ETHYLENICALLY UNSATURATED POLYMERIZABLE COMPOSITIONS

COMPOSITIONS POLYMERISABLES A INSATURATIONS ETHYLENIQUES

English Abstract

ABSTRACT
There is disclosed a process for the polymerization
of a non-air-curing monomer having at least two
ethylenically unsaturated groups in which an oxidative
prepolymerizate is incorporated into the monomer. The
prepolymerizate is an oxidatively polymerizable compound
in which there at least two unsaturations which are each
.beta. , .gamma. to oxygen or sulfur which is employed in an
amount of 1 - 200 parts by weight of the prepolymerizate
per mole of non-air-curing monomer, and is of the
formula
<IMG>
where R1 is a radical characterized by a molecular weight
less than about 2000, obtained by removal of active hydrogen
from an active hydrogen compound selected from the group
consisting of water, alcohols, thiols, carboxylic acids,
carboxylic amides, and amines, where the functionality of R1
is n, and is in the range of 1 to 10, where R2 is selected
from the group consisting of hydrogen and C1 to C10 organic
radicals, where E is a moiety containing a radical having an
activated olefinic unsaturation .beta.,.gamma. to the activating group
and is present in sufficient amount to provide a .beta.,.gamma.
-unsaturation equivalent of less than about 250, where
m is the average number of E moieties in the n segments of the
structure and where the product of m and n is in the range of
about 4 to about 60. Compositions are also disclosed of the
oxidative prepolymerizate described above together with the
polymerizable monomer. The resulting products formed after
polymerization have a wide field of utility in adhesives,
moldings, casting operations and the like. With the present
development, since the oxidative prepolymerizate and the
monomer copolymerize, varying of the properties of the final
product can be readily achieved.

Claims

The embodiments of the invention in which an exclusive property
or privilege is claimed are defined as follows:
1. A process for the polymerization of a non-air-curing
free-radical-polymerizable monomer having a structure
comprising at least two ethylenically unsaturated groups, which
comprises:
(A) incorporating into the monomer an oxidative
prepolymerizate of an oxidatively polymerizable compound having
a structure comprising at least two unsaturations which are
each .beta. , .gamma. to oxygen or sulfur atoms activating the
unsaturations towards oxidative polymerization, said
oxidatively polymerizable compound being represented by the
structure:
<IMG>
where R1 is a radical characterized by a molecular weight
less than about 2000, obtained by removal of active hydrogen
from an active hydrogen compound selected from the group
consisting of water, alcohols, thiols, carboxylic acids,
carboxylic amides, and amines, where the functionality of R1
is n, and is in the range of 1 to 10, and where R2 is
selected from the group consisting of hydrogen and C1 to
C10 organic radicals, where E is a moiety containing a
radical having an activated olefinic unsaturation .beta. ,.gamma. to the
29

activating group and is present in sufficient amount to provide
a .beta., .gamma. -unsaturation equivalent of less than about 250, where m
is the average number of E moieties in the n segments of the
structure and where the product of m and n is in the range of
about 4 to about 60; and wherein the non-air-curing monomer is
represented by the structure :
<IMG>
where R3 is selected from the group consisting of H, CH3
and C2H5, where p is an integer in the range of 2 to 10 and
Y is a residue of a polyol, a polycarboxylic acid, a polyamine,
a polyepoxide or a polyisocyanate of a number average molecular
weight less than about 2000 containing a hydrocarbon,
polyester, polyamide, polyether or polyurethane backbone; and
(B) activating the oxidative prepolymerizate to
copolymerize with the non-air-curing monomer composition.
2. The process according to claim 1 in which the
oxidatively polymerizable compound has a .beta.-.gamma.-unsaturation
equivalent less than about 150 and is the reaction product of
water, or an alcohol with allyl glycidyl ether.
3. The process according to claim 1 in which the
oxidatively polymerizable compound has a structure comprising
at least two groups with the formula -Q- CH2 -CH=CH2
wherein Q is selected from the group consisting of -O-, -S-,
and <IMG>.

4. The process according to claim 1 in which the
oxidative prepolymerizate is present in an amount that
represents from 0.5 to 99% of the combined weight of
non-air-curing free-radical-polymerizable monomer and oxidative
prepolymerizate.
5. The process according to claim 2 in which the
oxidative prepolymerizate is present in an amount that
represents from 0.5 to 99% of the combined weight of
non-air-curing free-radical-polymerizable monomer and oxidative
prepolymerizate.
6. The process according to claim 1 in which the
oxidative prepolymerizate is present in an amount that
represents 1 to 70% of the combined weight of non-air-curing
free-radical-polymerizable monomer and oxidative
prepolymerizate.
7, The process according to claim 2 in which the
oxidative prepolymerizate is present in an amount that
represents 1 to 70% of the combined weight of non-air-curing
free-radical-polymerizable monomer and oxidative
prepolymerizate.
8. The process according to claim 1 in which the
oxidative prepolymerizate is present in an amount that
represents 5 to 40% of the combined weight of non-air-curing
fee-radical-polymerizable monomer and oxidative
prepolymerizate.
31

9. The process according to claim 2 in which the
oxidative prepolymerizate is present in an amount that
represents 5 to 40% of the combined weight of non-air-curing
free-radical-polymerizable monomer and oxidative
prepolymerizate.
10. The process according to claim 1 in which up to 1% by
weight of a metallic drier salt is added to the composition to
initiate free-radical polymerization.
11. The process according to claim 1 in which the
copolymerization takes place under an oxygen free atmosphere.
12. The process according to claim 1 in which the
non-air-curing free-radical-polymerizable monomer comprises up
to 50 weight percent of a non-air-curing free radical
polymerizable monoethylenically unsaturated monomer.
13. The process according to claim 1 in which the
oxidatively polymerizable compound comprises a structure
resulting from the oxidation of a prepolymer precursor having
the formula:
<IMG>
32

wherein A is a moiety terminating in the residue of an active
hydrogen-containing group selected from the group consisting of
alcoholic hydroxyl, thiol, amide, carboxylic acid and secondary
amine with an active hydrogen atom removed, E is a moiety
containing a radical having an activating olefinic unsaturation
.beta. , .gamma. to the activating group, and m and n are integers and
where either is less than 4 the other is at least 4.
14. A copolymer produced by the process according to
claim 1, 2 or 3.
15. A copolymer produced by the process according to
claim 4, 5 or 6.
16. A copolymer produced by the process according to
claim 7 or 8.
17. A copolymer produced by the process according to
claim 9 or 10.
18. A composition of matter comprising:
(A) an oxidative prepolymerizate of an oxidatively
polymerizable compound having a structure comprising at least
two unsaturations which are each .beta. , .gamma. to oxygen or sulfur atoms
activating the unsaturations towards oxidative polymerization,
said oxidatively polymerizable compound being represented by
the structure:
<IMG>
33

