Note: Descriptions are shown in the official language in which they were submitted.
1 21489-7895
Stvrene oxide adducts
The present invention relates to novel styrene oxlde
adducts and to the use thereof as textile auxlllaries, in
particular as emulsifiers, wetting agents, antlfoams or dyeing
asslstants.
The styrene oxide products according to the present
invention are adducts of styrene oxide with polyalkylene glycol
ethers ox the formula
R - O - (CH CH O) - CH - CH - OH
(la') 2 2 m
Yl Y2
and their acid esters and salts thereof.
In the formula (la'), R is an aliphatic radical having
at least 4 carbon atoms, preferably at least 6 carbon atoms. One
of Y1 and Y2 is phenyl and the other is hydrogen, m is a number
from 1 to 100, advantageously from 2 Jo 100, preferably from 4 to
80.
The substltuent R is advantageously the hydrocarbon
radical of a unsaturated or saturated aliphatic mono alcohol
having 6 to 24 carbon atoms. The hydrocarbon radical can be
straight-chaln or branched. Preferably, R is an alkyl or alkenyl
radical having 8 to 22 carbon atoms.
Suitable aliphatic saturated mono alcohol ls a natural
alcohol, e.g. lauryl alcohol, myristyl alcohol, cetyl alcohol,
stearyl alcohol, arachidyl alcohol or behenyl alcohol, and also
synthetic alcohols, e.g. oxo process alcohols such as, in
partlcular, 2-ethylbutanol, 2-methylpentanol, 5-methylheptan-
la 21489-7895
3-ol, 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, 2-octanol,
isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol,
decanol, Cg-Clloxoalcohol, tridecyl alcohol, isotridecanol or
linear primary alcohols Allots having 8 to 18 carbon atoms.
Some Alfol representatives are Alfol (8-10), Alfol ~9-11), Alfol
(10-14), Alfol (12-13) or Alfol (16-18). ("Alfol" is a registered
trade mark).
,
39!~
Unsaturated aliphatic mono alcohols are for example dodecenyl alcohol, hexadecenyl
alcohol and oleyl alcohol.
The alcohol radicals can be present singly or in the form of mixtures of two or more
components, such as mixtures of alkyl and/or alkenyl groups derived from soyabean fatty
acids, palm kernel oil fatty acids or tallow oils.
(ALkylene-O)m- chains are preferably of the ethylene glycol, propylene-ethylene glycol or
ethylene-propylene glycol type; the first is particularly preferred.
m is preferably 4 to 40.
The styrene oxide adducts are prepared by first etherifying the aliphatic mono alcohol with
1 to 100 moles of alkylene oxide (ethylene oxide and/or propylene oxide) and then by the
addition of 1 mole of styrene oxide to the resulting polyalkylene glycol ether. The
etherification of the mono alcohol is carried out in a conventional manner using ethylene
oxide or propylene oxide or alternatively ethylene oxide and propylene oxide or a mixture
of ethylene oxide and propylene oxide. The addition of styrene oxide is advantageously
carried out in a virtually anhydrous or substantially anhydrous medium at a temperature of
40 to 90C under atmospheric or superatmospheric pressure and in the presence of an
acidic catalyst, e.g. boran trifluoride etherate, p-toluenesulfonic acid, phosphoric acid or in
particular sulfuric acid. The acid is then removed by neutralizing and filtering.
Specific examples of polyalkylene glycol ethers of formula (1) required for adduct
formation with styrene oxide are:
- product of the addition of 8 moles of ethylene oxide to 1 mole of Cg-Clloxo alcohol
- product of the addition of 2 moles of ethylene oxide to 1 mole of butanol
- product of the addition of 2.5 moles of ethylene oxide to 1 mole of Cg-Clloxo alcohol
- product of the addition of 4 moles of ethylene oxide to 1 mole of C9-Clloxo alcohol
- product of the addition of S moles of ethylene oxide to 1 mole of Cg-Clloxo alcohol
- product of the addition of 35 moles of ethylene oxide to 1 mole of stearyl alcohol
- product of the addition of 36 moles of ethylene oxide to 1 mole of stearyl alcohol
- product of the addition of 18 moles of ethylene oxide to 1 mole of Cl2-Cl8fatty alcohol
A mixture (Cetalol 50-55)
- product of the addition of 10 moles of ethylene oxide to 1 mole of 2-ethylhexanol
- product of the addition of 4 moles of ethylene oxide and 12 moles of propylene oxide to
/e, en
9~3
1 mole of Cg-Clloxo alcohol
- product of the addition of 8 moles of ethylene oxide and 12 moles of propylene oxide to
1 mole of Cl2-CI3fatty alcohol
- product of the addition of 6 moles of ethylene and 6 moles of propylene oxide to 1
mole of Cg-Clloxo alcohol
- product of the addition of 3 moles of propylene oxide and 3 moles of ethylene oxide to
1 mole of dodecyl alcohol
- product of the addition of 18 moles of ethylene oxide to 1 mole of cetyl alcohol
- product of the addition of 3 moles of ethylene oxide to 1 mole isotridecyl alcohol
- product of the addition of 9 moles of ethylene oxide to 1 mole of tridecyl alcohol
- product of the addition of 80 moles of ethylene oxide to 1 mole of oleyl alcohol
- product of the addition of 10 moles of ethylene oxide to 1 mole of tridecyl alcohol
- product of the addition of 20 moles of ethylene oxide to 1 mole of oleyl alcohol
- product of the addition of 3 moles of ethylene oxide to 1 mole of lauryl alcohol
- product of the addition of 2, 4, 6 or 15 moles of ethylene oxide to 1 mole of nonyl
alcohol, and also ethylene glycol monobutyl ether.
