DE2104523A1 - Detergents and cleaning products - Google Patents

Description

6th

P ε? * .. · η1 ~ Γγ // ΐν * 3

yuiff <-> r Si'r-

²⁹ Jan i37i

C, 428 London

Unilever N.T. Museum Park 1, Rotterdam / Holland

Detergents and cleaning agents

Addition to patent (application P 19 39 973.6

Priority: February 2, 1970, England, No. 4896/70

The invention relates to detergents and cleaning agents and in particular those in flake form which are suitable for washing fabrics.

Soap flakes are known and relatively easy to make, but satisfactory detergent flakes are difficult to make. Even if a detergent flake sufficiently thin - can be piliert, these tend to block to opaque and break: to be and have an unsatisfactory foam assets ₀ These problems are particularly acute when the detergent flake includes a conventional builder, such as sodium tripolyphosphate.

Soap and detergent flakes can vary in size, but to be satisfactory in use they must be less than 0.02 cm thick, preferably less than 0.01 cm, and though they form a qudarat with a side length of 1 cm usually the side is 0.4 cm long.

It is an object of the invention to provide a detergent flake create which with less than 0.02 cm thickness, preferably less than 0.01 µm thickness, can and cannot be made is brittle.

109838/1679

ORlQfNAL IhTSPEGTED

Heretofore, it has been proposed to produce a detergent composition which comprises an active detergent compound and a water-soluble salt of a dicarboxylic acid of the general formula R.CH (CO ₂ H). (OH ₂ ) _n .00 ₂ H, wherein η 0 or 1 and R is a primary one or secondary straight chain alkyl or alkenyl group of from 10 to 20 carbon atoms. The water-soluble salts of dicarboxylic acids, referred to below as dicarboxylic salts, are effective builders for detergents and such compounds cannot contribute to eutrophication problems, as is assumed for other nitrogen- or phosphate-containing builders, for example sodium tripolyphosphate.

According to the invention it was found that the above Dicarboxyl salts are particularly advantageous with Aktivdetergensver compounds of the olefin sulfonate type or the alkyl sulfate type or Mixtures of these two types of active detergent compounds to be used. Such combinations can easily be made into flakes * - form, which facilitates the production of detergents with good textile washing capacity in this advantageous form.

The dicarboxylic salts can be saturated or olefinic bonds contain. Examples of primary dicarboxylic acids which can be used in salt form are n-Dodeean-1,2-dicarboxy1-acid, n-Tetradecane -1,2-dicarboxylic acid, Μ3εϊμ ± χ n-Pentadee-4-en1,2-dicarboxylic acid, n-hexadecane-1,2-dicarboxyl acid, heptadecane-1,2-dicarboxylic acid, n-octadec-4-ene-1,2-dicarboxylic acid, n-Nonadec-4-en-1,2-dicarboxylic acid, n-eicosane 1,2-dicarboxylic acid, n-docosane-1,2-dicarboxylic acid, n-undecane-1,2-dicarboxylic acid, n-dodec-3-en-i, 1-dicarboxylic acid, n-tridecane-1,1-dicarboxylic acid, n-tetradec-3-en-1,1-dicarboxylic acid, n-pentadecane-1,1-dicarboxylic acid, n-hexadecane-1,1-dicarboxylic acid, n-heptadec-3-en-1,1-dicarboxylic acid, n-octadec-3-en-1,1-dicarboxylic acid, n-Nonadeoan-1,1-dioarbos: y! acid, n-Eicosan-1,1-dicarboxylic acid and n-Uncos-3-en-1,1-dicarboxy 1-acid « Examples of secondary carboxylic acids which can be used in salt form are 4-methyl (1 ', 1'-dicarboxyl-

