Composition comprising an epoxy compound

A novel composition is disclosed comprising an alicyclic epoxy compound formed by an epoxidation reaction of a polymerized cyclo olefin compound having double bonds with an epoxidating agent. A cured epoxy resin according to the present invention has excellent heat resistance, outdoor durability, and water resistance, attributable to the absence of ether units derived from the ring-opening of epoxy groups and hydroxyl groups derived from an initiating agent.

FIELD OF THE INVENTION 
The present invention relates to a novel composition comprising an 
alicyclic epoxy compound, which can be obtained by an epoxidation reaction 
of a polymerized composition having double bonds comprising a cyclo olefin 
compound with an epoxidating agent. 
A cured epoxy resin comprising the present composition has excellent heat 
resistance, outdoor durability, and water resistance. 
BACKGROUND OF THE INVENTION 
Hitherto, various types of epoxy resins have been widely made and used on a 
commercial basis. 
Epoxy resins which have been widely used in industries include so-called 
epi-bis type epoxy resins produced by reacting bisphenol A with 
epichrolhydrine. 
These resins have advantages, e.g., various products can be obtained, from 
a state of liquid to solid, and they can be cured at room temperatures 
with polyamines because the reactivity of the epoxy resins is high. 
However, the cured products thereof are defective in that the outdoor 
durability is poor, the electric properties such as anti-tracking 
property, etc., are poor, and the heat distortion temperature is low, 
although they do have desirable characteristics of good water resistance 
and strength. 
Recently, particularly epoxy resins prepared by reacting phenolic resin or 
novolak resin with epichrolhydrine have been used as resins for 
encapsulating VLSI (very large scale integrated circuit), etc., but 
chlorine contained in the resins, typically in an amount of several 
hundred parts per million, causes the problem of a deterioration of the 
electric properties of such electronic devices. 
Epoxy resins having excellent electric properties and heat resistance, and 
which do not contain chlorine are known, such as certain alicyclic epoxy 
resins which are produced by an epoxidation reaction of a compound having 
a 5- or 6-membered cycloalkenyl structure. 
The epoxy group in these resins is a so-called inner epoxy group, and 
curing is usually carried out with acid anhydride by heating. 
However, since their reactivity is low, they cannot be cured with 
polyamines at room temperatures, and therefore, the use of the alicyclic 
epoxy resins has so far been technically restricted. 
As alicyclic epoxy resins, those having a structure represented by formula 
(VII) or (VII) are presently used on a commercial basis. 
##STR1## 
(VII) is used as a heat resistible epoxy diluent, because of its very low 
viscosity. 
However, it has the disadvantage of possessing high toxicity and causes the 
problem of poisoning upon contact with the skin of the human body. 
(VIII) contains only a small amount of impurities and has a low color hue, 
and the cured products produced therewith have a high heat distortion 
temperature. 
However, much epoxy resins suffer from the problem that they possess poor 
water resistance due to the presence of ester bonds. 
In addition, because (VII) and (VIII) are epoxy resins having a low 
viscosity, it is impossible to apply molding systems for solid epoxy 
resins, such as transfer molding, etc., thereto. 
From the above viewpoint, novel alicyclic epoxy resins which have 
oxycyclohexane units derived from 4-vinylcyclohexene-1-oxide were 
disclosed in Japanese Publication (Kokai) No. 166675/1985, corresponding 
to U.S. Pat. No. 4,565,859. 
In addition, novel alicyclic epoxy resins which have oxynorbornane units 
derived from 4-vinylbicyclo[2.2.1]heptene-1-oxide in place of 
oxycyclohexane units were disclosed in Japanese Application (Priority) No. 
215526/1987, etc., corresponding to U.S. Pat. No. 4,841,017. 
Further, novel alicyclic epoxy resins, which have closslinked structures 
between the oxycyclohexane units, were disclosed in Japanese Application 
(Priority) No. 50361/1987, etc. 
Nevertheless, the above epoxy resins do not have a completely sufficient 
water resistance and resistance to hydrolysis, because of the ether units 
and hydroxyl groups. 
It is noted that the ether units are formed by the ring opening of the 
epoxy groups possessed by 4-vinylcyclohexene-1-oxide or 
4-vinylbicyclo[2.2.1]heptene-1-oxide, and that the hydroxyl groups are 
derived from an initiating agent for a ring-opening reaction. 
In addition, not only the overcoming of the above described problems, but 
also the number of methods or objects involving the use of epoxy resins 
have grown, and so have the desired characteristics of such epoxy resins; 
for example, demands for epoxy resins having excellent water resistance 
and excellent ductility have increased. 
