POLYSILOXANE-POLYOXYALKYLENE BLOCK COPOLYMERS AND THEIR USE AS ADDITIVES FOR HAIR COSMETICS

COPOLYMERES SEQUENCES DE POLYSILOXANE-POLYOXYALKYLENE ET LEUR UTILISATION COMME ADDITIFS DANS DES PRODUITS COSMETIQUES POUR CHEVEUX

English Abstract

The invention relates to polysiloxanes with (1) at
least two polyether groups A and B; polyoxyalkylene group
A, with an average molecular weight of 600 to 5,500,
consisting of 20 to 100% by weight of oxyethylene units and
of 80 to 0% by weight of oxypropylene units, and
polyoxyalkylene group B, with an average molecular weight
of 700 to 5,000, consisting of 0 to < 20% by weight of
oxyethylene units and of 100 to 80% by weight of
oxypropylene units, and with (2) hydrocarbon groups with 6
to 30 carbon atoms, linked to silicon. The invention
further relates to the synthesis of these polysiloxanes and
their use as additives for hair cosmetics, particularly as
additives for hair shampoos to improve the handle and the
combability of the hair.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polysiloxane-polyoxyalkylene block copolymer of the
general formula
<IMG>
wherein
R1 represents alkyl groups with 1 to 4 carbon atoms or phenyl
groups, with the proviso that at least 90% of the R1 groups
are methyl groups,
R2 (1) corresponds to the R1 groups, or
(2) represents groups with 6 to 30 carbon atoms, obtained
by the addition reaction between hydrocarbons with an
olefinic double bond and the SiH groups of the
siloxane, or
-23-

(3) -M-R3 groups, wherein
M is a divalent group having the formula -R4x O-, in
which R4 is a divalent alkylene group, which is
branched or unbranched, and x has a value of 0
or 1,
R3 is a mixture of polyether groups, which contains at least
one
(1) polyoxyalkylene group A with an average molecular
weight of 600 to 5,500, which consists of 20 to 100%
by weight of oxyethylene units and 80 to 0% by weight
of oxypropylene units, and one
(2) polyoxyalkylene group B with an average molecular
weight of 700 to 5,000, which consists of 0 to < 20%
by weight of oxyethylene units and 100 to 80% by
weight of oxypropylene units,
it being possible to replace up to 20% by weight of the
oxypropylene units by oxybutylene units and the molar ratio of the
polyoxyalkylene groups A to the polyoxyalkylene groups B being
1 : 4 to 4 : 1, with the proviso that
(I) the number of R2 groups having the meaning (2)
above, is at least equal to 1% and, at most, to
30% of the numerical value of the number of
silicon atoms, and
-24-

(II) there are at least two R3 groups in the average
block copolymer,
b has a value of 0 to 10,
a has a value of 10 to 100, when b = 0,
or a value of 3 to 70, when b > 0 and ~ 4,
or a value of 3 to 30, when b > 4.
2. The block copolymers of claim 1, wherein the
R2 group in (2) is selected from the group consisting of
<IMG>
-25-

3. The block copolymer of claim 1 or 2, wherein
the polyoxyalkylene blocks correspond to the
formula (C m H2m O-)n R5, the subscripts n and m being selected so that
conditions concerning the composition and the respective molecular
weight of the different polyoxyalkylene blocks are fulfilled, R5
being an alkyl group with 1 to 4 carbon atoms, an acyl group or an
-O-CO-NH-R6 group, wherein R6 is an alkyl or aryl group.
4. A method for the synthesis of block copolymers of the
general formula
<IMG>
wherein
R1 represents alkyl groups with 1 to 4 carbon atoms or phenyl
groups, with the proviso that at least 90% of the R1 groups
are methyl groups;
R2 (1) corresponds to the R1 groups, or
-26-

(2) represents groups with 6 to 30 carbon atoms, obtained
by the addition reaction between hydrocarbons with an
olefinic double bond and the SiH groups of the
siloxane, or
(3) -M-R3 groups, wherein
M is a divalent group having the formula -R4x O-, in
which R4 is a divalent alkylene group, which is
branched or unbranched, and x has a value of 0
or 1,
R3 is a mixture of polyether groups, which contains at least
one
(1) polyoxyalkylene group A with an average molecular
weight of 600 to 5,500, which consists of 20 to 100%
by weight of oxyethylene units and 80 to 0% by weight
of oxypropylene units, and one
(2) polyoxyalkylene group B with an average molecular
weight of 700 to 5,000, which consists of 0 to < 20%
by weight of oxyethylene units and 100 to 80% by
weight of oxypropylene units,
it being possible to replace up to 20% by weight of the
oxypropylene units by oxybutylene units and the molar ratio of the
polyoxyalkylene groups A to the polyoxyalkylene groups B being 1
: 4 to 4 : 1, with the proviso that
-27-

