Sunblocking polymers and their formulation

Novel polymeric compositions and their intermediates are provided, providing for broad range protection from ultraviolet radiation. Acryl polymers comprising at least two different ultraviolet absorbing moieties having different light absorbing ranges are employed in conjunction with another hydrophilic monomer to provide sunscreen formulations for invisibility, and enhanced protection, without deleterious effects in the dermis.

INTRODUCTION 
1. Technical Field 
The field of this invention is sunblock compositions for use in 
dermatological and ophthalmological applications. 
2. Background 
The role of ultraviolet radiation and skin aging in development of skin 
cancer, as well as eye cataracts, is being increasingly recognized. For 
the protection of the skin, the state of art utilizes various UV-absorbing 
compounds, primarily singular (monomeric) aromatic compounds and/or 
reflecting pigments, i.e. metal oxides,, formulated into creams and 
lotions. Intraocular and contact soft lenses are described with such 
compounds added into the hydrogel, or coating the lens surfaces with 
UV-absorbing preparations. Ophthalmologic solutions are described which 
claim protection against UV radiation using various compounds added to 
standard eyedrop formulations. 
There are many disadvantages to the known UV blockers. One is their lack of 
biological tolerance. Due to their toxicity and allergenicity, as well as 
other side-effects, the various UV-absorbing additives, in spite of being 
strictly limited and regulated, often exercise their toxicity potential. 
Also, as these UV-blocking compounds penetrate into the skin, they convert 
the absorbed UV radiation into heat, which in turn dilates the vessels 
which is perceived as unpleasant. 
The reflecting inorganic pigments, such as zinc or titanium oxides, are 
visible on the skin, even if micronized and/or tinted. 
For ophthalmic use, the protection afforded by the ophthalmic solutions 
containing the toxic monomers is inefficient. The concentration limitation 
imposed by the toxicity of the compounds prevents formulations providing 
adequate protection. In hydrogel lenses, the monomers leak out. Coating 
such lenses in a permanent way is, on the other hand, difficult and 
costly. 
An ideal sun radiation blocking agent should be non-toxic, should be 
invisible on the surface of the skin or eye, and non-absorbable to be 
biologically inert. The blocking agent should cover the entire UV range of 
atmospheric radiation. Desirably, the blocking agent should absorb, 
reflect or at least diffract the infrared radiation known to potentiate 
the carcinogenic and inflammatory effect of the ultraviolet light. There 
is, therefore, substantial interest in developing sun blocking agents 
which approximate this ideal. 
Relevant Literature 
Dromgoole and Maibach, J. Am. Academy of Dermatology, Mosby Year Book, 
1990, Chapter 8, describe contact sensitization and photocontact 
sensitization of sunscreening agents. Harber, et al., in Photosensitivity 
Diseases, Principles of Diagnosis and Treatment, B. Decker, Toronto, 1989, 
Chapter 10, page 141, describe intrinsic and extrinsic photoprotection 
against UV-B and UV-A radiation. Lowe, ibid., Chapter 11, page 161 
describes the screening of various sun protection compositions. 
In Japanese application No. 5-125118, filed Nov. 2, 1991, a para-amino 
benzoyl substituted polyacrylic acid as a sun blocking composition is 
reported, where a para-aminobenzoyl group is joined to the polyacrylic 
acid by a variety of linking groups. See also CA102:221311d which 
describes para-aminobenzoyl substituted acrylic polymers. 
SUMMARY OF THE INVENTION 
UV absorbing acrylic polymers are provided having a plurality of UV 
absorbing moieties which substantially cover the wave-length range of 
light (sunlight) which penetrates to the earth's surface. The polymers 
will include an additional monomer to render the polymer, in a given 
solvent, invisible, and they may include a cross-linker. The polymers may 
be formulated in conventional ways for invisibility and stability. The 
formulations provide for protection against deleterious effects of UV 
radiation on the skin and eyes. The compositions may also find use in 
opthamalogical applications.

DESCRIPTION OF SPECIFIC EMBODIMENTS 
Novel sun blocking polymeric compositions are provided comprising at least 
two different UV absorbing moieties and a moiety containing different 
substituents on the acrylic backbone. The compositions find use as sun 
blocking agents in a variety of contexts. The polymers may be prepared by 
combining the individual monomers under addition polymerizing conditions 
or precipitation or emulsification in appropriate amounts, taking into 
consideration the differential rates of incorporation of the different 
monomers, whereby a product is obtained having an effective proportion of 
monomers which absorb UV light in the wave length range to which skin is 
normally exposed on earth. 
