Aqueous solutions or dispersions of organooligosiloxanes or organopolysiloxanes that include one or more nitrogen-containing side chains and in which a radical containing a polyoxyalkylene unit is bonded to the second Si atom of the chain are suitable for treating fiber materials. A pleasantly soft handle is hereby imparted to the fiber materials, in particular textiles. The novel siloxanes can be obtained by reacting dialkoxysilanes containing substituents having amino groups with cyclic trisiloxanes or tetrasiloxanes, followed by reaction with silanes that contain substituents having polyoxyalkylene units.

DESCRIPTION 
The present invention relates to organooligosiloxanes or 
organopolysiloxanes that have, in addition to one or more 
nitrogen-containing radicals, also a radical that contains an 
oligooxyalkylene chain or polyoxyalkylene chain, at least a proportion of 
the oxyalkylene groups being oxyethylene groups. The invention also 
relates to a process for preparing such siloxanes, aqueous dispersions or 
solutions containing the latter, and to their use for the treatment of 
fiber materials. 
It is known to treat fiber materials, for example woven or knitted fabrics 
or nonwovens, with compositions that contain organooligosiloxanes or 
organopolysiloxanes. These compositions are normally solutions or 
dispersions, preferably aqueous dispersions of the corresponding 
siloxanes. Also, nitrogen-containing organopolysiloxanes have previously 
been used for the treatment of fiber materials; amino group-containing 
organopolysiloxanes have proved suitable, particularly if textiles treated 
with polysiloxanes are to have a soft handle. The siloxanes used for this 
purpose may be products containing amino groups and/or amido groups, as 
are described for example in EP-A 138 192, EP-A 342 830, EP-A 342 834 and 
WO 88/08436. Under certain conditions, dispersions of such N-containing 
polysiloxanes in the form of particularly stable aqueous microemulsions 
can be obtained; this is described in EP-A 138 192 and WO 88/08436. 
Amino group-containing and amido group-containing polysiloxanes can be 
obtained by known processes, for example by reacting a silane in which two 
reactive groups, e.g. alkoxy groups, and a radical R containing an amino 
group or amido group are bonded to a Si atom, with a cyclic siloxane. 
Suitable cyclic siloxanes include, inter alia, hexamethylcyclotrisiloxane 
or octamethylcyclotetrasiloxane. The chain ends of the resultant products 
are often capped by trimethylsilyl groups. In known processes 
hexamethyldisiloxane (CH.sub.3).sub.3 SiOSi(CH.sub.3).sub.3 is added to 
the reaction mixture for this purpose. However, this method of terminating 
the polysiloxane chain has the disadvantage that highly inflammable 
hexamethyldisiloxane has to be handled and appropriate safety measures are 
therefore necessary. Furthermore, with known polysiloxanes containing only 
amino or amido groups as functional groups, the hydrophilic/hydrophobic 
character is determined by the nitrogen-containing radical and can be 
selectively influenced only with difficulty. 
Often polysiloxanes containing amino and/or amido groups are dispersed in 
water by means of non-ionogenic dispersants in order to produce emulsions. 
The dispersants used for this purpose are for example compounds containing 
polyoxyalkylene groups, in particular polyoxyethylene groups. In order to 
obtain stable dispersions, considerable amounts of dispersants are 
frequently necessary, especially if microemulsions are to be prepared. 
Besides the expense and ecological problems, this also has the 
disadvantage that the textiles treated with the dispersions do not exhibit 
optimum rub fastnesses. 
It was therefore the object of the present invention to provide amino 
group-containing and/or amido group-containing organooligosiloxanes or 
organopolysiloxanes that can be prepared from starting materials that are 
less flammable than those used in the case of the preparation of known 
polysiloxanes, whose hydrophilic/hydrophobic character can be selectively 
influenced, and that can be converted with comparatively small amounts of 
dispersants into stable aqueous dispersions. 
This object has been achieved by nitrogen-containing organooligosiloxanes 
or organopolysiloxanes of the general formula (I) 
##STR1## 
where each radical R is either a methyl or a phenyl radical, where R" is a 
divalent, unbranched or branched organic radical containing 1 to 6 carbon 
atoms, preferably a saturated alkylene radical, in particular .paren 
open-st.CH.sub.2 .paren close-st..sub.3, 
n is a number from 5 to 25, 
m is a number from 20 to 1500, 
f has the value 0 or 1, 
where from 60 to 100% of all radicals T present are --CH.sub.2 --CH.sub.2 
--O and from 0 to 40% of all radicals T present are 
##STR2## 
all radicals Z are, independently of one another, either R' or R'" or 
R.sup.IV or R.sup.V, R'" being a radical of the general formula (IIa) or 
(IIb) and R.sup.IV being a radical of the general formula (III) 
##STR3## 
A being hydrogen or an alkyl group containing 1 to 4 carbon atoms, where Q 
and Q' are in each case a divalent, unbranched or branched alkylene 
radical containing 1 to 4 carbon atoms, where p=0 or 1 and where all 
radicals X present are, independently of one another, hydrogen, an alkyl 
radical containing 1 to 6 carbon atoms, which may be substituted by one or 
more hydroxyl groups, or are the cyclohexyl radical or the radical 
--CO--Y, Y being an aliphatic radical containing 1 to 6 carbon atoms which 
can have one or more hydroxyl groups as substituents, R.sup.V being a 
radical of the formula 
##STR4## 
where all radicals R.sup.VI present are, independently of one another, R', 
R'", R.sup.IV or R.sup.V, with the proviso that at least one of the 
radicals Z or R.sup.VI present is a radical R'" or a radical R.sup.IV, all 
radicals R' being in each case a radical R.sup.V or a phenyl radical or 
alkyl radical containing 1 to 4 carbon atoms, preferably a methyl radical 
or ethyl radical.