where R1 is a radical characterized by a molecular weight
less than about 2000, obtained by removal of active hydrogen
from an active hydrogen compound selected from the group
consisting of water, alcohols, thiols, carboxylic acids,
carboxylic amides, and amines, where the functionality of R1
is n and is in the range of 1 to 10, wherein R2 is selected
from the group consisting of hydrogen and C1 to C10 organic
radicals, where E is a moiety containing a radical having an
activated olefinic unsaturation .beta. , .gamma. to the activating group
and is present in sufficient amount to provide a .beta. , .gamma. -
unsaturation equivalent of less than about 250, where m is the
average number of E moieties in the n segments of the structure
and where the product of m and n is in the range of about 4 to
about 60;
(B) a non-air-curing free-radical-polymerizable
monomer having a structure comprising at least two
ethylenically unsaturated groups;
and wherein the non-air-curing free-radical-poly-
merizable monomer is represented by the structure:
<IMG>
where R3 is selected from the group consisting of H, CH3
and C2H5, where p is an integer in the range of 2 to 10 and
Y is a residue of a polyol, a polycarboxylic acid, a polyamine,
a polyepoxide or a polyisocyanate of a number average molecular
weight less than about 2000 containing a hydrocarbon,
polyester, polyamide, polyether or polyurethane backbone
34

19. The composition of claim 18 wherein the oxidatively
polymerizable compound has a .beta. - .gamma. -unsaturation equivalent of
less than 150 and is the reaction product of water, or an
alcohol with allyl glycidyl ether.
20. The composition of claim 18 wherein the oxidatively
polymerizable compound has a structure comprising at least two
groups with the formula -Q-CH2-CH=CH2 wherein Q is selected
from the group consisting of -O-, -S- and <IMG>.
21. The composition of claim 18 wherein the .beta. , .gamma. -un-
saturation equivalent is less than about 150.
22. The composition of claim 18 wherein the .beta. , .gamma. -un-
saturation equivalent is in the range of about 115 to about
120.
23. The composition of claim 18 wherein the peroxide
content of the oxidative prepolymerizate is in the range of
about 0.005 to about 2.0 millimoles per gram.
24. The composition of claim 18 wherein the peroxide
content of the oxidative prepolymerizate is in the range of
about 0.2 to about 1.0 millimoles per gram.

25. The composition of claim 18 wherein the oxidative
prepolymerizate is present in an amount that represents from
0.5 to 99% of the combined weight of non-air-curing
free-radical-polymerizable monomer and oxidative
prepolymerizate.
26. The composition of claim 22 wherein the oxidative
prepolymerizate is present in an amount that represents from
0.5 to 99% of the combined weight of non-air-curing
free-radical-polymerizable monomer and oxidative
prepolymerizate.
27. The composition of claim 18 in which up to 1% by
weight of a metallic drier salt was added to the composition.
28. The composition of claim 18 in which the oxidative
prepolymerizate is present in an amount that represents 1 to
70% of the combined weight of non-air-curing
free-radical-polymerizable monomer and oxidative
prepolymerizate.
29. The composition of claim 18 in which the oxidative
prepolymerizate is present in an amount that represents 5 to
40% of the combined weight of non-air-curing free-radical-
polymerizable monomer and oxidative prepolymerizate.
36

30. The composition of claim 18 wherein the oxidatively
polymerizable compound is represented by the structure:
<IMG>
wherein A is a moiety terminating in the residue of an active
hydrogen containing group selected from the group consisting of
alcoholic hydroxyl, thiol, amide, carboxylic acid and secondary
amine with an active hydrogen atom removed, E is a moiety
containing a radical having an activating olefinic unsaturation
.beta.,.gamma. to the activating group, and m and n are integers and
where either is less than 4 the other is at least 4.
31. The copolymer product obtained by curing the
composition of claim 18.
32. The copolymer product obtained by curing the
composition of claim 19, 20 or 21.
33. The copolymer product obtained by curing the
composition of claim 22, 23 or 24.
34. The copolymer product obtained by curing the
composition of claim 25, 26 or 27.
35. The copolymer product obtained by curing the
composition of claim 28, 29 or 30.
37

Description

3~
-1- 06~12 ~1098)A
ETH~LENICALLY UNSATURATED POL~MERIZABLE COMPOSITIONS
B~CKGROUND OF T~IE INVENTION
This invention relates to a free-radical-
polymerizable composition and to a polymerization
process and more specifically to a free-radical-poly-
merizable composition containing a polymerizable
initiator and to a process for initiating the poly-
merization of free-radical-polymerizable monomers
with a polymerizable initiator.
Thus the invention relates to compositions
containing a polymerizable initiator that not only
initiates polymerization reactions but also apparently
enters into the polymerization reactions and modifies
the properties of final polymers obtained.
DESCRIPTION OF THE PRIOR ART
Typically a free radical polymerization
initiator is a peroxide, a peracid, a perester or an
azo derivative that is capable of generating free
radicals which initiate polymerization of ethyleni-
cally unsaturated monomers. The molecule does not
2~ take part in the polymerization to the extent of
becoming incorporated into the polymer molecule as a
comonomer.
These initiators are highly active and
sometimes dangerously unstable and need to be handled
with great care. For this reason they are used under
carefully controlled conditions.
One constraint on conventional free-radical
initiation is that it is usually strongly inhibited
by the presence of oxygen such that polymerization
reactions have to be conducted in an inert atmosphere.
~ J~

~23~i3~3~
--2--
Conventional initiators have an activation
temperature below which they are not very active so that
free-radical polymerization reactions are conventionally
carried out at elevated temperatures. Since such
reactions are usually also exothermic it is necessary to
equip polymerization vessels with elaborate temperature
control facilities.
The initiators used in the present invention
however are not only highly stable and highly reactive
but they have the capacity actually to enter into a
copolymerization reaction with the ethylenically-
unsaturated, free-radical-polymerizable monomer and so
produce copolymers that can be tailored to the desired
end use. In addition the initiators are very active
even at room temperature so that the reaction mixture
need not be heated.
A further advantage is that, unlike conventional
initiators, they function as oxygen scavengers and so
work effectively in the presence of oxygen. Elaborate
closed reaction vessels are not therefore required.
It is recognized that often it is advantageous to
operate in the absence of air so as to reduce color body
formation and to maximise structural uniformity. The
initiators of the invention are even more effective in
the absence of air and permit ready access to these same
advantages.
DESCRIPTION OF THE INVENTION
The invention in one aspect provides a process for
the polymerization of a non-air-curing free-radical-
polymerizable monomer having a structure comprising atleast two ethylenically unsaturated groups, which
comprises: incorporating into the monomer an oxidative
prepolymerizate of an oxidatively polymerizable compound
having a structure comprising at least two unsaturations

3~9
-2~-
which are each ~, yto oxygen or sulfur atoms activating
the unsaturations toward~ oxidative polymerization, the
oxidatively polymerizable compound being represented by
the structures
Rl ~E)m ~ R2]
where Rl i~ a radical characterized by a molecular
weight less than about 2000, obtained by removal of
active hydrogen from an active hydrogen compound
selected from the group consisting of water, alcohols,
thiols, carboxylic acids, carboxylic amides, and amines,
where the functionality of Rl is n, and is in the range
of 1 to 10l and where R2 i5 selected from the group
consisting of hydrogen and Cl to C10 organic radicals,
where E is a moiety containing a radical having an
15 activated olefinic unsaturation ~, Y to the activating
group and i9 present in ~ufficient amount to provide a
~,y -unsaturation equivalent of less than about 250,
where m is the average number of E moieties in the n
segments of the structure and where the product of m and
n is in the range of about 4 to about 60; and wherein
the non-air-curing monomer is represented by the
structure: -
~3 ~ .
(CH2 = C - C )p ~
where R3 i~ selected from the group consisting of H, CH3
and C2H5, where p is an integer in the range of 2 to 10
and Y i~ a residue of a polyol, a polycarboxylic acid, a
polyamine, a polyepoxide or a polyisocyanate of a number
average molecular weight less than about 2000 containing
a hydrocarbon, polyester, polyamide, polyether or
.. . . ..

