Monohydric alcohol derived urethanes and their use in cosmetic formulations

The present invention relates to a dimeric urethane compounds derived from monohydric alcohols, generally fatty alcohols, and a diisocyanate according to the following reaction scheme: ##STR1## wherein R.sub.1 is selected from the group of saturated or halogen substituted linear, cyclic or branch-chained hydrocarbons and R.sub.2 is a linear, cyclic or branch-chained alkyl or aminoalkyl group ranging from two to 200 carbon atoms, preferably two to 50 carbons, more preferably 6 to 36 carbons, said urethane compound being substantially free from terminal hydroxyl groups.

FIELD OF THE INVENTION 
The present invention is directed to novel compositions of urethane 
emollients, solubilizers, clarifiers and emulsifiers derived from 
monohydric alcohols and having no free isocyanate groups. These urethane 
emollients are substantially free of terminal hydroxyl groups and are 
derived from linear, branch-chained or aromatic monohydric alcoholic 
compounds of synthetic or natural origin. 
BACKGROUND OF THE INVENTION 
Standard emollients for the cosmetic, toiletry and personal care industries 
have been esters (monohydric) such as isopropyl myristate, butyl stearate, 
cetyl octanoate and isostearyl isostearate covering a wide breadth of 
molecular weights. Monohydric esters have also been manufactured from high 
molecular weight compounds such as behenic acid and behenyl alcohol which 
yield a solid ester useful as an emollient for increasing the melting 
point characteristics of a given formulation. Synthetic spermacetic waxes 
have been utilized for the past thirty years to replace the natural rare 
variety. Such products as cetyl palmitate, cetyl myristate and mixed cetyl 
esters have essentially replaced the use of spermacetic wax. 
In the mid-seventies, there was a critical shortage of beeswax, and the 
synthesis of a synthetic version of this natural wax and emollients 
derived from this wax was sought. As one solution, the relatively high 
molecular weight dodecanedicarboxylic acid was esterified with a mixture 
of cetyl, stearyl and polyoxyethylene glycols to render a product that was 
found to be a suitable replacement. With the mixture of relatively high 
molecular weight alcohols and polyethers, the dicarboxylic acid of 
C.sub.12 yielded a perfectly usable product for skin applications-where 
natural beeswax had been used for numerous years. 
For many years, monohydric alcohol diesters used in the cosmetic and 
personal care industries have been synthesized from such difunctional 
carboxylic acids as adipic, sebacic, azeleic, dodecanedicarboxylic acid 
and dimer acid, as well as anhydrides such as maleic, succinic and 
phthallic, among others. Based on the molecular weight of the difunctional 
carboxylic acid and the alcohol used, it was possible for the synthetic 
organic chemist to obtain a wide range of properties from these 
compositions, including, for example, dryness, oiliness, spreadability, 
lubricity, freezing point depression, insect repellency (e.g., dicapryl 
adipate), melting and slip point modification, emulsion synergism, 
solvency and color dispersion. 
As the molecular weight of the dicarboxylic acid and corresponding alcohol 
increase, a greater degree of heaviness is imparted to the emollient, 
along with a higher degree of viscosity. As the degree of unsaturation of 
the alcohol used increases and becomes more olefinic in character, 
spreadability is enhanced. For example, diesters derived from oleyl or 
linoleyl alcohols have a greater degree of spreadability than does a 
corresponding diester derived from stearyl or isostearyl alcohol. 
It is possible to further influence the melting point and indeed the 
viscosity of a diester through the use of branched rather than linear 
structures. With the introduction of an ether linkage, the liquidity of a 
given diester is also enhanced. Diesters made from ethoxylated and/or 
propoxylated adducts of alcohols have also been used as emollients and 
emulsifiers. 
As a result of molecular weight and structure, diisopropyl adipate has been 
found to be an extremely dry ester with excellent solvency 
characteristics. Because of its physical properties, diisopropyl adipate 
finds use in products ranging from floating bath oils, after shaves, 
creams, lotions, deodorants, pre-electric shave lotions, to 
antiperspirants. Diisopropyl adipate has been widely used for numerous 
years in these applications because of the availability of raw materials 
and relatively low production cost. Diisostearyl adipate, on the other 
hand, is a relatively heavy, water white diester with little or no odor 
that imparts a luster and sheen to the skin and, as a result of its 
molecular weight and viscosity, has a tendency to linger on the skin. 
Dicapryl adipate is a diester derived from natural sources (through the 
cracking of castor oil to yield caprylene, then conversion to the 
corresponding alcohol) which has been found to exhibit insect repellency 
and has met with huge success in repellents for use in human and animal 
products. Diesters derived from dimer acids, such as diisopropyl dimerate 
and diisostearyl dimerate, in addition to being excellent, long lasting 
emollients because of their relatively high molecular weight, were shown 
to add anti-irritation characteristics to given skin formulations. 
Typical end-use applications of diesters of dicarboxylic acids in the 
personal care, cosmetic as well as toiletry industries include: skin care 
products, eye makeups, body shampoo, stick deodorants, protective skin 
formulations, lipsticks, lip glosses, pre-electric and after shave 
lotions, after-bath splashes, shampoos and rinses, presun and sun 
products, antiperspirants and sunscreens. 
OBJECTS OF THE INVENTION 
It is an object of the present invention to provide novel and unique 
urethanes of monohydric alcohols which are substantially free of terminal 
hydroxy groups as emollients in cosmetic, toiletry and personal care 
products. 
It is a further object of the present invention to provide urethanes of 
monohydric alcohols as emulsifiers for use in the cosmetic, toiletry and 
personal care area. 
It is another object of the present invention to provide novel urethanes of 
monohydric alcohols that are resistant to pH variable and thermal 
degradation that is commonly associated with mono- and diesters. 
