Process for producing an oil and water adsorbent polymer capable of entrapping solid particles and liquids and the product thereof

The present invention is directed to a porous polymer micro-particle, in the form of broken spheres, open to a porous oleophilic interior surface area, having a high oil and water absorbency and an apparent bulk density of about 0.02 to about 0.1 grams/cc. The preferred method of the present invention comprises the steps of: PA1 dissolving at least one and preferably at least two polyunsaturated monomers along with an effective amount of an organic polymerization initiator in a water-immiscible organic solvent to provide a monomer mixture; PA1 adding the monomer mixture to an aqueous solution, preferably having an effective amount of a suspension stabilizer dissolved therein, to form an organic/aqueous biphasic liquid system; PA1 vigorously agitating the biphasic liquid system at a rate sufficient to cause the water-immiscible organic phase to be suspended as micro-droplets in the aqueous phase; PA1 continuing vigorous agitating during polymerization of the monomers in the suspended micro-droplets to produce a microporous polymer micro-particle; and PA1 separating the microporous polymer micro-particle from the organic solvent to produce a microporous and oil sorbent polymer micro-particle having a mean unit diameter of less than about 25 microns and a total sorptive capacity for mineral oil that is at least about 72% by weight, preferably at least about 80% by weight dry polymer basis.

BACKGROUND OF THE INVENTION 
A. Field Of The Invention 
The present invention relates to a process for producing an oil and water 
adsorbent polymer in broken micro-particle form capable of entrapping any 
desired solid and/or liquid oleophilic and/or hydrophilic compound and 
composition (organic and/or aqueous) for delivery. More particularly, the 
present invention relates to a process for producing a highly porous and 
highly cross-linked hydrophilic/oleophilic polymer in the form of open 
(broken) spheres and sphere sections characterized by a mean unit particle 
size of about 0.5 to about 3000 microns, preferably about 1 to about 300 
microns, more preferably about 0.5 to about 100 microns, and most 
preferably, for cosmetic uses, about 0.5 to bout 80 microns. The 
micro-particles have an oil sorbency of at least about 72% by weight, 
preferably at least about 80% by weight (calculated as weight of material 
sorbed divided by total weight of material sorbed plus dry weight of 
polymer sorbent). The present invention is also directed to the oil and 
water adsorbent micro-particles produced by the process having an 
extremely low bulk density in the range of about 0.02 gm/cc to about 0. 1 
gm/cc, preferably about 0.03 gm/cc to about 0.07 gm/cc, more preferably 
about 0.03 gm/cc to about 0.04-0.05 gm/cc. The micro-particles produced by 
the process of the present invention are capable of holding and releasing 
oleophilic oils, creams, cleaners, medicaments and other organic active 
compounds and compositions, as well as hydrophilic active compounds and 
aqueous compositions, individually, or both oleophilic and hydrophilic 
materials simultaneously, for use in the cosmetic, cleaning, chemical 
process and pharmaceutical industries. 
B. Background 
Early disclosures of polymer particles appear in U.S. Pat. Nos. 3,493,500 
and 3,658,772, which issued on Feb. 3, 1970 and Apr. 25, 1972, 
respectively. They teach the production of aqueous suspensions of polymer 
particles from acrylic acid monomer and/or acrylamide monomer in an 
aqueous reaction medium at pH 1-4. Both patents teach that the resultant 
polymer suspensions, which were not characterized as to particle size or 
structure, were suitable for use as flocculating agents for sewage 
treatment. 
It was subsequently discovered that polymers could be made in a porous 
particulate form by a variety of techniques. The art has stated that "the 
type of polymerization technique used is an important factor in the 
determination of the resulting product." See U.S. Pat. No. 4,962,170 at 
column 2, line. 4. As stated in the '170 patent at column 2, lines 7-11, 
"within each type of polymerization, there are procedural alternatives 
which can have significant impact on the resulting product" "t!he 
differences in the polymerization techniques are enough that a procedure 
used in one type of polymerization technique that will not necessarily 
have the same effect if used in another polymerization technique." Thus, 
there is a significant degree of unpredictability in the art. 
Porous polymeric particles are capable of being prepared by one of two 
processes--precipitation polymerization in a single solvent system, or 
suspension polymerization in a two phase liquid system. The precipitation 
polymerization technique is presented in U.S. Pat. Nos. 4,962,170 and 
4,962,133 both of which issued on Oct. 9, 1990. The '170 patent discloses 
a precipitation polymerization process wherein the disclosed monomers are 
soluble in the single solvent system, whereas the resulting polymer, which 
is insoluble, precipitates out of solution once a critical size is 
obtained. In the '170 process, the solution of monomer consists 
exclusively of one or more types of polyunsaturated monomer. Because each 
monomer is polyunsaturated, each monomer also functions as a cross-linker, 
resulting in a highly cross-linked polymer particle. 
Like the '170 patent, the '133 patent also utilizes the precipitation 
polymerization process for producing a porous polymeric particle. However, 
unlike the '170 process, wherein the monomer solution consists exclusively 
of polyunsaturated monomers, the '133 process discloses the monomer 
solution may include one monosaturated monomer in combination with one 
polyunsaturated monomer, wherein the polyunsaturated monomer may comprise 
up to 90% by weight of the total weight of monomers. Because the 
precipitation polymerization technique relies upon the formation of 
polymer aggregates of precipitated polymer particles, the monomer solution 
is not vigorously agitated during polymerization to avoid separation of 
the aggregated polymer particles. 
U.S. Pat. No. 5,316,774 is directed to a suspension polymerization process, 
again limited to a maximum of 90% by weight polyunsaturated monomers based 
on the total weight of monomers. Accordingly, it is an object of the 
present invention to provide a process for making sorbent micropolymers 
from a monomer solution that contains more than 90% by weight, preferably 
about 92% to 100% polyunsaturated monomers, by weight based on the total 
weight of monomers in the monomer solution. 
The '133 process is limited to a solvent system that is an aqueous/organic 
azeotrope. Because the organic solvent cannot be separated from the water 
in an azeotrope, azeotropic solutions present special waste disposal 
problems. Accordingly, it is an object of the present invention to provide 
a process for making oil and water adsorbent micropolymers that does not 
require an azeotropic solution. Further, the particles produced by the 
'133 process range extensively in size from less than about 1 micron in 
average diameter for unit particles to about twelve hundred microns in 
average diameter for clusters of fused aggregates. The large variability 
in size limits the utility and properties of the polymeric particles. 
