Cured resin products

A novel class of cured products is derived from unsaturated polycylic ethers or esters comprising unsaturated ether or ester derivatives of a hydroxyaryl-substituted 1,6-diaza [4.4] spirodilactum having a hydroxyaryl substitute attached to each spiro ring nitrogen atom.

FIELD OF THE INVENTION 
This invention relates to a novel class of unsaturated ether or ester 
derivatives of spirodilactams having hydroxyaryl substituents on the spiro 
ring nitrogen atoms. More particularly, the invention relates to certain 
cured products derived from unsaturated ether or ester derivatives of a 
1,6-diaza [4.4] spirodilactam having hydroxyaryl substituents in the 1- 
and 6- positions. 
BACKGROUND OF THE INVENTION 
Unsaturated ether or ester derivatives of polyhydric phenols are well known 
as a class of compounds that can be cured or crosslinked to produce 
insoluble products which exhibit good solvent resistance and mechanical 
properties as well as high heat distortion temperatures. Such unsaturated 
ethers are crosslinked by reaction with catalytic or stoichiometric curing 
agents, i.e., polyfunctional curing agents, to produce tough, heat 
resistant products which are processed by conventional methods into 
sheets, laminates with fiber glass or other reinforcements, or shaped 
articles and the crosslinked products are also useful in adhesive 
formulations. Certain of the unsaturated ethers cure into such products 
merely upon the application of heat without the necessity of a curing 
agent. Such materials are termed self-curing. 
As indicated, much of the technology is broadly conventional. The 
disclosure of Zahir et al, U.S. Pat. No. 4,100,140, is illustrative. The 
compound 2,2-bis(4-hydroxyphenl)propane, also known as bisphenol A or BPA, 
is converted to the sodium salt and reacted with allyl chloride to produce 
the allyl ether of BPA, i.e., 2,2-bis(4-allyloxyphenyl)propane. The 
diallyl ether is converted to the diallyl-substituted BPA which is cured, 
but the diallyl ether is also curable without rearrangement. Curing takes 
place, for example, by reacting the diallyl ether with an imide-containing 
curing agent. 
Other types of unsaturated derivatives of polyhydric phenols which are 
cured by such conventional techniques include unsaturated ester 
derivatives such as the acrylate and methacrylate esters of polyhydric 
phenols described by Zahir et al, U.S. Pat. No. 4,468,524. 
On some occasions, the cured products which provide the more desirable 
properties, particularly in high temperature applications, are produced 
from unsaturated derivatives of aromatic phenolic compounds wherein some 
or all of the rings share common atoms with other rings of a polycyclic 
structure. It would be of advantage to provide a novel class of 
unsaturated derivatives of phenolic compounds having a plurality of rings 
within the molecular structure. Such unsaturated derivatives cure, with or 
without added curing agents, upon application of heat. 
SUMMARY OF THE INVENTION 
The present invention relates to a novel class of cured products produced 
from unsaturated derivatives of hydroxyaryl-substituted [4.4] 
spirodilactam compounds. More particularly, the invention relates to cured 
derivatives of unsaturated ether and ester derivatives of a 
1,6-diazaspiro[4.4]nonane-2,7-dione compound having hydroxyaryl 
substituents on the ring nitrogen atoms of the spirodilactam ring system. 
DESCRIPTION OF THE INVENTION 
The novel cured products of the invention are produced from unsaturated 
ether or ester derivatives of hydroxyaryl-substituted 
1,6-diazaspiro[4.4]nonane-2,7-dione having the hydroxyaryl substituents on 
the spiro ring nitrogen atoms and optionally having acyclic or cyclic 
substituents in the 3-, 4-, 8- and 9- positions of the spiro ring system. 
