoxybu
alysts, leaving the epoxy groups unaffected and, therefore, 5 toxy)-2-chlorocyclohexane, 1,3-bis(2,3-epoxypropoxy)
regularly or randomly dispersed along the polymer chains. benzene, 1,4-bis(2,3-epoxypropoxy)benzene, 1,3-bis(2-
Among such ethylenically unsaturated epoxy-containing hydroxy-3,4-epoxybutoxy)benzene, 1,4-bis(2-hydroxy
monomers are vinyl 2,3-glycidyl ether, ally 2,3-glycidyl 4,5-epoxypentoxy)benzene, 1,3-bis(4,5-epoxypentoxy)-5-
ether, methallyl 2,3-glycidyl ether, methallyl 3,4-epoxy chlorobenzene, 4,4'-bis(2,3-epoxypropoxy) diphenyl ether,
butyl ether, glycidyl acrylate, glycidyl methacrylate, 2,3- 20 and epoxy ethers of polybasic acids such as diglycidyl
epoxypropyl crotonate, vinyl cyclohexane monoxide, 4 Succinate, diglycidyl adipate, diglycidyl maleate, di
glycidyloxystyrene, and the like. Suitable comonomers glycidyl phthalate, diglycidyl hexachloroendomethylene
for copolymerization with these ethylenically unsaturated tetrahydrophthalate and diglycidyl 4,4'-isopropylidenedi
epoxy-containing monomers include styrene, acrylonitrile, benzoate, and the like.
methacrylonitrile, methyl acrylate, ethyl acrylate, methyl 25 Many of these polyepoxides, and particularly those
methacrylate, vinyl chloride, vinylidene chloride, vinyl which are polymeric, can be conveniently referred to in
acetate, diallyl phthalate, and the like. terms of epoxy equivalency, i.e., the average number of
Among the monomeric polyepoxides which can be cat epoxy groups per molecule in the polyepoxide material.
alyzed according to the practice of the present invention Where the polyepoxide is monomeric and all of its epoxy
are the di- and triepoxides represented by the general 30 groups are intact, its epoxy equivalency will be repre
formula: sented by an integer, usually 2 or greater. However,
where the polyepoxide is polymeric its epoxy equivalency
will usually be represented by a fractional value of at
least about 1.0 or greater, e.g., 1.5, 1.8, 2.3 and the like,
since the polymer will usually contain molecules of differ
ent molecular weight and can also contain some mono
meric polyepoxide or have some of its epoxy groups de
E. E. In (v) hydrated or otherwise reacted.
It will be appreciated by those skilled in the art that
wherein A through F represent hydrogen or an alkyl 40 the catalyzed polyepoxide-containing compositions which
group, preferably a lower alkyl group having from 1 to 4 can be prepared according to the practice of the present
carbon atoms, inclusive, such as methyl, ethyl, propyl, n invention are not limited to those containing the above
butyl and the like, and X represents a divalent radical described polyepoxides, but that said polyepoxides are to
which can be be considered merely as being representative of the class
O O O 45 of polyepoxides as a whole. Further details concerning
-CH2-O-C-, -CH2-O-C-Y-C-O-CH the nature and preparation of the above-described poly
O
epoxides can be found in U.S. Patents Nos. 2,633,458;
2,872,427 and 2,884,408, among others, which are incor
porated herein by reference.
-C-O-Z-O-C- 50 The above-described tetra- and pentaalkylguanidines
in which case n equals 2, or a trivalent radical which can be employed in amounts ranging from about 0.5 part
can be to about 30 parts by weight, and preferably from about 1.
part to about 10 parts by weight, per hundred parts of
O polyepoxide. Mixtures of two or more tetraalkylguani
-CH-O-3-Y- -O-CE 55 dines, or two or more pentaalkylguanidines, or one or
more tetraalkylguanidines with one or more pentaalkyl
guanidines can also be employed.
