DE2339991A1 - DETERGENTS AND DETERGENTS - Google Patents

Description

Priority: August 8, 1972, Japan, No. 78 803/72

The invention relates to a new detergent and cleaning agent having a superior synergistic effect over a wide range the proportions of the components.

Detergent and cleaning agent made from a mixture of a sulfated one higher fatty alcohol-ethylene oxide adduct and an alkanesulfonate are known. These cleaning agents are used in particular in the household as dishwashing detergents. The sulfated higher fatty alcohol-ethylene oxide adduct is derived from a primary alcohol. Detergent and cleaning agent from a sulfated higher primary alcohol-ethylene oxide adduct and an alkylbenzenesulfonate develop the highest cleaning effect, when the alkylbenzenesulfonate content in the v / ash-active

409809/1092

Substances is 70 to 80 percent. With increasing content of sulfated higher primary fatty alcohol-ethylene oxide adduct the detergency decreases considerably, and the optimum range of the mixing ratio is very narrow.

The object of the invention is to create detergents and cleaning agents which are made from a mixture of sulfated higher fatty alcohol-ethylene oxide adducts en and alkanesulfonates exist, and those in a wide range of the quantitative ratio of the components develop a high washing and cleaning power. This object is achieved by the invention. The invention lies based on the finding that to solve this problem, a mixture of sulfated higher secondary fatty alcohol ethylene oxide Adducts and alkanesulfonates are suitable.

Sulphated higher secondary fatty alcohol-ethylene oxide adducts were hitherto not available in uniform quality because the reactions used to produce them are not uniformly reproducible was. They were also considered unsuitable for economic reasons. Furthermore, one has been for several years endeavors to create detergents and cleaning agents that do not contain a benzene ring in the washing-active substances, since such compounds, hereinafter referred to as benzene derivatives, cannot be biodegraded. It was determined, that a mixture of an alkanesulfonate and a sulfated higher secondary fatty alcohol-ethylene oxide adduct washing and Detergents that are biodegradable result

Area through a superior cleaning effect in a wide, from

Mark out the proportions and do not cause skin irritation

4 0 9 8 0 9/1092

call.

The invention is accordingly a washing and

is cleaning agent that is characterized by a content of a

Mixture of

(a) about 5 to about 85 percent by weight of a sulfated higher secondary fatty alcohol-ethylene oxide adduct with 1 to 8

,. · "Lenoxide groups and ^ O to ^Λ 6 7.ο?" .?: ι -: ^ ::: ™ atoms in the secondary alcohol residue and

(b) about 95 to about ^-1 J% by weight ::. normal alkanesulfonate having 10 to 20 carbon atoms.

Components (a) and (b) of the detergent and cleaning agent can be in the form of salts, e.g. as sodium, potassium, ammonium or alkanolamine salt, such as the mono-, di- and trimethanolamine, mono-, di- and triethanoiamine, mono-, di- and tripropanolamine and mono-, di- and triisopropanolamine salt. The use and production of such salts is known.

The higher secondary fatty alcohols with 10 to 16 carbon atoms can be produced by oxidation of n-paraffins with 10 to 16 carbon atoms. You have the general formula

^ - CH - (CH ₂ ) _m -

OH

in which η + m + 3 has a value from 10 to 16. η and m are whole numbers. These secondary Fe ^J "tc, i;: onc_e are on the market

L ■

409 "-

BATHROOM OFMGINAL.

available under different names, e.g. as "Tergitol", "Softanol" and "Unitöl".

The sulfated higher secondary fatty alcohol-ethylene oxide adducts can in a manner known per se, e.g. according to the process given in US Pat. No. 2,870,220. This However, the process is not uniformly reproducible.

According to the invention it was found that higher secondary fatty alcohols are used -Ethylene oxide adducts can sulfate smoothly and reproducibly if these compounds are used under very mild reaction conditions, e.g. at normal pressure by reaction with chlorosulfonic acid at low temperatures or by treatment with a gas containing sulfur trioxide at low temperatures below. Use of conventional thin-film reactors brings to implementation. These methods are also the subject of the invention.

