Method of forming high-temperature resistant polymers

A method of forming high-temperature resistant polymers by a 2 step curing process comprising PA1 (a) curing a polymerizable composition at least one aromatic compound having alpha and/or beta instruction which is not substantially reactive under the curing condition of step a, particularly allyl or properyl, and PA1 (b) heating the cured composition of step a in the presence of acid to form a crosslinked resin.

CROSS REFERENCE TO RELATED APPLICATIONS 
This Application is related to application Ser. No. 07/625,725 filed on 
even date herewith now U.S. Pat. No. 5,084,490 entitled "Styryloxy 
Compounds and Polymers thereof" (McArdle, et al) the contents of which are 
incorporated herein by reference. 
BACKGROUND OF THE INVENTION 
This invention relates to a method of forming high-temperature resistance 
polymers by a 2-stage curing process, particularly for use in the field of 
adhesives, sealants, thread-locking compositions, gaskets and the like. 
U.S. Pat. No. 4,543,397 Woods et al, describes polyfunctional cationically 
polymerizable styryloxy compounds of the formula I or II 
##STR1## 
where R.sup.1 and R.sup.2 are H, or one of R.sup.1 and R.sup.2 is H and 
the other is methyl; R.sup.3 and R.sup.4 are H, lower alkyl or alkoxy if 
R.sup.2 is not methyl; R.sup.5 is a divalent hydrocarbon radical; G is a 
multivalent organic or inorganic radical free of amine, aliphatic 
hydroxyl, aliphatic thiol or other groups which interfere with cationic 
polymerisation; and n is an integer of two or more. 
The polyfunctional telechelic styryloxy monomers of the kind described in 
U.S. Pat. No. 4,543397 are generally of high molecular weight. Even so, 
example 10 of that Patent describes the preparation of 4-allyloxystyrene 
of the formula III 
##STR2## 
This compound is cationically active but it forms linear polymers which are 
purple/blue in colour and only 10% insoluble in organic solvents i.e. 
little if any crosslinking has occurred. That which may occur likely 
results from radical initiation of the allyl group since radicals may also 
be produced from the photocationic initiator. 
Our U.S. patent application Ser. No. 07/625,725 now U.S. Pat. No. 5,084,490 
entitled "Styryloxy Compounds and Polymers Thereof" of even date herewith 
describes styryloxy compounds of the formula IV 
##STR3## 
wherein R.sup.1 and R.sup.2 are H, or one of R.sup.1 and R.sup.2 is H and 
the other is methyl; R.sup.7 and R.sup.8 (which may be the same or 
different) are H, C.sub.1 -C.sub.5 alkyl or C.sub.1 -C.sub.5 alkenyl; or 
one of R.sup.7 and R.sup.8 may be --OR.sup.6 or C.sub.1 -C.sub.5 alkoxy or 
C.sub.1 -C.sub.5 alkenyloxy if R.sup.2 is not methyl; and R.sup.6 is 
selected from the group consisting of: 
##STR4## 
where R.sup.10 is C.sub.1 -C.sub.5 alkyl; and R.sup.11, R.sup.12 and 
R.sup.13, which may be the same or different, are H or C.sub.1 -C.sub.5 
alkyl. 
The most preferred compounds are of the formula V 
##STR5## 
wherein R.sup.9 is selected from the group consisting of: 
##STR6## 
The compounds of said Patent Application are monofunctional with respect to 
the styryl group but are difunctional because of the other cationically 
active substituent --OR.sup.6 or --OR.sup.9. They are compatible with 
photoinitiators and can be photocured to give highly transparent polymeric 
films with good mechanical properties after short irradiation times e.g. 
10 seconds or less. The Patent Application also describes mixed styryloxy 
compositions comprising a compound of the formula IV and allyloxystyrene. 
SUMMARY OF THE INVENTION 
The present invention provides a method of forming high-temperature 
resistant polymers which comprises a 2-stage curing process comprising: 
(a) curing a polymerisable composition (A) containing at least one compound 
of the formula VI: 
##STR7## 
wherein is a single or multiple aromatic ring structure, each R.sup.1, 
which may be the same or different, is H or alkenyl, which may optionally 
substituted; 
each R.sup.b, which may be the same or different, is alkenyl, which may 
optionally be substituted; 
each R.sup.c, which may be the same or different, is a polymerisable or 
non-polymerisable group which does not interfere with the polymerisation 
of the composition; 
n=1; 
m=0-3; 
(m+n).ltoreq.6; and 
0.ltoreq.s.ltoreq.r-(m+n) where r is the total number of substitutable 
positions on the ring structure: 
provided that 
(I) when the polymerisable composition A comprises a compound of formula VI 
and a matrix monomer, said matrix monomer being curable or polymerisable 
under the curing conditions of step (a), then (i) at least two of the 
moieties R.sup.a and/or R.sup.b must have unsaturation at the alpha or 
beta carbon atom or (ii) at least one of the moieties R.sup.a, R.sup.b, or 
R.sup.c is polymerisable or curable under the curing conditions of step 
(a) and at least one other of R.sup.a or R.sup.b has unsaturation at the 
alpha or beta carbon atoms: and 
(II) when the polymerisable composition A comprises a mixture of compounds 
of formula VI then (i) at least one of said compounds has at least one 
moiety R.sup.a, R.sup.b or R.sup.c which is polymerisable or curable under 
the curing conditions of step (a) and least one moiety R.sup.a or R.sup.b 
which has unsaturation at the alpha or beta carbon atom and (ii) the other 
compound has the same requirements as I (i) or II (i) above; and 
(III) when the polymerisable composition A contains as the only 
polymerisable component, a compound of formula VI, then said compound has 
at least one moiety R.sup.1, R.sup.b and/or R.sup.c which is polymerisable 
or curable under the curing conditions of step (a) and at least one moiety 
R.sup.a or R.sup.b which has unsaturation at the alpha beta carbon atom; 
and provided that the curing conditions for step (a) are not such as would 
cause the substantial polymerisation of the moieties R.sup.a and R.sup.b 
having or alpha or beta unsaturation, and 
provided that when m=0 or when the required number of moieties R.sup.a and 
R.sup.b having alpha or beta unsaturation is greater than the number of 
R.sup.b moieties having said alpha or beta unsaturation, then at least one 
substitutable position ortho to each --OR.sup.a (R.sup.a not equal to H) 
or the para position thereto, or in the case of a fused ring structure at 
least one position on the fused ring, is unsubstituted; 
the alpha carbon atom being that carbon atom nearest the oxygen atom (in 
the case of R.sup.a) or the ring (in the case of R.sup.b); 
and 
(b) subsequently heating the cured composition in the presence of acid to 
form a high temperature resistant crosslinked resin. 
