U.S. patent number 3,917,817 [Application Number 05/310,088] was granted by the patent office on 1975-11-04 for hair treating cosmetic compositions containing piperazine based cationic polymer.
This patent grant is currently assigned to L'Oreal. Invention is credited to Henri Sebag, Guy Vanlerberghe.
United States Patent |
3,917,817 |
Vanlerberghe , et
al. |
November 4, 1975 |
Hair treating cosmetic compositions containing piperazine based
cationic polymer
Abstract
Piperazine-based low molecular weight film-forming cationic
polymer is employed in a cosmetic hair-conditioner composition
comprising a solution of the polymer in amounts of about 0.1-5
weight percent of the composition in a solvent such as water,
acidified water, or aqueous alcohol solution.
Inventors: |
Vanlerberghe; Guy
(Montjay-la-Tour par Claie-Souilly, FR), Sebag; Henri
(Paris, FR) |
Assignee: |
L'Oreal (Paris,
FR)
|
Family
ID: |
19726890 |
Appl.
No.: |
05/310,088 |
Filed: |
November 28, 1972 |
Foreign Application Priority Data
Current U.S.
Class: |
424/70.17;
424/DIG.2; 424/47; 524/608; 528/392; 528/407; 544/357; 510/475;
510/119; 510/123; 510/125; 510/126; 510/121; 514/252.11; 424/DIG.1;
424/DIG.4; 524/389; 524/612; 528/405 |
Current CPC
Class: |
A61Q
5/02 (20130101); A61K 8/88 (20130101); C08G
73/0633 (20130101); A61Q 5/12 (20130101); C08G
73/0273 (20130101); Y10S 424/01 (20130101); Y10S
424/04 (20130101); Y10S 424/02 (20130101) |
Current International
Class: |
C08G
73/00 (20060101); C08G 73/02 (20060101); C08G
73/06 (20060101); A61K 007/06 () |
Field of
Search: |
;260/2EP,2BP,268PL,29.6HN ;424/47,70,71,DIG.1,DIG.2 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3069390 |
December 1962 |
Kline et al. |
3250682 |
May 1966 |
Wilmsmann et al. |
3267046 |
August 1966 |
Bonvicini |
3274312 |
September 1966 |
Compostella et al. |
3280044 |
October 1966 |
Bonvicini et al. |
|
Primary Examiner: Meyers; Albert T.
Assistant Examiner: Clarke; Vera C.
Attorney, Agent or Firm: Cushman, Darby & Cushman
Claims
What is claimed is:
1. Cosmetic composition for conditioning the hair comprising a
solution in a solvent selected from the group consisting of water
and water-lower alkanol, of a member selected from the group
consisting of
1. a film-forming cationic polymer having a molecular weight of
about 1,000 to 15,000 and having the formula
-- A -- Z -- A -- Z -- A -- Z --
wherein A represents ##SPC7##
and Z represents B and B' wherein B and B' each independently
represent a bivalent radical selected from the group consisting of
(i) hydroxypropylene, (ii) alkylene having up to 5 carbon atoms
inclusive and interrupted by 1-2 members selected from the group
consisting of -CONH and ##SPC8##
(iii) hydroxy alkylene wherein the alkylene moiety has up to 6
carbon atoms inclusive and interrupted by a member selected from
the group consisting of alkylamine wherein the alkyl moiety has
12-16 carbon atoms, benzylamine, oleylamine and oxygen, and (iv)
hydroxy propyl-piperazinyl-hydroxypropyl,
2. quaternary ammonium salt of the cationic polymer in (1) and
3. the oxidation product of the cationic polymer in (1),
said member being present in an amount of about 0.1 to 5 percent by
weight of said composition.
2. The composition according to claim 1, characterized by the fact
that it is in the form of a cream.
3. A method of conditioning the hair comprising applying to said
hair an effective amount of the composition of claim 1.
4. A cosmetic composition for conditioning the hair comprising a
solution in water-ethanol of a member selected from the group
consisting of
1. a film-forming cationic polymer having a molecular weight of
about 1,000 to 15,000 and having the formula
-- A -- Z -- A -- Z -- A -- Z --
wherein A represents ##SPC9##
and Z represents B and B' wherein B and B' each independently
represent a bivalent radical selected from the group consisting of
(i) hydroxypropylene, (ii) alkylene having up to 5 carbon atoms
inclusive and interrupted by 1-2 members selected from the group
consisting of -CONH and ##SPC10##
(iii) hydroxy alkylene wherein the alkylene moiety has up to 6
carbon atoms inclusive and interrupted by a member selected from
the group consisting of alkylamine wherein the alkyl moiety has
12-16 carbon atoms, benzylamine, oleylamine and oxygen and (iv)
hydroxy propyl-piperazinyl-hydroxypropyl,
2. quaternary ammonium salt of the cationic polymer in (1) and
3. the oxidation product of the cationic polymer in (1),
said member being present in an amount of about 0.1 to 5 percent by
weight of said composition.
5. The composition of claim 4 which also includes an anionic,
cationic, non-ionic or amphoteric surfactant.
6. The composition according to claim 4 having a pH between 3 and
11.
7. The composition according to claim 4 wherein said cationic
polymer has a molecular weight less than 15,000.