For example, obtained in the reaction of a solution of a higher sec-fatty alcohol ethylene oxide adduct at a temperature of -5 ° C with 1.2 equivalents of chlorosulfonic acid under in the solution for a period of about 2 hours at -5 ⁰ C Stirring are added dropwise, and subsequent separation of the hydrogen chloride formed by introducing air into the reaction mixture and neutralization with sodium hydroxide solution at a temperature of at most 50 ^° C. a valuable product of the general formula

J ^ 09809/1092

CH ₅ - (CH ₂ ) _n - CH - (CH ₂ ) _m - CH ₃ •. O- (C ₂ H ₄ O) ₅ SO ₃ H

in which m and η have the above meaning and ρ a whole Is a number with a value from 1 to 8. The reaction proceeds smoothly at normal pressure.

The alkanesulfonate used for the detergents and cleaning agents of the invention can be prepared by the following methods will:

1. Sulphoxidation of unbranched alkanes

An unbranched alkane is made with sulfur dioxide and oxygen in the presence of a free radical initiator or under irradiation with high-energy light, the radicals able to form, implemented. The sulfoxidation proceeds according to the following reaction scheme:

HH + SO ₉ ■ + ϊθρ ^ RSO ^ H

2 ^

R denotes an unbranched alkyl radical with 10 to 20 carbon atoms.

2. Sulfochlorination of unbranched alkanes

An unbranched alkane is made with sulfur dioxide and chlorine in the presence of a free radical initiator or under irradiation with high-energy light that is able to form radicals, converted. The resulting sulfonyl chloride is saponified. The reaction takes place according to the following reaction

scheme:

4 098 0 9/1092

RH + SO ₂ + Cl ₂ : ^ RSO ₂ Cl + HCl

RSO ₂ Cl + 2HaOH ■ ^. RSO ₃ Na + NaCl + H ₂ O

R has the above meaning.

3. Addition of a hydrogen sulfite to an α-01efin The reaction proceeds according to the following reaction scheme:

Rl / ΤΓΓ / "TTT JT \ T« - * TXQA ^ v Γ? I Α "Η" Γ * ΤΤ QA Τ \ Γα

011 = 0x1- + JMaribU "- τ -K- O rt_ Orip ßu " JN a

R ¹ denotes an unbranched alkyl radical having 8 to 18 carbon atoms.

• *

k. Oxidation of a mercaptan produced from an oc-olefin and hydrogen sulfide according to the following reaction scheme:

R ¹ CH = CH ₂ + H ₂ S> R ¹ CH ₂ CH ₂ SH ^ R ¹ CH ₂ CH ₂ SO ₃ H

R ¹ has the above meaning.

5. Reaction of an unbranched alkyl chloride with sodium sulfite according to the following reaction scheme:

RCl + Na ₂ SO ₃ > RSO Na + NaCl

R has the above meaning.

Of the processes described above, the processes indicated under (1) and (2) are carried out industrially. In particular the sulfoxidation (1) is an economically advantageous process. The preparation of the alkanesulfonates by Sulphoxidation is explained below. j

409809/1092

A mixture of η-paraffins with an average molecular weight of about 222 and with 13 to 18 carbon atoms in the molecule, and where 70 percent of the alkanes contain 15 Ms 17 carbon atoms, water, sulfur dioxide and oxygen, is in an amount ratio of 1000: 700: 235 ι 49 weight parts / hour fed continuously into a reaction vessel equipped with a high-pressure mercury lamp is that emits 3,000 to 5,000 2 ultraviolet light. During the reaction, oxygen gas and sulfur dioxide are added to the mixture initiated from alkane and water. The mercury lamp is with about 100 watts / 1 kg / hour. Alkane charging operated. The reaction temperature is generally 35 ° C and the residence time about 1 hour. The reaction mixture consists of n-paraffins, Water, sulfur dioxide, sulfuric acid, alkane monosulfonic acids and alkanedisulfonic acids in the ratio of 675: 674-: 40: 149: 407: 39 parts by weight / hour The selectivity of the Formation of the alkanesulfonic acids is about 87 mole percent per mole