The organooligosiloxanes or polysiloxanes according to the invention have 
the following advantages: 
1. They can be prepared from starting substances that are substantially 
less critical as regards flammability than the hexamethyldisiloxane or 
similar short-chain Si compounds often used hitherto for chain termination 
(of nitrogen-containing polysiloxanes). These products, which are 
substantially more advantageous as regards flammability and can be used 
for the preparation of siloxanes according to the invention, are described 
in more detail hereinafter. 
2. The amount of dispersant that is necessary to convert the siloxanes 
according to the invention into stable aqueous dispersions can be kept 
lower than in the case of polysiloxanes that contain only amino or amido 
groups but no groupings .paren open-st.T.paren close-st..sub.n, i.e. no 
polyoxyalkylene groups. This leads to ecological advantages and to 
improved rub fastnesses of fiber materials, in particular textiles, 
treated with products according to the invention. In special cases the 
addition of dispersants may be completely dispensed with, namely if the 
siloxanes according to the invention are per se water-soluble or 
self-emulsifying on account of suitable substitution. In many cases, 
dispersions or solutions of polysiloxanes according to the invention also 
have a lesser tendency to foam formation than emulsions of 
amido-functional or amino-functional polysiloxanes that do not contain any 
groups .paren open-st.T.paren close-st..sub.n and which have been 
emulsified by adding fairly large amounts of non-ionic emulsifiers. This 
reduced foam formation in the case of dispersions of products according to 
the invention can provide considerable processing advantages. 
3. The hydrophilic properties of products according to the invention can 
also be specifically adjusted in a simple way. This can be achieved by 
varying the number of --CH.sub.2 --CH.sub.2 --O-- units (varying the value 
of n in formula (I)), by using appropriate starting compounds in a 
preparation process which is described in more detail hereinafter. 
Accordingly, it is also possible to influence the handle of the textiles 
that have been treated with products according to the invention by 
choosing suitable values for the number n of the --CH.sub.2 --CH.sub.2 
--O-- units (T) (a proportion of which can be replaced by polyoxypropylene 
units). This selective influencing of the properties can also be achieved 
in another way, besides choosing suitable values for the number n of these 
aforementioned units, namely by maintaining specific quantitative ratios 
of the starting substances relative to one another in the preparation of 
the siloxanes according to the invention. Since the products formed in the 
inventive process always include only one radical .paren open-st.T.paren 
close-st..sub.n that contains --CH.sub.2 --CH.sub.2 --O-- units, the 
hydrophilic character imparted by the --CH.sub.2 --CH.sub.2 --O-- units 
can be influenced by increasing the amount of nitrogen-containing silane 
used. Particularly in the case where an especially soft handle of suitably 
treated textiles is required, this can be achieved by reducing the 
proportion of --CH.sub.2 --CH.sub.2 --O-- units, based on the total 
product; products can be obtained that impart to the treated textiles a 
more pleasing handle than do commercially available products ("comb 
surfactants"), which contain on several Si atoms of the same molecule 
radicals with --CH.sub.2 --CH.sub.2 --O-- units and, overall, a high 
proportion of such units. 
4. Compared to known "comb surfactants", which are products that include on 
several Si atoms of one and the same polysiloxane chain radicals that 
contain polyoxyethylene groups (these groups for example being bonded via 
alkylene groups to the relevant Si atoms), polysiloxanes according to the 
invention have the advantage that they impart a softer handle to textiles 
treated with them, with at the same time improved permanence of the 
effects with respect to washing. 
5. In many cases siloxanes according to the invention can very easily be 
convened into particularly advantageous stable aqueous microemulsions. 
These finely particulate microemulsions, which can be prepared according 
to known methods (as described in EP-A 138 192, WO 88/08436) have 
particularly favorable applicational properties. Moreover, microemulsions 
can also be prepared with siloxanes according to the invention that 
additionally contain fatty acid N-alkanolamides and that lead to a 
particularly soft and full handle of fiber materials, for example 
textiles, treated 
6. In the case of the preferred embodiment, in which aqueous dispersions 
are present that contain, in addition to siloxanes according to the 
invention, also one or more compounds of the formula R.sup.a 
--CH(R.sup.b)--R.sup.c --O--R.sup.d, these dispersions can be obtained 
having a high content (in some cases up to 80% by weight) of siloxane; 
despite this high proportion of active component, these dispersions can be 
diluted with water without causing any problems. The highly concentrated 
dispersions are advantageous, inter alia, on account of the reduced 
transportation costs. 
The organooligosiloxanes or organopolysiloxanes according to the invention 
contain nitrogen and are represented by the formula (I) given above. The 
compounds are described as oligosiloxanes or polysiloxanes depending on 
the value of m in this formula. The value of m is in each case from 20 to 
1500, preferably from 100 to 750. The ends of the main chains of siloxanes 
according to the invention are formed in each case by R.sub.3 Si groups. 