Accordingly, it is also an object of the present invention to provide a 
process for making polymeric micro-particles of a less diverse size 
distribution. 
Another process disclosed in the art for producing microscopic polymers is 
in situ suspension polymerization wherein an active ingredient included 
within the monomer mixture is retained in the formed polymer upon 
completion of polymerization. Examples of in situ suspension 
polymerization include U.S. Pat. No. 4,724,240 wherein polymerization of a 
monounsaturated monomer and a polyunsaturated monomer in an 
aqueous/polyvinylpyrrolidone system containing an emollient, as the active 
agent, produced relatively large micro-particles, having a mean diameter 
"between 0.25 to 0.5 mm" (250 to 500 microns) that contains the emollient 
therein upon completion of polymerization. A problem with a particle 
having a mean diameter of 250-500 microns is that the particle is capable 
of being sensed by touch. This is an undesirable property if the particle 
is to be used in a lotion or cream or other cosmetic formulations. 
Accordingly, it is also an object of the present invention to provide a 
process that is capable of manufacturing polymeric particles having a 
smaller mean diameter, e.g., about 0.5 .mu.m to about 120 .mu.m, 
preferably about 1 .mu.m to about 100 .mu.m, for a smoother skin feel. 
A second problem with the process of the '240 patent is that it is limited 
to those active ingredients that are capable of dissolving in the organic 
solvent. The polymeric micro-particles of the present invention are 
capable of adsorbing both (a) organic compounds and organic compositions 
containing oleophilic compounds dissolved in an organic solvent, as well 
as solid organic compounds entrapped within an interior of the open 
(broken) micro-particle sphere pores; and (b) liquid hydrophilic compounds 
and hydrophilic aqueous compositions containing water-soluble compounds 
dissolved in water, as well as solid hydrophilic solid compounds that are 
adsorbed on an exterior, porous surface area of the broken spheres. 
Further, the active ingredient(s), which may be proprietary, must be 
provided in bulk to the polymer manufacturer so that they may become 
trapped in the particles during the polymerization process. To overcome 
these problems, it is a further object of the present invention to provide 
polymeric micro-particles having evacuated internal pores, within broken 
(open) micro-particle spheres and sphere portions that are capable of 
adsorbing both oleophilic and hydrophilic solids and liquids in higher 
amounts than prior art micro-particless. It is theorized that the 
oleophilic solids and liquids are adsorbed within the interior porous 
surface area of each open sphere or sphere portion, in large amounts, so 
that they may be loaded within the interior of the spheres with adsorbed 
active oleophilic organic ingredient(s) in solid or solvent-dissolved 
form, and it is theorized that the exterior porous surface area of the 
broken spheres adsorb both hydrophilic and oleophilic solids and liquids 
via capillary adsorption in the porous outer surface (oleophilic 
materials) or by surface attraction of hydrophilic materials. 
A third problem with the '240 process is that it is not suited for use when 
the active ingredient is a mixture of components that differ significantly 
from one another as to oleophilicity. In such a situation, the more 
oleophilic of the active ingredients would be selectively isolated in the 
pores of the polymer made by the '240 process. To overcome this problem, 
the '240 process would have to be separately applied to each of the active 
ingredients, and thereafter, the resulting products would be mixed. 
However, such additional processing and mixing is costly. Accordingly, it 
is a further object of the present invention to provide a process for 
producing a micro-particle wherein the micro-particle is capable of 
receiving a plurality of oleophilic active ingredients, and/or a plurality 
of hydrophilic active ingredients. 
SUMMARY OF THE INVENTION 
It was unexpectedly discovered that the process of the present invention is 
capable of producing micro-particles that have not only a high oil 
adsorbency, but that also exhibit a high adsorbency of water and 
hydrophilic compounds and aqueous compositions in a more uniform and 
narrower particle size distribution. The oleophilic materials or 
hydrophilic materials may be adsorbed alone or together to deliver 
materials separately or simultaneously. Both materials can be held 
simultaneously in the micro-particles of the present invention. Prior art 
materials such as Dow DC-5640 can hold oleophilic or hydrophilic 
materials, but not both simultaneously. 
The present invention is directed to a process for making a porous polymer 
of micro-particulate size that exhibits a high oil and water adsorbency. 
The method of the present invention comprises the steps of: 
dissolving at least one and preferably at least two polyunsaturated 
monomers along with an effective amount of an organic polymerization 
initiator in a water-immiscible organic porogen that is inert (not 
reactive) to the monomers and resulting polymer to provide a monomer 
mixture; 
adding the monomer mixture to an aqueous solution, preferably having an 
effective amount of a suspension stabilizer dissolved therein, to form an 
organic/aqueous biphasic liquid composition including an organic phase and 
an aqueous phase; 
vigorously agitating the biphasic liquid composition at a rate sufficient 
to cause the water-immiscible organic phase to be suspended as 
micro-droplets in the aqueous phase; 
continuing vigorous agitation during polymerization of the monomers in the 
suspended micro-droplets to produce microporous polymer micro-particles in 
the form of broken (open) spheres; and 
separating the microporous polymer micro-particles from the organic solvent 
to produce a microporous, oil and water adsorbent polymer micro-particle 
having a mean unit diameter of less than about 50 microns, preferably less 
than about 25 microns, more preferably less than about 20 microns, and a 
new and unexpected adsorptive capacity for both hydrophobic and 
hydrophilic compounds, in both solid and liquid (organic solvent and 
aqueous) forms. 
The present invention is further directed to microporous, oil and water 
adsorbent micro-particles comprising a polymer that includes at least two 
polyunsaturated monomers, the micro-particle characterized by being open 
to its interior, by virtue of particle fracture upon removal of the 
porogen after polymerization, or by virtue of subsequent milling, and 
having a mean unit diameter of less than about 50 microns, preferably less 
than about 25 microns, having a total adsorption capacity for organic 
liquids, e.g., mineral oil, within the pores of the interior, porous 
surface area of the particles, that is at least about 72% by weight, 
preferably at least about 80% by weight, and an adsorption capacity for 
hydrophilic compounds and aqueous solutions of about 70% to about 93% by 
weight, preferably about 75% to about 93% by weight. In a preferred 
embodiment, the broken sphere micro-particles of the present invention are 
characterized by a mean unit diameter from about 1 to about 50 microns, 
more preferably from about 1 to about 25 microns, most preferably, from 
about 1 to about 20 microns.