Normally, UV absorbers of at least UV-A and UV-B will be present, and there 
could be an absorber for UV-C. In addition, there will be at least one 
other monomer which will have a hydrophobic or hydrophilic substituent on 
the acryl group, the latter having one or more hydroxy groups. For the 
most part, the number ratio of total UV absorbers to other monomer(s) in 
the polymer will be in the range of about 0.1-10:1, usually 0.5-5:1, more 
usually 1-5:1. Of the UV absorbers present, there will generally be about 
30-98 number percent of the UV-B absorber, more usually from about 50 to 
95 number %, at least 2 number percent of the UV-A absorber, usually at 
least about 5 number %, and the remainder being the UV-C absorber. 
Depending upon the individual monomers, the ratio of the UV absorbing 
monomers to the other monomers in the polymerization reaction mixture, the 
absence or presence of a cross-linking agent, and the like, the molecular 
weight may vary widely, where the composition of individual molecules may 
vary as the polymerization proceeds. To obtain high molecular weight 
polymer, it will be desirable to use small amounts of a cross-linking 
agent, generally from about 0.5-10 mole percent, more usually from about 
1-3 mole percent of total monomer. 
For eye lens applications, the polymeric composition will be insoluble in 
water, but desirably will swell in the aqueous media formulation. This can 
be readily achieved by appropriate ratios of the hydrophilic monomer to 
the UV absorbing monomers and the number of hydrophilic groups associated 
with the hydrophilic monomer and appropriate use of the crosslinker. 
In addition, the UV monomers should have high extinction coefficients, at 
least about 20,000, preferably in excess of about 25,000. 
The UV-A absorbers will, for the most part, be benzophenones or 
bis-benzoylmethane compounds, substituted with appropriate substituents 
for providing the desired light absorption characteristics, as well as for 
linking to the acryl group. For the most part, the UV-A absorbers of the 
subject composition will have the following formula: 
##STR1## 
wherein: 
n is 0-1; 
R is H, alkyl of from 1 to 3, usually 1 to 2, carbon atoms, which may be 
substituted with a functional group having from 1 to 2 heteroatoms, which 
are N or O; 
R.sup.2 is a divalent hydrocarbylene group or substituted hydrocarbylene 
group, having up to 2, usually up to 1 substituent, where the substituent 
will be composed of oxygen, nitrogen, phosphorus, carbon and hydrogen, 
having from 1 to 3 heteroatoms, usually 1 to 2 heteroatoms, where the 
heteroatom may be in the chain, and from 0 to 6, usually 0 to 4 carbon 
atoms, which group may be aliphatic, alicyclic or aromatic, generally of 
from 2-8, more usually of from 2-6 carbon atoms, particularly phenylene or 
alkylene; 
Z is oxy, particularly hydroxy or alkoxy of from 1-6, more usually 1-3 
carbon atoms, or amino having from 0-2 alkyl substituents having a total 
of from about 1-12, more usually from about 1-6 carbon atoms, or hydrogen; 
Z will preferably be at the para position to the carbonyl group; 
Y is non-oxo carbonyl, which includes the carboxylic acid, carboxyl ester, 
where the ester will normally have an alkyl group of from 1-6, usually 
from 1-3 carbon atoms, or carboxamide, where the amino may be substituted 
or unsubstituted, where the substituted amino will have from 1-2 alkyl 
substituents with a total of from 1-12 carbon atoms, usually of from 1-6 
carbon atoms; 
Y is preferably at the ortho position in relation to the carbonyl; 
W is oxy (--O--) or amino (--N(R.sup.1)), where R.sup.1 is hydrogen or 
alkyl of from 1-6, usually 1-3 carbon atoms, where W is preferably oxy, 
when n is 1; 
W is preferably substituted at the para position to the carbonyl; 
there being from 0-2, usually 0-1 Y. 
In addition, the rings may be substituted with from 0-3, usually 0-2 alkyl 
groups of from 1-6, more usually 1-3 carbon atoms, at available positions 
on the rings. 
For the UV-B absorbers, the compounds for the most part will be benzoyloxy 
derivatives, particularly substituted benzoyloxy derivatives, more 
particularly para-amino substituted benzoyloxy derivatives. For the most 
part, these compounds will come within the following formula: 
##STR2## 
wherein: 
R.sup.3 is hydrogen or alkyl of from 1-6, usually 1-3 carbon atoms, 
preferably methyl; 
and 
W, R and R.sup.2 are as defined previously. 
