Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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This application is a divisional of Canadian
application Serial No. 248,779, filed March 25, 1976.
The present invention relates to biodegradable non-
ionogenic emulsifiers with a high emulsifying effect and a wide
range of applications.
For ecological reasons biodegradable emulsifiers are
attaining ever greater importance. Known biodegradable non-
ionogenic emulsifiers include fatty acid glycerides, fatty acid
esters of mono- and polysaccharides and sugar alcohols as well
as alkyloxylated, especially ethoxylated natural or synthetic
fatty alcohols, acids and acid amides.
However, for many applications these emulsifiers
cannot prove satisfactory, since the stability of the emulsions
produced with these emulsifiers or the effectiveness with regard
to the required quantity of emulsifier and with regard to the
emulsion production often leave much to be desired. With
ethoxylated products a usable emulsifying effect is only obtained -
with fairly high degrees of ethoxylation. But biodegradability
deteriorates with an increasing degree of ethoxylation.
The invention relates to biodegradable emulsifiers
including straight chain alkyl sulphonic acid ethanol- and
isopropanol amides and tensides which emulsifiers avoid the
disadvantages mentioned.
According to the present invention, there is provided
an emulsifier comprising
a compound of the formula I
R - SO2- NH - CH2 - CIH - OH
1 (I)
-- 1 --
wherein R represents a straight chain C8 to C30 alkyl radical
which is unsubstituted or substituted by chlorine, and R
represents a hydrogen atom or a methyl radical, and
an anion-active, cation-active or non-ionogenic tenside.
The present invention also provides an emulsified
composition comprising water, at least one oil-soluble compound
in solution, and an emulsifier as described above.
The present invention further provides a process
for the production of emulsified compositions characterized
in that an oily and an aqueous phase are emulsified by the
use of an emulslfier as described above.
Preferably, R represents a straight chain C10-C20
alkyl radical, optionally substituted with chlorine.
The ethanol- and isopropanol-amides can be produced
according to known processes from the alkyl- or ehloroalkyl-
sulphonie aeid esters or preferably from the sulphonie aeid
ehlorides by reaetion with ethanolamine or isopropanolamine
(see Houben-Weyl, 4th Edition, vol. IX, p 398).
The alkylsulphonie aeid ehlorides ean be regarded as
espeeially preferred starting materials for reaetion with
ethanolamine and isopropanol -amine, being formed by the
sulphoehlorination of straight ehain alkanes or ehloroalkanes
having 8 - 30 C-atoms, preferably 10 and 20 C-atoms. The
individual steps of sulphoehlorination are familiar to all
skilled men, e.g. from F. Asinger on the ehemistry and
teehnology of paraffin hydroearbons, 1956, Akademie-Verlag-Berlin,
pp. 395-474.
.. ~ . .
The production of the alkylsulphonic acid ethanol-
and isopropanol amides can however also be carried out from the
sulphone amides, which are reacted with ethylene oxide or
propylene oxide or with ethylene- or propylene chlorohydrine
in a manner known from the literature to form the alkylsulphonic
acid ethanol- or isopropanolamides.
The emulsifiers according to the invention are
biodegradable. Depending on their carbon number they are oil-
viscous or wax-like. In their pure form they are only soluble
in water with some difficulty, but dissolve well in organic
solvents such as methanol, ethanol, benzene, toluene, petro-
ether, ligroine, acetone and acetic acid ester. Tensides
facilitate the usability of alkylsulphonic acid alkanol
amides in water by working with water to form a solution.
This combination of alkylsulphonic acid alkanol
amides and tensides has an increased emulsifying effect over the
alkylsulphonic acid alkanol amides alone. All conventional
anion-active, cation-active and non-ionogenic tensides can be
used here, e.g. salts of fatty acids or other surface-active
carboxylates, alkylsulphates, alkylsulphonates, quaternary
ammonium salts, amine oxides, esters of mono- and polysaccharides
and alkoxylated alcohols, phenols, alkylphenols, alkylcarboxylic
acids, alkylcarboxylic acid amides and alkylsulphonic acid
amides.
