Siloxane-containing glycidyl esters, curable compositions and cured products

Glycidyl esters containing at least one glycidyl ester group and at least one organo siloxane moiety per molecule are prepared by reacting (1) at least one compound containing at least one glycidyl ester group per molecule and at least one unsaturated aliphatic or cycloaliphatic group per molecule; with (2) a compound containing at least one hydrosiloxane moiety per molecule.

FIELD OF THE INVENTION 
The present invention pertains to glycidyl ester compounds containing at 
least one siloxane moiety. curable compositions thereof and cured 
products. 
BACKGROUND OF THE INVENTION 
Diglycidyl esters of cycloaliphatic diacids are commercially available such 
as (a) the diglycidyl ester prepared from cis-1,2,3,6-tetrahydrophthalic 
annydride commercially available from Ciba-Geigy as Araldite.TM. CY192 and 
(b) the diglycidyl ester of cis-1,2-cyclohexanedicarboxylic acid 
commercially available from Bayer as Lekutherm.TM. X100 and Ciba-Beigy as 
Araldite.TM. CY184. These diglycidyl esters of cycloaliphatic diacids are 
useful in casting and molding of electronic and electrical components for 
outdoor applications. 
Glycidyl esters of cycloaliphatic carboxylic acids are very reactive with 
anhydride curing agents. U.S. Pat. No. 4,906,677 discloses multi-component 
coating compositions comprising an anhydride containing polymer, a 
glycidyl component and a phosphonium catalyst. 
There are few polyglycidyl esters commercially available except for 
copolymers of glycidyl methacrylate esters and styrene and other acrylic 
esters. However, these copolymers are solid and need high levels of 
sovent(s) for processing. 
It would be desirable to have available multi-functional glycidyl esters 
which are easily prepared and have a low viscosity. 
It would also be desirable to have available glycidyl ester compounds which 
exhibit an improvement in one or more of the properties such as increased 
pot life when formulated with a curing agent, or when cured, an 
improvement in one or more of the properties such as moisture resistance, 
weatherability, or flexibility. 
The property improvement is observed when compared to like compositions 
which are free of any siloxane moieties. 
SUMMARY OF THE INVENTION 
One aspect of the present invention concerns compounds containing at least 
one glycidyl ester group and at least one organosiloxane moiety 
##STR1## 
per molecule: with the proviso that said compound containing at least one 
glycidyl ester group and at least one organosiloxane moiety per molecule 
contains at least one silicon atom linked to a carbon atom contained in 
the portion of the molecule which contains a glycidyl ester group. 
Another aspect of the present invention concerns to a process for preparing 
compounds containing at least one glycidyl ester group and at least one 
organosiloxane moiety per molecule. 
A further aspect of the present invention concerns compositions comprising 
(A) at least one compound containing at least one glycidyl ester group and 
at least one organosiloxane moiety per molecule; and (B) a curing quantity 
of at least one curing agent for component (A). 
A still further aspect of the present invention concerns the product or 
article resulting from curing the aforementioned curable compositions. 
A further aspect of the present invention concerns a coating composition 
comprising the aforementioned curable compositions. 
The glycidyl ester compounds of the present invention exhibit an 
improvement in one or more of the properties such as increased pot life 
when formulated with a curing agent, or when cured, an improvement in one 
or more of the properties such as moisture resistance, stain resistance, 
weatherability, or flexibility. Improvements in other mechanical, chemical 
or thermal properties may also be observed. 
The property improvement is observed when compared to like compositions 
which are free of any siloxane moieties. 
The present invention may suitably comprise, consist of, or consist 
essentially of, the aforementioned components and compounds. 
The invention illustratively disclosed herein suitably may be practiced in 
the absence of any component which is not specifically disclosed or 
enumerated herein and any of the compounds may contain or be free of any 
substituent not specifically named herein.

DETAILED DESCRIPTION OF THE INVENTION 
The compounds of the present invention containing at least one glycidyl 
ester group and at least one organosiloxane moiety per molecule are 
prepared by reacting (1) at least one compound containing at least one 
glycidyl ester group per molecule and at least one unsaturated aliphatic 
or unsaturated cycloaliphatic group per molecule with (2) a compound 
containing at least one hydrosiloxane moiety per molecule. 
The product resulting from the reaction of component (1) with component (2) 
is through the hydrogen atom attached to the silicon atom of component (2) 
and unsaturated aliphatic or unsaturated cycloaliphatic group of component 
(1), resulting in a direct bond between the silicon atom and a carbon atom 
containing the double bond before the double bond's disappearance by 
reaction with the hydrosiloxane moiety. 
The reaction is usually conducted at temperatures of from about 0.degree. 
C. to about 150.degree. C., preferably from about 30.degree. C. to about 
120.degree. C., more preferably from about 40.degree. C. to about 
100.degree. C. for a time sufficient to complete the reaction, usually 
from about 0.5 to about 15, preferably from about 1 to about 10, more 
preferably from about 2 to about 6 hours. 
At temperatures below about 0.degree. C., the reaction is very slow. 
At temperatures above about 150.degree. C., a severely exothermic reaction 
occurs. Such a reaction is very difficult to control and is undesirable. 
The reactants are employed in amounts which provide an equivalent ratio of 
hydrosiloxane groups to unsaturated glycidyl ester-containing compound of 
from about 0.25:1 to about 25:1, preferably from about 0.5:1 to about 
10:1, more preferably from about 0.75:1 to about 5:1. 
The reaction is usually and preferably conducted in the presence of a 
homogeneous catalyst such as, for example, chloroplatinic acid (H.sub.2 
PtCl.sub.6), as well as ((C.sub.2 H.sub.4)PtCl.sub.2).sub.2, 
bis-(triphenylphosphine)cobalt chloroiridium (IrClCo(PPh.sub.3).sub.2), 
dicobalt octacarbonyl (Co.sub.2 (CO).sub.8). Also, 10% Pd/C or 5% Pt/C and 
Raney Ni are effective catalysts for this reaction. Hydrosilylation 
catalysts which can be used also include those disclosed in U.S. Pat. Nos. 
3,775,442, 3,159,601, 3,220,972, all of which are incorporated herein by 
reference. An effective amount of a platinum catalyst is from about 0.0005 
to 1.05 percent by weight of platinum based on the weight of the 
hydrosilylation mixture. 
Also, if desired, the reaction can be conducted in the presence of a 
solvent such as, for example, aliphatic, cycloaliphatic or aromatic 
hydrocarbons, or any combination thereof. Particularly suitable solvents 
include, for example, n-hexane, cyclohexane, octane, methylene chloride, 
chloroform, chlorobenzene, toluene, xylene, any combination thereof and 
the like. 
The excessive unreacted .tbd.Si--H bonds are terminated, quenched, by 
addition of a mono- or di-unsaturated aliphatic or cycloaliphatic alkene 
having from about 4 to about 20, preferably from about 6 to about 16, more 
preferably from about 7 to about 12, carbon atoms or an aromatic compound 
substituted with an unsaturated aliphatic or cycloaliphatic alkene group 
having from 8 to about 20 carbon atoms, such as, for example, styrene, 
.alpha.-methyl styrene, noborylene, n-octene, cyclohexene, 
dicyclopentadiene, and the like. This is accomplished by reaction at a 
temperature of from about 0.degree. C. to about 150.degree. C., preferably 
from about 30.degree. C. to about 120.degree. C., more preferably from 
about 40.degree. C. to about 100.degree. C. for a time sufficient to 
complete the reaction, usually from about 0.5 to about 15, preferably from 
about 1 to about 10, more preferably from about 2 to about 6 hours. 