One class of such spirodilactams is represented by the formula 
##STR1## 
wherein Z independently is 
##STR2## 
in which Z' independently is hydrogen, lower alkyl of up to 4 carbon 
atoms, preferably methyl, halogen, preferably the lower halogens fluoro or 
chloro, or aryl, preferably phenyl, or Z is such that the two adjacent Z 
groups, taken together form a ring system Z'' of from 5 to 7 ring atoms, 
up to two of which are heteroatoms selected from nitrogen atoms, oxygen 
atoms or sulfur atoms with the remainder of the ring atoms being carbon 
atoms, there being up to 15 carbon atoms in each Z'', two of which connect 
the two carbon atoms connected by the adjacent Z groups. In the above 
formula I, R independently is aromatic of up to 15 carbon atoms and up to 
2 aromatic rings, inclusive, R' is R or an aliphatic group of up to 10 
carbon atoms inclusive. Each of R and R' is hydrocarbyl, i.e., contains 
only atoms of carbon and hydrogen, or is substituted-hydrocarbyl 
containing additional atoms in the form of inert substituents such as 
halogen, preferably the middle halogens chlorine or bromine. The term r in 
the above formula I independently is 0 or 1 and X is a direct valence 
bond, alkylene of up to 8 carbon atoms inclusive, oxy, thio, sulfonyl, 
carbonyl, dioxyphenylene, i.e. 
##STR3## 
2,2-di(oxyphenyl)propane, i.e., 
##STR4## 
dioxyphenyl sulfone, i.e., 
##STR5## 
or dioxyphenylene, i.e., 
##STR6## 
Spirodilactams of a considerable variety of structures are therefore 
suitably employed as a precursor of the unsaturated ether or ester 
derivatives of the invention. In the embodiment of the invention wherein 
the moieties of the above formula I are not part of a fused ring system 
and are therefor acyclic, i.e., Z is 
##STR7## 
the spirodilactam is illustrated by 
1,6-di(4-hydroxyphenyl)-1,6-diazaspiro[4.4]nonane-2,7-dione, 
1,6-di(3-hydroxy-4-chlorophenyl)-3,8-dimethyl-1,6-diazapiro[4.4]nonane-2,7 
-dione, 
1,6-di(3-hydroxyphenyl)-3,8-diphenyl-1,6-diazaspiro[4.4]nonane-2,7-dione, 
1,6-di[4-(4-hydroxybenzyl)phenyl]-1,6-diazaspiro[4.4]nonane-2,7-dione, 
1,6-di(4-hydroxypehnyl)-3,3,4,4,8,8,9,9-octamethyl-1,6-diazaspiro[4.4]nona 
ne-2,7-dione, 
1,6-di[4-(4'-hydroxybiphenyl)]-3,3-dimethyl-1,6-diazaspiro[4.4]nonane-2,7- 
dione, 1,6-di[2-(4-hydroxyphenyl)propyl]1,6-diazaspiro[4.4]nonane-2,7-dione 
and 
1,6-di[4-(4-hydroxyphenylisopropyl)-phenyl]-1,6-diazaspiro[4.4]nonane-2,7- 
dione. In the embodiment wherein adjacent Z moieties on each ring form a 
cyclic structure fused to the spiro ring system, illustrative 
spirodilactams include 
1,6-di(4-hydroxyphenyl)-3,4,8,9-dibenzo-1,6-diazaspiro[4.4]nonane-2,7-dion 
e, 
1,6-di[4-(4-hydroxyphenyl)phenyl]-3,4,-8,9-dipyrido-1,6-diazaspiro[4.4]non 
ane-2,7-dione and 
1,6-di[4-(4-hydroxyphenyloxy)phenyl]-3,4,8,9-di(cyclopentano)-1,6-diazaspi 
ro[4.4]nonane-2,7-dione. Also suitable are those spirodilactams wherein one 
spiro ring has a fused ring substituent and the other spiro ring is free 
of fused ring substituents, e.g., 
1,6-di(4-hydroxyphenyl)-3,4-benzo-8-methyl-1,6-diazaspiro[4.4]nonane-2,7-d 
ione and 
1,6-di[1-(4-hydroxynaphthyl)]3,4-cyclohexano-1,6-diazaspiro[4.4]nonane-2,7 
-dione. 