3~
-2b-
polyurethane backbone; and activating the oxidatlve
prepolymerizate to copolymerize with the non-air-curing
monomer compo~ition.
In another aspect the invention provldes a
composition of matter comprising: an oxidative
prepolymerizate of an oxidatively polymerizable compound
having a structure comprising at least two unsaturations
which are each ~ ,y to oxygen or sulfur atoms activating
the unsaturations towards oxidative polymerization, the
oxidatively polymerizable compound being represented by
the structure:
1~ (E)m ~ R2 ] n
where Rl is a radical characterized by a molecular
weight less than about 2000, obtained by removal of
active hydro~en from an active hydrogen compound
selected from the group consisting of water, alcohols,
thiols, carboxylic acids, carboxylic amides, and amines,
where the functionality of Rl is n and is in the range
of 1 to 10, wherein R2 is selected from the group
con~i~ting of hydrogen and Cl to C10 organic radicals,
where E is a moiety containing a radical having an
activated olefinic unsaturation ~ , Yto the activating
group and is present in sufficient amount to provide a
~, y-unsaturation equivalent of les~ than about 250,
25 where m i~ the average number of E moieties in the n
3egments of the structure and where the product of m and
n i~ in the range of about 4 to about 60 and a non-air-
curing free-radical-polymerizable monomer having a
structure compri3ing at lea3t two ethylenically
30 unsaturated groups; and wherein the non-air-curing free-
radical-polymerizable monomer is
,

3~
represented by the structure:
R O
13 ll
(CH2-- C - C ) p Y
- where R3 1~ selected from the group consisting of H, CH3
and C2H5 , where p i8 an integer in the range of 2 to 10
and Y is a residue of polyol, a polycarboxylic acid, a
polyamine, a polyepoxide or a polylsocyanate of a number
average molecular weight less than about 2000 containing
a hydrocarbon~ polyester, polyamide, polyether or
polyurethane backbone.
A third aspect of the invention i8 directed to the
polymerized product obtained from the polymerlzable
; composition.
OXIDATIVELY POLYMERIZABLE COMPOUND
The process of oxidative polymerization is most
widely known ln the context oE drying oils and alkyd
based palnts, (which are generally long chain
unsaturated acid triglycerides), and relates to a
mechanism by which, in contact with air, certain
molecules can cross-link. This occurs through initial
formation of peroxide group intermediates which then
decompose to form cross-link sites between the
molecules.
Reaainess to undergo oxidative polymerization is
also demonstrated by the prepolymers described in USP
4,145,248 which are further described below and which
provide some of the preferred oxidative prepolymerizates
used in the process of the invention.
An oxidative prepolymerizate of an oxida-
.. .. .. ;. . ... .~

~2~ 9
-4- 06-12(1098)A
tively polymerizable compound (monomer or prepolymer
as indicated above) is obtained by a process in which
oxygen is bubbled -through the compound, (if a liquid),
or its solution at a temperature that is preferably
below 30~C. This is continued until a significant
proportion of hydroperoxide groups has been generated.
The presence of hydroperoxide groups can be readily
detected by addition of acidified, solvent-soluble
iodide ion which is directly converted to iodine
giving a yellow/brown coloration.
The formation of the oxidative prepoly-
merizate is usually accompanied by an increase in vis-
cosity since the hydroperoxide groups begin slowly to
decompose and generate cross-links as soon as they
are formed. Usually therefore the oxidative prepoly-
merizate will have a Gardner viscosity at 25C of at
least B/C and is advantageously at least M and is
preferably higher, for example R/S or even higher.
It is however desirable that the oxidative prepoly-
merizate be readily miscible with the free-radical-
polymerizable monomer and this puts a practical
limitation on the viscosity that can be employed.
While oxidative prepolymerizates based on
oxidatively polymerizable monomers are not excluded,
those prepolymerizates that tend to be the more
effective in practice include the oxidative pre-
polymerizates derived from air-bodying of compounds
of the type described in USP 4,145,248. Such polymers
(which may be termed "prepolymers" to accord ~ith
the use of the term "oxidative prepolymerizates" to
describe the result of air-bodying such polymers are
represented by the following structure:
Rl~ (,Elm -R2~n

3~
-5- 06-12(]09~)~
where Rl is a radical of molecular weight less than
about 2000 obtained by removal of active hydrogen
frorn an hydrogen colnpound selected from the group
consisting of water, alcohols, thiols, carboxylic
acids, carbo~ylic amides, and amines. The preferred
active hydrogen compounds are water and alcohols.
The backbone of the radical Rl may be a hydrocarbon
moiety, a polyether moiety, a polyester moiety, a
polyamide moiety, or a polyurethane moiety and can be
selected to enhance the compatibility of the oxidative
prepolymerizate with the ethylenically-unsaturated free
radical polymerizable monomer. n is the functionality
of Rl and is in the range of 1 to 10, the product of
n and m (the number of E groups per segment) being in
the range of about 4 to about ~0. R2 is selected
from the group consisting of hyd~ogen and Cl to C10
saturated or unsaturated organic radicals. The R2
group may for example be a hydrocarbon radical, an
acyl group such as acetyl or acrylyl, or a 1,2-epoxy
group such as glycidyl. E is a moiety containing a
radical having an activà~ed olefinic unsaturation
~ , ~ to an activating-oxygen or sulfur atom and is -
present in sufficient amount to provide a ~ , 2
unsaturation equivalent of less than about 250.
~- The term ~ - runsaturation equivalent conforms to the
accepted definition of the term equivalent, i.e., it is
the weight containing one unit of unsaturation.
Preferably the ~ , a~ unsaturation equivalent is less
than about 150 and is more preferably in the range of
about 115 to about 120. AdvantageoUSly the value of
m is at least 3 and the allyloxy groups are present
in the molecule in groups of three or more to provide
a close spatial relationship between them. Advan-
tageously the ~ , ~unsaturation is supplied by an
ally] group provided by an E group represented by the
structure CH2 - CH - O
CH - O - CH - CH = CH

