ETHYLENICALLY UNSATURATED POLYMERIZABLE COMPOSITIONS

COMPOSITIONS POLYMERISABLES RENFERMANT UNE INSATURATION ETHYLENIQUE

English Abstract

ABSTRACT OF THE DISCLOSURE
There is disclosed a process for the polymerization of
a non-air-curing mono-ethylenically unsaturated free-radical
polymerizable monomer in which an oxidative prepolymerizate is
incorporated into the monomer. The prepolymerizate is an
oxidatively polymerizable compound in which there are 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 mono-ethylenically unsaturated free-radical-poly-
merizable monomer 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 activating the unsaturations
towards oxidative polymerization, to provide a concentration of
from about 1 to about 200 parts by weight of oxidative
prepolymerizate per mole of non-air-curing monomer, the
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, 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.
27

-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 in which the non-air-curing mono-ethylenically
unsaturated free-radical-polymerizable monomer is a (meth)-
acrylic ester containing from 4 to 14 carbon atoms; and
(B) activating the oxidative prepolymerizate to
copolymerize with the non-air-curing monomer.
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
concentration of oxidative prepolymerizate is in the range of 5
to 100 parts by weight per mole of the monomer.
28

5. The process according to claim 1 in which the
concentration of oxidative prepolymerizate is in the range of
about 10 to about 50 parts by weight per mole of the monomer.
6. 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.
7. The process according to claim 1 in which the
copolymerization takes place under an oxygen free atmosphere.
8. A process for the polymerization of a non-air-curing
mono-ethylenically-unsaturated free-radical-polymerizable
monomer which comprises:
(A) forming an oxidative prepolymerizate by bringing
into contact with air the reaction product of an alcohol and
allyl glycidyl ether comprising at least four (4) allyloxy
groups per hydroxy group of the alcohol.
(B) adding the non-air-curing free-radical-
polymerizable monomer to the oxidative prepolymerizate to
provide a concentration of oxidative prepolymerizate of 10 to
50 parts by weight per mole of non-air-curing monomer; and
(C) activating the oxidative prepolymerizate toward
free-radical copolymerization with the non-air-curing free-
radical polymerizable monomer by means of a cobalt drier salt.
29

9. The process according to claim 1 in which the
oxidatively polymerizable molecule comprises a structure
resulting from the oxidation of a prepolymer precursor having
the formula:
<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.
10. A copolymer produced by the process according to
claim 1, 2 or 3.
11. A copolymer produced by the process according to
Claim 4, 5 or 6.
12. A copolymer produced by the process according to
claim 7, 8 or 9.

13. 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
activating the unsaturations towards oxidative polymerization,
the oxidatively polymerizable compound being represented by the
structure:
<IMG>
where R1 is characterized as being a radical of molecular
weight less than about 2,000, 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;
31

(B) a non-air-curing mono-ethylenically unsaturated
free-radical-polymerizable monomer; wherein the concentration
of oxidative prepolymerizate is in the range of about 1 to
about 200 parts by weight per mole of non-air-curing monomer;
and wherein the non-air-curing mono-ethylenically unsaturated
free-radical-polymerizable monomer is a (meth)-acrylic ester
containing from 4 to 14 carbon atoms.
14. The composition of claim 13 wherein the oxidatively
polymerizable compound has a .beta. , .gamma.-unsaturation equivalent of
less than about 150 and is the reaction product of water or an
alcohol with allyl glycidyl ether.
15. The composition of claim 13 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>
16. The composition of claim 13 wherein the .beta. ,.gamma. -un-
saturation equivalent is less than about 150.
17. The composition of claim 13 wherein the .beta. ,.gamma. -un-
saturation equivalent is in the range of about 115 to about
120.
18. The composition of claim 13 wherein the peroxide
content of the oxidative prepolymerizate is in the range of
about 0.005 to about 2.0 millimoles per gram.
32

