Cyclohexenic additives for producing polycarbonate polymers of high refractive index and low yellowness

The yellowness of polymerizates formed form polymerizable compositions containing bisphenol bis(allylic carbonate)-functional material is reduced by inclusion of one or more cyclohexenic compounds in the polymerizable compositions.

BACKGROUND OF THE INVENTION 
Aliphatic polyol poly(allyl carbonate) monomer, most notably diethylene 
glycol bis(allyl carbonate), has for many years been used in producing 
ophthalmic lenses. Such lenses exhibit low yellowness when undyed, 
substantial hardness, and refractive indices that are sufficient for many, 
if not most, ophthalmic applications. There is a need, however, for 
polymeric lenses of higher refractive indices than those ordinarily 
provided by polymers of aliphatic polyol poly(allyl carbonate). 
This need centers around the desire to reduce the volume of material 
required to produce a lens of given size, minimum thickness, and optical 
correction, which volumetric reduction can be achieved through use of 
polymeric materials having higher refractive indices. It is known that 
polymers formed from bisphenol bis(allylic carbonate)-functional monomer 
often have higher refractive indices than those formed from aliphatic 
polyol poly(allyl carbonate) monomer, but the former polymers usually 
exhibit excessive yellowness to be widely acceptable for ophthalmic 
purposes. 
The present invention is directed to polymerizates having high refractive 
index and low yellowness, and to polymerizable, homogeneous compositions 
which may be free radically polymerized to produce such polymerizates. 
It has been discovered that the yellowness of polymerizates formed from 
polymerizable compositions containing bisphenol bis(allylic 
carbonate)-functional material may be reduced if one or more cyclohexenic 
compounds are included in the polymerizable compositions. 
Accordingly, one embodiment of the invention is polymerizable, homogeneous 
composition comprising (a) bisphenol bis(allylic carbonate)functional 
material comprising (i) bisphenol bis(allylic carbonate)-functional 
monomer, (ii) prepolymer of such monomer, or (iii) a mixture thereof; and 
(b) a yellowness reducing amount of cyclohexenic material which is a 
cyclohexenic compound or a mixture of such cyclohexenic compounds. 
As used herein and in the claims, "a yellowness reducing amount of 
cyclohexenic material" means an amount of cyclohexenic material in the 
polymerizable composition which will cause the yellowness of a 
polymerizate formed from the polymerizable composition to be lower than 
that of a polymerizate formed under similar conditions from a similar 
polymerizable composition not containing any cyclohexenic material. 
Another embodiment of the invention is polymerizate produced by 
free-radically polymerizing the polymerizable, homogeneous composition of 
the first embodiment, which polymerizate has a 15-second Barcol hardness 
of at least zero, a yellowness index at a sample thickness of about 3.3 
millimeters of about 4 or lower, and a refractive index at 20.degree. C. 
and a wavelength of 589.3 nanometers of at least about 1.52. 
In most cases the polymerizable, homogeneous compositions of the invention 
are pourable. The term "pourable" as used herein and in the accompanying 
claims means the viscosity of the composition is sufficiently low that it 
can be poured into molds commonly used in casting ophthalmic lenses and 
lens blanks. The temperature of reference is usually ambient temperature, 
but in some cases slightly elevated temperatures are employed to reduce 
the viscosity and facilitate pouring. In those instances where the 
composition contains free-radical initiator, the temperature should 
ordinarily be below that at which polymerization is initiated. Ordinarily 
the viscosity of the material is at least as low as about 6000 centipoises 
at 25.degree. C. In many cases the viscosity is at least as low as about 
2000 centipoises at 25.degree. C. Often the viscosity is at least as low 
as about 500 centipoises at 25.degree. C. It is preferred that the 
viscosity be at least as low as about 100 centipoises at 25.degree. C. 
The bisphenol bis(allylic carbonate)-functional monomer can be prepared by 
procedures well known in the art. In one method, the appropriate allyl 
alcohol is reacted with phosgene to form the corresponding allyl 
chloroformate which is then reacted with the desired bisphenol. In another 
method, the bisphenol is reacted with phosgene to form bischloroformate of 
the bisphenol which is then reacted with the appropriate allyl alcohol. In 
a third method, the bisphenol, the appropriate allyl alcohol, and phosgene 
are mixed together and reacted. In all of these reactions the proportions 
of reactants are approximately stoichiometric, except that phosgene may be 
used in substantial excess if desired. The temperatures of the 
chloroformate-forming reactions are preferably below about 100.degree. C. 
in order to minimize the formation of undesirable by-products. Ordinarily 
the temperature of the chloroformate-forming reaction is in the range of 
from about 0.degree. C. to about 20.degree. 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, a tertiary amine, an alkali metal hydroxide, or an alkaline 
earth metal hydroxide may be employed when desired. See, for example, U.S. 
Pat. Nos. 2,455,652; 2,455,653; and 2,587,437 the disclosures of which 
are, in their entireties, incorporated herein by reference. 
Ordinarily the bisphenol bis(allylic carbonate)-functional monomer 
comprises a bisphenol bis(allylic carbonate)-functional monomeric compound 
containing at least two phenylene groups separated by oxy, sulfonyl, thio, 
alkanediyl, or alkylidene; or a mixture of such compounds. 
Preferably, the bisphenol bis(allylic carbonate)-functional material 
comprises a bis(allylic carbonate)-functional monomeric compound 
containing at least two phenylene groups separated by oxy, sulfonyl, thio, 
alkanediyl, or alkylidene; or a mixture of such compounds. 
A subclass of monomeric compound which is of particular usefulness is 
represented by the formula 
##STR1## 
wherein (a) each R of the monomeric compound is independently hydrogen, 
halo, alkyl, or alkoxy, (b) each Q of the monomeric compound is 
independently oxy, sulfonyl, thio, alkanediyl, or alkylidene, (c) R.sub.1 
and R.sub.2 are each independently hydrogen or methyl, and (d) the value 
of n is an integer in the range of from 0 to about 3. 
In most cases the various groups represented by R are the same or some are 
different from others. When an R is halogen, it is most commonly chloro or 
bromo. When an R is alkyl, it usually contains from 1 to about 4 carbon 
atoms; methyl is preferred. When an R is alkoxy, it usually contains from 
1 to about 4 carbon atoms; methoxy is preferred. It is especially 
preferred that each R be hydrogen. 
Similarly, when n is a positive integer, the various groups represented by 
Q may be the same or they may differ. When a Q is alkanediyl, it 
ordinarily contains from 2 to about 4 carbon atoms; ethanediyl is 
preferred. When a Q is alkylidene, it usually contains from 1 to about 5 
carbon atoms; methylethylidene, viz., isopropylidene, is preferred. 
R.sub.1 and R.sub.2 may be different, but ordinarily they are the same. It 
is preferred that R.sub.1 and R.sub.2 are both hydrogen. 
For any particular compound, n is an integer in the range of from 0 to 
about 3. In most cases n is either 0 or 1. Preferably, the value of n is 
zero. While the value of n is an integer for an individual compound, it 
may be a whole or fractional number in the range of from 0 to about 3 when 
Formula I is used to represent mixtures of compounds falling therein. 