The resulting catalyzed polyepoxide-containing compo
sitions can be used in any of the applications for which
60 polyepoxides are customarily used, e.g., as adhesives, im
Or pregnants, surface coatings, potting and encapsulating
compositions, in laminates, and particularly in glass cloth
filled laminates for use in electrical applications such as
printed circuits and the like, in castings for electrical ap
65 paratus, and the like.
Various conventionally employed additives can be ad
mixed with these tetra- or pentaalkylguanidine-catalyzed
in which case n equals 3, with Y representing an aliphatic polyepoxide-containing compositions prior to final cure.
or aromatic hydrocarbon radical containing from 2 to 12 For example, in certain instances it may be desirable to
carbon atoms, inclusive, and Z representing a lower ali 70 add minor amounts of co-catalysts or hardeners along
phatic hydrocarbon radical or a lower oxyalkylene group, with the tetra- or pentaalkylguanidine. Included among
e.g., -alkylene-O-alkylene- and the like. Included among ?these known catalysts and hardeners are alkali metal hy
such di- and triepoxides are 3,4-epoxycyclohexylmethyl, droxides, e.g., sodium or potassium hydroxide; alkali
3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcy metal alkoxides and phenoxides, e.g., sodium phenoxide;
clohexylmethyl, 3,4-epoxy-6-methylcyclohexanecarboxyl- 75 primary, secondary and tertiary monoamines and poly
 3,308,094
7 8
mines, e.g., mono-, di- and trimethylamine, mono-, di Examples II-V
Lnd triethylamine, isopropylamine, diisopropylamine, bu The procedure employed in Example I was repeated
ylamine, dibutylamine, cyclohexylamine, dicyclohexyl
lmine, diethylaminopropylamine, benzylamine, benzyldi inII, everyI
detail except for the following. In Examples
and IV, the amounts of 1,1,3,3-tetramethylguan
nethylamine, diethylenetriamine, dipropylenetriamine, di- 5 11.
butylenetriamine, triethylenetetramine, tetraethylenepent- idine used were 1 part, 2 parts and 7 parts, respectively,
mine, N,N-diethyl-1,3-propanediamine, 1,2-diamino-2- and in each case curing was accomplished by heating the
methylpropane, 2,3-diamino-2-methylbutane, 2,4-diamino- casting cell in an oven at 94° C. for 4% hours. In Ex
2-methylpentane, ethanolamine, triethanolamine, diethyl- ample V, which served as a control, the tetramethylguan
2thanolamine, aniline, dimethylaniline, dimethylamino-
methylphenol, tri(dimethylaminomethyl)phenol, dicyan- "" idine was replaced
methyl)phenol by 12 parts ofa tri(dimethylamino
tri(2-ethylhexoate), commercially-used
iamide, melamine, diallylmelamine, and the like, as well curing catalyst, and curing was accomplisehd by heating
as fatty acid salts thereof, e.g., tri(dimethylaminomethyl) the casting cell in an oven at 94° C. for 4% hours. In
phenol tri(2-ethylhexoate), and the like; polycarboxylic every case, a hard, cured casting resulted, and various
acids, e.g., oxalic acid, succinic acid, phthalic acid, maleic a significant physical properties of these castings are also
acid, and the like, as well as the corresponding anhy- given in Table I.
TABLE

efiection
Flexual Flexural Rockwell Temper- Dielectric | Dissi
Example Modulus Strength 1 IHaldness 2 attle Constant pation
under Factor
load 3

0. 51X06 19,500 87 3.72 0.00

0.47X06 19,500 95 3.78 0.0033
0.47X106 19,900 88 95 3, 62 0.0038
0.48X106 18,800 80 82 3.53 0.004.4
V (control) --- 0.44X108 16, 200 78 68 3.50 0.005

1 In pounds per squal'e inch.

2 'M' Scale.