Likewise, this reaction is conducted in the presence of the aforementioned 
heterogeneous catalysts, and can also, if desired, be conducted in the 
presence of the aforementioned solvents. 
At temperatures below about 0.degree. C., excess unreacted .tbd.Si-H bonds 
cannot be fully terminated. 
At temperatures above about 150.degree. C., a severely exothermic reaction 
occurs. Such a reaction is very difficult to control and is undesirable. 
This hydrosilylation method is describe by John L. Speier in Advances in 
Organometallic Chemistry, vol. 17, Academic Press, Inc., pp 407-447, 1979 
which is incorporated herein by reference in its entirety. 
Suitable organosiloxane compounds which can be employed include, for 
example, those represented by the following general formulas I, II, III or 
IV 
##STR2## 
wherein each R' is independently a hydrocarbyl group or hydrocarbyl group 
substituted with N or F containing groups, said hydrocarbyl group having 
from 1 to about 20, preferably from 1 to about 10, more preferably from 1 
to about 4, carbon atoms; each Y is hydrogen; each x independently has a 
value from zero to about 500, preferably from zero to about 250, more 
preferably from zero to about 125; each x' independently has a value from 
2 to about 500, preferably from 2 to about 250, more preferably from 2 to 
about 125: x" has a value from 3 to about 50, preferably from about 3 to 
about 10, more preferably from about 3 to about 5; and the sum of x and x' 
is from about 2 to about 1000, preferably from about 2 to about 500, more 
preferably from about 2 to about 250. 
Particularly suitable organohydrosiloxane compounds which can be employed 
include, for example, 1,1,3,3-tetramethyldisiloxane; 
1,1,3.3,5,5-hexamethyltrisiloxane; 
1,1,3,3,'5',5,7,7-octamethyltetrasiloxane; 
1,3-diphenyl-1,3-dimethyldisiloxane; 1,1,3,3-tetraisopropyldisiloxane: 
1,3-diphenyl-1,1',3,3-tetrakis-(dimethylsiloxyl)disiloxane;; 
1,1,3,3-tetrakis-(trimethylsiloxyl)disiloxane; methyl hydrocyclosiloxane 
{(CH.sub.4 OSi)n where n=4-20} such as 
1,3,5,7-tetramethylhydrocyclotetrasiloxane, 
1,3,5,7,9-pentamethylhydrocyclopentasiloxane, 
1,3.5,7,9,11-hexamethylhydrocyclohexasiloxane, polymethylhydrosiloxane 
(weight average M.W.=300 to 50,000): methylhydro-dimethylsiloxane 
copolymer (weight average M.W.=120 to 100,000): 
dimethylterminated-methylhydro-phenylmethylsiloxane copolymer (weight 
average M.W.=120 to 100,000): any combination thereof and the like. 
Also included as suitable organosiloxane compounds having a terminal 
hydrosiloxyl structure are, for example, those represented by the general 
formulas HSi(CH.sub.3).sub.2 --O--(Si(CH3).sub.2).sub.n 
--O--Si(CH.sub.3).sub.2 --R--Si(CH.sub.3).sub.2 
--O--(Si(CH.sub.3).sub.2).sub.n --Si(CH.sub.3).sub.2 H, or 
##STR3## 
wherein R is a divalent saturated aliphatic or divalent saturated 
cycloaliphatic group having from about 4 to about 100, preferably from 
about 4 to about 50, more preferably from about 4 to about 20 carbon 
atoms. 
Suitable glycidyl ester compounds containing unsaturated aliphatic or 
unsaturated cycloaliphatic groups which can be employed herein include, 
those represented by the general formula 
EQU (R.sup.3 --OOC).sub.n --R.sup.2 --(COO--R.sup.1)m 
wherein R.sup.1 is an saturated or unsaturated aliphatic, saturated or 
unsaturated cycloaliphatic, aromatic. or sulfur, nitrogen or phosphorus 
containing heterocyclic saturated or unsaturated cycloaliphatic or 
aromatic group; R.sup.2 is a saturated or unsaturated aliphatic or 
saturated or unsaturated cycloaliphatic, or sulfur, nitrogen or phosphorus 
containing heterocyclic saturated or unsaturated cycloaliphatic group: 
R.sub.3 is a glycidyl group or lower alkyl (C.sub.1 -C.sub.4) substituted 
glycidyl group: and each n and m independently has a value from 1 to about 
20, preferably from 1 to about 10, more preferably from 1 to about 5: and 
with the proviso that there is at least one unsaturated moiety in each 
molecule undergoing hydrosilylation and when R.sup.2 contains an 
unsaturated moiety, R.sup.1 can be a glycidyl group. 
Particularly suitable R.sup.1 groups include, for example, --CH.sub.2 
--CH.dbd.CH.sub.2, --CH.dbd.CH.sub.2, --(CH.sub.2 --CHR"--O).sub.z 
--CH.sub.2 --CH.dbd.CH.sub.2 where R" is hydrogen or C.sub.1 --C.sub.6 
alkyl group and z has a value from 1 to 50, bicyclo-(2.2.1)-hept-1-enyl, 
styrenyl, vinylbenzyl, any combination thereof and the like. 
It is preferred that the glycidyl ester compounds containing unsaturated 
aliphatic or unsaturated cycloaliphatic groups contain an average of no 
more than two such unsaturated groups so as to prevent gellation during 
the silylation reaction in some instances. 
The glycidyl ester compounds containing unsaturated aliphatic or 
unsaturated cycloaliphatic groups which can be employed herein can be 
prepared by reacting an aliphatic, cycloaliphatic or aromatic dicarboxylic 
acid, polycarboxylic acid or anhydride or polyanhydride thereof with an 
unsaturated aliphatic, unsaturated cycloaliphatic or aromatic compound 
containing an aliphatic hydroxyl group. 
Suitable aliphatic, cycloaliphatic or aromatic dicarboxylic acids, 
polycarboxylic acids or anhydrides or polyanhydrides thereof which can be 
employed to prepared the glycidyl ester compounds containing unsaturated 
aliphatic or unsaturated cycloaliphatic groups usually have from about 2 
to about 50, preferably from about 4 to about 30, more preferably from 
about 6 to about 15, carbon atoms per molecule. Particularly suitable 
acids or anhydrides include, for example, oxalic acid, phthalic acid, 
maleic acid, succinic anhydride, citraconic anhydride, itaconic anhydride, 
dodecenyl succinic anhydride, phthalic anhydride, hexahyhdrophthalic 
anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, 
1,2-cyclobutane dicarboxylic anhydride, 
bicyclo2.2.1heptene-2,3-dicarboxyilic anydride isomers (Nadic Anydride), 
methylbicyclo[2.2.1]heptene-2,3-dicarboxyilic anydride isomers (Nadic 
Methyl Anydride), any combination thereof or the like. 