The acid esters can be present, depending on the acid radical, in the form of monoesters,
diesters or half esters and as free acids or preferably as salts, for example alkali metal salts
or aLIcaline earth metal salts or ammonium salts. Suitable aLkali metal salts are in particular
the sodium, potassium and lithium salts, suitable aLtcaline earth metal salts are magnesium
and calcium salts, and suitable ammonium salts are the arnmonium, dimethyl ammonium,
trimethyl arnmonium, monoethanol ammonium, diethanol ammonium and triethanol
ammonium salts. Preferably, the acid esters are prepared as ammonium salts. Mono- or
diethanol ammonium salts may additionally be etherified with 1 to 25 oxyethylene units.
The acid esters are prepared by reacting the styrene oxide adduct according to the present
invention with an at least dibasic oxygen acid and if desired converting the resulting acid
ester into the abovementioned salts.
Suitable polybasic oxygen acids for forming the acid esters are sulfonated or sulfonyl-free,
organic, preferably aliphatic, dicarboxylic acids of 3 to 6 carbon atoms, e.g. maleic acid,
malonic acid, succinic acid or sulfosuccinic acid, and polybasic inorganic oxygen acids,
e.g. sulfuric acid or orthophosphoric acid. In place of the acids it is also possible to use
their functional derivatives such as anhydrides, halides or amides. Examples of these
functional derivatives are maleic anhydride, phosphorus pentoxide, chlorosulfonic acid
~0C~ 9
and sulfamic acid. The phosphoric esters are advantageously formed as mixtures of a
monoester and diester.
The esterification is in general carried out by simply mixing the reactants and heating,
advantageously to a temperature between 50 and 100C. The free acids which are
initially formed can subsequently be converted into the corresponding aLkali metal or
ammonium salts. The conversion into the salts is carried out in a conventional manner by
adding bases, for example ammonia, monoethanolamine, triethanolarnine or an aLkali
metal hydroxide, for example sodium hydroxide or potassium hydroxide. In a particularly
preferred embodiment, sulfuric half-esters are directly prepared in the form of their
ammonium salts by heating the styrene oxide adducts with sulfamic acid in the presence
or absence of urea.
Industrially important styrene oxide adducts conform to the formula
(2) Rl-OtCH2CH20}~ CH- ~CH-OH
Yl Y2
where Rl is alkyl or alkenyl each having 8 to 22 carbon atoms, one of Yl and Y2 is phenyl
and the other is hydrogen, and ml is from 4 to 80.
Preferred acid esters prepared with an inorganic or organic acid have the formula
(3) Rl-OtCH2CH20~jj;r ~CH-CH-O-X or
yl Y2
the formula
(4) Rl-OtCH2CH203~(~CH-~CH03~ CH-~CH-O-X
Zl Z2 Yl Y2
where Rl, Yl, Y2 and ml are each as defined, one of Zl and Z2 is methyl and the other is
hydrogen, X is the maleic acid, sulfosuccinic acid, sulfuric acid or phosphoric acid radical,
and the sum nl + n2 is from 4 to 30, preferably from 6 to 18.
Particularly preferred acid esters of the formulae (3) and (4) contain either a maleic ester
C 9
- 5 -
group or a sulfuric ester group, which are each preferably present in the form of the alkali
metal salts or ammonium salts.