SUMMARY OF THE INVENTION 
An object of the present invention is to provide a novel composition 
comprising an alicyclic epoxy compound having excellent resistance to 
hydrolysis and water. 
From the above viewpoint, and as a result of intensive studies by the 
present inventors, it has been found that a composition obtained by an 
epoxidation reaction of a polymerized unsaturated compound having 
alicyclic structures in a molecule with an epoxidation agent can provide 
an epoxy resin having an excellent water resistance and resistance to 
hydrolysis. 
The composition of the present invention comprises at least one epoxy 
compound represented by formula (I), (II), or (III) described hereinafter, 
respectively, 
##STR2## 
wherein 
n is an integer of 2 to 1,000, X represents a mixture of 
##STR3## 
groups, in which R is either H, an alkyl group, an alkyl carbonyl group, 
or an aryl carbonyl group, provided that at least one 
##STR4## 
group is contained therein, 
Y represents a mixture of 
##STR5## 
groups contained therein, groups, in which R is either H, an alkyl group, 
an alkyl carbonyl group, aryl carbonyl group, provided that at least one 
##STR6## 
group is contained therein, and 
Z represents a mixture of 
##STR7## 
groups, in which R is either H. an alkyl group, a alkyl carbonyl group, or 
a aryl carbonyl group provided that at least one 
##STR8## 
group is contained therein. 
DETAILED DESCRIPTION OF THE INVENTION 
The present invention is described hereinafter in more detail. 
A composition comprising alicyclic epoxy compound represented by formula 
(I) 
##STR9## 
as a first embodiment of the present invention, for example, can be 
produced by an epoxidation reaction of side vinyl groups in polymerized 5 
vinyl-2-norbornene represented by formula (IV) 
##STR10## 
with an oxidation agent such as a peracid. 
A composition comprising an alicyclic epoxy compound represented by formula 
(II) 
##STR11## 
as a second embodiment of the present invention, for example, can be 
produced by an epoxidation reaction of an inner double bond of polymerized 
5-ethylidene-2-norbornene represented by formula (V) 
##STR12## 
with an oxidation agent such as a peracid. 
A composition comprising an alicyclic epoxy compound represented by formula 
(III) 
##STR13## 
as a third embodiment of the present invention, for example, can be 
produced by an epoxidation reaction of double bonds (inner olefin) in 
5-membered alicyclic structures of poly (dicyclopentadiene) represented by 
formula (VI), which is obtained by a polymerization of double bonds of 
norbornene structures of dicyclopentadiene, 
##STR14## 
with an oxidation agent such as a peracid. 
Poly(5-vinyl-2-norbornene) (IV),poly(5-ethylidenenorbornene) (V), 
poly(dicyclopentadiene) (VI) can be produced by a polymerization reaction 
of each of the above-described monomers in the presence of a catalyst 
composed of a mixture of a transition metal compound with an aluminoxane 
compound (described below) in a solvent such a hydrocarbon. 
The specific hydrocarbon solvent includes an aliphatic hydrocarbon such as 
butane, isobutane, pentane, hexane, heptane, and/or octane, an aromatic 
hydrocarbon such as benzene, toluene and xylene, and/or a petroleum 
distillate such as gasoline, kerosene oil, and/or light oil. 
An aromatic hydrocarbon is most preferably used. 
A conventional polymerization method such as a suspension polymerization or 
a solution polymerization, can be used without restriction in the present 
invention. 
Preferably polymerization temperatures are from about -50.degree. to 
230.degree. C., more preferably from -30.degree. to 200.degree. C., and 
most preferably from 0.degree. to 150.degree. C. 
The amount of the transition metal compound is from 10.sup.-7 to 10.sup.-1 
gram.atom /l, based on the concentration of the metal atom, and preferably 
from 10.sup.-5 to 10.sup.-2 gram.atom /l in the case of a liquid phase 
polymerization process of the present invention. 
The catalyst to be used is composed of a mixture of a transition metal 
compound with the aluminoxane. 
The preferable transition metal compound includes a transition metal 
selected from IV B, VB, or VI B group of the periodic table. 
The specific transition metal compound may, for example, include a compound 
of titanium, zirconium, hafnium, vanadium, or chromium, and is preferably 
titanium or zirconium, as these have a higher activity. 
The preferable form of the transition metal compound includes a compound 
having a halogen atom(s) and a hydrocarbon group(s) or a compound having a 
hydrocarbon group(s) or an alkoxy group(s). The specific halogen atom 
includes fluorine, chlorine, bromine or iodine. 