The UV-C absorbing compound will be an oxybenzoyl derivative bonded to an 
acryl group through a divalent bridging moiety. For the most part, the 
UV-C absorbing group will have the following formula: 
##STR3## 
wherein: 
R.sup.4 is hydrogen or alkyl of from 1-6, usually 1-3 carbon atoms, 
preferably methyl, and the remaining symbols have been defined previously. 
The remaining monomers may be substituted or unsubstituted will usually 
have at least one organic substituent, which may be the same or different 
as to the individual monomers, there usually being a total of not more 
than about 4 different groups, the substituent being unsubstituted or more 
usually having at least one polar group, particularly an oxy group on a 
side chain. For the most part, these compounds will be of relatively low 
molecular weight, generally being under about 800 Dal, more usually being 
under about 400 Dal. They will normally be aliphatic, particularly 
saturated aliphatic, i.e. alkyl, of from 1 to 6, usually 2 to 6 carbon 
atoms, have at least 1 oxy group and may have up to 4 oxy groups, 
generally having from 1-3 oxy groups, more usually having from 1-3 hydroxy 
groups. For the most part, these compounds will have the following formula 
: 
EQU R.sup.5 WCOC(R).dbd.CH.sub.2 FIGURE 4 
wherein: 
R.sup.5 is hydrogen, a counterion, e.g. alkali metal, ammonium, etc., an 
aliphatic group of from 1-8 carbon atoms, usually 1-6 carbon atoms, 
particularly alkyl, having from 1-5, usually 1-3 oxy groups, more usually 
hydroxy groups; 
the remaining symbols have been defined previously. 
Monomers of interest are acrylic acid, methacrylic acid, and their 
hydrophilic and hydrophobic amides or esters, such as hydroxyethyl and 
hydroxypropyl amides and esters, and ethyl, propyl, butyl, pentyl and 
hexyl amides and esters. 
In the above formulas, the oxy or amino substituent may be substituted with 
a 2-nitrovinyl group to provide the desired radiation absorbing 
characteristics. 
Compounds of interest include building blocks of p-aminobenzoic acid, 
p-methoxybenzoic acid, o-hydroxybenzoyl, p-dimethylaminobenzoic acid, 
p-aminobenzoyl, acetoxyhydroquinone, phenylenediamine, etc. 
Compounds of interest include N,N-dialkylamino, N'-acryl or methacryl 
phenylenediamine, p-acryloxy or methacryloxybenzoate alkyl ester, N-alkyl 
m-acrylamido- or methacrylamidobenzoatealkyl ester, 
p-benzoyloxyacrylanilide or -methacrylanilide, p-acrylamido or 
-methacrylamidobenzoate methyl ester, o-acryloxy or 
-methacryloxy-dibenzoylmethane, p-acryloxy or 
-methacrylamidodibenzoylmethane, 4-acetoxy-1-acryloxy or 
-methacryloxybenzene, 2,4-dimethylamino-1-acryloxy or 
-methacryloxybenzene, N,N-bis-(3-acryloxy or -methacryloxyphenyl) 
methylamine, m-acryloxy or -methacryloxy-dibenzoylmethane, p,p'-diacryloxy 
or -methacryloxydibenzoylmethane, m,m'-diacryloxy or 
-methacryloxydibenzoylmethane, m,p'-diacryloxy or 
-methacryloxydibenzoylmethane, m- or p-acryloxy or 
-methacryloxy-2-nitrostyrene, 4-acryloxy or 
-methacryloxy-4,-(1"-(2"-nitrovinyl))dibenzoyl-methane, and the like, 
where alkyl is 1-3, usually 1 carbon atom. 
Any convenient cross-linking agent may be employed, which will usually be a 
bis-acryl or -methacryl, where the linking group may be any convenient 
group. Thus, the linking group may be methylene, amino, particularly 
substituted amino, 1,2-dioxyethylene, oxyamino, diaminoethylene, 
1,4-dioxybutylene, dialkylenephosphate ester, 
.alpha.,.alpha.'-xylylenediamino, etc. 
Polymers of particular interest comprise from about 20 to 60, usually 25 to 
60 mol % acrylic acid. In addition, the mol ratio of the UV-B to UV-A 
monomers will generally be in the range of 75:25 to 98:2, preferably 85:15 
to 95:5. Of interest is to use a p-aminobenzoic acid derivative as the 
UV-B moiety. Polymers coming within this composition tend to readily form 
small particles without grinding, where the particles may be directly used 
in the sunscreen formulation. 