19. The composition of claim 13 wherein the peroxide
content of the oxidative prepolymerizate is in the range of
about 0.2 to about 1.0 millimoles per gram.
20. The composition of claim 13 wherein the concentration
of oxidative prepolymerizate is in the range of 5 to 100 parts
by weight per mole of non-air-curing monomer.
21. The composition of claim 13 in which up to 1% by
weight of a metallic drier salt is added to the composition to
initiate free-radical-polymerization.
22. The composition of claim 13 in which the
concentration of oxidative prepolymerizate is in the range of
10 to 50 parts by weight per mole of non-air-curing monomer.
23. The composition of claim 13 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
33

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.
24. The copolymer product obtained by curing the
composition of claim 13, 14 or 15.
25. The copolymer product obtained by curing the
composition of claim 16, 17 or 18.
26. The copolymer product obtained by curing the
composition of claim 19, 20 or 21.
27. The copolymer product obtained by curing the
composition of claim 22 or 23.
34

Description

S3~1
-1- 06-12~1099)A
ETHYLENICALLY UNSATURATED POLYMERIZABLE COMPOSITIONS
_
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
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 conventiQnal 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 atmosphPre.
"~

~6~
Conventional initiators have an activation
temperature below which they are not very active so that free-
radical polymerization reacti.ons are conventionally carried out
at elevated temperatures. Since such reactions are usually
also exothermix 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 structurai 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 INVE~TIO~
The present invention provides a process for the
polym2rization o~ a non-air-curable mono-ethylenically-
unsaturated, free-radical-polymerizable monomer which
comprises:
A process for the polymerization of a non-air-curing
mono-ethylenically unsaturated free-radical-polymerizable
monomer which comprises:
A. Incorporating in the monomer an oxidative
prepolymerizate of an oxidatively polymerizable compound having
a structure comprising at least two unsaturations which are
.j
~^ . ;.

6~
-2a-
each ~ ,y to oxygen or sulfur activating the unsaturations
towards oxidative polymerization, to provide a concentration of
from about l to abou-t 200 parts by weight of oxidative
prepolymerizate per mole of non-air-curing monomer, the
oxidatively polymerizable compound being represented by the
structure:
l ~ )m R2~ n
where Rl 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 Rl is n, and is in the
range of l to lO, where R2 is selected from the group
consisting of hydrogen and Cl and C10 organic radicals, where E
is a moiety containing a radical having an activated olefinic
unsaturation ~ ,y to the activating group and is present in
sufficient 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
in which the non-air-curing mono-ethylenically unsaturated
free-radical-polymerizable monomer is a (meth)-acrylic ester
containing from 4 to 14 carbon atoms; and
s. activating the oxidative prepolymerizate to
copolymerize with the non-air-curing monomer.
There is also provided, in a further embodiment to
this invention, a process for the polymerization of a non-air-
curing mono-ethylenically-unsaturated free-radical-
polymerizable monomer which comprises:
A. forming an oxidative prepolymerizate by bringing
into contact with air the reaction product of an
alcohol and allyl glycidyl ether comprising at least four (4)

63~
-2b-
allyloxy groups per hydroxy group of the alcohol.
B. adding the non-air-curing free-radical-
polymerizable monomer to the oxidative prepolymerizate to
provide a concentration of oxidative prepolymerizate of 10 to
50 parts by weight per mole of non-air-curing monomer; and
S C. activating the oxidative prepolymerizate toward
free-radical copolymerization with the non-air-curing free-
radical polymerizable monomer by means of a cobalt drier salt.
There is also provided, in accordance with this
invention, a composition comprising:
A. an oxidative prepolymerizate of an oxidatively
polymerizable compound having a structure comprising at least
two unsaturations which are each ~ , ~ to oxygen or sulfur
activating the unsaturations towards oxidative polymerization,
the oxidatively polymerizahle compound being represented by the
structure:
Rl~ (E)m ~ R2] n
where R1 is characterized as being a radical of molecular
weight less than about 2,000, 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 tunctionality 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 ~o C 10 organic radicals,
where E is a moiety containing a radical having an activated
olefinic unsaturation ~ , y to the activating group and is
~ .,J~

