Cationic polymers as antistatic additives for hair preparations

An aqueous hair-treatment preparation containing an antistatic additive imparting an antistatic effect to the hair, characterized in that said antistatic additive is at least one cationic polymer produced by the process of (1) epoxidizing 1,3-diene homopolymers or copolymers (2) reacting the epoxide compound so produced with low molecular weight amines selected from the group consisting of primary amines, secondary amines and tertiary amines, and (3) converting the reaction products into the salt form or into polymeric quaternary ammonium salts. The use of these polymeric amine salts or quaternary ammonium salts in cosmetic hair-treatment preparations provides these preparations with antistatic effects. Preferred cationic polymers are obtained by the epoxidation of polybutadiene, of which more than 50% of the monomer units show the 1,4-cis-configuration, reaction with dimethylamine or morpholine and conversion into the hydrochlorides or alkylation with glycidyl trimethylammonium chloride, 3-chloro-2-hydroxypropyl trimethylammonium chloride or ethylene oxide. The cationic polymers are preferably used in shampoos in quantities of from 0.5 to 5.0% by weight in addition to 5 to 30% by weight of alkylether sulfate tensides and 1 to 5% by weight of a zwitterionic or amphoteric washing-active substance.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to cosmetic hair-treatment preparations containing 
an antistatic additive imparting an antistatic effect to the hair. 
After washing with shampoos, shower and bath preparations based on 
synthetic tensides, but above all after cosmetic treatments, such as 
dyeing and shaping, hair is often in a cosmetically unsatisfactory state. 
It is difficult to comb when wet and has little hold and body after 
drying. Above all, it tends to become statically charged which causes 
freshly washed hair to "fly". 
It is known that conditioning preparations can be applied to hair after 
washing, dyeing or permanent waving. Conditioning preparations generally 
contain cationic interface-active compounds as their active ingredients. 
It is also known that certain substances may be added to normal shampoos 
based on anion-active tensides or on mixtures of tensides of different 
ionogenity in order to obtain a certain conditioning effect when the hair 
is washed. Examples of substances of the type in question are 
water-soluble proteins or protein degradation products, polycationic 
polymers, such as for example the synthetic polymers containing quaternary 
ammonium groups described in German published patent application No. 21 09 
081 (and equivalent Canadian Pat. No. 958,644) or the cellulose ethers 
containing quaternary nitrogen which are known from German published 
patent application No. 24 23 833 (and equivalent Canadian Pat. No. 
1,022,075). 
However, known conditioning agents have considerable drawbacks. Although 
cationic tensides are highly effective in nonionic formulations, they can 
only be used in ineffective quantities, if at all, in shampoos or, for 
example, hair dyes containing anionic tensides on account of their limited 
compatibility with anionic tensides. In addition, anionic tenside complex 
with quaternary ammonium compounds make the hair very "heavy", which is 
reflected in a greasy appearance and lack of body of the treated hair. 
This "heaviness" is also observed to a greater or lesser extent in the case 
of known, cation-active formulations for the after treatment of hair. 
Although polycationic polymers bring about a satisfactory improvement in 
wet compatibility, they do not effectively reduce the tendency of dry hair 
towards static charging. In many cases, particularly in anionic or 
anionic-amphoteric shampoo formulations, cationic polymers can even lead 
to an increase in the static chargeability of dry hair. 
2. OBJECTS OF THE INVENTION 
An object of the invention is to obtain a cosmetic hair-treatment 
preparation containing an antistatic additive imparting an antistatic 
effect to the hair. 