3. C.
drides, and phenolic compounds, e.g., phenol, cresols, Example VI
Xylenols, resorcinol, and the like. Conventional pig The pot life of an epoxy resinous condensate catalyzed
ments, dyes, fillers, flame-retarding agents and other com according to the practice of the present invention was
patible natural and synthetic resins can also be added. determined in the following manner. Samples of the
Furthermore, known solvents for the polyepoxide mate epoxy resin employed in Examples I-V containing no
rials, such as acetone, methyl ethyl ketone, methyl iso catalyst, 1 phr (parts per hundred parts of resin), 2 phr
butyl ketone, dioxane, Cellosolve acetate, methyl Cello and 7 phr of 1,1,3,3-tetramethylguanidine, respectively,
solve acetate, dimethylformamide, trichlorpropane, ben were maintained in suitable containers at room tempera
zene, toluene, xylene, and the like, can be used if desired, 40 ture, and viscosity measurements were made periodically,
(e.g., in coating formulations. using a Brookfield viscometer (No. 4 spindle at 12
Depending on the composition itself and the end use r.p.m.). These viscosity measurements are given in the
for which it is intended, curing, i.e., advancing the poly following table.
‘epoxy component of the composition and any other com
ponent co-reactable therewith to a state of substantial in TABLE II
solubility and infusibility, can take place at temperatures 45
ranging from about room temperature, i.e., about 25 C., Wiscosity 2
or below (when the amount of catalyst present is at or ine 1
near the upper limit of the above-stated range or, at No Catalyst 1 phr. 2phr. 7phr.
lower catalyst concentrations, over a relatively long pe
riod of time) to about 200° C. 9, 150 6, 750 2,750 2,150
In order that those skilled in the art may more fully 9,000
9, 250
5,750
5,900
2,900
3,325
2,250
2,750
understand the inventive concept presented herein, the 9,250 6,700 3,000 3,100
following examples are set forth. These examples are 9, 250 6,700 3, 150 2,750
given solely by way of illustration, and should not be - - - -- - - -- - - - - - - - 7,750
8, 250
3, 650
4, 150
3,000
3,300
considered as expressing limitations unless so set forth - -- - - - - - - - - - - - -- - - 9,400
10,000
4,600
5,500
3,500
4,000
in the appended claims. All parts and percentages are 10,800 6,700 5,300
by weight, unless otherwise stated. 11,350
22,250
7, 350
25,000
5,300
>100,000
Example I 23,500
28,500
29, 250
39, 500
>100,000
>100,000
One hundred parts of Epon 828, a commercially avaii >100,000 >100,000 >100,000
able bisphenol A-epichlorohydrin thermosetting epoxy
resinous condensate having a viscosity (measured at 25 1 In hours.
2 in centipoises.
C.) of 100-160 poises and an epoxide equivalent (grams
of resin containing one gram-equivalent of epoxide) of
175-210, were heated to 50° C. in a suitable container. As can be seen from the above data, epoxy resins cata
Next, 0.5 part of 1,1,3,3-tetramethylguanidine was added, lyzed according to the practice of the present invention
and the resulting mixture was stirred for a few moments have excellent pot lives.
to disperse the catalyst. Example VII
A casting cell made of two 6-inch square glass plates
separated by /8-inch thick gasketing material was filled 70 The procedure of Example I was again repeated in
with the catalyzed epoxy resin mixture and then heated every detail except for the following. The tetramethyl
in an oven for 20 hours at 100° C. followed by 2 hours guanidine was replaced with 10 parts of 1,1,2,3,3-penta
at 150° C. to give a hard, cured resin casting. Various methylguanidine, and curing was accomplished by heating
significant physical properties of this casting are given the casting cell in an oven at 100° C. for 6 hours. The
in Table below. . . . 75 resulting casting was hard and fully cured.