~L2:~L63~
-3-
present in sufficient amount to provide a ~ unsaturation
equivalent of less than about 250, where m is the average
number of E moieties in the n segments of the s-tructure and
where the product m and n is in the range of about ~ to about
60;
B. a non-air-curing mono-ethylenically unsaturated
free-radical-polymerizable monomer; wherein the concentration
of oxidative prepolymerizate is in the range of about 1 to
about 200 parts by weight per mole of non-air-curing monomer;
and wherein the non-air-curing mono-ethylenically unsaturated
free-radical-polymerizable monomer is a (meth)-acrylic ester
containing from 4 to 14 carbon atoms.
In still further embodiments, there is also provided
a copolymer product obtained by carrying out the above
described process.
OXIDATIVELY POLYMERIZABLE COMPOUND
The process of oxidative polymerization is most
widely known in the context of drying oils and alkyd based
paints, (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.
Readiness 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 oxid-

~Z~i3~
-4- 06-12(1099)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 30C. 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 VSP 4,145,248. Such polymers
(which may be termed "prepolymers" to accord with
the use of the term "oxidative prepolymerizates" to
describe the result of air-bodying such polymers are
represented by tne following structure:
~ (E)m~R2~n
.,~ .

~L2~6~
--5--
where Rl is a radical of molecular weight less than
about 2000 obtained by removal of active hyd.rogen from
an hydrogen compound selected from -the group consisting
oE water, alcohols, thiols, carboxylic acids, carboxy]ic
amides, and amines. 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 isthe functionality of Rl and is in the range oE 1 to 10,
the produc-t of n and m (the number of E groups per
segment) being in the range of about 4 to about 60. R2
is selected from the group consisting of hydrogen and C
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 activated olefinic unsaturation ~,y to
an activating oxygen or sulfur atom and is present in
sufficient amount to provide a ~,y unsaturation
equivalent of less than about 250. The ~,y unsaturation
equivalent conforms to the accepted definition of the
term equivalent, i.e., it is the weight containing one
unit of unsaturation. Preferably the ~, r unsaturation
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.
Advantageously the ~,y unsaturation is supplied by an
allyl group provided by an E group represented by the
structure
CH2 ~ ICH - 0
2 CH2 CH CH2 -
The "prepolymers" of a preferred group have a
backbone comprising at least one segment with the

~$3~
-6- 06-12(1099)A
formula:
{ CH ~ (I)
I
A - (E)m H
where A is a moiety terminating in the residue of an
active hydrogen-containing group selected from the
group eonsisting of alcoholic hydroxyl, thiol, amide,
earboxylic acid and secondary amine with an aetive
ilydrogen removed, E is a moiety containing a radieal
having an activated olefinie unsaturation, ~ , ~ to
the aetivating oxygen or sulfur atom, n is the number
of adjaeent (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 4. The prepolymers can
have a plurality of adjacent segments of the above
formula and by "adjacent" is meant that they are
directly eonnected through a carbon-carbon bond or are
indirectly connected through a
~ C-C ~ or ~ O-C
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
elose 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
provide a bond site, increases the structural strength
of the erosslinks that form both inter- and intramole-

-7- 06-12(1099)A
cularly during drying and/or aging.
The double bonds are activated, by which is
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 dxying 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 words, the polymer does not destro~ 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 dynesor less (Water has a surface tension of 72 dynes).
The prepolymers can be formed by the
reaction of a compound having an activated double
bond and epoxy group with a molecule having a
plurality of active hydrogen-containing groups

3~
-8- 06-12(1099)A
selected from alcoholic hydroxyl, thiol, amide,
carboxylic acid and secondary amine groups. ~here it
is also desirable that the polymer 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 ~ , zr
activated unsaturation equivalent is at most about
250 and is preferably less than about 150 and is even
more preferably in the range of about 115 to about 120.
Alternatively, the prepolymer can be formed
~rom 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
generation of adjacent allyloxy groups pendant from
the prepolymer backbone that can form a suitable
block of unsaturation conferring the desired
air-drying characteristics on the prepolymer.
Yet another method by which the prepolymer
may ~e prepared is by the Lewis acid promoted poly-