Another object of the invention is the development of an aqueous 
hair-treatment preparation containing an antistatic additive imparting an 
antistatic effect to the hair, characterized in that said antistatic 
additive is at least one cationic polymer obtainable by the process 
comprising 
(1) epoxidizing 1,3-diene homopolymer or copolymers containing at least 10 
1,3-diene units to a conversion of at least 10% of the double bonds 
present, 
(2) reacting the epoxidized poly-1,3-dienes with amines having the formula 
R.sup.1 NR.sup.2 R.sup.3, in which R.sup.1 is a member selected from the 
group consisting of hydrogen, lower alkyl containing from 1 to 4 carbon 
atoms and hydroxyalkyl containing from 2 to 4 carbon atoms, and R.sup.2 
and R.sup.3 are members selected from the group consisting of hydrogen, 
lower alkyl containing from 1 to 4 carbon atoms, and hydroxyalkyl 
containing from 2 to 4 carbon atoms, and together with the nitrogen atom, 
morpholino, piperidino and piperazino, with the proviso that at least one 
of R.sup.1, R.sup.2 and R.sup.3 is other than hydrogen, 
(3) converting the reaction products with mineral acids or lower molecular 
weight carboxylic acids into the salt form, preferably into the 
hydrochlorides, or converting the polymeric tertiary amines into 
quaternary ammonium salts by alkylation with compounds selected from the 
group consisting of 3-chloro-2-hydroxypropyl trimethylammonium chloride, 
RCl, RBr, R.sub.2 SO.sub.4, in which R represents methyl or ethyl or by 
the addition of ethylene oxide, propylene oxide, glycidol or glycidyl 
trimethylammonium chloride and conversion into the salt form, preferably 
into the hydrochlorides. 
A further object of the present invention is the development of an aqueous 
hair-treatment composition comprising at least one hair-treatment agent 
and an additive to impart an antistatic effect to the hair, wherein said 
hair-treatment composition contains an amount sufficient to impart an 
antistatic effect to the hair of at least one cationic polymer produced by 
the process comprising 
(1) epoxidizing an unsaturated polymer selected from the group consisting 
of 1,3-diene homopolymers and copolymers from 1,3-diene monomers, said 
unsaturated polymer containing at least 10 1,3-diene units up to a 
conversion of at least 10% of the double bonds present, 
(2) reacting the epoxidized unsaturated polymer with amines having the 
formula R.sup.1 NR.sup.2 R.sup.3, in which R.sup.1 is a member selected 
from the group consisting of hydrogen, lower alkyl group containing from 1 
to 4 carbon atoms and hydroxy-alkyl containing 2 to 4 carbon atoms and 
R.sup.2 and R.sup.3 are members selected from the group consisting of 
hydrogen, lower alkyl containing from 1 to 4 carbon atoms, hydroxyalkyl 
containing from 2 to 4 carbon atoms and together with the nitrogen atom, 
morpholino, piperidino and piperazino, with the provisio that at least one 
of R.sup.1, R.sup.2 and R.sup.3 is other than hydrogen, 
(3) converting the aminated polymer to the salt form by a process selected 
from the group consisting of 
(a) acidifying with an acid selected from the group consisting of mineral 
acids and low-molecular-weight carboxylic acids having from 1 to 7 carbon 
atoms, 
(b) quaternizing the tertiary aminated polymer by reaction with a 
quaternizing compound selected from the group consisting of 
3-chloro-2-hydroxypropyl trimethyl ammonium chloride, RCl, RBr and R.sub.2 
SO.sub.4, wherein R is member selected from the group consisting of methyl 
and ethyl and 
(c) quaternizing the tertiary aminated polymer by reaction with a 
quaternizing compound selected from the group consisting of ethylene 
oxide, propylene oxide, glycidol and glycidyl trimethyl ammonium chloride 
followed by acidifying with said acid of (a) above. 
A yet further object of the present invention is the development of a 
process for imparting an antistatic effect to hair which comprises 
applying to hair the above aqueous hair-treatment composition. 
These and other objects of the invention will become more apparent as the 
description thereof proceeds. 
DESCRIPTION OF THE INVENTION 
Accordingly, there was a need to find conditioning agents which are 
suitable for use as conditioning and antistatically active additives for 
hair treatment preparations and which are attended by the above-mentioned 
disadvantages to a far lesser extent, if at all. 