The preferred monomeric compounds are those represented by the formula 
##STR2## 
wherein (a) each X of the monomeric compound is independently hydrogen, 
chloro, or bromo, (b) Q is oxy, sulfonyl, thio, alkanediyl, or alkylidene, 
and (c) R.sub.1 and R.sub.2 are each independently hydrogen or methyl. The 
above discussion in respect of Q, R.sub.1, and R.sub.2 is applicable to 
Formula II. Some the the groups represented by X may be different from the 
others, but preferably all of the groups represented by X are the same. 
Examples of monomeric compounds that may be used in the invention include 
the bis(allyl carbonate) and the bis(methallyl carbonate) of bisphenols 
such as 4,4'-(1-methylethylidene)bis(phenol), 
4,4'-(1-methylethylidene)bis(2,6-dibromophenol), 
4,4'-(1-methylethylidene)bis(2,6-dichlorophenol), 
4,4'-(1-methylpropylidene)bis(phenol), 4,4'-(methylene)bis(phenol), 
2,2'-(methylene)bis(phenol), 4,4'-(sulfonyl)bis(phenol), 
4,4'(thio)bis(phenol), 4,4'-(oxy)bis(phenol), 4,4'-(oxy)bis(chlorophenol), 
4,4'-(oxy)bis(dimethylphenol), 
4,4'-[1,4-phenylenebis(1-methylethylidene)]bis(phenol), 
4,4'-[1,3-phenylenebis(1-methylethylidene)]bis(phenol), 
3,3'-[1,4-phenylenebis(oxy)]bis(phenol), 
4,4'-[1,4-phenylenebis(oxy)]bis(phenol), 
4,4'-[[2,5-bis(1,1-dimethylethyl)-1,4-phenylene]bis(oxy)]-bis[2,6-bis 
1,1-dimethylethyl)phenol], and 
4,4'-[1,4-phenylenebis(sulfonyl)]bis(phenol). 
The preferred monomeric compound is the bis(allyl carbonate) of 
4,4'-(1-methylethylidene)bis(phenol), which is commonly known as bisphenol 
A bis(allyl carbonate). 
A wide variety of cyclohexenic compounds may be used in the practice of 
this invention. Ordinarily the cyclohexenic material comprises at least 
one cyclohexenic compound represented by the formula 
##STR3## 
in which (a) each Y is independently alkyl containing from 1 to about 4 
carbon atoms, (b) Z is hydroxyl, 2-oxoethyl, hydroxyalkyl containing from 
1 to about 3 carbon atoms, alkoxycarbonyl containing from 2 to about 5 
carbon atoms, or R.sub.3 C(O)OR.sub.4 - in which R.sub.3 is alkyl 
containing from 1 to about 4 carbon atoms and R.sub.4 is alkanediyl 
containing from 2 to about 4 carbon atoms or alkylidene containing from 1 
to about 5 carbon atoms, (c) y is an integer in the range of from 0 to 
about 3, (d) z is 0 or 1, (e) w is 0 or 1, and (f) the sum of z and w is 0 
or 1. 
Methyl is the preferred alkyl group used for Y. The groups represented by Y 
may be the same or they may differ. 
When Z is hydroxyalkyl, it is usually hydroxymethyl, 2-hydroxyethyl, or 
1-hydroxy-1-methylethyl. When Z is alkoxycarbonyl, it usually contains 2 
or 3 carbon atoms. Methoxycarbonyl is preferred. R.sub.3 is most often 
methyl, ethyl or propyl. When R.sub.4 is alkanediyl, it may be straight or 
branched; ethanediyl is preferred. When R.sub.4 is alkylidene it is 
usually methylene or 1-methylethylidene. Preferably y is 0 or 1. Similarly 
it is preferred that z be 0 or 1. It is also preferred that w be zero. 
Examples of cyclohexenic compounds that may be used in the invention 
include cyclohexene, .alpha.-terpineol, terpinen-4-ol, .alpha.-terpinyl 
acetate, .alpha.-terpinyl propionate, .alpha.-terpinyl butyrate, 
1-methyl-1-cyclohexene, 3-methyl-1-cyclohexene, 4-methyl-1-cyclohexene, 
methyl 1-cyclohexene-1-carboxylate, 3-methyl-2-cyclohexen-1-ol, 
3-methyl-2-cyclohexen-1one, 4-isopropyl-2-cyclohexen-1-one, 
3,5-dimethyl-2-cyclohexen-1-one, 4,4-dimethyl-2-cyclohexen-1-one, 
isophorone, 2,6,6-trimethyl-1-cyclohexene-1-acetaldehyde, and 
3,5,5-trimethyl-2-cyclohexen-1-ol. The preferred cyclohexenic compounds 
are cyclohexene, .alpha.-terpinyl acetate, .alpha.-terpinyl propionate, 
and .alpha.-terpinyl butyrate. The especially preferred cyclohexenic 
material is cyclohexene, .alpha.-terpinyl acetate, or a mixture thereof. 
The bisphenol poly(allylic carbonate)-functional prepolymer which is useful 
in the practice of the present invention is prepared by partially 
polymerizing bisphenol bis(allylic carbonate)-functional monomer to 
utilize a fraction of the allylic groups without incurring significant 
gellation. The preferred bisphenol poly(allylic carbonate)-functional 
prepolymers are those prepared in accordance with the procedures described 
in detail in abandoned Application Ser. No. 549,850, filed Nov. 9, 1983 
and in abandoned Application Ser. No. 690,411, filed Jan. 10, 1985, the 
entire disclosures of which are incorporated herein by reference. 
In accordance with a method of Application Ser. No. 549,850 and application 
Ser. No. 690,411 bisphenol bis(allylic carbonate)-functional monomer is 
dissolved in a solvent in which the polymer produced from such monomer is 
also soluble. Preferably, the initiator used to conduct the polymerization 
is also soluble in the solvent. The resulting liquid solution comprising 
bisphenol bis(allylic carbonate)-functional monomer, solvent, and 
preferably initiator is then partially polymerized, e.g., by heating the 
liquid solution to polymerization temperatures. The polymerization 
reaction is allowed to continue until more than 12 percent allylic 
utilization is attained, i.e., until more than 12 percent of the 
unsaturated carbon - carbon linkages in the monomer are consumed. The 
degree of allylic utilization can be controlled by regulating the amount 
of initiator added to the liquid solution, the temperature at which the 
partial polymerization is performed, and the ratio of solvent to bisphenol 
bis(allylic carbonate)-functional monomer. Generally, the greater the 
amount of initiator used, the higher is the allylic utilization. The 
higher the temperature of polymerization, 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 utilization. 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 utilization without the formation of 
gel than in a system containing less solvent. 
In a preferred embodiment of Application Ser. No. 549,850 and Application 
Ser. No. 690,411, from about 0.1 to about 1.5 weight percent of initiator, 
basis the amount of monomer, from about 0.5 to 5 milliliters of solvent 
per gram of monomer, and polymerization temperatures of from 28.degree. C. 
to about 100.degree. C. are used. The degree of allylic utilization 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 bisphenol poly(allylic 
carbonate)-functional prepolymer in bisphenol bis(allylic 
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 centistokes to about 100,000 centistokes, 
typically from about 1000 to 40,000 centistokes, more typically from about 
500 to 2,000 centistokes, measured at 25.degree. C., and a bulk density at 
25.degree. C. of from about 1.1 to about 1.23 grams per cubic centimeter. 
