CS264704B1 - Penivophenic wetting agent effective in a wide range of pH - Google Patents

Abstract

A wetting agent with reduced foaming, effective in a wide pH range, which contains 60 to 94.9% by weight of a surfactant component consisting of 40 to 80% by weight of surfactants of the formula: R-O(C2H4O)nH and 20 to 60% by weight of surfactants of the formula: R-°(C2H4O)n(C3H6O)mH, 5 to 30% by weight of diol and/or triol with a molecular weight of 76 to 94 g.mol"! and 0.1 to 20% by weight of water, where R represents alkyl and/or alkylaryl with a number of carbon atoms in the alkyl chain of 8 to 16, n represents an integer of 5 to 15 and m represents an integer of 3 to 18. It can be used in particular in the textile industry.

Description

The invention relates to a wetting agent with reduced foaming, which is effective in a wide pH range and has a solidification temperature below 0 °C, suitable in particular for use in finishing processes in the textile industry.

Nowadays, there are very few sectors of the national economy where surfactants are not used - substances that, due to their specific structure, facilitate and accelerate some physical and chemical processes at the phase interface. Surfactants are used in geological exploration, in the extraction and processing of oil and ores, in the metalworking industry, in construction, in the pulp and paper industry, in the production of leather and furs, in pharmacy and cosmetics, in the production and processing of plastics, in the textile industry, in agriculture, in the food industry, as well as in household chemicals. A characteristic property of surfactants is that they are surface-active, they adsorb in a solution at the phase interface, thereby creating a surface film. Friction results in a decrease in the surface tension of the given solution, compared to the surface tension of the solvent.

In technical practice, surface phenomena often play a decisive role in a certain technological process. These are, for example, operations: adsorption, flocculation, formation of dispersions, suspensions, emulsions, foams, wetting, washing, cleaning, lubrication, solubilization, heterogeneous catalysis and many others. According to the specific action in a certain technological operation, the relevant surfactants are designated as dispersants, solubilizers, emulsifiers, foamers, wetting agents, detergents, etc.

An important group of surfactants are wetting agents, which are used in many refining processes where work is done in an aqueous environment. Wetting is generally understood as the creation of a new phase interface between the solid and liquid phases at the site of the original phase interface between the solid and gas phases. This is a complex phenomenon that depends on many factors, the most important of which are: the surface tension of the liquid, the nature of the physical and chemical structure of the surface of the solid phase, diffusion, adhesion, temperature, surfactant concentration, etc.

In addition to the textile industry, which is their largest consumer, wetting agents are also used in mechanical engineering (e.g. in electroplating), in the chemical industry (in the production of plant protection products), in the production of leather and fur (e.g. in soaking), as well as in other industries.

Many compounds have been developed to date that have wetting properties. Among the synthetic surfactants, the oldest was Turkish red oil (an alkaline salt of partially sulfated castor oil). Development continued with other anionic type wetting agents, sulfated esters of castor acid, sulfated amides and sulfonamides of unsaturated fatty acids. These also include sulfated products of primary and secondary fatty alcohols, as well as alkaline salts of alkylnaphthalenesulfonic acids. Alkyl sulfoesters of succinic acid with an alkyl chain containing 6-8 carbon atoms have very good wetting properties.

The above surfactants belong to the group of anionic surfactants. They have very good wetting efficiency, but they also have some negative properties such as high foaming, in some cases poor compatibility with other components of finishing baths, and possibly worse stability, especially in alkaline environments. For these reasons, nonionic surfactants are increasingly used, mostly based on reaction products of alkylene oxides with higher fatty alcohols, alkylphenols, alkanolamides, etc. They have somewhat lower wetting efficiency, but they have better compatibility and generally lower foaming than anionic surfactants.

Specific examples include a wetting agent according to NSR Pat. Appl. 2,030,131, which is a reaction product of a _C10 to _C14 alcohol with oxirane, low-foaming wetting agents according to NSR Pat. 2,126,918 and Jap. Pat. 74,127,951 based on reaction products of higher alcohols or alkylphenols with alkylene oxides and styrene oxide. A non-foaming wetting agent for washing or dyeing textiles according to NSR Pat. 2,213,383 is a reaction product of 5 to 8 moles of oxirane with 1 mole of _C10 to C14 diol. Other products with similar properties include oxyalkylated alkanolamides of higher fatty acids according to USSR AO 427 002. A wetting agent based on esters of alkyl polyglycol ethers with paraffin monocarboxylic acids according to Czechoslovakia AO 193 967 has high wetting efficiency with very low foaming.