Mole

converted alkane and about 41 percent pro / converted sulfur dioxide. The reaction products obtained are neutralized with sodium hydroxide solution and then purified and used as alkali metal salts the alkane mono- and alkane disulphonic acids separated. For example, if the reaction mixture is mixed with methanol, the reaction mixture separates into two layers. The unreacted η-paraffins are in the upper layer. After separating the two layers, residual sulfur dioxide is released by blowing oxygen into the lower layer separated from an alkanesulfonic acid mixture and a aqueous methanol solution of sulfuric acid. The solution obtained is neutralized with sodium hydroxide solution and cooled

409809/1092

The crystallized sodium sulfate (Glauber's salt) is filtered off and the filtrate is freed from residual n-alkanes by extraction with η-hexane. Then the sodium salt of
Alkanesulfonate can be spray-dried.

Preferred washing and cleaning agents of the invention contain components (a) and (b) in a weight ratio of 70 to 10:30 to 90. In this range of weight ratio, the washing and cleaning power is constant and at a maximum. Investigation of the detergency of the detergent and cleaning agent of the invention according to the method described below has shown that the detergency is about three times higher than that of component (a) and about 2.5 times higher than that of
Component (b) ..

The same cleaning test was carried out on a washing and cleaning agent containing (a) the sulfated higher secondary fatty alcohol-ethylene oxide adduct and (c) an alkene sulfonate with 10
contains up to 20 carbon atoms in the same proportion. This mixture develops the greatest cleaning power when
the components are present in the same quantitative ratio. the
However, the cleaning effect drops to about 1/3 of the value if
component (a) is used alone. Thus, the optimum range of the mixing ratio within which the
greatest synergistic effect is achieved extremely closely.

Furthermore, a detergent and cleaning agent is used for comparison
made, which consists of / component (b) and (d), namely / sulfa-

oriented higher primary fatty alcohol-ethylene oxide adduct with _j

AO9809 / 1092

1 to 8 moles of ethylene oxide and 10 to 16 carbon atoms in the alcohol residue, and examined for its cleaning ability. It was found that the maximum cleaning effect this detergent is at a mixing ratio of (b): (d) of 25:75, but that the detergency is reduced to about 70 percent of the cleaning power of the detergents and cleaning agents according to the invention. Also in this Trap is the optimal range of the mixing ratio ses with the greatest synergistic effect extremely narrow.

From the above it follows that the detergents and cleaning agents of the invention have a surprisingly high cleaning power develop due to a synergistic effect within a wide range of the proportions of the constituents and maintained within this range.

A detergent and cleaning agent with a sulfated secondary fatty alcohol-ethylene oxide adduct and an alkene sulfonate does not give good results. A detergent and cleaning agent an alkanesulfonate and a sulfated primary fatty alcohol-ethylene oxide adduct on the other hand, is only valuable in a narrow range of the mixing ratio of the constituents. In contrast, the detergents and cleaning agents of the invention have the advantage that they can be used in a relatively wide range of mixing ratios can be prepared, according to the cost of the starting compounds, the requirements of biodegradability and reduction regarding skin irritation.

4 09809/1092

Washing and cleaning agents of the invention contain the washing-active substances in such an amount that a sufficient cleaning effect is achieved. For household use, the cost and risk of skin irritation play a role. Taking all these factors into account, liquid detergents and cleaning agents of the invention contain about 50 parts of the mixture of detergent substances per 100 parts of water. Such liquid detergents and cleaning agents preferably contain about 15 to about 40 parts of the mixture of washing-active substances per 100 parts of water. These values can be varied over a relatively wide range. In general, however, detergents and cleaning agents with at least about 10 parts of the mixture of washing-active substances per 100 parts of water give good results. Instead of water can also alcohols, such as ethanol, propanol or isopropanol, _f in an amount of about 5 to 10 weight percent, based on the total weight of the washing and cleaning agent used ground v /.