It is yet another object of the present invention to introduce novel and 
unique urethanes of monohydric alcohols which are substantially free of 
terminal hydroxyl groups which function as vehicles to increase adhesion 
in given formulations in the cosmetic, toiletry and personal care 
industry. 
It is still another object of the present invention to introduce novel and 
unique urethanes of monohydric alcohols which are substantially free of 
terminal hydroxyl groups which will function to modify melting points in 
the cosmetic, toiletry and personal care products. 
It is yet a further object of the present invention to introduce novel and 
unique urethanes of monohydric alcohols which are substantially free of 
terminal hydroxyl groups which will be soluble in silicone fluids commonly 
used in the personal care, cosmetic and toiletry industries. 
It is still a further object of the present invention to introduce novel 
and unique urethanes of monohydric alcohols which are substantially free 
of terminal hydroxyl groups to act as vehicles for functional additives 
such as organic and inorganic sunscreens, vitamins and protein 
hydrolysates, among numerous others. 
These and/or other objects of the invention may be readily gleaned from the 
description of the invention, which follows. 
SUMMARY OF THE INVENTION 
The present invention relates to a dimeric urethane compounds derived from 
monohydric alcohols, generally fatty alcohols, and a diisocyanate 
according to the following reaction scheme: 
##STR2## 
wherein R.sub.1 is selected from the group consisting of saturated, 
unsaturated, aromatic or halogen substituted linear, cyclic, aromatic or 
branch-chained hydrocarbons and R.sub.2 is a linear, cyclic, aromatic, 
branch-chained alkyl, aminoalkyl, amino alkanol or alkoxide group ranging 
from two to 500 carbon atoms, preferably two to 50 carbons, more 
preferably 6 to 36 carbons, said urethane compound being substantially 
free of terminal hydroxyl groups. 
Compounds according to the present invention exhibit primary utility as 
emollients, wetting agents, dispersants, lubricants, plasticizers, 
stabilizers, emulsifiers, clarifying agents, solubilizing agents and 
adhesion and melting point modifiers in formulations of cosmetic, toiletry 
and personal care products. The emollient properties of compounds 
according to the present invention are primarily due to the hydrophobic 
nature of the fatty alkyl groups, which maintain a desirable moisture 
balance as it softens and soothes the skin and related mucous membranes. 
By proper selection of the diisocyanate and monohydric alcohol, it is 
possible to obtain a wide variety of properties in the resultant urethane 
compound, ranging from such characteristics as a grasslike, resinous 
product suitable as an extremely heavy emollient and replacement for 
diisostearyl adipate to a solid product such as an arichidyl urethane 
suitable as a substitute for beeswax in formulations. The monohydric 
alcohols reacted to produce the compounds with a diisocyanate group 
according to the present invention may be synthetically or naturally 
derived. 
One of the more innovative properties of compounds according to the present 
invention is the stability of the dimeric urethane of the monohydric 
alcohols over a wide pH range and temperature. Under conditions causing 
the prior art diesters of corresponding alcohols to readily decompose, 
their urethane counterparts will remain relatively stable. Consequently, 
the dimeric urethanes are versatile in their chemical properties, and are 
unique in their ability to resist hydrolysis and thermal decomposition. 
Stable storage compounds (those which are resistant to degradation at 
variable pH or at elevated temperature) may be readily formulated using 
compounds according to the present invention. 
Other properties of the compounds of the present invention which make them 
superior to the diesters currently used may include: 
Water-white color; 
Extremely low order of irritation and toxicity; 
Substantial absence of hydroxyl groups; 
Excellent compatibility in cosmetic and toiletry formulations; 
Solubility in sunscreens, i.e., octacrylene, octyl salicylate, octylmethoxy 
cinnamate, menthyl anthranilate, PABA; 
Solubility in mineral oil; 
Solubility in vegetable oil; 
Solubility in silicone fluids; 
Solubility in most esters; 
Solubility in most alcohols; 
Essentially odorless; 
Substantially Non-rancidifying. 
Another aspect of the present invention relates to compositions comprisng 
the previously described urethane compounds in combination with about 0.5% 
to about 100% by weight of a free or unreacted monohydric alcohol. The 
inclusion of the monohydric alcohol may be used as a viscosity control 
additive or as a solubilizing agent in this aspect of the present 
invention. Thus, in this aspect of the present invention, a composition 
for use in cosmetic, toiletry and personal care products consists 
essentially of about 0.25% to about 50% by weight of a free monohydric 
alcohol and about 50% to about 99.75% by weight of a urethane compound 
according to the present invention. Preferably, the composition according 
to this aspect of the present invention consists essentially of about 0.5% 
to about 25% by weight, more preferably about 1% to about 15% by weight 
free monohydric alcohol. 
Urethane compounds according to the present invention may be used in 
personal care, toiletry or cosmetic compositions in amounts ranging from 
about 0.05% to about 35% by weight, preferably about 0.5% to about 25% by 
weight, more preferably about 1% to about 15% by weight of the final 
personal care, toiletry or cosmetic composition. Urethane compounds 
according to the present invention find particular use in compositions 
which utilize pH variability or heat for manufacturing or utilize elevated 
temperatures during use (for example, in the case of shampoos, 
conditioners, sunscreens, etc.). Storage stability of the final 
composition is another feature which may be markedly improved by the 
inclusion of effective amounts of the present compounds. 