(I) the number of R2 groups having the meaning (2)
above, is at least equal to 1% and, at most, to
30% of the numerical value of the number of
silicon atoms, and
(II) there are at least two R3 groups in the average
block copolymer,
b has a value of 0 to 10,
a has a value of 10 to 100, when b = 0,
or a value of 3 to 70, when b > 0 and ~ 4,
or a value of 3 to 30, when b > 4,
the method comprising, wherein x has a value of 1, reacting
an organopolysiloxane of the general formula
<IMG>
wherein
-28-

R1 and the subscripts a and b have the meaning already
given,
R7 (1) corresponds to the R1 group, or
(2) is an SiH group,
with the proviso that at least three R7 groups are SiH
groups,
with
a) hydrocarbons having 6 to 30 carbon atoms and an olefinic
double bond, and
b) a mixture of polyethers having the formula
CH2=CH-R8-A and CH2=CH-R8-B
wherein A and B are as defined above and the R8 group
corresponds to the R4 group minus the -(CH2)2- group, and
the two polyethers are present in the molar ratio one to
the other of 1 : 4 to 4 : 1,
consecutively or simultaneously by a hydrosilylating addition
reaction in presence of a platinum catalyst.
-29-

5. A method for the synthesis of block copolymers of the
general formula
<IMG>
wherein
R1 represents alkyl groups with 1 to 4 carbon atoms or phenyl
groups, with the proviso that at least 90% of the R1 groups
are methyl groups,
R2 (1) corresponds to the R1 groups, or
(2) represents groups with 6 to 30 carbon atoms, obtained by
the addition reaction between hydrocarbons with an
olefinic double bond and the SiH groups of the siloxane,
or
(3) -M-R3 groups, wherein
-30-

M is a divalent group having the formula -R4x O-, in which
R4 is a divalent alkylene group, which is branched or
unbranched, and x has a value of 0 or 1,
R3 is a mixture of polyether groups, which contains at least one
(1) polyoxyalkylene group A with an average molecular weight
of 600 to 5,500, which consists of 20 to 100% by weight
of oxyethylene units and 80 to 0% by weight of
oxypropylene units, and one
(2) polyoxyalkylene group B with an average molecular weight
of 700 to 5,000, which. consists of 0 to < 20% by weight
of oxyethylene units and 100 to 80% by weight of
oxypropylene units,
it being possible to replace up to 20% by weight of the
oxypropylene units by oxybutylene units and the molar ratio of the
polyoxyalkylene groups A to the polyoxyalkylene groups B being 1
: 4 to 4 : 1, with the proviso that
(I) the number of R2 groups having the meaning (2)
above, is at least equal to to and, at most, to
30% of the numerical value of the number of
silicon atoms, and
(II) there are at least two R3 groups in the average
block copolymer,
-31-

b has a value of 0 to 10,
a has a value of 10 to 100, when b = 0,
or a value of 3 to 70, when b > 0 and ~ 4,
or a value of 3 to 30, when b > 4,
the method comprising, wherein x has a value of 0, reacting
an organopolysiloxane of the general formula
<IMG>
wherein
R1 and the subscripts a and b have the meaning already
given,
R9 (1) corresponds to the R1 group, or
(2) represents groups with 6 to 30 carbon atoms,
which are obtained by the addition reaction
between hydrocarbons with an olefinic double bond
and the SiH groups of the siloxane, or
-32-

(3) represents halogen or other acidic groups,
with the proviso that at least one R9 group has the
meaning given in (2) and at least two R9 groups have the
meaning given in (3),
in presence of an acid acceptor at temperatures not less than
50°C with such an amount of a mixture of polyethers
A-OH and B-OH,
which are present in a molar ratio one to the other of
1 : 4 to 4 : 1 and in which A + B are as defined above, that
at least two polyether groups are linked to the desired
organopolysiloxane.
6. The method of claim 4, wherein the platinum catalyst is
hexachloroplatinic acid.
7. The method of claim 5, wherein the acidic group
representing R9 is selected from the group consisting of -SO4/2 and
-CH3SO3.
8. A method of improving the handle and the combability of
hair, comprising adding an effective amount of a block copolymer
of the general formula
<IMG>
-33-

wherein
R1 represents alkyl groups with 1 to 4 carbon atoms or phenyl
groups, with the proviso that at least 90% of the R1 groups
are methyl groups,
R2 (1) corresponds to the R1 groups, or
(2) represents groups with 6 to 30 carbon atoms, obtained
by the addition reaction between hydrocarbons with an
olefinic double bond and the SiH groups of the
siloxane, or
(3) -M-R3 groups, wherein
M is a divalent group having the formula -R4x O-, in
which R4 is a divalent alkylene group, which is
branched or unbranched, and x has a value of 0
or 1,
R3 is a mixture of polyether groups, which contains at least
one
(1) polyoxyalkylene group A with an average molecular
weight of 600 to 5,500, which consists of 20 to 100%
by weight of oxyethylene units and 80 to 0% by weight
of oxypropylene units, and one
-34-