The ring structure .circle. may suitably be selected from phenyl, fused 
aromatic ring structures and 
##STR8## 
wherein R.sup.d represents a covalent bond, a substituted or unsubstituted 
alkylene group, 
##STR9## 
Preferably the ring structure is phenyl or a bridged biphenyl ring 
structure as shown in formula VII, most preferably phenyl. 
Preferably R.sup.a and/or R.sup.b is straight or branched chain alkenyl 
moiety, optionally substituted with halo or interrupted with --O--or 
--S--. More particularly, R.sup.a and/or R.sup.b is alkenyl having 2-10 
carbon atoms, especially 3-5 carbon atoms. However, when R.sup.a is H, at 
least one of the positions ortho or para, preferably ortho, to --OR.sup.a 
is substituted with R.sup.b having alpha or beta unsaturation. 
More particularly, R.sup.a and/or R.sup.b is selected from the group 
consisting of 
##STR10## 
wherein R.sup.10, R.sup.11, R.sup.12 and R.sup.13, which may be the same 
or different, are H or C.sub.1 -C.sub.5 alkyl; provided that at least one 
of R.sup.11, R.sup.12 or R.sup.13 is other than H. 
R.sup.c may be a polymerisable moiety which is polymerisable or curable 
under the curing or polymerisation condition of step (a). Said moiety may 
be reactive with other or like moieties R.sup.c or with either or both of 
moieties R.sup.a and/or R.sup.b. With respect to the latter, such 
reactivity should only be to a minor extent under the curing conditions of 
step (a). Alternatively, said moieties R.sup.c may be co-reactive with any 
reactive moieties of the matrix monomer if present. 
Preferably R.sup.c is a polymerisable group selected from 
##STR11## 
wherein R.sup.1 and R.sup.2 are H, or one of R.sup.1 and R.sup.2 is H and 
the other is methyl; 
a vinyl ether group; 
an acrylic group; or 
an epoxy group. 
Alternatively R.sup.c may be a non-polymerisable group, such as a 
substituted or unsubstituted alkyl group, free of amino, aliphatic 
hydroxyl or aliphatic thiol substitution. 
In the preferred embodiment, the polymerisable composition contains at 
least one compound of the formula IV above. Especially preferred compounds 
are those of the formula VIII as follows: 
##STR12## 
wherein R.sup.1 and R.sup.2 are as defined above; R.sup.3 and R.sup.4 are 
H, lower alkyl or, if R.sup.2 is not methyl, alkoxy; provided that at 
least one of R.sup.3 or R.sup.4 is H, and R.sup.9 is selected from the 
group consisting of 
##STR13## 
A preferred class of compositions useful in the practice of the present 
invention is that wherein the first stage of the curing process is by 
photocuring, said compositions additionally containing a photoinitiator. 
The second stage is then carried out at elevated temperatures in the 
presence of acid generated by the photoinitiator. However, in accordance 
with the teachings and practice of the present invention, the first stage 
may alternatively be carried out by other curing processes e.g. heat, 
redox, anionic, atmospheric, e-beam, X-ray, gamma-ray. The acid necessary 
for effecting the second stage of the curing process may be generated or 
released thermally or photochemically or by other means. Alternatively, 
the acid may be initially present in the composition, optionally sealed in 
microcapsules which are subsequently ruptured for the second stage. 
The conditions of temperature and time for the heat treatment in the second 
stage of the curing process will be readily apparent to those skilled in 
the art and will not necessitate undue experimentation. Generally, typical 
conditions for the formation of heat-resistant crosslinked resins may be 
employed. Preferably, temperatures above about 125.degree. C., most 
preferably of about 140.degree.-150.degree. C., will be required. The time 
period for the heat treatment will also vary and will generally be at 
least about one half hour or more, preferably about one hour or more (for 
temperatures of about 150.degree. C.). It is also recognised that 
treatments at a lower temperature for a longer period of time or at a 
higher temperature for a shorter period of time may also suffice and such 
parameters are within the scope of the process of the present invention. 