The subject monomers may be prepared from commercially available 
intermediates in accordance with known ways. A substantial number of 
starting monomers are provided in the accompanying working 
exemplification, which may serve as models for the production of a variety 
of monomers coming within the subject invention. In addition, the 
polymerization may be carried out in accordance with conventional ways, 
using free radical catalysts at relatively mild temperatures and a solvent 
system to achieve emulsion or suspension in situ. Thus, peroxy compounds, 
azo compounds, ultraviolet light, or the like may be used as a source of 
polymerization initiation at temperatures in the range of about 
10.degree.-70.degree. C. for the polymerization. Usually, the 
polymerization will take place in the absence of oxygen, preferably under 
an inert atmosphere. The time for the polymerization will usually be at 
least an hour, usually at least 2 hours, and may extend to 24 hours or 
more, depending upon the conditions for the polymerization. A solvent may 
be used, e.g. an alkanol, particularly methanol, or a hydrocarbon, such as 
toluene, or the like, in which the various monomers are soluble. 
Generally, the solvent may be present in from about 0.2-10:1 weight ratio 
to the monomer charge. In the preparation of hydrophobic particulate 
polymers, the acrylic acid derivative may serve as a solvent, and an 
inhomogeneous system containing water may be employed After completion of 
the polymerization, the polymer may be isolated in accordance with 
conventional ways, and purified as appropriate. 
The subject polymers may be readily formulated with appropriate vehicles to 
provide the desired composition. For dermatological use, the subject 
polymers may be formulated in creams, lotions, salves, and the like, to 
produce an adherent smooth invisible film and to partially diffract the UV 
and infrared radiation. A wide variety of emollients are taught in the 
literature and include polyethylene glycols, polypropylene glycols, 
silicone, mineral vegetable oils, petrolatum (purified petroleum 
hydrocarbon greases), and the like. Depending upon the nature of the 
polymeric product, the polymeric product may be milled, ground or 
otherwise reduced in particle size in the presence of an oil, conveniently 
a hydrocarbon oil. Of interest is the use of additives, such as other 
microparticles of other polymers, such as partially hydrolyzed 
polyacrylamides or ultrafine titanium or zinc oxides, although the latter 
do not absorb but only partially diffract or reflect UV light. Where other 
microparticles are added, the mixture may be further ground to provide a 
uniform mixture of microparticles. 
For the preparation of UV-absorbing eye lenses, the appropriate composition 
of monomers is polymerized in lens forms or molds. 
The polymers of the subject invention will be present in the formulation in 
at least about 5 weight percent and not more than about 70 weight percent, 
usually ranging from about 10-40 weight percent. The dermatological 
formulation may be coated, sprayed, spread or otherwise applied to the 
particular surface, e.g., skin, as required and will be retained at the 
surface for extended periods of time. 
The following examples are offered by way of illustration and not by way of 
limitation. 
EXPERIMENTAL 
Example 1: Synthesis of an Acrylamide Derivative of an Carboxy-Substituted 
Benzophenone 
40 g (210 mmol) of 2-aminobenzophenone-2'-carboxylic acid were placed in a 
L reaction flask followed by 500 ml of EtOH and 111 ml of 9.5 N NaOH (1.05 
moles). 100 ml of H.sub.2 O were added to dissolve sodium salts. With 
stirring and cooling to 0.degree.-5.degree. C., 4.0 eq of acryloyl 
chloride were added over 10 minutes. The reaction was monitored by reverse 
phase HPLC. After completion, EtOH was removed by evaporation, and the 
reaction mixture acidified with HCl. A solid precipitated and was 
filtered. The yield of 2-acrylaminobenzophenone-2'-carboxylic acid was 53 
g (86%). 
Example 2: Acylation of 4-Amino Benzophenone with Acryloyl Chloride 
4-Aminobenzophenone (10 g, 51 mmol, 1.00 eq) was dissolved in 40 ml of THF. 
After cooling to 5.degree. C., acryloyl chloride (4.62 g, 51 mmol, 1.00 
eq, in 10 ml THF) was added followed by triethylamine to scavenge the 
generated HCl. 
THF was removed by rotary evaporation, the resulting oil was dissolved in 
100 ml of ethyl acetate and the organic solution extracted with 3.times.50 
ml of H.sub.2 O. Ethyl acetate was removed by rotary evaporation and the 
product was collected as a solid in a yield of 10.5 g (82%). 