The present invention relates to the use of cationic polymers obtainable by 
(1) epoxidizing 1,3-diene homopolymer or copolymers containing at least 10 
1,3-diene units to a conversion of at least 10% of the double bonds 
present, 
(2) reacting the epoxidized poly-1,3-dienes with amines having the formula 
R.sup.1 NR.sup.2 R.sup.3, in which R.sup.1 is a member selected from the 
group consisting of hydrogen, lower alkyl containing from 1 to 4 carbon 
atoms and hydroxyalkyl containing from 2 to 4 carbon atoms, and R.sup.2 
and R.sup.3 are members selected from the group consisting of hydrogen, 
lower alkyl containing from 1 to 4 carbon atoms, and hydroxyalkyl 
containing from 2 to 4 carbon atoms, and together with the nitrogen atom, 
morpholino, piperidino and piperazino, with the proviso that at least one 
of R.sup.1, R.sup.2 and R.sup.3 is other than hydrogen, 
(3) converting the reaction products with mineral acids or lower molecular 
weight carboxylic acids into the salt form, preferably into the 
hydrochlorides, or converting the polymeric tertiary amines into 
quaternary ammonium salts by alkylation with compounds 
selected from the group consisting of 3-chloro-2-hydroxypropyl trimethyl 
ammonium chloride, RCl, RBr, R.sub.2 SO.sub.4, in which R is methyl or 
ethyl, or by the addition of ethylene oxide, propylene oxide, glycidol or 
glycidyl trimethyl ammonium chloride and conversion into the salt form, 
preferably into the hydrochlorides, as an antistatically active additive 
in cosmetic hair-treatment preparations. 
More particularly, the present invention relates to an aqueous 
hair-treatment composition comprising at least one hair-treatment agent 
and an additive to impart an antistatic effect to the hair, wherein said 
hair-treatment composition contains an amount sufficient to impart an 
antistatic effect to the hair of at least one cationic polymer produced by 
the process comprising 
(1) epoxidizing an unsaturated polymer selected from the group consisting 
of 1,3-diene homopolymer and copolymers from 1,3-diene monomers, said 
unsaturated polymer containing at least 10 1,3-diene units, to a 
conversion of at least 10% of the double bonds present, 
(2) reacting the epoxidized unsaturated polymer with amines having the 
formula R.sup.1 NR.sup.2 R.sup.3, in which R.sup.1 is a member selected 
from the group consisting of hydrogen, lower alkyl containing from 1 to 4 
carbon atoms and hydroxyalkyl containing from 2 to 4 carbon atoms and 
R.sup.2 and R.sup.3 are members selected from the group consisting of 
hydrogen, lower alkyl containing from 1 to 4 carbon atoms, hydroxyalkyl 
containing from 2 to 4 carbon atoms and, together with the nitrogen atom, 
morpholino, piperidino and piperazino, with the provisio that at least one 
of R.sup.1, R.sup.2 and R.sup.3 is other than hydroxygen, 
(3) converting the aminated polymer to the salt form by a process selected 
from the group consisting of 
(a) acidifying with an acid selected from the group consisting of mineral 
acids and low-molecular-weight carboxylic acids having from 1 to 7 carbon 
atoms, 
(b) quaternizing the tertiary aminated polymer by reaction with a 
quaternizing compound selected from the group consisting of 
3-chloro-2-hydroxypropyl trimethyl ammonium chloride, RCl, RBr and R.sub.2 
SO.sub.4, wherein R is a member selected from the group consisting of 
methyl and ethyl, and 
(c) quaternizing the tertiary aminated polymer by reaction with a 
quaternizing compound selected from the group consisting of ethylene 
oxide, propylene oxide, glycidol and glycidyl trimethyl ammonium chloride 
followed by acidifying with said acid of (a) above; as well as 
a process for imparting an antistatic effect to hair which comprises 
applying to hair the above aqueous hair-treatment composition. 
The cationic polymers suitable for use in accordance with the invention and 
the processes by which they are produced are known. 
Thus, the epoxidation of butadiene oligomers is described, for example, in 
Chemiker-Zeitung 95 (1971), No. 20, pages 857 to 863. The reaction of 
epoxidized polybutadienes with tertiary amines to form quaternary ammonium 
polymers is known from published German patent application Ser. No. 21 41 
941 (and corresponding British publication 1,342,269). The reaction of 
epoxidized butadiene homopolymers or copolymers with primary and secondary 
aliphatic and cycloaliphatic amines is described in published German 
patent application Ser. No. 27 32 736 (and corresponding British 
publication 1,602,560). Conversion of the polymeric tertiary amines, which 
are formed during the reaction of the polyepoxides with secondary amines, 
into polymeric quaternary ammonium salts may also be carried out in known 
manner by alkylation with 3-chloro-2-hydroxypropyl trimethylammonium 
chloride, methyl chloride, ethyl chloride, dimethyl sulfate, diethyl 
sulfate or by the addition of 1,2-monoepoxides, such as ethylene oxide, 
propylene oxide, glycidol or glycidyl trimethylammonium chloride. 