Description
The present invention relates to compositions for treating and
conditioning the hair. More particularly, the present invention
relates to cosmetic compositions for the hair, containing a low
molecular weight, film-forming cationic polymer.
Many people's hair, because of its general state or its sensitivity
due to relatively frequent periodic treatments such as bleaching,
dyeing or permanent waving, often is difficult to comb out and to
arrange especially in the case of abundant hair. To varying
degrees, such hair often is also dry, dull and rough or lacks vigor
and life. Further, such hair is very sensitive to humidity in the
air, which explains why hair-sets do not hold for an acceptable
length of time. Consequently, the frequency of such treatments, as
described above has to be increased, which, in turn increases the
above-mentioned disadvantages.
The present invention now makes it possible to substantially limit
or avoid these disadvantages by applying to the hair as a
conditioner therefor a low molecular weight, film-forming cationic
polymer that imparts to the hair an appearance of vigor and
radiance.
This polymer can be used alone or as the main component in a
hair-dressing lotion, cream, gel, hairsetting lotion hair-setting
reinforcer, or alternatively, as an adjuvant in a composition for
shampooing, setting, in permanent waving the hair, in a hair dyeing
composition, in a cream for treating dry or greasy hair, in an
anti-dandruff lotion or in similar compositions for application to
the hair.
The application of the hair conditioner cosmetic composition of
this invention results in improving the facility and ease of
combing out wet hair and imparts thereto brilliancy, softness and
manageability of dry hair. Hair treated with the composition of
this invention feels lighter, while at the same time appears
thicker and more alive.
The conditioner according to the invention, which acts as a
softener and emollient, produces after application of the same to
the hair in a shampoo, for example, a more brilliant, more
voluminous and more aerated hair without the appearance of static
electricity. Further, the cationic polymer of the present
invention, provides the additional advantage of avoiding a
powdering phenomenon which is frequently observed with numerous
conventionally employed polymers. Moreover, the inclusion of the
hair conditioner of the present invention in cosmetic compositions
for the hair, which comositions also include other components or
hair treating agents, does not entail any appreciable reduction of
the properties or effectiveness of these other components.
The cationic polymer of the present invention is characterized by
the fact that the cationic groups are part of the main polymer
chain and that they are essentially derived from bisecondary
heterocyclic amines, preferably, piperazine. Structurally, the low
molecular weight, filmforming, cationic polymer of the present
invention can be represented by the pattern
-- A -- Z -- A -- Z -- A -- Z -- (I)
wherein A represents a radical derived from a heterocycle
containing two secondary amine functions and, preferably, the
radical ##SPC1##
and Z represents the symbol P or B', each of which independently
represents a bivalent radical selected from the group consisting of
(i) hydroxypropylene, (ii) alkylene having up to 5 carbon atoms
inclusive and interrupted by 1 - 2 members selected from the group
consisting of -CONH and ##SPC2##
and (iii) hydroxy alkylene wherein the alkylene moiety has up to 6
carbon atoms inclusive and is interrupted by a member selected from
the group consisting of alkylamine wherein the alkyl moiety has 12
to 16 carbon atoms, benzylamine, oleylamine and oxygen.
Often, polymers of the present invention are those in which A has
the meaning given above and B and B' each independently represent a
branched or straight chain radical selected from the group
consisting of hydroxyalkylene having 1-6 and, preferably, 3 carbon
atoms, lower alkyl-carbonamide-lower alkyl-carbonamide-lower alkyl
having 5 to 8 and, preferably 6 to 7 carbon atoms,
hydroxypropyl-oxyhydroxypropyl,
hydroxypropyl-alkylaminohydroxypropyl wherein the alkyl moiety has
12 to 16 carbon atoms, hydroxypropyl-alkenylamino-hydroxypropyl
wherein the alkenyl moiety has 18 carbon
atoms,hydroxypropylpiperazinyl-hydroxypropyl,
propionyl-piperazinyl-propionyl and
hydroxypropyl-benzylamino-hydroxypropyl.
The polymers of the present invention are more generally strictly
alternated, i.e. of the type
-- A -- B -- A -- B --A -- B --tm (II)
wherein A and B have the meanings given above.