Styrene oxide adducts according to the present invention are suitable for a wide range of
uses in textile application, such as pretreatment, dyeing or finishing. Nonionic unesterified
products are useful in particular as assistants in the dyeing of wool-containing fibre
materials with anionic dyes or dye mixtures. The corresponding acid esters, in particular
dicarboxylic monoesters or acid esters of sulfuric acid, by contrast, are used in particular
as wetting agents and foam suppressants in aqueous systems, in particular in the dyeing of
natural or synthetic fibre material, primarily in the dyeing of cellulose textile materials,
polyester fibres or natural or synthetic polyamide fibre materials. Both as nonionic
products and as acid esters, the styrene oxide adducts according to the present invention
improve, if formulated as described, the affinity of the dyes and thereby speed up the
diffusion of the dyes into the fibre.
The present invention accordingly also provides a method for processing natural or
synthetic fibre material in the presence or absence of appropriate dyes, which comprises
processing in the presence of the nonionic and/or anionic styrene oxide adducts according
to the present invention.
The amounts in which the styrene oxide adducts according to the present invention are
added to the processing liquors, such as dyeing liquors or pretreatment or after treatment
liquors, vary with the substrate, advantageously between 0.5 and 20 g, preferably between
1 and 10 g, per litre of liquor.
Advantageous formulations of the styrene oxide adducts according to the present
invention contain them as nonionic and/or anionic products with or without water in
combination with nonionic or anionic dispersants, fatty alcohols, fatty acid amides,
aLIcylene bis fatty acid amides, aL~yl alkenyldicarboxylates, metal stearates, silicone oils,
e.g. -diaLkylpolysiloxanes, or even mineral oils or aLkanolamines in stable, wetting and/or
defoaming preparations. Such preparations are also capable of virtually completely
deaerating aqueous systems. It is thus possible to avoid air inclusions not only in the
application baths but also in the substrates. Such deaeration makes it possible to avoid
spotting in dyeing and finishing.
Preference is given to aqueous or water-free preparations which, based on the preparation
Z~ 99
as a whole, comprise
(A) 2 to 50 % by weight of an acid ester of the product of the addition of styrene oxide to a
polyalkylene glycol ether of the formula (1),
(B) 5 to 50 % by weight of a nonionic surfactant, preferably an aliphatic mono alcohol
having 6 to 22 carbon atoms or the product of the addition of 2 to 80 moles of ethylene
oxide to 1 mole of an aliphatic mono alcohol having 6 to 22 carbon atoms or a
polyoxyethylene derivative of a sorbitan fatty acid ester or a styrene oxide adduct of the
formula (2) or mixtures thereof and at least one of the following components:
(C) 1 to 30 % by weight of a silicone oil, for example a diaL1cylpolysiloxane such as
dimethylpolysiloxane,
A ` (D) 10 to 60 % by weight of a mineral oil, for example a paraffin oil such as Shell oil L
6189 or mineral oils Esso~301 to 312,
(E) 20 to 45 % by weight of a dialkyl ester of an ethylenically unsaturated aliphatic
dicarboxylic acid, preferably containing 4 to 12 carbon atoms per each alkyl moiety,
e.g. bis-2-ethylhexyl maleate or bis-2-ethylhexyl citraconate,
(F) 10 to 70 % by weight of a diffusion accelerant, in particular an aliphatic or aromatic
carboxylic ester such as C4-CI2alkyl lactate, C4-Cl2alkyl benzoate, phenyl benzoate or
benzyl benzoate, or else an alkylbenzene, such as trimethylbenzene or ethylbenzene,
(G) 0.5 to 5 % by weight of a salt of a C10-C24fatty acid and a polyvalent metal, e.g.
magnesium distearate, calcium dibehenate or aluminium tristearate, and
(H) 0.5 to 3 % by weight of a Cl-C4alkylenediamide of a fatty acid having 10 to 24 carbon
atoms, e.g. methylenebis-stearamide, ethylenebis-stearamide or ethylenebis-behenamide.
