JPS6012891B2 - Alkylaryl sulfonate-containing emulsifier composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to emulsifier compositions and their uses.

Alkylaryl sulfonates are widely used as multipurpose emulsifiers, including in the formulation of emulsifying lubricating compositions for use in metalworking processes. Natural product sulfonates have been used for many years. Although these are not expensive materials, they have defects. For example, their quality and therefore their emulsifying properties are not very constant. In order to improve the emulsifying power of these known sulfonate salts, it is customary to combine them with a second surfactant of a different type, in particular of non-ionic type or consisting of a fatty acid salt. However, to obtain consistent results, the amount of these second compounds required will vary depending on the quality of the sulfonate salt used. One of the objects of the present invention is to provide alkylaryl sulfonates with improved properties.

The present invention provides an emulsifier composition containing a salt of an alkylarylsulfonic acid and an organic base or an inorganic base, in which the acid comprises an alkylarylsulfonic acid having an average molecular weight M, and an alkylarylsulfonic acid having an average molecular weight M2. Including, M, is 270 or more, M2 is 350 to 600
, the difference M2 - M, is 80 or more, the alkyl group of the alkylarylsulfonic acid is a branched alkyl group, and a salt from an acid with an average molecular weight M and a salt from an acid with an average molecular weight M2. This is an emulsifier composition characterized in that the weight ratio of

The previously known alkylaryl sulfonates are mixtures of homologous compounds.

In these mixtures, the molecular weight distribution is mostly Gaussian (G
following either a female s) or a Poisson distribution. Since "C" is the concentration in the mixture of components having a molecular weight of M, the function C=f(M) exhibits one and only maximum value. The novel alkylarylsulfonic acid salts which form the object of the present invention are salts of alkylarylsulfonic acids with inorganic or organic bases, the molecular weight of the acid being according to a function C=f(M) with two different maxima. to be distributed.

The sulfonate salt of the present invention may be a salt with an inorganic base or a salt with an organic base.

Preferred inorganic salts are sodium salts. however,
Ammonium salts, rarely other alkali metal salts, or alkali metal salts are also possible. Organic bases that can be used are nitrogenous bases, such as primary, secondary or tertiary amines,
These include polyamines and alkanolamines. Preferred organic bases are monoethanolamine, diethanolamine,
Triethanolamine and mixtures of these ethanolamines. Generally the value of M is at least 27
Must be 0.

The value of M can be 270-360, preferably 270-400, more preferably 360-4
It is 00. Generally, the value of M2 needs to be 350 to 600, preferably 450 to 550.

According to an important feature of the invention, the difference M2-M is at least 80, preferably in the range 80-350.

The difference M2 - M is in the range of 80 to 350, especially 80 to 22
Particularly effective emulsifier compositions are obtained when the range is 0, with the latter two ranges being particularly preferred. The overall average molecular weight of the alkylaryl sulfonic acid contained in the alkylaryl sulfonic acid salt composition according to the invention is selected as a function of the nature of the base with which it is incorporated and the particular use intended for the emulsifier.

The most preferred total average molecular weight depends, among other things, on whether the organic layer to be dispersed in water is more or less polar. In most cases the total average molecular weight is between 300 and 550, preferably 3
00-500, more preferably 375-500. The alkylaryl sulfonic acid salt according to the present invention comprises an alkylaryl sulfonic acid salt containing an alkylaryl sulfonic acid having an average molecular weight of M, and an alkylaryl sulfonic acid salt containing an alkylaryl sulfonic acid having an average molecular weight of M2 in an appropriate ratio. It can be manufactured by mixing with

They can also be prepared by neutralizing a mixture containing an alkylaryl sulfonic acid having an average molecular weight of M and an alkylaryl sulfonic acid having an average molecular weight of 1 with a base in a suitable proportion.

The alkylaryl sulfonate according to the present invention can be obtained by further sulfonating a mixture containing an aromatic hydrocarbon having an average molecular weight of M.180 and an aromatic hydrocarbon having an average molecular weight of M2-80 in an appropriate ratio. It can also be produced by neutralizing sulfonic acid with a base.

The alkylaryl sulfonic acids derived from the sulfonate salts according to the invention may be of the same type as those obtained by sulfonation of the appropriate fraction of crude oil.

Preferred are sulfonate salts derived from alkylarylsulfonic acids obtained by sulfonation of alkylbenzenes.