(2) polyoxyalkylene group B with an average molecular
weight of 700 to 5,000, which consists of 0 to < 20%
by weight of oxyethylene units and 100 to 80% by
weight of oxypropylene units,
it being possible to replace up to 20% by weight of the
oxypropylene units by oxybutylene units and the molar ratio of the
polyoxyalkylene groups A to the polyoxyalkylene groups B being 1
: 4 to 4 : 1, with the proviso that
(I) the number of R2 groups having the meaning (2)
above, is at least equal to 1% and, at most, to
30% of the numerical value of the number of
silicon atoms, and
(II) there are at least two R3 groups in the average
block copolymer,
b has a value of 0 to 10,
a has a value of 10 to 100, when b = 0,
or a value of 3 to 70, when b > 0 and ~ 4,
or a value of 3 to 30, when b > 4,
to a hair cosmetic and applying the said hair cosmetic to the
hair.
-35-

9. The method of claim 8, wherein the hair cosmetic is a
hair shampoo and the effective amount of the block copolymer is
0.5 to 4% by weight, based on the total amount of shampoo.
10. The method of claim 4, wherein R2 is selected from the
group consisting of
<IMG>
-36-

11. The method of claim 5, wherein R2 is selected from the
group consisting of
<IMG>
12. The method of claim 8, wherein R2 is selected from the
group consisting of
<IMG>
-37-

13. An additive for a hair cosmetic comprising a block
copolymer of the general formula
<IMG>
wherein
R1 represents alkyl groups with 1 to 4 carbon atoms or phenyl
groups, with the proviso that at least 90% of the R1 groups
are methyl groups,
R2 (1) corresponds to the R1 groups, or
(2) represents groups with 6 to 30 carbon atoms, obtained
by the addition reaction between hydrocarbons with an
olefinic double bond and the SiH groups of the
siloxane, or
(3) -M-R3 groups, wherein
M is a divalent group having the formula -R4x O-, in
which R4 is a divalent alkylene group, which is
branched or unbranched, and x has a value of 0
or 1,
-38-

R3 is a mixture of polyether groups, which contains at least
one
(1) polyoxyalkylene group A with an average molecular
weight of 600 to 5,500, which consists of 20 to 100%
by weight of oxyethylene units and 80 to 0% by weight
of oxypropylene units, and one
(2) polyoxyalkylene group B with an average molecular
weight of 700 to 5,000, which consists of 0 to < 20%
by weight of oxyethylene units and 100 to 80% by
weight of oxypropylene units,
it being possible to replace up to 20% by weight of the
oxypropylene units by oxybutylene units and the molar ratio of the
polyoxyalkylene groups A to the polyoxyalkylene groups B being
1 : 4 to 4 : 1, with the proviso that
(I) the number of R2 groups having the meaning (2)
above, is at least equal to 1% and, at most, to
30% of the numerical value of the number of
silicon atoms, and
(II) there are at least two R3 groups in the average
block copolymer,
b has a value of 0 to 10,
-39-

a has a value of 10 to 100, when b = 0,
or a value of 3 to 70, when b > 0 and ~ 4,
or a value of 3 to 30, when b > 4.
14. The additive of claim 13 , wherein the hair cosmetic is
a hair shampoo and the effective amount of the block copolymer is
0.5 to 4% by weight, based on the total amount of shampoo.
15. The additive of claim 13 or 14, wherein R2 is
selected from the group consisting of
<IMG>
-40-

Description

z~42537
FIELD OF INVENTION
The invention relates to polysiloxane-polyoxyalkylene block
copolymers, their synthesis, and a method of improving the handle
and combability of a hair cosmetic by adding an effective amount
of the inventive block copolymers particularly to hair shampoos.
BACKQROUND INFORMATION AND PRIOR ART
A wide range of applications has been found for
polyoxyalkylene-polysiloxane block copolymers, which are referred
to in the following as polyethersiloxanes. They can be used as
surfactants, emulsifiers, dispersants, leveling agents for paints,
lubricants, auxiliary materials for the tertiary recovery of crude
oil, as foam stabilizers in polyurethane foaming, as a textile
auxiliary for brightening fibers, yarns or sheet-like textile
products, for hydrophilizing sanitary products of textile fibers
and for many other purposes.
..
The polyethersiloxanes therefore have manifold uses, since
their properties, particularly their hydrophilic/-hydrophobic
balance, can be influenced and brought to the desired value by
selecting a suitable siloxane block or siloxane blocks on the one
hand, and constructing the polyether block or blocks appropriately
on the other.
NY2~16149.1