Suitable unsaturated aliphatic, unsaturated cycloaliphatic or aromatic 
compound containing an aliphatic hydroxyl group include those represented 
by the formula 
EQU R.sup.1 --(OH).sub.m 
wherein R.sup.1 is a defined above and m has a value from 1 to about 4, 
preferably from 1 to about 3, more preferably from 1 to about 2. 
Particularly suitable unsaturated aliphatic, unsaturated cycloaliphatic or 
aromatic compound containing an aliphatic hydroxyl group include, for 
example, allyl alcohol, crotyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 
norbornene methanol, or any combination of any two or more such 
unsaturated aliphatic, unsaturated cycloaliphatic or aromatic compounds 
containing an aliphatic hydroxyl group. 
The reactants are employed in amounts which provide a molar ratio of acid- 
or anhydride-containing compound to hydroxyl-containing compound of from 
about 0.6:1 to about 1.5:1, preferably from about 0.8:1 to about 1.3:1, 
more preferably from about 0.9:1 to about 1.2:1. 
The reaction is conducted at a temperature of from about 10.degree. C. to 
about 200.degree. C., preferably from about 30.degree. C. to about 
150.degree. C., more preferably from about 40.degree. C. to about 
100.degree. C. for a time sufficient to complete the reaction, usually 
from about 0.5 to about 8. preferably from about 1 to about 6, more 
preferably from about 2 to about 4 hours. 
At temperatures below about 10.degree. C., the reaction is very slow and 
usually results in an incomplete reaction of the reactants. 
At temperatures above about 200.degree. C., the unsaturated compounds 
become unstable. 
If desired, the reaction can be conducted in the presence of a suitable 
inorganic or organic acid catalyst, such as, for example, HCl, H.sub.2 
SO.sub.4, BF.sub.3.etherate, TiCl.sub.4, ZrCl.sub.4, p-toluene sulfonic 
acid, methane sulfonic acid, trifluromethane sulfonic acid, any 
combination therof, or any combination thereof and the like. When 
employed, these catalysts are employed in amounts of from about 0.01 to 
about 5, preferably from about 0.5 to about 2 percent by weight based upon 
the weight of the reactants. 
Also, the reaction can be conducted in the presence of the aforementioned 
solvents. 
The resultant unsaturated ester-acid compound is then reacted, in the 
presence of a suitable catalyst, with at least a molar excess of an 
epihalohydrin or a C.sub.1 -C.sub.4 alkyl substituted epihalohydrin, such 
as, for example epichlorohydrin, epibromohydrin, epiiodohydrin, 
methylepichlorohydrin, methylepibromohydrin, methylepiiodohydrin, or any 
combination thereof and the like. 
The reaction is usually conducted at temperatures of from about 10.degree. 
C. to about 90.degree. C., preferably from about 20.degree. C. to about 
80.degree. C., more preferably from about 30.degree. C. to about 
70.degree. C. for a time sufficient to complete the reaction, usually from 
about 0.5 to about 8, preferably from about 1 to about 6. more preferably 
from about 2 to about 4 hours. 
At temperatures below about 10.degree. C., an incomplete reaction results. 
At temperatures above about 200.degree. C., side reactions occur which 
reduces the epoxide content of the unsaturated glycidyl ester compound. 
If desired, the reaction can be conducted in the presence of a suitable 
ammonium, phosphonium or phosphine catalyst, such as, for example, benzyl 
trimethyl ammonium chloride, benzyl trimethyl ammonium bromide, 
ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, 
tetramethyl ammonium bromide, ethyltriphenylphosphonium iodide, tetrabutyl 
ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium 
iodide, ethyltriphenylphosphonium acetate.acetic acid complex, tetrabutyl 
phosphonium acetate.acetic acid complex, triehtylphosphine, 
tripropylphosphine, triphenylphosphine, tetramethyl ammonium hydroxide, or 
any combination thereof and the like. 
The epihalohydrin and the compound having groups reactive with a vicinal 
epoxide group are employed in amounts which provide a ratio of moles of 
epihalohydrin per group reactive with an epoxide group from 1:1 to 15:1, 
preferably from 1.5:1 to 12:1, more preferably from 1.5:1 to 10:1. 
At ratios below 1:1, complete reaction of the reactive group with the 
epihalohydrin cannot be achieved. 
At ratios above 15:1, the productivity (capacity) of the reactor is 
reduced. 
After the coupling reaction is essentially complete, the epoxidation 
reaction is carried out by the addition of alkali or alkaline earth metal 
hydroxide solutions. 
Suitable alkali or alkaline earth metal hydroxides which can be employed 
herein include, for example, sodium hydroxide potassium hydroxide lithium 
hydroxide, barium hydroxide, calcium hydroxide, magnesium hydroxide, or 
any combination thereof and the like. Also suitably used in the present 
invention is manganese hydroxide either alone or in combination with the 
alkali or alkaline earth metal hydroxide. 
The alkali or alkaline earth metal hydroxide is employed in an amount which 
provides a ratio of hydroxide groups to carboxyl group of from 0.8:1 to 
about 1.2:1. 
The alkali or alkaline earth metal hydroxide can be employed in solution 
with water or an organic solvent such as alcohols, sulfoxides or amides; 
for example, methanol, ethanol, isopropanol, dimethylsulfoxide, 
dimethylacetamide, or any combination thereof and the like. Water is the 
preferred solvent for the alkali or alkaline earth metal hydroxide. The 
alkali or alkaline earth metal hydroxide solution is employed in a 
concentration from about 10 to about 70, preferably from about 30 to about 
50 percent alkali or alkaline earth metal hydroxide by weight. 
Suitable solvents which can be employed herein include, for example, 
ketones, linear cyclic ethers, primary, secondary and tertiary alcohols, 
glycol monoethers, glycol ether acetates, aromatic or cycloaliphatic or 
aliphatic hydrocarbons having from 6 to 12 carbon atoms, or any 
combination thereof and the like. Any of the aforementioned solvents can 
be employed herein so long as the solvent does not react with the 
components of the reaction mixture. In addition, the solvent should have a 
boiling point such that the solvent is not totally removed from the 
reaction mixture during co-distillation of the water, epihalohydrin and 
solvents. Particularly suitable such solvents include, for example, 
1-methoxy-2-hydroxy propane, 1-butoxy-2-hydroxy ethane, tert-amyl alcohol, 
tert-hexyl alcohol, 1-isobutoxy-2-hydroxy propane, 1-phenoxy-2-hydroxy 
propane, cyclohexanol, dioxane, 1,2-diethoxyethane, 2-methoxyethyl ether, 
ethylene glycol monomethyl ether acetate, ethyl acetate, isobutyl acetate, 
isoamyl acetate, methyl ethyl ketone, methyl isobutyl ketone, dimethyl 
sulfoxide, dimethyl acetamide, N-methylyrrolidinone, dimethyl formamide, 
dimethylsulfone, tetramethyil urea, hexamethyl phosphoramide, 
tetramethylenesulfolane, any combination thereof and the like. 