3~
-6- 06-12(1098)A
The "prepolymers" of a preferred group have
a backbone compri,sing at least one segment with the
formula:
~ fH ~ [I)
A - (E)mH n
where A is a moiety terminating in the residue of an
active hydrogen-containing group selected from the
group consisting of alcoholic hydroxyl, thiol, amide,
carboxylic acid and secondary amine with an active
hydrogen removed, E is a moiety containing a radical
having an activated olefinic unsaturation, ~ , Zrto
the activating oxygen or sulfur atom, n is the number
of adjacent (as the term is hereinafter defined)
segments having this formula, and n and m are integers
and are each at least 1, provided that where one is less
than 4 the other is at least 4O The prepolymers can
have a plurality of adjacent segments of the above
formula and by "adjacent" is meant that they are
directly connected through a carbon-carbon bond or are
indirectly connected through a
~ or -E -
group or an oxygen or sulfur atom.
The high activity of the preferred prepoly-
mers depends to a large extent on the provision of a
plurality of activated double bonds advantageously in
close spatial relationship or in blocks. These double
bonds are sites at which oxygen-initiated crosslinking
takes place during the drying or accelerated or
natural aging operation. Thus, the provision of
blocks of activated double bonds each of which can

63~\
-7~ 06-12(1098)A
provide a bond site, increases the structural strength
of the crosslinks that form both inter- and intramole-
cularly during drying and/or aging.
The double bonds are activated, by which is
S meant that by virtue of their proximity in the pre-
polymer molecule to strongly electron-donating oxygen
or sulfur groups they are more ready to form cross-
links during the air drying process. Examples of such
electron-donating groups include ether, sulfide, hydroxyl,
carboxyl, and olefinically unsaturated group. The
preferred electron-donating group is an ether group.
These prepolymers may be hydrophilic in
character, though hydrophilicity is not an essential
characteristic of the oxidative prepolymerizates
useful in the present invention. A hydrophobic
polymer such as a drying oil-based paint causes the
water to run off or form discrete droplets on a
treated surface which, in effect, is water-proofed.
A polymer possessing hydrophilic character, on the
other hand, allows the surface to become wetted and,
if of a porous material, allows the water to be
absorbed into the material by a "wicking" effect.
Qualitatively, the term "hydrophilic"
polymer is understood to describe a polymer that can
be applied to an unmodified cellulosic substrate
without causing water applied to the treated
substrate to run off or form discrete droplets. In
other ~ords, the polymer does not destroy the power
of the substrate to absorb water or to be wetted by
it.
Quantitatively, it is found that hydropho-
bic polymers have surface tensions of about 40 dynes
or less (Water has a surface tension of 72 dynes).
The prepolymers can be formed by the
reaction of a compound having an activated double

i3~
-8- 06-12(1098)A
bond and e~oxy group with a molecule having a
plurality of active hydrogen-containing groups
selected from alcoholic hydroxyl, thiol, amide,
carboxylic acid and secondary amine groups. ~here it
is also desirable that the polymex be hydrophilic it
is often preferred that hydroxyl groups should provide
the active hydrogen-containing groups. The prepolymer
preferably should not contain primary or secondary
amine groups or phenolic hydroxyl groups since such
groups may interfere with the drying reaction.
The prepolymers can for example, be pre-
pared by the reaction of a backbone compound having
at least one and preferably from 1 to 6 moieties
containing active hydrogen-containing groups with a
compound containing both an epoxide group and an
activated double bond in proportions such that from 1
to 20 epoxide radicals are provided for each active
hydrogen-containing groups on the backbone compound
and the polymer produced has at least four activated
double bonds and provided further that the f~ ,
activated unsaturation equivalent is at most about
250 and is preferably less than about 150 and is ~ven
more preferably in the range of about 115 to about 120.
Alternativ~ly, the prepolymer can be formed
from a polymer chain having a plurality of adjacent
pendant hydroxyl groups, reacted with, for example,
allyl chloride using the techniques of Williamson's
ether synthesis. Alternatively, the same Williamson
synthesis technique may be employed using a polymer
chain with pendant halogen atoms and an unsaturated
alcohol such as allyl alcohol. This results in the
generatio~ of adjacent allyloxy groups pendant from
the prepolymer backbone that can form a suitable
block of unsaturation conferring the desired
air-dryin~ characteristics on the prepolymer.

3~
-9- 06-12(1098)A
Yet another method by which the prepolymer
may be prepared is by the Lewis acid promoted poly-
merization of vinyl allyl ether. This reaction is '
selective to the vinyl group and results in a chain
of carbon atoms with an allyloxy group pendant from
every other carbon atom.
There are, therefore, two basic types of
prepolymer embraced by the formula [I] above. The
first type comprises a backbone molecule with as
little as one moiety containing an active hydrogen-
containing group which is reacted with a compound
containing an epoxy group and an activated terminal
double bond in proportions such that at least four
epoxy molecules are reacted with each backbone
molecule and preferably from 4 to 10 or even 20 epoxy
molecules are reacted per active hydrogen-containing
~roup. As a simple example reacting l mole of glycol
with 8 moles of allyl glycidyl ether produces a pre-
polymer having the average structure
IC 2 ICH2
O O
~CH2CH O ~ H CH2
O-CH2-CH=CH2 0-CH2--CH=CH2
- thus providing two blocks of four adjacent acti-
vated allyli~ groups-
assuming of course, uniform addition at both sides.
In this compound moiety lE]m is
Jc CH2CH~
CH2
O-CH2-CH--CH2
and has the double bond ~3, ~to the activating
oxygen group.
The other type of structure is obtained for

3~
-10- 06-12(1098)A
example, when a backbone molecule which comprises at
least four adjacent active hydrogen-containing groups
is reacted with an unsaturated epoxy compound as
described above or alternatively, using Williamson's
ether synthesis, with allyl chloride to produce a
block o~ pendant allylic groups. In the latter case
the ether oxy~en provides the activation for the
double bond in the allyl group and also the group "A".
An example of such a prepolymer is that produced by
the reaction o~ allyl chloride with polyglycidol to
produce a prepolymer having a structure with repeating
units of the formula
CH-CH2-0
C~2
O
PH2
CH=CH
Here the moiety E is ~ CH2-CH=CH ~ and
m is 1 and n is at least 4, and the olefinic unsaturation
is ~ , ~rto the activating oxygen.
The backbone compound can therefore, be a
polymeric polyol such as polyethylene glycol, poly-
glycerol, polyglycidol, polyvinyl alcohol, a
partially hydrolyzed polyvinyl acetate, a styrene/-
25 allyl alcohol copolymer, poly(2-hydroxyethyl acrylate),
poly(vinyloxy-ethanol), a monomeric polyol such as
sorbitol, mannitol, or ethylene glycol; a monomeric
alcohol such as methyl alcohol or allyl alcohol; the
corresponding th ols; and carboxylic acids such as
acetie acid, fumaric acid, maleic aeid, malonic acid
and phthalic aeid. Also, eompounds eontaining a
mixture of radieals ean be used sueh as hydroxy
acids, which are compounds containing the carboxy
and hydroxy radieals, hydroxy amides, hydroxy