Although the precise mechanism or mechanisms by which cross-linked resins 
are obtained in accordance with the process of the present invention is 
not known, it is believed that such resins form by way of a phenolic resin 
type crosslinking during the second stage of the curing process. This 
crosslinking is believed to take place, predominately, if not exclusively, 
through the alpha and/or beta unsaturation of the R.sup.a and R.sup.b 
moieties. Furthermore, where the required alpha or beta unsaturation is 
present in the R.sup.a moiety, then it is believed that a Claisen type 
rearrangement occurs whereby the oxygen-carbon bond in the --OR.sup.a 
moiety is broken and the R.sup.a radical rearranges to an ortho or para 
position, or a substitutable position on the other ring in the instance of 
fused ring structures, preferably the ortho position, and is replaced, on 
the oxygen, by H. This rearranged structure is then ammenable to the 
phenolic type crosslinking mechanism. Ultimately, then, the crosslink 
density of the final cured material will depend upon the extent to which 
compounds of formula VI are present in the polymerisable composition and 
on the number of moieties R.sup. a and R.sup.b which have alpha or beta 
unsaturation and, in the case of structures having the R.sup.a moiety, the 
extent to which the Claisen type rearrangement occurs. 
As mentioned above, when R.sup.a in the starting material of formula VI has 
alpha or beta unsaturation and a position ortho or para to --OR.sup.a is 
unsubstituted (i.e., H) then it is believed that a Claisen type 
rearrangement occurs. Such rearrangement may occur to a small extent 
during the first stage and to a greater extent during the second stage. 
The resultant structure is that of a substituted phenol preferably having 
the alkenyl group attached at a position ortho to the unprotected hydroxyl 
group. This mechanism is illustrated for a simple compound of formula VIII 
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are all H and R.sup.a is 
CH.sub.2 .dbd.CH--CH.sub.2 --in the following diagram: 
##STR14## 
It is believed that the structure on the right of diagram X is susceptible 
to electrophilic substitution at the 6-position on the ring (ortho to the 
--OH group) and can react by forming strong carbon-to-carbon crosslinking 
bonds of the phenolic resin type, particularly with the electrophilic 
allyl group on similar molecules. 
While a Claisen rearrangement of this kind is known to occur in the liquid 
state, the present inventors are not aware of such a rearrangement being 
obtained heretofore in the solid state. Furthermore, while applicants have 
set forth their belief as to the mechanism(s) involved in the process of 
the present invention, applicants do not desire nor should they be 
construed as being bound by the same. Rather, the foregoing discussion has 
been added to help in the understanding of what may be occurring. 
In accordance with the practice of the present invention, compounds of 
formula VI may be polymerised alone, in combination with other compounds 
of formula VI and/or in combination with other polymerisable monomers, 
e.g., matrix monomers. These variants of the present invention are 
discussed below. 
In instances wherein the polymerisable composition comprises only one 
compound of formula VI, it is preferred to use 4-propenyloxystyrene and 
other like compounds which have the crosslinking characteristics of a 
beta-vinyl ether, especially 4-propenyloxystyrene. Alternatively, the 
polymerisable composition may also comprise a mixture of styryloxy 
monomers of formula VI, especially those wherein at least one of the 
monomers is 4-propenyloxystyrene or a like compound having the 
crosslinking characteristics of a beta-vinyl ether. Exemplary of such a 
suitable mixture is 4-propenyloxystyrene and 4-allyloxystyrene. Generally, 
any ratio of styryloxy monomers may be employed depending upon the desired 
characteristics of cured product after each stage of the curing method of 
the present invention. Where only one of said monomers has the 
crosslinking characteristics of a beta-vinyl ether, preferably 
4-propenyloxystyrene, then said monomer will generally comprise from about 
20 to 95 %, preferably from 40 to 90 %, by weight of the mixture. 
Other suitable compounds of formula VI which are useful in the practice of 
the present invention include those having two or three alkenyloxy groups 
on the ring, preferably with one alkenyloxy group in the metal position 
relation to another e.g. a compound of the formula X 
##STR15## 
wherein R.sup.9 is as defined above. A preferred compound is the 
dipropenyl derivative of resorcinol i.e. 1,3-dipropenyloxy benzene. 
Another special feature of the present invention is the ability to use the 
compound(s) of formula VI together with other polymerisable monomers. 
Depending upon the polymerisation characteristics of both the specific 
compound of formula VI and the other monomer to be employed, said monomers 
may, during the first stage, copolymerise or concurrently polymerise or 
only one may polymerise in the first stage, with complete curing of all 
monomers in the second stage. The more common instance of the latter is 
where the compound of formula VI is non-polymerised under the curing 
conditions of the first stage and, thus, the other monomer comprises a 
matrix monomer. For the sake of brevity and convenience, the other 
monomer, regardless of whether it is or is not a true matrix monomer, as 
that term is understood by those skilled in the art, shall hereinafter be 
referred to as the matrix monomer. 
Generally, any polymerisable monomer may be employed as a matrix monomer so 
long as it does not interfere with the polymerisation or curing of the 
overall composition, especially the polymerisation or curing of the 
compound of formula VI. Obviously, the choice of suitable matrix monomers 
will depend upon the cure modality of the first step as well as the 
specific structure of the compound of formula VI. Suitable matrix monomers 
will be readily recognised by those skilled in the art. A few of such 
matrix monomers are discussed in the context of the present invention 
below. 
It is also contemplated, depending upon the constituents of the 
polymerisable composition, that the first stage of the curing process may 
also entail a minor, in comparison to the second stage polymerisation, 
degree of crosslinking: such first stage crosslinking providing strength 
and integrity to the cured product of the first stage. However, under the 
curing conditions (elevated temperatures) of the second stage, this 
crosslinking, if present, is believed to be broken, though the final 
product is more densely crosslinked during the second stage of the curing 
process through the alpha or beta unsaturation of the R.sup.a and R.sup.b 
moieties of the compound(s) of formula VI. 