Example 3: N-acylation of p-hydroxyaniline with p-anisoyl chloride 
p-Hydroxy aniline (152.6 g, 1.398 moles) was dissolved in 1.9 L 
tetrahydrofuran and 113 ml (110.6 g, 1.398 moles) pyridine. p-Anisoyl 
chloride (238.5 g, 1.398 moles) was added dropwise at 20.degree. C. over 
2.5 hours. After stirring an additional 2 hours at 20.degree. C., the 
solid was filtered and washed with tetrahydrofuran. The product, 466.5 g 
after drying, was refluxed in 3 L methanol for 1.5 hours, then cooled, 
filtered and washed with methanol. After vacuum drying, the solid weighed 
262.8 g, yield 77%. 
Example 4: Acylation of 4-methoxy-N-1-(4-hydroxyphenyl)! benzamide with 
methacryloyl chloride 
4-Methoxy-N-1-(4-hydroxyphenyl)! benzamide (200 g, 0.8221 moles) was 
dissolved in 650 ml dimethylacetamide and triethylamine (91.52 g, 0.9043 
moles) and then cooled to -15.degree. C. Methacryloyl chloride (94.53 g, 
0.9043 moles) was added dropwise over an hour at -10.degree. C., the 
suspension was suspension. After warming to 20.degree.-25.degree. C., the 
suspension was diluted with 650 ml acetonitrile. The resulting solid was 
filtered, washed with acetonitrile and vacuum dried to 300 g and then 
refluxed in 1.5 L methanol for 1.5 hours. After cooling to 
20.degree.-25.degree. C., the suspension was filtered, washed with 
methanol, and vacuum dried to 177 g of product, yield 69%. 
Example 5: Acylation of 4-aminobenzoic acid with acryloyl chloride 
4-Aminobenzoic acid (10.00 g, 0.073 moles) was dissolved in a mixture of 
water (20 ml), ethanol (50 ml) and 5 N NaOH (37 ml). After cooling to 
10.degree. C., acryloyl chloride (8.58 g, 0.095 moles) was quickly added 
with stirring. Additional 1 N NaOH (125 ml) and acryloyl chloride (8.58 g, 
0.095 moles) were added to push the reaction to completion. The reaction 
was acidified to pH 1 with 6 N HCl (25 ml) to produce a suspension that 
was filtered, washed with water and dried to a solid. Resuspension of the 
solid in acetonitrile (200 ml) at 60.degree. C., followed by filtration, 
led to a solid product that weighed 10.1 g (Yield 72%) after vacuum 
drying. 
Example 6: Amidation of 4-acrylamidobenzoic acid with aniline 
4-Acrylamidobenzoic acid (1.912 g, 10 mmol) was dissolved in 10 ml 
chloroform and triethylamine (1.113 g, 11 mmol). After cooling to 
-25.degree. C., chloroethylformate (1.193 g, 11 mmoles) in 3 ml chloroform 
was added dropwise with stirring. After 2 hours at -25.degree. C., aniline 
(0.931 g, 10 mmoles) in 2 ml acetronitrile was added dropwise with 
stirring. The reaction was slowly warmed to 20.degree. C., stirred for 16 
hours, filtered, washed with chloroform, and dried to a mass of 1.46 g. 
This solid was dissolved in a mixture of ethyl acetate and isopentyl 
alcohol, and extracted twice with a bicarbonate solution. The organic 
layer was separated, dried over MgSO.sub.4, filtered, and evaporated to 
dryness to give 1.30 g (50% yield). 
Example 7: Amidation of 4-dimethylaminobenzoyl chloride with ethanolamine 
4-Dimethylaminobenzoyl chloride (1.24 g, 6.75 mmoles) was dissolved in 15 
ml tetrahydrofuran and then added dropwise to a stirred solution of 
ethanolamine (0.865 g, 14.17 mmoles) in 6 ml tetrahydrofuran held at 
-5.degree. C. After the 20 minute addition, the reaction was slowly warmed 
to 20.degree.-25.degree. C. Tetrahydrofuran was removed in vacuo and the 
solids were stirred with 15 ml water for 25 minutes. The resulting product 
was filtered, washed with water and vacuum dried to 1.13 g. This solid was 
crystallized from N-propanol yielding 0.92 g (65%) of the desired product. 
Example 8: Chlorination of 4-dimethylaminobenzoic acid 
4-Dimethylaminobenzoic acid (250 g, 1.51 moles) was suspended in 2 L of 
ethyl acetate. Thionyl chloride (359.3 g, 3.02 moles) was added dropwise 
with stirring. After completion of the reaction, the solvent was removed 
by rotary evaporation affording a gray solid. The solid was crystallized 
from ethyl acetate to give 216 g of 4-dimethylaminobenzoyl chloride, yield 
78%. 