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214253'
For example, the siloxane block can be linear or branched,
and the absolute number of difunctional and trifunctional siloxy
units and their numerical ratio to one another can be varied
within wide limits.
Aside from the polyether blocks, it is also possible to
link other modifying groups to a silicon atom. Examples of such
groups are long-chain hydrocarbon groups with up to 30 carbon
atoms, hydrocarbon groups substituted with halogen atoms, cyano
groups or polar groups, hydroxyl groups, etc.
The polyether groups can likewise have different
structures. Each polyoxyalkylene block may be composed of
different oxyalkylene units, primarily of oxyethylene,
oxypropylene and oxybutylene units. Moreover, the molecular
weight ratio of these units to one another, as well as the
molecular weight of the polyoxyalkylene block, can be varied. The
end group of the polyoxyalkylene block, which can be reactive (for
example, an OH group) or inert (for example, an alkoxy group), is
also of importance.
The polyoxyalkylene block can be linked to the polysiloxane
block by a hydrolytically stable C-Si bond or by a hydrolytically
less stable C-0-Si bond.
NY3-16349.1
-2-

rs
v ~ ~ zi42537
It is also possible and, for many applications, desirable
to link different polyether blocks to the polysiloxane block. In
this connection, the different polyether blocks differ With
respect to their molecular weight and/or their hydrophilicity
and/or their inert or reactive end groups.
Polysiloxanes with different polyether blocks are
described, for instance, in the following patents and published
patent applications:
German Patent 15 70 647: Chloropolysiloxanyl sulfates are
reacted with mixtures of alkylene oxide adducts, which consist of
50 to 95 OH equivalent percent of polyalkylene glycol monoethers
comprising ethylene oxide and propylene oxide units, contain 40 to
70 mole percent of oxypropylene units and have a molecular weight
of 1,000 to 3,000, and the hydroxyl groups of which preferably are
secondary, and of 5 to 50 OH equivalent of alkylene oxide adducts
of polyhydric hydroxyl compounds with a molecular weight of 130 ~to
3500, the polyalkylene glycol components of which consist of
ethylene oxide and/or propylene oxide units and which have an OH
equivalent weight of up to 1750, and the hydroxyl groups of which
preferably are secondary, the quantitative ratios being chosen so
that there is at most 1.4 and, preferably, 1.05 to 1.2 OH
equivalents for each acid equivalent of the chloropolysiloxanyl
sulfate.
NY2-26D19.1
-3-
lr,.-

a
,~,
~r~
2142537
German Patent 16 94 366: This patent relates to
polysiloxane-polyoxyalkylene block copolymers, the polysiloxane
block of which has a conventional structure and the poly-
oxyalkylene block of which, however, consists of 25 to 70% by
weight of a polyoxyalkylene with an average molecular weight of
1, 600 to 4, 000 and an ethylene oxide content of 20 to 100% by
weight, the remainder being propylene oxide and, optionally,
higher alkylene oxides, and 30 to 75% by weight of a polyoxy-
alkylene with an average molecular weight of 400 to 1,200 and an
ethylene oxide content of 65 to 100% by weight, the remainder
being prc;pylene oxide and, optionally, higher alkylene oxides.
German Offenlegungschrift 25 41 865: The polysiloxane-
polyoxyalkylene block copolymers are defined with respect to their
polyoxyalkylene block so that one polyoxyalkylene block has an
average molecular weight of 900 to 1, 300 and consists of 30 to 55%
by weight of ethylene oxide, the remainder being propylene oxide,
and the other polyoxyalkylene block has an average molecular
weight of 3,800 to 5,000 and consists of 30 to 50% by weight of
ethylene oxide, the remainder being propylene oxide.
European Publication 0 275 563: The block copolymer,
described in this published European patent application, comprises
three different polyoxyalkylene blocks, namely one block which
contains 20 to 60% by weight of oxyethylene units and has a
molecular weight of 3,000 to 5,500, another block with 20 to 60%
by weight of oxyethylene units and a molecular weight of 800 to
2,900, and a third block which contains only polyoxy-propylene
units and has a molecular weight of 130 to 1200.
NY3-26319.1
-4-

