Homopolymers prepared from ammonium quaternary salts of aminoalkylacrylamides

The present invention is directed to a hair conditioning composition comprising as the active ingredient, a homopolymer of the formula. ##STR1## wherein R.sub.1 is hydrogen or methyl; R.sub.2 and R.sub.3 are independently lower alkyl; R.sub.4 is C.sub.2 -C.sub.25 alkyl or aryl group; n is 1-6; and X is lower alkyl sulfate or aryl sulfonate and to the use thereof for treating hair.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present application is directed to homopolymers prepared from ammonium 
quaternary salts of amino alkylacrylamides, the processes for preparing 
same, formulations containing these homopolymers and the use thereof in 
personal care formulations. 
2. Description of the Prior Art 
Polyquaternary polymers have been used in a variety of industrial 
formulations, including cosmetic formulations. However, to date, one of 
the most important applications is their use in hair and skin 
formulations, including hair shampoos and hair conditioning products. More 
specifically, they have been used to sufficiently condition the hair so 
that it holds a preset configuration. 
Hair shampoos generally are formulated with highly effective synthetic 
surfactants, such as anionic surfactants, that clean the hair. The anionic 
surfactants not only remove the dirt and soil from the hair but 
concomitant therewith, they unfortunately also remove all of the sebum 
naturally present on the surface of hair fibers. As a result, shampoo 
compositions containing these surfactants leave the hair with an 
undesirable harsh, dull and dry touch or feel, usually called "creak", 
after the hair is shampooed and then rinsed with water. 
Furthermore, thoroughly cleansed hair also is extremely difficult to comb, 
in either the wet or the dry state, because the individual hair fibers 
tend to snarl, kink and interlock with each other. If the hair is 
incompletely dried, such as hair dried with a towel, the hair has poor 
brushing properties, and after complete drying, the hair does not set 
well. The combing or brushing property of the hair remains poor and in low 
humidity atmospheres, the hair has undesirable electrostatic properties, 
causing the hair to "fly away", thereby reducing the brushing properties 
of the hair. The unsatisfactory combing or brushing property of hair 
immediately after shampooing also causes hair damage, such as split ends 
or hair breakage. In addition, shampooing of hair reduces the natural 
luster and resiliency of the hair, thereby giving the hair a dull 
appearance. 
Thus, shampoos usually neither aid in the detangling of wet hair nor impart 
any residual conditioning benefits to dry hair, such as manageability or 
styleability of hair sets. The overall unsatisfactory condition of the 
shampooed hair necessitates the use of a conditioning composition to 
improve these undesirable physical characteristics. The conditioning 
composition may be applied separately from the hair shampoo as a 
post-shampoo treatment of the hair or may be incorporated into the hair 
shampoo. However, because many of the most widely used products for 
treating hair contain anionic surfactants and as explained hereinbelow, 
conditioning compositions usually contain cationic polymers as the active 
ingredient, and because cationic material are usually inactivated by 
reaction with anionic surfactants, it is customary to employ conditioner 
containing cationic materials as a separate composition, such as 
post-shampoo rinse, separately applied. 
The conditioning agents that have been utilized in the prior art are 
cationic compounds such as cationic surfactants and cationic polymers. 
They render the hair more manageable. For example, the wet combing problem 
discussed hereinabove is solved by the use of these conditioners which 
coat the hair shaft and cause the individual hair shafts in a tress to 
resist tangling and matting because of the conditioner residue retained on 
the shaft. The ability of these cationic compounds to absorb or react with 
the keratinous material of the hair makes them the most desirable 
compounds for imparting the desired improvement in wet hair detangling and 
dry hair manageability. Many of these cationic compounds are 
polyquarternary polymers prepared from monomers with an ester 
functionality, for example, acrylate or methacrylate types, as a 
comonomer. 
Although they are useful, these polyquaternary polymers containing esters 
have several disadvantages associated therewith. For example, they tend to 
be hydrolytically unstable to the extent that the formulation must avoid 
conditions conducive to hydrolysis during formulation, such as acidic or 
basic conditions and higher temperatures such as temperatures greater than 
about 30.degree. C. Under these conditions, they decompose and 
catalytically hydrolyze as a result of contact with water, including trace 
amounts thereof, into the (meth) acrylic acid and the corresponding 
dialkylalkanolamine, resulting in significant lowering of viscosity and 
concomitant reduction in beneficial properties. 
Moreover, the esters used heretofore lack hydrogen bonding capability with 
skin protein or hair keratin; consequently the hair substantivity, when 
applied, is not satisfactory. 
