IE61528B1 - Partially polymerized bis (allylic carbonate) monomer having high allylic utilization. - Google Patents

Description

Bis(allylic carbonate) monomers are frequently free-radically polymerised to yield hard polymers. Many of these monomers yield rigid polymers which exhibit high transparency to visible light when undyed, substantial hardness» and refractive indices that are sufficient for many., if not most» ophthalmic applications. For these reasons„ such monomers find utility as precursors for optical lenses (especially ophthalmic lenses)» lens blanks, sunglass lenses» face shields, filters» flat or curved sheets» coatings» and other optical elements.

One problem associated with the polymerization of bis(allylic carbonate) monomers is the relatively high shrinkage of the material which occurs during the course of polymerization. For example» shrinkage during the homopolymerization of diethylene glycol bis(allyl carbonate) monomer is approximately 12.5 percent. Such large degrees of shrinkage are especially troublesome where polymerizable bis(allylic carbonate) monomer compositions are polymerized in substantially enclosed molds typical of many casting operations. Although it is not desired to bound by any theory, it is believed that much, if not most» of the shrinkage can be attributed to the conversion of allylic groups to polymer segments.

As used herein» the term shrinkage is equal to (Dp~Dm)/Dp where Dp is the density of the final thermoset polymerizate at 25°C and Dm is the density of the casting composition at 25°C. The term percent shrinkage is equal to shrinkage multiplied by one hundred. -2One manner of reducing the degree of shrinkage during the casting operation has been to form a liquid prepolymer from bis(allylic carbonate) monomer, charge the mold with the pre polymer (and added initiator's when necessary) s &nd polymerize the prepolymer to form a hard polymerizate... Inasmuch as a portion of the allylic groups have been converted prior to charging the mold, the shrinkage occurring during polymerization in the mold is reduced. The prepolymerization technique has therefore provided some success in dealing with the shrinkage problem.

The major obstacle to further reductions of shrinkage via the prepolymerization route has been gellation. Early prepolymerization techniques generally resulted in gellation when only a small proportion of the total available allyl groups had been utilized. For examples in forming prepolymers from diethylene glycol bis(allyl carbonate) monomers gellation was typically observed after about 12 percent of the allylic groups had been utilized. Further work led to further improvements and prepolymers of diethylene glycol bis(allyl carbonate) having allylic utilizations of up to about 17 percent could be achieved prior to gellation; see for example, JP-A-51[1976]9188.

A major advance in the art of forming poly(alkylic carbonate)-functional prepolymers has been described In detail in Irish Application No. 2872/84.

Xn accordance with a method of Application No. 2872/84 poly(allylic carbonate)-functional monomer is dissolved in a solvent in which the polymer produced from such monomer is 3θ also soluble. Preferably^. the initiator used to conduct the polymerization is also soluble in the solvent. The resulting liquid solution comprising poly(allylic carbonate)-functional monomer j, solvent , and preferably initiator is then partially polymerized by heating the liquid solution to polymerization temperatures. The polymerization reaction is allowed to -3» continue until more than 12 percent allylic utilisation is attained. The degree of allylic utilisation can be controlled by regulating the amount o£ initiator added to the liquid solution, the temperature at which the partial polymerisation is performed, and the ratio of solvent to poly(allylic carbonate)functional monomer. Generally, the greater the amount of initiator used, the higher is the allylic utilisation. The higher the temperature of polymerization, the lower is the degree of allylic utilisation. At constant temperature and employing a given amount of initiator, the higher the ratio of solvent to monomer, the lower Is the degree of allylic utilisation.

Ordinarily however, if at constant temperature the ratio of solvent to monomer is increased and the amount of initiator employed is also sufficiently increased, the reaction can be driven to a higher degree of allylic utilisation without the formation of gel then in a system containing less solvent.