Suitable starting products for producing the cationic polymers used in 
accordance with the invention are 1,3-diene homopolymers or copolymers. 
Suitable 1,3-dienes are, above all, butadiene, 1,3-pentadiene, isoprene 
and chloroprene. Liquid butadiene homopolymers or copolymers are 
preferably used. However, mono-olefins, such as ethylene, propylene, 
styrene, or acrylic acid derivatives may also be present as comonomers. 
The poly-1,3-dienes should contain at least 10 1,3-diene units per 
molecule. Liquid butadiene homopolymers are particularly suitable. The 
double bonds present in poly-1,3-dienes of the type in question may have 
the cis-configuration or trans-configuration or may be arranged in the 
vinyl position, depending on the polymerization conditions. It is 
preferred to use polymers of which more than 50% show the 
1,4-cis-configuration at the double bonds. 
The poly-1,3-dienes should be epoxidized up to a conversion of at least 10% 
of the double bond present. Polyepoxides containing from 3 to 6% by weight 
of epoxide oxygen are particularly suitable. 
Amines suitable for reaction with the polyepoxides are, for example, 
methylamine, ethylamine, isopropylamine, monoethanolamine, dimethylamine, 
diethylamine, diethanolamine, morpholine, piperidine, piperazine, 
trimethylamine, triethylamine, triethanolamine, N,N-dimethylethanolamine. 
The reaction products with dimethylamine and morpholine are preferred. 
The reaction with tertiary amines leads directly to polymeric quaternary 
ammonium compounds which are converted into the salt form by reaction with 
mineral acids or with low molecular weight carboxylic acids, preferably 
having from 1 to 7 carbon atoms, such as acetic acid, lactic acid, 
glycolic acid. Conversion with hydrochloric acid into the hydrochlorides 
is preferred. 
The reaction with primary and secondary amines leads to polymeric secondary 
and tertiary amines which, after conversion into the salt form, are 
suitable as cationic polymers for use in accordance with the invention. 
However, the polymeric tertiary amines obtained by reaction with secondary 
amines may also be converted by alkylation into polymeric quaternary 
ammonium compounds. It is preferred to convert reaction products of 
epoxidized poly-1,3-dienes with dimethylamine into polymeric quaternary 
ammonium salts by alkylation with glycidyl trimethylammonium chloride or 
with 3-chloro-2-hydroxypropyl trimethylammonium chloride. Another 
preferred group of cationic polymers for use in accordance with the 
invention is obtained by reacting the poly-1,3-diene epoxides with 
dimethylamine and quaternizing the reaction products obtained by the 
addition of ethylene oxide, followed by conversion into the salt form. 
The use of the cationic polymers obtainable as described in accordance with 
the invention in cosmetic hair treatment preparations provides these 
preparations with a distinct antistatic effect when applied to human hair 
without any of the increased "heaviness" which normally occurs with 
cation-active compounds. By virtue of this effect, cosmetic hair-treatment 
preparations of the type in question considerably improve the set and body 
of the hair. This effect is surprising insofar as known cationic polymers 
produce hardly any antistatic effects, particularly when applied from 
formulations containing anionic tensides. 
Antistatic activity may be tested, for example, as follows: 
Strands of hair approximately 20 cm long and weighing approximately 2 g are 
subjected to a single bleaching treatment and to a single cold-wave 
treatment using standard commercial preparations (without the cationic 
polymers used in accordance with the invention), washed, rinsed and dried. 
0.5 ml of a test solution containing, for example, 1% by weight of the 
cationic polymer is applied by pipette to the strands of hair thus 
pretreated and rubbed in. Instead of using the test solution, it is also 
possible to use any cosmetic hair-treatment preparation containing the 
cationic polymers to be used in accordance with the invention. After the 
treatment, the strands of hair are rinsed with clear, warm (35.degree. C.) 
water, dried for 30 minutes at 60.degree. C. and then conditioned for 24 
hours at 20.degree. C./50% relative air humidity. 
Thereafter, the strands of hair are combed 20 times using a hard rubber 
comb. In the case of the untreated hair samples, this produces 
considerable static charging of the strands of hair, as reflected in a 
distinct spreading of the hair ends. 
The strands of hair treated with the cationic polymers used in accordance 
with the invention or with preparations containing them are not statically 
charged and remain parallel after combing. 