 3,308,094
O
Example VIII part of phenol were heated, with stirring, to a temperature
One hundred parts of Araldite 6060, a commercially of about 40 C. in a suitable vessel until a substantially
available bisphenol A-epichlorohydrin thermosetting homogeneous blend was obtained. This blend was then
epoxy resinous condensate having a viscosity (measured added, with stirring, to 10 parts of Oxiron 2001, a com
at 130 C.) of 100 poises and an epoxide equivalent 5 mercially available thermosetting epoxidized polyolefin
(per 100 grams of resin) of 0.22, were admixed with 20 having a viscosity (measured at 25 C.) of 160 poises
parts of 1,1,3,3-tetramethylguanidine in an aluminum and an epoxide equivalent (grams of resin containing
dish. This mixture was warmed to 80 C, with stirring one gram-equivalent of epoxide) of 145, contained in an
to effect dispersion of the catalyst and then heated in an aluminum dish. The catalyzed mixture was warmed to
oven for 2 hours at 80° C., followed by 3 hours at O 80° C. with stirring to effect substantially complete dis
155° C. The resulting brittle, cured epoxy resin had a persion of the catalyst, then heated in an oven for 2
softening temperature of 88 C. hours at 80° C., followed by 18 hours at 148 C. to give
a cured epoxy resin.
Example IX Example XIX
One hundred parts of Araldite 6005, a commercially 15 The procedure of Example XVIII was repeated using 2
available bisphenol A-epichlorohydrin thermosetting epoxy 'parts of 1,1,3,3-tetramethylguanidine as the sole catalyst
resinous condensate having a viscosity (measured at 25 and Oxiron 2002, a commercially available thermosetting
C.) of 70-100 poises and an epoxide equivalent (per 100 epoxidized polyolefin having a viscosity (measured at 25
grams of resin) of 0.53-0.55, were admixed with 20 parts :20 C.) of 15 poises and an epoxide equivalent (grams of
of 1,1,3,3-tetramethylguanidine in an aluminum dish. resin containing one gram-equivalent of epoxide) of 232,
This mixture was warmed to 80° C. with stirring to effect in place of Oxiron 2001. A cured epoxy resin resulted.
dispersion of the catalyst, and then heated in an oven
for 2 hours at 80 C., followed by 3 hours at 155° C. Example XX
The resulting cured epoxy resin (Rockwell Hardness, M :25 The procedure of Example XIX was repeated using 0.45
Scale, of 77+5) had a softening temperature above part of phenol together with the tetramethylguanidine.
100° C. The resulting cured epoxy resin was rubbery in appear
Example X ance, and had a Rex Hardness of 41-4.
The procedure employed in Example IX was repeated It will be obvious to those skilled in the art that other
in every detail except for the following. Ten parts of 30 changes and variations can be made in carrying out the
1,1,2,3,3-pentamethylguanidine were employed as the cur present invention without departing from the spirit and
ing catalyst, and the catalyzed resin was heated for 3 scope thereof as defined in the appended claims.
hours at 80 C., followed by 18 hours at 148 C. The I claim:
resulting brittle, cured epoxy resin had a softening tem 1. A composition comprising (A) an organic resin
perature of 80° C. 35 forming polyepoxide compound selected from the group
Examples XI-XV consisting of monomeric and polymeric epoxides having
a plurality of reactive 1,2-epoxy groups, and an epoxide
In each of these examples, the procedure employed in equivalency of at least 1.0 and (B) a catalytic amount
Example IX was again repeated in every detail except for of a guanidine represented by the general formula:
the following. In Examples XI, XII and XIII, the penta 40
methylguanidine catalyst was replaced by 15 parts of
1-ethyl-1,3,3-trimethylguanidine, 15 parts of 1,1-diethyl N-C-N
3,3-dimethylguanidine and 15 parts of 1,1,3,3-tetraethyl R? Yi
guanidine, respectively. In Examples XIV and XV, the wherein each R represents an alkyl group having from 1
pentamethylguanidine catalyst was replaced by 15 parts 45 to 6 carbon atoms, inclusive, and R2 represents a member
of 1,1,3,3-tetramethyl-2-ethylguanidine and 15 parts of selected from the group consisting of hydrogen and a
1,1,2,3,3-pentaethylguanidine, respectively, and in each lower alkyl group.