Nowadays, in addition to good wetting efficiency and low foaming, other properties are required from a wetting agent for the textile industry, in particular stability and good solubility in alkaline and acidic solutions, as well as high efficiency in a wide pH range and, last but not least, good manipulability. When designing a modern universal wetting agent, anionic and nonionic surfactants, or their mixtures, are most often used. A wetting agent with high efficiency, low foaming and stability to alkalis at higher temperatures according to the ČSSR A. O. 190 937 is based on sulfated waste products from the production of 2-ethylhexanol.

Among nonionic products, we can mention a wetting agent according to Europ. pat. appl. 51 878 (Union Carbide Corp.) based on oxyalkylated alcohols, as well as a surfactant according to Europ. pat. appl. 36 550 (BASF A. G.), the active ingredient of which is an adduct of a fatty alcohol with oxirane, the polyoxyethylene chain of which is terminated by propylene oxide, or a surfactant according to US pat. 3 539 518, in which the polyoxyethylene chain of the alkyl polyglycol ether is terminated by an acyl group.

The disadvantage of the substances mentioned is that they have relatively high foaming, or rather their wetting efficiency in alkaline baths is low. Wetting agents based on anionic surfactants, especially 2-ethylhexylsulfonsuccinate, despite the fact that they are considered the most effective wetting agents, have high foaming in a neutral environment and in an alkaline environment, even at a concentration of 10 g.l”^

They decompose with NaOH and cannot be used.

The above-mentioned shortcomings in this area are largely eliminated by a wetting agent with reduced foaming, effective in a wide pH range, characterized by containing 60 to 94.9% by weight of a surfactant component consisting of 40 to 80% by weight of a surfactant of the formula:

RO(C ₂ H ₄ O) _n H and from 20 to 60% wt. surfactant formula:

^R -°< ^C 2 ^H 4 ⁰ »n ^ÍC 3 ^H 6 ^0, m ^H up to 30 wt. % of diol and/or triol with a molar mass of 76 to 94 g.mol ^- ''' and 0.1 to 20 wt. % of water, wherein:

R represents alkyl and/or alkylaryl with a number of carbon atoms in the alkyl chain of 8 to 16 n represents an integer of 5 to 15 m represents an integer of 3 to 18

The wetting agent can be diluted with water, organic solvents or combined with other surfactants regardless of ionicity as needed. The wetting agent modified with diol and/or triol has a lower freezing point, so there are no problems with its dosing and preparation of working solutions even in winter. For the above reasons, the use of this wetting agent in operational practice is advantageous in terms of lower thermal energy consumption. 1,2-propylene glycol and glycerin have proven themselves as diol and/or triol. Monoethylene glycol and diethylene glycol are not recommended due to their toxic properties. Lower polyethylene glycols are also not suitable due to the lower effect of lowering the freezing point.

The advantage of the wetting agent with reduced foaming, effective in a wide pH range according to the invention is, in particular, low foaming, good solubility in water and stability in neutral, alkaline and acidic solutions, as well as high wetting efficiency not only in neutral but also in acidic and alkaline solutions. By the term wide pH range we mean pH from 1 to 13. The advantage is the simultaneous achievement of a synergistic effect by combining the individual surfactant components, which favorably affects the application properties. This phenomenon, as well as other advantages, are evident from the examples.

Example 1

By homogenization at 60 °C, a surfactant mixture was prepared consisting of 50 wt. % nonylphenol with 10 moles of oxirane and 50 wt. % nonylphenol with 10 moles of oxirane, to which 12 moles of methyloxirane were further bound. The resulting concentrate was adjusted with 30 wt. % 1,2-propylene glycol and 10 wt. % water to an active ingredient content of 60 wt. %.

Wetting efficiency was determined in distilled water and in water containing 30 gl ^- '' NaOH according to ON 66 6129. The wetting time of cotton rings was measured at a wetting agent conc. of 1 gl The lower the wetting time, the higher the wetting efficiency. Foaming was determined at 20 °C and a product conc. of 1 gl ^- ''' by the method described in ČSSR AO 208 350. The foaming of the solution was 125%, the wetting time in distilled water was 16.5 sec. and in a NaOH solution with a conc. of 30 gl ² was 142.3 sec.