By alkylbenzene is meant benzene itself, the alkylation products of benzene congeners of up to 10 carbon atoms, such as toluene, xylene, and ethylbenzene, where the alkylating agent is an olefin, olefin oligomer, or chlorinated paraffin of a suitable average molecular weight. It is. According to another important feature of the invention, the alkyl group of the alkylaryl sulfonate is a branched alkyl group.

Unexpectedly improved emulsion stability is often found in such cases. Therefore, it is preferred that at least a portion of the emulsifier composition according to the invention is made of a branched alkyl type compound. It is preferable that the composition mainly consists of such a compound, and it is most preferable that the composition consists entirely of such a compound. Highly preferred are alkylaryl sulfonates derived from benzene and o-xylene, especially where the alkyl groups are branched, such as when propylene oligomers are used as alkylating agents. Preferred emulsifier compositions according to the invention have unexpected advantages, particularly in emulsion stability, and in many cases are superior to known sulfonate salts.

Furthermore, as mentioned above, they can be manufactured to substantially constant quality. Contains a low average molecular weight salt consisting of C8-C,6 alkyl (especially branched chain alkyl) o-xylene sulfonic acid and a high molecular weight salt consisting of C,8-C28 alkyl (especially branched chain alkyl) benzenesulfonic acid. Compositions are particularly preferred. More preferably, each of the above groups is C,o-C,6 and C2o-C28.

Particularly preferred compositions are obtained when the groups in question are respectively C,2-C,6 and C2o-C. It is most preferred in all cases that these alkyl groups are branched chain alkyl groups. In all cases the sodium salt is the preferred compound. One particular range of compositions having particularly preferred emulsion stability is an average molecular weight range of 360 to 400, preferably 370, in which the alkylaryl residue is the alkylation product of o-xylene with a propylene tetramer. ~395, more preferably 370-3
80 and 'b} alkylaryl residues are on average 2 per molecule.
Alkylation products of benzene with propylene oligomers having 4 carbon atoms, average molecular weight range 500-5
30, preferably from 515 to 530, more preferably about 520.

For such compositions, the total average molecular weight is between 400 and 52.
Particularly preferred compositions have a total average molecular weight of about 410-42, about 430-450, about 480.
~510.

The proportions of each component in the composition according to the present invention are M, 95 to 5% by weight of the salt of the acid, and 5 to 95% by weight of the salt of the base acid.
The most preferred range is .

Other suitable ranges are: [11] 90-10% on one side and 10-90% on the other, '2} 80-20% on one side and 20-80% on the other. Usually, alkylaryl sulfonates are very viscous substances and it is therefore advantageous to dilute them during or after their manufacture with a suitable diluent/solvent, such as a hydrocarbon oil of the light lubricating oil type.

In the present invention, the emulsifier composition contains 50 to 95% by weight and a solvent/diluent such as a light lubricant having a viscosity of 20 to 4 centistokes at 40 qo.
Concentrates containing % by weight are included within the scope of this invention. However, unless otherwise specified, the emulsifier compositions herein refer to sulfonate salts only, and any solvents/solvents deemed desirable to facilitate handling of the sulfonate salts may be used.
Nor is there any mention of diluents. Yet another feature of the invention provides an emulsifiable mineral oil composition comprising a natural oil and an emulsifier composition as described above.

Natural oil having a viscosity of 5 to 10 ratio St at 40°C is a dropper.

An unexpected and particularly advantageous rule obtained by the present invention is that the emulsifier composition used is one of the particularly preferred compositions described herein, when the mineral oil is of the naphthenic type, This means that it is not necessary. Thus, for example, according to the invention 1 to 5% by weight of one or more extreme pressure lubricants, 1 to 5% by weight of one or more corrosion inhibitors and 0.1 to 3% by weight of one or more or more of a fungicide and 10 to 5% by weight of an alkylaryl sulfonate salt as described herein, with a viscosity of 5% at 40qC.
-10 ratio St key oils, particularly naphthenic oil-based metalworking cutting oils are provided.

By dispersing this cutting oil in water, a stable aqueous emulsion for metal working can be obtained. This emulsion is also within the scope of the invention and contains 90 to 99%, preferably 9.
It can contain 5-98% water. The following non-limiting examples illustrate the features of the invention.