In a preferred embodiment of Irish Application No. 2872/84, from about 0.1 to about 1.5 weight percent of initiator, basis the amount of monomer, from about 0.5 to 5 millilitres of solvent per gram of monomer, and polymerisation temperatures of from 28°C to about 100°C are used. The degree of allylic utilisation can be monitored by nuclear magnetic resonance (NMR) and Infrared (IR) spectroscopy. The solvent In the resulting composition can be removed by known techniques, e.g., by evaporation or distillation, leaving a viscous liquid comprising a solution of poly(allylic carbonate)functional prepolymer in poly(allvlic carbonate)functional monomer. This solution Is typically a syrupy liquid having a kinematic viscosity (measured with a capillary viscometer) of from at least about 100 to about 100,000 mm2/s (centistokes), typically from * about 1,000 to 40,000 mm /s (centistokes), more typically from about 500 to 2,000 mm2/s (centistokes), measured at 25°C., and a bulk density at 25°C of from about 1.17 to about 1.23 grams per cubic centimetre. The solution is further characterised by -L·having more than 12 percent allylic utilization, preferably from st least 15 to 50 percent allylic utilization ,, and. in a particularly preferred exemplification., from about 20 to 50 percent allylic utilizations, as determined by infrared spectroscopy or nuclear magnetic resonance spectroscopy» Irish Application No. 2872/84 indicates that the process therein described is applicable to poly(allylic carbonate)functional monomers having an (allylic carbonate) functionality of from 2 to 55 preferably 2. Both aliphatic 10 diol bis(allylic carbonate) monomers and bisphenol bis(allylic carbonate) monomers are discussed.

The most salient point in respect of Irish Application No. 2872/84 Is that techniques are taught which permit the formation of poly(allylic carbonate)-functional prepolymers having up to 50 percent allylic utilization without gellation. This represents a major advance in the poly(allylic carbonate)-functional prepolymer art.

Contrary to what the prior art shows with respect to allylic utilization;, It has now been discovered that substantially gel-free prepolymer having an allylic utilization of more than 50 percent may be achieved by paying particular attention to the types of bis(allylic carbonate) monomers used in its preparation. The substantial lack of gellation is indeed unexpected when it is considered that more than half of the allylic groups in a substantially bis(allylic carbonate)“functional system have been reacted.

Accordingly,, one embodiment of the invention is a polymerizable, liquid, substantially gel-free, partially polymerized monomer composition vherein (a) the monomer which has been partially polymerized is bis(allylic carbonate) monomer of at least one 4,4'-alkylidene) bis[phenol]s bis(allylic carbonate) monomer of at least one 4,4'-[phenylenebis(alkylidene)jbistphenol), or a mixture thereof, and (b) the allylic utilization of the composition is at least 55 percent. -5Often the allylic utilisation is at least 60 percent. Allylic utilizations in the range of from 55 to 80 percent» especially from 60 to 80 percent are preferred.

The bis(allylic carbonate) monomer of at lease one 4»4'-(alkylidene)bis(phenol] and/or at least one 4»4’-[phenylene bis(alkyIIdene)bis[phenol] which is 'partially polymerized may be unsubstituted» substituted with one or more minor substituents» or some may be unsubstituted and some may be substituted. When mpre than one substituent is employed» they may be che same or different» or some may be the same while being different from one or more others. Examples of substituents which may be employed include halo» lower alkyl» and lower alkoxy. Halo is most commonly fluoro» chloro or bromo» chloro and bromo are the preferred halo groups. The lower alkyl generally contains from 1 to 4 carbon atoms; methyl and ethyl are the preferred lower alkyl groups. The lower alkoxy generally contains from about 1 to about 4 carbon atoms. Methoxy -and ethoxy are the preferred alkoxy groups. -6The numbers, identities, end locations of th® substituents, when used, should be such as not to preclude formation of the prepolymer composition of the invention.

Each alkylidene group independently contains at least one carbon atom and may be branched or unbranched» In many cases each alkylidene independently contains from 1 to 5 carbon atoms. Examples of suitable alkylidene groups include methylene, ethvlidena, propylidene, 1-methylethylίdene (viz.. Isopropylidene) , butylidene, X-methyIpropylidene, 2-methyIpropylidene, and 2-ethylpropylidene» 1-Methylethylidene is preferred.

The central phenylene group of the bis(allylic carbonate) monomer of 4,4’“[phenylenebis(alkylidene)]bis[phenol] may be 1,2-phenylene, 1,3-phenylene, or 1,4“phenylene. The preferred phenylene group is 1,3-phenylene.

