CA1216389A - Ethylenically unsaturated polymerizable compositions - Google Patents

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 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.

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~

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 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~

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 C~2 O

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:

(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.

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 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~

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.

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.

~ 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.

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.

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.

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.

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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~
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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~

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
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~ 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~

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.

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.

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~

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.

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 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.

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.

Claims (35)

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:

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 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 :

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 .

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.

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:

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:
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:
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

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 .

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.

30. The composition of claim 18 wherein the oxidatively polymerizable compound is represented by the structure:

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.