The specific hydrocarbon group includes an alkyl group such as methyl 
group, ethyl group, propyl group, isopropyl group, n-butyl group, secbutyl 
group, tert-butyl group or isobutyl group; an alkenyl group such as 
isopropenyl group or 1-butenyl group; a cycloalkadienyl group such as 
cyclo pentadienyl group, methyl cyclopentadienyl group, tetramethyl 
cyclopentadienyl group, indenyl group or tetrahydroindenyl group; and an 
aralkyl group such as benzyl group or neophyl group. 
The specific alkoxy group(s) includes an alkyl alkoxy group such as methoxy 
group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, 
isobutoxy group, sec-butoxy group, tert-butoxy group, and an alkoxy group 
having a cyclic structure, such as a cyclohexanoxy group and a menthoxy 
group. 
Specific transition metal compounds include: titanium compounds such as 
titanium tetrachloride, titanium trichloride, bis(pentadienyl)dimethyl 
titanium, dimethyl titanium, bis(cyclopentadienyl)dimethyl 
titanium,bis(cyclopentadienyl)diisopropyl 
titanium,bis(methylcyclopentadienyl)dimethyl titanium, 
bis(methylcyclopentadienyl)methyl titanium monochloride, 
bis(cyclopentadienyl)ethyl titanium monochloride, 
bis(cyclopentadienyl)isopropyl titanium monochloride, 
bis(cyclopentadienyl)methyl titanium monobromide, 
bis(cyclopentadienyl)methyl titanium monoiodide, 
bis(cyclopentadienyl)methyl titanium monofluoride, bis(indenyl)methyl 
titanium monochloride, bis(indenyl)methyl titanium monobromide, 
bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)titanium 
dibromide, bis(cyclopentadienyl) titanium diioide, bis(cyclopentadienyl) 
titanium difluoride, bis(indenyl) titanium dichloride, 
bis(indenyl)titanium dibromide, ethylenebis(indenyl)titanium, tetramethoxy 
titanium dichloride, tetramethoxy titanium dichloride, tetraethoxy 
titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, 
tetraisopropoxy titanium, tetra-secbutoxy titanium, tetra-tert-butoxy 
titanium, and tetramethoxy titanium; zirconium compounds such as zirconium 
tetrachloride, bis(cyclopentadienyl)dimethyl zirconium, 
bis(cyclopentadienyl)diethyl zirconium, bis(cyclopentadienyl)diisopropyl 
zirconium, bis(methylcyclopentadienyl)dimethyl zirconium, 
bis(cyclopentadienyl)methyl zirconium monochloride, 
bis(cyclopentadienyl)ethyl zirconium monochloride, 
bis(cyclopentadienyl)isopropyl zirconium monochloride, 
bis(cyclopentadienyl)methyl zirconium monobromide, 
bis(cyclopentadienyl)methyl zirconium monoiodide, bis(cyclopentadienyl) 
zirconium dichloride, bis(cyclopentadienyl) zirconium difluoride, 
bis(cyclopentadienyl) zirconium dibromide, bis(cyclopentadienyl) zirconium 
monochloridehydride, bis(indenyl) zirconium dichloride, bis(indenyl) 
zirconium dibromide, ethylenebis(indenyl) zirconium dichloride, 
ethylenebis(indenyl) zirconium dibromide, tetramethoxy zirconium, 
tetraethoxy zirconium, tetra-n-propoxy zirconium, tetraisopropoxy 
zirconium, tetra-n-butoxy zirconium, tetraisobutoxy zirconium, 
tetra-sec-butoxy zirconium, tetra-tert-buthoxy zirconium, and 
tetramenthoxy zirconium; hafnium compounds such as hafnium tetrachloride, 
bis(cyclopentadienyl) dimethyl hafnium, bis(cyclopentadienyl)methyl 
hafnium monochloride, bis(cyclopentadienyl)ethyl hafnium monochloride, 
bis(cyclopentadienyl) hafnium dichloride, bis(cyclopentadienyl)hafnium 
dibromide, bis(cyclopentadienyl)hafnium monochloridehydride, 
bis(indenyl)hafnium dichloride, ethylenebis(indenyl)hafnium dichloride, 
tetraethoxy hafnium, tetra-n-propoxy hafnium, tetraisopropoxy hafnium, 
tetra-n-butoxy hafnium, tetra-tert-butoxy hafnium, and tetramethoxy 
hafnium; vanadium compounds such as bis(cyclopentadienyl) vanadium, 
bis(cyclopentadienyl)vanadium monochloride, etc. 