The solution is further characterized by having more than 12 percent 
allylic utilization, preferably from at least 15 to 50 percent allylic 
utilization, and, in a particularly preferred exemplification, from about 
20 to 50 percent allylic utilization, as determined by infrared 
spectroscopy (IR) or nuclear magnetic resonance spectroscopy (NMR). 
Organic solvents useful in carrying out the solution polymerization are 
those which are non-reactive chemically with the monomer and resulting 
polymer, have a boiling temperature substantially below the monomer, i.e., 
a higher vapor pressure, so as to be easily separated from the monomer by 
distillation, and which serve as a solvent for the bisphenol bis(allylic 
carbonate)-functional monomer and the resulting bisphenol poly(allylic 
carbonate)-functional prepolymer (and preferably also the initiator). 
Useful solvents include the halogenated, e.g., chlorinated, C.sub.1 
-C.sub.2 hydrocarbon solvents, i.e., methyl chloride, methylene chloride, 
ethyl chloride, ethylene dichloride, 
1,1,2-trichloro-1,2,2-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 to solubilize all of the monomer and to maintain all of the 
resulting prepolymer in solution. This is generally from about 0.5 to 5 
milliliters of solvent per gram of monomer. Greater amounts of solvent can 
be used without deleterious effect. Lesser amounts of solvent often result 
in the formation of an insoluble, infusible, intractable gel when allylic 
utilizations above about 17 percent are employed. 
The concentration of initiator useful for the partial polymerization should 
be sufficient to result in the desired degree of allylic utilization at 
the conditions used, and generally can vary from 0.1 to about 1.5 weight 
percent initiator, basis weight of monomer. Greater amounts of initiator 
may result in either residual initiator in the product or formation of an 
infusible, insoluble, intractable gel. The initiators useful in carrying 
out the solution polymerization of the bisphenol bis(allylic 
carbonate)-functional monomer are free radical initiators, e.g., organic 
peroxides and azo catalysts, and are well known in the art. The preferred 
free radical initiators are organic peroxy compounds, such as 
peroxyesters, diacyl peroxides peroxydicarbonates and mixtures of such 
peroxy compounds. 
Examples of peroxy compounds include: peroxydicarbonate esters such as 
di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-n-butyl 
peroxydicarbonate, di-sec-butyl peroxydicarbonate, diisobutyl 
peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, diacetyl 
peroxydicarbonate, dicyclohexyl peroxydicarbonate, 
di(4-tert-butylcyclohexyl) peroxydicarbonate, and isopropyl sec-butyl 
peroxydicarbonate; diacetyl peroxides such as diacetyl peroxide, dibenzoyl 
peroxide, dilauroyl peroxide, and diisobutyryl peroxide; and peroxyesters 
such as tertiary-butyl perpivalate, tertiary-butyl peroctoate and 
tertiary-butyl perneodecanoate. 
Only one peroxy compound or a mixture of peroxy compounds may be used as 
desired. 
The solution polymerization is generally carried out at temperatures of 
from about 28.degree. C. to about 100.degree. C., for from about 1 to 
about 24 hours. The time and temperature depend on the initiator and the 
concentration thereof, and the solvent:monomer ratio used. 
The amount of bisphenol bis(allylic carbonate)-functional material present 
in the polymerizable, homogeneous composition is susceptible to wide 
variation. Ordinarily, the bisphenol bis(allylic carbonate)functional 
material is present in the polymerizable, homogeneous composition in an 
amount in the range of from about 40 to about 99.9 percent by weight. 
Often it is present in an amount in the range of from about 50 to about 
99.5 percent by weight. An amount in the range of from about 85 to about 
99 percent by weight is preferred. 
Similarly the amount of cyclohexenic material present in the polymerizable, 
homogeneous composition may be widely varied. Generally the cyclohexenic 
material is present in the polymerizable, homogeneous composition in an 
amount in the range of from about 0.1 to about 5 percent by weight. In 
many cases it is present in an amount in the range of from about 0.5 to 
about 4 percent by weight. An amount in the range of from about 1 to about 
3 percent by weight is preferred. 
There are many materials which may optionally be present in the 
polymerizable, homogeneous composition. 
Non-aromatic bis(allylic carbonate)-functional monomer is a material which 
can optionally be present in the polymerizable homogeneous compositions of 
the invention. Such monomer comprises one or more nonaromatic bis(allylic 
carbonate)-functional monomeric compounds which are bis(allylic 
carbonates) of linear or branched aliphatic glycols, cycloaliphatic 
glycols, or glycols containing at least one divalent aliphatic portion and 
at least one divalent cycloaliphatic portion. These monomers can be 
prepared by procedures well known in the art, for example, those described 
in U.S. Pat. Nos. 2,370,567 and 2,403,113, the entire disclosures of which 
are incorporated herein by reference. In the latter patent, the monomers 
are prepared by treating the non-aromatic glycol with phosgene at 
temperatures between 0.degree. C. and 20.degree. C. to form the 
corresponding bischloroformate. The bischloroformate is then reacted with 
an unsaturated alcohol in the presence of a suitable acid acceptor, as for 
example, pyridine, a tertiary amine, or an alkali or alkaline earth metal 
hydroxide. Alternatively, the unsaturated alcohol can be reacted with 
phosgene and the resulting chloroformate reacted with the non-aromatic 
glycol in the presence of an alkaline reagent, as described in U.S. Pat. 
No. 2,370,567. 
The non-aromatic bis(allylic carbonate)-functional monomeric compounds can 
be represented by the formula 
##STR4## 
in which R.sub.5 is the divalent radical derived from the non-aromatic 
glycol and each Ro is independently hydrogen, halo, or an alkyl group 
containing from 1 to about 4 carbon atoms. The alkyl group is usually 
methyl or ethyl. Most commonly both groups represented by Ro are hydrogen 
or methyl; hydrogen is preferred. 
The aliphatic glycol from which the non-aromatic bis(allylic 
carbonate)-functional monomeric compound may be derived, can be linear or 
branched and contain from 2 to about 10 carbon atoms. Commonly, the 
aliphatic glycol is an alkylene glycol having from 2 to 4 carbon atoms or 
a poly(C.sub.2 -C.sub.4) alkylene glycol. Examples of such compounds 
include ethylene glycol, propylene glycol, 1,3-propanediol, 
1,4-butanediol, 1,3butanediol, 1,5-pentanediol, 1,6-hexanediol, 
1,8-octanediol, 2-ethyl-hexyl-1,6-diol, 1,10-decanediol, diethylene 
glycol, triethylene glycol tetraethylene glycol, HOCH.sub.2 CH.sub.2 
CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2 OH, 
dipropylene glycol, tripropylene glycol, and tetrapropylene glycol. Other 
examples include alkylene carbonate and alkylene ether carbonate diols 
such as HOCH.sub.2 CH.sub.2 O--CO--OCH.sub.2 CH.sub.2 OH and HOCH.sub.2 
CH.sub.2 OCH.sub.2 CH.sub.2 O--CO--CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OH. 