DETAILED DESCRIPTION OF THE INVENTION 
The term "monohydric alcohol" is used throughout the specification to 
describe a linear, cyclic, aromatic or branch-chained hydrocarbon having a 
single hydroxy group located at one terminus of the molecule and/or a 
linear, cyclic or branched-chain amine having a single hydroxy group 
located at one terminus of the molecule and includes such amine-containing 
compounds as monoethanolamine, aminoethylethanolamine, amidoamines, 
diglycolamine, acetylated monoethanolamine, among numerous others. The 
amine may be a primary, secondary or tertiary amine. The compounds may be 
unsubstituted or halogen substituted. The inclusion of an amine may be 
advantageously employed because of the tendency of the amine to 
substantially protonate and become more water soluble at pH's below about 
10.0. In addition, the presence of the amine group, due to its cationic 
nature, imparts a more substantive character to the compound. In a 
preferred embodiment of the present invention, the length of the 
monohydric alcohol is between 2 and 200 carbons. In more preferred 
embodiments, the monohydric alcohol ranges from about 2 to about 50 
carbons and in even more preferred embodiments, the monohydric alcohol 
ranges from about 6 to about 36 carbons. Exemplary monohydric alcohols for 
use in the present invention include, range for example, from ethyl 
through C.sub.50 alcohols, more preferably C.sub.6 through C.sub.36 and 
include, for example, ethanol, isopropanol, butanol, isobutanol, amyl 
alcohol, isoamyl alcohol, hexanol, isohexanol, heptanol, n-octanol, 
2-ethylhexanol, isooctanol, n-nonanol, isononyl alcohol, n-decanol, 
isodecanol, n-lauryl alcohol, tridecanol, n-myristyl alcohol, n-cetyl 
alcohol, isocetyl alcohol, n-stearyl, isostearyl alcohol, octyldodecanol, 
archidyl alcohol, alcohols up through C.sub.50, more preferably up to 
C.sub.36, ethoxylated and/or propoxylated versions of the above-described 
alcohols, phenoxyethanols and ethoxylated and/or propoxylated nonyl 
phenols. Numerous additional monohydric alcohols also may be used in the 
present invention. 
The term "diisocyanate" is used throughout the specification to describe a 
linear, cyclic or branch-chained hydrocarbon having two free isocyanate 
groups. The term "diisocyanate" also includes halogen substituted linear, 
cyclic or branch-chained hydrocarbons having two free isocyanate groups. 
Exemplary diisocyanates include for example, isophorone diisocyanate, 
m-phenylenediisocyanate, p-phenylene diisocyanate, 4,4-butyl-m-phenylene 
diisocyanate, 4-methoxy-m-phenylene diisocyanate, 4-phenoxy-m-phenylene 
diisocyanate, 4-chloro-m-phenylene diisocyanate, toluenediisocyanate, 
m-xylylenediisocyanate, p-xylylenediisocyanate, 
1,4-napthalenediisocyanate, cumene-14,-diisocyanate, durenediisocyanate, 
1,5-napthylenediisocyanate, 1, 8-napthylenediisocyanate, 
1,5-tetrahydronapthylenediisocyanate, 2, 6-napthylenediisocyanate, 
1,5-tetrahydronapthylenediisocyanate; p,p-diphylenediisocyanate; 
2,4-diphenylhexane-1,6-diisocyanate; methylenediisocyanates; 
ethylenediisocyanates; trimethylenediisocyanate, 
tetramethylenediisocyanate, pentamethylenediisocyanate, 
hexamethylenediisocyanate, nonamethylenediisocyanate, 
decamethylenediisocyanate, 3-chloro-trimethylenediisocyanate and 
2,3-dimethyltetramethylene diisocyanates. 
The term "emollient" is used throughout the specification to describe 
compounds according to the present invention which soften, lubricate and 
moisturize the skin as as well as sooth irritation to the skin and mucous 
membranes, i.e., they are soothing to the skin. 
The term "emollient effective amount" is used throughout the specification 
to describe concentrations or amounts of compounds according to the 
present invention which are included in cosmetic and personal care 
products according to the present invention which provide effective 
emollient character for treating keratinous and epithelial tissue, 
including skin, nails (ungual tissue), hair and mucous linings of the 
mouth and nasal passages. 
The term "effective amount" is used throughout the specification to 
describe concentrations or amounts of compounds according to the present 
invention which are effective in conveying desired traits such as 
emulsification, clarification, adhesion, melting point modification or 
solubility to a formulation of a cosmetic, toiletry or personal care 
product. 
The term "substantially free` is used throughout the specification to 
describe preferred urethane compounds according to the present invention 
which essentially contain no free terminal hydroxyl groups, i.e., they 
appear to be all reacted and analytical methods do not detect terminal 
hydroxyl groups other than those which may appear as slight impurities in 
the compounds of the present invention. The term "substantially free" is 
not a theoretical absolute value, but merely reflects the practical limits 
of detecting free terminal hydroxyl groups in the present invention. 
Compounds according to the present invention may be prepared by synthetic 
methods known in the art. A general synthetic scheme involves reacting at 
least two molar equivalents of a monohydric alcohol, generally a fatty 
alcohol, with a diisocyanate in the presence of heat and a catalyst such 
as stannous octanoate. Each isocyanate moiety is thereby converted to a 
urethane moiety with the aliphatic portion of the alcohol extending out 
from the urethane moiety. The free alcohols are all reacted with 
isocyanate groups to form urethanes, leaving substantially no free 
hydroxyl groups at the ends of the side chains (i.e. the compounds of the 
present invention are not hydroxyl-terminated). Preferably, there are no 
free hydroxyl moieties anywhere on the side chains of the compounds of the 
present invention. Illustrative examples of the synthesis of particular 
compounds follow below. 
Compounds according to the present invention may be used as emollients for 
keratinous and epithelial tissue such as hair, ungual tissue (nails), skin 
and related mucous membranes. By addition of an emollient effective amount 
of these urethanes, formulations for use as cosmetic, toiletry or personal 
care products will acquire the desirable soothing characteristics. 