case the catalyzed resin was cured by heating it for 3 hours 2. A composition comprising (A) an organic. resin
at 80 C., followed by 18 hours at 148° C. In every forming polyepoxide compound selected from the group
case, the resulting epoxy resin was fully cured. 50 consisting of monomeric and polymeric epoxides having
Example XVI a plurality of reactive 1,2-epoxy groups, and an epoxide
One hundred parts of Araldite 506, a commercially equivalency of at least 1.0 and (B) a catalytic amount
of 1,1,3,3-tetramethylguanidine.
available bisphenol A-epichlorohydrin thermosetting 3. A composition comprising (A) an organic resin
epoxy resinous condensate having a viscosity (measured 55 forming polyepoxide compound selected from the group
at 25 C.) of 50-70 poises and an epoxide equivalent consisting of monomeric and polymeric epoxides having
(per 100 grams of resin) of 0.54-0.58, were admixed a plurality of reactive 1,2-epoxy groups, and an epoxide
with 20 parts of 1,1,3,3-tetramethylguanidine in an alumi equivalency of at least 1.0 and (B) a catalytic amount
num dish. This mixture was warmed to 80° C. with stir. of a 1,1,2,3,3,-pentaalkylguanidine wherein the alkyl
ring to effect dispersion of the catalyst and then heated in 60 groups contain from 1 to 6 carbon atoms, inclusive.
an oven for 2 hours at 80° C., followed by 3 hours at 4. A composition comprising (A) an organic resin
155 C. The resulting cured epoxy resin (Rockwell forming polyepoxide compound Selected from the group
Hardness, M Scale, of 80-5) had a softening tempera
ture of 95 C.
consisting of monomeric and polymeric epoxides having
Example XVII a plurality of reactive 1,2-epoxy groups, and an epoxide
65 equivalency of at least 1.0 and (B) a catalytic amount
The procedure of Example XVI was repeated in every of 1,1,2,3,3-pentamethylguanidine.
detail except for the following. Ten parts of 1,1,2,3,3- 5. A composition comprising (A) an organic resin
pentamethylguanidine were employed as the curing cata forming polyepoxide compound selected from the group
lyst, and the catalyzed resin was heated for 3 hours at consisting of monomeric and polymeric epoxides having a
80 C., followed by 18 hours at 148 C. The resulting 70 plurality of reactive 1,2-epoxy groups which comprises a
cured epoxy resin (Rockwell Hardness, MScale, of 84-2) thermosetting resinous reaction product of a polyhydric
had a softening temperature of 85° C. phenol and an epihalohydrin, having an epoxide equiva
Example XVIII lency of at least 1.0 and (B) a catalytic amount of a
1,1,3,3-tetraalkylguanidine wherein the alkyl groups con
TWO parts of 1,1,3,3-tetramethylguanidine and 0.45 75 tain from 1 to 6 carbon atoms, inclusive.
 3,308,094
2
6. A composition comprising (A): an organic resin ides having a plurality of reactive 1,2-epoxy groups hav
forming polyepoxide selected from the group consisting ing an epoxide equivalency of at least 1.0, and (B) a
of monomeric and polymeric epoxides having a plurality catalytic amount of 1,1,2,3,3-pentamethylguanidine.
of reactive 1,2-epoxy groups which comprises a thermoset 13. A substantially insoluble and infusible resinous
ting resinous reaction product of bisphenol A and epichlo 5 composition obtained by curing a composition compris
rohydrin having an epoxide equivalency of at least 1.0, ing (A) an organic resin forming polyepoxide selected
and (B) a catalytic amount of 1,1,3,3-tetramethylguani from the group consisting of monomeric and polymeric
dine. -- -epoxides having a plurality of reactive 1,2-epoxy groups
7. A composition comprising (A) an organic resin which comprises a thermosetting resinous reaction product
forming polyepoxide compound Selected from the group O) of a polyhydric phenol and an epihalohydrin having an
consisting of monomeric and polymeric epoxides having epoxy equivalency of at least 1.0, and (B) a catalytic
a plurality of reactive 1,2-epoxy groups which comprises annount of a 1,1,3,3-tetraalkylguanidine wherein the alkyl
a thermosetting resinous reaction product of a polyhydric groups contain from 1 to 6 carbon atoms, inclusive.