The detergents and cleaning agents can also contain other surfactants, such as alkyl sulfates, other known sulfated fatty alcohol-ethylene oxide adducts, Alkylolamides, fatty alcohol-ethylene oxide adducts or the sodium salt of p-toluenesulfonic acid, for Enhancement of the foaming, to improve the solubilization, to reduce the cloud point or the viscosity or to reduce skin irritation. These additives can be added to the detergent and cleaning agent, e.g. in an amount of up to approx 50 percent by weight can be incorporated. A specific example of such a detergent and cleaning agent has the following Composition:

.'Ό98 0 9/1092

Sodium salt of a sulfated 31 parts by weight sec-fatty alcohol-ethylene oxide adduct sodium salt of an alkanesulfonate 41 parts by weight Alkylolamide 28 parts by weight

This mixture is dissolved in the appropriate amount of water.

Typical alkylolamides that can be used have the general formula

C _n H _{2n + 1} CON (CH ₂ CH ₂ OH) ₂
where η is an integer with a value of 12 Ms 16.

To improve the sales value of detergents and cleaning agents these may also contain dyes, opacifiers or a perfume in small quantities.

The example illustrates the invention.

example

In the proportions given in Table I, the sodium salt of a sulfated higher secondary fatty alcohol-ethylene oxide adduct is used an average of three ethylene oxide groups and 14 to 15 carbon atoms in the secondary alcohol residue ("Unitol 45-S-3S "), hereinafter referred to as component A, with a Mixture of sodium alkanesulfonates with 13 to 18 carbon atoms in the alkyl radical, with 60 percent of the alkyl radicals containing 15 to 16 carbon atoms ("Hostapur-SAS"), hereinafter referred to as component B, mixed. The mixture is diluted with water to form a 20 percent strength by weight aqueous solution. With the aqueous solutions obtained, plates soiled with oil are rinsed under constant conditions, and the cleaning effect is determined ". _j

409803/1092 '

For comparison, a sodium salt of an α-olefin sulfonate, that differs from an α-olefin having 16 to 18 carbon atoms ("Soft Detergent-85")> hereinafter as component C. referred to, with the. Component A mixed in the same proportions.

Furthermore, the sodium salt of a sulfated fatty alcohol-ethyl oxide adduct from a mixture of primary alcohols with 11 up to 15 carbon atoms ("Diadol") and an average of 3 mol Ethylene oxide, hereinafter referred to as component D, mixed with component B in the same proportions. An aqueous solution of the detergent and cleaning agent is also produced from these mixtures. Furthermore, with these Solutions performed the same cleaning test. The results are shown in Table II.

The cleaning test is carried out as follows: 2 g of an oil made from a mixture of 40 parts by weight of beef fat, 60 parts by weight of soybean oil and 0.1 part by weight Rosaniline is evenly applied to flat plates with a diameter of 220 mm. A solution of 3 g of the 20 percent aqueous detergent and cleaning agent solution in 1500 ml of water is placed in a metal sink, and 500 ml of water are poured into the rinsing water from a height of 500 mm in order to make the rinsing solution foam. The front of each plate is covered 20 times with a cotton rag measuring 200 χ 200 mm and 5 times on the Wiped back in the rinse solution. The number of plates that are washed with the rinse water is determined

409809/1 092

can until the foam bubbles disappear and the average values are determined in order to determine the behavior of the washing and washing machine To evaluate cleaning agent. The results are summarized in Tables I and II.

409809/1092

Table I.