~639~
-9- 06-12(1099)A
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 baekbone
molecule and preferably from 4 to 10 or even 20 epoxy
molecules are reacted per active hydrogen-containing
group. As a simple example reacting 1 mole of glyeol
with 8 moles of allyl glycidyl ether produces a pre-
polymer having the average structure
CH2 ~CH2
O O
~CH2CH O ~ H ~ CH2CH ~ H
Cl H2 ICH2
O-CH -CH=CH O-CH -CH=CH
- thus providing two blocks of four adjacent aeti-
vated allylie groups-
assuming of course, uniform addition at both sides.In this co~ ound moiety [E]m is
t 21 ~
CF12
b-CH2--CH=CH2
3n and has the double bond ~ to the activating
oxygen group.
The other type of structure is obtained for
example, when a backbone molecule which comprises at
least four adjaeent active hydrogen-eontaining groups

-10- 06-12(1099)A
is reacted with an unsaturated epoxy compound as
described above or alternatively, using Williamson's
ether synthesis, with allyl chloride to produce a
block of pendant allylic groups. In the latter case
the ether oxygen 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 of allyl chloride with polyglycidol to
produce a prepolymer having a structure with repeating
units of the formula
~CH--CH2-0
CH2
o
CH
1 2
CH=CH2 r
Here the moiety E is t 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/-
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 thiols, and carboxylic acids such as
acetic acid, fumaric acid, maleic acid, malonic acid
and phthalic acid. Also, compounds containing a
mixture of radicals can be used such as hydroxy
acids, which are compounds containing the carboxy
and hydroxy radicals, hydroxy amides, hydroxy
ethers, hydroxy esters, and the like. However, poly-
hydric alcohols having from 2 to 6 carbon atoms are

~2~63~1D
~ 06-12(1099)A
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\
R4-CH-CH- [M] -CH=CH-R5
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 ~5 are each hydrogen or Cl to C4 alkyl groups.
It is important that the activating group
does 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 also readily available at relatively
low cost is allyl glycidyl ether.
An alternative preferred type of o~idative
prepolymerizate is obtained by the process described
in U.S. Application Serial No. 150,789, filed May lg,
1980 now U.S. Patent 4,289,864, 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 ~ , zr to a nucleophilic group
capable of activating the unsaturation towards oxi-
dative polymerization and selected from the group
consisting of -O-, -S- and -C-O-
I

~2~63~
-12- 06-12(1099)A
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 useful to
have the unsaturation that is ~ , a~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~CH3)=CH2,
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 functional 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
also to be relatively cheap. An excellent monomer
starting material is 1,2 diallyloxy-ethane. Other

~2~6~
-13- 06-12(1099)A
possible monomers include 1, ~-diallyloxy-2~butene,
1,3-diallyloxy-2-propanol, diallyl sulfide, ~ vinyl-
oxyethyl allyl ether, diallyl succinate, diallyl
maleate, 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 will
conventionally 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 polymerization 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 oxygen is absorbed, that is, in effect,
gas 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
cobaltous acetate, cobaltous octoate, manganous acetate,
and other salts or soluble chelates and complexes of

3 2~3~
-14- 06-12(1099~A
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 prepolymerization.
The passage of oxygen is continued until,
as a result of the oxidative polymerization, the
desired "built" viscosity for the oxidative prepoly-
meri~.ate 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
~/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 pressure of the oxygen in the reaction
mixture.

~2~63~0 - -
-15- 06-12(1099)A
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 mono-ethylenically-un-
saturated, free-radical-polymerizable monomer or
mixture of monomers. The nature of the molecule is
not critical so long as it is activated towards free-
radical polymerization via the double bond by free-
radical moieties present in the oxidative prepoly-
merizate as a result of the oxidative polymeriza~
tion process.
Suitable monomers include vinylaromatic
monomers such as styrene, chlorostyrene, d -methyl
styrene and vinyl toluene; vinyl derivatives such as
vinyl ethers, vinyl esters, vinylamides, vinylimides
and vinyl halides; acrylic derivatives such as (meth3-
acrylonitrile, (meth)acrylamide, (meth)acrylic acid,
and (meth)acrylic esters containing from 4 to 14 carbon