Further preferred aqueous preparations, which are in particular used as assistants for
dyeing natural or synthetic polyamide fibres, especially wool, with anionic dyestuffs,
comprise, based on the preparation as a whole,
(a) 15 to 50 % by weight of a nonionic styrene oxide adduct on a polyalkylene glycol
ether of the formula (1), in particular a styrene oxide adduct of the formula (2),
raa~-~7a ok
399
(b) 1 to 5 % by weight of an acid ester or salt thereof, for example an alkali metal or
ammonium salt, of a compound of the formula
lz~ lz~
(CH-CH-O~H
(5) R'-N
( ICH- ICH-O~zH
Z' Z"
or a quaternized product of the acid ester or salt thereof, where R' is alkyl or alkenyl
having 12 to 22 carbon atoms, one of Z' and Z" is hydrogen, methyl or phenyl and the
other is hydrogen and sl and s2 are each integers such that their sum, sl + s2, is from 2 to
100,
(c) 2 to 10 % by weight of a quaternary ammonium compound of the formula
z z
~CHCHO~H e
(6) R~ An
I f
Z'Z"
where R" is an alkyl or alkenyl radical having 12 to 22 carbon atoms, V' is a substituted or
unsubstituted alkyl, such as methyl, ethyl, benzyl or -CH2CONH2, one of Z' and Z" is
hydrogen, methyl or phenyl and the other is hydrogen, Ane is an anion of inorganic or
organic acid, and Pl and P2 are each integers such that the sum of Pl and P2 is from 2 to
100, with or without one or more of the following components:
(d) 0.5 to 25 % by weight of a polyalkylene glycol ether of the formula
(7) R"'-O (allylene-O~H
where R"' is an alkyl or aLkenyl radical having 4 to 22 carbon atoms, "alkylene" is
ethylene or propylene, and q is from 2 to 85, and
(e) 0.5 to 5 % by weight of a nitrogen-containing nonionic compound of the formula
20~;~i3~9
- 8 -
(8) H- ~CH-~-(CH2CH2-O~H
ye Y CH2-ÇH2
I
CH-CH-N-CH2~CH2
Y'Y" I
R"-N (CH2CH20~H
where R" is an aLtcyl or alkenyl radical having 12 to 22 carbon atoms, one of Y' and Y" is
phenyl and the other is hydrogen, and x and y are each integers such that the sum of x and
yisfrom80to 140.
Further details and preferred combinations and use forms of components (b), (c), (d) and
(e) may be found in DE-A-1,568,258, DE-A-1,619,385, EP-A-89004 and EP-A-312493.
In the preparation and use examples below, percentages and parts are by weight, unless
otherwise stated. The dye quantities are based on commercial, i.e. extended material, and
the auxiliary quantities are based on pure substance.
Preparation examples
Example 1: 163.8 g of a product of the addition of 4 moles of ethylene oxide to 1 mole of
Cg-Clloxo alcohol (OH number: 171) are mixed with 3.3 g of 96 % sulfuric acid, the
mixture is heated to 65C. 60 g of styrene oxide are then added dropwise in the course of
35 minutes, during which the temperature rises to 87C. The reaction product is
subsequently stirred at 75C for S hours, neutralized with sodium bicarbonate solution and
filtered. The filtrate is concentrated, and the residue is dried. The result obtained is a
yellowish, clear product of the formula
(11) Cg-Cll-allyl-O-(CH2CH20)-ClH-CH2-OH
~3
OH number: 127
Example 2: a) 350 g of the product of the addition of 35 moles of ethylene oxide to 1 mole
2~ 9
of stearyl alcohol (OH number: 32) are mixed with 5.6 g of 96 % sulfuric acid, and the
rnixture is heated to 70C. 24 g of styrene oxide are then added dropwise at 70-75C in the
course of 30 minutes. The mixture is then stirred at 75C for 8 hours and then neutralized
with sodium bicarbonate solution and filtered. The filtrate is concentrated, and the residue
is dried. The result obtained is a product which is waxy at room temperature and has the
formula
(12) cl8H37-o-(cH2-cH2-o~fH-cH2-oH
OH number: 30
b) 185 g of the product of the formula (12) prepared as per (a) are heated to 70C and are
mixed with 10 g of urea. 10 g of sulfamic acid are added after 15 minutes, and the mixture
is stirred at 80C for 1 hour and at 95C for 2 hours. The reaction product is then diluted
with 307.5 g of water and stirred at 65-70C until everything has dissolved. The result
obtained is a product which is gellike at room temperature and which has the formula
(13) C18H37-0~CH2-CH2-O~fH-CH2-O-SO3NH4
~3
Example 3: 112 g of the styrene oxide adduct of the formula (12) prepared as per Example
2(a) are slowly heated to 70C with 6.0 g of maleic anhydride and stirred at that
temperature for 1 hour. The reaction mixture is then stirred at 90C for a further 3 hours.
The result obtained is a product which is waxy at room temperature and has the formula
(14) cl8H37-otCH2-cH2-o3}cH-cH2-o-co-cH=cH-cooH
Acid number: 29
;~0~$~99
- 10-
Example 4: 105 g of the reaction product of 1 mole of C9-Cl loxo alcohol with 6 moles of
ethylene oxide and 6 moles of propylene oxide (OH number: 115) are mixed with 1.9 g of
96 % sulfuric acid, and the mixture is heated to 65C. 25.8 g of styrene oxide are then
added dropwise in the course of 15 minutes, during which the temperature rises to 86C.