Effective amounts of the urethanes of the present invention may also serve 
as emulsifiers, clarifiers and melting point modifiers in formulations of 
the personal care, cosmetic and toiletry industries, especially where 
diesters of dicarboxylic acid have been used in the past or in 
formulations of silicone fluids, in which these novel urethanes are 
soluble. The urethanes of the present invention have superior stability at 
high or low pH values and thermal variations, where the mono- and diesters 
of the prior art are subject to degradation. Consequently, the dimeric 
urethanes of the present invention provide a significantly greater degree 
of stability and flexibility in formulations than do the diesters. It is 
an unexpected result that the urethane compounds of the present invention 
would provide the variety of characteristics exhibits with a high degree 
of stability (to variations in pH and temperature). In addition, the 
present compounds are compatible with biological systems and are generally 
substantially non-toxic (i.e., they can be used safely in cosmetic, 
toiletry and personal care products). 
The present compounds instill a great degree of flexibility in formulating 
personal care products. The viscosity of a formulation for cosmetic, 
toiletry or personal care use can be dictated by adding an effective 
amount of a compound of the present invention with an appropriate length 
side chain. Shorter side chains, i.e., those derived from monohydric 
alcohols of about 1 to 3 carbon atoms product materials of a resinous 
consistency. Side chains of 6 to 10 carbon atoms produce compounds of 
lower viscosity, with maximum viscosity of approximately 1000 centipoise 
units. Longer side chains containing monohydric alcohols of about 12 to 
500 carbon atoms lead to higher viscosity, with compounds containing about 
6 to 24 carbon atoms leading to viscosities within the range of 
approximately 4000 to 5000 centipoise units. Those of ordinary skill 
engaging in routine experimentation will be able to readily identify the 
proper side chain length for any desired viscosity. Similarly affecting 
the viscosity and adhesion is the degree of branching of the side chains 
of the urethane; with increasing branching for the same number of carbon 
units, the viscosity decreases. In addition, as the amount of unsaturation 
in a side chain increases, the viscosity of the dimeric urethane from 
which such monohydric alcohol is derived will decrease. The ideal 
properties of emmolience are anticipated in compounds according to the 
present invention where the monohydric alcohol (side chain of the dimeric 
urethane) from which the present compounds are derived) comprise about 6 
to 24 carbon atoms, wherein the side chain is preferably an unsaturated 
hydrocarbon. 
The viscosity of the compounds of the present invention, and, therefore, 
the formulations in which they are used, may also readily be adjusted by 
adding about 0.5% to about 100% by weight of the dimeric urethane, 
preferably about 1% to about 50% by weight, more preferably about 2% to 
about 30% by weight, even more preferably about 10% to about 25% by weight 
of excess unreacted monohydric alcohols to the compounds of the present 
invention. These unreacted alcohols will reduce the viscosity of the 
compound or formulation in which they are included for modifying the 
characteristics of cosmetic, toiletry or personal care products according 
to the present invention. Unreacted alcohols in the formulation may 
readily be obtained by including an excess of monohydric alcohol to the 
diisocyanate before synthesis of the urethane. Alternatively, the addition 
of monohydric alcohol to the compounds of the invention after synthesis 
may also represent an appropriate option. 
In the present invention, a dimeric urethane compound according to the 
present invention which is derived from a C.sub.6 to C.sub.10 monohydric 
alcohol is considered a "light" emollient, i.e., an emollient which has a 
low viscosity falling within the range of about 10 centipoise units to 
about 1000 centipoise units. Light emollients are preferably included in 
personal care products where lower viscosity is a desirable feature. Such 
personal care products include shampoos, conditioners, fragrances, lotions 
including sunscreens and suntan lotions. "Heavy" emollients are those 
dimeric urethane compounds which are derived from monohydric alcohols 
which are C.sub.12 or greater in length. Heavy emollients generally have a 
high viscosity which is above 1000 centipoise units, and preferably fall 
within the range of about 2000 centipoise units to about 5,000 centipoise 
units. It is noted that emollients which have viscosities which fall at 
the upper range of viscosity, i.e., about 5,000 centipoise units and 
above, in order to be readily workable and useful in the present 
invention, may need to have their viscosities adjusted by including free 
monohydric alcohol in an amount up to about 100% by weight of the dimeric 
urethane compound according to the present invention. Heavy emollients 
find use in cosmetics and personal care products which require higher 
viscosities, for example, in creams, ointments, pastes and solid cosmetics 
such as make-up and lipstick products, deodorants/anti-perspirants, among 
numerous others.

THE FOLLOWING EXAMPLES OF COMPOUNDS ACCORDING TO THE PRESENT INVENTION HAVE 
BEEN PREED: 
Monoderm I-24: the reaction product of 2-decyltetradecanol with 
isophoronediisocyanate (IPDI); 
Monoderm I-20: the reaction product of octyldodecanol with IPDI; 
Monoderm I-18: the reaction product of isostearyl alcohol with IPDI; 
Monoderm I-180: the reaction product of oleyl alcohol with IPDI; 
Monoderm I-16: the reaction product of isocetyl alcohol with IPDI; 
Monoderm I-14: the reaction product of isotetradeceyl alcohol with IPDI; 
Monoderm I-10: the reaction product of isodecyl alcohol with IPDI; 
Monoderm N-12: the reaction product of dodecanol with IPDI; 
Monoderm 12-3: the reaction product of laureth-3 alcohol with IPDI; 
Monoderm N-10: the reaction product of decyl alcohol with IPDI; 
Monoderm I-9: the reaction product of isononanol with IPDI; 
Monoderm I-8: the reaction product of isooctanol with IPDI; 
Monoderm I-6: the reaction product of isohexyl alcohol with IPDI; 
Monoderm I-8-C4: the reaction product of Capryl alcohol with IPDI; 
Monoderm I-3: the reaction product of isopropanol with IPDI; 
Monoderm DGDE: the reaction product of glycol ether dimer with IPDI; 
Monoderm N18-100: the reaction product of PEG-100 stearyl ether dimer with 
IPDI; 
Monoderm N4-100: the reaction product of PEG-100 butyl ether dimer with 
IPDI. 