The solvents are employed in amounts such that the amount of solvent in the 
initial epihalohydrin solvent mixture is from about 5 to about 80, 
preferably from about 5 to about 50, more preferably from about 10 to 
about 40 percent solvent based upon the combined weight of solvent plus 
epihalohydrin. 
The process of the present invention can employ procedures for continuously 
removing the water produced in the reaction mixture by codistilling or 
azeotroping the water with epihalohydrin and solvent, if employed. The 
epihalohydrin and solvent, if employed, is separated from the water and 
returned to the reaction mixture. This method is described by Wang et al. 
in U.S. Pat. No. 4,499,255 and U.S. Pat. No. 4,778,863 which are 
incorporated herein by reference. 
The siloxane-containing glycidyl esters of the present invention can be 
represented by the following general formulas V, VI, VII and VIII 
##STR4## 
wherein R' is independently a hydrocarbyl group or hydrocarbyl group 
substituted with N or F containing groups, said hydrocarbyl group having 
from 1 to about 20, preferably from 1 to about 10, more preferably from 1 
to about 4, carbon atoms; each Z is an aliphatic or 
##STR5## 
cycloaliphatic group containing a glycidyl ester moiety represented by the 
general formula --X--R.sup.5 --(COOR.sup.4).sub.n ', with the proviso that 
the Z group is attached directly to a silicon atom; R.sup.5 is an 
aliphatic or cycloalilphatic or aromatic group or a S, N or P containing 
heterocyclic group having from 1 to about 50, preferably from 1 to about 
25, more preferably from 1 to about 15 carbon atoms; R.sup.4 is a glycidyl 
group or lower alkyl (C.sub.1-4) substituted blycidyl group; n' has a 
value from 1 to about 20, preferably from 1 to about 10, more preferably 
from 1 to about 5; each X is independently a divalent aliphatic or a 
divalent cycloaliphatic group or a divalent alkoxy or a divalent 
cycloalkoxy group having from 2 to about 30, preferably from 2 to about 
20, more preferably from zero to about 250, more preferably from zero to 
about 125; each x' independently has a value from 2 to about 500, 
preferably from 2 to about 250, more preferably from 2 to about 125; x" 
has a value from 3 to about 50, preferably from about 3 to about 10, more 
preferably from about 3 to about 5; and the sum of x and x' is from about 
2 to about 1000, preferably from about 2 to about 500, more preferably 
from about 2 to about 250. 
Of particular interest are the siloxane-containing glycidyl esters of the 
aforementioned formulas V-VIII wherein Z is selected from one of the 
following with the proviso that at least one of the Z groups within each 
molecule contain a glycidyl ester group: 
##STR6## 
The glycidyl ester functionalized organosiloxane compounds of the present 
invention can be blended with any epoxy resin, or reactive epoxide diluent 
i.e. any compound containing an average of one or more then one vicinal 
epoxide group per molecule. These epoxy resins can be aliphatic, 
cycloaliphatic or aromatic based epoxy resins. They can be glycidyl 
derivatives of saturated or unsaturated aliphatic or cycloaliphatic or 
aromatic compounds having an average of more than one active hydrogen atom 
reactive with an epoxide group. Such epoxy resins are usually prepared by 
reacting the active hydrogen-containing compound such as an acid, 
hydroxyl-containing compound or an amine with an epihalohydrin such as 
epichlorohydrin and subsequently or simultaneously dehydrohalogenating the 
resultant halohydrin intermediate with a basic acting compound such as an 
alkali metal hydroxide. Particularly suitable such epoxy resins include, 
for example, the glycidyl ethers of alkylene glycols, polyalkylene 
glycols, polyhydric phenols, biphenols, phenol- or substituted 
phenol-aldehyde novolak resins, trisphenol methine, any combination 
thereof and the like. Also suitable are the glycidyl esters of aliphatic, 
cycloaliphatic or aromatic carboxylic acids having an average of more than 
one carboxylic acid group per molecule, such as, for example, the 
diglycidyl esters of cis-1,2-cyclohexanedicarboxylic acid anhydride. Also 
suitable are the copolymers of glycidyl esters of methacrylic or acrylic 
acid polymerized with other acrylic esters, styrene, vinyl toluene, 
.alpha.-methyl styrene, or any combination thereof or the like. The weight 
average molecular weight of these copolymers are usually in the range of 
from about 200 to about 200,000, preferably from about 500 to about 
100,000, more preferably from about 1,000 to about 50,000. Also suitable 
are the cycloaliphatic or aliphatic epoxides prepared by the peroxidation 
of unsaturated double bonds. 
Any suitable curing agent for epoxy resins can be employed herein to cure 
the glycidyl ester compounds of the present invention including, for 
example, primary and secondary polyamines. carboxylic acids and anhydrides 
thereof, phenolic hydroxyl-containing compounds, guanidines, biguanides, 
urea-aldehyde resins, melamine-aldehyde resins, alkoxylated urea-aldehyde 
resins, alkoxylated melamine-aldehyde resins, or any combination thereof 
or the like. 
Particularly suitable curing agents include, for example, oxalic acid, 
phthalic acid, maleic acid, succinic anhydride, citraconic anhydride, 
itaconic anhydride, dodecenyl succinic anhydride, phthalic anhydride, 
hexahydrophthalic anhydride, tetrahydrophthalic anhydride, trimellitic 
anhydride, 1,2-cyclobutanedicarboxyic anhydride, 
benzophenonetetracarboxylic anhydride, pyromellitic anhydride, Nadic.TM. 
anhydride, methylNadic.TM. anhydride, or any combination thereof or the 
like. Also suitable are the anhydride derivatives of organosiloxane 
compounds which are disclosed by H. S. Ryang in U.S. Pat. No. 4,381,396, 
by H. S. Ryang in U.S. Pat. No. 4,511,701, by MK. A. Buese in U.S. Pat. 
No. 4,598,135, and by J. E. Hallgren et al. in U.S. Pat. No. 4,634,755, 
all of which are incorporated herein by reference. Particularly suitable 
such curing agents include, 
5,5'-(1,1,3,3-tetramethyl-1,3-disiloxanediyl)bis-norbornane-2,3-dicarboxyl 
ic anhydride, dianhydride terminated polydiorganosiloxanes having a weight 
average molecular weight of from about 200 to about 100,000, norborenyl 
anhydride substituted cyclicorganosiloxane having a weight average 
molecular weight of from about 250 to about 50,000, or any combination 
thereof and the like. 
Also included as suitable curing agents are the copolymers of Methyl Nadic 
Anhydride or maleic anhydride or maleic acid or fumaric acid with styrene, 
butadiene or other unsaturated monomers containing 2 to 20 carbon atoms, 
or any combination thereof such copolymers or the like. These copolymers 
are disclosed by Barsotti et al. in U.S. Pat. No. 4,906,677, which is 
incorporated herein by reference in its entirety. When the glycidyl ester 
compounds of the present invention are formulated with such curing agents, 
the formulated component has a longer pot life as compared to the 
formulated components from existing glycidyl esters. The weight average 
molecular weight of these copolymers range from about 100 to about 
350,000, preferably from about 500 to about 200,000, more preferably form 
about 1,000 to about 100,000. 