P'n
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z~42~3~
According to the state of the art, such polyether-siloxanes
can be prepared in various ways. In this connection, reference is
made to the following patents:
German Patent 10 12 602: Monohydric and dihydric polyether
alcohols are reacted in the presence of a solvent and a catalyst
with polysiloxanes, which have terminal ~Si-O-alkyl groups, the
aliphatic alcohol set free being distilled off from the reaction
mixture. The reaction therefore is a trans-esterification
reaction.
German Patent 17 95 557: Equilibrated siloxane mixtures
having the general formula RXSiOY (S04) ~X, _~z . ax . aY~ ~ wherein R is any
univalent hydrocarbon group, X represents a halogen or alkoxy
group, x has a value of 0.9 to 2.2, y has a value of 0.75 to 1.75
and z has a value of 0.0001 to 0.5, with the proviso that 4 >
(x + 2y + 2x) > 2, are reacted with monohydric polyether, the acid
set free during the reaction is neutralized and the reaction
product is filtered off and freed from solvent.
By both methods, polyethersiloxanes are obtained in which
the polyether groups) is (are) linked to the siloxane backbone
over an Si-O-C bond.
The synthesis of polyethersiloxanes, in which the polyether
groups(s) is (are) linked to the siloxane backbone over an Si-C
bond, is given in the German patent 31 33 869. According to the
method described there, allyl polyethers are reacted with
polysiloxanes, which have SiI~ groups, in the presence of special
platinum catalysts and, optionally, in the presence of inert
solvents.
NY2-76119.1
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..,.a,,.,~... ..
2142537
The invention is concerned with the technical problem of
finding polyethersiloxanes, which are particularly suitable for
- use in hair cosmetics and can be used, in particular, as additives
for hair shampoos. At the same time, a further aim is to improve
the handle and the combability of the hair.
OBJECT OF THE INVENTION
An object of the present invention is inventive
polysiloxane-polyoxyalkylene block copolymers. Another object of
the invention is a method of synthesizing the inventive block
copolymers. Yet another object of the invention is an additive
for hair cosmetics comprising the inventive block copolymers and
a method for improving the handle and combability of hair by
applying an effective amount of the block copolymers.
SUI~iARY OF THE INVENTION
The present invention thus relates to new polysiloxane-
polyoxyalkylene block copolymers of the general formula
R1 R' Ri R1 R1
RZ-sio- si-o- sio- sio- si-R'
R1 RZ ( Iz li
a ~ R a R
Rl- Si-Ra
a
Rl- Si-Rl
Rz b
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k~r
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- wherein
R1 represents alkyl groups with 1 to 4 carbon atoms or phenyl
groups, with the proviso that at least 90% of the R1 groups
are methyl groups,
RZ (1) corresponds to the R' groups, or
(2) represents groups with 6 to 30 carbon atoms, obtained
by the addition reaction between hydrocarbons with an
olefinic double bond and the SiH groups of the
siloxane, or
(3) -M-R' groups, wherein
M is a divalent group having the formula -R'x0-, in
'' which the R' is a divalent alkylene group, which
can also be branched, and x has a value of 0 pr
1,
R' is a mixture of polyether groups, which contains at least
one
(1) polyoxyalkylene group A with an average molecular
weight of 600 to 5,500, which consists of 20 to 100%
by weight of oxyethylene units and 80 to 0% by weight
of oxypropylene units, and one
- NY2-26749.1

(2) polyoxyalkylene group B with an average molecular
weight of 700 to 5,000, which consists of 0 to < 20%
by weight of oxyethylene units and 100 to 80% by
weight of oxypropylene units,
it being possible to replace up to 20% by weight of the
oxypropylene units by oxybutylene units and the molar ratio of the
polyoxyalkylene groups A to the polyoxyalkylene groups B being 1
. 4 to 4 . 1, with the proviso that
(I) the number of RZ groups having the meaning (2) is
at least equal to 1 and, at most, to 30% of the
numerical value of the number of silicon atoms,
and
(II) there are at least two R' groups in the average
block copolymer,
b has a value of 0 to 10,
a has a value of 10 to 100, when b = 0,
or a value of 3 to 70, when b > 0 and ~ 4,
or a value of 3 to 30, when b > 4.
An essential characteristic of the present invention is the
simultaneous presence of the hydrocarbon groups with 6 to 30
carbon atoms and the polyoxyalkylene groups, which are connected
with the polysiloxane backbone, as well as the nature and amount
of these groups.
HY2-X6349.1
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Preferably, R1 is a methyl group.
In the majority of the groups, R' corresponds to R1. It is,
however, an essential characteristic of the invention that some of
the RZ groups are groups with 6 to 8 carbon atoms, obtained by the
addition reaction between hydrocarbons with an olefinic double
bond and the SiFi group of the siloxane.
The following are preferred examples of such hydrocarbon
groups:
-~t cH2 s-fix, , --cxz-cxt ~ ~ --cx~ x
~~
a
. -CH2 ~H Hs .
~3
~H2_~g2-CH2 ~ H ~ -CH=-CIi=
C1
--CH Z--CH Z-CH ~ H and ~-CH p-CH 2--CH ' Q H a
~a oCHa
Furthermore, R~ groups may be groups having the formula
-R'x0- .
Preferably, the R' group is a - (CFiz) 2- or - (CFiz) 3- group.
NY3~t6319.1
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The polyoxyalkylene blocks preferably correspond to the
formula (CmHZmO-) nRS, the subscripts n and m being selected so that
conditions concerning the composition and the respective molecular
weight of the different polyoxyalkylene blocks are fulfilled. RS
is an alkyl group with 1 to 4 carbon atoms, an acyl group or an
-0-CO-NH-R6 group, wherein R6 is an alkyl or aryl group.
~~idependently of one another, the A and B polyoxyalkylene
groups preferably have- an average molecular weight of 1, 000 to
4,000.
The A and B blocks may be contained several times and be
linked to a common average molecule. In the event that the A and
B polyoxyalkylene groups are contained several times, the polyoxy-
alkylene groups of the individual types of blocks must not be
identical to one another. The A and B polyether groups must
correspond only to the respective conditions for the individual
types of blocks. ,
Preferably, the molar ratio of the A polyoxyalkylene groups
to the B polyoxyalkylene groups is 1 : 3 to 3 . 1.
The inventive block copolymers can be synthesized by known
methods, a differentiation being made depending on whether the
polyether blocks are linked by Si-C- or by Si-O-C- bonds with the
polysiloxane.
The following method is particularly preferred for
synthesizing the inventive compounds with Si-C- bonds:
NY3-16349.1
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_ .__ _,....~ . ,
2142537
Organopolysiloxanes of the general formula
R~ R3 R' R1 R1
R'-Si0-Si-0- Si0- Si0- Si-R'
R1 R' , 0
R1-Si-R'
a
0
Rl-Si-Rl
R7
wherein
R1 and the subscripts a and b have the meaning already given,
R' (1) corresponds to R1 groups, or
(2) is a SiH group, with the proviso that at least three
R' groups are SiH groups,
a) hydrocarbons with 6 to 30 carbon atoms and an olefinie
double bond, and
b) a mixture of polyethers having the formula
CHZ=CH-RB-A and CHZ=CH-RB-B
/''-.
wherein
NY3-16349.1
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..... ._... . .. _-
2142537
the RB group corresponds to the R° group minus the -(CHa)2- group
and the polyethers are present in the molar ratio of 1 : 4 to 4
1, are reacted consecutively or simultaneously by a hydro-
silylating addition reaction in the presence of platinum
catalysts, which are suitable for the hydrosilylation, such as
hexachloroplatinic acid.
It is thus possible to first add the olefinic hydrocarbons
to the hydrogensiloxane and then the polyether mixture to the
.% ... .
remaining SiH groups or to carry out both addition reactions
simultaneously.
A further preferred method relates to the synthesis of the
inventive compounds with Si-O-C bonds. This method is
characterized in that organopolysiloxanes of the general formula
R1 R1 R1 R1 R1
R'-Si0- Si-O- Si0- Si0- Si-R9
's li
a ~ R a R
Rl-Si-R9
a
l
S
3
R
-
i-R
R9
b
wherein
R1 and the subscripts a and b have the meaning already given,
HY~~263~9.1
-12-