The reaction product is then stirred at 75C for 5 hours, and thereafter neutralized with
sodium bicarbonate and filtered. The filtrate is concentrated, and the residue is dried. The
result obtained is a brownish, slightly cloudy product of the forrnula
(15) C9-Cll-alkYI-O~CH2CH20~CH2-CIH-0 6~1H-CH2-OH
~3
OH number: 96
Example 5: 184 g of the product of the addition of 2 moles of ethylcne oxide to 1 mole of
isononyl alcohol (OH number: 243) are mixed with 4.2 g of 96 % sulfuric acid, and the
mixture is heated to 65C. 96.0 g of styrene oxide are then added dropwise in the course of
60 minutes, during which the temperature rises to 81C. The reaction product is
subsequently stirred at 75C for 5 hours, neutralized with sodium bicarbonate solution and
filtered. The filtrate is concentrated, and the residue is dried. The result obtained is a
yellowish, clear product of the formula
(16) iso-CgHlg-O~CH2CH20tfH-CH2-OH
~3
OH number: 159
Example 6: 190 g of the product of the addition of 4 moles of ethylene oxide to 1 mole of
isononyl alcohol (OH number: 176) are mixed with 3.9 g of 96 % sulfuric acid, and the
mixture is heated to 65C. 72 g of styrene oxide are then added dropwise in the course of
60 minutes, during which the temperature rises to 80C. The reaction product is
subsequently stirred at 75C for 5 hours, neutralized with sodium bicarbonate solution and
9~3
filtered. The filtrate is concentrated in a rotary evaporator, and the residue is dried. The
result obtained is a yellowish, clear product of the formula
(17) iso-CgHl9-O~CH2CH2O}CH-CH2-OH
OHnumber: 119
Example 7: 200.5 g of a product of the addition of 6 moles of ethylene oxide to 1 mole of
isononyl alcohol (OH number: 139.6) are mixed with 3.9 g of 96 % sulfuric acid, and the
mixture is heated to 65C. 60 g of styrene oxide are then added dropwise in the course of
40 rninutes, during which the temperature rises to 83C. The reaction product issubsequently stirred at 75C for 5 hours, neutralized with sodium bicarbonate solution and
filtered. The filtrate is concentrated in a rotary evaporator, and the residue is dried. The
result obtained is a yellowish, clear product of the formula
(18) iso-CgHlg-O~cH2cH2otfH-cH2-oH
OH number: 105
Example 8: a) 288.5 g of a product of the addition of 9 moles of ethylene oxide to 1 mole
of tridecyl alcohol (OH number: 97) are mixed with 5.6 g of 96 % sulfuric acid, and the
mixture is heated to 70C. 60 g of styrene oxide are then added dropwise at 70-75C in the
course of 30 minutes. The mixture is subsequently stirred at 75C for 8 hours and
neutraliæd with sodium bicarbonate solution and filtered. The filtrate is concentrated, the
residue is dried. The result obtained is a product which is waxy at room temperature and
has the formula
;~oa~s
- 12-
(19) C13H27-0~CH2CH203 CH-cu2~0H
~3
OH number: 78
b) 185 g of the product of the formula (19) prepared as per (a) are heated to 70C and
mixed with 10 g of urea. After 15 minutes, 10 g of sulfamic acid are added, and the
mixture is subsequently stirred at 80C for 1 hour and at 95C for 2 hours. The reaction
product is then diluted with 307.5 g of water and stirred at 65-70C until everything has
dissolved. The result obtained is a product which is gellike at room temperature and has
the formula
(20) cl3H27-o{cH2cH2 ICH-CH2-O-SO3NH4
Example 9: 818.5 g of the product of the addition of 20 moles of ethylene oxide to 1 mole
of oleyl alcohol (OH number: 52) are mixed with 4.2 g of 96 % sulfuric acid and the
rnixture is heated to 65C. 91 g of styrene oxide are then added dropwise in the course of
60 minutes, during which the temperature rises to 81C. The reaction product is
subsequently stirred at 75C for 5 hours, neutralized with sodium bicarbonate solution and
filtered. The filtrate is concentrated in a rotary evaporator, and the residue is dried. The
result obtained is a yellowish, clear product of the formula
(21) Oleyl-O ~H2CH20tCH-CH2-OH
OH number: 47
Example 10: 88.2 g of the product of the formula (11) prepared as per Example 1 are