The proportions by which the compound(s) of formula VI and the matrix 
monomer are present within the mixture may be varied within wide limits, 
provided that a sufficient amount of the compound of formula VI is present 
to achieve the desired crosslinking in the second stage. Generally, the 
molar ratio of the compound of formula VI to the matrix monomer is from 
about 1:9 to 20:1, preferably from 2:1 to 9:1. As previously mentioned, 
the true make-up of the polymerisable composition will depend upon the 
desired characteristics of the cured product. Like the styryloxy monomers, 
the matrix monomer may be polymerisable by most any cure modality, e.g. 
cationic (including photocationic), heat, redox, anionic, atmospheric, 
electron beam, X-ray, gamma-ray or other suitable curing system. In each 
case, appropriate initiators, accelerators and other conventional 
adjuvants are included in the composition, in conventional amounts, as 
will be readily recognised by those knowledgeable in the art. 
A preferred mode of cure in the first stage is cationic cure, especially 
photocationic curing. Thus, although matrix monomers of other cure 
modalities may be employed, it is especially preferred that the matrix 
monomer be cationically polymerisable. Exemplary of such suitable 
cationically polymerisable matrix monomers are the photopolymerisable 
vinyl ether monomers, especially the divinyl ethers of polyalkylene 
oxides, e.g. those of the formula CH.sub.2 .dbd.CH--O--[--(CH.sub.2).sub.n 
--O--].sub.m --CH.dbd.CH.sub.2 wherein n=1-6 (preferably n=2) and m is 
greater than or equal to 2 (preferably m 2-10). A preferred compound is 
the divinyl ether of triethylene oxide, which is commercially available. 
Thus, such a first stage photocurable, second stage thermally crosslinkable 
composition may comprise: 
(A) one or more compounds of the formula VI as defined above, 
(B) a divinyl either of a polyalkylene oxide, and 
(C) a photoinitiator. 
Other suitable matrix monomers include the telechelic styryloxy monomers as 
described in U.S. Pat. No. 4,543,397, Woods et. al., especially the 
styryloxy capped polyether. 
It is also contemplated within the scope of the present invention that the 
compound of formula VI be produced in situ in the composition during the 
first stage of the curing, especially during photocuring, by cleavage 
beyond a phenolic oxygen and/or by rearrangement. For example, a 
cationically polymerisable divinyl ether as described in pending U.S. 
patent application Ser. No. 07/543,248 of Klemarczyk et al filed Jun. 25, 
1990 entitled "Aromatic Vinyl Ether Compounds and Compositions, and Method 
of Making the Same" assigned to Loctite Corporation, having the formula 
XI; 
##STR16## 
wherein R.sup.21, R.sup.22, R.sup.24, R.sup.25, R.sup.26, R.sup.28, 
R.sup.29 and R.sup.30 are each independently selected from hydrogen, 
halogen and C.sub.1 -C.sub.8 alkyl radicals; R.sup.23 and R.sup.27 are 
each independently selected from C.sub.1 -C.sub.8 alkylene radicals; and 
R.sup.31 and R.sup.32 are each independently selected from allyl and 
methallyl, on photocuring undergoes a small extent of cleavage beyond the 
phenolic oxygen atoms to form a compound of the formula XII: 
##STR17## 
This ortho-alkenyl compound then acts as the compound of formula VI. The 
remainder of the uncleaved divinyl ether may act as a matrix monomer in 
the 2-stage curing process, or another matrix monomer may be added. 
As previously mentioned, the acid required for the second stage of the 
curing process may be generated in situ or may be added to the 
polymerisable composition. In either instance, the acid or acid precursor, 
in the case of in-situ generated acid, will be present in conventional 
amounts, as is well known to those skilled in the art. It is especially 
preferred that the acid be generated in-situ so as to avoid or minimize 
any potential for adverse effects on the composition caused by the 
presence of free acid, e.g., instability of the composition. Such a result 
may occur where the encapsulant for the acid fails, in the case of 
microencapsulated acid, prematurely. Consequently, the process of the 
present invention is thus especially suited for photopolymerisable 
compositions whereby the acid may be generated by the photoinitiator. 
Generally, the photoinitiator may be any suitable UV cationic initiator. 
Such UV cationic photoinitiators include salts of complex halogenides 
having the formula: 
EQU [A].sub.b .sup.+ [MX.sub.e ].sup.-(e-f) 
where A is a cation selected from the group consisting of iodonium, 
sulfonium, pyrylium, thiopyrylium and diazonium cations, M isametalloid, 
and X is a halogen radical, b equals e minus f, f equals the valence of M 
and is an integer equal to from 2 to 7 inclusive, e is greater than f and 
is an integer having a value up to 8. Examples include di-p-tolyl iodonium 
hexaflourophosphate, diphenyl iodonium hexafluorophosphate, diphenyl 
iodonium hexafluoroarsenate and UVE (or GE) 1014 (trademark of General 
Electric), a commercially available sulfonium salt of a complex 
halogenide. 
The invention may be illustrated by reference to the following non-limiting 
examples. It should be noted that applicants' use of the term "A stage" or 
"stage A" refers to the first step of the polymerisation process of the 
present invention. Similarly, applicants' use of the term "B stage" or 
"stage B" refers to the second step (i.e., heat and acid treatment) of 
thepolymerisation process of the present invention.

EXAMPLE 1 
4-propenyloxy styrene was prepared by base-catalysed isomerisation of 
4-allyloxystyrene using methanolic KOH (6 hours, 150.degree. C.) as 
described in our copending Application of even date herewith entitled 
"Styryloxy Compounds and Polymers Thereof". 