:__ . ..---......_. . .:,,
21~253'~
R9 (1) corresponds to the R1 groups, or
(2) represents groups with 6 to 30 carbon atoms, which are
obtained by the addition reaction between hydrocarbons
with an olefinic double bond and the SiH groups of the
siloxane, or
(3) represents halogen or other acidic groups such as
-S0,~2 OR -CH,SO3, with the proviso that at least one R'
group has the meaning given in (2) and at least two R9
groups have the meaning given in (3),
are reacted in the presence of an acid acceptor at a temperature
not less than 50°C with such an amount of a mixture of the
polyethers
A-OH and B-OH,
which are present in a molar ratio of 1 . 4 to 4 . 1, that at
least two polyether groups are linked to the desired
organopolysiloxane.
Suitable acid acceptors are ammonia gas, triethylamine and
i-propylamine.
The inventive compounds show the desired properties as
additive for hair cosmetics. It is therefore a further object of
the invention to use the inventive compounds as additives for hair
cosmetics, particularly for hair shampoos, in amounts of 0.5 to 4%
by weight, based on the total' amount of the shampoos, to improve
the handle and the combability of the hair.
NYZ-26749.1
-13-

2.42 )37
In the following examples, the compounds below are used, it
being understood that the Examples are provided by way of
illustration and not by way of limitation.
Siloxanes:
I) (CH3) 3510- ( (CH3) ZSiO-) 58 ( (CH3) HSiO-) 9Si (CH3) 3
II) H (CH3) 2Si0- ( (CH3) ZSiO-) eo ( (CH3) HSiO-) eSi (CH3) ZH
TI1) (CH3) 3Si0- ( (CH3) ZSiO-) 130 ( (CHa) HSiO-) lBSi (CH3) 3
IV) (CH3) 3Si0- ( (CH3) ZSiO-) 100 ( (CH3) HSiO-) l2Si (CH3) 3
V)
i H3 i H3 i Ha
X-Si-O-Z-Si0- Z-Si-X
CH3 0 CH3
Z
CH3-Si-CH3
2
X
wherein
Z - - ( (CH3) ZSiO-) ., ( (CH3) (CBH1,,) Si0-) , and
X = 75% Cl and 25% SO4~2.
NY~~26349.1
-14-