These rigorously alternated polymers, which can be used in the
present invention, can be prepared by conventional processes such
as by polyaddition or polycondensation of (a) piperazine or a
derivative thereof such as, for example,
N,N'bis(hydroxyethyl)piperazine, on (b) a bifunctional compound
such as
1. alkyl or alkyl-aryl dihalides, such as ethylene chloride,
ethylene bromide or bis chloromethyl 1,4-benzene wherein the alkyl
moiety has 1-4 carbon atoms, the aryl moiety is phenyl and the
halide moiety is chloride or bromide;
2. more complex dihalogen derivatives, such as bis (chloroacetyl)
ethylene diamine;
3. bis halohydrins, such as bis 3-chloro 2-hydroxy propyl ether, or
other bis chlorohydrins which can be obtained by conventional
procedures such as by the condensation of epichlorohydrin on (i) a
primary amine, optionally hydroxylated, (ii) on a bisecondary
diamine such as piperazine, 4,4'-dipiperidyl, bis 4,4'
(N-methylaminophenyl) methane, N,N'dimethylethylene diamine or
propylene diamine, (iii) on .alpha.,.omega.-dimercaptoalkane, (iv)
on a diol such as ethylene glycol or (v) on a bis phenol such as
hydroquinone or "bis phenol A";
4. bis epoxide such as diglycidyl ether or N,N'bis (epoxy-2,3
propyl)piperazine, eventually obtained from the corresponding bis
halohydrin;
5. epihalohydrins, such as epichlorohydrin or epibromohydrin;
bisecondary bis unsaturated derivatives, such as divinyl sulfone,
bis maleimide derived from ethylene diamine, or bis acrylamide such
as methylene bis acrylamide or piperazine bis acrylamide derived
from biprimary or bissecondary diamines;
7. unsaturated acids, such as acrylic or methacrylic acid or their
methyl or ethyl esters;
8. diacids, such as succinic, adipic, 2,2,4-trimethyl or
2,4,4-trimethyl adipic or terephthalic acids, acid chlorides or the
corresponding methyl or ethyl esters; and
9. diisocyanates, such as toluene diisocyanate or 2,2,4- or
2,4,4-trimethyl hexamethylene isocyanate.
The polyaddition or polycondensation reaction can be carried out at
ambient pressure and at a temperature ranging from about 0.degree.
to 100.degree.C, the molar ratio of (a) to (b), defined above being
0.85 ; 1 to 1.15 ; 1.
Of course, the polymers of the present invention can in certain
cases advantageously be prepared in essentially the same way by
polycondensation or polyaddition of (a') N,N'bis(3-chloro 2-hydroxy
propyl) piperazine or N,N'bis (2,3-epoxy propyl) piperazine on (b')
a bifunctional compound such as a bisecondary diamine, a
dimercaptan, a diol, a diphenol, a diacid, and a primary amine such
as an alkylamine, alkenylamine, aralkylamine, of which the two
hydrogen atoms can be substituted and which behaves as a
bifunctional compound, the molar ratio of (a') to(b') ranging from
0.85 : 1 to 1.15 : 1.
Further, the cationic polymers of the present invention can also,
in certain cases, be of the pattern
-- A -- B -- A -- B' -- (III)
i.e. be made up of polymer chains in which A, representing a
bisecondary heterocyclic amine group, for example, the piperazine
group, is distributed regularly, the two B and B' groups designated
by Z in formula (I) being distributed statistically. This type of
polymer is obtained when piperazine or one of its derivatives is
condensed with a mixture of two bifunctional derivatives.
The polycondensates of type I, II or III can then, in accordance
with conventional procedures, be oxidized with hydrogen peroxide or
with peracids, or alternatively can be quaternized with known
quaternization agents such as, for example, the chloride, bromide,
iodide, sulfate, mesylate or tosylate of lower alkyl and preferably
of methyl or ethyl, benzyl chloride or bromide or they can be
condensed with ethylene oxide, propylene oxide, epichlorohydrin or
glycidol.
In those polymers of this invention wherein Z or B and B' groups do
not comprise base nitrogen or thioether, only the A groups will be
modified statistically or almost totally by quaternization or
oxidation. Otherwise, any group can be modified.
The oxidation reaction of the polycondensate of type I, II or III
can be performed with the amount of oxidizing agent being present
in amounts from 0 to 100 percent relative to the oxidizable groups,
while the quaternization reaction of the polycondensate of type I,
II or III can be performed with the amount of quaternization agent
being present in amounts of 0 to 50 percent.
The cationic polymers of the present invention are also
characterized by the fact that they are all filmforming and are
generally of relatively low molecular weight, i.e. less than 15,000
and generally about 1,000-15,000. They are water soluble in acid
medium and a number of them are also soluble as such in water
without addition of acid or in dilute alcohol medium such as
ethanol or isopropanol. The alcohol, i.e. lower alkanol, can be
present in amounts of about 0 to 50 percent by weight of said
composition. Generally, when an aqueous acidic medium is employed
as the solvent for the polymers of the present invention, the acid
employed can be hydrochloric, acetic, lactic, or tartaric acid in
amounts sufficient to solubilize the said polymer. Generally, the
acid will be present in amounts of about 0 to 5 percent by weight
of the composition. These polymers are particularly effective for
hair which has become sensitives as a result of such treatments as
bleaching, permanent waving, or dyeing. They can, however, also
advantageously be used for normal hair.
Thus, an object of the present invention is the provision of a
cosmetic composition for conditioning the hair comprising a
solution in a solvent selected from the group consisting of water
and an aqueous solution of a lower alkanol, of a member selected
from the group consisting of
(1) a low molecular weight, film-forming cationic polymer of the
formula
-- A -- Z --A -- Z -- A -- Z -- (I)
in which A represents a radical derived from a heterocycle carrying
two secondary amine functions and preferably the radical
##SPC3##
and Z represents the symbol B or B'; B and B' each independently
representing a bivalent radical selected from the group consisting
of (i) hydroxypropylene, (ii) alkylene having up to 5 carbon atoms
inclusive and interrupted by 1-2member selected from the group
consisting of - CONH and ##SPC4##
and (iii) hydroxy alkylene wherein the alkylene moiety has up to 6
carbon atoms inclusive and interrupted by a member selected from
the group consisting of alkylamine wherein the alkyl moiety has
12-16 carbon atoms, benzylamine, oleylamine and oxygen, or (2)
quaternary ammonium salt of the cationic polymer in (1) or (3) the
oxidation product of the cationic polymer in (1).