The cycloaliphatic glycols from which the non-aromatic bis(allylic 
carbonate)-functional monomeric compound may be derived, usually contain 
from about 5 to about 8 carbon atoms. Ordinarily, the cycloaliphatic 
glycol contains from about 6 to about 8 carbon atoms. Examples include 
1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 
1,4-cyclohexanediol and 1,5-cyclooctanediol. 
Examples of glycols containing at least one divalent aliphatic portion and 
at least one cycloaliphatic portion which may be used include 
4,4'-methylenebis(cyclohexanol), 
4,4'-(1-methylethylidene)bis(cyclohexanol), 
2,2'-(1,4-cyclohexanediyl)bisethanol, and 1,4-cyclohexane dimethanol. 
The non-aromatic glycol from which the non-aromatic bis(allylic 
carbonate)-functional monomeric compound may be derived may also be 
aliphatic diol-functional chain extended compounds. Examples of such 
compounds based on alkylene oxide extension include ethylene oxide 
extended trimethylolpropane, propylene oxide extended trimethylolpropane, 
ethylene oxide extended glycerol, and propylene oxide extended glycerol. 
Preferably, the non-aromatic bis(allylic carbonate)-functional monomeric 
compound is aliphatic bis(allylic carbonate)-functional monomeric 
compound. Most commonly, R.sub.5 is --CH.sub.2 CH.sub.2 --, --CH.sub.2 
CH.sub.2 --O--CH.sub.2 CH.sub.2 --, or --CH.sub.2 CH.sub.2 --O--CH.sub.2 
CH.sub.2 --O--CH.sub.2 CH.sub.2 --. 
Specific examples of aliphatic bis(allylic carbonate)-functional monomeric 
compounds useful in the practice of the invention include ethylene glycol 
bis(2-chloroallyl carbonate), ethylene glycol bis(allyl carbonate), 
1,4-butanediol bis(allyl carbonate), 1,5-pentanediol bis(allyl carbonate), 
1,6-hexanediol bis(allyl carbonate), diethylene glycol bis(2-methallyl 
carbonate), diethylene glycol bis(allyl carbonate), triethylene glycol 
bis(allyl carbonate), propylene glycol bis(2ethylallyl carbonate), 
1,3-propanediol bis(allyl carbonate, 1,3-butane diol bis(allyl carbonate), 
1,4-butanediol bis(2-bromoallyl carbonate), dipropylene glycol bis(allyl 
carbonate), trimethylene glycol bis(2-ethylallyl carbonate), and 
pentamethylene glycol bis(allyl carbonate. 
Industrially important aliphatic bis(allyl carbonate)-functional monomeric 
compounds which can be utilized in the invention herein contemplated are: 
##STR5## 
Diethylene glycol bis(allyl carbonate) is preferred. Monomer containing 
this compound is commercially available from PPG Industries, Inc. and is 
sold under the trademark CR-39 Allyl Diglycol Carbonate. 
The amount of non-aromatic bis(allylic carbonate)-functional monomer 
present in the polymerizable, homogeneous composition may be widely 
varied. When it is used, the weight ratio of the non-aromatic bis(allylic 
carbonate)-functional monomer to all ethylenically unsaturated material 
present in the composition is ordinarily in the range of from about 
0.1:100 to about 20:100. Often the weight ratio is in the range of from 
about 1:100 to about 15:100. A weight ratio in the range of from about 
2:100 to about 10:100 is preferred. 
Another material which may optionally be present is nonaromatic 
poly(allylic carbonate)-functional prepolymer. This material is prepared 
by partially polymerizing non-aromatic poly(allylic carbonate)functional 
monomer to utilize a fraction of the allylic groups without incurring 
significant gellation. The preferred non-aromatic poly(allylic 
carbonate)-functional prepolymers are those prepared in accordance with 
the procedures described in detail in abandoned Application Ser. No. 
549,850, filed Nov. 9, 1983 and in abandoned Application Ser. No. 690,411, 
filed Jan. 10, 1985. The preparation is analogous to the preparation of 
the bisphenol poly(allylic carbonate)-functional prepolymer, except that 
non-aromatic poly(allylic carbonate)-functional monomer is used rather 
than bisphenol bis(allylic carbonate)-functional monomer. Following 
partial polymerization, the solvent in the composition can be removed by 
known techniques, e.g., by evaporation or distillation, leaving a viscous 
liquid comprising a solution of non-aromatic poly(allylic 
carbonate)-functional prepolymer in non-aromatic bis(allyl 
carbonate)-functional monomer. The solution is typically a pourable, 
syrupy liquid having a kinematic viscosity (measured with a capillary 
viscometer) of from at least about 100 centistokes to about 100,000 
centistokes, typically from about 1000 to 40,000 centistokes, more 
typically from about 500 to 2,000 centistokes, measured at 25.degree. C., 
and a bulk density at 25.degree. C. of from about 1.17 to about 1.23 grams 
per cubic centimeter. The solution is further characterized by having more 
than 12 percent allylic utilization, preferably from at least 15 to 50 
percent allylic utilization, and, in a particularly preferred 
exemplification, from about 20 to 50 percent allylic utilization, as 
determined by IR or NMR analysis. IR analysis is preferred. 
According to one exemplification, a liquid mixture comprising 100 grams of 
diethylene glycol bis(allyl carbonate) monomer, 300 milliliters of 
methylene chloride and 1.1 milliliters of diisopropyl peroxydicarbonate 
was prepared. The liquid mixture was placed in a bottle and the bottle was 
purged with argon for 3 minutes. The bottle and its contents were held at 
70.degree. C. for 18 hours and then cooled to 25.degree. C. The liquid 
reaction mixture was placed in a one-liter round bottom flask and vacuum 
stripped at 50.degree. C. for 2 hours. Then the temperature was raised to 
60.degree. C. for 1 hour and the pressure lowered until an absolute 
pressure of 267 pascals was obtained. The residue remaining after vacuum 
stripping was a solution of aliphatic poly(allyl carbonate)-functional 
prepolymer in diethylene glycol bis(allyl carbonate) monomer and had a 
viscosity of 1900 centipoises and an allylic utilization of 34 percent. 
The amount of non-aromatic poly(allyl carbonate)-functional prepolymer 
present in the polymerizable, homogeneous composition may be widely 
varied. When it is used, the weight ratio of the non-aromatic poly(allyl 
carbonate)-functional polymer to all ethylenically unsaturated material 
present in the composition is ordinarily in the range of from about 
0.1:100 to about 20:100. Often the weight ratio is in the range of from 
about 1:100 to about 15:100. A weight ratio in the range of from about 
2:100 to about 10:100 is preferred. 
Another material that may optionally be present is diester represented by 
the formula 
##STR6## 
where R.sub.6 is a divalent organo group which may be aromatic, 
nonaromatic, or partially aromatic and partially non-aromatic, and where 
each R.sub.7 is independently hydrogen, halo, or an alkyl group containing 
from 1 to about 4 carbon atoms. Usually, both groups represented by 
R.sub.7 are either hydrogen or both are methyl. These diesters are 
esterification products of dihydroxy-functional materials with one or more 
acrylic acids. They are known compounds and may be prepared by well known 
procedures. 
The amount of the diester present in the polymerizable, homogeneous 
composition may also be widely varied. When it is used, the weight ratio 
of the diester to all ethylenically unsaturated material present in the 
composition is generally in the range of from about 0.1:100 to about 
20:100. Typically the weight ratio is in the range of from about 1:100 to 
about 15:100. A weight ratio in the range of from about 2:100 to about 
10:100 is preferred. 