Also suitable curing agents include phenolic compounds such as, for 
example, novolac resins prepared from phenol or C.sub.1 -C.sub.10 alkyl- 
or halogen-substituted phenols and an aldehyde. Suitable aldehydes 
include, for example, formaldehyde, acetaldehyde, furfuraldehyde. Suitable 
phenols include, phenol, cresol, bromophenol, any combination thereof and 
the like. Also suitable as the phenolic curing agent are the bisphenols 
such as, for example, biphenol, bisphenol A, bisphenol F, bisphenol K, 
bisphenol S, dicyclopentadienyl-bis(2,6-dimethylphenol), 
dicylopentadienyl-bisphenol, any combination thereof and the like. 
Also suitable as curing agents include, for example, 2-dimethylilimidazole, 
2-ethyl-4-methylimidazole, dicyandiamide, ethylendiamine, 
diethylenetriamine, triethylenetetramine, diaminocyclohexane, 
4,4'-methyilenedicyclohexylamine, 1,3-phenylenediamine, sulfanilimide, 
aminoethylpiperazine, 4,4'-diaminodiphenylmethane, 
3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, any combination 
thereof and the like. 
Also suitable as curing agents are the Lewis acids such as, for example, 
boron trifluoride or ether complexes thereof. 
Suitable catalysts for the curing agents include for example, Lewis bases 
such as, for example 2-methyimidazole, 2-ethylimidazole, 
benzendedimethylamine, 2,4,6-tri(dimethylamino)-phenol, any combination 
thereof and the like. 
Also suitable as catalysts are the latent catalysts taught by Bertram et 
al. in U.S. Pat. No. 4,925,901 and U.S. Pat. No. 5,946,817 which are 
incorporated herein by reference. 
The curing agents are employed in an amount which will effectively cure the 
composition containing the epoxy resin. These amounts will depend upon the 
particular modified epoxy resin and curing agent employed however, 
suitable amounts include, for example, from about 0.5 to about 1.5, 
preferably from about 0.75 to about 1.25, more preferably from about 0.9 
to about 1.1 equivalents of curing agent per epoxide equivalent for those 
curing agents which cure by reacting with the epoxy group of the epoxy 
resin or per hydroxyl group for those curing agents which cure by reacting 
with the aliphatic hydroxyl groups along the backbone of the epoxy resin. 
The Handbook of Epoxy Resins by Lee and Neville, McGraw-Hill, 1967 
contains various discussions concerning the curing of epoxy resins as well 
as compilation of suitable curing agents. This handbook is incorporated 
herein by reference. 
The glycidyl ester epoxy resins containing organosiloxane moieties of the 
present invention can be blended with other materials such as solvents or 
diluents, fillers, pigments, dyes, u. v. absorbants, flow modifiers, 
thickeners, reinforcing agents, any combination thereof and the like. 
These additives are added in functionally equivalent amounts e.g., the u. 
v. absorbants, pigments and/or dyes are added in quantities which will 
provide the composition with the desired color; however, they are employed 
in amounts of from about 0.001 to about 70, preferably from about 0.01 to 
about 50, more preferably from about 0.1 to about 25 percent by weight 
based upon the weight of glycidyl ester functionalized organosiloxane. 
Solvents or diluents or carriers which can be employed herein include, for 
example, hydrocarbons, ketones, glycol ethers, alcohols acetates, 
halogenate hydrocarbons, any combinations thereof and the like. 
Particularly suitable solvents or diluents include, for example, toluene, 
benzene, xylene, methyl ethyl ketone, methyl isobutyl ketone, diethylene 
glycol methyl ether, dipropylene glycol methyl ether, butanol, ethyl 
acetate, butyl acetate, 1-methoxy-2-propanol acetate, combinations thereof 
and the like. 
The modifiers such as thickeners, flow modifiers and the like can be 
employed in amounts of from about 1 to about 90, preferably from about 5 
to about 80, more preferably from about 10 to about 60 percent by weight 
based upon the weight of epoxy resin. 
Reinforcing materials which can be employed herein include natural and 
synthetic fibers in the form of woven, mat, monofilament, multifilament, 
and the like. Suitable reinforcing materials include, glass, ceramics, 
nylon, rayon, cotton, aramid, graphite, any combination thereof and the 
like. 
Suitable fillers which can be employed herein include, for example, 
inorganic oxides, ceramic microspheres, plastic microspheres, fumed 
silica, combinations thereof and the like. 
The fillers can be employed in amounts from about 1 to about 90, preferably 
from about 5 to about 80, more preferably from about 10 to about 70 
percent by weight based upon the weight of the epoxy resin. 
The solvents, diluents or carriers are usually employed in amounts which 
provide the composition with a suitable or appropriate application 
viscosity which varies with the application method being employed. Those 
to whom this invention is directed are well familiar with the application 
viscosities and methods employed to use the compositions of the present 
invention. 
The present invention is useful in the preparation of coatings, castings, 
laminates, composites, electrical and electronic encapsulants, adhesives, 
sealants,.and the like. 
The following examples are illustrative of the invention, but are not to be 
construed as to limiting the scope thereof in any manner. 
EXAMPLE 1 
(A) Preparation of the unsaturated mono-ester acid adduct from 
hexahydrophthalic anhydride and allyl alcohol 
A 250 ml four-necked round bottom flask equipped with a cooling condenser, 
mechanical stirrer, thermometer with temperature controller and nitrogen 
source is placed on a heating mantle. Hexahydrophthalic anhydride (HHPA, 1 
mole, 154.17 g, &gt;95% purity and allyl alcohol (1.1 mole, 63.88 g, &gt;98% 
purity) are charged into the flask and carefully heated to 70.degree. C. 
to 75.degree. C. A slightly exothermic reaction occurs. The melted mixture 
is reacted at 75.degree. C. to 80.degree. C. for 4-6 hours. The unreacted 
allyl alcohol is further stripped off from the viscous adduct of 
HHPA-allyl alcohol at &lt;100.degree. C./5 mm Hg. 194 g. of HHPA-allyl 
alcohol mono-ester adduct is obtained. IR shows that absorption bands at 
1860 cm.sup.-1 and 1800cm.sup.-1 for anhydride carbonyl group are 
substituted by two strong absorption bands at 1700cm.sup.-1 and 1735 
cm.sup.-1, which represents the carbonyl groups of both ester and 
carboxylic acid, together with a broad carboxylic acid OH absorption peak 
at 3000 cm.sup.-1 to 3500 cm.sup.-1. H NMR(CDCl.sub.3 -TMS) shows the 
appearance of unsaturated double bond of allyl alcohol at 5-6.3ppm 
together with the --OCH.sub.2 -- doublet peaks at 4.4 to 4.6 ppm for 
allylic mono-ester. The carboxilic absorption peak of the adduct is at 
10ppm which disappears later after epoxidation. 
(B) Preparation of the allyl-glycidyl hexahydrophthalate. 
