DE1809690A1 - Detergent mixtures - Google Patents

Description

'18 096 9ö

LAWYERS DR-JUR-DIPL-CHEM-WALTErBEII

ALFRED HOE ?? ENER 18 NOV. 1968

DR. JUX DIPL-CHSM. H.-J. WOLFF

DR. JUR. HAI, 3 CHR. AX

FRANKFURTAM MAIN-HOCHST

ADELONiTRASSEM

Our no.15178

Chevron Research Company San Francisco, CaI., V.bt.A.

Detergent mixtures.

The present invention relates to the field of biodegradable sulfonate detergents, particularly biodegradable Rapidly degradable olefin sulfonates with improved cleaning properties (detersive).

Because of their important property, biodegradability, Currently, linear alkyl benzene sulfonates are the main active ingredient in household diets. While olefin sulfonates are more biodegradable than linear alkylbenzene sulfonates, they were bisner with respect to the cleaning properties cannot be compared with these.

The present invention provides novel, readily biodegradable high-performance olefin sulfonate detergent mixtures, which are suitable to replace linear alkylbenzenesulfonates.

Bs was surprisingly found that ternary mixtures of Olefin sulfonates with 11 to 19 carbon atoms, alkali or Ammonium salts of pentavalent phosphoric acid and alkanol-1-

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~ ^{> Γ} "ORIGINAL

Compounds with 10 to 15 carbon atoms and both normal and 2-methyl isomers, unusually strong cleaning agents Possess properties. In particular, the ternary mixtures described show a significantly higher efficiency than was to be assumed based on the performance of corresponding binary mixtures or the respective individual components. The mechanism is based on the interaction of olefin sulfonates, alkali salts of pentavalent phosphoric acids and alkanols improved cleaning properties are not known. It is known, however, that to achieve the beneficial effect all three ingredients are required.

^{The term 11} olefin sulfonate as used in the present invention denotes a mixture which consists of 50-100% saturated olefin sulfonates. If the proportion of unsaturated olefin sulfonate is less than about 100 $, the remainder of the mixture consists essentially of hydroxysulfonates. Smaller amounts of others Compounds can also be present in the form of the impurities contained in the olefin feeds or caused by the side reactions of sulfonation. The relative proportions of hydroxy and unsaturated sulfonate vary depending on the method of preparation used "Reaction of Phosphate-Complexed Sulfur Trioxide with Alpha-Olefins" in Industrial and Engineering Chemistry, Product Research and Development 2, No. 3,229 (1963) described process an olefin sulfonate which consists essentially of 100 <? O unsaturated olefin sulfonate. Usually the amount of hydroxysulfonate is in the range I from 0 to 50 wt .-%, preferably less than 40 wt .-% of the total olefin sulfonates. The content of unsaturated sulfonates may be in the range of from to 100 wt .- ^ throughout the olefin, preferably the unsaturated sulfonates are more than 60 io of the total olefin.

The preparation of the olefin sulfonates according to the invention takes place by! sulfonation of straight-chain or normal olefins with 10 to 24 carbon atoms, usually with 11 to 19 carbon atoms,

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preferably with 15 to 18 carbon atoms. Individual olefins (carbon outs of olefins) that are within this range, e.g., hexadecene-1, can also be used. As olefins internal or alpha olefins can be used. Preferably however, alpha-olefins are used. The sulfonation can be carried out durohge by any suitable method that provides the right amounts of hydroxy and unsaturated sulfonates.

The preferred method of making the olefin sulfonates consists in SO-z-Luft sulfonation in one Layer reaction vessel (falling film reactor), neutralization and saponification or hydrolysis of the neutralized product. The reaction products of SO, air sulfonation can with an aqueous alkali solution containing a strongly basic compound, e.g. sodium hydroxide, potassium hydroxide, ammonium hydroxide, contains the corresponding oxides, carbonates and the like, be neutralized. A sufficient amount of the neutralizing solution is used for the subsequent hydrolysis Scheduled. The Hydrol ^ ou of the Neutralized Reaction Products yields the olefin sulfonates according to the invention.