Yet another optional material which may be present is monofunctional 
acrylate represented by the formula 
##STR7## 
where R.sub.8 is a monovalent organo group and R.sub.9 is hydrogen, halo, 
or an alkyl group containing from 1 to about 4 carbon atoms. 
The monofunctional acrylates represented by Formula IX are themselves well 
known compounds. The monovalent organo group, R.sub.8, may be aliphatic, 
cycloaliphatic, aromatic, or a combination of two or more of these 
properties. Most often R.sub.8 is alkyl containing from 1 to about 4 
carbon atoms, cycloalkyl containing from 5 to about 8 carbon atoms, 
phenyl, or benzyl. It is preferred that R.sub.8 be methyl, ethyl, isobutyl 
cycloalkyl, phenyl, or benzyl. R.sub.9 is usually hydrogen or methyl. 
Examples of monofunctional acrylates include: methyl acrylate, methyl 
methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl 
methacrylate, cyclohexyl methacrylate, phenyl methacrylate, and benzyl 
methacrylate. The methacrylic acid esters, as for example isobutyl 
methacrylate, are preferred. 
The amount of monofunctional acrylate present in the polymerizable, 
homogeneous composition may be varied considerably. When the 
monofunctional acrylate is used, the weight ratio of the monofunctional 
acrylate to all ethylenically unsaturated material present in the 
composition is ordinarily in the range of from about 0.1:100 to about 
25:100. Often the weight ratio is in the range of from about 1:100 to 
about 15:100. A weight ratio in the range of from about 2:100 to about 
10:100 is preferred. A weight ratio in the range of from about 3.5:100 to 
about 5.5:100 is especially preferred. 
One or more ethylenically unsaturated monomers not heretofore discussed may 
optionally be present in the pourable, polymerizable composition of the 
invention. Illustrative of such monomers are alkyl esters of ethylenically 
unsaturated dicarboxylic acids, cycloalkyl esters of ethylenically 
unsaturated dicarboxylic acids, allyl esters of saturated or ethylenically 
unsaturated dicarboxylic acids, vinyl esters of saturated monocarboxylic 
acids, vinyl benzoate, styrene, substituted styrene, divinylbenzene, 
diallylic esters of any of the phthalic acids, tris and higher functional 
acrylates, tris and higher functional allylic compounds which include tris 
and higher functional allylic carbonate compounds. It is preferred that 
the vinyl esters of saturated monocarboxylic acids contain from 4 to about 
6 carbon atoms. Vinyl acetate is especially preferred. When used, the 
weight ratio of these materials to all ethylenically unsaturated material 
present in the composition is usually in the range of from about 0.1:100 
to about 15:100. A weight ratio in the range of from about 0.1:100 to 
about 10:100 is preferred. When used, the weight ratio of vinyl ester of 
saturated monocarboxylic acid to all ethylenically unsaturated material 
present in the composition is usually in the range of from about 0.1:100 
to about 15:100; a weight ratio in the range of from about 0.1:100 to 
about 10:100 is preferred. From about 2:100 to about 6:100 is especially 
preferred. 
When, as is preferred, polymerization of the polymerizable composition is 
initiated by thermally generated free radicals, the polymerizable 
composition contains initiator. The 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 the radical 
pair are available to initiate addition polymerization of ethylenically 
unsaturated groups in the well-known manner. 
The preferred initiators are peroxy initiators. Examples of suitable peroxy 
initiators include those represented by any of the following formulae: 
##STR8## 
wherein R.sub.10 and R.sub.11 are each individually phenyl, phenylalkyl in 
which the alkyl portion is straight or branched and contains from 1 to 
about 10 carbon atoms, straight alkyl containing from 1 to about 20 carbon 
atoms, branched alkyl containing from 3 to about 20 carbon atoms, 
cycloalkyl containing from about 5 to about 12 carbon atoms, or 
polycycloalkyl containing from about 7 to about 12 carbon atoms. The 
specific groups used for R.sub.10 and R.sub.11 may be the same or they may 
be different. 
It is to be understood that unless otherwise qualified, either expressly or 
contextually, any of the above groups may be substituted with one or more 
minor substituents so long as their numbers and identities do not render 
the initiator unsuitable for its intended purpose. Halo groups, alkoxy 
groups containing from 1 to about 4 carbon atoms, haloalkyl groups 
containing from 1 to about 4 carbon atoms, and polyhaloalkyl groups 
containing from 1 to about 4 carbon atoms, are examples of substituents 
which may be used. Alkyl groups containing from 1 to about 4 carbon atoms 
may be used as substituents on non-aliphatic groups or on non-aliphatic 
portions of complex groups. 
The phenylalkyl groups used for R.sub.10, R.sub.11, or both R.sub.10 and 
R.sub.11 often contain from 1 to about 4 carbon atoms in the alkyl 
portion. Benzyl and phenylethyl are preferred. 
The branched alkyl groups often have at least one branch in the 1-position 
or the 2-position. In many cases each branched alkyl group contains from 3 
to about 8 carbon atoms. Preferably, each branched alkyl group contains 3 
or 5 carbon atoms. 
Examples of branched alkyl groups that may be used include isopropyl, 
secondary butyl, isobutyl, tertiary butyl, 1-methylbutyl, 2methylbutyl, 
tertiary pentyl, 1,2-dimethylpropyl, neopentyl, 1-methylpentyl, 
2-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 
2,2-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 2-ethylhexyl, 
2,4,4-trimethylpentyl, and 1-ethyldecyl. Preferred are secondary butyl, 
tertiary butyl, and neopentyl. 
The cycloalkyl often contains from about 5 to about 8 carbon atoms. 
Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, 
cyclooctyl, cyclodecyl, and cyclododecyl. Cyclohexyl is preferred. 
The polycycloalkyl typically contains from about 7 to about 10 carbon 
atoms. 
Examples of polycycloalkyl groups that may be used include 1-norbornyl, 
2-bornyl, and 1-adamantyl. 
Exemplary peroxy initiators include those described above in respect of the 
preparation of liquid aromatic-containing poly(allyl carbonate) polymer. 
Diisopropyl peroxydicarbonate and benzoyl peroxide are the preferred 
initiators. 
Other examples of suitable peroxy initiators include monoperoxycarbonates 
represented by the following formula: 
##STR9## 
wherein R.sub.12 is a tertiary C.sub.4 -C.sub.5 alkyl, e.g., tertiary 
butyl and tertiary amyl, and R.sub.13 is a C.sub.3 -C.sub.7 alkyl. 
Examples of alkyl radicals representative of R.sub.13 include: isopropyl, 
n-propyl, isobutyl, secondary butyl, n-butyl, secondary amyl, isoamyl, 
n-amyl, secondary hexyl, isohexyl, n-hexyl, n-heptyl and 
2,4-dimethyl-3-pentyl. Preferred as R.sub.13 are secondary C.sub.3 
-C.sub.7 alkyls such as isopropyl, secondary butyl, and 
2,4-dimethyl-3-pentyl. Particularly preferred monoperoxycarbonates are 
tertiary-butylperoxy isopropyl carbonate and tertiary-amylperoxy isopropyl 
carbonate. 