heated to 70C and mixed with 20.8 g of urea. After 15 minutes, 20.6 g of sulfamic acid
99
- 13-
are added, and the mixture is stirred at 80C for 1 hour and at 95C for 2 hours. The
reaction product is then diluted with 129.6 g of water and stirred at 65-70C until
everything has dissolved. The result obtained is a product which is gellike at room
temperature and has the formula
(22) Cg-CII-Alkyl-O~CH2CH2OtCI H-CH2-0-S03NH4
The procedure of Examples 2, 3 and 10 is repeated using appropriate starting materials to
obtain the following anionic styrene oxide adducts of the formulae (23), (24), (25) and
(26):
(23) Cl3H27-o~cH2cH2 ouch cH2 o SO3NH4
~3
(24) Cl8H35-~CH2CH2-O~cH-cH2-o so3NH4
(25) cl3H27-OtCH2CH2-O~fH-CH2-o-co-cH=cH-cooH
Acid number: 70.6
99
- 14-
(26) Cl3H27-OtCH2CH2-OtCH-CH2-O-Co-cH=cH-cooH
Acid number: 65
Exarnple 11: 361 g of ethylene glycol monobutyl ether are heated together with 1.84 g of
boron trifluoride etherate to 50C. 240 g of styrene oxide are then added dropwise in the
course of 1 hour, during which the temperature rises to 85C. The reaction mixture is then
stirred at 85C for 15 minutes and thereafter cooled down to room temperature. After the
excess ethylene glycol monobutyl ether has been distilled off, the residue is subjected to
fractional distillation under a high vacuum. The result obtained is 230 g of a colourless
product of the following formula
(27) C4Hs-O-CH2CH2-O-CH-CH2-OH
b.p.: 118-120C/10-2 OH number: 252
Example 12: 14.2 g of phosphorus pentoxide are added at room temperature with vigorous
stirring to 66.3 g of the adduct of formula (27) obtained as described in Example 11. In the
course of the addition, the temperature rises to 90C. The reaction mixture is then stirred
at room temperature for 4 hours. The result obtained is a clear and viscous product which
constitutes a mixture of compounds of the formulae
OH
(28a) C4HgO-CH2-CH2-O- I H-CH2-O-P-O
9~
C4Hg-O-cH2-cH2-o-f H-CH2-
(28b) [I !o
C4Hg-O-cH2-cH2-o-cl H-CH2-
The procedure of Examples 11 and 12 is repeated using the appropriate starting materials
to obtain the following styrene oxide adducts of the formulae (29), (30a) and (30b):
(29) c4HgOtCH2-CH2O)-cH-cH2oH
b.p.: 68-70C/10-2 OH number: 194
Mixture of mono- and diphosphoric-esters of the forrnulae
/o}~
(30a) C4HgOtCH2-CH2-O~lH~CH2~~P~
~3
zo~99
- 16-
C4H9-o-(cH2-cH2-otcl H-CH2-
(30b) \p-o
/
C4H9-o-(cH2-cH2-otfH-cH2-o
~3
Example 13: 508 g of the product of the addition of 3 moles of propylene oxide and 5
moles of ethylene oxide to 1 mole of dodecanol (OH number: 127.5) are mixed with 9.7 g
of methanesulfonic aid, and the mixture is heated to 70C. 138.8 g of styrene oxide are
then added dropwise at 70-80C in the course of 90 minutes. Thereafter the mixture is
stirred at 80C for 3 1/2 hours and then neutralized with sodium bicarbonate solution and
filtered. The filtrate is concentrated, and the residue is dried. The result obtained is a
yellowish, clear product of formula
(31) C12-H250-(CH2-~CH-O~CH2 CH2 OH CH20H
CH3
OH number: 90
Example 14: 483 g of the product of the addition of 8 moles of ethylene oxide to 1 mole of
Cg-Clloxo alcohol (OH number: 116) are mixed with 9 g of 96 % sulfuric acid, and the
mixture is heated to 65C. 12~ g of styrene oxide are then added dropwise in the course of
60 minutes, during which the temperature rises to 82C. The reaction mixture is
subsequently stirred at 75C for 5 hours, neutralized with sodium bicarbonate solution and
filtered. The filtrate is concentrated, and the residue is dried. The result obtained is a
yellowish, clear product of the formula
~0~ 99
(32) c9-cll-AlkyltcH2-cH2-o~fH-cH2-oH
OH number: 91
Use examples
Example 15: 100 g of wool serge are wetted out in a circulation machine at 40C in the
course of 15 minutes with a liquor comprising 1.1 litres of water and the following
additives:
3.2 g of 80 % acetic acid
5.0 g of calcined sodium sulfate
1 g of the styrene oxide adduct of the formula (11) prepared as described in Example 1.