In the case where the siloxanes according to the invention contain 
radicals R.sup.V, i.e. are branched oligosiloxanes or polysiloxanes that 
also contain Si atoms in side chains, the ends of the side chains can 
likewise be formed by R.sub.3 Si units; however, the side chains may also 
be terminated by R.sub.2 Si--OH-- units. The six or more radicals R that 
are present overall in the siloxanes according to the invention are all, 
independently of one another, either methyl or phenyl radicals. At least 
one radical R' is bonded to each silicon atom within the siloxane chain, 
though several Si atoms may be present in the chain, to which in each case 
two radicals R' are bonded; this is preferred and is normally the case, 
for only in exceptional cases are all radicals Z (see formula I)) 
different from R', i.e. only in rare exceptional cases is it that all 
radicals Z are R'" or R.sup.IV or R.sup.V. 
All radicals R' are, independently of one another, radicals R.sup.V of the 
aforementioned type, phenyl radicals, or alkyl radicals containing 1 to 4 
carbon atoms, and in particular from 70% to 100% of all radicals R' are 
preferably methyl radicals. Particularly preferred are products in which 
all radicals R and all radicals R' and also all radicals Z that are not 
R'" or R.sup.IV or R.sup.V are methyl radicals. In addition to the 
aforementioned radicals R and R', the siloxanes according to the invention 
contain exactly one grouping of the formula --R.sup."--O.paren 
open-st.T.paren close-st..sub.n .paren open-st.CH.sub.2 .paren 
close-st..sub.1 H, the divalent radical R" of this grouping being bonded 
to the second (i.e. the penultimate) silicon atom of the siloxane main 
chain. The radical R" is a divalent, branched or unbranched organic 
radical containing 1 to 6 carbon atoms, and is preferably a saturated 
alkylene radical, in particular of the formula .paren open-st.CH.sub.2 
--).sub.s where s=1 to 6, and particularly preferably R" is .paren 
open-st.CH.sub.2 .paren close-st..sub.3. The number n in the 
aforementioned grouping specifies the number of .paren open-st.T.paren 
close-st. units and is in the range from 5 to 25. Preferably, n is in the 
range from 10 to 20. The grouping .paren open-st.T.paren close-st. bonded 
to the second Si atom of the siloxane chain contains polyoxyethylene 
units, and may additionally contain polyoxypropylene units. The value of n 
is obviously an average value, since in the preparation of compounds 
containing polyoxyalkylene groups them is always a certain chain length 
distribution. A unit containing polyoxyalkylene groups .paren 
open-st.T.paren close-st. .sub.n is bonded via R" to the second (or 
penultimate) Si atom of the polysiloxanes according to the invention. This 
unit must contain polyoxyethylene (EO) groups, and in fact at least 60% of 
all existing groups T must be polyoxyethylene groups. The remaining 40% 
may likewise be polyoxyethylene groups, though a proportion or all of 
these residual groups T may also be polyoxypropylene (130) groups. If both 
EO and 130 units are present in a side chain --R".paren open-st.T.paren 
close-st..sub.n .paren open-st.CH.sub.2 .paren close-st..sub.f H, these 
may be distributed randomly or in the form of blocks. Preferably, 100% of 
all units T are polyoxyethylene groups. The grouping containing .paren 
open-st.CH.sub.2 CH.sub.2 O.paren close-st. units, which is bonded via 
--R"O-- to the second Si atom of the siloxane chain, has a hydroxyl or a 
methoxy group at the other end (f in formula (I) is 0 or 1). The 
oligosiloxanes or polysiloxanes according to the invention may also be 
present in the form of a mixture of compounds in which in one pan of the 
molecules f=0 and in the other pan f=1, i.e. there is partial 
etherification with methyl groups. 
In the siloxanes according to the invention a radical R' of the 
aforedescribed type and a radical Z are bonded to all silicon atoms of the 
main chain with the exception of the two terminal atoms and one of the two 
Si atoms attached thereto. In the case where the siloxanes according to 
the invention are branched, i.e. have Si-containing side chains, the 
chain--terminated by two R.sub.3 Si groups--that contains the Si atom to 
which --R"--O .paren open-st.T.paren close-st..sub.n .paren 
open-st.CH.sub.2 .paren close-st..sub.f H is bonded is termed the main 
chain. 
All radicals Z are, independently of one another, a radical R' of the 
aforedescribed type or a radical R'" or a radical R.sup.IV or a radical 
R.sup.V. Preferably, all radicals Z are either R' or R'" or R.sup.IV. 
However, at least one of the radicals Z must be a radical R'" or R.sup.IV, 
except in those cases in which at least one radical R.sup.V (side chain 
containing Si atoms) and thus also at least one radical R.sup.VI (of the 
aforementioned type) is present that is a radical R'" or R.sup.IV. The 
requirement according to which at least one of all radicals Z or R.sup.VI 
present must be a radical R'" or R.sup.IV means that the siloxanes 
according to the invention must include at least one nitrogen-containing 
radical covered by the formula (IIa) or (IIb) (radical R'") or the formula 
III (radical R.sup.IV). However, a plurality of such radicals of the 
formula (IIa) or (IIb) and/or of the formula III may also be present. 
Those siloxanes according to the invention in which all radicals Z are R' 
or R.sup.IV (at least one of them being R.sup.IV) have proved particularly 
suitable for the treatment of fiber materials. 
One or more of the radicals Z may be a radical R.sup.V of the formula 
##STR5## 
In the case (which however is not particularly preferred) where none of the 
radicals Z is a nitrogen-containing radical R'" or R.sup.IV, at least one 
of the radicals Z present must be a radical R.sup.V, and in this case at 
least one of the radicals R.sup.VI present (in radicals R.sup.V) must be a 
radical R'" or R.sup.IV, i.e. must be a nitrogen-containing radical of the 
formula (IIa) or (IIb) or of the formula III. 