A 500 ml four-necked, round bottom flask equipped with a cooling condenser, 
mechanical stirrer, thermometer with temperature controller and addition 
funnel is placed on a heating mantle. 85 g (0.39 mole) of the mono-ester 
acid adduct prepared in (A) above, epichlorohydrin (298 g, 3.12 mole), and 
tetramethyl ammonium hydroxide.5H.sub.2 O (0.55 g, 0.002 mole) are charged 
into the flask. The mixture is carefully heated to 60.degree. C. and kept 
at 60.degree. C.-62.degree. C. for another 3 hours. IR spectra of the 
reaction mixture shows all carboxylic groups of the mono-ester acid adduct 
from HHPA and allyl alcohol reacts with epichlorohydrin to form 
chlorohydrin ester. Seventy-five grams of t-amyl alcohol is then added to 
the mixture. The reaction mixture is then cooled to 50.degree. 
C.-52.degree. C. where 35.2 g (0.68 mole) of 50% NaOH aqueous solution 
(0.68 mole) is added at this temperature over about a period of about 4 
hours at reduced pressure (85 to 100 mm Hg) with azeotropic or 
co-distillation of water, solvent and epihalohydrin from the mixture and 
subsequently returning the solvent and epichlorohydrin to the reactor. 
After the completion of addition, the reaction is maintained at 50.degree. 
C.-52.degree. C. for another 30 minutes. After filtering to remove the 
precipitated salt, to the solution (filtrate) is added 500 ml methyl ethyl 
ketone (MEK), followed by neutralization with dry ice, followed by washing 
successively with water (100 ml/each for five times). The unreacted 
epichlorohydrin and MEK is then stripped off under vacuum (&lt;5 mm Hg) at 
100.degree. C. to 130.degree. C. 95 g. of glycidyl ester of HHPA-allyl 
alcohol adduct is obtained having an epoxide content of 15.39% (EEW=279). 
Theoretical epoxide content is 16.03% (EEW=268.2). 
(C) Preparation of Glycidyl Ester Functionalized Organosiloxane Oligomer 
from Glycidyl Esters Prepared in Example (1B) and 
Polyhydromethylsiloxane-dimethyl Siloxane Copolymer 
To a 25 ml toluene solution containing 34 g (0.13 mole) glycidyl ester from 
(B) above and 0.18 g of 5% H.sub.2 PtCl.sub.6 in t-amyl alcohol is added a 
25 ml toluene solution of 50 g hydromethylsiloxane-dimethylsiloxane 
copolymer terminated with trimethylsiloxyl groups (30% hydromethylsiloxyl 
content: M.W.=2050; Si-H equivalent: 60g/per --CH3SiH-0-. Therefore, 50g 
copolymer containing 0.25 Si-H equivalent) at 70.degree. C. for 10 minutes 
and heated at 75.degree. C. to 80.degree. C. for 6 hours. A 10 ml toluene 
solution containing 0.1 g of 5% H2PtC16 in t-amyl alcohol and 17.7g 
norborylene (0.22 mole) is then added at 50.degree. C. and heated at 
60.degree. C. for another 7 hours. The mixture is dissolved in 100 ml 
methyl ethyl ketone, and the solution is washed succesively four times 
with 50 ml portions of H.sub.2 O. The organic layer is collected and 92 g 
of viscous liquid (5.0 equiv. glycidyl ester per mole of organosiloxane 
copolymer, based upon charge and conversion) is obtained after stripping 
off the solvent and excessive norborlyene at 120.degree. C. to 140.degree. 
C./&lt;5 mm Hg. The organosiloxane oligomer with glycidyl ester functional 
groups has an epoxide content of 5.3% (EEW=811.32) and the structure is 
confirmed by IR and 1H NMR spectra: The Si--H bond absorption at 2100 
cm.sup.-1 and unsaturated double bond at allyl substituent at 1650 
cm.sup.-1 to 1670 cm.sup.-1 in IR (neat) disappears; In 1H NMR, a strong 
resonance peak at 0.2ppm to 0.8 ppm for methylsilyl group (Si--CH.sub.3 
and Si--CH.sub.2) appears, while unsaturated allylic double bond at 5 ppm 
to 6.2 ppm (m, CH.sub.2 .dbd.CH--CH.sub.2 --) disappears. 
(D) Preparation of Glycidyl Ester Functionalized Cyclosiloxane Oligomer 
from Glycidyl Ester (Example 1B) and 
1,3,5,7-tetramethylhydrooctacyclotetrasiloxane 
To a 20 ml toluene solution containing 42 g (0.16 mole) glycidyl ester from 
(B) above and 0.15 g of 5% H.sub.2 PtCl.sub.6 in t-amyl alcohol is added a 
10 ml toluene solution of 10 g of 1,3,5,7-tetramethyl cyclotetrasiloxane 
(M.W.=240.51) at 65.degree. C. to 70.degree. C. in 10 minutes and kept at 
this temperature for another 6 hours. The mixture is dissolved in 100 ml 
methyl ethyl ketone, and the solution is washed successively four times 
with 50 ml portions of H.sub.2 O. The organic layer is collected and 40 g 
of viscous liquid (4.0 equiv. glycidyl ester per mole of cyclic 
organosiloxane, based upon charge and conversion) is obtained after 
stripping off the solvent at 120.degree. C. to 140.degree. C./&lt;5 mm Hg. 
The structure is confirmed by IR and 1H NMR spectra. The cyclic 
organosiloxane with glycidyl ester functional groups has an epoxide 
content of 10.6% (EEW=405.7) and the structure is confirmed by IR and 1H 
NMR spectra. The Si--H absorption at 2100 cm.sup.-1 and unsaturated double 
bond at allyl substituent at 1650 cm.sup.-1 to 1670 cm.sup.-1 in IR(neat) 
disappeared; In 1H NMR, a strong resonance peak at 0.2 to 0.8 ppm for 
methylsilyl group (Si--CH.sub.3 and Si--CH.sub.2) appears, while 
unsaturated allylic double bond at 5-6.2ppm (CH.sub.2 .dbd.CH--CH.sub.2 
--) disappears. 
(E) Preparation of Glycidyl Ester Functionalized Cyclosiloxane Oligomer 
from Glycidyl Ester (Example 1 -B) and Methylhydrocyclosiloxanes(n=4-8) 
To a 30 ml toluene solution containing 72.98(0.27 mole) glycidyl ester from 
example 1 and 0.15 g of 5% H2PtC16 in t-amyl alcohol is added a 15 ml 
toluene solution of 15 g. of methylhydrocyclosiloxanes(n=4-8, e.g=60/ per 
Si--H, from Huls, Petrarch co.) at 50.degree.-52.degree. C. in 60 min. and 
kept at 55.degree. C. for another 6 hrs. The mixture is dissolved in 150 
ml methyl ethyl ketone, and the solution is washed successively four times 
with 50 ml portions of H2O. The organic layer is collected and 81 g of 
viscous liquid (4.0-6.0 e.g. glycidyl ester/per mole cyclicorganosiloxane 
, based upon charge and conversion) is obtained after stripping off the 
solvent at 10.degree.-110.degree. C./&lt;5 mmHg. The cycloorganosiloxane with 
glycidyl ester functional groups has epoxide content 11.74%(EEW=366) and 
the structure is confirmed by IR and 1H NMR spectra: The Si bond 
absorption at 2100-2200 cm.sup.-1 and unsaturated double bond at allyl 
substituent at 1650-1670 cm.sup.-1 in IR(neat) disappeared; In 1H NMR, a 
strong resonance peak at 0.2-0.8ppm for methylsilyl group (m, Si--CH3 and 
Si--CH2) appeared, while unsaturated allylic double bond at 5-6.2ppm (m, 
CH2.dbd.CH--CH2--) disappeared. 