The monomers themselves are either well known or can be prepared by procedures well known in the art (see, for example, US-A-2,370,567; 2,455,652; 2,455,653 and 2,587,437). In one method, the appropriate allylic alcohol is reacted with phosgene to form the corresponding allylic chloroformate which is then reacted with the desired 4,4s-(alkylidene)bis[phenol] and/or 4,4!-[phenylenebis(alkylidene)]bis[phenol]. In a second method the 4,4’-(alkylidene)hls[phenol] and/or 4,4phenylenebis(alkylidene)]bis-7[phenol] is reacted with phosgene to form bischloroformate which is then reacted with the appropriate allylic alcohol. In a third method, the 4,4s-(alkylidene)bis(phenol] and/or 4,4’-[pheaylenebis(alkylidene)]bis[phenol], the appropriate allylic alcohol, and phosgene are mixed together aad reacted. In all these reactions the proportions of reactants are approximately stoichiometric, except that phosgene may be used ia substantial excess if desired, and in the second method, an excess of the allylic alcohol may be employed. Tha temperatures of the chloroforaata-forming reactions are preferably below about 100°C in order to minimise the formation of undesirable by-products. Ordinarily the temperature of the chloroformate-forming reaction is ia the range of from 0°C to 20°C. The carbonate-forming reaction is usually conducted at about the same temperatures, although higher temperatures may be employed. Suitable acid acceptors, e.g., pyridine, tertiary amine, alkali metal hydroxide, or alkaline earth metal hydroxide may be employed when desired. The reactions are usually liquid phase reactions. Preferably they are conducted in the absence of extrinsic solvent, although extrinsic solvent may ba used when desirable or when necessary to solubilize one or more of the reactants. Examples of suitable extrinsic solvents that may be used include benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, o-chlorotoluene, acetone, methylene chloride, chloroform, perchloroethylene, trichloroethylene, and carbon tetrachloride. The pressures at which the reactions are conducted may vary widely, but usually they are at about ambient pressure or a little higher depending upon the pressure drop through the equipment.

It will be recognized that one bisphenolic compound described above or a mixture of such bisphenolic compounds may be used in forming the bis(allylic carbonate) monomer. When a mixture is employed, each may be a member of the class 4,4’-(alkylidene)bis[phenol], each may be a member of the class 494?-[phenylenebis(alkylidene)bis[phenol]s or one or more may be from one class and one or more from the other class.

The bisphenolic compounds which can be used in preparing the bis(allylic carbonate) monomer may each be represented by the formula -8HO-A-OH where A is represented by the formula (X) (ix) is independently hydrogen or a minor substituent as discussed above, and che value of n is 0 or 1.

When the value of n is X, it is preferred that A ba represented by the formula (III) or by the formula R R R R (IV) where Qs R, and n are as discussed in respect of Formula II.

Ic is preferred that the value of n be 09 in which case A is represented by the formula (V) where Q and R are as discussed in respect of Formula II.

Examples of hisphenolic compounds which can be used include -94 g4’-(methylene)bis[phenolj 4,45 ~ ( X-methylethylidene)bis [phenol ] 4»4 *-(1-methylethylidene)bis[2 » δ-dichlorophanol] 4,4' - (l“methylethylidene)bis [ 2,, δ-dibrosnophenol] 4,4'-(X-methylpropylidene)bis[phenol] 4,,4e“[lg4“phenyXenebis(I“asthyle£hylIdene) ]bis[phenol] , and 4 a 45 ~[18 3-phenyleneb is (1-methylethylidena)]b is[phenol].

The monomeric compositions prepared by the processes described above chiefly comprise one or more bis(allylic carbonate)-functional mono10 meric compounds represented by the formula Ro Ro I I CH =CCH OCO~A~OCOCH0C=CH„ 2 Ί a 2 2 (VI) in which A is as discussed above in respect of Formula I and each Ro is independently hydrogen or methyl. In most cases both of the Ro groups are the same, preferably both are hydrogen.

