DE2014427A1 - Low - foaming wetting agent and detergent - Google Patents

Abstract

Rapidly wetting detergent and wetting agents of low foam content consist of anion-active salts of partially oxyalkylated phosphoric acid monoester/diester mixtures obtained by reacting P2O5 are phosphorus oxychloride with straight-chain or branched, pri., sec., or tert. aliphatic alcohols with 3-13C, pref. 6-8C. Agents can be used as auxiliaries in textile manufacture.

Description

Low-foaming wetting agents and detergents Among the numerous in the textile industry Aids used in industry practice the so-called wetting agents an important one Function off. According to their name, they have the task of cooking, washing, Dyeing and finishing processes for rapid and even wetting of the natural or synthetic fibers in the respective treatment baths to care.

Mainly substances from the class of anionic and nonionic Surface-active compounds represent a large contingent of network-active commercial products. Examples of anion-active auxiliaries are the alkali metal salts of alkanesulfonic acids, alkylarylsulfonic acids or of alkyl sulfates called wetting agents of non-ionic nature can be found in numerous variants under the ethylene or Propylene oxide adducts or mixed adducts of the two alkylene oxides of preferably aliphatic alcohols, carboxylic acids, alkylphenols and amines.

Almost all of the compound classes listed here show next to the desired one Wetting power is a more or less pronounced foaming in the aqueous phase. This latter property leads them to the same degree as those to be processed Processes - due to the increasing improvement of the machine facilities - in your Speed progress increase, becoming more and more noticeable impacting disturbances. The high speed throughput of textile fabrics in the treatment baths or those under powerful pump pressure When the liquor is circulated, the wetting agents used very frequently cause them to so much foaming that the processing sequence is severely disturbed.

The annoying foaming of the wetting agent is tried once by adding it of foam-suppressing silicones or low molecular weight phosphoric acid triesters, such as Triisobutyl phosphate, to counter the treatment baths. Both substance classes can effectively reduce already existing foam, but only temporarily and must therefore be used repeatedly when the foam height increases again will. Silicones are effective even in very small quantities, their application However, due to the high price of these substances, they are not cheap in the long run The phosphoric acid triesters have to produce the same defoaming effects in higher Concentrations as silicones are used, which is also unfavorably priced affects. In addition, both silicones and phosphoric acid triesters can result aggregate into larger droplets due to their insolubility in water in the application liquors, deposit on the textile material and so z. B. in color processes to blotchy product failure to lead.

It has been proposed to reduce the viewing power of wetting agents by combining the actual wetting-active substances with water-insoluble ones and therefore look attenuating connections, like middle or higher Fatty alcohols, fatty acids and their Ca or

Mg salts, hydrocarbons and the like. Such combined Products are available in large numbers as so-called low-foam wetting agents. she show in their foam development - compared to the unmixed wetting agents - a certain amount of damping, but this effect is for machines that run rapidly Processes are usually not effective enough because the liquors are still foaming too much0 Moreover, on the other hand, the network ability is impaired in many cases.

The present invention relates to extremely low foaming network-active connections that have a uniform structure.

So they do not represent a combination of wetting, but foaming, Connections with foam suppressors represent surprisingly and technically one Real progress in this is the realization that it is therefore possible to use substances to synthesize which with good network properties also with high mechanical Are practically foam-free for long periods of time0 This finding is somewhat contradicting itself to the theoretically founded and confirmed by practice view that effective Wetting agents always show considerable foam development or that low foaming Connections only develop a very weak network effect. Subject of invention are fast-wetting, low-foaming, anion-active salts partially ox-ethylated, -propylated or -butylated or

mixed oxyalkylated phosphoric acid mono- / diester mixtures of straight-chain or branched, primary, secondary or tertiary aliphatic Alcohols with 3 - 13, preferably 6 - 8 carbon atoms in the molecule. To produce this low-foam and rapidly wetting salts, mixtures of the alcohols mentioned can also be used for Use the synthesis of the mono- or diester mixtures. Suitable alcohols are e.g. i-butyl alcohol, n-hexanol, 2-ethyl-butanol- (1), methylisobutylcarbinol, 2-ethyl-hexanol- (1), 2-ethyl-4-methyl-pentanol- (1), n-octanol, i-octyl alcohol, i-decyl alcohol, tert. Amyl alcohol and the like.

The compounds are produced in a manner known per se by Reaction of the alcohols with phosphorus pentoxide or phosphorus oxychloride.

The acidic phosphoric acid ester mixtures are according to the invention with Alkylene oxides without the addition of special catalysts at low temperatures partially further esterified and the residual acidity with alkali, ammonia, amine bases, amino alcohols, Morpholines, neutralized. The highly concentrated ones resulting from this process Compounds according to the invention are colorless, clear, viscous oils. In the application concentration from 0.5 - 5 g / l the solutions are slightly cloudy to opal. The use of ethoxylated Compounds that received propylene oxide grafted on as foam army surface-active Substances is known. However, it was very surprising to find that the Salts partially esterified with alcohols of the order of magnitude mentioned and ethylene oxide Phosphoric acid with excellent wetting properties show only minimal foam development. This observation is completely in contrast to previous experience with ethoxylated Links.

In addition to good wetting effect with practically no foam development demonstrate some representatives of the compounds according to the invention have very pronounced antistatic properties Effectiveness, especially on polyamide fibers and other polyamide bodies but also on other synthetic fibers.