In general, compounds of the above formula I wherein R and R' are aromatic 
and hydrocarbyl are preferred, especially such compounds wherein each r is 
0. The class of 1,6-di(hydroxyphenyl) spirodilactams is particularly 
preferred. Within the spirodilactam portion of the molecule, spirodilactam 
rings which are substituted with hydrogen or methyl or fused with benzo 
rings are generally preferred, particularly the 
1,6-diazospiro[4.4]nonane-2,7-diones. 
The hydroxyaryl-substituted spirodilactams of the above formula I are 
compounds which are described and claimed as compositions of matter in 
U.S. Pat. No. 4,847,388. 
The general method for the production of these spirodilactams, also 
described in this copending application and copending U.S. patent 
application Ser. No. 172,000, filed Mar. 23, 1988, now abandoned, and Ser. 
No. 172,052, filed Mar. 23, 1988, now abandoned, each of which is 
incorporated herein by reference, is by reaction of at least one 
hydroxy-containing primary amino compound and a spirodilactam precursor. 
In terms of the spirodilactam of the above formula I, the 
hydroxy-containing primary amino compound is represented by the formula 
##STR8## 
wherein R, R', X and r have the previously stated meanings. The 
spirodilactam precursor is a 4-oxoheptanedioic acid compound or a 
1,6-dioxospiro[4.4]nonane-2,7-dione. In terms of the spirodilactam of the 
above formula I, the 4-oxoheptanedioic acid compound spirodilactam 
precursors are represented by the formula 
##STR9## 
wherein Z has the previously stated meaning and A is hydroxy, lower alkoxy 
or halo, preferably middle halo. The spirodilactone spirodilactam 
precursor, in terms of the spirodilactams of formula I, is represented by 
the formula 
##STR10## 
wherein Z has the previously stated meaning. 
Many of the acyclic 4-oxoheptanedioic acid compounds are known, but certain 
of the esters are also produced by the reaction of formaldehyde and 
unsaturated carboxylic acid esters by the process disclosed and claimed in 
U.S. Pat. No. 4,800,231. Interconversion of the acids, esters or acid 
halides of formula IIIa is by conventional methods. The production of 
4-oxoheptanedioic acid compounds of formula IIIa which contain cyclic 
moieties is by the process of Cava et al, J. Am. Chem. Soc., 20,6022 
(1955). The spirodilactones of formula IIIb are produced by the process of 
Pariza et al, Synthetic Communications, Vol. 13(3), pp. 243-254 (1983), or 
if the spirodilactones have additional fused rings by the process of U.S. 
Pat. No. 1,999,181. 
The hydroxy-containing primary amino compound and the spirodilactam 
precursor react in a molar ratio of 2:1 although in practice reactant 
ratios from about 8:1 to about 1:1.5 are satisfactory. Reactant ratios of 
hydroxy-containing primary amino compound to spirodilactam precursor which 
are substantially stoichiometric are preferred. Reaction is conducted in a 
liquid phase solution in an inert reaction diluent such as an 
N-alkylamide, e.g., N,N-dimethylformamide, N,N-dimethylacetamide or 
N-methyl-2-pyrrolidone. Reaction takes place under reaction conditions at 
an elevated temperature, typically from about 80.degree. C. to about 
250.degree. C., and at a reaction pressure sufficient to maintain the 
reaction mixture in a liquid phase, e.g., pressures up to about 20 
atmospheres. Subsequent to reaction the spirodilactam product (of formula 
I) is recovered from the product mixture by conventional methods such as 
solvent removal, precipitation and chromatographic separation. Recovery of 
the spirodilactam product is not required, however, and particularly in 
cases where substantially stoichiometric quantities of reactants were 
employed the spirodilactam may be reacted further in situ to form 
derivatives such as the unsaturated ether or ester derivatives of the 
hydroxyaryl-substituted spirodilactams of the invention. 