Furthermore, commercial formulations used heretofore are indiscriminate in 
the anion utilized. For example, many hair care products utilize anions 
derived from organic and inorganic acids, such as hydrochloric acid, 
sulfuric acid, phosphoric acid, hydrobromic acid, hydroiodic acid, acetic 
acid, propionic acid, formic acid and the like. In the prior art 
conditioners, the preferred acid is hydrochloric acid, with the anion 
being a chloride ion. See, e.g., U.S. Pat. No. 4,973,637. However, the 
presence of a chloride is undesirable, especially because it is a skin 
irritant. In addition, many conditioning agents are adapted for use as a 
spray from a container. However, chlorides have corrosive properties, and 
over a period of time, results in the corrosion of the spray container. 
Another problem associated with conditioners heretofore, especially those 
that absorb particularly strongly to the hair, is that they reduce the 
elasticity, body and set of the dried hair. 
The need for improved compositions that condition the hair has long been 
recognized in the art. Therefore, although conditioning compositions for 
applications to freshly shampooed hair are well known, new and improved 
conditioning formulations based on cationic compounds are continually 
sought. These new conditioning compositions must overcome the problems 
discussed hereinabove. They must also be aesthetically acceptable to 
consumers, improve the wet combing and dry combing properties of hair, 
leave the dry hair with satisfactory cosmetic and physical properties, 
including, in particular, dry combing and feel, less hair coating, 
manageability, and body. The conditioners sought must be substantive to 
hair. 
The present inventors have found a homogenous and clear cationic polymer 
which, when formulated into a hair conditioning composition, does not 
suffer from the disadvantages enumerated hereinabove. The resulting 
formulation is an excellent hair conditioner which gives the hair body 
moisture, combability, etc. Such formulations are not corrosive or 
skin-irritants, but yet are stable to pH changes and impart improved 
physical and cosmetic properties to the hair. 
SUMMARY OF THE PRESENT INVENTION 
Accordingly, the present invention is directed to a hair conditioning 
composition comprising as the active ingredient a homopolymer prepared by 
polymerizing a monomer of the formula: 
##STR2## 
wherein 
R.sub.1 is hydrogen or methyl; 
R.sub.2 and R.sub.3 are independently lower alkyl or lower alkenyl; 
R.sub.4 is C.sub.1 -C.sub.25 alkyl or aryl group; 
n is 1-6 and 
X is lower alkyl sulfate or aryl sulfonate. 
It is also directed to a hair conditioning product containing said 
homopolymer. The present invention is also directed to a method of 
treating the hair, whereby the hair is conditioned by contacting the hair 
with a composition containing said homopolymer.

DETAILED DESCRIPTION OF THE INVENTION 
The present compositions of the present invention finds wide application in 
formulations to provide hair conditioning properties, and viscosity 
building characteristics and to impart resistance to hydrolysis in acidic 
and alkaline solutions. They have excellent hair substantivity so that 
their conditioning effects endure for extended periods. As used herein, 
the term "conditioning" is intended to include the functions that enhance 
the feel and appearance of hair, including, inter alia, moisturizing, 
softening, lustering, and body building, of the hair. 
As defined herein, unless indicated to the contrary, the term "lower alkyl" 
when used alone or in combination, refers to an alkyl group containing 1-6 
carbon atoms. The alkyl group may be straight chained or branched. 
Examples include methyl, ethyl, n-propyl isopropyl, n-butyl, isobutyl, 
sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, and the like. 
The preferred alkyl group contains 1-5 carbon atoms, and the more 
preferred alkyl group contain 1-3 carbon atoms. Methyl is the preferred 
"lower alkyl" group. 
As used herein, the term "aryl" when used alone or in combination, is an 
aromatic group containing only carbon ring atoms and containing 6-10 
carbon ring atoms and up to a total of 15 carbon atoms. It also includes 
alkyl substituted aryl groups. Examples of aryl include phenyl, .alpha.- 
or .beta.-naphthyl, tolyl, xylyl, and the like. The preferred aryl groups 
are phenyl and tolyl. 
In Formula I, R.sub.1 is defined as hydrogen or CH.sub.3. When R.sub.1 is 
CH.sub.3, the homopolymer is derived from a methacrylamide derivative. It 
is preferred that R.sub.1 is CH.sub.3. 
R.sub.2 and R.sub.3, as defined hereinabove, are independently preferably 
C.sub.1 -C.sub.5 alkyl. It is preferred that R.sub.2 and R.sub.3 are the 
same. The most preferred alkyl is C.sub.1 -C.sub.3 alkyl, including ethyl, 
and especially methyl. It is most preferred that R.sub.3 and R.sub.2 are 
the same and are both alkyl, e.g., ethyl and especially methyl. 
The preferred R.sub.4 groups are lower alkyl, especially C.sub.1 -C.sub.5 
alkyl, and aryl. The preferred alkyl group contain 1-3 carbon atoms. They 
are preferably methyl and ethyl. It is also preferred that when R.sub.2 
and R.sub.3 are alkyl, that R.sub.2, R.sub.3 and R.sub.4 are the same. 