3 ~ 9
~ 06-1211098)A
ethers, hydroxy esters, and the like. However, poly-
hydric alcohols having from 2 to 6 carbon atoms are
preferred and sorbitol is especially preferred.
The epoxy compound reacted with the backbone
compound comprises an epoxide group and an activated
double bond.
The epoxy compounds that can be used have
the general formula
/o\
R -CH-CH-[M]-CH=CH-R
wherein M is absent or is a group capable of activ-
ating the double bond selected from the following
moieties -CH2-O-CH2-,and -CH2-S-CH2-' and wherein
R4 and R5 are eacn nyQrogen or Cl-lo C4 alk-~1 g-Lo~Ps.
It is impcrtant that the activating group
aoes not comprise a moiety that will inhibit or deac-
tivate the air-curing mechanism. Such disfavored
groups include free primary and secondary amine,
phenolic hydroxyl, and thiol groups.
Preferred compounds include allyl glycidyl
ether, and butadiene monoxide. The most preferred
reactant which is aiso readily available at relatively
low cost is allyl glycidyl ether.
- An alternative preferred type o~ oxidative
prepolymerizate is obtained by the process aescribed
in U.S. Application Serial No. 150,789, filed May 19,
1980 now U.S. Patent 4,289 r 864, issued September 15,
1981. The process therein described comprises passing
oxygen through an oxidatively polymerizable monomer
maintained at a temperature of 30C. or below, said
monomer having a structure comprising at least two
unsaturations, with no more than three of said
unsaturations being ~ , ~fto a nucleophilic group
capable of activating the unsaturation towards oxi-
dative polymerization and selected from the group
~ .

63~3
-12- 06-12(10983A
consisting of -O-, -S- and -C-O-
o
so as to polymerize the monomer oxidatively and raise
the viscosity of the system to a desired level.
For the purposes of the present invention
the monomer that is oxidatively polymerized by the
above process preferably comprises at least two
groups with the formula -Q-CH2-CH=CH2 where Q is
one of the nucleophilic groups indicated above,
and is preferably an -0- group. Of course the same
group can be used to "activate" several unsaturated
bonds as for example in diallyl ether.
The group containing the activated unsatu-
ration is usually an allyl radical. It can, however,
be a homolog of such a group. It is often use~ul to
have the unsaturation that is ~ , Z~ to the activating
group conjugated with another unsaturated group in the
same chain.
Typical unsaturated groups include, for
example: -CH2CH=CH2, -CH2-CH=CH-CH3 ("cis" and
"trans" versions), -CH2-CH=C ~, CH2C(C~3)=CH~,
and -CH(CH3)CH=CH2. Since the monomer comprises at
least two or three such groups it is convenient to
refer to them as di/tri olefinic monomers.
The molecule need not contain only the
groups and moieties indicated. Other non-interfering
functional or non-functional groups such as ester,
amide, nitrile, carboxylic acid~ ketone, carboxy-
aldehyde, sulfonamide, and the like can be present in
the molecule. Indeed, sometimes fun~tional groups
can be very significant in providing a monomer that
will result in a polymer with an appropriate degree
of hydrophilicity, polarity, and substantivity.
Very often, however, the preferred
molecules are as simple as possible since these tend

~2~3~
-13- 06-12(109~)A
also to be relatively cheap. An excellent monomer
startinq material is 1,2 diallyloxy-ethane. Other
possible monomers include 1, 4 diallyloxy-2-butene,
1,3-diallyloxy-2-propanol, diallyl sulfide, ~ vinyl-
oxyethyl allyl ether, diallyl succinate, diallylmaleate, diallyl fumarate, diallyl adipate, diallyl
phthalate, triallyl cyanurate, triallyl orthoformate
and dimethallyl malonate. Of these, the polyallyl
ethers are preferred.
FORMATION OF THE_OXIDATIVE PREPOLYMERIZATE
The oxidative polymerization process is
preferably carried out at temperatures of 50C. or
lower such as from 5 to 30C. and preferably from
10C. to 25C. and can involve the oxidatively poly-
merizable prepolymer or monomer alone, (either willconventionally be a liquid under normal conditions)
or a solution or emulsion of the prepolymer/monomer
in a solvent.
The temperature of the reaction is found to
be important in that low temperatures are required if
reactive peroxy and hydroperoxy sites that are applic-
able to air-curing chemistry are to be obtained and
accumulated in adequate numbers. Advantageously the
oxidative polymeri2ation process is carried out under
the above stated conditions for a sufficient time to
provide a concentration of from 0.005 to 2.0 millimoles
peroxide and hydroperoxide per gram and preferably
from 0.2 to 1.0 millimoles per gram.
The time during which the oxygen is passed
through the prepolymer/monomer depends largely on the
rate at which oxyqen is absorbed, that is, in effect,
qas depression effectiveness, prepolymer/monomer reac-
tivity, and the viscosity of the desired oxidative
prepolymerizate. The time may be shortened by the
presence of soluble metallic drier salts such as

63~
-14- 06-12(1098)A
cobaltous acetate, cobaltous octoate, manganous acetate,
and other salts or soluble chelates and complexes of
transition metals that are known generically as
"metallic driers" in the paint field. Organic peroxides
such as benzoyl peroxide and similar hydroperoxides
are also found to be effective either alone or in
conjunction with tertiary amines (for peroxides) or
with the metallic driers described above. Generally,
from 0.001 to 5.0 percent by weight of such an additive
or additive combination based on the prepolymer/monomer
weight is found to be effective.
The oxygen can be supplied either as a pure
gas or as a mixture with other inert gases such as,
for example, air. In general, air is preferred even
though the reaction may be longer than when a gas
with a higher oxygen content is used. The oxygen
partial pressure may be widely varied but in practice
atmospheric pressure is usually found to be con-
venient. Conditions which favor oxygen dissolution
such as sparging, agitation, stirring, dispersing,
counter current mixing and the like will also speed
oxidative polymerization.
The passage of oxygen is continued until,
as a result of the oxidative polymerization, the
desired "built" viscosity for the oxidative prepoly-
merizate is reached. This viscosity may be, for
example, a Gardner viscosity at 25C. at least B/C,
is advantageously at least M and is preferably from
R/S to Z-4~ A viscosity in this range may be reached
in a matter of hours, days, or even weeks depending
primarily on the reactivity of the monomers, the number
of activated saturations in the molecule, the number
of polyunsaturate blocks, the presence/absence of
solvent, the reaction temperature, the presence/absence
of metallic driers or other catalysts and the partial