Many of the polymers of formula (1) are new compounds.
Among the preferred polymers are those in which A is ##SPC5##
and B and B', each independently represent a branched or straight
chain radical selected from the group consisting of hydroxyackylene
having 1-6 carbon atoms, preferably 3 carbon atoms, lower
alkyl-carbonamide-lower alkyl-carbonamide-lower alkyl having 5-8
and preferably 6-7 carbon atoms, hydroxypropyl-oxyhydroxypropyl,
hydroxypropyl-alkylamino-hydroxypropyl wherein the alkyl moiety has
12-16 carbon atoms, hydroxypropyl-alkenylamino-hydroxypropyl
wherein the alkenyl moiety has 18 carbon atoms,
hydroxypropyl-piperizinyl-hydroxypropyl,
propionylpiperizinyl-propionyl and
hydroxypropyl-benzylamino-hydroxypropyl.
The polymer can be present in amounts of about 0.1 to 5 percent and
preferably 0.2 to 3 percent by weight in the various cosmetic
compositions of the present invention. These compositions include
hair-dressing lotions, creams or gels as the main constituent,
shampoos, hair-setting compositions, permanent wave composition or
hair dye compositions, etc. The polymers can also be employed as an
adjuvant in the presence of other components such as anionic,
cationic, non-ionic, amphoteric or zwitterionic surfactants,
oxidizing agents, foam stabilizers or synergists, sequestrants,
superfatting agents, thickeners, softeners, antiseptics,
preservatives, dyes, perfumes, germicides or other anionic,
cationic, amphoteric or non-ionic polymers.
The polymers can be used in different compositions whose pH varies
from 3 to 11, or in the form of inorganic or organic acid salts, or
in the form of free base or, alternatively, the quaternary ammonium
salt thereof.
The cosmetic compositions for hair according to the present
invention can be in the form of an aqueous solution, a dilute
alcohol solution, a cream, a paste, a gel, or a powder. They can
also contain a conventional aerosol propellant such as
dichlorodifluoromethane, monochlorotrifluoromethane, mixtures
thereof or other conventional aerosol propellants, and can be
packaged in a conventional aerosol bomb under pressure.
The hair shampoo compositions according to the invention are
characterized by the fact that they contain, in addition to an
anionic, cationic, non-ionic, amphoteric and/or switterionic
surfactant, one or more compounds of formula I and optionally foam
stabilizers or synergists, sequestrants, superfatting agents,
thickeners, one or more other cosmetic resins, softeners, dyes,
perfumes, antiseptics, preservatives and any other adjuvant usually
used in cosmetic compositions.
The polymers of formula I also make it possible to prepare
hair-setting lotions, hair-setting reinforcers, treatment creams,
hair conditioners, anti-dandruff lotions and other similar
compositions characterized by the fact that they contain one or
more polymers of formula I having a molecular weight, determined by
lowering of the vapor tension, between 1,000 and 15,000, or the
quaternary ammonium salt or amine oxide of these polymers, possibly
mixed with other cosmetic resins.
EXAMPLES OF PREPARATION OF THE POLYMER
Example 1
Polycondensation of piperazine and epichlorohydrin.
To a solution of 97 g (0.5 mole) of piperazine hexahydrate in 125 g
of water, there are added, drop by drop, over a period of 1 hour,
46.3 g (0.5 mole) of epichlorohydrin, with stirring, while
maintaining the temperature at 20.degree.C. Stirring is continued
for 1 hour at 20.degree.C. The reaction mass is then heated at
90.degree.-95.degree.C for 2 hours. Over a period of one hour, 0.5
mole of sodium hydroxide is then added in the form of a 40 percent
(50 g) NaOH solution. A cloud then appears in the solution. The
temperature is maintained at the 90.degree.-95.degree.C level for
15 minutes more, and the reaction mixture is then cooled with
stirring while adding 182 g of water to bring the concentration to
20 percent of dry extract (14.5 percent active material and a 5.5
percent NaCl).
A limpid and almost colorless solution is thus obtained, having a
viscosity of 2.5 poises, measured at 25.degree.C.
On evaporation of a dilute solution of the polymer thus prepared,
there is obtained a wrinkled film, opaque because of the presence
of the sodium chloride, but hard and not sticky.
Example 2
Polycondensation of N,N'bis-(2,3-epoxy propyl) piperazine and
piperazine.
A polymer similar to that of Example 1, but free of sodium
chloride, is prepared by polycondensation of piperazine and N,N'
bis(2,3-epoxy propyl) piperazine in an aqueous medium and in
stoichiometric proportions. The N,N'bis-(2,3-epoxy propyl)
piperazine can be prepared in the following way:
To 86 g (1 mole) of anhydrous piperazine, dissolved in 540 g of
isopropanol, there are added, over a 30 minute period at a
temperature of 10.degree.-15.degree.C, 185 g of epichlorohydrin (2
moles). This temperature is maintained at this level while the
reaction mixture is stirred for 7 hours.