(F) Preparation of Glycidyl Ester Functionalized Organosiloxane from 
Glycidy Ester (Example 1-b) and 1,1,3,3-tetramethyldisiloxane 
To a 30 ml toluene solution containing 54 g (0.2 mole) allyl glycidyl 
hexahydrophthalate from(1-B) and 0.1g of 5% H2PtC16 in t-amyl alcohol is 
added a 20 ml toluene solution of 14.9g of 
1,1,3,3-tetramethyldisiloxane(0.1 mole) at 52.degree. C. in 75 min. After 
completion of additon, the mixture is reacted at 52.degree. C. for another 
7 hrs. The mixture is then dissolved in 150 ml methyl ethyl ketone, and 
the solution is washed successively four times with 50 ml portion of 
H2O/each. The organic layer is collected and 55 g of product is obtained 
after stripping off the solvent at 90.degree. C./5 mmHg. The adduct has 
epoxide content 11.96%(EEW=360) and viscosity 230 cps/40.degree. C. The 
structure is confirmed by IR and 1H NMR spectra. The Si--H absorption band 
at 2100 cm.sup.-1 and unsaturated double bond at allyl substituent at 1650 
cm.sup.-1 in IR(neat) disappeared; In 1H NMR, a strong resonance peak at 
0.2-0.5ppm for methylsilyl group(Si--CH3 and Si--CH2) appears, while 
unsaturated allylic double bond at 5-6.2ppm disappeared. 
(G) The Preparation of Glycidyl Ester Functionalized Organosiloxane form 
Allylglycidyl Ester Hexahydrophthlate of 1B and 
1-methyl-1,1,1-tri-(dimethylsiloxyl)-silane 
To a 25 ml toluene solution containing 34.6g of allyl-glycidyl 
hexahydrophthalate(0.12 mole) from 1B and 0.1 g of 5% H2PtC16 in t-amyl 
alcohol is added a 15 ml toluene solution of 10.75 g 
1-methyl-1,1,1-tri(dimethylsiloxyl) silane(0.04 mole) at 50.degree. C. for 
30 min. slightly exothermic is observed. After completion of addition, the 
mixture is reacted at 55.degree. C. for another 3 hrs, until IR spectrum 
showed all Si--H absorption band at 2100 cm.sup.-1 disappeared. The 
mixture is then dissolved in 150 ml ethylmethylketone and the solution is 
washed successively with water for four times(50 ml/each). The organic 
layer is separated and 41 g of adduct is obtained after stripping off the 
solvent at 120.degree.-130.degree. C./5 mmHg. The glycidyl ester -siloxane 
adduct has epoxide content 11.70% with EEW 367, viscosity 250 
cps/40.degree. C. 
(H) Preparation of Glycidyl Ester Functionalized Organosiloxane Oligomer 
from Glycidyl Ester(Example 1-B) and 
Polyhydromethylsiloxanedimethylsiloxane Copolymer 
To a 40 ml toluene solution containing 42.69 g (0.16 mole) glycidyl ester 
from example 1 and 0.1 g of 5% H.sub.2 PtCl.sub.6 in t-amyl alcohol is 
added a 20 ml toluene solution of 50 g of 
polymethylhydrosiloxanesdimethylsiloxane copolymer (18% hydromethyl 
siloxane content; M.W.=2250; Si--H equivalent: 60g/per Si--H, from Huls 
Co.) at 50.degree.-52.degree. C. in 120 min., and kept at 55.degree. C. 
for another 1.5 hrs. The mixture is dissolved in 150 ml methyl ethyl 
ketone, and the solution is washed successively four times with 50 ml 
portions of H2O. The organic layer is collected and 90 g of viscous liquid 
is obtained after stripping off the solvent at 100.degree.-110.degree. 
C./5 mm Hg. The organosiloxane with glycidyl ester functional groups has 
an epoxide content of 7.18% (EEW=599) and the structure is confirmed by IR 
and 1H NMR spectra: The Si bond absorption at 2100-2200 cm.sup.-1 and 
unsaturated double bond at allyl substituent at 1650-1670 cm.sup.-1 in 
lR(neat) disappears: In 1H NMR, a strong resonance peak at 0.2-0.8ppm for 
methylsilyl group (m, Si--CH.sub.3 and Si--CH.sub.2) appeared, while 
unsaturated allylic double bond at 5-6.2ppm (m, CH.sub.2 .dbd.CH--CH.sub.2 
--) disappears. 
EXAMPLE 2 
(A) Preparation of the Unsaturated Mono-ester Acid Adduct from 
Hexahydrophthalic Anhydride and Norborene Methanol 
A 500 ml four-necked, round bottom flask equipped with a cooling condenser, 
mechanical stirrer, thermometer with temperature controller and nitrogen 
source is placed on a heating mantle. Hexahydrophthalic anhydride (HHPA, 
0.75 mole, 115.6 g, &gt;95% purity and norborenemethanol (0.75 mole, 97 g, 
&gt;98% purity) are charged into the flask and carefully heated to 65.degree. 
C. to 70.degree. C. The melted mixture is reacted at 85.degree. C. for 8 
hours. The unreacted norborene methanol is further stripped off from the 
viscous adduct of HHPA-norborenemethano at 130.degree. C./&lt;5 mm Hg. 205 g. 
of HHPA-norborenemethanol monoester adduct is obtained. IR shows that 
absorption bands at 1860 cm.sup.-1 and 1800 cm.sup.-1 for anhydride 
carbonyl group are substituted by two strong absorption bands at 1700 
cm.sup.-1 and 1730 cm.sup.-1, which represents the carbonyl groups both of 
ester and carboxylic acid, together with a broad carboxylic acid OH 
absorption peak at 3000 cm.sup.-1 to 3500 cm.sup.-1. 1H NMR (CDCl.sub.3 
-TMS) shows the appearance of unsaturated double bond of norborene at 5.7 
ppm to 6.3 ppm together with the --OCH.sub.2 -multiple peaks at 3.8 ppm to 
4.2 ppm (diastereotropic position) for norborenemethanol mono-ester. The 
carboxilic absorption peak of the adduct is at 10 ppm to 11 ppm which 
disappears later after epoxidation. 
(B) Preparation of the Glycidyl Ester of the Unsaturated Mono-ester Acid 
Adduct from Hexahydrophthalic Anhydride and Norborene Methanol 
A 500 ml four-necked round bottom flask equipped with a cooling condenser, 
mechanical stirrer, thermometer with temperature controller and addition 
funnel is placed on a heating mantle. 64 g (0.23 mole) of the mono-ester 
acid adduct from HHPA and norborenemethanol prepared in (A) above, 
epichlorohydrin 171 g, 1.84 mole), and tetrabutyl ammonium chloride 
(0.50g, 0.002 mole) are charged into the flask. The mixture is carefully 
heated to 65.degree. C. and kept at 65.degree. C. for another 2.5 hours. 