The unsaturated derivatives of the hydroxylaryl-substituted spirodilactams 
are ether or ester derivatives of the hydroxyaryl substituents derivatized 
at the hydroxyl group through ether or ester formation. The unsaturated 
moiety which becomes bound to the oxygen of the oxyaryl moiety (derived by 
loss of hydrogen from the hydroxyaryl moiety) is a group of up to 10 
carbon atoms inclusive which contains carbon-carbon unsaturation located 
at least adjacent to the carbon atom of the unsaturated moiety which is 
bound to an oxyaryl residue of the hydroxyaryl substituents of the 
hydroxyaryl-substituted spirodilactam. Although unsaturated moieties of a 
number of types are useful in the ether or ester derivatives of the 
invention, the preferred unsaturated ether or ester moieties are selected 
from 2-alkenyl, 2-alkynyl, vinylarylmethyl and 2-alkenoyl. Illustrative 
alkenyl groups include allyl, methallyl and crotyl while alkynyl groups 
include propargyl and 2-octynyl. Vinylarylmethyl groups are exemplified by 
4-styrylmethyl and 4-vinyl-2-methylbenzyl. The alkenoyl groups present 
when ester derivatives are desired include acrylyl, methacrylyl, 
2,4-hexadienoyl and 2-hexenoyl. Preferred unsaturated moieties are allyl, 
propargyl and 4-vinylbenzyl in the case of ether derivatives and acrylyl 
and methacrylyl when ester derivatives are contemplated. 
These preferred derivatives of the hydroxyaryl-substituted spirodilactams 
are represented by the formula 
##STR11## 
wherein R, R', X, r and Z have the previously stated meanings and E 
independently is an unsaturated moiety of up to 10 carbon atoms inclusive 
containing carbon-carbon unsaturation at least adjacent to the carbon atom 
of E through which E is bound to the oxyaryl moiety. E is preferably 
allyl, propargyl, 4-styrylmethyl, acrylyl or methacrylyl. 
These derivatives are typically produced by reacting a compound containing 
the desired ether or ester moiety with an alkali metal salt of the 
hydroxyaryl-substituted spirodilactam. Although lithium, sodium, 
potassium, rubidium and cesium salts of the hydroxyaryl-substituted 
spirodilactams are usefully employed in the production of the unsaturated 
ether derivatives of the invention, the use of a sodium salt or a 
potassium salt is preferred. In one modification, the alkali metal salt of 
the hydroxyaryl-substituted spirodilactam is produced by contacting the 
spirodilactam with a substantially stoichiometric quantity of alkali metal 
hydroxide, i.e., substantially 2 moles of alkali metal hydroxide for each 
mole of the spirodilactam. Sodium or potassium hydroxide is preferred. 
Reaction is conducted in the liquid phase in a suitable reaction solvent 
such as N,N-dimethylacetamide or N,N-dimethylformamide while removing the 
water present or formed by distillation, preferably azeotropic 
distillation employing a second solvent such as toluene or ethylbenzene 
with which water forms an azeotrope. The use of an alkali metal hydroxide 
is not specifically required and employment of an equivalent amount of 
alkali metal carbonate or bicarbonate is satisfactory. The alkali metal 
salt of the hydroxyaryl-substituted spirodilactam is isolated if desired 
by conventional procedures such as solvent removal but the salt is 
typically used in situ in the media of its production for reaction with 
the compound containing the unsaturated ether moiety. 
The unsaturated moiety, E, is provided to the reaction with the alkali 
metal salt of the hydroxyaryl-substituted spirodilactam in the form of a 
halide or an alkoxide. The compound employed as the reactant which 
contains the unsaturated ether moiety is therefore represented by the 
formula 
EQU E-G (V) 
wherein E is the unsaturated ether or ester moiety as above defined and G 
is halo, preferably middle halogen chlorine or bromine, or lower alkoxy of 
up to 4 carbon atoms. When an ether derivative of the 
hydroxyaryl-substituted spirodilactam is desired the E moiety is 
preferably allyl, propargyl or 4-styrylmethyl and is generally provided as 
the halide. Allyl chloride, allyl bromide, propargyl bromide and 
p-vinylbenzyl chloride are illustrative. When an ester derivative of the 
hydroxyaryl-substituted spirodilactam is desired, the preferred acrylyl or 
methacrylyl moiety is typically provided as the alkoxide, i.e., as the 
acrylic or methacrylic ester, or as the halide, i.e., the acid halide. 
Methyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylyl 
chloride or acrylyl bromide are illustrative of suitable sources of the 
unsaturated moiety for unsaturated ester derivatives. 
The reaction of the alkali metal salt of the hydroxyaryl-substituted 
spriodilactam and the E-G compound is conducted in liquid phase solution 
in the presence of a reaction diluent. Preferred diluents are polar 
diluents in which the compounds undergoing are soluble, at least at 
reaction conditions. Suitable reaction diluents include N-alkylamides such 
as N,N-dimethylacetamide, N,N-dimethylformamide and 
N-methyl-2-pyrrolidone, phenols such as phenol and m-cresol and sulfur 
containing diluents such as sulfolane and dimethylsulfoxide. The compound 
which provides the unsaturated ether or ester moiety, i.e., the compound 
E-G, is utilized in a molar amount equal to or in excess over the alkali 
metal salt. Molar ratios from about 5:1 to about 1:1 are suitable. The 
stoichiometry of the reaction would suggest reaction of the E-G compound 
and the alkali metal salt in a 2:1 ratio. Molar ratios of from about 3:1 
to about 1.5:1 are preferred. 
Reaction is effected by charging the unsaturated moiety compound, the 
alkali metal salt of the hydroxyaryl-substituted spirodilactam and the 
reaction diluent to a suitable reactor and maintaining the reaction 
mixture under reaction conditions. Alternatively, the alkali metal salt is 
employed as produced in the media of its production and the E-G compound 
is added to the solution of the alkali metal salt if produced in a 
suitable reaction diluent. 
Reaction to produce the unsaturated ether or ester derivatives of the 
hydroxyaryl-substituted spirodilactam is conducted over a range of 
reaction conditions, typically including a reaction temperature of from 
about -30.degree. C. to about 200.degree. C., preferably from about 
-10.degree. C. to about 175.degree. C. The higher portion of the 
temperature range is preferred for ether production while esters are more 
often formed in the lower portion of the temperature range. A suitable 
reaction pressure is one which will maintain the reaction mixture in the 
liquid phase. Such pressures are typically up to about 20 atmospheres but 
more often are from about 0.8 atmosphere to about 5 atmospheres. Reactant 
contact is maintained during reaction by conventional methods such as 
shaking or stirring and subsequent to reaction the desired ether or ester 
product is recovered by typical methods such as selective extraction, 
solvent removal or precipitation followed by filtration or decantation. 
The ether and ester derivatives of the hydroxy-substituted spirodilactams 
find utility as thermosetting resins which are employed in the production 
of the cured or crosslinked products of the invention. These products are 
useful as surface coatings, in adhesive formulations and in 
fiber-reinforced composites wherein, for example, the fiber is glass or 
carbon. The cured products are also useful in the production of hollow 
objects as by filament winding and are employed as impregnating and 
casting resins. The processing of the cured products for these 
applications is by conventional methods. 
The curing of the unsaturated ethers or esters is accomplished by 
conventional methods such as thermal curing, e.g., heating to a 
temperature above about 200.degree. C., by photochemical excitation, e.g., 
as by exposure to high energy radiation, by catalyzed polymerization 
employing cationic or anionic catalysts or by reaction with a 
polyfunctional curing agent. Anionic polymerization uses alkali metal 
alkoxides, hydroxides or amides as the catalyst typical cationic 
polymerization catalysts are organic or inorganic acids or are Lewis 
acids. Such cationic catalysts include sulfuric acid, phosphonic acid, 
p-toluenesulfonic acid, boron trifluoride and tin tetrachloride. Catalytic 
catalysts are generally employed in a quantity of from about 0.05% by 
weight to about 5% by weight, based on total composition. In an alternate 
modification, the unsaturated ether or ester derivatives are cured by 
heating with a substantial amount, e.g., from about 20% by weight to about 
50% by weight, based on total composition, of a polyfunctional curing 
agent. 