These various tensides are described in detail in K.
Lindner's "Tenside, Textilhilfsmittel, Waschrohstoffe",
Wissenschaftliche Verlagsgesellschaft mbH, Stuttgart 1964 and
are familiar to every skilled man. However, alkarylsulphonates
or alkylsulphonates are used in preference, with the latter
occurring to a large extent as alkali- or alkanolamine salts
as by-products in the production of alkanol amides and being
contained in the emulsi-fiers according to the invention.
The production of the emulsions can be effected by
the stirring together of the oily and aqueous phase with the
emulsifier or by other conventional pub]ished processes
(P. Becker, Emulsions: Theory and Practice, Reinhold Publishing
Corp., New York, 1957, p. 209, Houben-Weyl, vol. I 2, p. 97).
It proves to be of advantage here that the alkylsulphonic acid
alkanolamides are soluble in organic solvents, so that they
can also be applied in an organic phase. Thus the emulsifier
can be prepared in the oily or aqueous phase and second phase
can be stirred in. Alternatively, the emulsifier-free phase
can be prepared and the emulsifier-containing oily or aqueous
phase can be emulsified while stirring after the addition of the
emulsifier of the invention simultaneously by stirring. Finally,
it is also possible to produce the emulsions by any other feed
process.
A particular advantage of the emulsifiers of the
invention is that as a rule in the production of the emulsions
only simple stirrers are necessary. This achieves a considerable
simplification of the process in comparison with other
biodegradable emulsifiers.
A further advantage relative to other emulsifiers is
that emulsions produced with the alkylsulphonic acid alkanol-
amides have only a very slight tendency to foaming. This proves
to be especially favourable when the emulsions are produced
with high power or turbine stirrers, because if high-foam
emulsifying systems are used with this method the foam
generated is too great for practical use.
The emulsifiers according to the invention can be
added in the desired quantity to the phase to be emulsified.
The quantities employed are determined according to the desired
emulsifying effect. It can fluctuate within wide limits and
depends on the phase to be emulsified. Preferably 0.01 - 50%
by weight, and in particular 0.1 - 20% by weight of alkyl-
sulphonic acid alkanolamide compound are used relative to thephase to be emulsified.
The emulsions produced with the emulsifiers according
to the invention exhibit outstanding emulsion stabilities. In
the event of separation due to a long period of storage, this
is reversible, light stirring restores the original emulsion.
A very great variety of emulsions can be produced with
the emulsifiers according to the invention. But they are
preferably used in those areas in which non-ionogenic
emulsifiers are described, e.g. for the emulsification of anti-
aging agents, softeners and other auxiliaries for the rubbersector, of biologically effective substances in the plant
protection field and of dyeing, textile and leather auxiliaries
and in polymerisation technology.
The emulsifiers according to the invention can also
be used in emulsion polymerisation, in which case, the tensides
are preferably alkali- or alkanol-amine salts of alkyl or
alkylarylsulphonic acids. They lead to separation-free latices
without hindering radical polymerisation in the case of high
monomer conversions. In cases in which with current emulsi-Eiers
no coagulate-free latices are obtained, it is possible by means
of the partial replacement of the emulsifier used by the
emulsi-fier according to the invention, to arrive at separation-
free latices. In addition, higher monomer conversions are often
achieved by also using the emulsifiers according to the invention
in emulsion polymerisation.
Monomers for aqueous emulsion polymerisation include
all radically polymerisable olefinically unsaturated compounds,
e.g. mono- and diolefines, such as ethylene, propylene, butadiene,
isoprene, 2-chlorobutadiene-1,3, styrene, vinyl toluene ~-
methylstyrene, chlorostyrene, vinylsulphonic acid and
divinylbenzene; vinyl halides such as vinyl chloride and
vinylidene chloride; vinyl esters of straight-chain and branched
chain aliphatic carboxylic acids, such as vinyl acetate,
propionate, _-butyrate, -pivalate, -laurate and -stearate;
vinyl ethers such as vinylmethyl-, -ethyl-, -n-butyl- and -sec.