Because of the nature of the processes by which the monomeric compositions are prepared» the monomeric compositions can contain minor amounts of related species. In the case of monomeric compounds represented by Formula VI, individual related species can be represented by the formula Ro i CH =CCH„OCO2 2 η or the formula HOor the formula HO-A-OCO|l A-OCO0 A-OCOII Ro I —ch7c=ch2 (VII) _ii Ro I -A-OCOCH.C=CH„ II 2 2 (VIII) -A-OH (IX) wherein each R is as discussed above with respect to Formula VI, each A is independently as discussed with respect to Formula Is i is a whole 10number from 2 to 5, is a whole number from 0 to , and k is & whole number from 0 to 5.

The reaction mixture may be purified so as to contain essentially no related species, but this is rarely done. Although the reaction mixture may contain only a single related species, it usually contains a mixture of different related species. Typically all of the related species taken together constitute from 0.5 to weight percent of the reaction mixture on an extrinsic solvent-free basis.

Similarly, one compound represented by Formula VI or a group of such compounds may be Isolated from the reaction mixture, but this also is rarely done.

The partially polymerised monomer composition is prepared by partially polymerising the bis(allylic carbonate) monomer of 4,4 ’ -alkylidene)bis[phenol] and/or the bis(allylic carbonate) monomer of 4,4'-[phenylenebis(alkylidene)jbis[phenol] to utilise more than half of the allylic groups without Incurring significant gellation. By terms such as significantly gel-free and without Incurring significant gellation is meant that the composition contains less than 5 percent by weight, based on the original bis(allylic carbonate) monomer, of gel. In many cases the composition contains less than 2 percent gel by weight, based on the original bis(allylic carbonate) monomer. Preferably no gel is present In the composition.

The polymerisable, liquid, substantially gel-free, partially polymerised monomer compositions of the invention may be conveniently prepared by solution polymerisation.

The bis(allylic carbonate) monomer is dissolved In solvent in which the partially polymerised monomer is also soluble. Initiator, which Is preferably also soluble In the solvent, is included In the reaction mixture. The resulting -11liquid solution comprising bis(allylic carbonate) monomer, solvent, aad preferably initiator is then partially polymerised by heating th® reaction mixture to polymerisation temperatures» The polymerisation is allowed to continue until more than 50 percent allylic utilisation is attained, that is, until more than 50 percent of the ethvlenic unsaturation initially provided by the monomer have been consumed.

The degree of allylic utilisation can be controlled by regulating tbe amount of initiator present in the liquid solution, the temperature at which the partial polymerisation is performed, and the ratio of solvent to bis(allylic carbonate) monomer. Generally, the greater the amount of initiator used, the higher is the allylic utilization. The higher the temperature of polymerisation, the lower is the degree of allylic utilization. At constant temperature and employing a given amount of initiator, the higher the ratio of solvent to monomer, the 'lower is the degree of allylic utilisation. Ordinarily however, if at constant temperature the ratio of solvent to monomer is increased and the amount of initiator employed is also sufficiently increased, the reaction can be driven to a higher degree of allylic utilisation without the formation of gel than In a system containing less solvent.

Upon reaching the desired degree of allylic utilization, polymerisation Is terminated. This may be accomplished by reducing the temperature of the reaction mixture to values where the polymerization reaction for all practical purposes ceases, by the addition of an inhibitor which destroys tha free radicals necessary for further polymerization, or both.

After the polymerization reaction has been terminated, the solvent is preferably removed. This can be accomplished by known techniques, as for example, by evaporation, stripping, or distillation, leaving a solution of poly(allylic carbonate)-functional polymer in bis(allylic carbonate) monomer. This solution is essentially free of the solvent used during the polymerisation process. The essentially solvent-free solution is typically a syrupy liquid having a kinematic 2 viscosity at 25°C in the range of from 100 to 100,000 mm /s (centistokes). In many cases the kinematic viscosity is in the range of ο from 1000 to 90,000 mm /s (centistokes) at 25°C. Frequently tha -12klnematle viscosity at 25eC ie is th© tang© of fro® about 5000 to 2 about 30,000 wi/s (centistok&s). The density of the essentially solvent-free solution ia ordinarily in th© range -¾. The substantially solvent-free solution is further characterized by having an allylic utilisation of wore than 50 percent as determined by infrared spectroscopy or nuclear magnetic resonance spectroscopy.