The preferred values of n are 1-4, with 3 being the most preferred value. 
The anion X is preferably C.sub.1 -C.sub.3 alkyl sulfate or aryl sulfonate. 
The most preferred aryl sulfonate is p-toluene sulfonate. 
The homopolymers of the present invention are prepared by subjecting the 
monomer of Formula I to polymerization, and especially free radical 
polymerization. The reaction is conducted in an oxygen-free environment, 
such as in the presence of an inert gas (e.g., helium, argon and the 
like), or nitrogen. The polymerization is carried out in an inert solvent, 
preferably lower alcohols and most preferably water. 
Polymerization is initiated by adding a polymerization initiator. The 
initiators utilized are the usual free radical polymer initiators. 
Examples include organic peresters (e.g., t-butyl peroxypivalate, t-amyl 
peroxypivalate, t-butyl peroxy-.alpha.-ethylhexanoate, and the like); 
organic azo compounds (e.g. azobisamidinopropanehydrochloride, 
azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, and the like); 
inorganic and organic peroxides, (e.g., hydrogen peroxide, benzyl 
peroxide, and butyl peroxide and the like), and oxidizing agents, such as 
persulfates (such as ammonium or alkali metal persulfate, and the like), 
chlorates and bromates (including inorganic or organic chlorates and/or 
bromates), the sodium salt of ethylene diamine tetraacetic acid (EDTA), 
reducing agents, such as sulfites and bisulfites (including inorganic 
and/or organic sulfites or bisulfites) oxalic acid, and ascorbic acid, and 
combinations thereof. The preferred initiators are water soluble. The most 
preferred initiators are sodium persulfate and 
azobisamidinopropanehydrochloride. Alternatively, initiation of 
polymerization can be instituted by irradiation with ultra-violet light. 
The amount of initiator utilized is in general a sufficient amount to 
effect initiation of polymerization. Preferably they are present in 
amounts ranging from about 0.001 to about 10% by weight of monomer and 
more preferably less than about 0.5% by weight based on the total weight 
of the monomer, and most preferably from about 0.005 to about 0.5% by 
weight based upon the weight of the monomer. The initiator is added in the 
polymerization either continuously or in incremental additions. The 
continuous or incremental addition of the initiator promotes the 
polymerization reaction. It is also essential to insure high molecular 
weight polymer. It has been found that repeated contact of unreacted 
monomers with fresh initiator, particularly during the final stages of 
reaction when monomer concentration is greatly reduced, drives the 
reaction to completion. The gradual or incremental addition also promotes 
more efficient and conservative use of initiator while permitting a 
shorter overall reaction time. 
The polymerization is conducted under reaction conditions effective to 
polymerize the monomer of Formula I under an oxygen free atmosphere. 
Preferably, the reaction is conducted at a temperature ranging from about 
30.degree. C. to about 100.degree. C. and more preferably from about 
60.degree. C. to about 90.degree. C. The oxygen free atmosphere is 
maintained for the duration of the reaction, for example, the nitrogen 
purging is maintained throughout the reaction. The continuous purging of 
the reaction by constant ebullition of inert gas maintains the oxygen free 
atmosphere. 
The quaternized monomer of Formula I is prepared by reacting an amino alkyl 
(meth)acrylamide of the formula 
##STR3## 
with sufficient amounts of quaternizing agent (X(R.sub.4).sub.2) to form 
the compound of Formula I under conditions effective for said 
quaternization. Preferred quaternizing agents include dialkyl sulfate, 
such as dimethyl sulfate, diethyl sulfate, and sulfonates, e.g., dodecyl 
p-toluene sulfonate, and the like. The reaction is preferably conducted in 
an inert solvent such as water, and the reaction is conducted at 
temperatures ranging from about room temperature to about 120.degree. C. 
Alternatively, the homopolymer can be prepared by first polymerizing a 
compound of Formula II in the presence of a free radical initiator under 
the free radical polymerization conditions described hereinabove followed 
by quarternizing the product therefrom under the quaternary reaction 
conditions described hereinabove. It is preferred that the polymerization 
is conducted on the quaternized product. Owing to this procedure, the 
homopolymer has substantially better reproducibility with regard to color, 
odor, molecular weight and viscosity, and in addition, the color, clarity 
of the polymer solution and odor are substantially improved. By using the 
quaternized dialkylaminoalkyl meth(acrylate) for the polymerization, the 
auto-catalytic hydrolysis of the dialkylaminoalkyl(meth)acrylate is 
suppressed, and it is thus possible to prepare the homopolymers having 
substantially greater product consistency and improved color and odor 
while, surprisingly, also exhibiting an extremely low residual monomer 
content. 