Cosmetic hair-treatment preparations suitable for use in accordance with 
the invention are, for example, shampoos, hair after treatment 
preparations, for example hair rinses, hair cure preparations, hair 
lotions, hair lacquers, hair sprays, hair dyes and hair waving 
preparations. However, the products may also be used with advantage in 
bath additives, shower baths and liquid body shampoos because they are 
also used for washing the hair or come into contact with the hair in use. 
The cationic polymers used in accordance with the invention are 
incorporated in the cosmetic hair-treatment preparations mentioned above 
in quantities of from 0.1% to 10% by weight and preferably in quantities 
of from 0.5% to 5.0% by weight, based on the preparation as a whole or in 
the case of aerosol preparations, on the propellent-free active solution. 
The cationic polymers used in accordance with the invention are 
particularly effective in cosmetic hair-treatment preparations containing 
anionic surface-active compounds, because an antistatic effect would 
otherwise be impossible to obtain with preparations such as these. 
Suitable anionic surface-active compounds are, for example, alkali metal, 
magnesium, ammonium and/or lower alkanol ammonium salts of alkyl sulfuric 
acid half esters containing from 8 to 18 and preferably from 12 to 16 
carbon atoms in the alkyl (so-called alkyl sulfates) or of alkyl 
polyethyleneglycol ether sulfuric acid half esters containing from 8 to 18 
and preferably from 12 to 16 carbon atoms in the alkyl and from 1 to 6 
ethyleneglycol ether groups in the molecule (so-called alkyl ether 
sulfates). Other suitable anionic surface-active compounds are primary and 
secondary, linear alkane sulfonates containing from 10 to 18 carbon atoms, 
alkene sulfonates containing from 10 to 18 carbon atoms and hydroxy alkane 
sulfonates containing from 10 to 18 carbon atoms, of the type obtained by 
sulfonating linear olefins containing from 10 to 18 carbon atoms, higher 
fatty acid alkylol amide sulfates and higher fatty acid alkylol amide 
polyethyleneglycol ether sulfates, sulfated higher fatty acid 
monoglycerides, sulfosuccinic acid monoalkyl esters containing from 8 to 
18 carbon atoms in the alkyl or dialkyl esters containing from 6 to 10 
carbon atoms in the alkyls, alkyl polyethyleneglycol ether carboxylates 
containing from 8 to 18 carbon atoms in the alkyl and from 2 to 6 
polyethyleneglycol ether groups in the molecule, acyl sarcosines, acyl 
taurides and acyl isethionates containing from 8 to 18 carbon atoms in the 
acyl groups. 
In addition to the anionic surface-active compounds, zwitterionic or 
amphoteric wash-active substances may be used in quantities of up to about 
half the content of anionic surface-active compounds. Suitable 
zwitterionic wash-active substances are, for example, alkyl betaines, 
alkyl aminopropyl betaines, alkyl imidazolinium betaines, alkyl 
amidocarboxylic acids, in each case containing from 8 to 18 carbon atoms 
in the alkyl. Examples of such suitable zwitter-ionic tensides are 
cocoalkyl dimethylaminoacetic acid, cocoalkylamidopropyl 
dimethylaminoacetic acid or N-hydroxyethyl-N-cocoalkylamidoethyl glycine. 
The cationic polymers are preferably used in accordance with the invention 
in a shampoo which, in addition to 0.5 to 5% by weight of the cationic 
polymer, contains from 5 to 30% by weight of alkylether sulfate tensides 
and from 1 to 5% by weight of a zwitterionic or amphoteric wash-active 
substance. 
In addition, refatting constituents, such as for example ethoxylated higher 
fatty acid partial glycerides or glycerol polyethyleneglycol ether higher 
fatty acid esters, ethoxylated sorbitan higher fatty acid esters and also 
cosmetic oil components may be used in addition to the above-mentioned 
components. 
The cosmetic hair-treatment preparations may also contain non-ionic wash 
active substances and the usual additives and auxiliaries, active 
substances, solvents, propellent gases, thickeners, dyes, opacifiers, 
fragrances, preservatives, stabilizers and buffers appropriate to the 
particular application or formulation. 
The following Examples are intended to illustrate the invention without 
limiting it in any way.