All radicals R.sup.VI present are, independently of one another, a radical 
R', a radical R'", a radical R.sup.IV or a radical R.sup.V of the 
described types. In any case it must be ensured that the siloxanes 
according to the invention contain at least one radical Z or one radical 
R.sup.VI that is a nitrogen-containing radical R'" of the formula (IIa) or 
(IIb) or a radical R.sup.IV of the formula III. 
The fact that one or more of the radicals Z may be a radical R.sup.V means 
that a branched polysiloxane may be present. Since the Si atoms contained 
in the branching contain radicals R.sup.VI, which in mm may be radicals 
R.sup.V, it is also possible for the siloxanes according to the invention 
to include Si-containing side chains, which in turn are themselves 
branched. The meanings of R, R' and m given for the radical R.sup.V in the 
above formula are the same as specified in claim 1 and for formula (I). In 
the case where R.sup.V is a radical (of the above-specified formula) in 
which Si--OH units are present, these OH groups can be involved in 
crosslinking reactions. 
The number m of the groupings --Si(R')(Z)--O-- in the siloxanes according 
to the invention is in the range from 20 to 1500, preferably in the range 
from 100 to 750. The number m can be adjusted via the reaction conditions, 
for example by the quantitative ratios of starting compounds used, adopted 
in the preparation of the siloxanes. In the case where radicals R.sup.V 
are present, the upper limit of the extent of the branching and of the 
total number of Si atoms present should expediently be governed by the 
products, becoming difficult to handle due to their excessive viscosities. 
If Si-containing side chains are present the sum of the two values of m 
(main chain and side chain) is preferably not more than 1500, in 
particular not more than 750. 
One or more of the radicals Z in the siloxanes according to the invention 
is a radical R'" or R.sup.IV or R.sup.V. All radicals R'" present are a 
radical of the following formula (IIa) or (IIb), and all radicals R.sup.IV 
are a radical of formula III. Siloxanes according to the invention in 
which several radicals R'" or R.sup.IV, different from one another, are 
present may be obtained for example by using a mixture of different 
dialkoxyarninosilanes in their preparation according to a process as 
described hereinbelow. Each radical R'" is a radical of the formula (IIa) 
##STR6## 
and each radical R.sup.IV is a radical of the formula (III) 
##STR7## 
In these formulae A is hydrogen or an alkyl group containing 1 to 4 carbon 
atoms, in particular a methyl group. Q and Q' are in each case a divalent, 
branched or unbranched alkylene radical containing 1 to 4 carbon atoms, 
preferably in each case a saturated alkylene radical containing 2 to 4 
carbon atoms. The index p is 0 or 1, and all radicals X present are, 
independently of one another, either hydrogen, an alkyl radical containing 
1 to 6 carbon atoms, which may contain one or more hydroxyl groups as 
substituents, the cyclohexyl radical, or the radical --CO--Y. The 
last-mentioned case (X=--CO--Y) thus corresponds to siloxanes with amido 
group-containing side chains. Such amido group-containing (poly)siloxanes 
are in many cases advantageous since they produce no or only a slight 
yellowing of textiles treated therewith; similar advantages are obtained 
with siloxanes containing piperazino groups or morpholine units (formula 
II (a) and (IIb)). Amido group-containing polysiloxanes according to the 
invention (X=--CO--Y) may for example be obtained by reacting, according 
to the process described below, dialkoxyaminosilanes of the formula 
(R'O).sub.2 Si(R').paren open-st.CH.sub.2 --).sub.3 --NH.paren 
open-st.CH.sub.2).sub.2 --NH.sub.2 with hexamethylcyclotrisiloxane and a 
polyoxyethylene group-containing silane (component c) of the process 
described hereinbelow) and then converting the terminal primary and/or 
secondary amino groups present in the side chains into amido groups. This 
can be effected by means of a lactone, e.g. butyrolactone, or by means of 
a carboxylic acid anhydride, e.g. acetic anhydride, according to known 
methods (EP-A 342 830 and EP-A 342 834). In the case of the reaction with 
butyrolactone, products are formed in which the radical Y contains a 
terminal hydroxyl group. 
If X is --CO--Y, then Y is an aliphatic radical containing 1 to 6 carbon 
atoms. This radical may contain one or more hydroxyl groups as 
substituents, particular preference being given to products that contain a 
hydroxyl group as substituent on the terminal carbon atom. Polysiloxanes 
with amido group-containing radicals are described in EP-A 342 830 and in 
EP-A 342 834. The structures given there for the amido group-containing 
radicals bonded to Si atoms are also suitable as radicals R.sup.IV for the 
siloxanes according to the invention. The radicals containing amino groups 
but no amido groups, which am bonded to Si atoms and are mentioned in EP-A 
138 192 and WO 88/08436, are likewise suitable as radicals R.sup.IV for 
siloxanes according to the invention. 
Polysiloxanes according to the invention in which a radical R.sup.IV is 
present and in which X is --CO--Y may also be obtained by replacing 
butyrolactone in the aforementioned conversion of amino groups by other 
lactones containing several hydroxyl groups. A suitable variant for this 
purpose is the reaction of the aforementioned amino group-containing and 
polyoxyethylene group-containing oligosiloxanes and polysiloxanes with 
delta-gluconolactone. In this case products are formed in which X is CO--Y 
and Y contains several hydroxyl groups, i.e. products in which Y is 
--(CHOH).sub.4 --CH.sub.2 OH. 