Aluminoxane, which is another catalytic component used to prepare the raw 
materials of the present invention, is represented by the formulae: 
##STR15## 
wherein R is a hydrocarbon group and m is an integer of 1 or more. 
R is a hydrocarbon group unsubstituted or having one or more substituent 
groups such as a methyl group, ethyl group, propyl group, isopropyl group, 
and/or butyl group, more preferably a methyl group, in the aluminoxane, 
and m is an integer of 1 or more, preferably more than 5, and more 
preferably 10 to 100. 
The aluminoxane can be produced by either the following method (1) or (2). 
(1) a compound having absorbed water or a compound having water of 
crystallization, such as a hydrate of copper sulphate or a hydrate of 
aluminum sulphate, is suspended in an organic solvent, followed by 
reacting while adding trialkyl aluminum. 
(2) a reaction of trialkyl aluminum suspended in an organic solvent with 
water added directly thereto. 
The above method (1) is more preferable than the above method (2). 
In addition, aluminoxane can also include a small amount of organic 
metallic compound. 
For reference, it is noted that a detailed process for the production of 
polymers (IV), (V) and (VI), which are starting materials of the present 
novel epoxy composition (I), (II), and (III) respectively is provided in 
the specification of Japanese Application (Priority) No. 332330/1988 
(filed in Jan. 4, 1989). 
The present novel compositions (I), (II), and (III) can be produced by an 
epoxidation reaction of unsaturated double bonds in (IV), (V) and (VI). 
In the present epoxy compositions (I), (II), and (III), the unsaturated 
double bonds are at least partially epoxidized, on a commercial basis, and 
n is 2 to 1000, preferably 10 to 1000. 
Accordingly, n in formula (IV), (V) and (VI) must be 2 to 1000. 
The size of n, which corresponds to the degree of polymerization, can be 
adjusted by controlling the amount of catalyst and the temperature. 
When it is desired to produce a higher molecular weight compound, smaller 
amounts of catalyst and higher temperatures are usually applied during the 
polymerization reaction. 
On the other hand, when it is desired to produce a lower molecular weight 
compound, increased amounts of catalyst and lower temperatures are usually 
applied during the polymerization reaction. 
n in the formula (I), (II) and (III) is not more than 1000, because much 
long chain compositions are insoluble in organic solvents. 
On the other hand, it is preferred that n is not less than 10, because 
cured resins of such epoxy compositions are relatively brittle and have a 
low strength. 
Upon an epoxidation reaction in which compositions (IV), (V) or (VI) are 
epoxidized with an epoxidating agent to produce the present compositions 
(I), (II) or (III), peracetic acids or hydroperoxides can be used as the 
epoxidating agent. As the peracids, performic acid, peracetic acid, 
perbenzoic acid and trifluoroperacetic acid can be used. 
Of these peracids, peracetic acid is the preferred epoxidating agent, 
because it is available on an industrial basis at a moderate price and has 
a high stability. 
As the hydroperoxides, hydrogen peroxide, tertiary butyl hydroperoxide, 
cumen peroxide, and methachloroperbenzoic acid can be used. 
When carrying out the epoxidation, a catalyst can be used as appropriate to 
the circumstances. 
In the case of peracids, for example, alkalis such as sodium carbonate, and 
acids such as sulfuric acid, can be used as a catalyst. 
In the case of using hydroperoxide, it is possible to obtain a catalytic 
effect, for example, by using a mixture of tungstic acid and sodium 
hydroxide together with hydrogen peroxide, or hexacarbonylmolybdenum 
together with tertiary butyl hydroperoxides. The epoxidation reaction is 
carried out in the absence or presence of a solvent, while controlling the 
reaction temperature according to the apparatus used and the properties of 
the raw materials. 
The temperature region of the epoxidation reaction can be selected 
according to the reactivity of the epoxidating agent. In the case of 
peracetic acid, which is the preferable epoxidating agent, the preferable 
temperature is from 0.degree. to 70.degree. C. 
If the temperature is under 0.degree. C., the reaction velocity is slow, 
but if the temperature is over 70.degree. C., decomposition of the 
peracetic acid can occur. 
In the case of a tertiary butyl hydroperoxide molybdenum dioxide diacetyl 
acetate, which is an example of a hydroperoxide, the preferable 
temperature range is from 20.degree. to 150.degree. C., based on the same 
considerations. 
The use of solvents for dilution is effective for lowering the viscosity of 
raw materials and stabilizing the epoxidation agent. 