Example 9: Acylation of 2-hydroxyethyl methacrylate with 
4-dimethylaminobenzoyl chloride 
4-Dimethylaminobenzoyl chloride (216 g, 1.18 moles) was suspended in 500 ml 
of ethyl acetate. 2-Hydroxyethyl methacrylate (169 g, 1.30 moles) was 
dissolved in 500 ml ethyl acetate and 165 ml triethylamine (119 g, 1.18 
moles) and was added to the acid chloride with stirring. After completion 
of the reaction, the product was dissolved in ethyl acetate and extracted 
with dilute sodium bicarbonate. Ethyl acetate was removed by rotary 
evaporation and the crude product was crystallized from ethanol to give 
188.9 g, yield 58%. 
Example 10: Esterification of 4-hydroxydibenzoyl methane with methacryloyl 
chloride 
4-Hydroxydibenzoyl methane (1.97 g, 8.2 mmol) was dissolved in 15 ml of 
ethyl acetate and 1.25 ml of triethylamine (0.91 g, 8.98 mmol). 
Methacryloyl chloride (0.98 g, 9.4 mmol) was dissolved in 5 ml of ethyl 
acetate and added dropwise with stirring. Triethylamine hydrochloride was 
removed by extraction and ethyl acetate was removed by rotary evaporation. 
Crystallization from ethanol yielded 1.65 g of product, yield 65%. 
Example 11: 4-Tetrahydropyranyloxyacetophenone 
4-Hydroxyacetophenone (75.00 g, 0.55 mol) was dissolved in ethyl acetate 
(300 ml) and a catalytic amount of methanesulfonic acid. The solution was 
cooled to 0.degree.-4.degree. C. Dihydropyran (204 ml, 2.20 moles, 4.0 eq) 
was slowly added. At the end of the addition, the ice-water bath was 
removed and the reaction was allowed to proceed at room temperature. A few 
minutes later a heavy white precipitate was formed and the slurry was 
transferred into a separatory funnel where it was washed with water. The 
organic layer was dried over anhydrous sodium sulfate. Removal of the 
solvent under reduced pressure afforded a white fluffy solid. The solid 
was recrystallized from hexane. The yield was quantitative. 
Example 12: 4-Hydroxydibenzoyl methane 
4-Tetrahydropyranloxyacetophenone (0.50 g, 2.11 mol) was dissolved in 
freshly distilled THF (6.0 ml). Sodium hydride (60% suspended in mineral 
oil, 170 mg, 4.23 mmol) was added. The mixture was stirred at room 
temperature and methyl benzoate (0.53 ml, 4.23 mmol) was added. The 
mixture was stirred at room temperature for an additional three hours. The 
reaction was quenched with the addition of methanol. After solvent 
removal, the crude oil was dissolved in methylene chloride and washed with 
a 0.02 N aqueous solution of oxalic acid. The organic layer was then dried 
over anhydrous sodium sulfate. The crude product was dissolved in methanol 
(30 ml) and a 2 N aqueous solution of oxalic acid (10 ml) was added. The 
solution was stirred for 2 hours at 42.degree. C. The solvent was 
partially removed with the Rotavapor and a yellow solid was recovered upon 
filtration. The solid was dissolved in a minimum of hot ethanol and was 
precipitated by addition of hexane. A yellow solid (0.456 g, 1.90 mmol, 
90%) was isolated. 
Example 13: Acylation of 4-hydroxydibenzoylmethane with acryloyl chloride 
4-Hydroxydibenzoyl methane (10.00 g, 41.62 mmol) was dissolved in freshly 
distilled THF (25.0 ml). The solution was cooled to 0.degree. C. and 
diazobicycloundecene (DBU) (7.50 ml, 50.00 mmol) was slowly added at 
0.degree. C. Acryloyl chloride (5.92 ml, 72.84 mmol) was then added slowly 
at 0.degree. C. After one hour stirring, the reaction was quenched by 
addition of methanol. Solvent removal afforded an oil. The crude oil was 
dissolved in a dichloromethane/hexane mixture. Purification was carried 
out by flash chromatography on silica gel utilizing hexane/dichloromethane 
as eluent. After pooling all relevant fractions and removing the solvent, 
a clear solid (5.60 g, 46%) was obtained. 
Example 14: Acylation of p-hydroxymethacrylanilide with p-anisoyl chloride 
p-Hydroxymethacrylanilide (20.0 g, 113 mmol) was suspended in 250 ml ethyl 
acetate and 17.3 ml (12.6 g, 125 mmol) triethylamine. p-Anisoyl chloride 
(19.26 g, 113 mmol) was added dropwise at 25.degree. C. over 15 minutes. 