The examples above all use isophorone diisocyanate, but the following 
isocyanates are among those which may be used to yield acceptable 
products: 
m-phenylenediisocyanate; p-phenylene diisocyanate; 4,4-butyl-m-phenylene 
diisocyanate; 
4-methoxy-m-phenylene diisocyanate; 4-phenoxy-m-phenylene diisocyanate; 
4-chloro-m-phenylene diisocyanate; toluenediisocyanate; 
m-xylylenediisocyanate; 
p-xylylenediisocyanate; 1,4-napthalenediisocyanate; 
cumene-14,-diisocyanate; 
durenediisocyanate; 1,5-napthylenediisocyanate; 1,8-napthylenediisocyanate; 
1,5-tetrahydronapthylenediisocyanate; 2, 6-napthylenediisocyanate; 
1,5-tetrahydronapthylenediisocyanate; p,p-diphylenediisocyanate; 
2,4-diphenylhexane-1,6-diisocyanate; methylenediisocyanates; 
ethylenediisocyanates; tri, tetra, penta, hexa, nona and decamethylene 
diisocyanates; 3-chloro-trimethylenediisocyanate; and 
2,3-dimethyltetramethylene diisocyanates. 
The present invention also relates to a method of decreasing the viscosity 
of a urethane compound to be added to a toiletry, cosmetic or personal 
care product comprising adding a viscosity reducing effective amount of at 
least one unreacted monohydric alcohol to the urethane compound(s) in an 
amount ranging from about 0.5% to about 100% by weight of the urethane 
compound. The compositions which consist essentially of a urethane 
compound and monohydric alcohol may be added to any number of cosmetic, 
toiletry and personal care formulations to increase the workability and 
reduce the viscosity of the formulation. 
Listed below are studies comparing the stability of diesters derived from 
dicarboxylic acids in comparison to difunctional urethanes: 
Stability Studies 
The following stability study was conducted to determine the structural 
stability of dimeric urethane compounds according to the present invention 
compared to mono- and diesters under conditions of pH and thermal 
variation. Because the decomposition products of the mono- and diesters 
are alcohol and acid, the degree of decomposition may be accurately 
determined by measuring the acid value. The measurable decomposition 
product of the urethane compound is alcohol, which is accurately measured 
by determining the hydroxyl value. 
The following Mono- and diester products were tested: 
Isocetyl salicylate (ICSA); 
Diisopropyl adipate (DIA); 
Diisopropyl dilinoleate (DID); 
The following urethane products were tested: 
2-ethyl hexanol dimer with IPDI (I-8); 
Isocetyl alcohol dimer with IPDI (I- 16); 
Isostearyl alcohol dimer with IPDI (I-18); 
Octyl dodecanol dimer with IPDI (I-20); 
Eicosanyl alcohol dimer with IPDI (I-24); 
III. Procedure for determining mono- or diester stability 
The following steps were performed on each ester sample: 
(1) Run acid value test. 
(2) Into three ground glass Erlenmeyer flasks A, B, and C, weigh a 20 g 
sample of the ester. 
(3) Into each flask, pipette 50 ml of a neutralized (to phenolpthalein end 
point) Solution of 70% Isopropanol in water. Boiling stones are added. 
(4) Connect flask A to a 4-5 ft. Reflux condenser and heat so that it 
refluxes 1 ft. high (to approximately 80-90.degree. C.). After connecting 
flasks A, B and C, proceed to step (7). 
(5) Add 10% Aq. Hcl solution to adjust pH of solution in flask B to 
pH=2.5-3.5. See step (4). 
(6) Add 20% Aq. KOH Solution to adjust pH of solution in Flask C to 
pH=13-14. See step (4). 
(7) Reflux for 1 hour. 
(8) For each flask, A, B and C, disconnect condenser. Pour Alcoholic 
solution into wide diameter beaker (A, B and C). Add spin bar. Under hood, 
evaporate alcohol/water solvent on spin/hot plate until it is reduced to 
80-90% of volume. Put beaker in oven (105.degree. C.) until remainder of 
alcohol/water is evaporated. 
(9) Run acid value test on solution in beaker A. 
(10) Wash solution in beakers B and C twice with water. Add 20 ml of hot 
water, mix, add to separatory funnel, drop bottom water layer. Put beakers 
back into oven until water is evaporated. 
(11) Run acid value test on solution in beaker B and solution in beaker C. 
The acid value method used is A.O.C.S. (AMERICAN OIL CHEMISTS SOCIETY) 
T.M. #Cd3a-63. SAMPLE SIZE: 10 g.+-.0.1 mg KOH, Aq.: 0.1213N KOH Aq.: 
0.4724N 
IV. Procedure for urethane stability 
The following steps were performed on each urethane sample: 
(1) Run hydroxyl value test. 
(2) Follow steps 2-8 for mono- and diester (above). 
(3) Run hydroxyl value test on solution in beaker A. 
(4) Perform step 10, from above. 
(5) Run hydroxyl value test on solution in Beaker B and Beaker C. Hydroxyl 
value method: A.O.C.S. (AMERICAN OIL CHEMISTS SOCIETY) TM #Cd 13-16. 