In the case that peracetic acid is used as the epoxidating agent, a 
preferable solvent is an aromatic compound ether or ester. 
The molar ratio of the epoxidating agent to be used to the unsaturated 
bonds, i.e., the vinyl groups, is selected according to the proportion of 
unsaturated bonds which it is desired retain. 
When preparing epoxy compositions having many epoxy groups, an equal or 
higher molar ratio of the epoxidating agents to the unsaturated bonds is 
preferably used, but using amounts of the epoxidating agents at a molar 
ratio of more than 10 with respect to the unsaturated bonds is not 
preferable, because of the cost and of the side reactions described below. 
In the case of peracetic acid, preferably the molar ratio is 1/1 to 5/1. 
Esterified groups are produced by the sidereaction between epoxy groups and 
acetic acid byproduct, depending upon the epoxidating conditions, with a 
generation of the epoxy groups from olefin groups. 
That is, the present compositions (I), (II) or (III) comprising epoxy 
compounds may contain units corresponding respectively to a formula (IV), 
(V) or (VI), in part. 
In addition, the present compositions (I), (II) or (III) may also contain 
units having a substituent group formed by an esterification of epoxy 
groups generated during the epoxidating reaction with acids generated from 
the peracids. 
For example, where the present composition (I) is produced by an 
epoxidation reaction of the composition (IV) with peracetic acid, X in 
formula (I) is composed of a mixture of 
##STR16## 
In the present composition (I), at least one 
##STR17## 
group is contained, and more preferably, the number of 
##STR18## 
groups is relatively large and the number of 
##STR19## 
groups is relatively small. 
On the other hand, where the present composition (II) is produced by an 
epoxidation reaction of the composition (VII) with peracetic acid, Y in 
formula (II) is composed of a mixture of 
##STR20## 
In the present composition (II), preferably the number of 
##STR21## 
group is relatively large and the number of 
##STR22## 
groups is relatively small. 
Also, where the present composition (III) is produced by an epoxidation 
reaction of the composition (VI) with peracetic acid, Z in formula (III) 
is composed of a mixture of 
##STR23## 
In the present composition (III), preferably the number of 
##STR24## 
groups is relative large and and the number of 
##STR25## 
groups is relatively small. 
The relative amounts of the three different substituent groups including at 
least one epoxy group described hereinabove depend on the ratio of the 
epoxidating agents to the double bonds, the kinds of epoxidating agents, 
and the reaction conditions. 
The desired compound can be separated from the crude reaction solution by a 
conventional chemical process such as concentration.

The present invention is now illustrated by examples, as follows. 
EXAMPLE 1 Preparation of aluminoxane: 
Preparation of aluminoxane was carried out while streaming nitrogen gas 
through the reaction flask. 
First, 18.4 g of CuSO.sub.4.5H.sub.2 O and 67 ml of toluene were charged 
into a flask having a capacity of 300 ml, which was replaced with 
sufficient nitrogen gas, and agitated to obtain a suspension liquid. 
Then, 24 ml of trimethyl aluminum diluted with 150 ml of toluene was 
charged dropwise into the suspension liquid while maintaining the 
temperature thereof at from -30.degree. to -20.degree. C. 
The liquid was agitated while maintaining a temperature of 0.degree. C. for 
6 hours, was then gradually warmed, and then reacted at temperature of 
40.degree. C. for 12 hours. 
Thereafter, a solid was separated from solution by filtration to obtain an 
aluminoxane solution. 
The aluminoxane solution was used in polymerization reaction described 
hereinafter. 
POLYMERIZATION EXAMPLE-1 
Polymerization of 5-vinyl-2-norbornene 
35 ml of toluene and 2 milli mole of the methyl aluminoxane obtained in the 
above described preparing method and 0.1 milli mole of zirconium chloride 
were charged into a pressure resistible glass flask having a capacity of 
100 ml replaced with nitrogen gas. 
In succession, 5 ml of 5-vinyl-2-norbornene was added, followed by being 
heated to 80.degree. C. and being polymerized for 24 hours. After the 
completion of the polymerization, the reaction mixture was put into 
methanol-hydrochloric acid to stop the reaction, followed by filtration of 
a produced polymer and drying thereof, whereby 0.91 g of the polymer was 
obtained. 
It was confirmed that the polymer was represented by the formula (I) based 
on absorption peaks of vinyl groups at 3070, 1630, 980, and 900 cm.sup.-1 
of IR the spectrum. 