4-propenyloxystyrene formulated with 15 .mu.l/gm of the commercially 
available latent acid photoinitiator GE 1014 from General Electric Co. 
formed a composition capable of undergoing dual cure to give a highly 
thermally resistant, crosslinked polymer. The A Stage involved a 
cationically photoinitiated polymerisation with 100 mW/cm.sup.2 of UV 
light for 5-10 seconds. This stage also formed small amounts of 
photogenerated phenolic residues which have aromatic C-2 (ortho) alkenyl 
substitution, as evidenced by the formation and splitting of 
characteristic --OH bands in the 3500 cm.sup.-1 region of the infra red 
spectrum where the higher energy band corresponds to free --OH and the 
lower energy band corresponds to an intramolecular hydrogen bonded - pi 
complex, as is already known for simple ortho-alkenyl phenols (Kalc, J. et 
al., J. Phys. Chem., 71 (12), 4045 (1967) and Baker, A. et al., J. Am. 
Chem. Soc., 89, 5358 (1958)). 
The photocured film formed during the A stage polymerisation was 
transparent and either colourless or slightly coloured. When this 
photocured film was subsequently heated from ambient temperature to 
300.degree. C. at a rate of 5.degree. C. per minute, or, heated to 
140.degree. C. at this rate, and held at the latter temperature for one 
hour, the polymer underwent a structural rearrangement and developed into 
an intensely coloured reddish transparent film which was not decomposed. 
The said rearranged polymer had a glass transition temperature (Tg) around 
300.degree. C. (1 Hz by Dynamic Mechanical Thermal Analysis--DMTA) and 
retained approximately 98% of its room temperature log modulus (log G') at 
300.degree. C. The rearranged polymer was further characterised by a very 
low Tan.delta. value, typically &lt;0.10 (1 Hz by DMTA). No loss in 
performance was noted on repeatedly recycling the film between 25.degree. 
and 300.degree. C. in a Dynamic Mechanical Thermal Analyser. Thermal 
Gravimetric Analysis (TGA) indicated the rearranged polymer to lose &lt;4% wt 
at 300.degree. C. 
EXAMPLE 2 
When Example 1 was repeated using allyloxystyrene in place of 
propenyloxystyrene as the initial monomer, a rearranged material also 
resulted after the dual cure stages A and B. The rearrangement was 
conveniently followed by DMTA when a large drop in log G' from 7 to about 
3-5 occurred at around 60.degree. C. The modulus started to climb again at 
temperatures greater than 150.degree. C. After scanning to 300.degree. C. 
the polymer was red in colour and a rescan by DMTA showed retention of the 
initial log G' value of 7 PA. 
Thermal treatment alone as observed by Dielectric Thermal Analysis (DETA) 
experiments showed that allyloxystyrene will not rearrange itself at 
temperatures less than about 250.degree. C. 
EXAMPLE 3 
A mixture of 4-allyloxystyrene and 4-propenyloxystyrene was prepared and 
analysed by the GC-MS technique. The instrument used was a Hewlett-Packard 
58-90 GC system with an electron impact mass selective detector. The 
column head pressure was 15 p.s.i. of Helium as carrier, column type was a 
25m capillary type of 0.25mm with a BP10 coating. Injection was made at 
300.degree. C. from Analar (Trade Mark) grade chloromethane. Total ion 
current traces for the styryloxy mixture indicated three components to be 
present. Two components were isomeric and had molecular mass of 160 units. 
In order of ascending boiling points these two were identified as 
propenyloxystyrene and allyloxystyrene. The analysis also indicated the 
presence of a third compound referred to hereafter as K. The concentration 
of K in the gas chromatogram was dependent upon the temperature of sample 
injection. Integration of GC data at 300.degree. C. injection temperature 
characterised the styryloxy mixture as 22% propenyloxystyrene, 63% 
allyloxystyrene and 15% K. Proton NMR run at room temperature in 
CDCl.sub.3 as solvent and TMS as reference indicated the styryloxy mixture 
to contain propenyloxystyrene and allyloxystyrene only. 
When a photocurable composition containing 75% of this styryloxymixture and 
25% of the commercially available vinyl ether known as DVE-3 from the GAF 
Company and 15 .mu.l/gm of photoinitiator GE 1014 from General Electric 
Co. was cured in stage A with 100 mW/cm.sup.2 of UV light for 5-10 seconds 
and then subjected to a heating cycle (stage B) as described in Example 1, 
a red polymeric material resulted with good high temperature performance. 
Thermal Gravimetric Analysis of the composition indicated an approximately 
8% weight loss at 300.degree. C. as compared to a 30% weight loss at this 
temperature for a cured polymer from DVE-3 alone. Pin-to-glass tensile 
testing after aging in an oven set at 200.degree. C. for 16 hours showed 
bond strengths in the order of 120 dN/cm.sup.2 for the rearranged polymer. 
Bond strength for a polymer of DVE-3 alone could not be measured because 
it had disintegrated entirely when subjected to such treatment. The bond 
strengths of the thermally aged composition (stage B) were often higher 
than those of the purely photocured composition (stage A) at room 
temperature. 
Dielectric Thermal Analysis (DETA) of the photocured composition mentioned 
above, in the temperature range of 25.degree.-300.degree. C. and at 1, 10 
and 50 kHz, indicated on first scan two loss processes, one at 85.degree. 
C. and the other at 210.degree. C., which were nominally frequency 
independent. These corresponded to peaks in log .epsilon.' at 85.degree. 