The resulting dichlorohydrin, derived from piperazine, is filtered
and dried. It is a white crystallized product having a melting
point of 108.degree.-110.degree.C.
50.7 g (0.18 mole) of the dichlorohydrin thus obtained are
dispersed in 100 ml of benzene. The suspension is cooled to
10.degree.C. There are then added by fractions, over a 30 minute
period, 15.5 g (0.37 mole) of ground sodium hydroxide. This
temperature is maintained for 2 1/2 hours. The sodium chloride
precipitate is filtered and rinsed with three times 100 ml of
benzene.
After elimination of the benzene, under partial vacuum, there are
collected 26 g of white solid corresponding, according to
functional analyses, to N,N'bis-(2,3-epoxy propyl) piperazine.
25 g (0.125 mole) of product thus prepared are heated with reflux
with 10.8 g (0.125 mole) of anhydrous piperazine in 60 g of
isopropanol for 3 1/2 hours. The cationic polymer is then partially
precipitated. The solvent is eliminated under partial vacuum and an
almost white powder is thus obtained which is soluble in water and
which exhibits a melting point of 190.degree.C. The molecular
weight of this polymer, measured in chloroform by the method of
lowering the vapor tension, is 2460.
Example 3
Quaternization of the piperazine and epichlorohydrin
polycondensate.
To 200 g of solution obtained according to Example 1 which contains
0.4 equivalent of base nitrogen, there are added 170 g of absolute
ethyl alcohol and then 25.3 g (0.2 mole) of benzyl chloride. The
reaction mixture is heated at 80.degree.C for 11/2 hours. The
ethanol is then eliminated under partial vacuum, while re-adding
water, to obtain a 10 percent solution of dry extract.
Example 4
Oxidation of the piperazine and epichlorohydrin polycondensate.
To 100 g of solution obtained according to Example 1 which contains
0.2 equivalent of base nitrogen, there are added, at a temperature
of 50.degree.C, 7.2 ml (0.13 mole) of 200 volume hydrogen peroxide.
The temperature is maintained at this level for 10 hours.
The polymer solution obtained is perfectly limpid and yields, on
evaporation, films comparable to those of Example 1.
Example 5
Polycondensation of piperazine, benzylamine and
epichlorohydrin.
To a solution of 97 g (0.5 mole) of hexahydrated piperazine, in 384
g of isopropyl alcohol, there are added, drop by drop at
15.degree.C, 92.5 g (1 mole) of epichlorohydrin. The resulting
solution is maintained, with stirring, at 15.degree.C for 2 hours.
Thereafter it is heated to 70.degree.C, and over a 15 minute
period, 54 g (0.5 mole) of benzylamine are added. The resulting
mixture is heated with reflux for an hour. There are then added,
drop by drop, 160 g of methanol solution of sodium methylate (0.98
mole). Heating is continued for 1 hour.
After cooling, the formed sodium chloride is filtered and the
isopropanol is eliminated under partial vacuum. After drying under
vacuum and in the presence of phosphoric anhydride, a hard,
brittle, colorless solid is obtained, having a softening point of
65.degree.C and a molecular weight, measured in absolute ethanol of
1600.
The compound thus obtained is soluble in water in an acid medium
and in a dilute alcohol medium. It yields beautiful, hard and very
brilliant films, after evaporation of its dilute alcohol
solvent.
Example 6
Polycondensation of N,N'-bis(2,3-epoxy propyl) piperazine and
cetylamine.
24 g (0.1 mole) of cetylamine and 20 g (0.1 mole) of
N,N'bis(2,3-epoxy propyl) piperazine prepared according to Example
2, are heated with reflux in 45 g of isopropanol for 15 hours. The
resin obtained is soluble in water in an acid medium, such as
hydrochloric acid.
Example 7
Quaternization of the product obtained in Example 6.
To 68 g of the above isopropanol solution (0.23 equivalent in base
nitrogen) there are added, drop by drop at 30.degree.C, 14.6 (0.11
mole) of dimethyl sulfate. Stirring is continued for 2 hours. The
solvent is then eliminated under partial vacuum, with water being
added to produce a final aqueous solution that is 10 percent by
weight.
The film obtained by evaporation of the dilute solution is rather
hard and not sticky.
Example 8
Polycondensation of N,N'bis(2,3-epoxy propyl) piperazine and
dodecylamine.
18.5 g (0.1 mole) of dodecylamine and 20 g (0.1 mole) of
N,N'bis(2,3-epoxy propyl)piperazine, prepared according to Example
2, are dissolved in 90 g of isopropyl alcohol. After 10 hours of
heating at reflux, the solvent is eliminated under partial vacuum.
There is thus obtained a soft, colorless, transparent resin,
soluble in water in the presence of hydrochloric acid and also in
alcohol such as ethanol or isopropanol.
The molecular weight of this resin, measured in absolute ethanol,
is 2900.
By evaporation of dilute solutions, soft, slightly sticky films are
obtained.
Example 9
Quaternization of the N,N'-bis(2,3-epoxy propyl) piperazine and
dodecylamine polycondensate.
To 30 g of resin obtained according to Example 7 (0.21 equivalent
in base nitrogen), dissolved in 40 g of isopropanol, there are
added, drop by drop at 30.degree.C, 13.5 g (0.1 mole) of dimethyl
sulfate. Stirring is kept up for 2 hours at the same temperature.