5 g of the dye Acid Black 172 C.I. 15711 are then added. After 10 minutes, the dyeing
liquor is heated to 85C in the course of 45 minutes, and the textile material is maintaine
at that temperature for 60 minutes with constant circulation. The textile is then rinsed and
dried. A deep and fast black dyeing is obtained on the wool without the conventional
heaeing to the boil. The final liquor is viItually colourless. The fastness properties
correspond to a dyeing at the boil (98C).
Example 16: A circulation dyeing machine is entered with 100 kg of wool packages on a
spindle support. In the make-up vessel, 1200 l of water are heated to 60C. A solution is
prepared therein of 1200 g of an aqueous preparation which, based on the preparation,
contains
12 % of silicone oil, for example dimethylpolysiloxane,
15 % of 2-ethyl-n-hexanol
15 % of paraffin oil
2 % of a water-soluble, surface-active siloxaneoxyalkylene copolymer
8 % of the maleic halfester prepared as described in Example 3 and
2 % of the styrene oxide adduct prepared as described in Example 9, and which has been
adjusted to pH 8 with monoethanolamine. The liquor is then pumped from the make-up
;~OC~$~99
vessel through the material into the dyeing machine and subsequently circulated in
alternating direction. Owing to the addition of the product, the dyeing system is
spontaneously deaerated and consequently the textile material is thoroughly penetrated.
Thereafter 2 kg of the dye of the formula
NH--CH3
S03H
(101) CH2 =C--CO--NH~--N=N~
Br HO
S03H
are added to the liquor, followed by 1 kg of a 1:1 mixture of the
chloroacetamide-quaternized product of the addition of 7 moles of ethylene oxide to 1
mole of a Cl6-CI8fatty amine mixture and the ammonium salt of the sulfuric acid ester of
the product of the addition of 7 moles of ethylene oxide to 1 mole of a Cl6-CI8fatty amine
mixture (50 % aqueous preparation), the dyeing is heated to the boil in the course of 30
minutes, and the wool is dyed at the boil for 60 minutes. Virtually no foam develops
during dyeing. The result obtained is a strong and uniform dyeing of the package.
The preparation used in this Example is prepared as follows:
12 parts of silicone oil are dissolved in 15 parts of 2-ethylhexanol. 15 parts of paraffin oil,
2 parts of water-soluble, surface-active siloxaneoxyalkylene copolymer, 8 parts of the
maleic half ester prepared as described in Example 3, 2 parts of the styrene oxide adduct
prepared as described in Example g, 47.6 parts of water and 0.4 parts of
monoethanolamine are then added with continuous stirring, and the mixture is
subsequently stirred for a further 30 minutes. The result obtained is a stable formulation
having a wetting, deaerating and in particular foam-suppressing effect.
ZOCI 19
- 19-
Example 17: In a winch beck, 100 kg of cotton knitwear are wetted out in 3000 l of water
containing 3 kg of an aqueous preparation containing, based on the preparation,
7 % of a silicone oil
11 % of 2-ethylhexanol and
11 % of the sulfuric acid ester prepared as described in Example 10. The cotton is
completely wetted and deaerated within 30 seconds. 2 kg of a dyestuff of the formula
NUN
503H OH NH~ NH2
(102) ~=~N =N
H03S S03H
are then added to the liquor together with customary chemicals such as electrolytes and
alkalis, and the knitwear is then dyed at the boil for two hours. There are no problems with
foaming. The dyed material has a uniform and non-spotty shade.
The composition used in the Example is prepared as follows:
First, 70 parts of silicone oil are dissolved in 110 parts of 2-ethylhexanol at room
temperature. 110 parts of the sulfuric acid ester prepared as described in Example 10 are
then added, followed 30 minutes later by 710 parts of water, and thereafter the mixture is
stirred for a further 30 minutes. The result obtained is a stable product having excellent
wetting and deaerating properties.
Example 18: In a short liquor jet, 100 kg of cotton tricot are wetted out in 600 litres of
water at 40C. The liquor is then turned into a dyebath by adding 36 kg of sodium
chloride, 5 kg of the dye of the formula (102) and 0.5 kg of a preparation containing
186.75 g of mineral oil (for example Shell Oil L 6189),
185 g of bis-2-ethylhexyl maleate,
g of magnesium distearate,
8.25 g of N,N-ethylenebisstearamide,
g of a polyoxyethylene derivative of sorbitan tristearate with 20 oxyethylene
æoo~99
- 20 -
units,e.g.Tween 65, and
g of the sulfuric acid ester prepared as described in Example 8.
