DE1809690B2 - DETERGENT MIXTURES - Google Patents

Description

45

The present invention relates to the field of biological degradable sulfonate detergents, especially the rapidly biodegradable olefin sulfonate with improved cleansing properties.

Because of its important property, the biological one Degradability, linear alkylbenzenesulfonates are currently the main active ingredient in household detergents although olefin sulfonates are more biodegradable than linear alkylbenzenesulfonates, but have so far not been comparable to these in terms of the cleaning properties.

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

It has surprisingly been found that ternary mixtures of olefin sulfonates with 11 to 19 carbon atoms, alkali and ammonium salts of the pentavalent Phosphoric acid and alkanol-1 compounds having 10 to 15 carbon atoms, both normal and 2-methyl isomers, are uncommon have strong cleaning properties. In particular, the ternary mixtures described show a significant higher performance than due to the performance of corresponding binary mixtures or the respective individual components was to be assumed. The mechanism of why by working together cleaning improved by olefin sulfonates, alkali salts of pentavalent phosphoric acids and alkanols Properties to be achieved is not known, but it is known that to achieve the beneficial effect all three components are required.

The term "olefin sulfonate" used in the present invention denotes a mixture which 50 - 100% consists of saturated olefin sulfonates. With a proportion of unsaturated olefin sulfonate below about 100%, the remainder of the mixture consists essentially of hydroxysulfonates. Smaller amounts of others Compounds can also be in the form of the impurities contained in the olefin feeds or caused by the side reactions of sulfonation. The relative Hydroxy and unsaturated sulfonate ratios will vary depending on the manufacturing method used. According to the approach proposed by T urb a k, A. F., et al., in "Reaction of Fhosnhate-Complexed Sulfur Trioxide with Alpha-Olefn. - in Industrial and Engineering Chemistry, Product Research and Development 2, No. 3, 229 (1963) an olefin sulfonate consisting essentially of 100% unsaturated olefin sulfonate. Usually lies the amount of hydroxysulfonate in the range of 0 to 50% by weight, preferably below 40% by weight of the total Olefin sulfonates. The proportion of unsaturated sulfonates can range from 50 to 100% by weight of the total Olefin sulfonates are, preferably the unsaturated sulfonates are more than 60% of the total olefin sulfonates.

The olefin sulfonates according to the invention are prepared by sulfonation of straight-chain or normal olefins with 10 to 24 carbon atoms, usually with 11 to 19 carbon atoms, preferably with 15 to 18 carbon atoms. Individual olefins (carbon cuts of olfins) falling within this range, e.g. B. hexadecene-1, can also be used. Internal or alpha-olefins can be used as olefins. However, alpha-olefins are preferably used. The sulfonation can be carried out by any suitable method which provides the appropriate amounts of hydroxy and unsaturated sulfonates.

The preferred method for producing the olefin sulfonates consists of SO ₃ air sulfonation in a layered reaction vessel (falling film reactor), neutralization and saponification or hydrolysis of the neutralized product. The reaction products of SO _r air sulfonation can be mixed with an aqueous alkali solution containing a strongly basic compound, e.g. B. sodium hydroxide, potassium hydroxide, ammonium hydroxide, the corresponding oxides, carbona'e and the like contains, are neutralized. A sufficient amount of the neutralizing solution is added for the subsequent hydrolysis. The hydrolysis of the neutralized reaction products gives the olefin sulfonals contained in the detergent mixture according to the invention.

Usually the sulfonation conditions cause the double bond to migrate into the unsaturated sulfonates and determine the distribution

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development of the position of the double bonds. Table 1 shows the analysis of an alpha-olefin fraction having 15 to 18 carbon atoms which can be used in the present invention _{and is sulfonated with SO 3 air.}

Table 1

Product composition, after saponification

Alkene sulfonates,% ^a ) 53

Hydroxysulfonates,% ^a ) 47

RCH = CH - (CH ₂ ) χ SO ₃ Na

ν mol%

0
1

2
3
4th
5
6th
7th
8th
9
10

9
21
16

5
6th
6th
7th
6th
7th
S.
9

2S

^a ) Including from Disu'.fonalen.