The desired molecular weight of the polymer is attained by varying 
polymerization conditions in ways known to the skilled artisan, such as 
varying polymerization temperature (with the lower temperatures being 
conducive to the formation of high molecular weight polymers), monomer 
concentration, amount of initiator, and the like. However, the molecular 
weight of the polymerized product can be regulated by adding regulators 
such as isopropyl alcohol. 
The homopolymer is also quite viscous, having a Brookfield viscosity (LVT, 
#3, 6 rpm, 25.degree. C.) of at least about 7500 cps, at about 40% solids. 
In fact, the viscosity under these conditions preferably ranges to at 
least 100,000 cps or more, but it is more preferred that the viscosity 
range from about 7500 cps to about 20,000 cps at about 40% solids. 
The intrinsic viscosity thereof ranges from about 0.5 to about 1.5 when 
measured in a 1N NaNO.sub.3 solution at 30.degree. C. Intrinsic viscosity 
is directly related to the molecular weight of the homopolymer, as 
described by the Mark Houwink Equation: 
EQU Intrinsic Viscosity=KMW.sup.-.alpha. 
wherein 
K is a constant for a specific polymer; 
.alpha. is a different constant for a specific polymer; and 
MW is the molecular weight. 
It is preferred that the intrinsic viscosity of the homopolymer in 1N 
NaNO.sub.3 solution measured at 30.degree. C. ranges from about 0.7 to 
about 0.9. 
It is critical to the product of the present process that it maintains the 
anion of the quaternizing agent utilized in the present process, and that 
it is not removed or replaced. It is the presence of the alkyl sulfate 
and/or the aryl sulfonates that permits the product to be non-corrosive 
and non-irritating to the skin or hair. 
It has been found that the homopolymer of the present invention is more 
soluble in aqueous solutions relative to other commercial cations utilized 
in hair conditioning compositions. 
The homopolymer produced by the process described hereunder is formulated 
into a hair conditioning composition. It is the active conditioning 
ingredient in the formulation and is present in hair conditioning 
effective amounts. The product is preferably present in an amount ranging 
from about 0.5% to about 5% by weight of the composition. Preferably, the 
product is present in an amount ranging from about 1% to about 4% by 
weight of the composition, and more preferably from about 1% to about 2.5% 
by weight of the composition. 
In hair conditioning formulations the homopolymer produced by the present 
process is present in the hair condition composition in association with a 
cosmetic vehicle. The vehicle of the present composition is predominantly 
water, but organic solvents also can be included in order to facilitate 
manufacturing of the composition or to provide esthetic properties to the 
compositions, such as viscosity control. Suitable solvents include the 
lower alcohols, like ethyl alcohol and isopropyl alcohol; glycol ethers, 
like 2-butoxyethanol: ethylene glycol monoethyl ether; propylene glycol 
and diethylene glycol monoethyl ether or monomethyl ether, and mixtures 
thereof. These non-aqueous solvents can be present in the clear hair 
conditioning composition of the present invention in an amount from about 
1 to about 50% by weight and in particular from about 5% to about 25% by 
weight relative to the total weight of the composition. 
The compositions of the present invention are clear relatively viscous 
compositions that are stable to phase separation at a temperature of about 
25.degree. C. for an indefinite period of time. 
The pH of the composition of the present invention ranges from about 3.5 to 
about 8.0 and more preferably from about 5 to about 7.5. 
The composition of the present invention optionally contains additional 
ingredients. For example, the conditioning composition may be formulated 
into a hair shampoo product, and then is associated with nonionic, 
anionic, amphoteric and zwitterionic surfactants, well known in the art. 
Examples of anionic surfactants include sulfates such as alkyl sulfate, 
preferably containing 10-20 carbon atoms, (e.g., lauryl sulfate), alkyl 
ether sulfate, preferably containing 10-40 carbon atoms (e.g., lauryl 
ether sulfate), alkylamide sulfates preferably containing 10-20 carbon 
atoms, alkyl arylpolyether sulfate preferably containing 10-20 carbon 
atoms, monoglyceride sulfates; sulfonates, e.g. alkyl sulfonate, 
preferably containing 10-20 carbon atoms, alkylamide sulfonates, 
preferably containing 10-20 carbon atoms, alkylaryl sulfonates preferably 
containing 10-40 carbon atoms and .alpha.-olefin sulfonates, preferably 
containing 10-20 carbon atoms; sulfosuccinic acid derivatives, e.g., alkyl 
(C.sub.10 -C.sub.20) sulfosuccinates, alkyl (C.sub.10 -C.sub.20) ether 
sulfosuccinates, alkyl (C.sub.10 -C.sub.20) amide sulfosuccinates, and 
alkyl (C.sub.10 -C.sub.20) amide polyether-sulfosuccinates; sarcosinates, 
e.g., (C.sub.8 -C.sub.22) alkyl or (C.sub.8 -C.sub.22)alkenyl 
sarcosinates; phosphate surfactants, e.g., alkyl (C.sub.10 -C.sub.20) 
phosphates, or alkyl (C.sub.10 -C.sub.20) ether phosphates, and the like. 