The reaction was allowed to proceed for 24 hours with stirring at room 
temperature. The solid was filtered, washed with water (100 ml.times.3), 
and then washed with saturated bicarbonate solution (100 ml.times.3). The 
solid crystallized from methanol weighed 27.1 g, yield 77%. 
Example 15: Acylation of 2-hydroxyethyl methacrylate with p-anisoyl 
chloride 
2-Hydroxyethyl methacrylate (5.00 g, 38.5 mmol) was dissolved in 25.0 ml 
ethyl acetate and triethylamine (4.25 g, 42.0 mmol). p-Anisoyl chloride 
(6.48 g, 38.5 mmol) was added dropwise at 5.degree. C. over ten minutes. 
After addition, the reaction was allowed to reach room temperature and 
stir for 24 hours. The triethylamine hydrochloride was filtered off and 
the filtrate washed with water (3.times.25.0 ml) and saturated bicarbonate 
solution (3.times.25.0 ml). The ethyl acetate layer was dried over 
MgSO.sub.4, then stripped to a light yellow oil. The oil was distilled at 
200.degree. C. (0.1 mmHg) to yield the desired product. 
Example 16: Acylation of N-2-hydroxyethyl acrylamide with p-anisoyl 
chloride 
N-2-hydroxyethyl acrylamide (5.00 g, 43.4 mmol) was dissolved in 35.0 ml 
ethyl acetate and triethylamine (4.83 g, 47.7 mmol). p-Anisoyl chloride 
(7.40 g, 43.4 mmol) was added dropwise at 5.degree. C. over ten minutes. 
After addition, the reaction was stirred for 24 hours at room temperature. 
The solid was filtered and washed with water (3.times.25 ml), to remove 
triethylamine hydrochloride, followed by saturated bicarbonate solution 
(3.times.25 ml), and then dried (6.43 g). The initial ethyl acetate 
filtrate was washed with water (3.times.25 ml) and saturated bicarbonate 
solution (3.times.25 ml). Concentration of the ethyl acetate layer gave 
two further crops of crystals. Total yield of the three crops: 9.36 g, 
93.6%. 
Example 17: Acylation of N-2-hydroxypropyl! methacrylamide with 
4-dimethylaminobenzoyl chloride 
4-Dimethylaminobenzoyl chloride (56.21 g, 0.306 mol) was combined with 
N-2-hydroxypropyl! methacrylamide (42.96 g, 0.30 mol) and 250 ml 
acetonitrile. The mixture was stirred at room temperature and a solution 
was briefly obtained before the desired HCl salt of the product 
crystallized. After filtration, washing with cold acetonitrile and drying, 
81.93 g (83.5% yield) of product was obtained. 
80.00 g (0.2447 mol) of the HCl salt was suspended in 400 ml 
dichloromethane while a solution of sodium bicarbonate (21.00 g, 0.25 mol) 
in 300 ml water was added dropwise. The two phases were filtered to remove 
turbidity and then separated. The CH.sub.2 Cl.sub.2 layer was dried on 
MgSO.sub.4, filtered, and evaporated to an oil that was crystallized from 
ethyl acetate to give 48 g of the free base of the product. 
Example 18: Polymerization of a UV-A monomer, a UV-B monomer, and a UV-C 
monomer 
A 10 ml vial was charged with 4-methoxy-N-1-(4-methacryloxyphenyl)! 
benzamide (156 mg, 0.5 mmol); 4-(dimethylamino) benzoyloxyethyl acrylate 
(138 mg, 0.5 mmol); 4-acryloxydibenzoyl methane (148 mg, 0.5 mmol); 
2-hydroxyethyl methacrylate (98 mg, 0.75 mmol); N,N-methylene bis 
acrylamide (10 mg, 0.067 mmol); 2,2'-azobisbutyronitrile (3.7 mg, 0.022 
mmol); and 3.5 ml methanol. The vial was flushed with argon, sealed and 
warmed to 60.degree. C. for 20 hours with stirring. The resulting 
polymeric precipitate was filtered off, washed with methanol, dried to a 
mass of 0.50 g, and then ground to a fine light yellow powder. 
Example 19: Polymerization of a UV-A monomer, a UV-B monomer, and a UV-C 
monomer 
A 1 liter flask was charged with 30.83 g (0.1 moles) UV-A monomer 
4-methacryloxydibenzoyl methane, 29.04 g (0.1 moles) UV-B monomer 
N-2-(4'-dimethylaminobenzoyl)oxypropyl! methacrylamide, 31.13 g (0.1 
moles) UV-C monomer 4-methoxy-N-1-(4-methacryloxyphenyl)! benzamide, 9.76 
g (0.075 moles) 2-hydroxyethylmethacrylate, 1.73 g (0.01125 moles) 
N,N-methylene bisacrylamide, and 500 ml methanol. After flushing with 
argon, 0.951 g (0.00579 moles) of 2,'2-azobis butyronitrile was added 
along with 250 ml of MeOH. After stirring at 60.degree. C. for 20 hours 
the sunscreen polymer was filtered, washed with methanol, and vacuum dried 
to a mass of 90.66 g. 