i 3 5~! ~
-15- 06-12(1098)A
pressure of the oxygen in the reaction mixture.
It should be noted that the reaction
conditions chosen are those which unmistakably lead
to oxidative polymerization or oxygen promoted poly-
merization of the metallic drier-promoted, air-curing
alkyd resin type, not that of vinyl (addition) poly-
merization typified by the styryl, acrylic/methacrylic,
vinyl, etc. systems. The latter, as is known to those
skilled in the art, occurs only in the presence of
free radical producing additives (i.e. initiators)
and near total absence of radical inhibitors--including,
among others, free dissolved oxygen, hydroquinones
and their derivatives, homologs, etc., phenols,
mercaptans, quinones, and (poly) primary or secondary
amines. Since the oxidative polymerization reaction
systems are continually sparged with air (2)' the
initial oxygen rich phase assures that the reaction
will overwhelmingly be of the oxidative polymerization
type.
FREE RADICAL POLYMERIZABLE COMPOSITION
The other component of the copolymer of the
invention is a non-air-curing, free-radical-polymer-
izable monomer or mixture of monomers having a struc-
ture comprising at least two ethylenically unsatur-
ated groups. The nature of the molecule is notcritical so long as it is activated towards free-
radical polymerization via the double bonds by free-
radical moieties present in the oxidative prepoly-
merizate as a result of the oxidative polymeriza-
tion process. Such polyfunctional non-air-curing,
free-radical-polymerizable monomers are particularly
preferred where fast reaction and a high degree of
cross-linking is desired. Such polyunsaturated
monomers include among other types, acrylic monomers,
styrenic monomers, vinyl ethers, vinyl esters, vinyl

~ ~ 3 ~ ~
3~
-16- 06-12(103~
imides, vinyl amides, maleates and fumarates. Preferred
monomers are represented by the structure:
1 3 11
(CH2 = C - C ) p Y
where R3 is selected from the group consisting of H,
CH3 and C2H5, where p is an integer in the range of
2 to lO and Y is a residue of a polyol, a polycar-
boxylic acid, a polyamine, a polyepoxide or a poly-
isocyanate of a number average molecular weight less
10 than about 2000 containing a hydrocarbon, polyester,
polyamide, polyether or polyurethane backbone. Such
monomers may be obtained by reaction of acryloyl,
methacryloyl or ethacryloyl chloride with a polyol
or a polyamine or by the reaction of acrylic acid,
15 methacrylic acid or ethacrylic acid with a polyepoxide
or a polyisocyanate, or by the reaction of a
hydroxyalkyl acrylate, methacrylate or ethacrylate
with a polycarboxylic acid, a polyepoxide or a
polyisocyanate. Such include 1,3-butylene glycol
20 diacrylate; 1,6-hexanediol diacrylate; polyethylene
glycol 200 dimethacrylate; pentaerythritol tetracrylate;
trimethylolpropane triacrylate; ethoxylated bisphenol A
dimethacrylate; and dipentaerythritol monohydroxy-
pentacrylate.
Mixtures of such non-air-curing monomers can
be used to achieve any desired balance of properties
in the final copolymers. Generally however it is
preferable to select the monomers such that all can be
brought together at room temperature to react. It is
30 generally most convenient therefore if the reactants
can be dissolved in a common solvent which is most
preferably one of the reactants. It is not however
beyond the scope of this invention to provide that the
reaction occurs in a suitable non-polymerizable solvent
35 or that a gaseous reactant be contacted with the others

6;3~a
-17- 06-12(1098)A
in a multiphase reaction.
Mono unsaturated monomers may be included,
advantageously up to 50 wt. percent in admixture with
the non-air-drying polyunsaturated monomers. Pre-
ferably the mono unsaturated monomer in the admixture
is in the range o~ 10 to 30 weight percent.
THE PROCESS
Activation of the reaction between the
oxidative prepolymerizate and the non-air-drying
free-radical polymerizable comonomer can take place
without any outside agent being involved. Generally
such activation requires an elevated temperature of
at least 60C. and often about 80~C. before a reason-
able reaction rate can be achieved. It is found
however that the addition of minor amounts of a
metallic drier to the oxidative prepolymerizate,
- is extremely beneficial.
Where the oxidative prepolymerizate is
derived from the prepolymers such as those described
in USP 4,145,2~8 it is possible to add the prepolymer
itself. This is because the prepolymer is able to
take up oxygen from the air and form autogenously the
oxidative prepolymerizate. Such a reaction is however
usually too slow for efficient use of the present
~5 invention.
The addition of from 0.001 to 1.0% by weight
of a metallic drier markedly speeds up the copoly-
merization and enables rapid reaction to occur even
at room temperature or lower. The metallic driers
are salts and soluble complexes of transition elements
such as cobalt and manganese and the typical represen-
tatives include cobaltous acetate, citrate, acetyl-
acetonate and 2-ethyl hexanoate, and the corresponding
soluble manganous salts and complexes. Generally
salts are preferred to complexes since they appear to

-18- 06-12(1098)A
generate higher reaction rates. The metallic drier is
usually added in the form of a solution in a suitable
solvent that will ensure dispersion of drier through-
out the reaction mixture.
The proportions of the components can vary
very widely depending on the nature of the product to
be obtained and in general a range of weight propor-
tions of from 99:1 to 0.5:99.5 (oxidative prepoly-
merizate to non-air-curing ethylenically unsaturated
monomer composition) can be used. More usually this
ratio will be in the range 70:30 to 1:99 and preferably
40:60 to 5:95. As above indicated the proportions
selected depend largely on the intended use. It is
possible for example to use the oxidative prepoly-
merizate as a catalyst for polymerizing a monomer at
room temperature without use of traditional free-radical
generators. Such reactions are very useful since the
reacting monomers can be selected such that the
mixture with the oxidative prepolymerizate is a liquid
that is relatively stable at ambient temperatures but
which polymerizes within seconds on addition of a
metallic drier. This promises a wide field of
utility in adhesives,moldings and casting operations.
These uses are particularly favo~éd by the relative
insensitivity of the system to the presence of oxygen
which would normally inhibit free-radical reactions.
In such applications the weight percentage of
oxidative prepolymerizate would conveniently range
from 1 to 25~ of the combined monomer composition/
oxidative prepolymerizate weight. Other fields of
use require a larger percentage of the oxidative
prepolymerizate than is required for merely
initiating the monomer polymerization. As an example,
it is known from USP 4,145,248 and USP 4,289,864 that
certain hydrophilic oxidative prepolymerizates are

3~?)~
-19- 06-12(1098)A
exceptionally useful for improving the physical
properties of fibrous substrates. This end use is
particularly significant in improving the wet and dry
strengths of cellulosic substrates. The present
invention provides a method of improving the properties
obtained even further by incorporation of a suitable
non-air-drying monomer as a component of the mixture
applied to the substrate~ Since the oxidative pre-
polymerizate and the monomer actually copolymerize,
wide variation in the properties of the final product
may be achieved by varying the nature and proportions
of these components.
It will be noted that the use of the oxida-
tive prepolymerizate as an initiator results in no
by-products since the initiator is a polymer that is
incorporated into the final product. Thus it is
capable of acting as a genuine internal plasticizer
or other property modifier.
The use of an oxidative prepolymerizate as
an initiator is ideal for paints and adhesives in
view of its relative insensitivity to air and
temperature and because it leads to simultaneous
drying throughout the mass, not merely at the surface
initially with slower solidification of the body
material.
DESCRIPTION OF PREFERRED EMBODIMENTS
The invention is now described in more
detail in the context of the following Examples which
illustrate various compositions and processes
relating to the invention claimed.
EXAMPLE I
This Example describes the production of an
oxidative prepolymerizate catalyst composition useful
in the process of the invention.
A reaction vessel was charged with ethylene