All proportions stated in these examples are calculated by weight.
All concentrates considered in these examples contained 60% active substance.
% and diluent 40%. The diluent was a hydrocarbon oil characterized by a viscosity of 3 St at 4000. Example 1 Alkylaryl sulfonate concentrate XI was prepared according to the invention by mixing 73% Concentrate A and 27% Concentrate B.

Concentrate A contained 60% sodium alkylbenzene sulfonate having an average molecular weight of 370 prepared from the alkylation product of o-xylene and technical propylene tetramer.

Concentrate B contained 60% sodium alkyl bezene sulfonate with an average molecular weight of 520 prepared from the alkylation product of benzene and propylene oligomers.

The average carbon content of this oligomer was 2 hearts per molecule. Concentrate XI thus contains 60% sodium alkylbenzenesulfonate with an average molecular weight of 405, and its molecular weight distribution is 2 with molecular weights of 370 and 520.
It showed two maxima.

Example 2 Concentrate A 75% and Concentrate C 25% as specified in Example 1
A concentrate X2 of alkylaryl sulfonate was prepared according to the present invention by mixing.

Concentrate C contained 60% sodium alkylbenzene sulfonate with an average molecular weight of 580 and was prepared from the alkylation product of o-xylene and propylene oligomers. The average carbon content of this propylene oligomer was 27 atoms per molecule. Therefore, concentrate X2 is 60% sodium alkylbenzenesulfonate with an average molecular weight of 405.
The molecular weight distribution showed two maxima corresponding to molecular weights of 370 and 580. Example 3 Concentrate X3 of alkylaryl sulfonate was prepared according to the invention by mixing 65% of Concentrate D and 35% of Concentrate B as defined in Example 1.

Concentrate D contained 60% sodium alkylbenzenesulfonate with an average molecular weight of 300 and was prepared from the alkylation product of benzene and technical propylene trimer.

Concentrate X3 therefore contained 60% sodium alkylbenzeso sulfonate with an average molecular weight of 353, but its molecular weight distribution showed two maxima corresponding to molecular weights of 300 and 520.

Test Example The emulsifying power of the alkylbenzene sulfonates X1, X2, and X3 defined in the above example for natural oil dispersed in water was compared with the emulsifying power of various commercially available alkylaryl sulfonates.

Naphthenic oils obtained from crude oil by conventional distillation and refining operations were used to conduct these tests.

This oil had a viscosity of 37.800 and 27 cSt. The hardness of the water used was 2 (France hardness).

Each magazine test was conducted according to the following test method.

Mix 1 part by weight of the concentrate to be tested with 4 parts by weight of oil.

5 parts by weight of the emulsifiable composition thus prepared are dispersed in 95 parts by weight of water. The resulting emulsion is left for 7 days at 20 qC in a stoppered graduated test tube. An emulsion is considered stable if the volume of the salting out phase (oil or cream) after 7 days is less than 1% of the total volume of the emulsion.

The emulsions obtained with products X1, X2 and x3 are stable under these conditions.

Under the same conditions, five commercially available alkylaryl sulfonates obtained by sulfonating mineral oils each having individual peaks in the average molecular weight range of 350 to 550 were tested.

None of these alkylaryl sulfonates gave stable emulsions. In addition, under the same conditions, Examples 1 to
Alkylbenzenesulfonate A, B, C specified in 3.
and D were tested.

When all of these sulfonates were used separately, more than 4% by volume was dissolved. Among the concentrates mentioned above, concentrate XI of Example 1 was found to give the most desirable emulsifying properties.

However, when C24 benzene sulfonate was replaced by C,8 benzene sulfonate, the stability of the resulting emulsion was much lower. This shows that it is a highly desirable feature that the difference M2-M, as described herein, should be at least 80. Concentrate X2 has less desirable properties than XI and contains components of the type designated by XI (
That is, it is shown that unexpected effects can be obtained by using a high molecular weight benzene type and a low molecular weight o-xylene type.

The above results are shown in Table 1.

Examples 4-6 (i) 8% by weight of the diethylamine salt of a C,2 alkyl orthoxylene sulfonic acid was mixed with 1% by weight of the diethylamine salt of a C24 alkylbenzenesulfonic acid (Example 4).

(ii) % by weight of the monoethanolamine salt of C,2 alkyl orthoxylene sulfonic acid 7 and % by weight of the monoethanolamine salt of C24 alkylbenzenesulfonic acid 3;
(Example 5).