Only one initiator or a plurality of initiators may be used as desired. 
When used, the amount of initiator present in the polymerizable, 
homogeneous composition may be widely varied. Ordinarily the weight ratio 
of the initiator to all ethylenically unsaturated material present in the 
composition is in the range of from about 0.5:100 to about 7:100. In many 
cases the weight ratio is in the range of from about 1:100 to about 5:100. 
A weight ratio in the range of from about 2:100 to about 4:100 is 
preferred. 
It will be recognized 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 ethylenically unsaturated materials present in the composition. 
Another material which may optionally be present in the polymerizable, 
homogeneous composition is mold release agent. When used, the mold release 
agent is employed in the polymerizable composition in amounts sufficient 
to ensure an intact, that is, unbroken and uncracked, casting which 
releases easily from the mold. The mold release agent should be compatible 
with the polymerizable composition and not adversely affect the physical 
properties of the casting. More particularly, the mold release agent 
should not adversely affect the physical properties most characteristic of 
the polymerizate such as its rigidity, hardness, index of optical 
refraction, transmission of visible light and absence of coloring which 
affects optical clarity. The mold release agent should, therefore, be a 
liquid or, if a solid, be soluble in the polymerizable composition. 
Mold release agents that may be used include alkyl phosphates and 
stearates. Among the alkyl phosphates that may be used as a mold release 
agent are the mono and dialkyl phosphates (and mixtures of mono and 
dialkyl phosphates) which are commercially available from E. I. DuPont de 
Nemours & Co. under the trade names ORTHOLEUM.RTM. 162 and ZELEC.RTM. UN. 
These alkyl phosphates are reported to have straight chain alkyl groups of 
from 16 to 18 carbon atoms. 
Other mold release agents that may be used include stearic acid and the 
metal salts of stearic acid, e.g., stearic acid salts of the metals zinc, 
calcium, lead, magnesium, barium, cadmium, aluminum, and lithium. Other 
fatty acids and fatty acids salts may also be used, provided that they do 
not adversely effect the physical properties of the casting. Other mold 
release agents known to the art may be used. 
When used, the mold release agent is ordinarily present in the 
polymerizable, homogeneous composition in an amount between about 1 and 
about 2000 parts by weight of mold release agent per million parts by 
weight of all ethylenically unsaturated material present (PPM). In many 
cases, between about 20 and about 200 PPM is used. Between about 25 and 
about 100 PPM is preferred. 
Dyes are optional materials that may be present when high transmission of 
light is not necessary. 
Further examples of optional materials that may be present include small 
amounts of polymerization inhibitors to promote stability during storage 
and ultraviolet light absorbers. 
The listing of optional ingredients 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 seriously 
interfere with good polymer formulating practice. 
In the polymerizable composition, the ethylenically unsaturated material 
should be in the form of a solution in the proportions used. 
The polymerizable, homogeneous compositions of the invention are usually 
prepared by admixing the various ingredients. Mixing may be 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 
polymerization is initiated. It is preferred to employ heating in the 
absence of initiator, to cool the resulting solution, and then to 
introduce the initiator and other ingredients which enter the solution 
without undue difficulty. 
The polymerizable, homogeneous compositions of the invention can be 
free-radically polymerized (viz., cured) by the known conventional 
techniques for polymerizing (allylic carbonate)-containing compositions to 
form solid, crosslinked polymer. 
Preferably, polymerization is accomplished by heating the polymerizable 
composition to elevated temperatures in the presence of free-radical 
initiator. Typically polymerization is conducted at temperatures in the 
range of from about 28.degree. C. to about 100.degree. C. In many cases 
post curing, that is, heating beyond the time thought necessary to 
substantially fully polymerize the composition is employed. The post cure 
is often carried out above about 100.degree. C., but below the 
temperatures at which thermal degredation provides undesirable yellowness, 
e.g., about 125.degree. C., and preferably for a time sufficient to attain 
either substantially constant or maximum Barcol hardness. For example, 
when the cure cycle shown in Table 2 below is followed, the polymerizate 
may be maintained at 100.degree. 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 about 5 to 8 units. 
In most cases, the polymerizable, homogeneous composition is conformed to 
the shape of the final solid polymerized article before polymerization. 
For example, the composition 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 
composition 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 ophthalmic lenses. In a particularly preferred embodiment, 
the composition is poured into a lens mold and polymerized therein to 
produce an ophthalmic lens. 
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 coating, 
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 in forming polymerizates 
according to the present invention, but they are, however, only exemplary, 
and others may be used. 
TABLE 1 
______________________________________ 
Standard Cure Cycle for Diisopropyl Peroxydicarbonate 
Cumulative Hours 
Oven Temperature, .degree.C. 
______________________________________ 
0 44 
2 46 
4 48 
6 50 
8 54 
10 58 
12 64 
14 69 
16 85 
17 105 (End of Cycle.) 
______________________________________ 
TABLE 2 
______________________________________ 
Standard Eighteen Hour Cure Cycle for Benzoyl Peroxide 
Cumulative Hours 
Oven Temperature, .degree.C. 
______________________________________ 
0 63 
2 63 
4 65 
6 67 
8 77 
10 80 
12 85 
14 88 
16 92 
18 100 (End of Cycle.) 
______________________________________ 
TABLE 3 
______________________________________ 
Standard Five Hour Cure Cycle for Benzoyl Peroxide 
Cumulative Hours 
Oven Temperature, .degree.C. 
______________________________________ 
0 90 
1 90 
2 90 
3 90 
3.5 96 
4 103 
4.5 109 
5 115 (End of Cycle.) 
______________________________________ 
TABLE 4 
______________________________________ 
Standard Cure Cycle for 
Tertiary-Butylperoxy Isopropyl Carbonate 
Cumulative Hours 
Oven Temperature, .degree.C. 
______________________________________ 
0 90 
2 91 
4 92 
6 93 
8 95 
10 97 
12 100 
14 103 
16 110 
17 120 (End of Cycle.) 
______________________________________ 
The polymerizates of the present invention, on an undyed and untinted 
basis, not only have high refractive indices, but they also exhibit low 
yellowness and 15-second Barcol hardness values which are acceptable for 
ophthalmic purposes. Prior to the present invention, the achievement of 
all three properties concurrently in a polymerizate was accomplished only 
with difficulty. 
The present polymerizates have 15-second Barcol hardnesses of at least 
zero. In many cases the Barcol hardness is at least about 15, 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 present polymerizates on an undyed and untinted basis, also have 
yellowness indices at a sample thickness of about 3.3 millimeters of about 
4 or lower. Often the yellowness index is about 2.5 or lower. Preferably, 
the yellowness index is about 1.5 or lower. As used herein, yellowness 
index is determined on specimens having a thickness of about 3.3 
millimeters in accordance with ASTM Test Method D 1925-70 (Reapproved 
1977) using a Hunterlab Tristimulus Colorimeter Model D25P employing a 
collimated Illuminant C standard light source. 
The present polymerizates also have refractive indices at 20.degree. C. and 
a wavelength of 589.3 nanometers of at least about 1.52. Often the 
refractive index under the same conditions is at least about 1.53. 
Preferably it is at least about 1.55. 