Examples of these ionic surfactants are described in U.S. Pat. No. 
4,419,344 to Strasella, et al., the contents of which are incorporated by 
reference. If present, these ionic surfactants are preferably present in 
amounts ranging from about 0.1% to 5% by weight and more preferably from 
about 0.1% to 2% by weight. 
Examples of nonionic surfactants include fatty acid alkanolamides, e.g., 
mono or diethanolamine adduct (lauric diethanolamide, coconut 
diethanolamide), amine oxides, and ethoxylated nonionics, e.g., 
ethoxylated forms of alkylphenols, fatty alcohols, fatty esters, and mono 
and diglycerides, and the like; these examples all contain preferably 
10-22 carbon atoms. These are described in Kirk-Othmer, Encyclopedia of 
Chemical Technology, Vol. 12, p. 887, John Wiley and Sons, Inc. 1994 and 
U.S. Pat. No. 4,954,335 to Janchipraponvej; the contents of which are 
incorporated by reference. They are present in amounts ranging from 0.1% 
to about 5% by weight and more preferably from about 0.1 to about 2% by 
weight. 
The amphoteric surfactants, also known as ampholytics, are both positively 
and negatively charged, and are usually derivatives of imidazolines or 
betaines, such as oleamidopropylbetaine and the like. They may also be 
associated with the homopolymer of the present invention in the hair 
conditioning compositions of the present invention. Sodium 
lauroamphoacetate may also be utilized in non-stinging shampoos. They are 
present in amounts ranging from about 0.1% to about 5% by weight and more 
preferably from about 0.1% to about 2% by weight. 
Another optional ingredient in the composition includes a polyhydric 
compound. The polyhydric compound is present especially when the 
composition contains surfactants for it helps couple the homopolymers and 
the surfactant to provide a clear non-turbid aqueous-based hair 
conditioning composition. The polyhydric compound can be a glycol, a triol 
or polyol. Specific examples include, but are not limited to ethylene 
glycol, propylene glycol, butylene glycol, hexylene glycol, diethylene 
glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 
glycerol or polyethylene or polypropylene glycol having an average 
molecular weight up to about 500. If present, it is present in amounts 
ranging from about 1% to about 20% by weight of the composition. 
In addition, additives may also be optionally added to the compositions of 
the present invention, such as fragrances, dyes, hair colorants, dandruff 
control agents, hydrotropes, foam stabilizers, preservatives, (e.g., 
methyl and propyl parabens, DMDM hydantoin, diazolidinyl urea, 
imidazolidinyl urea, and the like), water softening agents, acids, bases, 
buffers and the like. These optional additives if present usually will be 
present in weight percentages of less than about 2% each, or from about 5% 
to about 10% by weight of the composition in total. 
The clean hair conditioning compositions of the present invention also may 
optionally include thickeners that are generally used in this art. Example 
includes sodium alginate, guar gum; xanthan gum; gum arabic, cellulose 
derivatives, such as methylcellulose, hydroxyethyl cellulose, 
hydroxypropyl methyl cellulose, and carboxymethylcellulose; and various 
polymeric thickeners, such as carboxyvinyl polymers, e.g., polyacrylic 
acid derivatives, and polyvinylalcohols and the like. These thickeners if 
present, are present in an amount ranging from about 0.1% to about 3%, and 
preferably from about 0.25% to about 1% by weight relative to the total 
weight of the composition. 
Other optional materials include inorganic salts (e.g., alkali halides, 
sulfates or acetates, such as sodium, potassium, lithium, ammonium 
chloride, bromides, sulfates or acetates), humectants and similar material 
to provide esthetic properties and desirable physical properties to the 
composition. Preferably, such optional materials, if present, are present 
in weight percentages ranging from about 0.1% to about 10% each and from 
about 0.1% to about 20% in total, relative to the total weight, of the 
composition. 
The composition of the present invention may be formulated into a solution, 
cream, spray, lotion or mousse, in accordance with procedures known to the 
skilled artisan. For example, if made into a spray, the composition is 
introduced to a suitable aerosol container; it is then pressurized with 
propellents. 
As indicated hereinabove, the cationic homopolymer prepared by the present 
invention has a greater solubility in aqueous solutions than other 
cationic homopolymers used in hair conditioning compositions. As a result, 
the hair conditioning composition of the present invention is easier to 
prepare. Without wishing to bound, it is believed that the increased 
solubility facilitates the mixing of the various components, especially in 
a water carrier. 
In addition, as a result of the increased solubility of the homopolymer in 
water, it is easier to remove the hair conditioning composition from the 
hair after application thereof by rinsing with water. 