phenol and an epihalohydrin, having an epoxide equiva 14. A substantially insoluble and infusible resinous
lency of at least 1.0 and (B) a catalytic amount of a 5 composition obtained by curing a composition comprising
1,1,2,3,3-pentaalkylguanidine wherein the alkyl groups (A) an organic resin forming polyepoxide selected from
contain from 1 to 6 carbonatoms, inclusive. the group consisting of monomeric and polymeric epox
8. A composition comprising (A) an organic resin ides having a plurality of reactive 1,2-epoxy groups which
forming polyepoxide selected from the group consisting of comprises a thermosetting resinous reaction product of
monomeric and polymeric epoxides having a plurality of 20 bisphenol A and epichlorohydrin having an epoxy equiva
reactive 1,2-epoxy groups which comprises a thermoset lency of at least 1.0, and (B) a catalytic amount of
ting resinous reaction product of bisphenol A and epi 1,1,3,3-teramethylguanidine.
chlorohydrin having an epoxide equivalency of at least 15. A substantially insoluble and infusible resinous
1.0, and (B) a catalytic amount of 1,1,2,3,3-pentamethyl composition obtained by curing a composition comprising
guanidine. (A) an organic resin forming polyepoxide selected from
9. A substantially insoluble and infusible resinous com the group consisting of monomeric and polymeric epox
position obtained by curing a composition comprising (A) ides having a plurality of reactive 1,2-epoxy groups which
an organic resin forming polyepoxide selected from the comprises a thermosetting resinous reaction product of
group consisting of monomeric and polymeric epoxides a polyhydric phenol and an epihalohydrin having an epoxy
having a plurality of reactive 1,2-epoxy groups having 30 equivalency of at least 1.0, and (B) a catalytic amount
an epoxide equivalency of at least 1.0, and (B) a catalytic 'of a 1,1,2,3,3-pentaalkylguanidine wherein the alkyl groups
amount of a 1,1,3,3-tetraalkylguanidine wherein the alkyl contain from 1 to 6 carbon atoms, inclusive.
groups contain from 1 to 6 carbon atoms, inclusive. 16. A substantially insoluble and infusible resinous
10. A substantially insoluble and infusible resinous composition obtained by curing a composition comprising
composition obtained by curing a composition comprising (A) an organic resin forming polyepoxide selected from
(A) an organic resin forming polyepoxide selected from the group consisting of monomeric and polymeric epox
the group consisting of monomeric and polymeric epox ides having a plurality of reactive 1,2-epoxy groups which
ides having a plurality of reactive 1,2-epoxy groups hav comprises a thermosetting resinous reaction product of
ing an epoxide equivalency of at least 1.0, and (B) a bisphenol A and epichlorohydrin having an epoxy equiva
catalytic amount of 1,1,3,3-tetramethylguanidine. 40 lency of at least 1.0, and (B) a catalytic amount of
11. A substantially insoluble and infusible resinous 1,1,2,3,3-pentamethylguanidine.
composition obtained by curing a composition comprising
(A) an organic resin forming polyepoxide selected from References Cited by the Examiner
the group consisting of monomeric and polymeric epox UNITED STATES PATENTS
ides having a plurality of reactive 1,2-epoxy groups hav 3,028,342 4/1962 Katz et al. ----------- 260-47
ing an epoxide equivalency of at least 1.0, and (B) a
catalytic amount of a 1,1,2,3,3-pentaalkylguanidine where FOREIGN PATENTS
in the alkyl groups contain from 1 to 6 carbon atoms, 133,819 8/1949 Australia.
inclusive.
12. A substantially insoluble and infusible resinous 50 SAMUEL H. BLECH, Primary Examiner.
composition obtained by curing a composition comprising WILLIAMH. SHORT, Examiner.
(A) an organic resin forming polyepoxide selected from
the group consisting of monomeric and polymeric epox T. D. KERWIN, Assistant Examiner.