In the present invention the preferred cured products are obtained by 
reacting the unsaturated ether or ester derivatives with a polyfunctional 
curing agent. Such curing agents are organic compounds having at least two 
substituents with multiple bonds between adjacent atoms. Such substituents 
are hydrocarbyl with multiple bonds between adjacent carbon atoms or are 
non-hydrocarbyl with multiple bonds between atoms at least one of which is 
not a carbon atom. Preferred polyfunctional curing agents have up to 30 
carbon atoms inclusive and contain frunctional groups selected from 
alkenyl, alkynyl, styrylmethyl, cyanato or maleimido. Particularly 
preferred are the maleimido-substituted polyfunctional curing agents, 
especially di(4-maleimidophenyl)methane. This class of curing agents is 
described in greater detail by Zahir et al, U.S. Pat. No. 4,100,140. The 
other classes of polyfunctional curing agents are also well known in the 
art, and include such preferred curing agents as triallyl isocyanurate, 
di(4-cyanatophenyl)methane and 2,2-di(4-cyanatophenyl)propane.

The invention is further illustrated by the following Illustrative 
Embodiments which should not be construed as limiting the invention. 
ILLUSTRATIVE EMBODIMENT I 
To a three liter three-necked flask was added a mixture of 202.8 g (0.6 
mole) of 1,6-di(4-hydroxyphenyl)-1,6-diazaspiro[4.4]nonane-2,7-dione, 
91.22 g (0.6 mole) of potassium carbonate, 200 ml of toluene and 1 liter 
of N,N-dimethylacetamide. The mixture was heated to 
150.degree.-160.degree. C. and water removed by azeotropic distillation. 
When the water removal was complete, the temperature was lowered to 
80.degree.-90.degree. C. and 200.2 g (1.66 mole) of allyl bromide in 200 
ml of N,N-dimethylacetamide was added over the next 80 minutes. The 
reaction temperature was then raised for 12 hours and then the resulting 
mixture was cooled and filtered. The filtrate was concentrated and then 
poured slowly into a mixture of heaxane and ether. The precipitated 
product was recovered by filtration and dried in a vacuum oven at 
80.degree. C. The product had a melting point of 152.degree.-155.degree. 
C. and the nuclear magnetic resonance spectra were consistent with the 
formula 1,6-di(4-allyloxyphenyl)-1,6-diazaspiro[4.4]nonane-2,7-dione. 
ILLUSTRATIVE EMBODIMENT II 
The product of Illustrative Embodiment I was mixed with an equal portion by 
weight of bismaleimide, i.e., di(4-maleimidophenyl)methane. The resulting 
mixture was heated at 170.degree. C. for 2 hours, at 210.degree. C. for 2 
hours and finally at 250.degree. C. for 6 hours. The resulting cured 
product was insoluble in common solvents and had a glass transition 
temperature of 312.degree. C. 
ILLUSTRATIVE EMBODIMENT III 
To a three liter three-necked flask was added a mixture of 135.2 g (0.4 
mole) of 1,6-di(4-hydroxyphenyl)-1,6-diazaspiro[4.4]nonane-2,7-dione, 58.0 
g (0.42 mole) of potassium carbonate, 500 ml of N,N-dimethylformamide and 
200 ml of toluene. The mixture was heated to 150.degree.-160.degree. C. 
and the water was removed by azeotropic distillation. When the water 
removal was complete, the temperature was lowered to 80.degree.-90.degree. 