Another advantage of the alkali salts according to the invention is that for Esters surprisingly high resistance to electrolytes, especially alkalis. In contrast, the sulfosuccinic acid esters known as good and low-foaming wetting agents lose their network activity very quickly in alkaline media as a result of hydrolysis. Apart from that of the already identified possible uses also showed that these Body as a corrosion-inhibiting and lubricating effect-enhancing additive to mineral and synthetic lubricants are suitable.

In contrast to the phosphoric acid triesters mentioned in the prior art the compounds according to the invention do not show any undesirable physiological Side effects.

Example 1 11.1 mol of 2-ethylhexanol- (1) are mixed with 3.8 mol of phosphorus pentoxide implemented in a known manner. That after about 5 hours of reaction time The ester mixture obtained has an acid number of 290 + 10. It is then left at a lower value Temperature without the addition of a catalyst about 10.5-10.9 moles of ethylene oxide drip. The residual acid number of the ester obtained is about 110 + 10 return. This reaction product is then with 50 pointer sodium hydroxide solution up to pH 7 neutralized O The end product has an active content of 89%.

Network values according to DIN 53 901 concentration lg / l at 20 °: 20 - 22 sec. at 50 °: 30 sec.

Foam values (shaking method) at an initial height of 200r 0o3 - 0.5 cm breaks within 2 sec.

at 500: initial height 0.0 cm Example 2 As mentioned in Example 1, 3.7 mol of 2-ethylhexanol- (1) are reacted with 1.23 mol of phosphorus pentoxide. the SZ of the ester mixture obtained is included after a reaction time of about 5 hours about 290 t 10.

3.7 mol of propylene oxide are then added with cooling. The received The adduct has an acid number of 183 t 10. The final neutralization, i. H. the salt formation is made with 50 ffi KOH.

Network values according to DIN 53 901 concentration lg / l at 200: 50 - 55 sec. at 70 ° 47 - 48 sec.

Foam values (shaking method) at 200: initial height 1 cm, breaks in 5 sec. To 0 cm at 700: initial height 1 cm, breaks in 1 - 2 sec. To 0 cm Example 3 3 mol of methyl isobutylcarbinol are cooled with 1 mol of phosphorus pentoxide implemented. The resulting ester mixture has an acid number of 327. After addition the acid number has dropped to 91 from 3 moles of propylene oxide. The neutralization on pH 7 with 50% NaOH provides a clear, viscous oil with an active content of around 90 0 This product shows excellent washing effects with minimal foam development.

Example 4 That obtained according to Example 1. Ethylene oxide adduct SZ 110 + 10 delivers NE3-Lsg0 during neutralization with 25%. instead of NaOH a colorless one Oil with the following network and foam values: Network values according to DIN 53 901 concentration lg / l at 20 °: 22 - 24 sec. at 500: 22 - 23 sec.

Foam values (shaking method) at 200r starting height 1 cm, breaks in 2 sec. To 0.5 cm at 500: initial height 1 cm, breaks in 1 - 2 sec. To 0 cm Example 5 The propylene oxide adduct prepared according to Example 2 with SZ 183 + 10 is through Neutralization with morpholine converted into an orange, clear, viscous oil.

Network values according to DIN 53 901 concentration lg / l at 20 °: 58 sec. At 50 °: 60 sec.

Foam values (shaking method) at 20 °: initial height 1 cm, breaks in 13 sec0 to 0.1 cm at 50 °: initial height 1 cm, breaks in 4 sec. To 0 cm Example 6 If the neutralization of the acidic propylene oxide adduct is not included in Example 5 Morpholine, but made with N-Cocosfettalkyl-morpholine, one obtains a clear, golden yellow oil that dissolves perfectly in mineral oils.

Example 7 3 mol (393 g) of a mixture of 80% 2-ethyl-4-methyl-pentanol- (1) and 20% 2-ethylhexanol- (1) are reacted with 1 mol of P2O5. The acidic ester mixture with SZ 280 + 10 3 moles of ethylene oxide are added.

The adduct with SZ 130 + 10. delivers neutralized with 50% NaOH a colorless, clear oil with 90% active content.

Network values according to DIN .53 901 concentration 1 g / l at 200r 27 - 28 sec. at 500: 22 - 23 sec.

Foam values (shaking method) at 200r starting height 1 cm, breaks in 10 sec0 to 0 cm at 500t starting height 1 cm, breaks in 2 sec. To 0 cm

Claims (3)

Patent claims 1) Fast-wetting, low-foaming wetting agents and detergents, characterized in that it consists essentially of the anion-active salts partially Oxalkyli erter phosphoric acid mono / diester mixtures exist, which by reaction of phosphorus pentoxide or phosphorus oxychloride with straight-chain or branched, primary, secondary or tertiary aliphatic alcohols with 3-13, preferably 6 - 8 carbon atoms were obtained. 2) Fast-wetting, low-foam wetting agents and detergents, characterized in that that the phosphoric acid mono- / diester mixtures lt. Claim 1 to be partially further esterified with ethylene oxide and the remaining acidity is neutralized with inorganic and / or organic bases will. 3) Fast-wetting, low-foaming wetting agents and detergents, characterized in that that they essentially consist of the anion-active salts of phosphoric acid mono / diester mixtures, which were partially further esterified with propylene oxide and in which the remainder Acidity with inorganic and / or organic bases neutralized Nurde, consist, 4) Fast nctsande, low-foaming agent and detergent, characterized in that they essentially consist of the anion-active ones Salts of phosphoric acid mono / diester mixtures, which were partially further esterified with butylene oxide and in which the remainder Acidity neutralized with inorganic and / or organic bases exist.