Then the solvent is eliminated under partial vacuum, with water
being added to obtain the resin in the form of a 10 weight percent
solution in water.
On evaporation of the dilute aqueous solutions, films are obtained
which are always soft but which are no longer sticky.
Example 10
Polycondensation of piperazine and N,N'-bis(chloroacetyl)ethylene
diamine.
To a solution of 10.6 g (0.05 mole) of N,N'-bis chloroacetyl
ethylene diamine in 125 g of water, there are added 9.7 g (0.05
mole) of hexahydrated piperazine. The mixture is heated for 3 hours
at 100.degree.C. While the heating is continued, the acid formed is
neutralized by addition, in several fractions, of 0.1 mole of
sodium hydroxide in the form of a 40 percent (10 g) NaOH
solution.
A colloidal solution having good film-forming properties is thus
obtained.
Example 11
Polycondensation of N,N'-bis(2,3-epoxy propyl) piperazine,
oleyamine and piperazine.
To a solution of 20 g (0.1 mole) of N,N'-bis(2,3-epoxy propyl)
piperazine in 47 g of isopropanol, there are added 10.7 g (0.04
mole) of oleylamine and 5.16 g (0.06 mole) of anhydrous piperazine.
After 4 hours of heating at reflux, the solvent is eliminated under
reduced pressure. There is then obtained a white solid having a
softening point of around 100.degree.C, the product being insoluble
in neutral water, but soluble in ethanol and in water in an acid
medium such as HCl.
Films obtained by evaporation of the dilute solution are
transparent, not sticky and slightly hard.
Example 12
Polycondensation of piperazine and diglycidyl ether.
To 6.63 g (0.077 mole) of anhydrous piperazine in 11 g of
isopropanol there are added over a 15 minute period at 30.degree.C,
10 g (0.077 mole) of diglycidyl ether. The mixture is heated at
reflux for 41/2 hours. Then the solvent is eliminated, at reduced
pressure, while water is added to obtain a colloidal solution of 5
weight percent active material, i.e. polymer.
Films obtained by evaporation of the dilute solution are
opalescent, hard and not sticky.
The diglycidyl ether is prepared by reacting at
15.degree.-20.degree.C a stoichiometric amount of sodium hydroxide
on bis(3-chloro 2-hydroxy propyl) ether. The diglycidyl ether is
isolated by distillation under reduced pressure. The boiling point
is 80.degree.-85.degree.C/0.05 mm Hg.
Example 13
Polycondensation of piperazine and methylene bisacrylamide.
To 15.4 g (0.1 mole) of methylene bisacrylamide provided in paste
form with 18.6 g of water, there are added with agitation at a
temperature between 0.degree.and 5.degree.C and under a nitrogen
atmosphere 86 g of a 10 percent aqueous solution of piperazine (0.1
mole). The mixture is left standing for 30 hours at
25.degree.C.
The polymer is precipitated by flowing the aqueous solution into a
great excess of acetone.
There is thus obtained a white solid having a softening point of
about 205.degree.C and a melting pont of 260.degree.C.
By evaporating the dilute aqueous solution, there is obtained very
hard transparent and non-sticky films.
Example 14
Polycondensation of piperazine and piperazine bisacrylamide.
To a solution of 19.4 g (0.1 mole) of piperazine bisacrylamide in
35 g of water, there are added with agitation at a temperature
between 0.degree. and 5.degree.C and under a nitrogen atmosphere,
86 g of a 10 percent aqueous solution of piperazine (0.1 mole). The
mixture is left standing for 30 hours at 25.degree.C.
The polymer is precipitated by flowing the aqueous solution in a
great excess of acetone.
There is thus obtained a white solid having a softening point of
about 205.degree.C and a melting point greater than
260.degree.C.
By evaporating the dilute aqueous solution there is obtained very
hard, transparent and non-sticky films.
Example 15
Polycondensation of 1,3-bis piperazine-2-propanol and methylene
bisacrylamide.
Method 1
To 15.4 g (0.1 mole) of methylene bisacrylamide provided in paste
form with 23.1 g of water there are added with agitation at a
temperature between 0.degree. and 5.degree.C under a nitrogen
atmosphere, 152.5 g of a standardized aqueous solution containing
22.8 g (0.1 mole) of 1,3-bis piperazine-2-propanol. The mixture is
left standing for 30 hours at 25.degree.C.
The polymer is precipitated in accordance with the procedure
outlined in Example 14.
There is thus obtained a white solid exhibiting a softening point
of 176.degree.C and a melting point of
200.degree.-210.degree.C.
By evaporating the dilute aqueous solution, there is obtained very
hard, transparent and non-sticky films.
The 1,3-bis-piperazine-2-propanol, utilized above, can be prepared
as follows:
To 688 g (8 moles) of anhydrous piperazine dissolved in 1500 g of
isopropanol, there are added 92.5 g (1 mole) of epichlorohydrin
over a period of 1 hour at a temperature of 20.degree.C. The
resulting reaction mixture is then heated for a period of 1.5 hours
at 80.degree.C throughout said period. There are then added over a
period of one-half hour 250 g of sodium methylate. The reaction
mixture is then cooled and filtered to remove sodium chloride
formed during the reaction. The remaining reaction mixture is then
concentrated under a partial vacuum thereby eliminating the
greatest part of the excess piperazine. The desired compound is
isolated by distillation. It is a white solid having a melting
point of 78.degree.C and a boiling point of
147.degree.-152.degree.C/0.07 mm Hg.