Usually the suIfon conditions cause the migration of the double bond in the unsaturated sulfonates and determine the distribution of the position of the double bonds. Table 1 shows the analysis of an SO-2 air sulfonated alpha-olefin fraction useful in the present invention with 15 to 18 carbon atoms.

Table 1:

Product composition, after saponification

Alkene sulfonates,% ^a 53

Hydroxysulfonate,% ^a 47 RCH = CH- (CH ₂ ) XSO ₅ Na

χ mol $>

0 9

1 21st

2 16

⁵ I.

4 6

^{5 6} 9 09832/1318

6th 7th 7th 6th 8th 7th 9 8th 10 9

Table 1 (port setting):

^a Including disulfonatesn

The sulfonation also gives various isomers of the hydroxysulfonates. As the beta- or 2-hydroxysulfonates in water are fairly insoluble, it is preferable to use those processes "in which these are only formed to a small extent. A suitable method is described by Marquis et al, "Alpha Olefin Sulfonates from a Commercial SO-z-Heactor", JAOCS, Vol. 43, No. 1, Pp. 607-614, 1966. British Patent 1,030,648 describes another applicable sulphonation process.

The olefin sulfonates prepared according to the invention can be modified by mild hydrogenation to give hydrogenated olefin sulfonates. Hydrogenated olefin sulfonates, alone or in mixtures with olefin sulfonates, provide excellent active ingredients useful in the present invention. As a result of the hydrogenation of the olefin sulfonates, essentially all of the unsaturated sulfonates are reduced to alkane sulfonates, with only very little or no effect whatsoever being exerted on the hydroxy sulfonates. The hydrogenation can be carried out using hydrogen over 5% Pd on carbon or barium sulfate as a catalyst at a pressure of 4t5 - 57.2 kg / cm and a temperature of 45-80 ° C. for 60 minutes.

The primary alkanol constituent of the detergent mixture contains 10 to 15 carbon atoms. The alkanols preferably used show the normal configuration or the Configuration of the 2-methyl isomers. Suitable alcohols include decanol-1, undecanol-1, dodecanol-1, tridecanol-1, tetradeoanol-1, ' Pentadecanol-1, 2-methylnonanol, 2-methyldecanol-1,

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2-methylundecanol-l, 2-methyldodecanol-l, 2-methyltridecanol-l and 2-methyltetradecanol. The alkanols preferably used can be added separately or in any combination, for example 75 $> dodecanol-1 and 25 $> 2-methyldodecanol-1.

To the suitable salts of pentavalent phosphoric acid include the tripolyphosphates, pyrophosphates, metaphosphates and the orthophosphates. The cation content of the phosphates can consist of sodium, potassium, ammonium and the like. Suitable phosphates include e.g. sodium tripolyphosphate, Potassium tripolyphosphate, ammonium tripolyphosphate, tetrasodium pyrophosphate, Tetrapotassium pyrophosphate, trisodium phosphate, tripotassium phosphate, ammonium phosphate, sodium hexametaphosphate, Potassium hexametaphosphate, ammonium hexametaphosphate, monosodium orthophosphate, Monopotassium orthophosphate, disodium orthophosphate, Dipotassium orthophosphate and the like.

The ternary mixtures according to the invention can be prepared in the usual manner known in the art. The order in which the components are combined is irrelevant. The mixtures prepared in this way can optionally find use as effective detergents. Preferably, however, the detergent mixtures according to the invention are added to detergent formulations with the addition of further constituents processed.

The quantities prescribed for detergent formulations of surface-active ingredient makes about 15 to 35 wt. of the entire detergent mixture. For using the The same concentrations apply to olefin sulfonates according to the invention, but preferably 15 to 25 #. Accordingly, determines the amount used in a detergent formulation of olefin sulfonate, the amount of pentavalent phosphoric acid salt and alkanol-1 to be used.

An effective amount of alkali salts of pentavalent phosphoric acid to olefin sulphate is usually about 1/4 up to 3 parts by weight per part of olefin sulfonate. Preferably the ratio is 1 to 2 parts by weight per part of olefin sulf onat.

