DE1814439A1 - Low-foaming nonionic detergents - Google Patents

Description

OI L QOlWMI _% P GlTGA ΟΙ'Ιΐ.

.. 'enip; foaming nonionic detergents.

This invention relates to a low foaming nonionic üetergens-Susanuriiensosition, which essentially from a mixture of surface-active compounds consists of a hydrophobic alkyl or ulkaryl group, a hydrophilic tolyoxyethylene part and a terminal hydroxybutyloxy group e included.

An important class of nonionic detergents is formed by the compositions generally known as iitho: xylates, which are obtained by condensation of a hydrophobic compound containing a replaceable hydrogen atom with a large number of ethylene oxide molecules. Particularly suitable compounds which contain the hydrophobic part of such ethoxylates are either the higher alkanals or an alkyl substituted phenol. These nonionic compositions are excellent detergents and are characterized as high foaming agents; because they tend to foam over during cleaning operations under highly turbulent conditions. In some industrial and many household applications, a low foam level is desirable. 2. B. excessive foaming of the non-ionic detergents in household washing machines is unpleasant, since the foam mixes with the rinse water and in some cases impairs the cleaning effect; furthermore, high foaming detergents can cause mechanical difficulties. It is known to those skilled in the art that the wetting and / or cleaning power of a surface-active agent is not necessarily synonymous with its ability to foam. Therefore, investigations have been made to obtain modifications of high-foaming non-toxic detergents in which the tendency to foam is reduced without impairing the cleaning power. In this connection, a further condensation of the itoxylate with Frapylenoucyd was carried out, so that a terminal polyoxypropylene part was formed.

9C98A2 / 16U

ORIGINAL BATHROOM

18U439

The disadvantages here are twofold. ». Rt. _inm :: l must do that hydrophobic radical such modified compositions have a relatively low molecular weight, which is why only Alkenols with non-optimal detergent characteristics are used can be, and also the terminal ro Iyoxypropylen-'üeil be undesirable o'roii if the preferred Alcohols with higher alcohols are weighted or substituted by alkyl Phenols perish / end “earth”.

In contrast, this invention is by a little; jchäui.; endes non-iono-renes detergent, which is produced by the reaction γόη C, 3-1 »P t-ol £ ut; ylenox ₍ / d r.i with a condensation product of 4-10 LoI iltliylenorjd and a LoI sine 3 alkanol; . dt 8-1S C-.itoiaen or I.Iol an alkylphenol uit c-12 C - ^ lkyl-Ltoraen in Jubstituenten obtained v / ith i) ie Z \ ^r i3 js: dien setzuns i corresponds to the following general ? ormel:

where ± i is a, lk.vl- or ^ lksjcjl- ^ vnxi-y ^ ... it l-'ic C - ^. tones and η represents a range of whole numbers, d ^ r by the statistical division of Cxyethylene Any resulting from the condensation of 4-1C LoI ethylene oxide with an oil of a higher aliphatic alcohol or an alkyl. As higher aliphatic alcohols, alcohols are primarily grounded in accordance with The linear primary alcohols are suitable for the Ziegler synthesis or secondary alcohols according to the Gxo process This range is the alcohols with 1G-14-O-atoms and Seiaische thereof.For the production of v / eni: / foaming non-ionic detergents for the causal ^; suitable aich ti. '; oncer-J Deeanol- (1) or 3 -mixtures of these with smaller amounts before, dodecanol- (I) and / or letradecanol- (i). «.1s substituted phenols who those used to produce the detergents of this invention contain about 8-12 O atoms in the alkyl substituent or in the substituents attached to the benzoid nucleus. Mono- or disubstituted phenols with straight-chain alkyl substituents are preferred. These priorities can either be primary or secondary G - :. jor :. _{= be} bound to the aromatic ring.

909842/1614

BAD ORIGJNÄ * - "' ^A *

y the * voi-rji. vine iden connections Liit one he:.> etz-

brren, / a.-Htjrstcfxatoi.i köiiren after conveixtionoliyn letiiods produced by "-m. oaurs" or basic L · tu-lf / ie is applicable. However, basic catalysis leads to the condensation of ethylene oxide with the alcohol or jrhenol preferred, for example Suitable bases are hydroxide solutions. - .. Ig. Acidic catalyst becomes i-L luoride preferred.