____-.;
2142~~'~
Polyethers of TSrpe A:
a) CH2=CH-CH20- (C2H40-) 12CH3
b) CH2=CH-CH20- (C2H40-) 12H
c) CH2=CH-CH20- (C2H40-) 21CH3
d) C4H9O- (C2H40-) 12H
~~,.__ a ) C4H9C- ( C2H4C- ) a2 ( C3H60- ) s.4H
f ) CH2=CH-CH20- ( C2H4~- ) 45 ( C3Hso- ) 34CH3
g) CH2=CH-CH20- (C2H4o-) 42 (C3H6d ) 34C~~3
h) CH2=CH-CH20- ( C2H40- ) 46 ( C3Hso- ) 16CH3
i ) CH2=CH-CH20- ( C2H40- ) 16 ( C3H60- ) 12CH3
Ic) CH2=CH-CH20- (C2H4O-) 45 (C3H6~ ) 34H
C4H90- ( C2Hq0- ) 23 ( C3Hs~ ) 33H
NY2-76349.1
-15-

......-~_... ..
'.~.
X142537
Polvethers of Type B:
m) CHz=CH-CHzO- ( CZH4O- ) 5 ( C3H60- ) zlCH3
n ) CHz=CH-CHzO- ( CZH4O- ) z ( C3H60- ) 3zCH3
o) CH2=CH-CHzO- (C3H60-) 13CH3
p) C4H90- (C2H4O-)6(C3H60-)z5H
Hvdrosilylvzable olefins:
C6 - 1-hexene
Ce - 1-octene
Clz - 1-dodecene
Czoiza = mixture of a-olefins with 20 - 24 carbon atoms
and an average molecular weight of 301
ST - styrene
AMS - a-methylstyrene
DCPD = dicyclopentadiene
LIM - limonene
ALPH = allylphenol
VBC - vinylbenzyl chloride
NYZ-~6J49.1
-16-

zi4~~3~
EXAMPLE 1
To a flask equipped with a stirrer, thermometer, gas inlet
and distillation head, 18.7 g (0.0188 moles) of polyether c),
150:9 g (0.0375 moles) of polyether f), 47.2 g (0.0313 moles) of
polyether m) and 320 mL of toluene are added.
Toluene (150 mL) is distilled off in a nitrogen atmosphere
for the azeotropic drying of the polyether mixture. After that,
the flask is equipped with a reflux condenser and further,
.. nitrogen is passed through the apparatus. At a temperature of
105°C, 6.3 g (0.375 moles) of 1-dodecene and
55.6 g (0.1 mole of SiH) of siloxane I are added to the flask.
After a thorough mixing of the flask contents, 0.18 g of a
10% solution of HZPtCI6~6H20 in i-propanol are added. The mixture
is allowed to react out for 3.5 hours, after which time an SiH
conversion of 97.8% is attained (determined by the hydrogen that
can be split off in an alkaline medium with n-butanol). The
mixture is treated with 3 g of bentonite, stirred for 30 minutes
and filtered. Subsequently, the toluene is distilled off at 80°C
and 20 mbar. A clear, yellowish product is obtained.
EXAMPLES 2 TO 12
The following products have been synthesized under the
conditions of Example 1 (see Table). As a catalyst, HZPtCls~6H20
is used. About 0.7 g of a 10% solution of HzPtCls~6Ha0 in i-
propanol are employed per 1000 g of formulation (siloxane +
polyether). Toluene (300 to 800 mL per 1,000 g of formulation) is
used as solvent for the reactions.
NY2-16349.1
-17-

21423'7
0
G1 t!1 M M d~ C1 r-I
.5 Q~ 01 Ov 01 01 01
G
ew
M 00 M ~ ~ M
l H
U1 e-i M r N N M
M d~ M
O O O O O O
O O O O O O
.H
O t~ d~ l0 O rl
M 01 N M d~
y o ~o o ~ H tn
U V UU ~ ~ A
Il1 Ll1 L(1 00 If1 ~ tl1 t!1 CD
M U1 V1 t!1 In 00 00
CO N ~ ~
l!1 N
N ~ N N N CO N N N aD
rl GO N N r OD M
O (~ O H O ~
O
~ r-I rl r-I rl r-I rl rl ~-1 rl
M r-1 v-i rl M ri d
M
O ~ O O O O O O ~ O O ~ O O O
O O O ~ 0 O O
~ O O O O.O O O O O O O O O O O
O O
~ ~ I!7 ~ l0 Lf1 O M N ~ I~
N 00 v-1 d~ M 10 N ~-1
t~ Il1
l0
~ p N I~ ~ ~ O N CO ~ p ~ l0
I~ fW lf1 CO ri 1G tf1
!1 t0
N d W -1 N ~1 e-1 01 N ll1 lf1 t~
M N l~ ri W 1C
t~
W.
N
rtsw ~.~.~ rt.~x v tn-~ .cxw rt~x
~ G ~ o ~ E
~,
~~ 0 0 0 0 0 0
N
W l1 O C1 O O lt1
~0 ~O ~0 v0 l0
H H ,' H H H
H H H H H
H
H H
N M er 1!1 10 l~