Organic solvents useful ia carrying out th© solution polymerization are those which are non-reactive chemically with the monomer aad resulting polymer, have a boiling temperature substantially below the monomer, i.e., a higher vapor pressure, so as co be easily separated from the monomer by distillation, aad which serve as a solvent, for the bis(allylic carbonate monomer (and preferably also for th© initiator)) and the resulting liquid aromatic-containing poly(allyl carbonate)-functional polymer, useful solvents include the halogenated, (e.g.. chlorinated). to hydrocarbon solvents, i.e., methyl chloride, methylene chloride, ethyl chloride, ethylene dlchloride, 1,1,2-trichloro-l, 2,2,-trifluoroethane, and mixtures thereof. Methylene chloride is preferred because of its high vapor pressure, low boiling point, ease of separation, and relatively low toxicity.

The amount of solvent used in the partial polymerization process should be sufficient co solubilize all of ths monomer and co maintain all of the resulting polymer in solution. This is generally from 0.5 co 5 milliliters of solvent per gram of monomer. Greacer amouncs of solvent can be used without deleterious efface. Lesser amounts of solvent often result in che formation of an insoluble, infusible, Intractable gel when allylic utilization above 50 percent are employed.

When, as is preferred, polymerization of the polymerizable composition is initiated by thermally generated free radicals, th® polymerisable formulation contains initiator. Tne thermal initiators which may be used in the present invention may be widely varied, but in general they are thermally decomposable to produce radical pairs.

One or both members of che radical pair are available co initiate additional polymerization of ethylenically unsaturated groups in the -13well-known manner. The initiators useful in carrying out the solution polymerisation of the bis(allylic carbonate) monomer are free radical initiators, e.g., organic peroxides and azo catalystsThe preferred free radical initiators are organic peroxy compounds» such as peroxyesters» diacyl peroxides peroxydicarbonsces and mixtures of such perosty compounds.

Tee; preferred thermal initiators are peroxy initiators.

There are many different peroxy initiators which can be used.

Examples of such peroxy Iniciacors includes peroxydicarbonace esters such, as di-a-propyl peroxydicarbonace, diisopropyl peroxydicarbonace, di-n-butyl peroxydicarbonace, di-sec-butyl peroxydicarbonace, diisobueyl peroxydicarbonace, di(2~echylhexyl) peroxydicarbonate, diacetyl peroxydicarbonace,, dicyclobexyl peroxydicarbonace, di(A-cert-butylcyclohexyl) peroxydicarbonace* and isopropyl see-butyl peroxydicarbonace; monoperoxycarboaaces such as certlary-butylperoxy isopropyl carbonate and tertiary-aiaylperoxy isopropyl carbonate;, diacecyl peroxides such as diacetyl peroxide» dlbensoyl peroxide, dllauroyl peroxide, and dilsobutyryl peroxide; and peroxyesters such as tertiary-butyl perplval&te, tertiary-butyl paroctoace and tertiary-butyl pemeodecanoace.

Only one initiator or a plurality of initiators any be used as desired.

The concentration of initiator useful for the partial polymerisation should be sufficient so result ia She desired degree of allylic utilization at the conditions used, and generally can vary fro© 0.1 to 3 «eight percent initiator» basis weight of monomer. Greater amounts of initiator may result ia either residual initiator is tfee product or formation of aa infusible, insoluble, intractable gel. The solution polymerisation is generally carried out at temperatures of from 28^C. to 100‘C., for from 1 So -1424 hours. The ciae and tenperacure depend on che initiator and the eo&eessracios thereof, and eh® solvent:aonomer ratio used™ In nose eases the polyaerizable composition is pourable. Such pourable? polymerisable compositions ar® especially useful for casting leases,» lens blanks, and other shapes hy pouring che composition into suitable molds ass then polymerising the composition to form a solid, thermoset polymer of the desired shape.

Although che partially polymerized monomer composition may itself be polymerized to tors hard polymerizates? more frequently tha 0 .composition ia formulated with one or more ocher materials prior co such polyssrizacion.

It is preferred that che formalacioa be. essentially free ©f t the solvent used ia she polymerization process ia which the partially polymerized monomer composition was formed» 15 Accordingly, in another embodiment of the invention such a polymerizable, liquid composition further comprises one or more other materials. When other materials are used, the amount of initiator present in the polymerizable composition may be widely varied.