Weight ratio (A) Weight ratio of (A): parts

O 5 10 20 30 40 50 60 70 80 85 90 100

(B) or (C)

Weight 100 95 90 80 70 60 50 40 30 20 15 10 0

share

Number of plates,
which rinsed with (B)
can be 5 12th 13.5 14 * 1 13th , 5 14th 13.5 13th 12th 8th 6th 4.5 Number of plates,
which rinsed with (C)
can be 1 1 1 1 1 , 5 1 »5 2 2 2.5 3 4th 4.5

Ca) GO CD CD

Table II

- 15 -

Weight "(B) Weight- _{1 (χ)}

naxT-ms from ΐ6ΐχ6

or (D) _{(A) or (D)}

_{gQ 8Q}

_{20 15 10 0}

Weight - 0 5 10 20 30 40 50 60 70 80 85 90 100 parts

Number of dishes that ■ 'with (A) can be rinsed

12 13.5 14 14 13.5 14 13.5 13 12 8 6 4.5

Number of plates that can be washed with (d) 6.5 8 9 10 8.5 7

3.5 3.5 3 3 2.5

CO CO CO

The results of these comparative tests are also shown graphically in FIG. 1 for the mixture (A) - (B) and (A) - (C) and in FIG 2 given for the mixture (A) - (B) and (A) - (D). On the ordinate of Figure-.1 and Figure 2, the number of plates is given, that can be rinsed. On the abscissa of Figure 1 and Figure 2 are the parts by weight of components (A), (B), (C) and (D) indicated.

From Table I it can be seen that when combining

(A) with (B) a strong synergistic effect can be observed compared to component (A) or (B) alone, namely in a wide range of mixing ratios of (A) and (B). The mixture of components (A) and (C) could be independent no synergistic effect can be achieved by the mixing ratios. This can be seen clearly from FIG.

From Table II it can be seen that with the mixture of components (B) and (D) a synergistic effect can be achieved. However, the maximum value is only 70 percent of the cleaning capacity the combination of components (A) and (B). Furthermore, this synergistic effect of the combination of

(B) and (D) achieved only in a very narrow range.

409809/10 9 2

Claims (4)

Claims η \ detergents and cleaning agents, characterized by a content of a mixture of (a) about 5 to about 85 percent by weight of a sulfated higher secondary fatty alcohol-ethylene oxide adduct with 1 to 8 ethylene oxide groups and 10 to 16 carbon atoms in the secondary alcohol radical and (b) about 95 to about 15 weight percent of an alkanesulfonate with 10 to 20 carbon atoms. 2. Washing and cleaning agent according to claim 1, characterized in that that the weight ratio of components (a): (b) is 70-10: 30-90. 3. Washing and cleaning agent according to claim 1, characterized in that that components (a) and (b) are in the form of the sodium, potassium, ammonium or alkanolamine salts. 4. Washing and cleaning agent according to claim 1, characterized in that that component (a) as a sodium, potassium, monoethanolamine, diethanolamine or triethanolamine salt or whose mixture is present. 5. Washing and cleaning agent according to claim 1, characterized in that that component (a) as a mixture of the sulfated higher secondary fatty alcohol-ethylene oxide adducts 10 to 16 carbon atoms is present in the secondary alcohol residue. 40 9'8 09/1092 7339991 6. washing and cleaning agent according to claim 1, characterized in that that component (a) as a mixture of the sulfated higher secondary fatty alcohol-ethylene oxide adducts with 14 up to 15 carbon atoms is present in the secondary alcohol residue. 7. Washing and cleaning agent according to claim 1, characterized in that component (a) an average of three
Contains ethylene oxide groups. 8. detergent and cleaning agent according to claim 1, characterized in that component (b) as sodium, potassium,
Monoethanolamine, diethanolamine or triethanolamine salt or a mixture thereof is present. 9. Washing and cleaning agent according to claim 1, characterized in that that components (a) and (b) are present as sodium salts. 10. Washing and cleaning agent according to claim 1, characterized in that that it also contains water. 11. Washing and cleaning agent according to claim 10, containing about 10 to about 50 parts by weight of the mixture of components (a) and (b) per 100 parts by weight of water. 12. Washing and cleaning agent according to claim 10, containing 15 to 40 parts by weight of the mixture of components (a) and (b) per 100 parts by weight of water. 4 09809/1092