r
_..
z142~3~
M l'~ O1 ri 01
~'; 01 t0 t0 01 l~
01 01 Q~ 01 01
M M M
wl rl r-I 1t1 L~ N
Vl M M M O M O
N O O O
H O O O
O O O O
girl
N., M N o0 er N ~N
4J ~
er cf~ er CO d~ M
U O
H ~ rl H
a ~ ~ v ~a
.
00 a0 00 tf1 U1 O
M GO OD ~ tl1
M M M ~ Cb
00 a0 aD N M N H
'~' M M N N 00
rl ri ~-I
H rt rl rl ri ~
O d~ cr O e-I
M M M O rl
O O O O O O ~ O O
~ O O ~ O O
O
O O O O O O O O
O O O O
M ~ ~ ~. ~ ~
~
N M M ll1 e-1
N N CO CD
~ ~ -i r"~ -I r ~ ,N..~
l~ l~ ~ l~ ~ O
(~ LW f~ l~
r, ~ r-~ r-I rl ll1
i v-i ,-~ H ~'~1 M
Q d~ er d~
:
rtw bw rtsu-~rtt4..aU.~x
~ E E ~ ~
N
~, ~,
0 0 0 0 0
0 0 0 0 0
cn:
H H H H H
H H H H H
H H H H H
O rl N
H H H
Cq

._.~... . _ . _.._... .. . ...__
z~~z~~~
EXAMPLE 13
To a Flask equipped with a stirrer, thermometer, gas inlet
and stillhead, 13.2 g (0.022 moles) of polyether d), 87.9 g (0.022
moles) of polyether e), 66.0 g (0.022 moles) of polyether 1),
78.7 g (0.044 moles) of polyether p) and 1,100 mL of toluene are
added. Toluene (150 mL) is distilled off in a nitrogen atmosphere
for the azeotropic drying of the polyether mixture. At 50°C, the
stillhead is exchanged for a reflux condenser. Subsequently,
83 g (0.1 moles of SiX) of siloxane V are added. Ammonia ctas is
then passed in at 60°C until the contents of the flask react
positively for ammonia. The reaction is allowed to continue for
a further hour, the passing in of ammonia being continued at a
greatly reduced rate. The precipitated salt is subsequently
filtered off. After that, the toluene is distilled off at 70°C
and 20 raar. A light brown, almost clear product is obtained.
EXAMPLE 14
(not of the invention)
Polyether a) (7.5 g, 0.0125 moles), 301.8 g (0.075 moles)
of polyether f) and 56.6 g (0.0375 moles) of polyether m) are
reacted under the conditions of Examples 2 to 12 with 65.5 g (0.1
moles of SiH) of siloxane II. The SiH conversion is 99.4%.
HY2-26149.1
-20-

:.
k
Z142~~7
TESTING THE APPLICATION
The above-described properties were found in comparison
trials of conditioning shampoos on strands of Indo-European human
hair:
For this purpose, in each case
2.0% of the polyethersiloxane to be tested with
3.0% of TEGOSOFT GC (glycerin cocoate with 7
moles of ethylene oxide)
40.0% of Texapon N 25 (lauryl ether sulfate)
43.2% of water
10.0% of TEGO betaine F 50 (cocosoamidopropylbetaine)
1.3% of ANTIL 171 (thickener), and
0.5% of NaCl
were mixed into a shampoo formulation..
In the comparison test, grades are awarded from zero to
four, zero being the worst (deficient) and four the best (very
good) rating. By comparing the seven shampoos with one another,
the following grades, averaged over ten candidates, were obtained.
HY~-16149.1
-21-

y
2~4~53'~
PRODUCT
OF
EXAMPLE
2 3 4 8 12 14 ABIL
B 8852
In Wet Hair
Knotting 2.5 2.3 2.5 2.4 2.5 2.2 2.2
Combability 2.2 2.2 2.3 2.3 2.2 1.9 2.2
Handle 2.2 2.2 2.3 2.2 2.3 2.2 2.2
In Dry Hair
Combability 3.0 3.0 3.1 3.0 3.1 2.8 2.8
Handle 2.6 2.6 2.8 2.7 2.6 1.8 1.8
Gloss 2.2 2.1 2.2 2.2 2.2 2.0 2.0
The products of Examples 2, 3, 4, 8 and 12 are of the
invention.
The product of Example 14 and ABIL B 8852 (a commercial
product of Th. Goldschmidt AG) are not of the invention.
In this comparison, particularly the handle of the dry
hair, is rated better when treated with the shampoo of the
inventive compounds of Examples 2, 3, 4, 8 and 12 than when
treated with the products of the comparison examples, which are
not of the invention. The knotting and the combability of the wet
hair are also rated somewhat better after treatment with a shampoo
based on the inventive compounds. The same is true for the
combability of the dry hair.
NYi~t6D19.1
-22-