-butylethers; esters of the acrylic and methacrylic acids of
mono or polyolene, such as methylacrylate and -methacrylate,
ethylacrylate and -methacrylate, butylacrylates and -methacry-
lates, hexylacrylates and -methylacrylates, 2-ethylhexyl-
acrylate and -methacrylate, _-decylacrylate and -methacrylate,
_-dodecylmethacrylate, glycolmono-acrylate and -methacrylate,
butanediole-1,4-acrylate and -methacrylate, ethyleneglycol-
bis-acrylate and -methacrylate and trimethylolpropane-tris-
acrylate and -methacrylate; diesters and semi-esters of
~ 3~ ~
unsaturated dicarboxylic acids, such as maleic, fumaric and
itaconic acid-di- and mono-methyl-, -ethyl-, butyl- and
hexylester, ~,~-unsaturated di- and monocarboxylic acid, such
as acrylic, methacrylic, crotonic, maleic, fumaric and itaconic
acid; amides, methylolamides, and alkoxymethylarnides of these
~,~-unsaturated di- and monocarboxylic acids, such as acryl-
amide, methacrylamide, maleic acid amide, maleic acid imide,
methylene-bis-acrylic and methacrylic amide; N-methylolacryl-
and methacrylamide, N-methoxymethylacryl- and methacrylamide;
allyl compounds such as diallylphthalate and heterocyclic
compounds such as N-vinyl phthalimide, n-vinyl-pyrrolidone and
N-vinylimidazol. The monomers can be used alone or in
combination with one another.
The emulsion polymerisation can be initiated with
radical forming substances, preferably with organic peroxide
compounds, which are used in quantities of from 0.01 to 2% by
weight, relative to monomers. Depending on the monomer
combination, in order to lower the molecular weight of the
polymer, small quantities of regulators can also be used,
e.g. mercaptans, halide hydrocarbons. The emulsion poly-
merisation is possible in two ways: the total quantity of themonomers and the greater part of the aqueous phase containing
the emulsifiers can be prepared, polymerisation can be started
by the addition of an initiator and in the course of poly-
merisation the rest of the aqueous phase can be added
continuously or at intervals. It is also possible to employ the
"Monomer feed" technique, by which only a part of the monomers
and the aqueous phase containing the emulsifying agent are
prepared and then artcr polymerisation is started the rest of
the monomers and the aqueous phasc are added evenly or at
intervals according to the proportion o-f the reaction. The
proportion of monomers added can be pre-emulsified in the
aqueous phase. Both processes are known.
The following example illustrates the invention:
Example
200 g Styrene, ~00 g demineralised water, 8 g Na-
alkyl-sulphonate (mersolate * K 30) and 2 g of a straight chain
C12-C18-alkylsulphonic acid ethanolamide mixture were prepared
in a 2 litre three necked flask with stirrer and reflux
condenser. The contents of the flask were flushed with nitrogen
and then heated to 95C and activated with a solution of 0.2 g
potassium peroxidisulphate in 10 g demineralised water. After
the initiation of the reaction the mixture was stirred for
half an hour and then within one hour the following solutions
were added evenly at 95C internal temperature:
1) a solution of 0.4 g potassium peroxidisulphate in 100 g
water; and
2) a solution of 0.2 g triethanolamine in 80 g water. After
the termination of the addition process the mixture was
restirred for a further two hours at 95C.
A polymer emulsion was obtained which was free from
coarse or fine precipitates and the monomer conversion was 100%.
In a comparision test under otherwise identical reaction
*Trade mark - 8 -
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conditions, in which however no alkylsulphonic acid ethanolamidewas used, 10 g mersolate K 30 being used exclusively as the
emulsifier, only a 98% monomer yield was achieved. In addition,
this comparision contained a larger quantity of coagulate.