6~
-16- 06-12(1099)A
atoms and mono- and di-esters of maleic and fumaric acid
containïng from 5 to 20 carbon atoms. The preferred
monomers are (meth~-acrylic esters containing from 4
to 14 carbon atoms.
Mixtures of such monomers can be used to
achieve any desired balance of properties in the
final interpolymers. Generally however it is preferable
to select the monomers such that all can be brought
together at room temperature to react. It is
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 or that a gaseous
reactant be contacted with the others in a multiphase
reaction.
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 6~C. and often about 80C. 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.
~here the oxidative prepolymerizate is
derived from prepolymers such as those described in
USP 4,145,248 it is possible to add the prepolymer
itself. This is because the prepolymer is able to
take up oxygen from the air and form au~ogenously the
oxidative prepolymerizate. Such a reaction is however
usually too slow for efficient use of the present

3~ .
-17- 06-12(1099)A
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
generate higher reaction rate. 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 varyvery widely depending on the nature of the ~roduct to
be obtained and in general a range of from about 1 to
about 200 parts by weight of the oxidative prepolymer-
izate per mole of the non-air-curing ethylenically
unsaturated monomer can be used. More usually this
range will be from about 5 to about 100 parts by
weight of the oxidative prepolymerizate per mole of
the monomer and more preferably from about 10 to
about 50 parts by weight of the oxidative prepolymer-
izate per mole of the monomer. As above indicated
the proportions selected depend largely on the
intended use. It is possible for example to use the
oxidative prepolymerizate as a catalyst for polymer-
izing a monomer at room temperature without use oftraditional free-radical generators. Such reactions
are very useful since the reacting monomers can be
selected such that the mixture with the oxidative
polymerizate is a liquid that is relatively stable at
at ambient temperatures but which polymerizes within

3~
-18- 06-12(1099)A
seconds on addition of a meta:Llic drier. This promises
a wide field of utility in adhesives, moldings and
casting operations. These uses are particularly
favored by the relative insensitivity of the system
to the presence of oxygen which would normally inhibit
free-radical reactions. In such an application the
weight percentage of oxidative prepolymerizate would
conveniently range from l 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
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
monomer as a component of the mixture applied to the
substrate. Since the oxidative prepolymerizate and
the monomer actually copolymerize, the possibilities
of varying the properties of the final product by
varying the nature and proportions of the components
are endless.
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

63~
-19- 06-12(1099)A
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
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. for 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-
n~ining 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:~5. 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

~Z~63~3
-20-
solution, the ~lask was stoppered and the mixture was stirred for
15 minutes. One hundred ml o~ deaerated distilled water and
approximately 0.2 g. o~ 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 moles per gram.
EXAMPLE 2
This Example illustrates the process of the invention.
A glass tube was charged with 4.0g of methyl
methacrylate (containing about 50 to 100 ppm of hydroquinone as
stabilizer) and 0.4g of the oxidative prepolymerizate catalyst of
Example 1. The two mixcible liquids were stirred for 30 seconds
to effect homogeneity; then 0.025g of a 12% cobaltous octoate
solution in cyclohexane was added with stirring.
A srnall quantity of the mixture obtained was spread as
a moderately thick film on a stainless steel strip of metal and
allowed to cure. The liquid became tacky after 15-20 minutes
while remaining optically very clear. No signs o~ cracking,
chipping or brittleness were observed after a three hour cure
period.
The film had good adhesion to the metal surface and a
hardness, as measured by ASTM Method D 3363-4, of HB/F after
three (3) hours and better than 4H after a day. For purposes of
comparison the oxidative prepolymerizate
alone, activated by the cobalt catalyst was cast on a

~63~
~21-
stainless steel strip. Even after six (6) hours from the point
at which a film formed over the surface of the liquid, it had
only a 2B hardness, (measured by the above technique), and showed
low adhesion to the stainless steel plate and poor toughness. It
tended to break into crumbs when rubbed between the fingers.
It would appear therefore that a genuine
copolymerization has occurred to produce a new copolymer.
EXAMPLE 3
This Example illustrates the ineffectiveness of the
cobaltous octoate catalyst per se or a benzoyl peroxide catalyst
acting alone in the initiation of polymerization of inhibited
methyl methacrylate.
Two samples of 49 of methyl methacrylate, each
containing 25-50 ppm of hydroquinone as inhibitor, were prepared.
Both samples were treated with 0.025g of a 12% solution
in cyclohexane of cobaltous octoate and the second sample
additionally received O.lg of benzoyl peroxide. Both were left
at room temperature in the presence of air for four (4) hours.
Neither sho~ed any evidence of reaction by increased viscosity.
Each sample was then treated with Q.4g of the oxidative
prepolymerizate of Example 1 stirred in at room temperature until
a homogeneous liquid was obtained. Both produced a hard, tough,
clear, solvent insolu~le resin.
EXAMPLE 4
This Example demonstrates the relative stability
of methyl methacrylate monomer in the presence of the
oxidative prepolymerizate when allowed to stand at room
.," . ~
,. ,,;