C. and 220.degree. C. At the end of the thermal dielectric scan the 
initially colourless polymer was now deep red over its entire area of 
about 5 cm.sup.2 indicating that a rearrangement had occurred. On 
re-running the DETA from 25.degree.-300.degree. C. on the previously 
scanned (i.e., rearranged) photocured composition, the first loss process 
disappeared and the high temperature loss process moved to 265.degree. C. 
and was again largely frequency independent. 
If the A stage is omitted and the aforementioned photocurable composition 
is simply heated in the DETA between 25.degree.-300.degree. C. under the 
same conditions as before, the sample retains the permittivity behaviour 
of a liquid until about 250.degree. C. and does not behave in the same way 
as before. Eventually the sample thermally polymerises showing strongly 
frequency dependent DETA characteristics. The film appears yellowish at 
300.degree. C. 
Dynamic Mechanical Thermal Analysis of the said mixture provided a means 
for imposing stage B on an already photocured composition whilst 
simultaneously probing its mechanical properties. At 1 Hz and scanning 
between 25.degree. and 300.degree. C. at a rate of 5.degree. C./min a Tg 
was noted for styryloxy (unrearranged) polymer plasticised by the DVE-3 
material at about 48.degree. C. with Tan .delta.=0.88. If DVE-3 were not 
present the Tg value would normally be around 70.degree. C. and Tan 
.delta..gtoreq.1.0. As the stage B treatment was imposed, changes in 
mechanical properties were noted above 150.degree. C. and a new loss 
process occurred at around 220.degree. C. The resultant cured composition 
was of a deep red colour after this treatment and stable to 300.degree. C. 
On thermal rescan the aforementioned low temperature loss process (at 
48.degree. or 70.degree. C., depending on the presence or abscence of 
DVE-3) disappeared, only the high temperature loss process persisted at 
around 220.degree. C. and the log G' value at temperatures of greater than 
250.degree. C. was around 6.5 PA, a figure close to its initial room 
temperature modulus after stage A only. 
EXAMPLE 4 
When propenyloxystyrene was formulated with allyloxystyrene or the vinyl 
ether DVE-3 together with cationic photoinitiator GE 1014 at 15 .mu.l/gm, 
and subjected to photocure followed by thermal cure, the initially 
colourless transparent photocured compositions were transformed into 
red-brown undecomposed solids with temperature resistant properties as 
illustrated by DMTA and/or TGA. Increasing the propenyloxystyrene content 
in mixtures thereof with allyloxystyrene caused an increase in Tg as shown 
below. In this case TGA gave an average of 3% weight loss at 350.degree. 
C. 
______________________________________ 
Propenyloxy- 
styrene: 
allyloxystyrene 
25:75 50:50 75:25 100:0 
______________________________________ 
Tg (.degree.C.) 
110 140 180 300 
Tan .delta. 
@ Tg 0.5 0.41 0.1 0.1 
log G' at 300.degree. C. 
6.0 5.6 6.75 6.8 
(PA) 
______________________________________ 
Increasing the propenyloxystyrene content in mixtures with GAF divinylether 
DVE-3 showed reduction in high temperature weight loss as shown below. 
______________________________________ 
Propenyloxystyrene: 
DVE-3 0:100 25:75 50:50 72:25 100:1 
______________________________________ 
weight loss 30 15 11 8 3 
@ 300.degree. C. % 
______________________________________ 
EXAMPLE 5 
When resorcinolic type materials were derivatised with alkenyloxy type 
systems and mixed into cationically photocurable matrices which hitherto 
had no known high temperature resistant characteristics, rearrangements 
within the polymeric system resulting from stage A (photocure), stage B 
(thermal secondary cure), cationic photoinitiator residues and aromatic 
alkenyloxy systems, transformed the said matrices into polymers of 
orange/red colour which now had superior high temperature performance. 
Thus when the commercially available divinyl ether known as DVE-3 from GAF 
Co. was scanned in a Dynamic Mechanical Thermal Analyser, its initial log 
G' value of around 6.5 PA was retained steadily to around 140.degree. C. 
However, within the next few degrees of higher temperature the polymer 
decomposed as indicated by a drastic loss in modulus (several orders of 
magniture) and a rapid increase of Tan .delta., which is characteristic of 
decomposition. When DVE-3 was formulated with a 50% loading of 
1,3-dipropenyloxy benzene (dipropenyl resorcinol) and photocured using 15 
.mu.l/gm GE 1014 as photocatalyst, the mechanical properties of the 
resulting film were transformed as a result of the heat treatment during 
thermal scan in the instrument. Initially the log G' value of the mixed 
composition was 7.25, higher than before, but this dropped to around 6 
following an .alpha.-process, typifying a polymeric transition. The value 
log G'=6 was retained to around 280.degree. C. by which time the film had 
also changed colour to a reddish-like material. The Tg for this subsequent 
material was .gtoreq.300.degree. C. 
Similar behaviour was noted when diallyl resorcinol was used in place of 
dipropenyl resorcinol. When the allyl-like material was used, the 
attainment of high temperature resistant properties was slower and the 
resulting films were, on first thermal cycle (stage B or first DMTA scan), 
more yellowish than red. Mixtures of alkenyloxy resorcinols with thermally 
labile formaldehyde sources such as trioxane in photocured DVE-3 matrices 
also showed colouration and temperature resistance following stage B 
thermal treatment. 
EXAMPLE 6 
The divinylether of the structure shown below (Formula XIII) and previously 
claimed as a photocurable material in U.S. patent application Ser. No. 
07/543,248 of Klemarczyk et al, mentioned above, can also be rearranged to 
give a polymer of orange/red colour with high temperature resistant 
properties. 