DETAILED DESCRIPTION OF THE INVENTION 
The present invention has two aspects. In its first aspect, it is directed 
to a process for making a polymer in a porous micro-particle form that is 
capable of sorbing high volumes of one or both of oleophilic (hydrophobic) 
and hydrophilic compounds in solid and/or liquid forms. Oleophilic 
compounds are adsorbed within the interior of the broken spheres, and 
adsorbed by capillary adsorption within pores in the outer surface area, 
and hydrophilic compounds are adsorbed on the exterior surfaces of the 
spheres, theoretically by electrostatic attraction with the exterior 
surfaces of the spheres by virtue of the surrounding water molecules 
present during the polymerization process. The preferred process of the 
present invention comprises the steps of: 
dissolving at least one or preferably at least two polyunsaturated monomers 
along with an effective amount of an organic polymerization initiator in a 
water-immiscible organic solvent to provide a monomer mixture; 
adding the monomer mixture to an aqueous solution, preferably having an 
effective amount of a suspension stabilizer dissolved therein, to form an 
organic/aqueous biphasic liquid system including an organic phase and an 
aqueous phase; 
vigorously agitating or otherwise shearing the biphasic liquid system at a 
rate sufficient to cause the water-immiscible organic phase to be 
suspended as micro-droplets in the aqueous phase e.g., by rotating a 
stirring paddle at a tip speed of about 1 to about 15 meters per second 
preferably at least about 5 meters per second, most preferably about 8 
meters per second. 
continuing said vigorous agitation or other shear means during 
polymerization of the monomers in the suspended micro-droplets to produce 
a microporous polymer micro-particle; and 
separating the microporous polymer micro-particle from the organic solvent 
to produce microporous, oil and water adsorbent polymer micro-particles in 
the form of broken spheres having a mean unit diameter of less than about 
50 microns and a new and unexpected adsorptive capacity for both 
oleophilic and hydrophilic compounds, in both solid and liquid (organic 
solvent and aqueous) forms. 
The term "sorptive" (or "sorption") is used herein to refer to the 
capability or capacity of the micro-particles of the present invention to 
both adsorb and absorb lipophilic and hydrophilic materials. However, the 
amount of liquid that is absorbed is negligible in comparison to the 
amount of oleophilic and hydrophilic solids and/or liquids that are 
adsorbed on both the interior and exterior, respectively, of the broken 
spheres. In discussing micro-particles, the art loosely uses the term 
"adsorptive," such as in "total adsorptive capacity" or in "free flowing 
adsorptive capacity." However, it is understood that references in the art 
to "total adsorptive capacity" inherently include the total absorptive 
capacity of a particle as well as its adsorptive capacity, unless 
otherwise defined. Likewise, references in the art to "free flowing 
adsorptive capacity" also inherently include both the absorptive and 
adsorptive capacities. 
The process of the present invention copolymerizes at least two 
polyunsaturated (polyethylenically unsaturated) monomers, preferably allyl 
methacrylate, and an ethylene glycol dimethacrylate. Both the allyl 
methacrylate and the ethylene glycol dimethacrylate are diunsaturated 
monomers. The diunsaturated monomers also function as cross-linking 
agents. 
The highly cross-linked polymeric micro-particles of this invention are 
prepared by polymerizing at least one and preferably at least two monomers 
having at least two unsaturated bonds (hereinafter referred to as 
"polyunsaturated" monomers) said monomers being polymerized including no 
more than about 40% by weight, preferably less than about 9% by total 
monomer weight of monounsaturated comonomers. Examples of polyunsaturated 
monomers can be poly-acrylates ("poly" meaning two or more), 
-methacrylates, or -itaconates of: ethylene glycol, propylene glycol; di-, 
tri-, tetra-, or poly-ethylene glycol and propylene glycol; trimethylol 
propane, glycerine, erythritol, xylitol, pentaerythritol, 
dipentaerythritol, sorbitol, mannitol, glucose, sucrose, cellulose, 
hydroxyl cellulose, methyl cellulose, 1,2 or 1,3 propanediol, 1,3 or 1,4 
butanediol, 1,6 hexanediol, 1,8 octanediol, cyclohexanediol, or 
cyclohexanetriol. Similarly, bis(acrylamido or methacrylamido) compounds 
can be used. These compounds are, for example, methylene bis(acryl or 
methacryl)amide, 1,2 dihydroxy ethylene bis(acryl or methacryl)amide, 
hexamethylene bis(acryl or methacryl)amide. 
Another group of useful monomers could be represented by di or poly vinyl 
esters, such as divinyl propylene urea, divinyl-oxalate, -malonate, 
-succinate, -glutamate, -adipate, -sebacate, -maleate, -fumerate, 
-citraconate, and -mesaconate. 
Other suitable polyunsaturated monomers include divinyl benzene, divinyl 
toluene, diallyl tartrate, allyl pyruvate, allyl maleate, divinyl 
tartrate, triallyl melamine, N,N'-methylene bis acrylamide, glycerine 
dimethacrylate, glycerine trimethacrylate, diallyl maleate, divinyl ether, 
diallyl monoethyleneglycol citrate, ethyleneglycol vinyl allyl citrate, 
allyl vinyl maleate, diallyl itaconate, ethyleneglycol diester of itaconic 
acid, divinyl sulfone, hexahydro 1,3,5-triacryltriazine, triallyl 
phosphite, diallyl ether of benzene phosphonic acid, maleic anhydride 
triethylene glycol polyester, polyallyl sucrose, polyallyl glucose, 
sucrose diacrylate, glucose dimethacrylate, pentaerythritol di-, tri- and 
tetra- acrylate or methacrylate, trimethylol propane di- and triacrylate 
or methacrylate, sorbitol dimethacrylate, 2-(1-aziridinyl)-ethyl 
methacrylate, tri-ethanolamine diacrylate or dimethacrylate, 
triethanolamine triacrylate or trimethacrylate, tartaric acid 
dimethacrylate, triethyleneglycol dimethacrylate, the dimethacrylate of 
bis-hydroxy ethylacetamide and the like. 