SAMPLE SIZE 10 g.+-.0.1 mg KOH, Aq.=0.4724N 
V. Summary of results 
______________________________________ 
ESTER STABILITY 1 
ACID VALUE UNIT = mg KOH g 
ACID V ACID V ACID V 
ACID V .DELTA. = 1 HOUR .DELTA. = 1 HOUR .DELTA. = 1 HOUR 
PRO- INITIAL mg KOH/g mg KOH/g mg KOH/g 
DUCT mg KOH/g "A" "B" "C" 
______________________________________ 
ICSA 0.91 81.6 95.3 88.6 
DIA 0.26 93.1 101.2 106.3 
DID 0.32 41.8 62.4 58.1 
______________________________________ 
A.O.C.S. T.M. # Cd 3a63 
.DELTA. = HEAT/REFLUX 
______________________________________ 
Urethane Stability 
HYDROXYL VALUE UNIT: mg KOH g 
HYDROXYL HYDROXYL 
HYDROXYL V V 
HYDROX- V .DELTA. = 1 HOUR .DELTA. = 1 HOUR 
YL V .DELTA. = 1 HOUR pH = 2.5-3.5 pH = 13-14 
PRO- INITIAL mg KOH/g mg KOH g mg KOH/g 
DUCT mg KOH/g "A" "B" "C" 
______________________________________ 
I-8 10.3 11.1 10.0 10.8 
I-16 7.3 7.9 8.1 7.1 
I-18 5.3 5.0 6.0 4.9 
I-20 16.1 15.9 16.9 16.4 
I-24 9.3 10.1 9.9 8.9 
______________________________________ 
A.O.C.S. T.M.# Cd 1360 
.DELTA.:HEAT/REFLUX 
VI. Conclusion of Testing 
Under conditions of this study, that is, 
"A": Product in alcoholic/water solution, heat 
"B": Product in alcoholic/water solution, heat, pH=2.5-3.5 
"C": Product in alcoholic/water solution, heat, pH=13-14 
The mono and diesters demonostrated less stability than did the dimeric 
urethane compounds of the present invention to heat and pH chances, 
whether those changes are primarily acidic or basic. 
The present invention is now described, purely by way of illustration, in 
the following examples. It will be understood by one of ordinary skill in 
the art that these examples are in no way limiting and that variations of 
detail can be made without departing from the spirit and scope of the 
present invention. 
Materials and Methods 
In performing the following syntheses, the following reagents were used. 
Solvents, where used, are generally distilled prior to use. 
3-isocyanatomethyl-3,5,5-trimethyl cyclohexylisocyanate (IPDI) was 
obtained from Huls America, Inc., Piscataway, N.J. The monohydric alcohols 
used in these experiments for condensation with the diiosocyanate were 
generally obtained from Vista Condea, Houston, Tex. Sources of other 
materials are indicated in the appropriate experimental section. 
EXAMPLE 1 
Synthesis of Dimeric Urethane From Isocetyl Alcohol and Isophorone 
Diisocyanate 
To a 1 liter flask equipped with three necks, dropping funnel, nitrogen, 
heat and vacuum, charge 532 grams(2.2 moles) of isocetyl alcohol. A vacuum 
of approximately 29 inches is applied and heat is applied to approximately 
110.degree. C. to dehydrate the alcohol. Stannous octanoate is added 
(approximately 1.0 grams), after the temperature is reduced to 40.degree. 
C. Heat is slowly added to a temperature of 85.degree. C. at which point a 
nitrogen blanket is placed on the system. Once the temperature has 
stabilized, a slow addition of 3-isocyanatomethyl-3,5,5-trimethyl 
cyclohexylisocyanate is added at a rate which maintains the temperature of 
85-90.degree. C. A total of 222 grams (1 mol) of the isocyanate is added 
and once the addition is completed, isocyanate groups are monitored by IR 
to ensure complete reaction of the alcohol. When the diiosocyanate has 
been consumed as indicated by IR, the reaction is complete. The 
temperature of the product is reduced to 60.degree. C., then to room 
temperature. The product may be used directly without further 
purification. 
EXAMPLE 2 
Synthesis of Dimeric Urethane from Isostearyl Alcohol and Isophorone 
Diisocyanate 
To a 2 liter flask equipped with a dropping funnel, nitrogen, agitation, 
heat and vacuum, a charge of 594 grams (2.2 Moles) of isostearyl alcohol 
was added. A vacuum of approximately 29 inches was applied to remove water 
with heat application of 110.degree. C. The isostearyl alcohol was then 
reduced to a temperature of 40.degree. C. and approximately 1.0 gram of 
stannous octanoate was added. The temperature was brought up to 85.degree. 
C., nitrogen was introduced as a blanket and a slow addition of isophorone 
diisocyanate (222 grams, 1 Mol) was initiated in which the rate of 
addition of the isocyanate was used to maintain a temperature of 
85-90.degree. C. in the flask. Once the addition was complete, samples 
were taken to determine via the use of an infrared that all of the 
isocyanate was consumed. Any unreacted hydroxyl groups that remain the in 
flask can be attributed to the excess of isostearyl alcohol that was used 
to push the reaction to the right. 
EXAMPLE 3 
Synthesis of Dimeric Urethane from Isocetyl Alcohol and Isophorone 
Diisocyanate--Excess Isocetyl Alcohol 
To a 2 liter flask equipped with three necks, a dropping funnel, nitrogen 
heat and vacuum, charge 532 grams (2.2 moles) of isocetyl alcohol. A 
vacuum of approximately 29 inches is applied to dehydrate the alcohol and 
heat is applied to a temperature of 110.degree. C. The temperature is 
reduced under vacuum to 40.degree. C. and approximately 1.0 grams of 
stannous octanoate are added. Nitrogen is introduced into the flask and 
heat is applied to a temperature of approximately 85.degree. C. The heat 
is turned off and a slow addition of the isophorone diisocyanate is begun 
such that the temperature is maintained by the addition of the isocyanate 
in the range of 85-90.degree. C. A total of 222 grams (1 mol) of 
isophorone diisocyanate is added. Once the addition has been completed, 
the temperature is maintained at 85-90.degree. C. and the peaks for free 
isocyanate and free hydroxyl groups are monitored. 