For Jurclifüiirur_j d ^ x- I-.oj: ensationsreaktio.n; / ird the required length -lt.x, / lenc: --- lu dea -i.lkohol or flonol zmeumeii with the selected kit il -.3- "Tor; e ^ even and then · τ> ιΓ 3Xa-j -.- rliuhte Tem ^ er ^ .tur heated under c.utogenic pressure. DIq condensation can be carried out in a temperature range of about 16-1 ^ 3 ° G. The preferred temperature range is about 171-132 ° G. The temperature ranges mentioned are for the preferred L; .jMlysator, .-. o.tronls.u ^ e, anwciiabc-r. ..em: an acidic L: taly: 3ator, for example, boron trifluoride is employed, lie _o -t -i ^l eiaperatur lower. i ^? ÜR such cases is a temperature range of about 79> 5-1C - '+ -' + ⁰ C jjeei ^ net. The amount Cie s Äthylenoxyds reacting with the tlkohol or alkyl-substituted 1-henol is mainly -dependent of their molecular weight. If the molecular weight of the hydrophobic part increases, larger amounts of ethylene oxide may also be used up. 3 ^{1 For} the alcohols considered, the corresponding ken _o -en Ätliylenoicyd are 4-1C Hol r, ro mol alcohol. Ethyleno> ^ yd in the range of $ -3 LoI based on eii_ LoI alcohol is applicable to the preferred alcohols with 10-14 C-atoms. .The preferred light weight ratio:; from i: .thylenoxycJ to any; =; e.-ebe: .eii alcohol or ^ Ikylj-henol lie; t at 1.3-1.8. The resulting condensate is be but 'each ± using an alcohol xür the specified Äthyleno. -_ "yd range optimum properties in accordance with this -ilrfindung' .verden then reacted with butylene oxide which beschriebensn Äthozylate so dai it> a terminal Hydroxybutyloi ^ fG group obtained. In this division, Butylenos ^^ d is used in an amount of 0.5- '";" i: I-oil per LIoI iithoxylate. JJie preferred compositions arise through further condensation of the etho: ;; - lats with something like Liol Butyleno: iyd. Js can Angev again a basic or n ui * e catalysis / ends

909842 / 16U
BAOORiQfNAt

- * - 181U39

A base such as sodium hydroxide is used from the standpoint of convenience Method preferred. However, the use of an acidic catalyst such as boron trifluoride results in one Product with better physical properties. The temperature ranges including the preferred ranges discussed for ethoxylate manufacture also apply for condensation with butylene oxide. A wide variety of butylene oxides can be used to produce the nonionic detergents be used. 1,2-butylene oxide is preferred.

Example

φ A series of ethoxylates with a terminal hydroxybutyloxy group was obtained by reacting ethylene oxide with an alcohol at about 177-182 ° C in the presence of HaOH as a catalyst in an amount of about 0.125% based on the alcohol weight and then reacting with 1.2- Butylene oxide (or propylene oxide in comparison) produced at approximately the same temperature. In the experiment in which the condensation with butylene oxide was carried out in the presence of BF ₀ as a catalyst (about 0.1 % based on the ethoxylate weight), the crude i-thoxylate was first neutralized with glacial acetic acid and then filtered. All end capped products were then heated to 171-182 ° G to remove light ends at 10 mm Hg. It was then neutralized and filtered. Details of the compositions, their properties in foam tests and their wettability according to the Draves test are given in Table 1 below. The table also shows the general resistance of the various products compared to biological assimilation in a standard test for biological degradation.

909842 / 16U

BATHROOM

1-8UA39

Tabel

Primary alcohol mixture Percent iO LIoIe BO 'per mole attempt or ■ * G ₁₀ -S / j σ _1έ in ethorsylate i-thoxylate 1 -85> > '· - -7 / Ä 59 1.0 ir 60 -1.0 3 61 1.0 4th Il 58 5 5 & 0 6th 45;. 60 5 0

1) BF ^ as a catalyst for the condensation with Butylenoxjd

2) Condensation with the indicated charged propylon oxide

Eye test - ITr « 2fr . dd No.' 3 No. 4 Wetting test Biological attempt number 1 "0 , 4 0.3 0.7 br. ρ Ability to dismantle 1 ■ C. ,, 5 0.3. 0.8 7.2 , JUt 2 -: 1 * 2 ■ 0. ,, 5 0.5 0.7 7, c out 3 1.7. 0 , 4 0.3 O ₁ S- 6.2 , -Ut. 4th 1.4 2 , 0 0.9 1.3 11.2 SUt 5 2, δ O 0 0.2 6.3 Well 6th 0 * 5 16.7 bad

-Ifr. 1 -

Summary of the different test methods:

0.1 % surface active substance in 200 ml aq. Isg. Agitated in a malt mixer at high speed and 23.9 0/3 min.tfaoh 2 min., Leaving to stand, the foam height was measured in cm.

iße STest-Nr * 1 at 60 ° G.

0 _f GG6 % surfactant and 0.194 % sodium silicate in 200 ml aq. Lag. Stirred in a malt mix at high speed and 60 Q / 3 sum * Haeh 4 ^> see the oehaumhöhe in em

^ Kr. 2
3

firmly ~ IIr, _4-0,.; 006 % surface-active substance, 0.194 A sodium

silicate and O ₁ I % Miloh powder in 200 ml aq. Lag * Bas ^ estverfabren is the same v / ie in the Sest-Iir. 3 The winners 3 and 4- measure the defoaming ability in the presence of. Proteins.

- I & gfc the wetting time of a 0 _t i surface active fabric with 23 * Dicaves cotton yarn and a 3 g ha applies *

^ des

G * A 5 g en were ver

BADORI ^ NAU ,, ",, ..

Claims (1)

181U39 "Patent Entrepreneurship 1. .i / little foaming non-ionic detergent produced by Kealrbion of 0.5-1.5 ^ ol Eutyleno?: Yd with a londen.Tction.jprodulct aua 4-1C hol itti ^ lenoryd and a LoI a »- ; Alkanols with 6-16 C-atoms or a hol ο ine ^ ... Hz; 'l ^ henols. with Ö-12 G-atoms in .illc / l- Jubstituenten obtained v / ird. 2 · Little foaming niohtiono ^ enes detergent η. ch .jupruch 1, characterized in that ^r lv.L · das ^ lkanol lir.G & r and is orimary. 909842/1614 BATH ORIGINAL