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Selected alkanols or mixtures thereof can be used in the ratio of about 4 to 40 parts by weight per 100 parts Olefin sulfonate can be used. The most favorable ratio is usually 8 to 30 parts by weight per 100 parts of olefin sulfonate .

According to the invention, in the detergent mixtures for To increase their cleaning properties, further compatible ingredients can be incorporated. Such components are including corrosion-preventing, anti-graying and chemical bleaching agents and complexing agents, optical brighteners and certain inorganic salts other than phosphates' e.g. inorganic Sulfates, carbonates or borates. The appropriate amounts and mixtures of these additives, agents, and builders are off known in the art.

An effective means of determining the value of the cleansing Properties of detergent mixtures is known under the Designation "hand dishwashing test", which is based on a method that was approved by the ASTM D-12 subcommittee for detergents on March 10, 1949 in New York, New York. In the experiment, the plates or dishes are shared counted, which can be washed under household conditions until the foam formed is used up. This The experiment was designed to evaluate the improved performance achieved by the disclosed detergent compositions.

The ternary mixtures according to the invention were made by adding water alone or together with other ingredients Detergent formulations. The formulations were adjusted so that the percentage of Alcohol and olefin sulfonate 25% by weight of the total detergent formulation fraud.

Those in the procedures of the following examples in the hand-dishwashing test used concentrations were 0.15 wt.% based on the total detergent formulation.

Example 1 shows a suitable detergent formulation prepared from the ternary mixtures according to the invention.

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Example 1 ;

A detergent formulation was prepared containing the following ingredients in the following percentage amounts on the total weight of the preparation, contained:

Preparation ternary G-emic

alpha-olefin (G ₁₅ -G ₁₈ ) sulfonate 21 32

Sodium tripolyphosphate 40 62

Dodecanol-1 4 6

Sodium silicate 7

Carboxymethyl cellulose 1

Sodium sulfate 19

Water 8

The formulation has been tested and proven in Hand dishwashing test effective for treating 24 parts.

The values given in Table 2 give the relative dishwashing ability of 01 · ... - "insulfonates alone and in binary form Mixing with phosphate and alkanol-1. The presence of phosphate appears to have a substantially negative effect on the dishwashing ability of the olefin sulfonates.

Table 2;

Composition of the mixture in wt .- #.

1 ?

Example phosphate sulfonate dodecanol-1 plate

2 O 100 0 20th 3 0 84 16 20th 4th 28 ³ 62 0 18th 5 44 ³ 56 0 17th 6th 623 38 0 15th 7th 62 ⁴ 38 0 18th

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Table 2 (continued):

1 2

Example phosphate sulfonate dodecanol-1 plate

8th 62 ⁵ 38 0 18th 9 ⁶ 71 ⁵ 29 O 17th

alpha-olefin sulfonate fraction ^ (carbon cut) with 15-18 carbon atoms;

Value found on the basis of the hand dishwashing test:

^ Sodium tripolyphosphate;
Trisodium phosphate;

"* Tetrasodium pyrophosphate;

Contains inert builders such as sodium silicate, carboxymethyl cellulose and sodium sulfate.

Tables 3 and 4 show values obtained using formulations containing all three ingredients became. Both tables show the importance of alcohol concentrations for dishwashing ability.

Table 3:
Composition of the ternary mixture in wt .- $ »·

1 2

Example phosphate sulfonate dodecanol-1 plate

10 28 52 10 22nd 11th 44 37 9 - 24 12th 62 32 6th 23

E sodium tripolyphosphate;

alpha-olefin sulfonate fraction. with 1 ^ -18 carbon atoms;

^J value was found based on the hand dishwashing test

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Table 4:
Composition of the ternary mixture in wt .- ^.

example phosphate SuIfοnat ² Dodecanol-1 Plate ⁵ 13th 62 26th 12th 15th 14th 62 28 10 20th 15th 62 32 6th 24 16 62 35 3 22nd

Tetrasodium pyrophosphate;

alpha-olefin sulfonate fraction with 15-18 carbon atoms;

The values were found on the basis of the "hand dishwashing test".