Siloxanes according to the invention in which one or more radicals X are an 
alkyl radical that contains an hydroxyl group as substituent can for 
example be obtained by adding ethylene oxide to the corresponding primary 
and/or secondary amino groups, instead of the aforedescribed addition of 
lactone, the addition of ethylene oxide yielding monoethanolamine or 
diethanolamine derivatives. Instead of ethylene oxide, derivatives thereof 
may also be used, for example an ethylene oxide substituted by a 
--CH.sub.2 OH group. As already mentioned, in the normal case only some of 
the radicals Z in the siloxanes according to the invention (see formula 
(I)) are in each case a radical R'" or R.sup.IV or R.sup.V, i.e. normally 
a proportion of the radicals Z is in each case a radical R', preferably 
from 70 to 100% of all radicals R' being methyl groups. It is also 
possible for all radicals Z with the exception of one radical to be R', R' 
having the meaning given above and in claim 1, and preferably from 70 to 
100% of all radicals R' are methyl groups. Particularly preferred 
siloxanes according to the invention are notable for the fact that from 25 
to 95% of all radicals Z present are methyl groups and the remaining 
radicals Z are radicals R'" or R.sup.IV of the formula (IIa) or (IIb) or 
(III). In particular, preference is given to products of the formula 
##STR8## 
or of the formula 
##STR9## 
or of the formula 
##STR10## 
or of the formula 
##STR11## 
where t is 2 or 3. 
Y has the meaning given above. The proportion of the radicals Z that are 
methyl groups can be regulated via the quantitative ratios employed in the 
preparation of the siloxanes. 
A number of organooligosiloxanes or organopolysiloxanes according to the 
invention can be prepared in an advantageous manner by reacting together 
the following in the presence of water, preferably at a temperature of 
from 80.degree. to 130.degree. C.: 
a) a nitrogen-containing silane of the formula 
##STR12## 
or of the formula 
##STR13## 
b) a cyclic siloxane of the formula 
EQU (R'.sub.2 SiO).sub.r 
and 
c) a silane of the formula 
##STR14## 
R, R', R", R'", T, R.sup.IV and n having the meanings given above and in 
claim 1, r being 3 or 4, and f having the value 0 or 1, with the 
restriction that in the silanes according to the formulae given for 
component a), the radicals R' bonded to oxygen are not R.sup.V. 
If desired the reaction can be carried out in such a way that all three 
components a), b) and c) and water are present in the reaction mixture at 
the start of the reaction. When performing the synthesis it may however be 
advantageous to react together firstly only the components a) and b) in 
the presence of water, preferably with the co-use of a catalyst, for 
example potassium hydroxide, and only then to add the component c). In 
this connection the first stage, i.e. the reaction of a) with b), may for 
example be performed at a temperature in the range from 80.degree. to 
90.degree. C., and the second stage, i.e. the reaction with component c), 
may be carried out at a higher temperature, e.g. from 100.degree. to 
130.degree. C. In the presence of water, alcohol (R'OH) is released from 
the R'O group-containing silane (component a)). The amount of water 
present should accordingly be at least sufficiently large that all R'O 
groups present can be eliminated as R'OH. The reaction is carried out in a 
preferred embodiment in the presence of a base. An alkali metal hydroxide 
may be used as base. 
In the aforementioned synthesis it may often be expedient not to use amido 
group-containing radicals R.sup.IV, but only amino group-containing 
radicals R'" or R.sup.IV. If it is desired that the end products according 
to the invention contain amido groups, these can also be introduced 
subsequently by the reaction of a primary amino group with a lactone or a 
carboxylic acid anhydride. Suitable compounds for this purpose are 
butyrolactone or acetic anhydride. 
The component a) is a silane in which a radical R' and R'" or R.sup.IV of 
the aforementioned type are bonded to the Si atom. Also, two radicals R'O, 
preferably two alkoxy radicals (in particular methoxy radicals) or phenoxy 
radicals are bonded to the Si atom. These reactive radicals R'O permit the 
reaction with component b), a cyclic siloxane, with ring opening. The 
component c), a silane of the aforementioned type, effects the 
introduction of the unit --R"--O.paren open-st.T.paren close-st..sub.n 
.paren open-st.CH.sub.2 .paren close-st..sub.f H into the siloxanes 
according to the invention, in which this unit is bonded to the second Si 
atom of the chain. Also due to component c) the two chain ends of the 
siloxanes according to the invention are in each case formed by R.sub.3 Si 
radicals. Particularly suitable as component b) are cyclic siloxanes in 
which r is 3 or 4, preferred examples being (R'=methyl) 
hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane. These cyclic 
oligosiloxanes are commercially available products. If desired r may 
however also have values higher than 4, e.g. up to 10. Products suitable 
as component a), i.e. products of the formulae 
##STR15## 
are available on the market, e.g. Dynasylan.RTM.1411 or 
Dynasylan.RTM.1505, from Huls AG, Marl, Germany. 
Products that can be used as component c), i.e. products of the formula 
##STR16## 
are also commercially available, an example being the product 
Tegopren.RTM.5878 from Th. Goldschmidt AG, Essen, Germany. 
In addition, products that are suitable as component a) or as component c) 
can be prepared according to methods known from silicon chemistry. 