Example 20: Formulation of a Polymeric Sunscreen 
2.5 g of the polymeric sunscreen described in Example 19 was mixed with 3 g 
of petroleum vaseline to produce a fine emulsion with the consistency of a 
spreadable paste. Upon skin application, the emulsion produced a 
well-adhering flexible and non-visible film. 
Example 21: Preparation of a sunscreen cream "C" 
1.33 g of light mineral oil was placed in a stainless steel ball grinder 
and 2 g of polymer were added and ground for 10 minutes. After reducing 
the speed, 1.617 g of a hydrophilic grease base is added and all 
components are mixed for 5 minutes, and 50mg of TiO.sub.2 (aluminum 
hydroxide and stearic acid coated) is added and grinding at high speed is 
pursued 5 minutes to obtain the product. 
Example 22: Preparation of a sunscreen cream "D" 
1.33 g of light mineral oil was placed in the ball grinder and 2 g of 
polymer was added followed by 1.67 g of vaseline. The mixture is ground in 
a manner analogous to the preparation of the sunscreen cream "C" 
Example 23: Preparation of a sunscreen cream "E" 
1.33 g of light mineral oil was placed in the ball grinder and 2 g of 
polymer was added. A mixing technique identical to example 21 was used. 
Then, 1.665 g of vaseline was added and mixed for 5 minutes. 50 mg of 
TiO.sub.2 (aluminum hydroxide and stearic acid coated) was added and the 
mixture milled for 5 minutes, to obtain a fine spreadable cream. 
Example 24: Preparation of a sunscreen cream "G" 
2.97 g of vaseline was placed into a stainless steel grinder, and 1.98 g of 
polymer was added, and the mixture ground for 10 minutes. 50 mg of 
TiO.sub.2 (aluminum hydroxide and stearic acid coated) is added, and 
ground/mixed for 10 minutes to obtain the product. 
Example 25: Polymerization of a UV A monomer and a UV B monomer with 
acrylic acid 
A 250 mL flask was charged with a 4-methacryloxydibenzoyl methane (1.2 g, 
3.89.times.10.sup.-2 mol), N-2-(4'-dimethylamino benzoyl)oxy!propyl 
methacrylamide (14.65 g, 5.04.times.10.sup.-2 mol), 140 mL toluene 
followed by acrylic acid (3.91 g, 5.43.times.10.sup.-4 mol), and ethylene 
glycol dimethacrylate (0.19 g, 9.08.times.10.sup.-4 mol). After achieving 
a homogenous solution with stirring, the vessel was flushed with nitrogen, 
and 2,2'-azobis isobutyronitrile (0.1 g, 6.09.times.10.sup.-4 mol) was 
added to the flask. After stirring, (35-40 RPM) at 65.degree. C. for 20 
hours, the formed solid was filtered and washed with toluene. Resuspension 
with ethyl acetate at reflux for 30 hours and filtration afforded a pure 
powdery solid of particles, ranging from 0.7 to 3.mu., which was vacuum 
dried to a mass of 17.34 g (86.5% yield). 
In accordance with the invention, novel compositions are provided which 
give skin and eye protection from erythema, carcinogenicity and other 
deleterious effects of ultraviolet radiation, while biologically inert. 
The compositions have good retentive capability, provide a smooth coating 
on the skin, and do not unduly penetrate into the dermal layer, where the 
light absorbing moieties could have adverse effects. The compositions may 
be readily prepared from readily available compounds in accordance with 
conventional ways. For eye lenses, novel compositions are purified which 
are biologically and optically integral covalent parts of the lens to 
protect the eve from UV radiation, while the compositions are also 
biologically inert. 
All publications and patent applications cited in this specification are 
herein incorporated by reference as if each individual publication or 
patent application were specifically and individually indicated to be 
incorporated by reference. 
Although the foregoing invention has been described in some detail by way 
of illustration and example for purposes of clarity of understanding, it 
will be readily apparent to those of ordinary skill in the art in light of 
the teachings of this invention that certain changes and modifications may 
be made thereto without departing from the spirit or scope of the appended 
claims.