Other suitable polyethylenically unsaturated cross-linking monomers include 
ethylene glycol diacrylate, diallyl phthalate, 
trimethylolpropanetrimethacrylate, polyvinyl and polyallyl ethers of 
ethylene glycol, of glycerol, of pentaerythritol, of diethyleneglycol, of 
monothio- and dithio-derivatives of glycols, and of resorcinol; 
divinylketone, divinylsulfide, allyl acrylate, diallyl fumarate, diallyl 
succinate, diallyl carbonate, diallyl malonate, diallyl oxalate, diallyl 
adipate, diallyl sebacate, diallyl tartrate, diallyl silicate, triallyl 
tricarballylate, triallyl aconitrate, triallyl citrate, triallyl 
phosphate, divinyl naphthalene, divinylbenzene, trivinylbenzene; 
alkyldivinylbenzenes having from 1 to 4 alkyl groups of 1 to 2 carbon 
atoms substituted on the benzene nucleus; alkyltrivinylbenzenes having 1 
to 3 alkyl groups of 1 to 2 carbon atoms substituted on the benzene 
nucleus; trivinylnaphthalenes, and polyvinylanthracenes. In addition, 
acryl or methracryl-encapped siloxanes and polysiloxanes, methacryloyl 
end-capped urethanes, urethane acrylates of polysiloxane alchols and 
bisphenol A bis methacrylate and ethoxylated bisphenol A bis methacrylate 
also are suitable as polyunsaturated monomers. 
Still another group of monomers is represented by di or poly vinyl ethers 
of ethylene, propylene, butylene, and the like, glycols, glycerine, penta 
erythritol, sorbitol, di or poly allyl compounds such as those based on 
glycols, glycerine, and the like, or combinations of vinyl allyl or vinyl 
acryloyl compounds such as vinyl methacrylate, vinyl acrylate, allyl 
methacrylate, allyl acrylate, methallyl methacrylate, or methallyl 
acrylate. In addition, aromatic, cycloaliphatic and heterocyclic compounds 
are suitable for this invention. These compounds include divinyl benzene, 
divinyl toluene, divinyl diphenyl, divinyl cyclohexane, trivinyl benzene, 
divinyl pyridine, and divinyl piperidine. Furthermore, divinyl ethylene or 
divinyl propylene urea and similar compounds may be used, e.g., as 
described in U.S. Pat. Nos. 3,759,880; 3,992,562; and 4,013,825, which are 
hereby incorporated by reference. Acryloyl- or methacryloyl end-capped 
siloxane and polysiloxanes such as those described in U.S. Pat. Nos. 
4,276,402; 4,341,889, French Patent 2,465,236, and German Publication GER 
OLS Patent 3,034,505, which are hereby incorporated by reference, are 
suitable for this invention. Methacryloyl end-capped urethanes, such as 
those described in U.S. Pat. Nos. 4,224,427; 4,250,322; and 4,423,099, 
German Publications GER OLS No. 2,365,631 and 2,542,314, Japanese Patent 
Application Nos. 85/233,110; 86/09,424, and 86/30,566, and British Patent 
1,443,715, are suitable for this invention. Urethane acrylates of 
polysiloxane alcohols as described in U.S. Pat. Nos. 4,543,398 and 
4,136,250 and bisphenol A bis methacrylate and ethoxylated bisphenol A bis 
methacrylate are also suitable monomers for this invention. 
Monoethylenically unsaturated monomers suitable, in an amount up to about 
40% preferably less than about 9% by weight, based on the total weight of 
monomers, for preparing polymer micro-particles include ethylene, 
propylene, isobutylene, disobutylene, styrene, vinyl pyridine 
ethylvinylbenzene, vinyltoluene, and dicyclopentadiene; esters of acrylic 
and methacrylic acid, including the methyl, ethyl, propyl, isopropyl, 
butyl, sec-butyl, tert-butyl, amyl, hexyl, octyl, ethylhexyl, decyl, 
dodecyl, cyclohexyl, isobornyl, phenyl, benzyl, alkylphenyl, ethoxymethyl, 
ethoxyethyl, ethoxyproyl, propoxymethyl, propoxyethyl, propoxypropyl, 
ethoxyphenyl, ethoxybenzyl, and ethoxycyclohexyl esters; vinyl esters, 
including vinyl acetate, vinyl propionate, vinyl butyrate and vinyl 
laurate, vinyl ketones, including vinyl methyl ketone, vinyl ethyl ketone, 
vinyl isopropyl ketone, and methyl isopropenyl ketone, vinyl ethers, 
including vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and 
vinyl isobutyl ether; and the like. 
Other monounsaturated monomer materials which may be utilized in accordance 
with the present invention, in an amount up to about 40%, preferably less 
than about 9% by weight, based on the total weight of monomers in the 
monomer solution, include hydroxy alkyl esters of alpha, beta-unsaturated 
carboxylic acids such as 2-hydroxy ethylacrylate or methacrylate, 
hydroxypropylacrylate or methacrylate and the like. Many derivatives of 
acrylic or methacrylic acid other than the esters mentioned are also 
suitable as starting monounsaturated monomer materials for use in forming 
the unsaturated polymer micro-particles of the present invention. These 
include, but are not limited to the following monomers: 
methacrylylglycolic acid, the monomethacrylates of glycol, glycerol, and 
of other polyhydric alcohols, the monomethacrylates of dialkylene glycols 
and polyalkylene glycols, and the like. The corresponding acrylates in 
each instance may be substituted for the methacrylates. Examples include 
the following: 2-hydroxyethyl acrylate or methacrylate, diethylene glycol 
acrylate or methacrylate, 3-hydroxypropyl acrylate or methacrylate, 
tetraethyleneglycol acrylate or methacrylate, pentaethyleneglycol acrylate 
or methacrylate, dipropyleneglycol acrylate or methacrylate, acrylamide, 
methacrylamide, diacetoneacrylamide methylolacrylamide 
methylolmethacrylanide, any acrylate or methacrylate having one or more 
straight or branched chain alkyl groups of 1 to 30 carbon atoms, 
preferably 5 to 18 carbon atoms, and the like. Other suitable examples 
include isobornyl methacrylate, phenoxyethyl methacrylate, isodecyl 
methacrylate, stearyl methacrylate, hydroxypropyl methacrylate, cyclonexyl 
methacrylate, dimethylaminoethyl methacrylate, t-butylaminoethyl 
methacrylate, 2-acrylamido propane sulfonic acid, 2-ethylexyl 
methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 
2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate and 
methoxyethyl methacrylate. 
Examples of monounsaturated monomers containing carboxylic acid groups as 
functional groups and suitable for use as starting materials in accordance 
with the invention include the following: acrylic acid, methacrylic acid, 
itaconic acid, aconitic acid, cinnamic acid, crotonic acid, mesaconic 
acid, maleic acid, fumaric acid and the like. 