The average chain length (value of m in formula (I)) of the siloxanes 
according to the invention, and similarly the proportion of the radicals Z 
that is R', relative to that proportion of the radicals Z that is R'" or 
R.sup.IV, can conveniently be controlled via the relative quantitative 
ratios of the components a), b) and c). It is particularly preferred to 
carry out the process mentioned above and in claim 10 in such a way that 
the compounds a), b) and c) are reacted in quantitative ratios such that 
from 1 to 40 mol of component b) and from 0.5 to 2 mol of component c) are 
used per mole of component a). 
The average chain length can also be controlled by the timing of the 
addition of the component c) (termination). Preferably, the process is 
carried out at a temperature in the range from 80.degree. to 130.degree. 
C.; in the case where the process is carried out in the aforedescribed 
manner in two stages, the temperature of the first stage may be different, 
for example about 20.degree. C. lower, than the temperature of the second 
stage. 
Besides the aforedescribed particularly preferred process, 
organooligosiloxanes or polysiloxanes according to the invention can also 
conveniently be prepared in the following way: component b) (cyclic 
oligosiloxane) in the aforedescribed process is replaced by an open-chain 
siloxane that has a reactive group at both ends. Suitable for this purpose 
are for example linear oligosiloxanes of the structure 
##STR17## 
where R' is preferably CH.sub.3, though all radicals R' may, independently 
of one another, also have the other meanings given above, with the proviso 
that they are not R.sup.V. The value of q is preferably 2 to 5, though if 
desired it may also be larger. 
If the process is carried out in the specified manner, namely with an 
open-chain siloxane instead of a cyclic siloxane as component b), the 
components a), b) and c) are preferably employed in the molar ratios 
mentioned above, though with the following change: instead of using in 
general from 1 to 40 mol of component b) per 1 mol of component a), the 
chain length and the number of Si atoms of the open-chain siloxane 
(component b)) should be taken into account. If this siloxane has 3 or 4 
Si atoms, then from 1 to 40 mol are used by analogy with the case of the 
cyclic siloxane. If the open-chain siloxane contains more Si atoms, the 
number of moles preferably used is correspondingly lower. It is therefore 
preferred to use such a number of moles of open-chain siloxane per mole of 
component a) that this amount contains about the same number of Si atoms 
as 1 to 40 mol of cyclic trisiloxane or tetrasiloxane. 
The two aforedescribed process variants, namely using cyclic or open-chain 
oligosiloxane as starting substance, can be carried out using catalysts, 
preferably basic catalysts, such as are known from the literature for 
corresponding reactions. Suitable catalysts are potassium hydroxide and 
potassium silanolates. 
In the described process according to the invention compositions are formed 
that contain the organooligosiloxanes or organopolysiloxanes described 
above as principal products. Secondary products are also formed to a 
lesser extent. Normally these secondary products do not have to be 
separated before the products according to the invention are used for the 
treatment of fiber materials. This is also particularly advantageous if 
the reaction mixture after the reaction in aqueous medium is already 
present in the form of an aqueous solution or dispersion. However, if 
necessary the pH of this solution or dispersion still has to be adjusted, 
depending on the intended use, for example by neutralizing alkali metal 
hydroxide still present. 
The aforedescribed process is suitable for preparing (preferred) examples 
of the siloxanes according to the invention in which one or more of the 
radicals Z is a radical R'" or R.sup.IV. If radicals R.sup.V are to be 
incorporated into the siloxanes according to the invention, i.e. the 
siloxane chain is to be branched, this can be achieved by using in 
addition trifunctional compounds (R'O).sub.3 Si--R' or (R'O).sub.3 Si--R'" 
or (R'O).sub.3 Si--R.sup.IV in the aforedescribed preparation process. 
If a novel polysiloxane or oligosiloxane formed as principal product in the 
described process is not water-soluble or self-dispersing, or if aqueous 
compositions according to the invention are to contain further 
water-insoluble products, it is recommended to use a dispersant or a 
mixture of several dispersants. These dispersants may be added to the 
reaction mixture before or during the reaction according to the process of 
the invention. They may also be added after the completion of the 
reaction, for example by adding to the reaction mixture obtained after the 
reaction an aqueous dispersion that contains a further product that is to 
be used for the treatment of the fiber materials. 
The organooligosiloxanes or organopolysiloxanes according to the invention 
are ideally suitable for treating fiber materials, for example textiles in 
the form of woven or knitted fabrics or nonwovens. A pleasantly soft 
handle and also--by choosing appropriate compounds containing a larger or 
smaller number of --CH.sub.2 --CH.sub.2 O-- or polyoxypropylene 
units--graduated hydrophilic properties can be imparted in this way to the 
fiber materials. The use in particular of siloxanes in which the radical 
R'" or R.sup.IV is an amido group, a morpholine ring or a piperazine ring 
results in a particularly low yellowing tendency. The handle of the 
textiles can be influenced further by using the siloxanes according to the 
invention in combination with fatty acid alkanolamides or with dispersed 
polyethylene waxes. Products suitable for this purpose are described 
further hereinbelow. 
For the treatment of fiber materials, organooligosiloxanes or 
organopolysiloxanes according to the invention are used especially in the 
form of solutions or dispersions which may be diluted to the desired 
concentration before use and to which may be added further agents that are 
conventionally used for the treatment of fiber materials, for example 
flameproofing agents or cellulose crosslinking agents in order to improve 
the crease properties. The application of the dispersions or solutions to 
the fiber materials can be performed according to generally known methods, 
e.g. using a pad mangle. 