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acid) -decane, 5-ethyl (1 ', 2'-dicarboxylic acid) decane, 5-methyl (1'-1'-dicarboxylic acid) -undec-5-ene, 6-ethyl (1', 2'-dicarboxylaic acid) -undec-6-en, 3-ethyl (1 ', 2'-dicarboxylic acid) -dodec-3-en, 7-ethyl- (1', 2 '-dicarboxylic acid) tetradecane, 2-methyl (1, 1' -dicarboxytic acid) -tetradec-2-ene, 6-ethyl (1 ', 2'-dicarboxylic acid) ~ pentadecar 4-ethyl (1', 2'-dicarboxylic acid) hexadec-3-ene, 7-methyl (1 ', 1 ^f dicarboxylic acid) hexadecane, 2-methyl (1Ί'-dicarboxylic acid) -heptadec-2-ene, 5-ethyl (1'2'-dicarboxylic acid) octadecane, 8-methyl- (1 · 1'-dicarboxylic acid) nonadec- 8-en, _ 9-methyl (1 '>1'-dicarboxylic acid) -eicosane and 9-ethyl (1', 2'-dicarboxylic acid) -eicos-9-en.

The dicarboxylic salts used are preferably those of dicarboxylic acids of the above formula wherein R is from 12 to 16 Contains carbon atoms. The dicarboxylic acids can be one Have range of carbon chain lengths as such materials are more readily available and generally cheaper than compounds are of uniform carbon chain length. Mixtures of various alkyl and alkenyl dicarboxylic salts can also be used to be used. Alkali metal and especially sodium salts are preferred.

Standard methods of making suitable dicarboxylic acids include the condensation of straight chain alpha olefins with maleic anhydride to form alkene-1,2-dicarboxylic anhydrides. The condensation products obtained are mixtures of the desired alkene-1,2-dicarboxylic acid anhydrides and of polymeric materials and mxg of unreacted olefins. The anhydrides can easily be converted into the corresponding

Salt

SMwtkh can be converted by treatment with alkali and the polymers and olefins can, if necessary, be removed by conventional methods,

Alkanoic and alkene-1,1-dicarboxylic acids can easily, for example produced by standard malonic ester synthesis we:;. en.

Dicarboxylic acids with secondary straight chain alkyl or alkenyl groups can similarly be prepared from internal olefins, various types of which are available. For example, paraffins can be dehydrogenated, chlorinated and then dehydrochlorinated to produce mixtures of internal m a-ei-na ττλλ a · *. «^^« · «. short chain al-nha — 01 efing can

109838/1679

are disproportinated to long chain internal olefins and To yield ethylene. Alpha-olefins can be randomized using catalytic procedures.

The term "olefin sulfonate * is used here to refer to the mixture of anionic active detergent agents obtained when the products of olefin sulfonation neutralized and completely or almost completely hydrolyzed. Alpha olefins or arbitrary olefins can be used but alpha olefins are particularly preferred. Alkali and especially sodium olefin sulfonates are preferred.

Alpha-olefin sulfonates suitable for use in flakes according to the invention are derived from the sulfonation of Cg-Cp2 alpha-olefins. The olefins should preferably contain between 12 and 20 carbon atoms, and in particular from 14-16 carbon atoms. The olefins should preferably consist almost entirely of monounsaturated straight-chain «! alpha-olefins consist "Commercially available supplies of alpha-olefins are generally derived from the ^w cracked-wax" process, wherein the olefins from a paraffin-cracked distillate extracted sfegex

are, or according to the "Ziegler" process, in which the olefins are xjubzx οοdgl by polymerizing a low molecular weight unsaturated hydrocarbon, for example ethylene, by means of a * Ziegler catalyst. can be synthesized. Instead, olefins can be produced by the dehydration of primary alcohols, which can be produced, for example, by hydrogenating esters of naturally occurring fatty acids, e.g. those derived from the saponification of animal and vegetable oils and fats, or olefins can be produced by the dehydrogenation of paraffins although this latter method is not preferred. Preferably, olefin sulfonates from Ziegler olefins should for the purposes of - ^ rfindung / f since Ziegler olefins usually comprise about 90% by weight alpha-olefins and contain only an insignificant proportion of branched-chain material.However, cracked wax olefins are also suitable , since they generally contain between 85 and 90% by weight of alpha-olefins together with smaller amounts of internal olefins and diolefins .