Method 2
To a solution of 116.4 g (0.6 mole) of piperazine hexahydrate in
353 g of water, there are added in small portions a total of 46.2 g
(0.3 mole) of solid methylene bisacrylamide, with agitation at a
temperature between 0.degree. to 5.degree.C and under a nitrogen
atmosphere. The resulting reaction mixture is left to stand for 24
hours at 25.degree.C. There are then added, little by little, 27.75
g (0.3 mole) of epichlorohydrin over a period of 1 hour while
maintaining the temperature of the reaction mixture at
20.degree.C.
The reaction mixture is stirred again for a period of 1 hour at a
temperature of 20.degree.C. Then there are added at this
temperature over a 1 hour period, 30 g (0.3 mole) of a 40 percent
NaOH solution.
After an additional 1 hour period of stirring the reaction mixture
at 20.degree.C, the reaction mixture is heated for 1 hour at
60.degree.C. There is thus obtained a 20 percent solution of the
polymer exhibiting a very light opalescence and being nearly
colorless. By evaporating the dilute aqueous solution there is
obtained a very hard, transparent and non-sticky film.
Example 16
Polycondensation of 1,3-bis piperazine-2-propanol and piperazine
bisacrylamide.
To a solution of 19.4 g (0.1 mole) of piperazine bisacrylamide in
39.1 g of water there are added with stirring at a temperature
between 0.degree. to 5.degree.C and under a nitrogen atmosphere
152.5 g of a standardized aqueous solution containing 22.8 g (0.1
mole) of 1,3-bis piperazine 2-propanol. The resulting reaction
mixture is left to stand for 30 hours at 25.degree.C. The polymer
is precipitated from the reaction mixture in accordance with the
procedure outlined in Example 14 thereby yielding a white solid
having a melting point of about 205.degree.-210.degree.C. By
evaporating the dilute aqueous solution there is obtained a hard,
transparent and non-sticky film.
The following Table summarizes the reactions of Examples 1-16.
##SPC6##
__________________________________________________________________________
EXAMPLE OF APPLICATION Example 17 Setting lotion for very dry hair
Compound prepared according to Example 1 1 g Propyl
para-hydroxybenzoate 0.4 g Neolane pink dye, C.I. 18810 0.005 g
Perfume 0.2 g Water, q.s.p. 100 g Example 18 Setting reinforcer for
damaged hair Compound prepared according to Example 1 1 g Polyvinyl
pyrrolidone/vinyl acetate 60/40 copolymer (m.W. 50,000 to 70,000)
0.5 g Trimethyl cetyl ammonium bromide 0.2 g Perfume 0.1 g Methyl
para-hydroxybenzoate 0.1 g Water, q.s.p. 100 g Example 19 Setting
reinforcer for normal hair Compound prepared according to Example 1
1 g Vinyl acetate/crotonic acid copolymer (M.W. 20,000) 1 g
Trimethyl cetyl ammonium bromide 0.1 g Methyl violet dye, C.I.
42535 0.002 g Perfume 0.1 g Ethyl alcohol, q.s.p. 50.degree. Water,
q.s.p. 100 g Example 20 Anionic shampoo Compound prepared according
to Example 1 1 g R--(OCH.sub.2 --CH.sub.2).sub.2 --OSO.sub.3 Na
wherein R = alkyl C.sub.12 -C.sub.14 in proportions of 70/30 10 g
Diethanolamide of copra fatty acids 3 g Water, q.s.p. 100 g pH = 7
Example 21 Anionic shampoo Compound prepared according to Example 1
0.75 g Triethanolamine alkyl sulfate wherein alkyl = C.sub.12
/C.sub.14 70/30 15 g Monoethanolamide of copra fatty acid 4 g
Sodium N-lauryl sarcosinate 3 g Acetylated lanolin 3 g Water,
q.s.p. 100 g pH = 7.5 Example 22 Non-ionic shampoo Compound
prepared according to Example 1 2.5 g R-- OCH.sub.2 --CH--OH
wherein R = alkyl C.sub.12 H.sub.25 15 g .vertline. CH.sub.2
OH.sub.4 Alkoxylated anhydrous lanolin sold under the trademark
"Lantrol AWS" by Malstrom Chemical Corporation, New Jersey 1.5 g
Hydroxypropyl methyl cellulose 0.3 g Citric acid, q.s.p. pH 6
Water, q.s.p. 100 g Example 23 Cationic shampoo Compound prepared
according to Example 8 1.5 g Bromide of dodecyl, tetradecyl and
hexadecyl trimethylammonium sold under the tradename "Cetavlon" 5 g
Lauryl alcohol oxyethylenated with 12 moles of ethylene oxide 12 g
Lauryl diethanolamide 5 g Ethyl cellulose 0.25 g Lactic acid,
q.s.p. pH 4 Water, q.s.p. 100 g Example 24 Amphoteric shampoo
Compound prepared according to Example 1 1.2 g OH
.vertline.CH.sub.2 --COONa C.sub.11 H.sub.23 --C------N.angle.