63~9
-20- 06-12(1098)A
glycol which was reacted with allyl glycidyl ether in
a 1:10 mole ratio in the presence of boron trifluoride/
etherate catalyst. The allyl glycidyl ether was
added gradually over a period of several hours and
the liquid product obtained had a Gardner viscosity
at 25C. of F. The allyloxy equivalent was about 120.
Five Hundred grams of this product were
vacuum stripped, placed in a flask and air-sparged at
50C. ~or 54-hours. After this period the Gardner
viscosity had increased to Z-2. The resin was just
pourable and was clear and colorless.
The following procedure was used for deter-
mining the peroxide content. A 2 gram sample of the
resin was added to a flask and was dissolved in 50 ml
of a solvent mixture of acetic acid and chloroform in
the weight ratio of 35:65. Four lumps of dry ice,
each approximately 1 ccm in volume were added to the
solution which was swirled to allow dissolved oxygen
to be removed by entrainment in the subliming carbon
dioxide. One ml of a freshly prepared saturated
potassium iodide solution was added to the sample
solution, the flask was stoppered and the mixture was
stirred for 15 minutes. One hundred ml of deaerated
distilled water and approximately 0.2g. of an iodine
titration indicator, sold by Taylor Chemical Company
under the tradename Paragon were added and the mixture
was titrated with sodium thiosulfate to a colorless
end-point, permanent for one-minute. During the
titration the mixture was stirred vigorously under a
nitrogen blanket. The peroxide content calculated as
hydrogen peroxide was 0.89 mmoles per gram.
EXAMPLE 2
This Example illustrates the process of the
invention.
A glass tube was charged with 4.0g of

31~
-21- 06-12(1098)A
ethylene glycol dimethacrylate (containing about 50
to 100 ppm of hydroquinone as stabilizer) and O.~y of
the oxidative prepolymerizate catalyst of Example l.
The two miscible liquids were stirred for 30
seconds to effect homogeneity; then 0.0~5g of a 12%
cobaltous octoate solution in cyclohexane was added
with stirring.
Within a minute the contents had begun to
heat up, gel formed rapidly and within two minutes
the tube was too hot to handle.
The product was hard, clear, quite brittle,
insoluble in methanol, acetone, methyl ethyl ketone,
toluene and various cellosolves and carbitols.
The reaction was used successfully to make
castings and to adhere surfaces together. The
presence of air made no difference to the efficacy of
the reaction or the progress of the polymerization.
EXAMPLE 3
Example 2 was repeated with the difference
that in exchange for the oxidative prepolymerizate of
Example l there was substituted the precursor
prepolymer obtained by reaction of allyl glycidyl
~ether with ethylene glycol (Gardner viscosity at
25C of F). Thus the difference lay in the omission
of the air-bodying process that results in the pro-
duction of the oxidative prepolymerizate.
It is known from the teaching in ~SP 4,145,248
that such prepolymers gradually pick up air and are
oxidatively polymerized in situ in the same way but
3~ at a slower rate.
In confirmation of this expectation it was
observed that the yellow/purple color associated with
the cobaltous octoate catalyst slowly changed over 15
minutes to a khaki/green indicating oxidation state
change of the metal. No rapid exotherm could be
observed but after 70 minutes there was a slight
increase in viscosity and after 2 hours 10 minutes
` the contents had set to a hard crosslinked casting.

3~
- 22 -
EXAMPLE ~
This Example demonstrates that the molecular
` weight of the oxidative prepolymerizate is not a major
factor in determining -the course or result of the
reaction.
Example 1 was repeated with the difference
that air-sparging was discontinued after 72-hours
when the Gardner viscosity at 25C was R/S. The
peroxide content was 0.72 mmoles per gram.
This oxidative prepolymerizate was used in
a repeat of Example 2 with essentially identical
results.
EXAMPLE 5
This Example demonstrates the effectiveness
of another type of oxidative prepolymerizate in the
process of the invention.
Trimethylolpropane diallyl ether was oxida-
tively polymerized by sparging with air at 70C for
68.5 hours to a Gardner viscosity at 25C of Z-4. No
cobalt catalyst was used. The peroxide content was
0.37 mmoles per gram.
A homogeneous mixture was prepared by
stirring together 0.5g of the above oxidative
prepolymerizate and 5.0g of ethylene glycol dimeth-
acrylate. To this solution was added 0.015g of a
12~ solution in cyclohexane of cobaltous 2-ethyl-
hexanoate and the solution was quickly mixed.
In 270 seconds the mixture had gelled and
had formed a hard casting after about 400 secondsO
By comparison, when the oxidative prepoly-
merizate of Example 1 was used in the same reaction
the gel time was 25-seconds and the hard casting was
formed in 35-40 seconds. This difference probably
reflects the greater number of potential polymeriza-
tion sites in the latter oxidative prepolymerizate.

- 23 -
EXAMPLE 6
~ This Example illustrates the process of the
invention applied to various vinyl and allyl monomers.
A series of three(3) reaction mixtures was
prepared~ Each contained lg of ethylene glycol
dimethacrylate and 0.25g of the prepolymerizate of
Example 1 and the monomer indicated in Table 1
below. Each reaction was conducted at room tempera-
ture with nitrogen sparging until after the addition
of 0.02g of a 6~ solution of cobaltous naphthenate.
The times for each to gel and to set to a hard
casting were recorded.
TABLE 1
MONOMER REACTION TIMES
C,EL TIME HARD CASTING
_ _ _
Diallyl phthalate 2.25 min. 5.33 min.
Vinyl acetate 3.75 min. ¦ approx.15 min.
Triallyl Isocyanurate 1.17 min. ¦ 2.0 min.
EXAMPLE 7
This Example illustrates the importance of
ensuring that the catalyst is supplied in the
appropriate phase.
An emulsion was made of 4.0g of ethylene
glycol dimethacrylate, 4.3g of deionized water and
0.3g of the oxidative prepolymerizate of Example 4
(Gardner viscosity at 25C of R/S) by shaking the
mixture with approx 0.005g of an alkyl aryl
polyether-alcohol detergent. Four drops of a 5.0~
aqueous solution of cobaltous acetate tetrahydrate
were added with swirling of the container. The
container was then allowed to sit for 15 minutes
during which time no exotherm ~r viscosity rise was
observed.