Partial esters of the above acids are also suitable as monosaturated 
monomers for use in accordance with the invention. Instances of such 
esters include the following: mono-2-hydroxypropyl aconitate, 
mono-2-hydroxyethyl maleate, mono-2-hydroxypropyl fumarate, mono-ethyl 
itaconate, monomethyl cellosolve ester of itaconic acid, monomethyl 
cellosolve ester of maleic acid, and the like. 
Instances of suitable monounsaturated monomers containing amino groups as 
functional groups include the following: diethylaminoethyl acrylate or 
methacrylate, dimethylaminoethyl acrylate or methacrylate, 
monoethylaminoethyl acrylate or methacrylate, tert, butylaminoethyl 
methacrylate, para-amino styrene, ortho-amino styrene, 2-amino-4-vinyl 
toluene, piperidinoethyl methacrylate, morpholinoethyl methacrylate, 
2-vinyl pyridine, 3-vinyl pyridine, 4-vinyl pyridine, 2-ethyl-5-vinyl 
pyridine, dimethylaminopropyl acrylate and methacrylate, 
dimethylaminoethyl vinyl ether, dimethylaminoethyl vinyl sulfide, 
diethylaminoethyl vinyl ether, amonoethyl vinyl ether, 2-pyrrolidinoethyl 
methacrylate, 3-dimethylaminoethyl-2-hydroxy-propylacrylateormethacrylate, 
2-aminoethyl acrylate or methacrylate, isopropyl methacrylamide, N-methyl 
acrylamide or methacrylamide, 2-hydroxyethyl acrylamide or methacrylamide, 
1-methacryloyl-2-hydroxy-3-trimethyl ammonium chloride or sulfomethylate, 
2-(1-aziridinyl)-ethyl methacrylate, and the like. Polyethylenically 
unsaturated monomers which ordinarily act as though they have only one 
unsaturated group, such as isopropene, butadiene and chloroprene, should 
not be calculated as part of the polyunsaturated monomer content, but as 
part of the monoethylenically unsaturated monomer content. 
The process of the present invention preferably utilizes an effective 
amount of an organic polymerization initiator to cause polymerization to 
occur in the organic phase solvent. However, other methods of initiating 
polymerization may be used instead, such as UV light, actinic radiation, 
or the like. By way of example, suitable organic initiators include the 
organic peroxide initiators, such as dibenzoyl peroxide or t-butyl 
peroctoate, or the azo initiators. Preferred initiators are the azo 
initiators such as 2,2'-azobisisobutyronitrile and 2,2'-azobis 
(2,4-dimetylpentanenitrile). An especially preferred azo initiator is 
2,2'-azobis(2,4-dimetylpentanenitrile), which is commercially available 
under the tradename VAZO 52 from DuPont, Wilmington, Del. A typical 
effective amount of organic initiator relative to dry monomer was found to 
be about 0.5-2% by weight, preferably about 1-1.2% by weight. 
Examples of redox systems include secondary or tertiary amines and, most 
preferably amine (preferably tertiary) and peroxide combinations. The 
ratio between the peroxide and the amine may vary from 0.1 to 5 moles of 
amine per mole of peroxide. It is useful to first dissolve the peroxide in 
a part of the solvent, and separately dissolve the amine in the other part 
of the solvent, then mix the peroxide part with the monomer solution at 
room temperature and, subsequently, add the amine part. The charging of 
the peroxide and amine part can be done at the beginning of the reaction 
or in portions throughout the reaction period. These amines are generally 
of the formula R.sub.2 NH or R.sub.3 N wherein R is an alkyl or 
substituted alkyl, cycloalkyl, or aryl group. Preferably the amine is a 
tertiary amine. 
Illustrative reducing agents of this invention are methylbutyl amine, 
bis(2-hydroxyethyl)butyl amine, butyldimethyl amine, dimethyl amine, 
dibenzylethyl amine, diethylmethyl amine, dimethylpentyl amine, diethyl 
amine, 2,2',2"-trihydroxy dipropyl ethyl amine, di-n-propylene amine, 
2,2',2"-trimethyl tributyl amine, triethyl amine, dimethyl aminoacetal, 
pentylhexyl amine, triethanolamine, trihexyl amine, trimethyl amine, 
trioctadecyl amine, tripropyl amine, trisopropyl amine, tetramethylene 
diamine, and esters of para-amino benzoic acid, e.g., p-dimethyl 
amino-2-ethylhexyl-benzoate, dimethyl aminoethyl acetate, 
2-(n-butoxy)ethyl 4-dimethylaminobenzoate, 2-(dimethylamino) ethyl 
benzoate, ethyl-4-dimethylaminobenzoate, methyldiethanolamine, dibutyl 
amine, N,N-dimethylbenzylamine, methylethyl amine, dipentyl amine and 
peroxide Fe.sup.2+. 
Other preferred initiators are selected from inorganic initiators such as 
sodium, potassium, and/or ammonium persulfates, and hydrogen peroxide. 
In the preferred process of the present invention, the monomers and the 
organic initiator are dissolved in a substantially water-immiscible 
organic solvent porogen to produce the organic phase. Suitable 
substantially water-immiscible organic porogens include the aliphatic and 
aromatic hydrocarbons. Typical of these solvents are toluene, cyclohexane, 
silicone solvents, including fluoro silicone, chlorinated solvent, such as 
trichlor ethylene, tetrachloromethane; dichlormethane and the like, and 
one or more of the heptanes, alone or in combination. Based upon 
considerations of boiling point, volatility, toxicity, and solubility, a 
heptane is the more preferred solvent; most preferably, n-heptane. 
Polymerization is accomplished by dissolving the monomers or their mixtures 
in an inert porogen which does not react with the monomers or the 
resulting polymer. Based on the parts by weight of the monomer and the 
solvent totalling 100 parts by weight, the monomers are used from 0.1 to 
less than about 25 parts by weight, preferably, from about 2 to less than 
about 25 parts by weight, and, more preferably, from about 5 to about 20 
parts by weight. Correspondingly, the solvent porogen is present from 
greater than about 60 parts by weight, preferably greater than about 70 
parts by weight, more preferably greater than about 75-80 parts by weight 
to 99.9 parts by weight, preferably, from greater than about 75 parts by 
weight to about 98 parts by weight, and, most preferably, from about 80 
parts by weight to about 95 parts by weight. No surfactant or dispersing 
aid is required. 