EXAMPLES 
(A) Preparation of the Cationic Polymers 
Example 1: Epoxidation of polybutadiene 
In a glass apparatus consisting of a 4-liter three-necked flask, stirrer 
and intensive condenser, 540 g of a polybutadiene of which the viscosity 
at 20.degree. C. according to DIN 53015 amounted to approximately 3 poises 
and the iodine number (according to Wijs) amounted to approximately 450 
g/100 g and which predominantly contained 1,4-cis-double bonds (Polyol 
huls 130, a product of Chem. Werke Huls A. G., Germany were dissolved in 
2000 ml of chloroform. 190 g of 40% peracetic acid (in glacial acetic 
acid) containing 19 g of dissolved sodium acetate were added dropwise over 
a period of 7.5 hours with vigorous stirring to the solution previously 
heated to 50.degree. C. in such a way as to produce a steady, gentle 
reflux of the chloroform boiling under the effect of the heat of reaction. 
Thereafter, the reaction mixture was stirred for another 2 hours at 
50.degree. C. and then cooled to 30.degree. C. The epoxide was 
precipitated by pouring the reaction mixture into 12,000 ml of methanol 
under continuous stirring. The viscous oil, precipitating to the bottom of 
the container, was separated off, mixed three times with 5 liters of 
methanol and separated and then washed until neutral. The oily reaction 
product was freed from volatile constituents in vacuo. The yield amounted 
to 95% of the theoretical. The product contained 2.5% by weight of epoxide 
oxygen. 
Examples 2 to 8 
Starting with 540 g of polybutadiene, epoxidation was carried out in the 
same way as in Example 1 using the quantities of peracetic acid (40% in 
glacial acetic acid) shown in Table 1. The yields and epoxide oxygen 
contents indicated were obtained. 
TABLE 1 
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Exam- Quantity of peracetic 
Yield [% of 
ple acid (40% in glacial 
the theo- % Epoxide oxygen 
No. acetic acid) retical] [% by weight] 
______________________________________ 
190 g 95 2.5 
2 285 g 93 3.6 
3 380 g 88.5 4.7 
4 570 g 83.7 6.7 
5 665 g 64.3 7.4 
6 950 g 79.0 9.3 
7 1140 g 71.1 10.3 
8 1425 g 47.5 5.8 
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Example 9 
Reaction of the epoxidized polybutadienes with dimethylamine 
50 g of a 40% aqueous solution of dimethylamine were added to 50 g of 
epoxidized polybutadiene (Example 1) dissolved in 600 g of dioxane and the 
combined solutions introduced into an autoclave of V4A-steel. After 
purging twice with nitrogen, the contents of the autoclave were stirred 
under an initial pressure of 5 bars and at the same time heated to 
200.degree. C., producing a maximum pressure of 32 bars. After cooling to 
20.degree. C., the autoclave was vented and opened and the reaction 
product precipitated by pouring into 2.5 liters of distilled water. The 
isolated reaction product was purified by dissolution in dioxane and 
precipitation in water and, after drying, was characterized by the amine 
number. The reaction product had an amine number of 55.3. The yield 
amounted to 60% of the theoretical. 
Examples 10 to 16 
The reaction of the epoxidized polybutadienes (Examples 2 to 8) was carried 
out in the same way as in Example 9 starting with 50 g of the epoxides in 
600 ml of dioxane, the amines shown in Table 2 being used. Reaction 
products having the amine numbers indicated in Table 2 were obtained. 
TABLE 2 
__________________________________________________________________________ 
Amine used Reaction product 
Example No. 
Epoxide used 
Type Quantity 
amine number 
__________________________________________________________________________ 
9 Example 1 
dimethylamine* 
50 g 55.3 
10 Example 2 
dimethylamine* 
70 g 69.1 
11 Example 5 
dimethylamine* 
90 g 134.8 
12 Example 5 
monoethanolamine 
61 g 98.5 
13 Example 6 
dimethylamine* 
120 g 
107.8 
14 Example 6 
methylamine* 
225 g 
240.4 
15 Example 8 
dimethylamine* 
105 g 
168.2 
16 Example 8 
morpholine 
81 g 153.8 
__________________________________________________________________________ 
*40% aqueous solution 
Examples 10a to 16a 
Preparation of the hydrochlorides 
The amine reaction products of Examples 9 to 16 were dissolved in dioxane 
and an equivalent quantity of 18% aqueous hydrochloric acid calculated 
from the amine number was added to the resulting solutions. The solvent 
was then removed by evaporation in vacuo. 