Although in principle the siloxanes according to the invention can also be 
used as a solution or dispersion in an organic solvent, it is preferable 
for environmental and cost reasons to use them in the form of an aqueous 
solution or dispersion; preferably aqueous solutions or dispersions 
containing from 10 to 50% by weight, in some cases also up to 80% by 
weight, of organooligosiloxane or organopolysiloxane, based on the total 
dispersion or total solution, are first of all prepared. Solutions or 
dispersions of products according to the invention can be stored, 
transported and delivered to the consumer in this form. For use in the 
treatment of fiber materials, expediently from about 3 to 50 g of these 
solutions or dispersions are used per liter of water. The mount used in 
each individual case depends on the application technology. Before use, 
further products conventionally used in the treatment of fiber materials 
can be added to these liquors diluted to the ready-for-use concentration. 
Known dispersants and emulsifiers, for example non-ionogenic dispersants 
from the group comprising ethoxylated alcohols or ethoxylated fatty acids, 
can be used to disperse siloxanes according to the invention in water (if 
these are not self-dispersing or soluble). The dispersion is performed 
using known methods and apparatus. In many cases it is possible to 
disperse siloxanes according to the invention in water so as to produce 
microemulsions. These microemulsions, which may contain further additives 
such as fatty acid alkanolamides, are notable for the fact that the 
dispersed substances are present in a particularly finely divided form. 
The microemulsions are in many cases optically clear and have outstanding 
stability. Processes as are described in EP-A 138 192 or WO 88/08436 may 
be used for their preparation. 
In preferred embodiments the aqueous solutions or dispersions also contain, 
besides siloxanes according to the invention, one or more of the following 
constituents: fatty acid alkanolamides, dispersed polyethylene waxes and 
compounds of the formula (VII) 
##STR18## 
These compounds of the formula VII are discussed in more detail 
hereinbelow. 
The handle of textiles that are treated with dispersions or solutions 
according to the invention can be influenced, i.e. a particularly soft 
handle can be obtained, by adding one or more fatty acid alkanolamides. 
Fatty acid alkanolamides have previously been used to achieve a soft 
handle in fiber materials; in combination with siloxanes according to the 
invention fatty acid alkanolamides in the form of microemulsions can be 
obtained. Suitable fatty acid alkanolamides are for example 
monoalkanolamides or diakanolamides of the formulae 
EQU R CON[(CH.sub.2 CH.sub.2 O--).sub.k --H].sub.2 and RCONH(CH.sub.2 CH.sub.2 
O).sub.k H 
R being a saturated or unsaturated hydrocarbon radical containing 12 to 18 
carbon atoms and k being a number from 1 to 10. Also suitable are 
alkanolamides that are derived from aromatic carboxylic acids, e.g. 
salicylic acid. If, as illustrated in the first-mentioned formula, two 
such alkanol radicals are bonded to the nitrogen atom, then k may 
obviously have a different value for one radical than for the other 
radical. 
Fatty acid alkanolamides that are suitable as additives for dispersions of 
siloxanes according to the invention are commercially available products, 
as can be obtained for example by reacting the corresponding fatty acids 
with alkanolamines. 
The handle of textiles treated with agents according to the invention can 
also be influenced by adding dispersed polyethylene waxes, as well as by 
adding fatty acid alkanolamides. It is known for example from EP-A 0 412 
324, U.S. Pat. No. 4,211,815, DE-A 28 24 716, and DE-A 19 25 993 to impart 
a soft handle to textiles by means of dispersed polyethylene waxes. The 
dispersed or dispersible polyethylene waxes described in these citations 
are also suitable for dispersions according to the invention. These waxes 
are chemically modified polyethylenes. The modification normally comprises 
the introduction of acidic (--COOH) groups. Suitable dispersed or 
dispersible polyethylene waxes are commercially obtainable. 
The amounts of fatty acid alkanolamide and/or of polyethylene wax and/or of 
one or more compounds of the formula VII described hereinbelow, which are 
expediently added to the dispersions or solutions according to the 
invention depend on the desired properties (handle of the treated 
textiles), but also on the stabilities of the dispersions. These amounts 
can easily be determined by simple experiments. 
In many cases advantages as regards the properties of dispersions according 
to the invention can be achieved by adding one or more compounds coming 
under the formula (VII) 
##STR19## 
These compounds can act as solubilizers. Depending on the nature and amount 
of the individual components, in many cases highly concentrated 
dispersions can thus be obtained that can be diluted without difficulty 
with water to a ready-for-use concentration without passing through a 
range, during the dilution, in which a separation of the dispersion into 
two phases occurs. 
According to a preferred embodiment of a dispersion or solution according 
to the invention, the latter contains, in addition to a siloxane of the 
formula (I), a compound of the aforementioned formula (VII), where 
EQU R.sup.a is H or CH.sub.3, 
##STR20## 
R.sup.d is an unbranched or branched alkyl radical containing 1 to 4 carbon 
atoms, which may have an OH group or an OR.sup.e group as substituent, 
R.sup.e is an unbranched or branched alkyl radical containing 1 to 4 carbon 
atoms, which may have an OH group as substituent. 