Preferably, the porogen is relatively volatile, having a boiling point of 
less than about 200.degree. C., more preferably less than about 
180.degree. C., at one atmosphere and is water-miscible. The removal of 
the porogen can be accomplished by filtration and evaporation, e.g., by 
heat and/or vacuum, or the porogen can be left adsorbed by the polymeric 
spheres, on the interior of the spheres if lipophilic or on the outer 
surfaces of the spheres if hydrophilic. The polymer can be washed with a 
suitable solvent, e.g., isopropyl alcohol, acetone, silicone fluids, and 
mixtures thereof, before it is dried. 
Suitable porogens include a wide range of substances, notably inert, 
non-polar organic solvents. Some of the most convenient examples are 
alkanes, cycloalkanes, and aromatics. Specific examples of such solvents 
are alkanes of from 5 to 12 carbon atoms, straight or branched chain 
cycloalkanes of from 5 to 8 carbon atoms, benzene, and alkyl-substituted 
benzenes, such as toluene and the xylenes. 
Porogens of other types include C.sub.4 -C.sub.20 alcohols, perfluoro 
polyethers, and silicone oils. Examples of silicone oils are 
polydimethylcyclosiloxane, hexamethyldisiloxane, cyclomethicone, 
dimethicone, amodimethicone, trimethylsilylamodimethicone, 
polysiloxane-polyalkyl copolymers (such as stearyl dimethicone and cetyl 
dimethicone), dialkoxydimethylpolysiloxanes (such as stearoxy 
dimethicone), polyquarternium 21, dimethicone propyl PG-betaine, 
dimethicone copolyol and cetyl dimethicone copolyol. Removal of the 
porogen may be effected by solvent extraction, evaporation, or similar 
conventional operations. 
The process of the present invention also utilizes an aqueous phase. The 
aqueous phase comprises an aqueous solution, preferably having an 
effective amount of a suspension stabilizer dissolved therein. Suspension 
stabilizers are well known in the art. Suitable suspension stabilizers 
include starch, gum arabic, polyvinyl alcohol, sodium polymethacrylate, 
magnesium silicate, sodium bentonite clay, methyl cellulose, magnesium 
hydroxide (M.sub.g (OH).sub.2); polyvinyl pyrolidone (PVP); poly vinyl 
alcohol (PVOH); calcium phosphate; magnesium phosphate and lignites. A 
preferred suspension stabilizer is methyl cellulose, such as is 
commercially available from Dow Chemical Company, Midland, Mich., under 
the tradename Methocel A4C Premium. 
In performing the process of the present invention, the organic phase is 
combined under an inert (e.g., Argon or Nitrogen) atmosphere with an 
aqueous phase. The combination is typically performed at about room 
temperature (about 23.degree. C.) and at a ratio of organic phase to water 
phase of 10% to 90% by weight organic phase with 90% to 10% by weight 
water phase. Preferably about 50%-90% by weight water is included to 
assure that each suspended organic phase droplet is completely surrounded 
by water during polymerization of the monomer(s) in the organic phase. The 
combined phases should be vigorously stirred, or otherwise subjected to 
sufficient shear to separate the organic phase into micro-droplets (having 
a diameter of about 1 .mu.m to 120 .mu.m) surrounded by the aqueous phase. 
The stirring or shearing may commence during or after the combination of 
the two phases. Preferably, the vigorous stirring is employed during the 
combination of the two phases. More preferably, the organic phase is added 
slowly with vigorous stirring or vigorous agitation to the aqueous phase. 
By the phrase "vigorous agitation" as used herein is meant that the 
stirring paddle or impeller is rotated at a tip speed of about 1 meter per 
second to about 15 meters per second preferably at least about 5 meters 
per second, more preferably about 5-10 meters per second, most preferably 
about 8 meters per second. For example a paddle stirrer is rotated at a 
speed between about 800-2000 revolutions per minute ("rpm"), preferably at 
about 1400-1600 rpm. The function of the vigorous agitation is to 
facilitate the separation of the organic phase into micro-droplets that 
become isolated from one another as discrete mini-reaction vessels that 
are surrounded by water. In the process of the present invention, the 
water functions not only to separate the micro-droplets but also as a heat 
transfer vehicle for the transfer of heat to micro-droplets of monomers to 
initiate the exothermic polymerization reactions occurring in each 
micro-droplet, and to render the outer surfaces of the micro-particles 
hydrophilic for adsorption of hydrophilic compounds and aqueous 
compositions. 
The polymerization reaction is allowed to proceed in the vigorously 
agitated reaction mixture by raising the reaction temperature. As 
disclosed in Example 1, at about 46.degree. C., some polymerization was 
observed in the stirred reaction mixture. At about 53.degree. C., massive 
polymerization was observed. The mixture is then preferably heated to 
about 60.degree. C. to 65.degree. C. to drive the polymerization reaction 
to completion. Once the monomers have been polymerized through gelation 
and cross-linking, vigorous agitation can be stopped while maintaining 
slow agitation for heat transfer and homogeneity during subsequent polymer 
curing; or vigorous agitation can be continued. 
Once polymerization is completed, the resulting microporous polymer 
micro-particles are separated from the reaction mixture, such as by 
filtering or by screening. At this point, however, the separated particles 
are filled with the water-immiscible porogen of the reaction mixture. By 
selecting a porogen that is also volatile, the porogen can be removed 
readily from the internal pores of the polymer particles, preferably by 
steam distillation. Most of the micro-particle spheres are fractured via 
escape of porogen from an interior of the micro-particle spheres at this 
point in the process. If the porogen is left in place as an active 
ingredient of the polymer product, the spheres can be broken by milling. 
Once the microporous polymer micro-particles have been separated from the 
water-immiscible organic solvent, such that the oleophilic interior 
surfaces of the broken spheres are now evacuated, they become the 
preferred embodiment of the microporous, oil and water adsorbent polymer 
micro-particles of the present invention. Theoretically, the interior of 
the spheres adsorb oleophilic compounds and the exterior of the spheres 
adsorb both oleophilic and hydrophilic compounds. Alternatively, the 
porogen(s) can remain in place as an active material (in situ suspension 
polymerization). 