The composition of the present invention imparts exceptional hair 
conditioning properties to treated hair. It has curl retention capability. 
It can be used to treat untangled as well as tangled hair. It is also 
consumer appealing. The product is clear and maintains product stability 
over long storage times. The clear composition of the present invention 
coats the hair very effectively and also is especially easy to rinse from 
the hair. 
In addition, the hair conditioning composition of the invention also 
provides the further benefits of not leaving the hair flacky or sticky; 
not forming a crust and thereby providing combability and providing 
manageable and styleable hair having body. In addition, after treating the 
hair with the composition of the present invention, the hair has a soft, 
silky natural feel, has body, and is shiny, thickened, manageable and 
combable. 
Other properties provided by the present composition is that when applied 
to the hair, the hair maintains a firm but flexible hold and has curl 
retention. Furthermore, it softens permed and treated hair. In addition, 
it has a pH stability over a broad range. 
Thus, the easy to apply, clear composition of the present invention provide 
excellent wet comb and excellent dry comb properties to the hair, and the 
hair demonstrates improved and physical and cosmetic properties such as 
gloss, thickness, softness, manageability, body and less coating. In 
short, the treated hair has an enhanced sensitivity imparted thereto. 
The following non-limiting examples further illustrate the invention. 
Unless indicated to the contrary, all percentages and parts are by weight. 
EXAMPLE 1 
Preparation of Quaternary Monomer of Dimethylaminopropyl Methacrylamide and 
Dimethylsulfate 
To a 5 liter reaction flask, demineralized water (900.0 g), and 
dimethylamino propyl methacrylamide (DMAPMA) (2107.7 g) were added. While 
maintaining the temperature below 35.degree. C., the mixture was purged 
with a slow stream of air and dimethylsulfate (DMS) (1514.4 g) was added 
to the mixture. The reaction mixture was held at 30.degree. C. for two 
hours following the complete addition of DMS. The pH of the resulting 
solution of the quaternary monomer was then adjusted to about pH 7 with 
concentrated sulfuric acid (18.3 g). The concentration of the resulting 
monomer was about 80% (w/w), and the viscosity was about 90 cps. 
EXAMPLE 2 
Preparation of Quaternary Monomer of Dimethylaminopropylmethacrylamide and 
Dimethylsulfate 
The above quaternary monomer was prepared from DMAPMA (534.7 g) and 
diethylsulfate (DES) (460 g) using the procedure of Example 1. The 
concentration of the resulting monomer was about 80% (w/w) and the 
viscosity was about 80 cps. 
EXAMPLE 3 
Preparation of Quaternary Monomer of Dimethylamino Propylacrylamide with 
Dimethyl Sulfate 
The above-identified quaternary monomer was prepared from 
dimethylaminopropylacrylamide (DMAPA) (410.5 g) and dimethylsulfate (313.0 
g) utilizing the procedure of Example 1. The concentration of the monomer 
in the product was about 80%, and the viscosity was about 90 cps. 
The results of Experiments 1-3 are tabulated hereinbelow in Table 1. 
TABLE I 
______________________________________ 
PREATION OF QUATERNARY MONOMERS 
Aminoalkyl 
Quatern- 
MON- (Meth) arizing Appear- 
OMER Acrylamide 
Agent ance Viscosity 
pH Solids 
______________________________________ 
I DMAPMA DMS Clear 90 cps 7.3 80% 
II DMAPMA DES Clear 80 cps 6.6 80% 
III DMAPA DMS Clear 80 cps 6.9 80% 
______________________________________ 
EXAMPLE 4 
Homopolymerization of DMAPMA and DMS 
Into a 3-liter reaction flask were added the quaternary monomer of Example 
1 (66.3 g), demineralized water (875.0 g) and Versene 100.RTM., i.e., the 
sodium salt of EDTA (0.66 g). The mixture was then heated under slow 
nitrogen purging to 75.degree. C. 
The quaternary monomer solution thus prepared (80%, 1283.7 g) was metered 
separately but simultaneously into the reaction vessel with initiator Wako 
V-50 (azobisamidinopropanehydrochloride) solution (0.99 g in 473.4 g 
demineralized water). The addition time for the monomer solution was 150 
minutes, while it was 180 minutes for the initiator solution. The 
temperature was maintained at 75.degree. C. for 30 minutes following the 
completion of the additions, then the mixture was heated to 90.degree. C. 
Another portion of Wako V-50 initiator (0.27 g in 1.35 g demineralized 
water) was added to the resulting mixture all at once and the reaction 
temperature was maintained at 90.degree. C. for 60 minutes. After 60 
minutes at 90.degree. C., a third portion of Wako V-50 initiator (10.55 g 
in 1.35 g demineralized water) was added and maintained at 90.degree. C. 
for another 60 minutes. The resulting polymer solution was clear and 
viscous. 