The sulfonation also produces various isomers of the hydroxysulfonates. Since the beta or 2-hydroxysulfonates are rather insoluble in water, it is preferred to use processes in which only a small amount of H is formed. A suitable method is described by Marquis et al., "Alpha Olefin Sulfonates from a Commercial SO ₃ Reacior," JAOCS, Vol. 43, No. 11, pages 607-614, 1966. British Patent Specification 10 30 648 describes another applicable sulphonation process.

The olefin sulfonates can be modified to hydrogenated olefin sulfonates by mild hydrogenation. Hydrogenated Olefin sulfonates, alone or in mixtures with olefin sulfonates, provide for the present invention suitable, excellently effective ingredients. The hydrogenation of the olefin sulfonates essentially the total unsaturated sulfonates are reduced to alkanesulfonates, with only a very small amount or no action is exerted on the hydroxysulfonates. The hydrogenation can be carried out using Hydrogen 60 minutes over 5% Pd on carbon or barium sulfate as a catalyst at a pressure of 4.5-57.2 kg / cm 'and a temperature of 45-48 ° C.

The constituent of the detergent mixture, which consists of primary alkanol, 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 <> o decanol-1, undecanol-1. Dodecanol-1, tridecanol-1. 1-tetradecanol, 1-pentadecanol, 2-methylinunanol, 1-methyldecanol-1, 2-methylundecanol-1, 2-methyldodecaniol-1, 2-methyltridecanol-1 and 2-methyletradecanol. The alkanols preferably used can be used separately or in any combination, e.g. 75% 1-dodecanol and 25% 1-methyldodecanol.

Suitable salts of pentavalent phosphoric acid include the tripolyphosphates, pyrophosphates, Metaphosphates and the orthophosphates. The cation content of phosphates can be made up of sodium, potassium, ammonium and the like exist. Suitable phosphates include e.g. B. 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 like that.

The ternary mixtures according to the invention can be prepared in the usual manner known in the art will. The order in which the components are combined is irrelevant. That kind of Mixtures produced can optionally be used as effective detergents. Preferably However, the detergent mixture according to the invention with the admixture of further constituents processed into detergent formulations.

The amounts of surfactant required for detergent formulations make about 15 to 35% by weight of the total detergent mixture. For the use of the invention The same concentrations apply to olefin sulfonates, but preferably 15 to 25%. Accordingly the amount of olefin sulfonate used in a detergent formulation determines the amount of to using salt of hydrofluoric phosphoric acid and alkanol-1.

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

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

According to the invention, further detergent mixtures can be added to increase their cleaning properties compatible ingredients are incorporated. Such components include: corrosion-preventing, Anti-graying and chemical bleaching agents and complexing agents, optical brighteners and certain inorganic salts other than phosphates e.g. B. inorganic sulfates, carbonates or borates. The appropriate ones Quantities and mixtures of these additives, agents and builders are known from the art.

An effective means of determining the value of the cleaning properties of detergent mixtures is known under the designation "hand dishwashing test" (hand dishwashing test), which is based on a procedure established by the ASTM D-12 Subcommittee for Detergents on Mar 10? 194 ° in New York. New York. In the attempt the I eller or Counts dishes that can be washed under household conditions until the foam has formed is upset. This attempt served to get through the disclosed detergent blends achieved improved results Rate performance / u.

The ternary mixtures according to the invention were converted into by adding water alone or together with other ingredients detergent formulations

manufactured. The formulations were adjusted so that that the percentage of alcohol and olefinsuM'onat Was 25% by weight of the total detergent formulation.

The concentrations used in the procedures of the following examples in the hand dishwashing test was 0.15% by weight based on the total detergent formulation.

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

example 1

A detergent formulation was prepared containing the following ingredients in the following percentages Amounts based on the total weight of the preparation contained:

preparation

Tertiary mixture

alpha-olefin (C, ₅ -Ci ₈ ) sulfonate 21 Sodium triphosphate 40 Dodecanol-1 4th Sodium silicate 7th Carboxymethyl cellulose 1 Sodium sulfate 19th water 8th

32

62

The formulation was tested and found in the hand dishwashing test to treat 24 plates effective.

The values contained in Table 2 give the relative dishwashing ability of olefin sulfonates alone and in binary mixtures with phosphate and alkanol-1 at. The presence of phosphate appears to have a substantially negative effect on dishwashing ability exercise of the olefin sulfonates.