Particularly preferred compounds of the formula (VII) are methyl lactate, 
ethyl lactate or an ether derived by elimination of 1 molecule of water 
from 2 molecules of 1,2-propylene glycol. Mixtures of such compounds (VII) 
may also be used. Ethers that are derived from 2 molecules of 
1,2-propylene glycol by elimination of 1 molecule of water are the 
following compounds: 
EQU CH.sub.3 --CH(OH)--CH.sub.2 --O--CH.sub.2 --CH(OH)--CH.sub.3 
EQU CH.sub.3 --CH(OH)--CH.sub.2 --O--CH(CH.sub.3)--CH.sub.2 OH 
EQU HO--CH.sub.2 --CH(CH.sub.3)--O--CH(CH.sub.3)--CH.sub.2 OH 
The invention is now illustrated by examples of implementation. 
EXAMPLE 1 (according to the invention) 
A mixture of 36 g of Dynasylan.RTM.1411 (Huls AG, Germany), 2.23 kg of 
silicone oil Z 020 (Wacker-Chemie GmbH, Germany), 12 g of water and 5 g of 
45% strength potassium hydroxide was boiled under reflux for one hour in a 
reaction vessel. 120 g of Tegopren.RTM.5878 (Th. Goldschmidt AG, Germany) 
were next added. The mixture was then heated to 110.degree. C. and boiled 
under reflux for 5 hours. 
In order to prepare an aqueous dispersion of the resultant polysiloxane 
according to the invention, 6.94 kg of water. 280 g of Genapol.RTM.X 080 
(Hoechst AG, Germany), 280 g of 1,2-propylene glycol and 90 g of 60% 
strength acetic acid were successively added to the product obtained 
according to the above procedure. The mixture obtained was first of all 
pre-emulsified and then subjected to a high-pressure emulsification at 300 
bar and at about 70.degree. C. 
Dynasylan.RTM.1411 is a product (about 100% active substance)of the formula 
EQU H.sub.2 N(CH.sub.2).sub.2 NH(CH.sub.2).sub.3 Si(CH.sub.3)(OCH.sub.3).sub.2. 
Tegopren.RTM.5878 is an oligosiloxane terminally capped with trimethylsilyl 
groups (about 100% active substance) having a side chain containing about 
12 polyoxyethylene units that is bonded via an alkylene group to a Si 
atom. Silicone oil Z 020 (about 100% active substance) is 
hexamethylcyclotrisiloxane. Genapol.RTM.X 080 (about 100% active 
substance) is an ethoxylated isotridecyl alcohol. 
EXAMPLE 2 (comparative example, not according to the invention) 
Example 1 was repeated, but with the following change: the product 
Tegopren.RTM.5878 was added only at a later point in time, namely together 
with Genapol X 080. Under these conditions Tegopren 5878 no longer reacts 
with the product obtained from Dynasylan and silicone oil Z 020. The 
product of Example 1 thus differs from that of Example 2 by the fact that 
in Example 2 a polysiloxane is present, to which no polyoxyethylene units 
are bonded and which is dispersed by means of a polyoxyethylene 
group-containing dispersant (Tegopren). In the product of Example 1 on the 
other hand there is no free Tegopren present or at least no significant 
amounts of Tegopren. 
Whereas in Example 1 a stable dispersion was obtained, the product obtained 
according to Example 2 separated after a relatively short time into two 
phases. 
EXAMPLE 3 
Samples of blue-dyed polyester knitted fabrics were treated with a product 
obtained according to Example 1 and with a commercially available 
amino-functional polysiloxane. The commercially available polysiloxane 
contained, per siloxane chain, on average several side chains having in 
each case a terminal primary amino group and a secondary amino group in 
the middle of these side chains. The commercially available product 
contained no polyoxyalkylene groups and contained about 3.5 times the 
amount of nitrogen (in % by weight of N, based on active substance) 
compared to the novel product according to Example 1. The dispersion of 
the commercial product was performed in a similar way to that described in 
Example 2 (i.e. with the addition of Tegopren 5878 together with Genapol). 
The further details regarding the emulsification corresponded to those of 
Example 1 (addition of water, acetic acid, propylene glycol, 
pre-emulsification and high-pressure microemulsification). The dispersion 
of the product according to the invention had, for the same amount of 
active substance, a considerably lower cloud point index, and was 
therefore substantially more transparent than the dispersion of the 
commercial product. The rub fastness of the polyester sample that had been 
treated with the dispersion according to the invention was significantly 
better than the rub fastness of the comparison sample that had been 
treated with the dispersion of the commercially available polysiloxane. 
EXAMPLE 4: Preparation of a microemulsion according to the invention 
1.58 kg of silicone oil Z 020, 26 g of Dynasylan.RTM.1411, 8 g of water and 
4 g of 45% strength potassium hydroxide were boiled together under reflux 
for 1 hour. After adding 85 g of Tegopren.RTM.5878, the mixture was boiled 
under reflux for a further 30 minutes. 2.39 kg of water was added to the 
resultant mixture, the latter was cooled to 60.degree. C., and 375 g of an 
ethoxylated (8 EO) isotridecyl alcohol and 15 g of an ethoxylated (20 EO) 
isotridecyl alcohol were added. 175 g of a fatty acid diethanolamide 
(mainly based on stearic acid), which still contained some free 
diethanolamine, 75 g of coconut oil fatty acid polyglycol ester, 150 g of 
dipropylene glycol and 125 g of 60% strength acetic acid were then added 
in succession. The mixture was heated to 70.degree. C. and kept for 15 
minutes at this temperature. After adding 5 kg of water, a stable, pale 
yellowish microemulsion was obtained.