In addition, it was confirmed that absorption peaks at 710 to 720 cm.sup.-1 
caused by inner double bonds were not substantially observed. 
Furthermore, it was confirmed that absorption peaks at 4.8 to 5.2 ppm from 
protons of vinyl groups were observed, but a sharp absorption peak at 6.0 
ppm from protons of an inner double bond was not substantially observed by 
an analysis with .sup.1 H--NMR spectrum. 
From the above analysis, it was clarified that the reaction proceeded 
simply by an addition polymerization of the inner double bond of 
5-vinyl-2-norbornene. 
The molecular weight Mn (Mn indicates number average molecular weight) and 
the molecular weight distribution Mw/Mn (Mn indicates weight average 
molecular weight) were 1170 (value determined based on polystyrene 
standard) and 2.40, respectively, by gel permeation chromatography 
analysis. 
POLYMERIZATION EXAMPLE 2 
Polymerization of 5-vinyl-2-norbornene 
50 ml of toluene and 30 milli mole of the methylaluminoxane obtained in the 
above described preparing method and 1 milli mole of 
bis(cyclopentadienyl)zirconium dichloride were charged into a pressure 
resistible glass flask having a capacity of 100 ml replaced with nitrogen 
gas. 
In succession, 100 ml of 5-vinyl-2-norbornene was added, followed by being 
heated to 80.degree. C. and being polymerized for 12 hours. 
After the completion of the polymerization, the reaction mixture was put 
into methanol-hydrochloric acid to stop the reaction, followed by a 
filtration of a produced polymer and drying thereof, whereby 38.0 g of a 
polymer was obtained. 
It was confirmed that the polymer was represented by the formula (I) based 
on absorption peaks of vinyl groups at 3070, 1630, 980 and 900 cm.sup.-1 
of infra-red chromatograph spectrum. 
In addition, it was confirmed that absorption peaks at 710 to 720 cm.sup.-1 
from the inner double bond were not substantially observed. 
Furthermore, it was confirmed that absorption peaks at 4.8 to 5.2 ppm from 
protons of vinyl groups were observed, but a sharp absorption peak at 6.0 
ppm from protons of inner double bond was not substantially observed by an 
analysis with .sup.1 H--NMR spectrum. 
The molecular weight Mn and the molecular weight distribution Mw/Mn were 
1050 and 2.59, respectively, by gel permeation chromatography analysis. 
POLYMERIZATION EXAMPLE-3 
Polymerization of 5-vinyl-2-norbornene 
First, 50 ml of toluene and 20 milli mole of the methylaluminoxane obtained 
in the above described preparing method and 0.5 milli mole of 
bis(cyclopentadienyl)zirconium dichloride were charged into a pressure 
resistible glass flask having a capacity of 100 ml replaced with nitrogen 
gas. 
In succession, 100 ml of 5-vinyl-2-norbornene was added, followed by being 
heated to 80.degree. C. and being polymerized for 12 hours. After 
completion the polymerization, a reaction mixture was put into 
methanol-hydrochloric acid to stop the reaction, followed by filtration of 
a produced polymer and drying thereof, whereby 49.4 g of the polymer was 
obtained. 
It was confirmed that the polymerization proceeded by only an addition of 
the inner double bonds by an analysis with infra-red absorption spectrum 
and an .sup.1 H--NMR spectrum analysis. 
The molecular weight Mn and the molecular weight distribution Mw/Mn were 
1020 (a value converted into polystyrene) and 1.80, respectively, by gel 
permeation chromatography analysis. 
EPOXIDATION EXAMPLE-1 
Epoxidation of the Obtained Poly(5-Vinyl-2-Norbornene) 
First, 0.1 g of the poly(5-vinyl-2-norbornene) was charged into a flask 
having a capacity of 10 ml, then 3.0 g of chloroform was added and 
agitated to dissolve while being maintained at 20.degree. C. for 30 
minutes. 
Then 0.26 g of ethyl acetate solution containing 30 % of peracetic acid was 
added at once to the chloroform solution, followed by being reacted at 
temperature of 40.degree. C. for 3 hours. 
After the reaction, 3.0 g of pure water was put into the crude reacted 
solution, followed by agitating at a temperature of 30.degree. C. for 10 
minutes and maintaining a temperature of 30.degree. C. for 20 minutes to 
form an interface between two phases. 
The two phases were composed of an upper water solution and a lower 
chloroform solution. 
The upper water solution was removed by an injection, and the lower 
chloroform solution was washed with water two times. 