EXAMPLE 5 
Suntan Lotion 
(Water Resistant) 
______________________________________ 
INGREDIENTS %, WEIGHT INCI NAME 
______________________________________ 
A. Water(Deionized) 
68.6 
Dowicil-200.sup.1 0.2 Quaternium-15 
Propylene Glycol 3.0 Propylene Glycol 
Triethanolamine 0.5 Triethanolamine 
B. Dermol IPM.sup.2 5.0 Isopropyl Myristate 
Dermol 20SS.sup.2 5.0 Octyldodecyl Stearoyl Stearate 
Dermophos IS-2K.sup.2 2.0 Potassium Isosteareth Phosphate 
Monoderm I-16.sup.2 3.0 N/A 
Cetyl Alcohol 0.7 Cetyl Alcohol 
Dermol GMS.sup.2 1.5 Glycerol Stearate 
Stearic Acid-TP 2.0 Stearic Acid 
Dermoblock OS.sup.2 5.0 Octyl Salicylate 
Dermoblock MA.sup.2 3.5 Menthyl Anthranilate 
C. Color, Fragrance q.s. 
100.0 
______________________________________ 
.sup.1 Dow Chemical 
.sup.2 Alzo Inc 
Procedure for Preparation: 
1. Heat Part A to 50 C.-55 C. with mixing until uniform. 2. 
2. Heat Part B to 60 C.-65 C. with mixing until uniform. 
3. With good agitation, add Part B to Part A 
4. Add Part C 
EXAMPLE 6 
Sun Protection Cream 
(Water Resistant) 
______________________________________ 
INGREDIENTS %, WEIGHT INCI NAME 
______________________________________ 
A. Water(Deionized) 
67.3 
Dowicil-200.sup.1 0.2 Quaternium-15 Phosphate 
Propylene Glycol 3.0 Propylene Glycol 
Triethanolamine 0.8 Triethanolamine 
B. Dermol IPM.sup.2 5.0 Isopropyl Myristate 
Dermol 20SS.sup.2 4.5 Octyldodecyl Stearoyl Stearate 
Dermophos IS-2K.sup.2 2.0 Potassium Isosteareth Phosphate 
Dermol DISD.sup.2 3.0 Diisostearyl Dimer Dilinoleate 
Monoderm I-16.sup.2 2.0 N/A 
Cetyl Alcohol 0.7 Cetyl Alcohol 
Dermowax.sup.2 1.5 Glycerol Stearate 
Stearic Acid 2.0 Stearic Acid 
Dermoblock OS.sup.2 5.0 Octyl Salicylate 
Dermoblock MA.sup.2 3.5 Menthyl Anthranilate 
C. Color, Fragrance q.s. 
100.0 
______________________________________ 
.sup.1 Dow Chemical 
.sup.2 Alzo Inc 
PROCEDURE: 
1. Heat Part A to 50.degree. C.-55.degree. C. with mixing until uniform. 
2. 
2. Heat Part B to 60.degree. C.-65.degree. C. with mixing until uniform. 
3. With constant agitation, add Part B to Part A 
5. Add Part C 
EXAMPLE 7 
Instant Hair Conditioner 
______________________________________ 
INGREDIENTS %, WEIGHT INCI NAME 
______________________________________ 
PHASE A 
Glycerol 5.00 Glyceryl 
Monoderm I-16 0.5 Bis-(Isocetyl)-3-IPDI 
Isocyanate 
Sodium Benzoate 0.1 
Water 81.70 
PHASE B 
Dermowax GMS S.E. 4.00 Glycerol Monostearate 
S.E. 
Cetyl Alcohol 0.75 Cetyl Alcohol 
Stearyl Alcohol 0.75 Stearyl Alcohol 
Lanolin 1.00 Lanolin 
PEG 400 Monooleate 5.00 PEG-8 Laurate 
Neconlo 1.00 
Perfume 0.20 
Color, D & C Yellow #5 q.s. 
(1% Solution) 
______________________________________ 
Procedure: 
Heat Phase A with exception of Sodium Benzoate to 180.degree. F. Heat Phase 
B to 180.degree. F. Add Part B to Part A with agitation. Cool to room 
temperature, add color, perfume and Sodium Benzoate at 110.degree. F. 
EXAMPLE 8 
Alcoholic Emulsion #763 
______________________________________ 
INGREDIENTS %, WEIGHT INCI NAME 
______________________________________ 
PHASE A 
Monoderm I-16 1.00 Bis-(Isocetyl)-3-IPDI 
Isocyanate 
Alpine Fragrance #103-601 2.00 
Alcohol SDA #40 30.00 
PHASE B 
Carbopol 941 (2% Aqueous 30.00 Carbomer 
Solution) 
(B. F. Goodrich, Inc.) 
Distilled or Deionized Water 37.00 
______________________________________ 
Method of Manufacture: 
Weigh the ingredients of Phase A into a container of sufficient size to 
hold the entire batch and stir. Weigh the ingredients for Phase B into a 
separate container and stir until smooth. Add B to A and stir rapidly 
until uniform emulsion is formed. 