Thus, the present invention is also directed to a composition of matter--a 
microporous and oil and water adsorbent micro-particle in the form of 
broken spheres comprising a polymer formed by polymerizing at least one 
and preferably at least two polyunsaturated monomers (each containing at 
least two carbon to carbon double bonds) optionally including one or more 
monounsaturated monomers, in an amount up to about 40% by weight 
preferably no more than about 9% by weight, most preferably 0 to about 5% 
monounsaturated monomers based on the total weight of monomers. It has 
been found that adsorptive capacity increases dramatically as the 
percentage of monounsaturated monomers approaches zero. The resulting 
micro-particles, in the form of broken hollow spheres having non-smooth, 
irregular porous interior surfaces that provide more surface area than the 
outer surface of the spheres, having a mean unit diameter of less than 
about 50 microns, preferably less than about 25 microns, have total 
adsorption capacity for mineral oil that is 72% by weight or greater, 
based upon the total weight of the polymer plus adsorbed oil, preferably 
at least about an 80%, most preferably about 80% to about 93% by weight 
adsorptive capacity for oleophilic compounds and compositions, e.g., 
organics, such as mineral oil, and an adsorption capacity for hydrophilic 
compounds and aqueous solutions thereof of at least about 70% by weight, 
and preferably about 75% to about 90% by weight adsorption capacity for 
aqueous solutions/dispersions and hydrophilic solids, based on the total 
weight of polymer plus adsorbed aqueous/hydrophilic material. The phrase 
"mean unit diameter" refers to mean diameter of the individual particle 
and not to the diameter of agglomerates which may form from time to time 
due to static charge or otherwise. The mean unit diameter of the 
micro-particle is more preferably from about 1 to about 25 microns; most 
preferably, from about 1 to about 20 microns. 
Particles can be manufactured having particle sizes up to about 3000 um, 
particularly about 1000 um to about 2000 um. A preferred particle size 
distribution spans about 1-100 microns, more preferably about 1 to about 
80 microns, with particles generally not less than about 0.5 micron in 
size, with most particles being about 1 micron or larger. 
Preferably, the micro-particles of the present invention have a total 
adsorption capacity for mineral oil of about 74% by weight or greater; 
more preferably, about 76% by weight or greater; most preferably about 
78-80% by weight or greater. The most preferred particles have an 
adsorption capacity for mineral oil of at least about 90% by weight, based 
on the total weight of particles plus adsorbed oil. It is not expected 
that the sorption capacity of the polymers of the present invention for 
light mineral oil would exceed about 95% by weight, based on the total 
weight of polymer plus adsorbed mineral oil. 
The micro-particles of the present invention appear as a white powder and 
constitute free flowing discrete solid particles even when loaded with a 
hydrophilic and/or oleophilic material to their "free flowing" sorption 
capacity, e.g., about 85% by weight for the particles of Example 1 (POLY 
PORE.TM. E 200) when loaded with mineral oil. In a preferred microporous, 
oil and water adsorbent micro-particle of the present invention, two 
diunsaturated monomers are copolymerized--one of the polyunsaturated 
monomers being an ethylene glycol dimethacrylate, preferably monoethylene 
glycol dimethacrylate. The preparation of such a micro-particle is 
described in Example 1 herein, wherein the other diunsaturated monomer is 
allyl methacrylate and the mole ratio of allyl methacrylate: monoethylene 
glycol dimethacrylate was within a preferred molar ratio of allyl 
methacrylate: ethylene glycol dimethacrylate of 1:1 to 1:2, specifically 
1:1.22. 
The polymers of the present invention, containing at least one and 
preferably at least two polyunsaturated monomers, have a superior total 
adsorption capacity for mineral oil over the (BMA/EGDM) copolymers and a 
commercially available copolymer (MMA/EGDM). In particular, the polymer of 
Example 1 exhibited a total sorption capacity for mineral oil of 91.7% by 
weight, compared to 72.2% by weight for the best reported BMA/EGDM 
copolymer of the prior art and 64% by weight for the commercially 
available product (Dow Corning Product No. 5640). 
The abbreviations used herein are identified as follows: 
______________________________________ 
BMA butyl methacrylate 
EGDMA monoethylene glycol dimethacrylate 
AMA allyl methacrylate 
MMA methyl methacrylate 
______________________________________ 
EXAMPLE 1 (2 diunsaturated monomers Poly Pore.TM. E 200) 
5.25 grams of Methocel A4C Premium was dissolved in 573.3 grams of water in 
a 2000 ml three-necked resin equipped with a stirrer, thermometer, 
condenser and Argon purge. A solution of 40.92 grains of allyl 
methacrylate, 76.48 grams of ethylene glycol dimethacrylate, 765.20 grams 
of n-heptane and 2.33 grams of Vazo 52 was bubbled with Argon for 10 
minutes. The resultant mix was slowly added to the 1,500 rpm stirred 
aqueous solution of the Methocel at 23.degree. C. under Argon. The 
temperature was raised to 46.degree. C. with constant agitation when 
precipitation started. Massive polymerization was observed at 53.degree. 
C. The reaction mixture was then heated to 60.degree. C. to 65.degree. C. 
and that temperature was held for an additional six hours. Thereafter, the 
reaction mixture was subjected to steam distillation to remove the heptane 
and residual monomers. The copolymer was separated from the reaction 
mixture by filtration. The separated copolymer was washed with deionized 
water and dried in an oven at 80.degree. C. The dried polymer was an 
odorless, white, soft powder having a total adsorption capacity for light 
mineral oil of 11.1 grams/1 gram, and apparent density of 0.032 g/cc, a 
mole ratio of allyl methacrylate: ethylene glycol dimethacrylate 1:11.22, 
and a corresponding ratio mole percent 46:54. The particle size 
distribution was analyzed and was as follows: 
__________________________________________________________________________ 
High 
Under 
High 
Under 
High 
Under 
High 
Under 
High 
Under 
High 
Under 
Size 
% Size 
% Size 
% Size 
% Size 
% Size 
% 
__________________________________________________________________________ 
80.0 
100 24.9 
67.5 
7.75 
11.0 
2.41 
2.2 0.75 
0.3 0.23 
0.0 
71.9 
99.8 
22.4 
58.6 
6.97 
9.5 2.17 
1.9 0.68 
0.2 0.21 
0.0 
64.7 
99.5 
20.1 
49.7 
6.27 
8.2 1.95 
1.7 0.61 
0.2 0.19 
0.0 
58.2 
99.0 
18.1 
41.4 
5.64 
7.1 1.75 
1.5 0.55 
0.1 0.17 
0.0 
52.3 
98.2 
16.3 
34.3 
5.07 
6.1 1.58 
1.3 0.49 
0.1 0.15 
0.0 
47.1 
97.1 
14.6 
28.6 
4.56 
5.3 1.42 
1.1 0.44 
0.1 0.14 
0.0 
42.3 
95.1 
13.2 
23.9 
4.10 
4.5 1.28 
1.0 0.40 
0.0 0.12 
0.0 
38.1 
92.0 
11.8 
20.1 
3.69 
3.9 1.15 
0.9 0.36 
0.0 0.11 
0.0 
34.2 
88.2 
10.7 
17.1 
3.32 
3.4 1.03 
0.7 0.32 
0.0 0.10 
0.0 
30.8 
82.8 
9.58 
14.8 
2.98 
2.9 0.93 
0.6 0.29 
0.0 
27.7 
75.7 
8.62 
12.7 
2.68 
2.5 0.83 
0.4 0.26 
0.0 
__________________________________________________________________________ 
EXAMPLE 2 
The copolymer powder of Example 1 was mixed with zinc pyrithione (solids 
having a particle size of 3 to 5 microns slurried in water) to a content 
of 12 grams of slurry per one grain of the polymer and dried in an oven at 
80.degree. C. to evaporate water. The dry polymeric powder was of white, 
fine powder with 85% entrapped zinc pyrithione, i.e., 5.76 grams per gram. 