(iii) 45% by weight of the jetanolamine salt of a C,2 alkyl orthoxylene sulfonic acid was mixed with 55% by weight of the jetanolamine salt of a C alkylbenzenesulfonic acid (Example 6).

20% by weight of the compositions of Examples 4, 5 and 6 above were dissolved in naphthenic oil, 5% by weight of this oil was mixed with 95% by weight of water, emulsified and allowed to stand.

In all examples, phase separation was 1% by volume after 4 field hours. Example 7 The following test shows that the difference in average molecular weight must be greater than or equal to 80.

A mixture of sodium dodecyl (C,2) orthoxylene sulfonate and sodium C24 alkylbenzene sulfonate (difference in molecular weight of 150) was prepared to obtain composition E with an overall average molecular weight of 405.

This was compared to Composition F, which had an overall average molecular weight of 405, prepared from sulfonate salts with a molecular weight difference of 55. Mix 1% by weight of composition (E or F), 4% by weight of naphthenic oil, and 95% by weight of water. It was measured as the time required for % phase separation to occur.

Phase separation of composition E with a molecular weight difference of 150 did not occur even after 24 hours, but phase separation of composition F with a molecular weight difference of 55 did not occur even after 24 hours.
occurred within hours. Furthermore, using sulfonate salts with a molecular weight difference of 55, emulsifier compositions having various overall average molecular weights were prepared and their emulsion stability was measured, but in all cases, stable naphthenic oil emulsions were obtained. It was not possible to obtain. Example 8 The following tests demonstrate that the emulsifier compositions of the present invention do not require the non-sulfonate cosurfactants traditionally used to achieve emulsion stability. It is.

The stability of an emulsion is expressed as the time required to cause phase separation of 1% by volume in an emulsion obtained by mixing 5% oil in 20% tap water.

Comparisons were made with equal emulsifier active ingredient to oil ratios. Composition of Comparative Example Emulsifying oil composition of emulsifier High amount of active ingredient) (high weight) Mahogany-) V form, phosphate 2 2.0 1
1.0 (molecular weight 465, active ingredient 50 weight) Soda・
Rosin soap 3.5 3.5 (cosurfactant) C,2 alkynolebenzene 1.5
1.5 Sodium phosphate mineral oil
73.0 Total 100.0 16.0 Emulsifying oil composition of the composition emulsifier of the present invention Active ingredients (*) (Hitomi) CI2 Anonkylorthoxylene, sodium oxate 2 0.0 12
．． 0 (active ingredient 60% by weight) C24 alkylbenzene
6.7 4.0) Sodium Panphonate Mineral Oil 73.3 Total 100.0 16.0 1% by volume phase separation of these compositions occurred after 10 holding periods.

In the above comparative example, the stability of the composition of the invention without the soap and with the same ratio of sulfonate to oil was investigated.

Comparative Example Composition Emulsifying Oil Composition Active Ingredients (Hitomoko) (Hitomoko) Mahogany Cov Lephonate (Active Ingredient 50% by Weight) 2 2.0 11.0
C,2 Anomethylbenzene 1.5
1.5 Genjutsu Acid Nashu Mineral Oil 76.5 total loo. 0 12.5 1% by volume phase separation of this composition occurred after 6 minutes.

Emulsifying oil composition active ingredient of the composition of the present invention (Hitomikyo Hitota) C,2-alkynohyorthoxylene 1 5.6
9.4) ◇Sodium lephonate (active ingredient 60 weight association) C,2 alkylbenzene 5.2 3.
Sodium phonate (active ingredient 60 wt.) Mineral oil 79.2 Total 100.0 12.5 1% by volume phase separation of this composition occurred after 2 hours.

Claims (1)

[Claims] 1. An emulsifier composition containing a salt of an alkylarylsulfonic acid and an organic base or an inorganic base, wherein the acid contains an alkylarylsulfonic acid with an average molecular weight M_1 and an alkylarylsulfonic acid with an average molecular weight M_2, and M_1 is 270 or more, M_2 is 350-6
00, the difference M_2 - M_1 is 80 or more, the alkyl group of the alkylaryl sulfonic acid is a branched chain alkyl group, and the salt from the acid with an average molecular weight M_1 and the salt from the acid with an average molecular weight M_2 Weight ratio is 5:95-95:
An emulsifier composition characterized in that the emulsifier composition is within the range of 5.