In many cases the polymerizates of the present invention, on an undyed and 
untinted basis, also exhibit one or more other favorable properties. Among 
these favorable properties may be mentioned high luminous transmission, 
low haze, a density of about 1.3 grams per cubic centimeter or lower and 
low heat distortion. 
As used herein luminous transmission and haze value are determined on 
specimens having a thickness of about 3.3 millimeters in accordance with 
ASTM Test Method D 1003-61 (Reapproved 1977) using a Hunterlab Tristimulus 
Colorimeter Model D25P employing a collimated Illuminant C standard light 
source. As the luminous transmission approaches one hundred percent, the 
difference in luminous transmissions for two samples of the same material 
but of differing thicknesses approaches zero. Consequently, values of 
luminous transmission of about 90 percent or greater ascertained from 
samples having thicknesses within about a millimeter of the 3.3 millimeter 
standard, approximate reasonably well the luminous transmission at the 
standard thickness. In similar fashion, haze values of about one percent 
or less ascertained on samples having thicknesses within about a 
millimeter of the 3.3 millimeter standard, approximate reasonably well the 
haze value at the standard thickness. Although the yellowness index seems 
to vary more with sample thickness than luminous transmission or haze 
value, nevertheless yellowness indices ascertained from samples having 
thicknesses within about a millimeter of the 3.3 millimeter standard do 
provide a useful general indication of the yellowness index at the 
standard thickness. 
In most cases the luminous transmission of the present polymerizates on an 
undyed and untinted basis, is at least about 80 percent. Frequently the 
luminous transmission is at least about 85 percent. Preferably the 
luminous transmission is at least about 90 percent. When the polymerizate 
is dyed or tinted for use in sunglasses or filters, the luminous 
transmission of the dyed and/or tinted, sample is usually at least about 
20 percent. 
Often the haze value of the polymerizates, on an undyed and untinted basis 
is about 5 percent or lower. In many cases the haze value is about 4 
percent or lower, and preferably it is about 2 percent or lower. 
The density of most of the polymerizates of the invention is usually about 
1.3 grams per cubic centimeter (g/cm.sup.3) or lower. Frequently the 
density is about 1.27 g/cm.sup.3 or lower, and preferably it is about 1.25 
g/cm.sup.3 or lower. As used herein, density is determined in accordance 
with ASTM Test Method C729-75 and reported for a temperature of 25.degree. 
C. 
The heat distortion test is conducted as described in ASTM Standard Test 
Method D 648-72. Preferably the heat distortion temperature of the 
polymerizates of the present invention is at least 45.degree. C. 
The invention is further described in conjunction with the following 
examples which are to be considered illustrative rather than limiting, and 
in which all parts are parts by weight and all percentages are percentages 
by weight unless otherwise specified.

EXAMPLE I (COMATIVE) 
A casting solution was formed by admixing 100 parts of bisphenol A 
bis(allyl carbonate) monomer and 1.8 parts of diisopropyl 
peroxydicarbonate. 
A portion of the casting solution was charged into a glass mold constructed 
of two glass sheets separated by a pliable gasket that was about 3.56 
millimeters thick. The glass mold was held together by large binder clips. 
After filling the mold, it was placed in a hot air oven and exposed to the 
Standard Cure Cycle for Diisopropyl Peroxydicarbonate of Table 1. When the 
cure cycle was completed, the mold was removed from the oven and allowed 
to cool to room temperature. The resulting polymerizate was then removed 
from the mold and was found to be about 3.4 millimeters thick. Various 
properties of the polymerizate are shown in Table 5. 
TABLE 5 
______________________________________ 
Yellowness Index 4.8 
(3.4 mm thickness) 
Barcol Hardness 
0-second 39 
15-second 39 
______________________________________ 
EXAMPLE II 
A casting solution was formed by admixing 99 parts of bisphenol A bis(allyl 
carbonate) monomer, one part of .alpha.-terpinyl acetate, and 1.8 parts of 
diisopropyl peroxydicarbonate. A sheet of polymerizate was prepared from 
the casting solution according to the procedure of Example I. The 
polymerizate was found to be about 3.3 millimeters thick. Various 
properties of the polymerizate are shown in Table 6. 
TABLE 6 
______________________________________ 
Yellowness Index 2.0 
(3.3 mm thickness) 
Barcol Hardness 
0-second 36 
15-second 36 
______________________________________ 
EXAMPLE III 
A casting solution was formed by admixing 294 parts of bisphenol A 
bis(allyl carbonate) 6 parts of .alpha.-terpinyl acetate, and 5.4 parts of 
diisopropyl peroxydicarbonate. A sheet of polymerizate was prepared from 
the casting solution according to the procedure of Example I. The 
polymerizate was found to be about 3.3 millimeters thick. Various 
properties of the polymerizate are shown in Table 7. 
TABLE 7 
______________________________________ 
Yellowness Index 1.2 
(3.3 mm thickness) 
Luminous Transmission, percent 
92.8 
(3.3 mm thickness) 
Haze Value, percent 0.3 
(3.3 mm thickness) 
Barcol Hardness 
0-second 35 
15-seconds 34 
Refractive Index, n.sub.D.sup.20 
1.5626, 1.5617, 1.5620 
Abbe Number 37.7 
Heat Distortion Temperature 
54, 50 
(264 psi; 1820 kPa), .degree.C. 
______________________________________ 
EXAMPLE IV 
A casting solution was formed by admixing 39.6 parts of bisphenol A 
bis(allyl carbonate) monomer, 0.4 parts of cyclohexene, and 0.8 part of 
diisopropyl peroxydicarbonate. A sheet of polymerizate was prepared from 
the casting solution according to the procedure of Example I. The 
polymerizate was about 3.3 millimeters thick. Various properties of the 
polymerizate are shown in Table 8. 
TABLE 8 
______________________________________ 
Yellowness Index 1.2 
(3.3 mm thickness) 
Luminous Transmission, percent 
91.9 
(3.3 mm thickness) 
Haze Value, percent 0.6 
(3.3 mm thickness) 
Barcol Hardness 
0-second 21 
15-seconds 16 
______________________________________ 
EXAMPLE V 
A first solution was formed by admixing 472.5 parts of bisphenol A 
bis(allyl carbonate) monomer, 7.5 parts of .alpha.-terpinyl acetate, 5.0 
parts of benzyl acetate, 2.5 parts of cyclohexene, 2.5 parts of 
cyclohexanone, and 10 parts of diethylene glycol bis(allyl carbonate) 
monomer. 
A casting solution was formed by admixing 100 parts of the above first 
solution, 3 parts of diisopropyl peroxydicarbonate, and 0.005 part of 
Zelec.RTM. UN mold release agent. 
A sheet of polymerizate was prepared from the casting solution according to 
the procedure of Example I. The polymerizate was found to be about 3.2 
millimeters thick. Various properties of the polymerizate are shown in 
Table 9. 
TABLE 9 
______________________________________ 
Yellowness Index 1.1 
(3.2 mm thickness) 
Luminous Transmission, percent 
92.1 
(3.2 mm thickness) 
Haze Value, percent 0.5 
(3.2 mm thickness) 
Barcol Hardness 
0-second 39 
15-seconds 37 
Heat Distortion Temperature 
67.5 
(264 psi; 1820 kPa), .degree.C. 