##STR18## 
This material photocured when formulated with the cationic photoinitiator 
GE 1014 and subjected to UV light to give a clear (transparent) yellow 
polymer film. During photolysis some ortho-alkenyl phenolic like material 
was formed as evidenced from Infrared Spectroscopic Analysis (cf. Example 
1). In stage B, i.e. heating the said cationically photocured composition, 
rearrangement occurred to give a deep orange polymer now with much more 
intense --OH absorbance in the infrared spectrum at approximately 3400 
cm.sup.-1. The said polymer showed low weight loss at 300.degree. C. (8%). 
On first scan in the Dynamic Mechanical Thermal Analyser the material 
which had an initial Tg of 55.degree. C. (1 Hz) indicated secondary cure 
by an upturn in modulus at temperatures greater than 100.degree. C. The 
sample was repeatedly scanned to 300.degree. C. with the 2nd to the 9th 
scans indicating Tg moving to higher temperatures (94, 108, 134, 135, 136, 
147, 165 and 170) and an average log G' value of 6.5 PA at 300.degree. C. 
The said divinyl ether when formulated with styryloxy monomers or other 
vinyl ethers and subjected to the dual curing process as described above 
in the presence of photoinitiator residues, gave red/orange materials with 
good thermal resistance properties as illustrated by DMTA and/or TGA and 
detailed below: 
______________________________________ 
Bisphenol A based 
vinyl ether: 
DVE-3 monomer 
0:100 25:75 50:50 75:25 100:0 
______________________________________ 
weight loss @ 300.degree. C. 
30 18 14 9 8 
(%) 
______________________________________ 
EXAMPLE 7 
(a) Preparation of 4-(2'-hydroxyethoxy) benzaldehyde 
A 5-liter glass reactor equipped with a reflux condenser, mechanical 
stirrer and powder inlet port, was charged with 366 g of 
4-hydroxybenzaldehyde, 528 g of ethylene carbonate and 1.5L of 
methylisobutyl ketone (MIBK). The mixture was stirred. On solution of 
aldehyde and carbonate 414 g of anhydrous potassium carbonate was slowly 
added. The stirred mixture was refluxed for four hours after which time 
t.1.c. analysis indicated complete consumption of the phenolic starting 
compound. The reaction mixture was cooled and 1.5L of 3M sodium hydroxide 
solution added. The organic layer was separated, washed with H.sub.2 O and 
dried over anhydrous sodium sulfate. The dried solution was filtered and 
the solvent removed under reduced pressure to give 496 g of an orange 
coloured oil. Gel permeation chromatographic analysis (G.P.C.; 10 styrogel 
columns, 10.sup.3, 500 and 100 Angstrom, CH.sub.2 Cl.sub.2 eluent; R.I. 
detector) showed the oil to consist mainly of 2 components with elution 
volumes of 24.9 mls (Approx. 80%) and 23.7 mls (Approx. 20%) along with 
minor quantities of higher molecular weight products. Vacuum distillation 
of the crude product gave 330 g. (66%) of 4-(2'-hydroxyethoxy) 
benzaldehyde (formula Ia) (170.degree.-190.degree. C. at 0.4 mbar) which 
was shown by G.P.C. to also contain approx. 5% of a higher molecular 
weight product. The infra-red (NaCl disc) spectrum of the distilled 
product showed peaks at 3,580 cm.sup.-1 (--OH group); 1675, 2920 cm.sup.-1 
(AR--CHO group); 1590 cm.sup.-1 (AR-H group) and 1255cm.sup.-1 (AR--O--C 
group) which confirms the structural assignment. 
##STR19## 
(b) Preparation of 4-(2'- hydroxyethoxy)styrene 
A 5 liter glass reactor, equipped with a reflux condenser, N.sub.2 purge, 
powder inlet port, dropping funnel and mechanical stirrer was charged with 
dry tetrahydrofuran (1.5 L) and sodium amide (91 g of 90%, 2.1 m). To the 
stirred suspension was added methyltriphenylphosphonium bromide (750 g, 
2.1 m), and the mixture stirred at room temperature for 3 hours. A 
solution of 290.5 g of 4-(2'-hydroxyethoxy) benzaldehyde (prepared as 
described in Example 7 (a)) in 200 mls of dry tetrahydrofuran was added 
dropwise over 1.5 hours. The stirred mixture was refluxed for 3 hours 
after which time t.l.c. analysis indicated complete consumption of the 
starting aldehyde. The mixture was cooled and H20 (4L) added. The mixture 
was extracted with dichloromethane (4.times.500 mls) and the combined 
extracts dried over anhydrous Na.sub.2 SO.sub.4. The desiccant was removed 
by filtration and the solvent distilled under reduced pressure to yield 
850 g of a viscous semi-solid residue. The residue was extracted with 
petroleum spirit b.p. 40.degree.-60.degree. C. (5.times.500 mls) followed 
by an 80/20 blend of petroleum spirit and diethyl ether, until GPC and 
t.l.c. analysis indicated the residue to comprise only triphenylphosphine 
oxide. The extracts were combined and the solvent reduced by vacuum 
distillation to approximately one liter. The triphenylphosphine oxide, 
which had precipitated, was removed by filtration and the remainder of the 
solvent in the filtrate was removed under reduced pressure to yield an oil 
(413 g). The oil was distilled under vacuum to yield 4-(2'-hydroxyethoxy) 
styrene (114.4 g, 40%, 140.degree.-160.degree. C. at 0.8 mbar) as a 
colourless oil which solidified on cooling. G.P.C. analysis indicated only 
one component (i.e. 100% purity). The structure of the product, formula 
IIa, was confirmed by spectroscopic analysis. 