This procedure was repeated several times and the results are tabulated in 
Table 2. 
EXAMPLE 5 
Homopolymerization of the Product of DMAPMA and DES 
The above product was prepared utilizing the procedure of Example 4 except 
that the quaternary monomer resulting from DMAPMA and DES was utilized. 
The results are tabulated in Table 2. 
EXAMPLE 6 
Homopolymerization of the Product of DMAPA+DMS 
The above product was prepared utilizing the procedure of Example 4, except 
that the quaternary monomer resulting from DMADA and DMS was utilized. The 
results are tabulated in Table 2. 
TABLE 2 
__________________________________________________________________________ 
RESULTS HOMOPOLYMERS 
Polymerization 
Solids 
Example 
Monomer 
Initiator 
Temperature 
% Viscosity 
pH 
__________________________________________________________________________ 
4a I Wako V-50, 0.092% 
75 C. 40.0 
10,000 cps. 
6.6 
4b I Wako V-50, 0.092% 
75 C. 39.4 
10,400 cps. 
6.5 
4c I Wako V-50, 0.092% 
75 C. 39.9 
10,800 cps. 
6.5 
4d I Wako V-50, 0.092% 
75 C. 39.6 
14,600 cps. 
5.5 
4e I Wako V-50, 0.092% 
75 C. 40.1 
11,000 cps. 
6.2 
4f I Wako V-50, 0.092% 
75 C. 40.3 
10,700 cps. 
6.2 
4g I Wako V-50, 0.092% 
75 C. 40.3 
11,200 cps. 
6.4 
4h I Wako V-50, 0.092% 
75 C. 40.1 
11,600 cps. 
6.8 
4i I Wako V-50, 0.092% 
75 C. 40.0 
11,800 cps. 
3.9 
4j I Wako V-50, 0.092% 
75 C. 40.0 
12,000 cps. 
3.8 
4k I Wako V-50, 0.092% 
75 C. 39.9 
14,800 cps. 
4.0 
4l I Wako V-50, 0.092% 
75 C. 39.9 
14,200 cps. 
4.1 
5 II Wako V-50, 0.122% 
75 C. 40.0 
12,400 cps. 
6.8 
6a III Wako V-50, 0.046% 
75 C. 40.0 
7,800 cps. 
5.0 
6b III Wako V-50, 0.092% 
65 C. 40.0 
83,000 cps. 
5.0 
__________________________________________________________________________ 
EXAMPLE 7 
A shampoo formulation was prepared from the following ingredients, which 
are indicated in parts by weight 
______________________________________ 
Sodium Lauryl Ether Sulfate 
50.0 
Sodium chloride 4.0 
Coconut Diethanolamide 
10.0 
Poly Ethylene Glycol 6000 Distearate 
2.0 
Oleamidopropyl Betaine 
30.0 
Sodium Lauryl Sulfate 96.0 
DMDM Hydantoin 0.6 
Distilled Water 6.0 
Homopolymer of Example 4a 
1.0 
______________________________________ 
The resulting formulation was clear and showed excellent compatibility of 
the quaternary homopolymer with the formulation. The viscosity of the 
formulation was about 3200 cps and had a pH of about 7.2. 
The Shampoo Formulations utilizing the other homopolymers of Example 4 are 
also prepared. 
EXAMPLE 8 
A shampoo formulation is prepared as in Example 7 except that the 
homopolymer of Example 5 was utilized. 
EXAMPLE 9 
Two shampoo formulations are prepared as in Example 8 each one containing 
one of the homopolymers product of Example 6. 
EXAMPLE 10 
A shampoo formulation is prepared as in Example 8, except that the 
homopolymer of Example 7 was utilized. 
EXAMPLE 11 
A styling mousse formula is prepared from the following ingredients: 
______________________________________ 
% by Weight 
______________________________________ 
MIRATAINE BET 0-30 .RTM. 
1.5 
MIRATAINE CBC .RTM. 1.5 
A Homopolymer of Example 4 
2.0 
Fragrance, Dye, 0.5 
preservative 
Water 95.0 
______________________________________ 
The MIRATAINE BET 0-30.RTM. (oleamidopropyl betaine) and MIRATAINE CBC.RTM. 
(cocoamidopropyl betaine) are slowly blended with water in a mixing vessel 
until uniform. With smooth agitation, a homopolymer of Example 4 is 
blended in and mixed until uniform. Finally, compatible fragrance, dye and 
preservatives are added. 
EXAMPLE 12 
A moisturizing styling spray is prepared as follows: 
______________________________________ 
% by Weight 
______________________________________ 
SD Alcohol 40 15.0 
Propylene Glycol. 