IR spectra of the reaction mixture shows all carboxilic groups of 
mono-ester acid adduct from HHPA and norborenemethanol reacts with 
epichlorohydrin to form chlorohydrin ester. The reaction mixture is then 
cooled to 45.degree. C. 33.12 g of 50% NaOH aqueous solution (0.42 mole) 
is added at this temperature over a period of about 30 minutes, and 
occasionally cooling is necessary in order to prevent exothermic reaction. 
After the completion of addition, the reaction is maintained at 45.degree. 
C. for another 4 hours. After filtrations, to the solution is added 250 ml 
to 300 ml methyl ethyl ketone (MEK) and successively neutralized with dry 
ice followed by washing with water (100 ml each for five times). The 
unreacted epichlorohydrin and MEK is then stripped off under vacuum (&lt;5 
mmHg) at 100.degree. C. to13.degree. C. 68 g. of glycidyl ester of 
HHPA-norborenemethanol mono-ester acid adduct is obtained having an 
epoxide content of 12.8% (EEW =335.9). Theoretical epoxide content is 
12.8% (EEW =335.9). 
(C) Preparation of Hydrosilylation Adduct of Glycidyl Ester (Example 2B) 
and 1,1,3,3-tetramethyldisiloxane 
To a 20 ml toluene solution containing 53.5g (0.16 mole) glycidyl ester 
prepared in (B) above and 0.15g of a 5% solution of H.sub.2 PtCl.sub.6 in 
t-amyl alcohol is added a 20 ml toluene solution containing 10.8 g (0.078 
mole) tetramethyldisiloxane at 65.degree. C. The addition is complete in 
15 minutes no exothermeric reaction is observed. The mixture is heated at 
65.degree. C. to 70.degree. C. for another 9 hours. Toluene, 100 ml, is 
added into the reactor, after washing successively with water (50 ml each 
for 4 times), 55 g of the viscous product: 
1,3-bis-(5-norborenyl-2-methyl-(2'-glycidyl 
carboxy)-1'-cyclohexanecarboxylate)-1,1,3,3-tetramethyldisiloxane is 
obtained after stripping off solvent at 1205.degree. C./&lt;5 mm Hg. Epoxide 
content=11.56% (EEW=371.9). The structure of the hydrosilylation adduct is 
confirmed by 1H NMR and IR analysis: The Si-H bond absorption at 2100 
cm.sup.-1 in IR (neat) disappears; In 1H NMR, a strong resonance peak at 
0.2 ppm to 0.8 ppm for methyl silyl group (Si--CH.sub.3 and Si--CH.sub.2) 
appears, while unsaturated norborene double bond at 5.8 ppm to 6.2 ppm 
(--CH.dbd.CH--) disappears. 
EXAMPLE 3 
Reactivity And Cured Product Properties Of Example 1 
The reactivity of the mixture of uncured glycidyl ester functionalized 
siloxane (Examples 1-C, 1-D, 1-E, and 1-F) with hexahydrophthalic 
anhydride/catalyst is measured by differential scanning calorimetry(DSC) 
method using a Du Pont series 2100 thermal analysis system with DSC model 
no. 912. The results are given in the following Table I. 
TABLE I 
______________________________________ 
DSC Exotherm Temp. 
Resin Curing Agent 
Catalyst Init. (.degree.C.) 
Max. (.degree.C.) 
______________________________________ 
1C HHPA.sup.a 2-MI.sup.b 
121 161 
(2.43 G) 
(0.44 g) (0.01 g) 
1D HHPA 2-MI.sup.b 
115 150 
(2.0 g) 
(0.73 g) (0.01 g) 
1E HHPA 2-MI.sup.b 
121 150 
(1.95 g) 
(0.73 g) (0.01 g) 
1E HHPA A-1.sup.c 
124 157 
(1.95 g) 
(0.73 g) (0.01 g) 
1F HHPA 2-MI.sup.b 
115 144 
(2.16 g) 
(0.73 g) (0.01 g) 
1F HHPA A-1 125 158 
(2.16 g) 
(0.73 g) (0.01 g) 
CY-184.sup.d * 
HHPA 2-MI.sup.b 
122 143 
(0.77 g) 
(0.73 g) (0.01 g) 
______________________________________ 
*Not an example of the present invention. 
.sup.a HHPA is hexahydrophthalic anhydride. 
.sup.b 2MI is 2methylimidzole. 
.sup.c A1 is a 70 percent methanol solution of ethyl triphenyl phosphoniu 
acetatate.acetic acid complex. 
.sup.d CY184 is diglycidyl ester of hexahydrophthalic acid (EEW 184) from 
CibaGeigy. 
EXAMPLE 4 
Coating compositions (Formulations 4-A to 4-D) containing 
organosiloxane-glycidyl esters of the invention is formulated using a 
phosphonium catalyst and anhydride curing agent. 
The anhydride curing agent is cyclohexane-1,2dicarboxylic anhydride. The 
curing agent is used in an amount corresponding to 95 equivalent percent 
of the epoxide equivalent. The catalyst is 4.5% weight of anhydride used. 
The curing catalyst is 70% methanol solution of ethyltriphenylphosponium 
acetate.acetic acid complex (ETPPA.HAc) and is employed in an amount of 
4.5 weight percent of the amount of anhydride employed. 
A comparative coating composition (Formulation 4-E) using diglycidyl ester 
of hexahydrophthalate (DGEHHPA, epoxide content=27.04%, EEW=159) instead 
of organosiloxane-glycidyl esters is also formulated using the same 
phosphonium catalyst and anhydride curing agent. 
The compositions (formulations 4A-E) are reduced to a spray viscosity of 
30-32 seconds measured with a No.2 Zahn cup by adding butyl acetate. The 
coating compositions are sprayed onto a steel panel and cured at 
250.degree. F. (121.1.degree. C.) for 30 minutes and at 325.degree. F. 
(162.8.degree. C.) for another 30 minutes to form a 2 mil (0.0508 mm) 
coating thickness. The coatings containing the organosiloxane moiety gave 
excellent flexibility compared to the coating containing only the 
diglycidyl ester of hexahydrophthalate (DGEHHPA). The results are given in 
the following Table II. 
TABLE II 
__________________________________________________________________________ 
Formulation 
A B C D E* 
__________________________________________________________________________ 
Glycidyl Ester 
Ex 1-E/15 
Ex 1-H/15 
Ex 1-E/13.5 
Ex 1-H/3.5 
DGEHHPA/15 
Type/grams Ex 1-H/3.5 
DGEHHPA/13.5 
Curing Agent 
6.53 3.68 6.88 13.47 13.82 
(HHPA), grams 
Catalyst, ETPPA.HAc 
0.30 0.16 0.30 0.61 0.60 
grams 
Solvents, grams 
n-butyl acetate 
3 3 3 3 3 
Xylene 1 1 1 1 1 
Aromatic 100 
1 1 1 1 1 
Properties 
Forward Impact 
In-lb 60-80 &gt;100 100-120 
50 20-40 
Kg-cm 69-92 &gt;115 115-138 
58 23-46 
__________________________________________________________________________ 
*Not an example of the present invention.