______________________________________ 
EXAMPLE VI 
A first solution was formed by admixing 922.5 parts of bisphenol A 
bis(allyl carbonate) monomer, 13.6 parts of .alpha.-terpinyl acetate, 9 
parts of benzyl acetate, 4.5 parts of cyclohexene, 4.5 parts of 
cyclohexanone, and 45.5 parts of isobutyl methacrylate. 
A casting solution was formed by admixing 100 parts of the above first 
solution, 3 parts of diisopropyl peroxydicarbonate, and 0.005 part of 
Zelec.RTM. UN mold release agent. A sheet of polymerizate was prepared 
from the casting solution according to the procedure of Example I except 
that the pliable gasket was about 2.84 millimeters thick. The polymerizate 
was found to be about 2.76 millimeters thick. Various properties of the 
polymerizate are shown in Table 10. 
TABLE 10 
______________________________________ 
Yellowness Index 1.0 
(2.76 mm thickness) 
Barcol Hardness 
0-second 32 
15-seconds 30 
Refractive Index, n.sub.D.sup.20 
1.5554 
______________________________________ 
EXAMPLE VII 
A first solution was formed by admixing 940 parts of bisphenol A bis(allyl 
carbonate) monomer, 15 parts of .alpha.-terpinyl acetate, 15 parts of 
benzyl acetate, and 30 parts of diethylene glycol bis(allyl carbonate) 
monomer. 
A casting solution was formed by admixing 100 parts of the above first 
solution, 2 parts of diisopropyl peroxydicarbonate, and about 0.005 part 
of Zelec.RTM. UN mold release agent. A sheet of polymerizate was prepared 
from the casting solution according to the procedure of Example I. The 
polymerizate was found to be about 3.4 millimeters thick. Various 
properties of the polymerizate are shown in Table 11. 
TABLE 11 
______________________________________ 
Yellowness Index 1.2 
(3.4 mm thickness) 
Luminous Transmission, percent 
92.0 
(3.4 mm thickness) 
Haze Value, percent 0.6 
(3.4 mm thickness) 
Barcol Hardness 
0-second 43 
15 seconds 42 
Refractive Index, N.sub.D.sup.20 
1.5597, 1.5599 
Abbe Number 37.7 
Heat Distortion Temperature 
64, 64 
(264 psi; 1820 kPa), .degree.C. 
Density at 25.degree. C., g/cm.sup.3 
1.224 
______________________________________ 
EXAMPLE VIII 
A first solution was formed by admixing 2835 parts of bisphenol A bis(allyl 
carbonate) monomer, 45 parts of .alpha.-terpinyl acetate, 30 parts of 
benzyl acetate, 15 parts of cyclohexene, 15 parts of cyclohexanone, and 60 
parts of diethylene glycol bis(allyl carbonate) monomer. 
A second solution was formed by admixing 1000 parts of the above first 
solution, 40 parts of isobutyl methacrylate, and 12.5 parts of 
4-bromodiphenyl. 
A casting solution was formed by admixing 100 parts of the above second 
solution and 3 parts of diisopropyl peroxydicarbonate. A sheet of 
polymerizate was prepared from the casting solution according to the 
procedure of Example I except that the pliable gasket was about 2.84 
millimeters thick. The polymerizate was found to be about 2.51 millimeters 
thick. Various properties of the polymerizate are shown in Table 12. 
TABLE 12 
______________________________________ 
Yellowness Index 1.2 
(2.51 mm thickness) 
Barcol Hardness 
0-second 37 
15-second 35 
Refractive Index, n.sub.D.sup.20 
1.5582 
______________________________________ 
EXAMPLE IX A stock solution was formed by admixing 451.6 parts of 
.alpha.-terpinyl acetate, 290.3 parts of benzyl acetate, 112.9 parts of 
cyclohexene, and 145.2 parts of cyclohexanone. 
A first solution was formed by admixing 12.4 parts of the above stock 
solution, 10 parts of vinyl acetate, and 377.6 parts of bisphenol A 
bis(allyl carbonate) monomer. 
A first casting solution was formed by admixing 100 parts of the above 
first solution and 3 parts of diisopropyl peroxydicarbonate. 
A second solution was formed by admixing 12.4 parts of the above stock 
solution, 14 parts of vinyl acetate, and 373.6 parts of bisphenol A 
bis(allyl carbonate) monomer. 
A second casting solution was formed by admixing 100 parts of the above 
second solution and 3 parts of diisopropyl peroxydicarbonate. 
A third solution was formed by admixing 12.4 parts of the above stock 
solution, 20 parts of vinyl acetate, and 367.6 parts of bisphenol A 
bis(allyl carbonate) monomer. 
A third casting solution was formed by admixing 100 parts of the above 
third solution and 3 parts of diisopropyl peroxydicarbonate. 
Sheets of first, second, and third polymerizates were prepared respectively 
from the first, second, and third casting solutions according to the 
procedure of Example I except that the pliable gasket for each mold was 
about 2.84 millimeters thick. The thicknesses of the first, second, and 
third polymerizates were found to be about 2.49, 2.45, and 2.57 
millimeters, respectively. Various properties of the polymerizates are 
shown in Table 13. 
TABLE 13 
______________________________________ 
Polymerizate 
First Second Third 
______________________________________ 
Yellowness Index 
(2.49 mm thickness) 
1.2 
(2.45 mm thickness) 1.3 
(2.57 mm thickness) 1.4 
Luminous Transmission, percent 
(2.49 mm thickness) 
92.0 
(2.45 mm thickness) 92.3 
(2.57 mm thickness) 92.4 
Haze Value, percent 
(2.49 mm thickness) 
0.3 
(2.45 mm thickness) 0.4 
(2.57 mm thickness) 0.5 
Barcol Hardness 
0-second 34 37 38 
15-seconds 33 37 37 
Refractive Index, n.sub.D.sup.20 
1.5592 1.5573 1.5554 
1.5594 1.5575 1.5560 
1.5558 
______________________________________ 
EXAMPLE X 
A first solution was formed by admixing 15 parts of .alpha.-terpinyl 
acetate, 5 parts cyclohexene, 50 parts of vinyl acetate, and 930 parts of 
bisphenol A bis(allyl carbonate) monomer. 
A casting solution was formed by admixing 100 parts of the above first 
solution and 2.75 parts of diisopropyl peroxydicarbonate. A sheet of 
polymerizate was prepared from the casting solution according to the 
procedure of Example I except that the pliable gasket was about 2.84 
millimeters thick. The polymerizate was found to be about 2.44 millimeters 
thick. Various properties of the polymerizate are shown in Table 14. 
TABLE 14 
______________________________________ 
Yellowness Index 1.1 
(2.44 mm thickness) 
Luminous Transmission, percent 
92.7 
(2.44 mm thickness) 
Haze Value, percent 0.6 
(2.44 mm thickness) 
Barcol Hardness 
0-second 36 
15 seconds 35 
Refractive Index, n.sub.D.sup.20 
1.5564, 1.5563 
Abbe Number 37.7 
Density at 25.degree. C., g/cm.sup.3 
1.217 
______________________________________ 
Although the present invention has been described with reference to 
specific details of certain embodiments thereof, it is not intended that 
such details should be regarded as limitations upon the scope of the 
invention except insofar as they are included in the accompanying claims.