Ordinarily the weight ratio of the initiator to all ethylenically unsaturated material present in the formulation is in the range of from 0.5:100 to 7:100. In many cases the weight ratio is in the range of from -15= 1:100 to 5:100. A weight ratio in the range of from l.SslOO to 2.53100 is preferred.

It will be recognised by those skilled in the art that the most preferred weight ratios of initiator will depend upon the nature of the initiator used (its active oxygen content) as well as the nature and ratios of the variously ethylenieally unsaturated materials present in the formulation.

Other ethylenieally unsaturated compounds» as for example, acrylates» methacrylates, ethacrylates» haloacrylates» vinyl-functional compounds, other allylic-functional compounds, other alkyl or halo substituted allylic-functional compounds, and/or esters of ethylenieally unsaturated dicarboxylic acids may be present in the polymerisable formulation. When the other ethylenieally unsaturated compounds are present» they usually constitute from 1 to 50 percent by weight of the polymerizable formulation. In many cases they constitute from 2 to 25 percent by weight of the polymerisable formulation. From 5 to 20 percent is preferred.

Other materials which may be present in the polymerizable formulation include mold release agents and dyes.

The listing of other materials discussed above is by no means exhaustive. These and other ingredients may be employed in their customary amounts for their customary purposes so long as they do not preclude the formation of solid, crosslinked polymer.

In most cases the polymerizable formulation comprises from 50 to 99.5 percent by weight of the partially polymerized monomer composition. Often the polymerizable formulation comprises from 70 to 98 percent by weight of the partially polymerized monomer composition. From 80 to 95 percent hy weight is preferred. It is also preferred that the partially polymerized monomer composition employed in the polymerizable formulation be substantially free of the solvent in which the monomer composition was formed.

In the polymerizable formulation, the ethylenieally unsaturated materials should be in the form of a solution in the proportions used. Insoluble materials, such as for example pigments, while not preferred, may also be present. -16The polymerisable formulations of the invention are usually prepared by admixing the various ingredients. Mixing may ba accompanied with heating when it is desirable to hasten dissolution of any of the ingredients. However, if initiator is present during heating, the temperature should ordinarily be maintained below that at which polymerisation is initiated. It is preferred to employ heating in the absence of initiator, to cool the resulting solution, and then to introduce the initiator aad other ingredients which enter th® solution without undue difficulty.

The formulations of the invention can be free-radically polymerized by known conventional techniques for polymerizing (allylic carbonate)-containing formulations to form solid, crosslinked polymer.

Preferably, polymerization Is accomplished hy heating the polymerisable formulation containing free-radical initiator to elevated temperatures. Typically polymerization is conducted at temperatures in the range of from 28°C to 100eC. In many cases post curing, that is, heating beyond the time thought necessary to substantially fully polymerize the formulation is employed. The post cure is often carried out above 100°C, but below the temperatures at which thermal degredation provides undesirable yellowness, e.g., about 125°C, and preferably for a time sufficient to attain either substantially constant or maximum Barcol hardness. For example, when the cure cycle shown ia Table 2 below is followed, the polymerizate may be maintained at 100° for an additional 1 to 4 hours or more. Although not wishing to be bound by any theory, the additional 1 to 4 hours of post cure is believed to decompose, primarily by initiation and chain termination, from 83 percent to 99.9 percent of the peroxide initiator remaining unreacted at the end of the normal 18 hour cure cycle. Moreover, the additional 1 to 4 hours of cure often increases the Barcol Hardness by 5 to 8 units.

In most cases, the polymerisable is conformed to the shape of the final solid polymerised article below polymerization. For example, the formulation can be poured onto a flat surface and heated, whereby to effect polymerization and form a flat sheet or coating. According to a still further exemplification, the polymerizable -17formulation is placed in molds, as for instance glass molds, and the molds heated to effect polymerization, thereby forming shaped articles such as lens blanks or lenses. In one particularly preferred embodiment,, the formulation is poured into a lens mold and polymerised therein to produce an ophthalmic lens. In another particularly preferred embodiments the formulation is poured into a lens blank mold and polymerized therein to produce a lens blank.