The textile material is dyed at 40C for 45 minutes. 0.6 kg of calcined sodium carbonate is
then added, followed after a further S minutes by 1.2 kg of aqueous 36 % sodium
hydroxide solution. The tricot is then dyed for a further 40 minutes, and then rinsed and
washed. The result obtained is a fast, level red dyeing on the tricote. During the dyeing
process, there is no foarn and there are no problems with the circulation of the textile
material.
The preparation used in this Example is prepared as follows:
186.75 g of mineral oil, 185 g of bis-2-ethylhexyl maleate, 10 g of magnesium distearate
and 8.25 g of N,N-ethylene-bisstearamide are heated with continuous stirring at 110C
until a clear solution is obtained. The solution is cooled down to 45C in the course of 5
minutes, and 55 g of a polyoxy ethylene derivative of sorbitan tristearate with 20
oxyethylene units, e.g. Tween 65, and 55 g of the sulfuric acid ester prepared as described
in Example 8 are dispersed therein. The result is a stable formulation which is very
effective in particular as an antifoam in alkaline liquors and at high shearing rates.
Example 19: 100 parts of polyester fabric are introduced into a hot dyeing liquor at 60C
containing 1300 parts of water, 2 g/l of ammonium sulfate, 2.5 parts of dye of the formula
Cl NH~
(103) N2 ~--N8N~ ~_NH--CH2CH3
N02 NH--CH2CH20H
and 2 parts of an assistant formulation consisting of
16 parts of the maleic monoester prepared as described in Example 3,
24 parts of the product of the addition of 18 moles of ethylene oxide to 1 mole of a
Cl2-Cl8fatty alcohol mixture and
60 parts of benzyl benzoate
~ra6/~ k
'~OC~99
- 21 -
and has been adjusted to pH 5 with formic acid. The liquor temperature is raised to 130C
in the course of 30 minutes and left at that level for 60 minutes.
The liquor is then cooled down to 70C, and dropped, and the polyester fabric is rinsed.
Even without the customary reduction clearing a level and rub-fast red dyeing is obtained
with a high colour yield.
The assitant formulation used in this Example is prepared as follows:
In a heatable stirred vessel, 60 parts of benzyl benzoate are heated to 60C with
continuous stirring, and 24 parts of the product of the addition of 18 moles of ethylene
oxide to 1 mole of a Cl2-CIgfatty alcohol mixture and 16 parts of the maleic monoester
prepared as described in Example 3 are then stirred in. Cooling down to room temperature
leaves a stable formulation which is suitable in particular for dyeing polyester fibres.
Example 20: 100 parts of textured polyester yarns in package form are introduced into an
HT dyeing machine which contains 800 parts of hot water, 40C, 2 parts of ammonium
sulfate, 4 parts of a dye of the formula
CH3
(104) HO--CH2CH2~N=N~LN=N C OH
OCH3
.
and 2 parts of the assistant formulation described in Example 19 and whose liquor has
been adjusted to pH 5.5 with formic acid. The temperature of the liquor is then raised to
128C in the course of 40 minutes, and the textile material is dyed at that temperature for
60 rninutes.
During the heating-up phase no increase in the differential pressure between the inside and
the outside of the yarn package is detectable. Thereafter the liquor is cooled down to 70C,
and the substrate is as usual Teduction cleared, rinsed and dried. The result obtained is a
strong and level orange dyeing which is notable for good penetration and good fastness
properties.
Z00~399
Example 21: 100 g of wool serge are wetted out in a circulation machine, for example an
Ahiba-turbomat, at 40C in the course of 15 minutes with a liquor comprising 1.1 Iiters of
water containing the following additions:
3.2 g of 80 % acetic acid
S g of calcined sodium sulfate
2 g of an aqueous preparation containing, based on this preparation, 30 % by weight
of the styrene oxide adduct of the formula (11) prepared as described in
Example 1,
10 % by weight of the assistant mixture Al described in EP-A-0089004 and
20 % by weight of triethylene glycol monobutyl ether.
4 g of the dye Acid Black 172 C.I. 15711 are then added. After 10 minutes, the dyeing
liquor is heated to 90C in the course of 50 minutes, and the textile material is kept at that
temperature with continuous circulation for 60 minutes. The textile material is then rinsed
and dried.
The result obtained is a deep, level and fast black dyeing on the wool. The dye bath is
95 % exhausted, although the dyeing is carried out at 90C. The fastness properties
correspond to those of a conventional dyeing at the boil (98C).
~raa~e,~k