109838/1679

which are used to make the olefin sulfonates for the invention "should contain as high a proportion of linear alpha olefins as possible and if supplies of $ 100 alpha-olefin are available, these would be ideal. However, the prior art is incapable of producing such a material. The inspection specialist is familiar with this Problem and use of the term "alpha-olefin sulfonate" is understood by him to mean that discussed Material is derived from an olefin material which is im essentially from alpha-olefins, e.g. firacked-wax-olefins or Ziegler olefins. It should therefore be noted that In this document this specification of the term "alpha-olefin sulfonate" is used to denote the Mixture of olefin sulfonates, which from the Sulphonation are derived from commercially available supplies of alpha-olefins.

Alpha-olefin sulfonates are mixtures of various compounds including various hydroxyalkane sulfonates as well as disulfonates and a larger proportion of alpha-alkene sulfonate. The proportion of 2-hydroxyalkanesulfonate in the mixture should be kept as low as possible, preferably to less than 5% by weight of the mixture. In contrast, it is often preferred to keep the proportion of 3-hydroxyalkane as high as possible, preferably above 20 wt.% Of the blend, and even more particularly about 30 $> the weight of the mixture. A detailed description of the types and amounts of the various ingredients commonly found in alpha-olefin sulfonate is given in U.S. Patent 3,332,880.

Although generally the alpha olefin sulfonate, as above declared derived from alpha-olefins, it should be noted that when alpha-olefins are in the presence of acidic products be left to stand, as is the case with batch sulfonation processes the pail is, some isomerization will occur and Olefins in which the double bond is not terminal, are formed. It should be noted that products containing minor proportions of olefin sulfonates, which

109838/1679

originate from olefins with a non-terminal double bond, are also still within the scope of the invention.

The olefin can be sulfonated in many different ways, for example in reactors with a stirrer or in falling film reactors. The preferred sulfonated ^A gene is a sulfur trioxide / air mixture, although other agents, such as oleum can also be used. "

Alkyl sulfates suitable for use in the agents according to the invention are alkali, in particular sodium, salts of sulfates, prepared from natural or synthetic fatty alcohols. ^C10 ~ ^C20 alcohols are preferred and these are most preferably linear or substantially linear. Sulfates from alcohols of a single chain length, or from mixtures of alcohols of different chain lengths, can be used if desired. Examples of suitable sulfates are those derived from n-decyl, n-undeeyl, n-dodecyl (lauryl), n-tridecyl, n-tetradecyl (myristyl), n-pentadecyl, n-hexadecyl (cetyl) -, n-heptadecyl (margaryl) -, n-octadecyl (stearyl) -, n-nonadecyl and eicosyl (arachidyl) alcohol and from mixtures of alcohols derived from saturated sources, e.g. Coconut oil, palm oil, palm kernel oil, babassu oil, peanut oil and soft oil come from

The agents according to the invention usually contain water in amounts of about 2-15, preferably about 5-10 ^

The inventive compositions may also contain conventional additives to detergent compositions, for example, foam inhibitors, foam boosters, such as alkylolamides, fluorescent st de substances, dye, perfumes, soil suspending agents, for example sodium carboxymethylcellulose, inorganic salts such as sodium sulfate, fabric softeners, and enzymes. If so desired, however, such additives can instead be mixed with the detergent flakes of the invention to form compositions of mixed physical form, for example a mixture of flakes and a pulser.

The ratio of the dicarboxylic salt to the active detergent compound is preferably about 20: 1 to 1: 1. If the active

109838/1679

detergent compound and the dicarboxyl salt are the only ingredients are in the flake, the proportion will vary Active detergent compound from about $ 5 to $ 50 and that of the Carboxylic salt from about 50 to 95 # «in complete detergent Agents which contain the usual additives, it is preferred that the active detergent compound and the dicarboxyl salt present in an amount of at least about $ 50 of the agent are.