A wide variety of cure cycles, that is, time-temperature sequences, may be used during polymerization. Ordinarily the cure cycle employed is based upon a consideration of several factors including the size of the casting, the identity of the initiator, and the reactivity of the ethylenically unsaturated material. For casting ophthalmic lenses or lens blanks, several standard cure cycles have been developed and these are shown in Tables 1-4. These standard cure cycles are useful ia forming polymerizates according to the present invention, but they are, however, only exemplary, and others may be used.

Table 1 Standard Cure Cycle for Diisopropy! Peroxydicarbonate Cumulative Hours Oven Temperature, °C 0 44 2 46 4 48 6 50 8 54 10 58 12 64 14 69 16 85 17 105 (End of Cycle.) /· -18Table 2 Standard Eighteen Hour Cure Cycle for Benzoyl Peroxide Cumulative Hours Oven Temperature. 0 63 2 63 4 65 δ 67 S 77 10 80 12 85 14 88 16 92 18 100 Table 3 Standard Five Hour Cure Cycle for Benzoyl Peroxide 100 (End of Cycle.) Cumulative Hours Oven Temperature, aC 0 90 1 90 2 90 3 90 3.5 96 4 103 4.5 109 5 115 (End of Cycle.) -19Table 4 Standard Curs Cycle for Tertlary-Butylperoxy Isopropyl Carbonate Cumulative Hours Oven Temperature, °C 0 90 2 91 4 92 6 93 8 95 10 97 12 100 14 103 16 110 17 120 (End of Cycle.) Usually thermoset polymers have 15-second Barcol hardnesses of at least zero. In many cases the Barcol hardness is at least about 15s and preferably It is at least about 25. As used herein, 15-second Barcol hardness is determined in accordance with ASTM Test Method D 2583-81 using a Barcol Impressor and taking scale readings 15 seconds after the impressor point has penetrated the specimen.

The invention is further described in conjunction with the following Examples which are to be considered illustrative rather than limitings and in which all parts are parts by weight and all percentages are percentages by weight unless otherwise specified. t -20EXAMPLE I A solution was formed by admixing 150 grams of the bis(allyl carbonate) monomer of 4?&’-(l~methylethylidene)bIs[phanol], 450 milliliters of methylene chloride, and 3 grams of diisopropyl peroxydicarbonate. The solution was poured into a glass bottle. The bottle was purged vith argon for 3 minutes, sealed, and placed in a 70°C water bath where it remained for 18 hours. The bottle was then removed from the water bath and opened. An inhibited solution was formed by admixing 0.0015 gram of hydroquinone monomethyl ether dissolved in methylene chloride with the material in the bottle. The methylene chloride solvent was removed under vacuum In a rotary evaporator from two portions of the inhibited solution to produce two product samples of polymerizable, liquid, partially polymerized monomer composition which were gel-free and substantially free of methylene chloride. Infrared spectrographic analysis of the original bis(allyl carbonate) monomer and the two product samples showed the allylic utilizations of the two product samples to be 65.52 percent and 64.12 percent, respectively.

EXAMPLE II A solution was formed by admixing 50 grams of the bis(allyl carbonate) monomer of 4,4’-[1,3-phenylenebis(1-methylethylidene)]bis~ [phenol], 150 milliliters of methylene chloride, and 0.75 grams of diisopropyl peroxydicarbonate. The solution was poured into a glass bottle. The bottle was purged with argon for 3 minutes, sealed, and placed in a 70°C water bath where it remained for 18 hours. The bottle was then removed from the water bath and opened. An inhibited solution was formed by admixing 0.0005 gram of hydroquinone monomethyl ether dissolved in methylene chloride with the material in the bottle. The methylene chloride solvent was removed under vacuum In a rotary evaporator from two portions of the inhibited solution to produce two product samples of polymerizable, liquid, partially polymerized monomer composition which were gel-free and substantially free of methylene chloride. Infrared spectrographic analysis of the original bis(allyl carbonate) monomer and the two product samples showed the allylic utilizations of the two product samples to be 57.54 percent and 59.23 percent, respectively. -21EXAMPLE III A solution was formed by admixing 50 grams of the bis(allyl carbonate) monomer of 4,4?“[l,3~phenylenabi3(l-mathylethylidene)Ibis[phenol], 150 milliliters of methylene chloride, and 1.25 grams of diisopropyl peroxydicarbonate. The solution was poured into a glass hottie. The bottle was purged with argon for 3 minutes, sealed, and placed In a 70°C water bath where it remained overnight. The bottle was then removed from the water bath and opened. An inhibited solution was formed by admixing 0.0005 gram of hydroquinone monomethyl ether with the material in the hottie. The methylene chloride solvent was removed under vacuum in a rotary evaporator from two portions of the inhibited solution to produce two product samples of polymerizable, liquid, partially polymerized monomer composition which were gel-free and substantially free of methylene chloride. Infrared spectrographic analysis of the original bis(allyl carbonate) monomer and the two product samples showed the allylic utilizations of the two product samples to be 79.36 percent and 78»64 percent, respectively.