The changes in the dishwashing ability of the mixtures according to the invention that are longer due to the change in the carbon chains of the alkanol are shown in Table 5.

Table 5: Plate example n-alkanol (Number of carbon atoms) 16 17th 8th 23 18 " 10 24 19th 11th 24 20th 12th 23 21 13th 21 22nd 14th 15th 23 16

Composition of the ternary mixture:

Phosphate 61%, alkanol 6 $, olefin sulfonate 33 $,

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Table 6 shows a comparison of the dishwashing properties of formulations containing different alcohols with that of the formulations according to the invention.

Table 6:
Example · Alcohol plate

24 primary "oxo" alcohols with 24

12-15 carbon atoms and 70-80 #
straight-chain connections

25 2-methyldodecane oil-l 24 26. 4- and 6-methyloldodecane 15

27 4- and 6 methyl oil undecane 15

28 Oxo alcohol with 14 carbon atoms 17

and 30 ^a / o straight chain links

29 branched chain oxo alcohol 18

with 13 carbon atoms

30 mixed secondary dodecanols 15

31 mixed secondary tetradecanols 15

Composition of the ternary mixture;
$ 6 alcohol, $ 61> phosphate, $ 33> olefin sulfonate.

Table 7 shows the dishwashing ability of formulations which contain hydrogenated olefin sulfonate as the main active ingredient contained alone or in a mixture with olefin sulfonates.

Table 7:
Composition of the ternary mixture in wt .- ^

Example Dodecanol-1 Hydrogenated Olefin-

Olefin sulfonate sulfonate dish

32 0 38 0 25th 33 6th 32 0 31

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Table 7 (continued):

Example Dodecanol-1 Hydrogenated Olefin-

Olefin sulfonate sulfonate dish

34 ¹ 62 « O 19th 19th 23 35 6th 16 16 28 1 » phosphate.

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Claims (1)

180969Ü Pat entansprü before: 1, detergent mixture with improved cleaning properties consisting essentially of normal en _s water-soluble olefin sulfonates with 11 to 19 carbon atoms _s a salt of a pentavalent phosphoric acid in a ratio of about 1/4 to 3 parts per part by weight. Sulphonate and an alkanol-1 with 10 to 15 carbon atoms, and z-was eirtir / eaer in S'orffl of the normal compound or the 2-Metiiylisoiftöx ¹ eii in the ratio '/ on about 4 to 40 parts per 100 wt. Parts sulfonates 2 ».Det>;i'g.jnsgsiaisoii according to claim I ₈ characterized). because ' ³ , the alteanol-I is nodecaiiol-1. 3- DetisrgensgeBiisc.ü :: c .. ^ Claim 2 _; , characterized in that the salt of the Pho ^ hüi-iiäurs Ba-crxumtrxpalyphos TetraiiatriuBipyrophosphat oaer l'rinatriumxjho-ypha ^ = 4. detergent mixture according to claim 5s characterized aeichnet that the salt of phosphoric acid in a ratio There is about 1 to 2 ropes per Q-e and part of SuIfonat 5t detergent gel according to claim A ₀ characterized in that the alkanol-1 is present in a ratio of about 8 to 30 parts per 100 parts by weight of sulfonate. 6, detergent mix according to. Claim 5 _9, characterized in that the 1-alkanol consists of a mixture of the normal compound with the 2-meth.vl isomers thereof., 7. detergent mixture according to claim 3, characterized in that the 01efinsulfonat of a 15 to 18 carbon atoms ent- -9 0-9-8-3 2- / 1 318 holding fraction is derived from alpha-olefins. 8, detergent mixture according to claim 5 »characterized in that the olefin sulfonate is a hydrogenated olefin sulfonate 9 · Detergent mixture according to claim 7 »characterized in that that the olefin sulfonate is a mixture of hydrogenated olefin sulfonates and olefin sulfonates. • 10. Petergensgemiach according to claim 7, characterized in that that the olefin sulfonate is a hydrogenated olefin sulfonate is. for Chevron Research Company Lawyer , 4 ORIGiivAL:.: 3Board 009832/1311