EXAMPLE 9 
Bath Gel #766 
______________________________________ 
INGREDIENTS %, WEIGHT INCI NAME 
______________________________________ 
PHASE A 
TEA Lauryl Sulfate (40%) 20.00 Tea Lauryl Sulfate 
Foamid SLM 15.00 Lauramide DEA 
Monoderm I-16 1.00 Bis-(Isocetyl)-3-IPDI 
Isocyanate 
PHASE B 
Methyl Parasept 0.15 
Propylene Glycol 1.00 
PHASE C 
PEG 12 2.00 
Hydroxy Propyl Methyl Cellulose 60.35 
(3% Aqueous Solution) 
PHASE D 
Fragrance 0.50 
______________________________________ 
Method of Manufacture: 
Heat the ingredients of Phase A to 60.degree. C. Dissolve the Methyl 
Parasept in Propylene Glycol and add to Phase C. Stir mixture of B, C 
until smooth. Add B, C to A and stir. Then add perfume. 
EXAMPLE 10 
Dispersible Bath Oil 
______________________________________ 
INGREDIENTS %, WEIGHT INCI NAME 
______________________________________ 
Monoderm I-16 
10.00 Bis-(Isocetyl)-3-IPDI 
Isocyanate 
Dermol IPM 10.00 Isopropyl Myristate 
Dermol 1012 3.00 Laureth-2-Octanoate 
PEG 200 Dilaurate 4.00 PEG-4 Laurate 
Mineral Oil, Light 69.00 
Fragrance 4.00 
______________________________________ 
Procedure: 
Add all of the oils into a vessel and blend until homogeneous (No heat is 
necessary). Add the fragrance and continue to mix until the product is 
clear and uniform. Allow to age 24 hours at room temperature and filter if 
necessary. 
EXAMPLE 11 
Cleansing Cream #694 
______________________________________ 
INGREDIENTS %, WEIGHT INCI NAME 
______________________________________ 
PHASE A 
Beeswax USP Bleached 15.00 Besswax 
Petrolatum White 15.00 Petroleum 
Mineral Oil 15.00 Mineral Oil 
Dermol IPM 2.00 Isopropyl Myristate 
Dermol CP 1.50 Cetyl Palmitate 
Monoderm I-16 1.50 Bis-(Isocetyl)-3-IPDI 
Isocyanate 
Methyl Paraben 0.10 Methyl Paraben 
Propyl Paraben 0.10 Propyl Paraben 
Dermol 126 1.00 Laureth-2 Benzoate 
PHASE B 
Borax USP 1.25 Sodium Borate 
Polysorbate 80 0.30 Polysorbate 80 
Glycerin 3.00 Glycerin 
Distilled or Deionized Water 43.75 
PHASE C 
Perfume 0.50 
______________________________________ 
EXAMPLE 12 
Floating Bath Oil 
______________________________________ 
INGREDIENTS %, WEIGHT INCI NAME 
______________________________________ 
Monoderm I-16 
12.00 Bis-(Isocetyl)-3-IPDI 
Isocyanate 
Dermol IPM 12.00 Isopropyl Myristate 
Light Mineral Oil 71.00 Mineral Oil 
Dermol 1012 1.00 Laureth-2-Octanoate 
Fragrance 4.00 
______________________________________ 
Procedure: 
Add all of the oils into a vessel, and blend until homogeneous (No heat is 
necessary). Add the fragrance and continue to mix until the product is 
clear and uniform. Allow to age 24 hours at room temperature and filter if 
necessary. 
EXAMPLE 13 
Foot Balm #602 
______________________________________ 
INGREDIENTS %, WEIGHT INCI NAME 
______________________________________ 
PHASE A 
NECON LO 0.25 Dimethyl Lauramine 
Oleate 
Squalene 1.00 Squalene 
Stearic Acid T.P. 2.00 Stearic Acid 
Dermowax GMS 2.50 Glycerylmonostearate 
Monoderm I-16 4.50 Bis-(Isocetyl)-3-IPDI 
Isocyanate 
Phytostearol Isocyanate 3.00 
Cetyl Alc. N.F. Flake 1.00 Cetyl Alcohol 
Dermolan GLH 3.50 Glycereth-7- 
Hydroxystearate 
Dermol 185 1.00 Isostearyl 
Neopentanoate 
PHASE B 
Allantoin 0.20 
Propylene Glycol 2.00 
Triethanolamine 99% 1.00 
Preservative Mix (5 parts Methyl 0.25 
parasept to 1 part Propyl Parasept) 
Distilled or Deionized Water 47.03 
PHASE C 
Veegum-5% Slurry 25.00 
PHASE D 
Alcohol SDA 39C 5.00 
Menthol U.S.P. 0.02 
Perfume 0.75 
______________________________________ 
EXAMPLE 14 
Hand And Body Lotion 
______________________________________ 
INGREDIENTS %, WEIGHT INCI NAME 
______________________________________ 
PHASE A 
Cetyl Alcohol N.F. Flakes 0.50 Cetyl Alcohol 
Dermowax DEGS 0.50 Diethylene Glycol 
Monostearate Pure 
Stearic Acid T.P. 2.00 
Triethanolamine 99% N.F. 0.75 
Beeswax White U.S.P. 0.50 
Dermol 185 2.00 Isostearyl Neopentanoate 
PHASE B 
Propylene Glycol 2.00 
Sorbitol (70%) 2.00 
Allantoin 0.20 
Preservative 0.25 
Distilled or Deionized Water 70.55 
Monoderm I-16 1.00 Bis-(Isocetyl)-3-3IPDI 
Isocyanate 
PHASE C 
Carbopol 941 10.00 Carbomer 
PHASE D 
Veegum (0.5% Aqueous) 7.50 
PHASE E 
Perfume 0.25 
______________________________________ 
It is to be understood by those skilled in the art that the foregoing 
description and examples are illustrative of practicing the present 
invention, but are in no way limiting. Variations of the detail presented 
herein may be made without departing from the spirit and scope of the 
present invention as defined by the following claims.