35~0
-22-
temperature in the presence of air but absence of the cobaltous
salt.
A loosely capped vial containing 3g of methyl
methacrylate and lg of the oxidative prepolymerizate of Example 1
~as stirred until the solution was homogeneous and left at room
temperature. No change in viscosity was observed after 24-days.
However within 30-minutes of the addition of 0.012g of
12% cobaltous octoate the contents had polymerized to a hard
~ough casting.
EXAMPLE 5
In this Example a number of catalysts were evaluated
for their activity in initiating polymerization of a mixture of
~.0g of methyl methacrylate; 0.4g of ethylene glycol
dimethacrylate and 0.5g of the oxidative prepolymerizate of
Example l. 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 mi~ture.
It was found that cobaltous and cobaltic salts (the
acetates, octanoates, 2-ethylhexanoates, naphthenates and
tallates) promote extremely fast polyrnerizations. These salts
are also known to promote rapid gelat:lon of the oxidative
prepolymerizates alone.
On the other hand the corresponding largely covalent
acetylacetonates (chelates) are comparatively slow reacting
catalysts.
EXAMPLE 6
This Example illustrates the effectiveness of the
process of the invention with vinylaromatic monomers such as
styrene,

3~
-~3-
A mixture was prepared of 4.0g of inhibited styrene
monomer, (commercial styrene conventionally contains an inhibitor
to prevent autogenous or premature reaction), and 0.4g of the
oxidative prepolymerizate of Example 1. The mixture was
thoroughly mixed and nitrogen-sparged for 15 minutes before the
introduction of 0.0125g of a 12% solution in cyclohexane of
cobaltous octanoate.
The mixture gelled after 45 minutes and set to a hard
brittle casting after 90 minutes.
EXAMPLE__7
This Example illustrates the process of the invention
applied to a vinyl monomer.
A reaction mixture was prepared containing lg of
ethylene glycol dimethacrylate and 0.25g of the preplymerizate of
Example 1 and vinyl acetate. The reaction mixture was sparged
with nitrogen at room temperature until after the addition of
0.02g of a 6% solution of cobaltous naphthenate. The mixture
gelled in 3.75 rninutes and set to a hard casting in approximately
15 minutes.
EXAMPLE ~
This Example illistrates 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
~eight 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
rnixture for the duration of the reaction until the mixture had
gelled. All runs were per~ormed at room temperature in screw
capped glass tubes. The results are set forth in Table 1.
, ~
,~,,..~,,

-24-
The above runs show clearly that although oxygen is an
inhibitor of free-radical 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 i5 comparatively ineffective in the
presence of air to effectuate polymerization.

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EXAMPLE 9
This Example illustrates the utility of another type
of oxidative prepolymerizate in the process of this invention
in the formula-tion of an adhesive composition.
Trimethylolpropane diallyl ether was oxidatively
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 peroxlde content was 0.37 moles per gram.
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 prepolymerizate based on trimethylol
propane diallyl ether was stirred until homogeneous.
A 12% solution of cobaltous 2-ethyl hexanoate in
cyclohexane (0.012g) was added and quickly stirred into the
reaction mixture at room temperature. This mixture was then
applied in roughly equal amounts onto flat, dry, clean surfaces
of two polywood blocks. The blocks were then clamped together
for one minute. While much of the curing probably occurs in
the first 6-8 hours under these conditions, it is possible that
full cure is not reached for 1-2 days. The cured composite
withstands mechanical shock and twisting forces without bond
rupture.
The above 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 descibed above could be made
without departing from the essential scope of the invention.
t is intended that all such modifications and variations
should be embraced within the purview of this invention.