.parallel..vertline.CH.sub.2 --CH.sub.2 --O--CH.sub.2 --COONa
NCH.sub.2 .angle. CH.sub.2 sold under the name Miranol "C2M" by
Miranol Chemical Corporation, Irvington, New Jersey 20 g Dimethyl
alkylamine oxide prepared from copra fatty acids 5 g Lauryl
diethanolamide 2.5 g Lauryl alcohol, oxyethylenated with 12 moles
of ethylene oxide 8 g Lactic acid, q.s.p. pH 6 Water, q.s.p. 100 g
Example 25 Amphoteric shampoo Compound prepared according to
Example 1 1 g Sodium salt of N,N(diethylamino propyl)N.sup.2 -
dodecyl asparagin 5 g R--OCH.sub.2 --CH--OH wherein R = alkyl,
C.sub.12 H.sub.25 15 g .vertline. CH.sub.2 OH.sub.4 Lactic acid,
q.s.p. pH 5 Water, q.s.p. 100 g Example 26 Anionic shampoo Compound
prepared according to Example 9 1 g Sodium alkyl sulfate (alkyl =
C.sub.12 -C.sub.14) 10 g Sodium N-lauryl sarcosinate 3 g Lauryl
monoethanolamide 4 g Glycol distearate 3 g Water, q.s.p. 100 g pH =
7 Example 27 Anionic shampoo Compound prepared according to Example
9 0.5 g R--O(CH.sub.2 CH.sub.2).sub.2 OSO.sub.3 Na wherein R =
C.sub.14 H.sub.29 10 g Sodium salt of N,N(diethylamino
propyl)--N.sup.2 - dodecyl asparagin 3 g Diethylanolamide of copra
fatty acids 3 g Hydroxypropyl cellulose 0.2 g Water, q.s.p. 100 g
pH = 6.5 Example 28 Cream for treating dry hair Compound prepared
according to Example 1, q.s.p. 3 g Cetyl alcohol 2 g Stearyl
alcohol 2 g Cetyl-stearyl alcohol oxyethylenated with 15 moles of
ethylene oxide 4 g Hydroxyethylcellulose 2 g Perfume 0.2 g Water,
q.s.p. 100 g Application of this cream is followed by rinsing of
the hair. Example 29 Conditioner for dry hair Compound prepared
according to Example 1, q.s.p. 0.5 g Polyvinylpyrrolidone/vinyl
acetate copolymer 70/30 (M.W. 40,000) 0.5 g Perfume 0.15 g Water,
q.s.p. 100 g This conditioner is to be used after shampooing and
before setting, without intermediate rinsing. Example 30
Anti-dandruff lotion for daily use Compound prepared according to
Example 1, q.s.p. 0.5 g Lauryl isoquinolinium bromide 1.3 g Lactic,
acid, q.s.p. pH = 5-5.3 Ethyl alcohol 55 cc Menthol panthotenate
0.1 g Perfume 0.3 g Water, q.s.p. 100 g Example 31 Anionic shampoo
in the form of a clear solution Ammonium alkylsulfate (alkyl
derived from copra) 3 g Sodium alkyl ether sulfate wherein the
alkyl moiety is derived from copra fatty acids and oxyethylenated
with 2 moles of ethylene oxide 7 g Compound prepared according to
Example 4 1 g Lauryl diethanolamide 3 g Mixture of mono- and
di-glycerides of fatty acids, sold under the tradename "ARLACEL
186" by Atlas 0.5 g Lactic acid, q.s.p. pH 7.5 Water, q.s.p. 100 g
Example 32 Anionic shampoo Sodium alkyl ether sulfate wherein the
alkyl moiety is derived from copra fatty acids and oxyethylenated
with 2 moles of ethylene oxide 10 g Copra diethanolamide 3 g
Compound prepared according to Example 13 0.8 g Sodium monolauryl
sulfosuccinate 2 g Lactic acid, q.s.p. pH 7.5 Water, q.s.p. 100 g
__________________________________________________________________________
Hair treated with the above composition is easy to comb, exhibits
good volume, is shiny and lively.
Example 33
Anionic shampoo
The composition of Example 32 is repeated except that the compound
prepared according to Example 13 is replaced with an essentially
equivalent amount of the compound prepared according to Example 14.
Essentially similar effective and advantageous results are achieved
with this composition.
______________________________________ Example 34 Anionic shampoo
______________________________________ Triethanolamine lauryl
sulfate 10 g Lauryl diethanolamide 2 g Compound prepared according
to Example 3 1 g Hydroxy propyl methyl cellulose 0.1 g Lactic acid,
q.s.p. pH 7.2 Water, q.s.p. 100 g
______________________________________
This solution imparts to hair a lively and shiny appearance.
Further in Examples 17-22, 24, 25 and 28-30, the compound prepared
in accordance with Example 1 is replaced with the compound prepared
in accordance with Example 15 and 16 in essentially equivalent
amounts to provide equally effective hair treating
compositions.
In all of the Examples of Application given above, the weight of
the polymer is expressed as the active material therein.
* * * * *