##STR20## 
'HNMR(CDCl.sub.3,60MHz) .tau.2.90,m, 4H, AR--H, .tau.3.35,m,1H, 
AR--CH.dbd.C; .tau.4.4, q, 1H, AR--C.dbd.C--H.sub.a' (Jax.dbd.18Hz, 
Jab.dbd.2Hz); .tau.4.86, q, 1H, AR--C.dbd.C--H.sub.b' (Jbx.dbd.11 Hz, 
Jba.dbd.2Hz); .tau.5.99, m, 4H, --OCH.sub.2 CH.sub.2 --O--; .tau.7.3, 1H 
broad S, --OH, I.R. (NaCl); 3540 cm.sup.-1 --OH group, 1620 cm.sup.-1 
AR--CH.dbd.CH.sub.2 ; 1590 cm.sup.-1, Ar--H; 1245 cm.sup.-1 AR--O--C--. 
(c) Preparation of .alpha., .omega.-bistosyloxypoly(oxybutylene) 
A solution of freshly purified p-toluenesulfonyl chloride (83.9 g, 0.44 
moles) in toluene (200 mls.) was added dropwise over one hour to a stirred 
solution of dry poly(1,4-oxybutylene) glycol (130 g: molecular weight 
average=650, Polymeg 650 supplied by QO Chemicals, Inc.; 0.2 moles) and 
dry freshly distilled triethylamine (80.8 g, 0.8 moles) in toluene (150 
mls) under a dry N.sub.2 atmosphere. After 64 hours, the reaction mixture 
was filtered and the filtered solid washed with toluene. The filtrate was 
allowed to stand for a further 24 hours and refiltered. The solvent was 
removed from the filtrate on a rotary evaporator to yield a straw coloured 
oil (155.86 g, 81%) which was shown by I.R. spectroscopy and HP liquid 
chromatography to comprise mainly the required bis-tosylate ester of the 
structure shown in formula IIIa: 
##STR21## 
I.R. NaCl (film): 1595 cm.sup.-1, C--C stretching vibration, aromatic group 
##STR22## 
(d) Preparation of Styryloxy Capped Poly (1, 4-oxybutylene)glycol 
Sodium hydride (2.76 g, 0.115 moles) was added to a stirred solution of 
4-(2'-hydroxyethoxy)-styrene (18.86 g, 0.115 moles) (prepared as described 
in Example 7(b) in dry tetrahydrofuran (THF) (100 mls.). After evolution 
of hydrogen gas had ceased, a solution of the 
.alpha.,.omega.-bistosyloxypoly(oxybutylene) product of Example 7(c) 
(55.14 g, 0.0575 moles) in THF (300 mls) and tetrabutylammonium bromide (9 
g) were added sequentially to the reaction mixture. After stirring for 17 
hr. at room temperature, the reaction mixture was filtered and the solvent 
removed from the filtrate under reduced pressure. The residue was 
dissolved in dichloromethane (200 mls), washed with water (50 mls) and 
dried (Na.sub.2 SO.sub.4). The solvent was removed under reduced pressure 
and the residue dissolved in THF (150 mls). Addition of Petroleum spirit 
b.p. 40.degree.-60.degree. C. (450 mls) to this solution afforded the 
required crude product as an oily precipitate (38.1 g, 80%), [which 
crystallized to a low melting solid on standing]. The structure of the 
product was confirmed by 'H NMR and IR spectrocopy to be: 
##STR23## 
60 MH.sub.z 'H NMR (CDCl.sub.3): 
2.6-3.2, m, 8H, aromatic protons 
3.3-3.7, m, 2H, AR--CH.dbd.C 
4.45, q, 2H, Ar--C.dbd.C--H.sub.a (Jax=18Hz, Jab.dbd.2 Hz) 
4.95, q, 2H, Ar--C.dbd.C--Hb (Jbx.dbd.11 Hz, Jba.dbd.2Hz) 
5.8-6.9, m, 44H, C--CH.sub.2 --O 
8.0-8.7 m, 36H, C--CH.sub.2 --C 
I. R. Spectrum (NaCl film), 1620cm.sup.-1, C.dbd.C stretching vibration of 
aromatic vinyl group. 
The styryloxy capped polyether thus formed was formulated in a 
photocationically curable composition with the styryloxy monomer mixture 
of Example 3 in various proportions, together with photoinitiator GE 1014 
at 15 .mu.l/gm. After the 2-state curing process as described above, the 
thermal resistance properties as determined by DMTA Analysis (1 Hz, 
5.degree. C./min) were as set forth below. 
______________________________________ 
% Styryloxy- 
capped % Styryloxy 
Polyether 
Monomer Result 
______________________________________ 
100 0 Material decomposes at 100.degree. C. 
75 25 Material decomposes at 180.degree. C. 
50 50 No decomposition. Secondary cure 
is indicated by upturn in modulus 
at .congruent. 150.degree. C. The sample can be 
cycled to 300.degree. C. 
25 75 No decomposition. Secondary cure 
is indicated by upturn in modulus 
at .congruent. 150.degree. C. The sample can be 
cycled to 300.degree. C. 
______________________________________ 
Obviously, other modifications and variations to the present invention are 
possible and may be apparent to those skilled in the art in light of the 
above teachings. Thus, it is to be understood that such modifications and 
variations to the specific embodiments set forth above are to be construed 
as being within the full intended scope of the present invention as 
defined by the appended claims.