Zinc pyrithione is supplied by Ruetger Nease Company as mixture of 48% of 
zinc pyrithione, 51% water and 1% zinc chloride and is used as 
antidandruff component in hair care products, e.g., antidandruff shampoos. 
EXAMPLE 3 
The copolymer of Example 1 was loaded with methanol/salicylic acid solution 
to a content of 12 grams per gram, and dried in an oven at 80.degree. C. 
to evaporate methanol. The dry polymeric powder was white, fine powder, 
with 74% entrapped salicylic acid, i.e, 2.8 grams per gram. Entrapped 
salicylic acid is not light sensitive, nor explosive. Salicylic acid is an 
antiseptic and antifungel agent. 
EXAMPLE 4 
Solution was made by dissolving 1 gram of dibenzoyl peroxide in 8 grams of 
chloroform. The solution was adsorbed in 1 gram of polymer of Example 1, 
thereafter chloroform was evacuated, and entrapped dibenzoyl peroxide 
polymer system was pulverized to very fine white powder. Usually dibenzoyl 
peroxide is shock sensitive and has tendency to explode at contact with 
metals. The entrapped dibenzoyl peroxide polymer system was inactive to 
friction, to shock and to contact with metals. The loading capacity of 
dibenzoyl peroxide was 50%, i.e., 1 gram per gram. 
EXAMPLE 5 
Retinol was dissolved in same amount of ether 5.5. grams of the solution 
was adsorbed in 1 gram of the polymer powder of Example 1. Thereafter 
ether was evacuated by vacuum and free flowing light yellow powder was 
obtained. The Retinol capacity was 2.5 grams per gram, i.e., 71%. Usually 
Retinol is in the form of sticky crystals, it is light sensitive, and skin 
irritant, is used in cosmetic formulations and as vitamin. 
EXAMPLE 6 
The procedure for preparation of the polymer in the Example 1 was repeated 
except that 46 mole percent allyl methacrylate monomer (cross-linker #1) 
was copolymerized with 54 mole percent ethylene glycol dimethacrylate 
(cross-linker #2), mole ratio 1:1.22. Porogen (n-heptane) content was 69% 
by weight to monomers weight. 
Total adsorption capacity for light mineral oil of the resultant polymer 
was 81%, i.e., 4.3 grains of mineral oil per one gram of the polymer. 
EXAMPLES 7-11 
The same monomers with same mole ratio were employed, as in Example 6, 
however porogen (n-heptane) concentration was increased in each series of 
syntheses. Due to the augmented porogen concentration, the adsorption 
capacities were enhanced and the apparent densities were decreased. In 
each instance submicron size copolymeric powders, in the form of broken 
micro-spheres, were produced. Adsorption capacities of the various 
copolymeric powders for light mineral oil were determined and are shown in 
Table 1. 
TABLE 1 
______________________________________ 
Adsorption 
Apparent 
Capacity Density 
Example No. 
Porogen % g/1 g g/cc 25 
______________________________________ 
7 69 4.3 0.084 
8 80 5.9 0.069 
9 82.5 6.5 0.049 
10 86 9.7 0.036 
11 87.7 11.1 0.032 
______________________________________ 
EXAMPLES 12-14 
Adsorptive polymers were obtained following the procedure of Examples 7-11, 
except that various monomer combinations were employed, all with 87.7% of 
n-heptane as a porogen. Adsorption capacities of the various polymeric 
powders were determined and are shown in Table 2. 
TABLE 2 
______________________________________ 
Adsorption Apparent Bulk 
Capacity Density 
Example No. 
Porogen % g/g Min. Oil 
g/cc 
______________________________________ 
12 85 9.1 0.038 
DMAEMA/BGDM 
13 85 8.7 0.049 
VAC/ST/EGDM 
14 85 10 0.036 
1,4 BDDMA 
______________________________________ 
The abbreviations used in Table 2: 
DMAEMA Dimethylaminoethyl Methacrylate 
BGDM Ethylene Glycol Dimethacrylate 
VAC Vinyl Acetate 
ST Styrene 
1,4 BDDMA 1,4 Butandiol Dimethacrylate 
______________________________________ 
The micro-particles of Example 1 (Poly-Pore .TM. E 200) was tested for 
adsorption of various solid and liquid hydrophilic and oleophilic 
materials for adsorption and free-flowing capacities with the results 
shown in TABLE 3: 
TABLE 3 
______________________________________ 
Total (g/g) 
Free-Flowing (g/g) 
______________________________________ 
Water 7.8 6.0 
Mineral Oil 10.4 8.1 
Artificial Sebum 10.8 8.1 
Glycerin 8.0 6.0 
Cyclomethicone (DC 244) 
12.0 9.6 
Isopropyl Myristate 
10.7 8.0 
Vitamin E Acetate 
7.2 5.6 
Benzophenone-3 12.3 9.2 
PEG 200 11.2 8.8 
Benzyl Acetate 12.3 10.2 
Fragrance/Floral Lavender 
11.1 8.1 
(Q-12512) 
Dimethicone (DCC 10) 
10.6 8.5 
Dimethicone (DCC 200) 
10.2 7.1 
Dimethicone (DCC 350) 
10.0 6.9 
Dimethicone (DCC 1000) 
10.0 6.9 
Motor Oil (10 W 40) 
10.1 
Heptane 8.0 
Toluene 10.0 
Xylene 9.6 
Methylene Chloride 
18.8 
Irgasan DP 300 10.0 
5-chloro-2-(2,4 dichloro- 
phenoxy) phenol 
______________________________________