C. and 95.2 g (0.8 mole) of propargyl bromide in 100 ml of 
N,N-dimethylformamide was added over a 2.5 hour period. The reaction 
temperature was then raised to 100.degree. C. and maintained at that 
temperature for 12 hours. The resulting solution was then cooled, filtered 
and reduced in volume upon a rotary evaporator. The concentrated solution 
was poured slowly into water to give a precipitated product which was 
recovered by filtration and dried in a vacuum oven at 80.degree. C. The 
product had a melting point of 210.degree. -216.degree. C. and the nuclear 
magnetic resonance spectra were consistent with the structure 
1,6-di(4-propargyloxyphenyl)-1,6-diazaspiro[4.4]nonane-2,7-dione. 
This product was cured by heating for 12 hours at 210.degree. C. The cured 
product had a glass transition temperature of 305.degree. C. 
ILLUSTRATIVE EMBODIMENT IV 
To a two liter, 3-necked round-bottomed flask was added 135.2 g (0.4 mole) 
of 1,6-di(4-hydroxyphenyl)-1,6-diazaspiro[4.4]nonane-2,7-dione, 58.0 g 
(0.42 mole) of potassium carbonate, 200 ml of toluene and 250 ml of 
N,N-dimethylacetamide. The flask and contents were heated to 
150.degree.-160.degree. C. and the water present or formed was removed by 
azeotropic distillation. When the water removal was complete, the 
temperature of the resulting mixture was lowered to 80.degree.-90.degree. 
C. and 152.6 g (0.84 mole) of vinylbenzyl chloride in 50 ml of 
N,N-dimethylacetamide were added over the next 30 minutes and the 
temperature was maintained for 12 hours. The resulting midxture was then 
cooled, filtered and poured into 3 liters of water. The insoluble porduct 
was removed by filtration, washed with water and dried. The product had a 
melting point of 153.degree.-154.degree. C. and the nuclear magnetic 
resonance spectra of the product were consistent with the structure 
1,6-[4-(4-vinylbenzyl)oxyphenyl]-1,6-diazaspiro[4.4]nonane-2,7-dione. 
ILLUSTRATIVE EMBODIMENT V 
The vinylbenzyl ether of Illustrative Embodiment IV was heated at 
200.degree. C. and then at 220.degree. C. for an additional 4 hours. The 
resulting cured product had a glass transition temperature of 273.degree. 
C. 
ILLUSTRATIVE EMBODIMENT VI 
An equal mixture by weight of the vinylbenzyl ether of Illustrative 
Embodiment IV and di(4-maleimidophenyl)methane was melted at 
150.degree.-160.degree. C. and then heated in an oven in a first stage to 
200.degree. C. for 2 hours and in a second stage at 220.degree. C. for an 
additinoal 4 hours. The resulting cured product had a glass transition 
temperature in excess of 300.degree. C. 
ILLUSTRATIVE EMBODIMENT VII 
An equal mixture by weight of the vinylbenzyl ether of Illustrative 
Embodiment IV and di(4-cyanatophenyl)methane was melted at 
100.degree.-120.degree. C. The resulting mixture was heated in an oven in 
a first stage at 200.degree. C. for 2 hours and in a second stage at 
220.degree. C. for an additional 4 hours. The resulting cured product had 
a glass transition temperature of 229.degree. C. 
ILLUSTRATIVE EMBODIMENT VIII 
A mixture of 50 parts by weight of the vinylbenzyl ether of Illustrative 
Embodiment IV, 45 parts by weight of di(4-cyanatophenyl)-methane and 5 
parts by weight of di(4-maleimidophenyl)methane was melted at 
100.degree.-120.degree. C. The resulting mixture was then heated in an 
oven in a first stage at 200.degree. C. for 2 hours and at 220.degree. C. 
for an additional 4 hours. The resulting cured product had a glass 
transition temperature of 226.degree. C. 
ILLUSTRATIVE EMBODIMENT IX 
An equal mixture by weight of the vinylbenzyl ether of Illustrative 
Embodiment IV and triallylisocyanurate was melted at 
100.degree.-120.degree. C. The resulting mixture was heated in an oven in 
a first stage at 200.degree. C. for 2 hours and then in a second stage at 
220.degree. C. for an additional 4 hours. The resulting cured product had 
a glass transition temperature of 205.degree. C.