Claims (11)

1. A polymerizable, liquid, substantially gel-free, polymer composition containing less than 5 percent by weight, based on the original bis(allylic carbonate) mono5 aer, of gel comprising a partially polymerized bononer wherein said ©oraomer is bis(allylic carbonate) monomer of at least one 4,4'-{alkylidene)bis[pheRol], bis(allylic carbonate) ©onomer of at least one 4,4*-[phenylenebis(alkylidene)]bis[pheno1], or a mixture thereof, 1 o characterized in t h a t at least 55 percent of the allylic groups have been reacted.

2. - The composition of claim 1 wherein at least 60 percent of the allylic groups have been reacted.

3. » The composition of claim 1 wherein in fro© 55 to 80 percent of the allylic groups reacted. the range of have been

4. The composition fro© 60 to 80 percent reacted. sf of claim 1 wherein in th® allylic groups the range of have been

5. The composition of claim 1 wherein the monomer which has been partially polymerized is bis(al1y1ic carbonate) aonoser of one or more hisphenolic compounds, each represented by the foraula -23-HO-A-OK Ir which each Q is alkylidene independently containing from 1 to 5 -carbon atoms, each R ia independently hydrogen, halo, lower alkyl containing' from 1 to 4 carbon atoms, methoxy, or ethoxy, and the value of n, is 0 or 1.

6. The composition of claim 5 wherein each Q is 1-methylethylidene.

7. The composition of claim 5 wherein said his(a11ylic carbonate) monomer is bis(allyl carbonate) monomer.

8. The composition of claim 1 wherein the monomer which has been partially polymerized is bis(allyl carbonate) monomer of at least’ one bisphenolic compound selected from 4,4’-(1-methy1ethy1idene)bis[phenol], 4,4 1 -(1-methylethylidene)bis[2,6-dichlorophenol], 4,4 1 (l-methy1ethylidene)his[2,6-dihromopheno1], and 4,4 8 -(1,3-phenyl enebis(1-methylethylidene)]bis[phenol]

9. The composition of claim 8 wherein the monomer which has been partially polymerized is bis(ally! carbonate) monomer of 4,4’-(l-methylethylidene)bis10. The composition of claw 8 wherein the monomer which has been partially polymerized is bisfallyl carbonate) monomer of 4,4'-[l,3-phenylanebis(l-methylethylidene)]bis[phenol] . -2411,, The composition of any of claims 1 to 10 wherein the cosaoosi ti on cosaorisas at least one thermal initiator* 12.-, The composition of claim ll wherein said thers initiator is a peroxy initiator* 5 13» The composition of any of claims 1 to 12 wherein the composition is essentially solvent-free. 14» The composition of any of claims 1 to 13 wherein other ethylenieally unsaturated compounds selected froi acrylates» methacrylates» ethacrylates,, haloacrylates ,

10. Vinyl-functional. compounds» other allylic-functional compounds, other alkyl or halo substituted allylicfunctional compounds» and/or esters cf ethylenieally unsaturated dicarboxylic acids are present.

11. 15. A polymerizable, liquid, substantially gel-free 15 polymer composition, substantially as hereinbefore described F. R. KELLY & CO., AGENTS FOR THE APPLICANTS.