Example 17 
Quaternization with glycidyl trimethylammonium chloride 
10 g of the amine reaction product of Example 9 was dissolved in 100 ml of 
dioxane, followed by the addition of 50 mg of KOH and mixing with 1.8 g of 
glycidyl trimethylammonium chloride (80%, moist). The reaction mixture was 
heated under reflux to boiling point over a period of 2 hours and kept at 
that temperature for another 5 hours, during which it became slightly 
cloudy. The reaction mixture was then concentrated to a volume of 50 ml 
and precipitated by pouring into 250 ml of distilled water. The substance 
precipitated was separated off and dried. The yield amounted to 9.7 g 
(i.e. 82.2% of the theoretical). 
Conversion into the hydrochloride was carried out as in Examples 9 to 16. 
Examples 18 and 19 
The amine reaction products indicated in Table 3 were alkylated as in 
Example 17 with the indicated quantities of glycidyl trimethylammonium 
chloride (GMAC) and the yields of the hydrochloride obtained are 
indicated. 
TABLE 3 
__________________________________________________________________________ 
Yield 
Example No. 
Amine reaction product 
GMAC, 80% 
% of theoretical 
Cl.sup.(-) (% by weight) 
__________________________________________________________________________ 
17 Example 9 1.8 g 82.2 0.48 
18 Example 10 2.2 g 72.9 2.18 
19 Example 11 4.4 g 55.6 0.36 
__________________________________________________________________________ 
Example 20 
Quaternization with ethylene oxide 
20 g of the reaction product of Example 10 were dissolved in 400 ml of 
anhydrous dioxane and 0.5 g of sodium methylate added to the resulting 
solution. The solution was then transferred to an autoclave, followed by 
the addition of 5.4 g of ethylene oxide (i.e. approximately 5 mols/mol of 
amino groups). After heating to 70.degree. C. the solution was stirred for 
5 hours at that temperature. In that time, the pressure which was 
initially 5 bars fell to 4.1 bars. After cooling, the reaction mixture was 
concentrated to dryness under reduced pressure. An addition of 
approximately 1 mol of ethylene oxide per amino group is calculated from 
the yield of 21.1 g obtained. 
The quaternization product was converted into the readily water-soluble 
hydrochloride by dissolution in dioxane followed by the addition of 
approximately 5 g of 18% hydrochloric acid and concentration to dryness. 
(B) Application Examples 
Example 21 
______________________________________ 
Hair Shampoo 
______________________________________ 
Fatty alcohol (C.sub.12-18) + 2 EO- 
30% by weight 
sulfate, Na salt (28%) 
Cocoalkylamidopropyl betaine (30%) 
15% by weight 
Cationic polymer of Example 10 
2.0% by weight 
(hydrochloride) 
Formaldehyde (40%) 0.2% by weight 
Water, perfume oil, dyes 
ad 100% by weight 
______________________________________ 
EO = mols of ethylene oxide 
Example 22 
______________________________________ 
Hair rinse 
C16, a product of E.I. 
1.5% by weight 
DuPont Corp., U.S.A. "Lorol" 
Glycerol mono-/distearate 
GMS, a product of Henkel 
1.5% by weight 
KGaA, F.R. Germany "Cutina" 
Cationic polymer of Example 16 
(hydrochloride) 1.5% by weight 
Cetyl trimethylammonium 
chloride (25%) 2.0% by weight 
Water, perfume oil, dye 
ad 100% by weight 
______________________________________ 
Example 23 
______________________________________ 
Hair dye (brown) 
______________________________________ 
Tallow fatty alcohol 
8.0% by weight 
Fatty alcohol (C.sub.12-18) + 2 EO- 
sulfate, Na salt (28%) 
25.0% by weight 
Cationic polymer of Example 18 
3.0% by weight 
p-tolylene diamine 1.5% by weight 
2,4 diaminoanisole 0.04% by weight 
p-aminophenol 0.23% by weight 
Resorcinol 0.4% by weight 
Ammonia, 25% 4.5% by weight 
Water ad 100% by weight 
______________________________________ 
The preceeding specific embodiments are illustrative of the practice of the 
invention. It is to be understood however that other expedients known to 
those skilled in the art or disclosed herein, may be employed without 
departing from the spirit of the invention or the scope of the appended 
claims.