3f~
- 2~ -
A 12~ solution of cobal-tous 2~ethyl
hexanoate ~0.012g) was then added with stirring and
after 30 seconds, during which the newly added
catalyst appeared to dissolve in the organic phase, a
rapid exothermic reaction was observed and a hard
casting was obtained. Water was converted to steam
which was then evolved from the mixture.
A comparison of this result with that of
Example ~ indicates that supply of the catalyst in an
aqueous phase is ineffective unless it can be
persuaded to enter the organic phase comprising the
monomer and the oxidative prepolymerizate.
This could take place for example if an
aqueous phase were to be gradually removed from an
emulsion either by evaporation or by absorption into
a substrate. This then indicates a valuable means of
delaying reaction until a desired condition is
reached.
EXAMPLE 8
This Example illustrates the retardant
effect of oxygen on the polymerization rate of the
process of the invention.
In each of the following runs the monomer
was a 10:1 by weight mixture of methyl methacrylate
and ethylene glycol dimethacrylate. The oxidative
prepolymerizate was that obtained in Example 1. The
gas indicated was sparged through the reaction mixture
for the duration of the reaction until the mixture
had gelled. All runs were performed at room tempera-
ture in screw capped glass tubes. The results are set
forth in ~able 2.

~2~ 3~
- 25 -
tJ~ . X X ~X
~. ~ O O ~ O O O
o~ ,1 a~ CU h u~ h
o ~ O,) ul U~ ~ h Q~
~ .C Q~ Q,
~-~1 o o (~1 ~ o 1
t`~ C ) E~ c~ ~ _ 1~
~D In . 0>~
a~ .,~ . tn . u~
E~ ~ ~ ~ ~ Q.
a)-,~ In ~O ~ O r~ ~ Q~ +
In 0~1 ~ .
I a)
~1 0 N ~1 ~1~1 r-l,~ Q) a) Q)
Q,--l ~
, o o o
o S~ ~ Z Z ~;
__ _
a~
U7
O ~ ~r ~r ~ ~r
~_ :
~ a
E~
a) ~
X
O O O O O
~:4
~ ~ a) ~ a) o
C~ U C)
:~ ~ ~ s
~ o - o - ~ - ~ ~ - ~ ~ -
u~ ~ L~ n ~ n a) u a) u~ a) u~
U~ r~ ~ r~ ~ r.~ N C~ N ~,
~1 ~ O ~10 r~l Id ~t (d ~1 (T~ ) O
O O O O O O O U~ ~ O
.. .. .. .. .. .. .. ~Q .
~ 00 oo 000 o 00 000 o~ I
C~ O--U-- O--~ _
~' ~ ~
a) a
.
~ U~ O O O
5~ ~ ~ ~ S~
h ~ S-l ~ h ~ ~1
. ~1 ~1 ~ 1 .,~ 1
U~ fl ~ ,'3Z ~ Z~:1
.
P~

3~
- 26 -
The above runs show clearly that although
oxygen is an inhibitor of free-radlcal polymerization
reactions, the oxidative prepolymerizate is able, in
effect, to remove it from the reaction when operating
in its oxidative polymerization mode and generate the
catalytic entities that permit the free~radical
copolymerization of the reaction mixture.
Run #7 shows clearly that even an active
conventional hydroperoxide catalyst is comparatively
ineffective in the presence of air to effectuate poly-
merization.
EXAMPLE 9
This Example investigates the effect of
temperature on a typical copolymerization reaction.
The results should be compared'with those from
Examples 2 to 13 which were all conducted at room
temperature.
In each of the following runs the oxidative
prepolymerizate was that from Example 1 and the
monomer was ethylene glycol dimethacrylate. The
catalyst was cobalt acetylacetonate charged at 0.20%
based on total reactant weight.
The weight ratio of monomer to oxidative
prepolymerizate was 95:5. The results are set forth
in Table 3.
TABLE 3
Run Polym. Conditions¦ Temperature Gel Hard Casting
l Air present- ¦ 70-75C 5-7 10 mins.
catalyst mins.
2 N2 sparged- 70-75C lO-l 60 sec.
catalyst sec.
3 N2 sparged-no 95-100C 13.5 approx.
_ catalyst l mins. 30 mins.
For purposes of comparison, the monomer
polymerization was initiated at 90-95C in the
presence of air using a) 5.0 wt. %, and b) 15.0 wt. %

~2~;3~
- 27 -
of benzoyl peroxide dissolved in warm monomer. In the
first case no polymer was formed even after two days
but the solution color had changed to a bright yellow.
In the second, rapid polymerization began after 6.0
minutes and a hard white casting was obtained after
7.0 minutes.
From the above it can be seen that the pre-
polymerizate, even acting without the cobalt salt, is
an effective polymerization initiator at elevated
temperatures. There is also clear evidence of the
retardant effect of oxygen on the polymerization
_ reaction.
EXAMPLE 10
This Example illustrates the use of the
copolymerizate of the reaction as an adhesive.
A mixture of 5.0g of ethylene glycol
dimethacrylate and 0.5g of the oxidative prepoly-
merizate of Example 1 was stirred till a homogeneous
solution was obtained. A 12% solution of cobaltous
2-ethylhexanoate was added, quickly mixed (along with
air), and the reaction mixture quickly poured in
roughly equal amounts onto flat, dry, clean surfaces
of two plywood blocks. The blocks were then clamped
together for l.0 minute. The whole reaction was con-
ducted at room temperature. While much of the curingprobably occurs in the first 6-8 hours under these
conditions, it is possible that full cure is not
re,ached for 1-2 days. The cured composite withstands
mechanical shock and twisting forces without
bond-rupture.
EXAMPLE ll
This Example illustrates the utility of an
oxidative prepolymerizate in -the formulation of an adhesive
composition.

3~3
-28-
A mixture of 2.5g of n-butyl acrylate, 2.5g of the
product known by the Trade Mark "Carbowax 200" dimethacrylate and
0.5g of the oxidative prepolymeriza~e based on trimethylol
propane diallyl ether (oxidatively polymerized as described in
Example 5), w~s stirred until homogeneous.
A 12% solution of cobaltons 2-ethyl hexanoate in
cyclohexane (0.112G) was added and quickly stirred into the
reaction mixture. This mixture was then applied to blocks of
plywood as described in Example. A firm strong bond was obtained
even at room temperature.
EXAMPLE 12
In this Example a number of catalysts were evaluated
for their activity in initiating polymerization of a mixture of
4.0y of methyl methacrylate; 0.4g of ethylene glycol
dimethacrylate and 0.5g of the oxidative prepolymerizate of
Example 1. All reactions were run in loosely-capped 2-dram vials
and were allowed to proceed to rigid castings.
In each case 0.010 to 0.012g of tas supplied) metallic
drier composition was added to the above mixture.
It was found that cobaltous and cobaltic salts (the
acetates, octanoates, 2-ethylhexanoates, naphthenates and
tallates) promote extremely fast polymeri~ations. These salts
are also known to promote rapid gelation of the oxidative
prepolymerizates alone.
On the other hand the corresponding largely covalent
acetylacetonates (chelates) are comparatively slow reacting
catalysts.
The abave Examples are for the purpose of illustration
only and are not intended to imply any necessary limitation on
the inherent scope of the invention. It will be appreciated that
many minor modifications to, or variations in, the formulations
and processes described above could be made without departing
from the essen-tial scope of the invention. It is intended that
all such modi~ications and variations should be embraced within
the purview of this invention.