The agent can easily be converted into a floe form, for example by forming a layer of the hot agent on a cooled roller or belt, from which the solidified flakes are scraped off or removed in some other way. the Layer can be treated during their presence on the roller or the belt to make flakes of regular or irregular To deliver shape,

example 1

A flake detergent was prepared on a conventional basis Flake plant made from a piled mixture of the active ingredients, both to remove excess Water had been drum dried.

Components

C.jE ₁₈ -alpha-olefin sulfonate disodium octadec-4-en-1,2 ^f -dicarboxylate water

Example 2

28

61.2 8.8

A detergent flake, prepared according to Example 1, had the following composition:

Components

Sodium Cj C ₁₈ -alpha-01ef insulphonate disodium octadec-4-en-i, 2-dicarboxylate water

47.9 46
6.1

Example 5

A detergent _flake produced according to Example 1 had the following composition:

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Components %

Sodium Lauryl Alkyl Sulphate 48

Disodium octadene-4-en-1,2-dicarboxylate 45> 5

Water 6.5

Example 4

A detergent flake, prepared according to Example 1, had the following composition:

Components £

Sodium tallow alkyl sulfate 49

Disodium octadec-4-en-1,2-dicarboxylate 45.1

Water 5.9

These agents were effective detergent products for textile laundry ₀

109838 / 1e79

Claims (15)

-9 claims 1. Detergents and cleaning agents in flake form, characterized in that that it is a water-soluble salt of a dicarboxylic acid of the general formula R.OH (OO ₂ H). (GH ₂ ) _n .0O ₂ H where η is 0 or 1 and R is primary or secondary straight-chain alkyl or alkenyl group with 10 to 20 carbon atoms and an active detergent compound which is an olefin sulfonate or an alkyl sulfate comprises » 2. Agent according to claim 1, characterized in that the weight ratio of the water-soluble salt of dicarboxylic acid to the active detergent compound is from 20: 1 to 1: 1. 3. Agent according to one of the preceding claims, characterized in that the water-soluble salt of dicarboxylic acid and the active detergent compound combined make up at least about 50 percent by weight of the detergent. 4. Agent according to one of the preceding claims, characterized in that the water-soluble salt of dicarboxylic acid 50 to 95 wt. # Of the detergent and the active detergent compound 5 to 50% by weight of the detergent. 5. Agent according to one of the preceding claims, daduöeh characterized in that R contains from 12 to 16 carbon atoms. 6. Agent according to one of the preceding claims, characterized in that the active detergent compound is an alkali metal 0g-0 ₂₂ -01efinsulfonat. 7. Agent according to claim 6, characterized in that the active detergent compound is a C ^ ₂ -a ₂₀ 01efinsulfonat « 9 · Mltttl according to claim 7 _f, characterized in that the active detergent compound is an O ^ .- O ^ olefin sulfonate. 9. Agent according to one of the preceding claims, characterized in that the active detergent compound is an alpha-olefin sulfonate 109 838/1679 -1 ΟΙΟ. Agent according to one of Claims 1-5, characterized in that the active detergent compound is an alkali metal C. _{o is} -C _2O alkyl sulfate. 11.Means according to one of the preceding claims, characterized characterized in that the water-soluble salt of dicarboxylic acid is an alkali metal salt. 12. Composition according to claim 11, characterized in that the water-soluble salt is a sodium salt. 13. Means according to one of the preceding claims, characterized characterized in that the active detergent compound is a sodium salt is. 14. Composition according to one of the preceding ^ claims, characterized in that it contains from 2-15 wt _o ? 6 water. 15. Means according to claim 14, characterized in that it contains 5-10 wt. ^ water. 109838/1679