0.50 
Homopolymer of Ex. 4 
2.00 
Water 82.50 
Fragrance Dye and 
0.50 
Preservative 
______________________________________ 
Propylene glycol is mixed with water with rapid but smooth agitation. One 
of the homopolymers of Ex. 4 is slowly blended in, and slowly mixed until 
completely uniform. The SD Alcohol 40 is then added followed by the 
addition of fragrance, dye and preservatives, and the resulting product is 
mixed until uniform. 
The following experiments relate to various tests that were conducted on 
the formulation prepared in Example 4a. 
EXAMPLE 13 
Wet Comb Evaluation 
1 mL of 0.5% aqueous solution of the polymer prepared in Example 4a was 
added (0.5% solids) to the wet tress, European brown hair which was 
oxidatively damaged. The tress was massaged for one minute. After a 1-2 
minute standing period, the hair was rinsed for 30 seconds. The testing 
involved the use of a Dia-Stron stress tester which measures combing 
force. The force was calculated by use of Dia-Stron software in 
combination with multiple combing cycles. Eight combings per tress were 
used before and after treatment with the polymer. As a standard, hair 
tresses which were identically processed, except for the addition of the 
conditioning agent, were used. Lower values for work and peak loads as 
compared to the untreated samples are considered desirable. 
The results are given in the following Tables. 
TABLE 3 
______________________________________ 
TOTAL WORK LOAD (Kg of combing force) 
TRESS ID 
UNTREATED TREATED % REDUCTION 
______________________________________ 
A 0.186 0.122 34.41 
B 0.202 0.112 44.55 
C 0.228 0.119 47.81 
______________________________________ 
AVG % WORK LOAD REDUCTION: 42.26 
TABLE 4 
______________________________________ 
TOTAL PEAK LOAD (grams of combing force) 
TRESS ID 
UNTREATED TREATED % REDUCTION 
______________________________________ 
A 268 150 44.03 
B 307 146 52.44 
C 306 144 52.94 
______________________________________ 
AVG % PEAK LOAD REDUCTION: 49.80% 
The product in 0.5% aqueous solution (w/w) showed excellent work load 
reduction of untreated damaged. In addition, the product exhibited 
excellent peak load reduction indicating excellent conditioning of tangled 
hair. 
EXAMPLE 14 
The next set of experiments tested the curl retention of the polymer 
prepared in Example 4a. 
The tresses were prepared as follows: 1 mL of the polymer prepared in 
Example 4a (4.0% solids) was applied to the wet tress with no rinse and 
massaged into the tress for one minute. The tress was curled onto a 1 inch 
roller and then placed in oven at 45.degree. C. for 2 hours. At the 
conclusion of the two hours, the curled tress was allowed to stand at room 
temperature for 16 hours and placed in a humidity chamber thereafter. The 
tress was carefully removed from the roller and immediately suspended 
vertically from a holding fixture. The length of the tress was recorded. 
The test conditions were 25.degree. C./90% RH. The % curl retention was 
determined by the length of the hair at different time levels of exposure. 
Constant values for retention over extended periods of time was considered 
desirable. 
However, after the first two hours, some problems were encountered with the 
humidity chamber whereby the humidity become erratic, dropping to 65% RH 
for the remainder of the test. 
The results are given in the following Table. 
TABLE 5 
__________________________________________________________________________ 
CURL RETENTION 
INITIAL (% Curl Retention) 
RUN 
LENGTH** 
0.25 
0.5 
1.0 
1.5 
2 3 4 6 24 
# (cm) HR. 
HR. 
HR. 
HR. 
HRS. 
HRS.* 
HRS.* 
HRS.* 
HRS.* 
__________________________________________________________________________ 
1 17.5 71.2 
38.4 
25.0 
23.5 
22.7 
22.7 
15.2 
20.5 
20.5 
2 17.5 54.2 
36.5 
24.0 
22.9 
22.9 
22.9 
22.9 
22.9 
21.9 
3 17.5 59.2 
19.0 
12.2 
11.6 
11.6 
11.6 
11.5 
11.6 
10.9 
4 17.5 53.8 
36.8 
18.9 
15.1 
15.1 
15.1 
15.1 
15.1 
15.1 
5 17.5 50.0 
40.9 
31.8 
29.1 
28.2 
27.3 
27.3 
27.3 
27.3 
6 17.5 41.2 
31.8 
18.8 
18.8 
17.6 
17.6 
17.6 
17.6 
17.6 
AVG 54.9 
33.6 
21.8 
20.2 
19.7 
18.3 
18.3 
19.2 
18.9 
__________________________________________________________________________ 
* Relative humidity dropped from 90% to 65% 
**Length of hair before curling 
The curl retention of the tested polymer was excellent. 
The above preferred embodiments and examples were given to illustrate the 
scope and spirit of the present invention. These embodiments and examples 
will make apparent to those skilled in the art other embodiments and 
examples. These other embodiments and examples are within the 
contemplation of the present invention. Therefore, the present invention 
should be limited only by the amended claims.