Table 2

Composition of the mixture in% by weight

Example phosphate sulfonate ¹¹ dodecanol-1 plate ²¹

20 20 18 17 15 18 18 17

2 O 100 0 3 O 84 16 4th 28 ³¹ 62 0 5 44 ³¹ 56 0 6th 62 ³¹ 38 0 7th 62 ⁴¹ 38 0 8th 62 ⁵ > 38 0 71 ⁵¹ 29 0

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

Table 3

Composition of the ternary mixture in% by weight.

Example phosphate ¹ ) sulfonate ² ) dodecanol-1 plate ³ )

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

') Sodium tripolyphosphate;

² ) alpha-olefin sulfonate fraction with 15-18 carbon atoms; ³ ) Value was found on the basis of the hand dishwashing test

Table 4

^2S Composition of the ternary mixture in% by weight.

example Phosphate ¹ ) Sulfonate ² ) Dodecanol-1 Plate') 13th 62 26th 12th 15th 14th 62 28 10 20th 15th 62 32 6th 24 16 62 35 3 22nd

') Tetrasodium pyrophosphate;

² ) 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 invention Mixtures obtained by changing the carbon chain length of the alkanol are given in Table 5.

Table 5

Example n-alkanol ¹ )

(Number of carbon atoms)

Plate

8th
10
11th
12th
13th
14th
16

16

23 24 24 23 21 15

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

²⁾ Due to the value Handgeschirrspültests found:) sodium tripolyphosphate;
⁴ ) trinalrium phosphate:
') Tetranate pyrophosphate;

``) Hnthiili inert skeleton such as / B. sodium silicate, carboxvm '.' Ihvl / clulnso and sodium sulphate.

) Composition of the ternary mixture: Phosphate 61 V alkanol 6%, olefin sulfonate 33 7 ».

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

ζ 18

690

Table 6

Example alcohol

Plate

24 primary "oxo" alcohols with 24 12-15 carbon aioms and 70-80 "A
straight-chain connections

25 2-methyldodecanol-l 24

26 4- and 6-methyloldodecane 15

27 4- and 6-methylolundecane 15

28 oxo alcohol with 14 carbon atoms 17 and 30% straight-chain compounds

29 branched-chain oxo alcohol with 18 13 carbon atoms

30 mixed secondary dodecanols 15

31 mixed secondary tetradecanols 15

') Composition of the ternary mixture - 6% alcohol, 61% phosphate, 33% olefin sulfonal.

Table 7 shows the dishwashing ability of Formulations that are "hydrogenated" as skin active ingredients Olefin sulfonal alone or in admixture with olefin sulfonal contained alone or in a mixture with olefin sulfonates.

Tabel

Composition of the ternary mixture in weight ⁰ /, ¹ ).

Example Dodecanol-1 Hydrogenated Oliefin Plate

Olefin sulfonate sulfonate

IS

20th

32 0 38 33 6th 32 34 0 19th 35 6th 16 ') 62% Phosphate.

I)

19th

16

25 31 23 28

Claims (8)

'■ f patent claims: 1. Detergent mixture with improved cleaning properties, consisting essentially of normal, water-soluble olefin sulfonates with 11 to 19 carbon atoms, a salt of a phosphoric acid of phosphorus in a ratio of about V ₄ to 3 parts per part by weight of sulfonate and an alkanol-1 with 10 to 15 carbon atoms, either in the form of the normal compound or of the 2-methyl isomers in a ratio of about 4 to 40 parts per 100 parts by weight of sulfonaL 2. detergent mixture according to claim 1, characterized in that the salt of phosphoric acid is present in a ratio of about 1 to 2 plates per part by weight of the sulfonate 3. detergent mixture according to claim 2, characterized in that the alkanol-1 in a ratio from about 8 to 30 parts per 100 parts by weight of the sulfonate is present 4. detergent mixture according to claim 3, characterized in that the alkanol-1 from a mixture normal association with the 2-methyl isomers thereof. 5. detergent mixture according to claim 3, characterized in that the olefin sulfonate of one The fraction containing 15 to 18 carbon atoms is derived from alpha-olefins. 6. detergent mixture according to claim 3, characterized in that the olefin sulfonate is a hydrogenated Is olefin sulfonate 7. detergent mixture according to claim 5, characterized in that the olefin sulfonate is a mixture from hydrogenated olefin sulfonates and olefin sulfonates. 8. detergent mixture according to claim 5, characterized in that the olefin sulfonate is a hydrogenated Is olefin sulfonate. 4c