The solution obtained after washing with water was evaporated to remove the 
low boiling fraction, with a rotary evaporator at a temperature of 
100.degree. C. and vacuum of 10 mmHg for two hours, whereby 0.11 g of a 
white colored solid was obtained in the flask. 
It was confirmed that 70 % of the solid was epoxidized by infra-red 
absorption spectrum analysis in which 70% of the absorption peak at 1633 
cm.sup.-1 by vinyl group was lower and an absorption peak at 1232 
cm.sup.-1 by epoxy group was observed. In addition, it was confirmed that 
70% of the vinyl group at .delta.(ppm) 5.8 to 6.0 was decreased, by H--NMR 
spectrum analysis. 
EPOXIDATION EXAMPLE-2 
Epoxidation of the Obtained Poly(5-Vinyl-2-Norbornene) 
First, 0.1272 g of the poly(5-vinyl-2-norbornene) was charged into a flask 
having a capacity of 10 ml, and 3.0 g of chloroform was then added and 
agitated to dissolve while maintained at 20.degree. C. for 30 minutes. 
Then 0.33 g of ethyl acetate solution containing 30% of peracetic acid was 
added at once to the chloroform solution, followed by being reacted at 
temperature of 50.degree. C. for 8 hours. 
After the reaction, 3.0 g of pure water was put into the crude reacted 
solution, followed by agitating at a temperature of 30.degree. C. for 10 
minutes and maintaining same at the temperature of 30.degree. C. for 20 
minutes to form an interface between two phases. 
The two phases were composed of an upper water solution and a lower 
chloroform solution. 
The upper water solution was removed by an injection, and the lower 
chloroform solution was additionally washed with water two times. 
The solution obtained after washing with water was evaporated to remove the 
low boiling fraction with a rotary evaporator at temperature of 
100.degree. C. and vacuum of 10 mmHg for 2 hours, whereby 0.1200 g of a 
white colored solid was obtained in the flask. 
It was confirmed that 80% of the solid was epoxidized by infra-red 
absorption spectrum analysis in which 80% of the absorption peak at 1633 
cm.sup.-1 group was lowered, and an absorption peak at 1232 cm.sup.-1 by 
epoxy group was observed. 
In addition, it was confirmed that 80% of the vinyl group at 6(ppm) 5.8 to 
6.0 was decreased by .sup.1 H--NMR spectrum analysis. 
EPOXIDATION EXAMPLE-3 
Epoxidation of the obtained poly(5-vinyl-2-norbornene) 
First, 0.1120 g of the poly(5-vinyl-2-norbornene) was charged into a flask 
having a capacity of 10 ml, and 3.0 g of chloroform was then added and 
agitated to dissolve while maintained at 20.degree. C. for 30 minutes. 
Then 0.48 g of ethyl acetate solution containing 30% of peracetic acid was 
added at once to the chloroform solution, followed by being reacted at 
temperature of 50.degree. C. for 16 hours. 
After the reaction, 3.0 g of pure water was put into the crude reacted 
solution, followed by agitating at a temperature of 30.degree. C. for 10 
minutes and maintaining same at the temperature of 30.degree. C. for 20 
minutes to form an interface between two phases. 
The two phases were composed of an upper water solution and a lower 
chloroform solution. 
The upper water solution was removed by an injection, and the lower 
chloroform solution was additionally washed with water two times. 
The solution obtained after washing with water was evaporated to remove the 
low boiling fraction with a rotary evaporator at temperature of 
100.degree. C. and vacuum of 10 mmHg for 2 hours, whereby 0.110 g of a 
white colored solid was obtained in the flask. 
It was confirmed that 90% of the solid was epoxidized by infra-red 
absorption spectrum analysis in which 100% of the absorption peak at 1633 
cm.sup.-1 by vinyl group was lowered, and an absorption peak at 1232 
cm.sup.-1 by epoxy group was observed. 
In addition, it was confirmed that 100% of the vinyl group at .delta.(ppm) 
5.8 to 6.0 disappeared by .sup.1 H--NMR spectrum analysis. 
POLYMERIZATION EXAMPLE-4 
Polymerization of 5-ethylidene-2-norbornene 
The same procedures as described in Polymerization Example-1 were repeated, 
except that 5 ml of 5-vinyl-2-norbornene was replaced with 5 ml of 
5-ethylidene-2-norbornene, and 1.41 g of poly(5-ethylidene-2-norbornene) 
was obtained. 
From .sup.1 H--NMR spectrum analysis, it was confirmed that the reaction 
proceeded only by an addition polymerization of the inner double bond of 
5-vinyl-2-norbornene. 
The molecular weight Mn and the molecular weight distribution Mw/Mn were 
1066 and 1.26, respectively, by gel permeation chromatography analysis. 
EPOXIDATION EXAMPLE-4 
Epoxidation of the obtained poly(5-ethylidene-2-norbornene) 
The same procedures as described in Epoxidation Example-1 were repeated, 
except that 0.1 g of poly(5-vinyl-2-norbornene) was replaced with 0.10 g 
of poly(5-ethylidene-2-norbornene) and 0.26 g of ethyl acetate solution 
containing 30% of peracetic acid was replaced with 0.45g, whereby 0.11 g 
of white colored solid was obtained in the flask. 
It was confirmed that 100% of the solid was epoxidized by infra-red 
absorption spectrum analysis in which 100% of an absorption peak at 1620 
cm.sup.-1 cm by vinyl group was decreased, and an absorption peak at 1230 
cm.sup.-1 by epoxy group was observed. 
In addition, it was confirmed that 100% of vinyl group at .delta.(ppm) 5.8 
to 6.0 disappeared by .sup.1 H--NMR spectrum analysis. 
POLYMERIZATION EXAMPLE-5 
Polymerization of dicyclopentadiene 
The same procedures as described in Polymerization Example-1 were repeated, 
except that 5 ml of -vinyl-2-norbornene was replaced with 5 ml of 
cyclopentadienee, and 1.50 g of poly(cyclopentadiene) was obtained. 
From .sup.1 H--NMR spectrum analysis, it was confirmed that the reaction 
proceeded only by an addition polymerization of the inner double bond of 
dicyclopentadiene. 
The molecular weight Mn and the molecular weight distribution Mw/Mn were 
572 and 1.19, respectively, by gel permeation chromatography analysis. 
EPOXIDATION EXAMPLE 5 
Epoxidation of the poly(cyclopentadiene) obtained in Polymerization 
Example-5 
The same procedures as described in Epoxidation Example-1 were repeated, 
except that 0.10 g of poly(5-vinyl-2-norbornene) was replaced with 0.10 g 
of poly(cyclopentadiene) and 3 g of pure water was put into the crude 
reacted solution after reaction, whereby 0.12 g of white colored solid was 
obtained. 
It was confirmed that 100% of the solid was epoxidized by infra-red 
absorption spectrum analysis in which an absorption peak at 1625 cm.sup.-1 
by vinyl group was decreased to 0% and an absorption peak at 1235 
cm.sup.-1 by epoxy group was observed. 
In addition, it was confirmed that 100% of vinyl group at .delta.(ppm) 5.8 
to 6.0 disappeared, by .sup.1 H--NMR spectrum analysis. 
EPOXIDATION EXAMPLE-6 
Epoxidation of poly(5-vinyl-2-norbornene) 
First, 55.67 g of the poly(5-vinyl-2-norbornene) and 504.29 g of chloroform 
were charged into a flask, 235.07 g of ethyl acetate solution containing 
30% of peracetic acid was added to the chloroform solution for 2 hours, 
followed by being reacted while maintained at a temperature of 50.degree. 
C, and being additionally aged for 1 hour after the reaction. 
Then, 200 g of chloroform and 200 g of water were put into the crude 
reacted solution, followed by agitating for 20 minutes and then 
maintaining at the temperature of 50.degree. C. for 20 minutes to form an 
interface between two phases. 
The two phases were composed of an upper water solution and a lower 
chloroform solution. 
The water solution was removed and 200 g of water was added into the 
chloroform solution for washing followed by removing the water solution. 
The washing with 200 g of water was repeated two times. 
The solution obtained after washing with water was evaporated to remove the 
low boiling fraction with a rotary evaporator at a temperature of 
100.degree. C. and vacuum of 100 to 120 mmHg for 1 hour, followed by being 
additionally evaporated with a vacuum pump at the same temperature for two 
hours, whereby 52.45 g of a white colored solid was obtained. 
It was confirmed that 70% of the solid was epoxidized by infra-red 
absorption spectrum analysis in which an absorption peak at 1625 cm.sup.-1 
by vinyl group disappeared and an absorption peak at 1235 cm.sup.-1 by 
epoxy group was observed. 
In addition, it was confirmed that vinyl group at 67 (ppm) 5.8 to 6.0 
disappeared, by .sup.1 H--NMR spectrum analysis. 
While the invention has been described in detail and with reference to 
specific embodiments thereof, it will be apparent to one skilled in the 
art that various changes and modifications can be made therein without 
departing from the spirit and scope thereof.