In an acidic environment with a concentration of 4.5 g ^/ l of 98% sulfuric acid, the wetting time was 21.0 sec. The solidification temperature was minus 15 °C. For comparison, sodium 2-ethylhexyl sulfosuccinate had a foaming capacity of 274% under these conditions, a wetting time in distilled water of 17.1 sec. and in NaOH with a concentration of 30 g/l ² it lost its wetting effect because it decomposed.

Example 2

Mixtures of the following basic surfactant components were prepared:

A - nonylphenol with 10 moles of oxirane

B - nonylphenol with 10 moles of oxirane plus 12 moles of methyloxirane

C - nonylphenol with 10 moles of oxirane plus 15 moles of methyloxirane

mixture number surfactant (% wt.) foaming (%) wetting time in seconds, ratio of wetting times in NaOH of conc. 30 gl ^-1 theoretical/ /measured A B c end of week ₂ 0 . 1 gl in NaOH with a concentration of 30 gl ^-1 measured theoretical 1 100 - 178 22.3 33.8 33.8 1.0 2 90 10 - 146 - 38.1 99.0 2.6 3 80 20 - 140 18.0 26.5 164.0 6.2 4 70 30 - 135 - 30.4 229.0 7.5 5 50 50 - 125 16.5 142.0 360.0 2.5 6 20 80 - 93 17.0 352.0 555.0 1.6 7 - 100 - 17 22.0 686.3 686.3 1.0 8 100 - - 178 22.3 33.8 33.8 1.0 9 90 - 10 155 - 38.2 138.2 3.6 10 80 - 20 141 20.7 30.1 242.7 8.0 11 70 - 30 134 - 32.9 347.1 10.2 12 50 - 50 114 19.5 39.4 556.0 14.1 13 20 - 80 80 39.6 385.0 869.4 2.2 14 - - 100 8 75.9 1078.3 1078.3 1.0 From example 2 is to see, that by mixing components A with component B, , covering C foaminess increases-

with it, the components B and C decrease, the wetting time in distilled water is, except for mixture No. 13, better than for the basic components and the wetting time in a strongly alkaline environment in NaOH with a concentration of 30 g/l ² (pH = 12.6) is better than the theoretical value. The maximum synergistic effect is manifested at a ratio of component A of 70 to 80% by weight and 20 to 30% by weight of component B, and in the second case at a ratio of 50 to 80% by weight of component A and 50 to 20% by weight of component C.

Example 3

A surfactant mixture consisting of 40 wt. % nonylphenol with 9 moles of oxirane and 60 wt. % fatty alcohol with 12 to 15 carbon atoms with 10 moles of oxirane and 7 moles of methyloxirane was prepared. 90 wt. % of the surfactant concentrate mixture was treated with 5 wt. % 1,2-propylene glycol and 5 wt. % water. The wetting agent prepared in this way, under the conditions given in Example 1, had a foaming capacity of 125.0%, a wetting time in water of 31.9 sec. and in NaOH of a conc. of 30 gl ^-1 41.0 sec. The freezing point was minus 5 °C.

Example 4

A surfactant mixture consisting of 80 wt. % of a fatty alcohol with a number of carbon atoms of 12 to 15 with 10 moles of oxirane and 7 moles of methyloxirane and 20 wt. % of nonylphenol with 9 moles of oxirane was prepared. 80 wt. % of the concentrate was treated with 19.9 wt. % of 1.2 propylene glycol and 0.1 wt. % of water. The wetting agent prepared in this way had a low foaming capacity of 145.0%, a wetting time in water of 17.8 sec. and in NaOH of a conc. of 30 gl ^- ^ 44.2 sec.

The freezing point was minus 12 °C.

Example 5

A surfactant mixture consisting of 50 wt. % octylphenol with 15 moles of oxirane, 50 wt. % nonylphenol with 15 moles of oxirane and 18 moles of methyloxirane was prepared. 70 wt. % of the concentrate was treated with 29.5 wt. % dipropylene glycol and 0.5 wt. % water. The wetting agent prepared in this way, under the conditions given in Example 1, had a foaming capacity of 117.0%, a wetting time in water of 23.7 sec. and in NaOH of a conc. of 30 gl ^{1 of} 31.5 sec. The solidification temperature was minus 12 °C.

Example 6

A surfactant mixture was prepared consisting of 70 wt. % of a fatty alcohol with a number of carbon atoms of 13 to 15 with 10 moles of oxirane and 30 wt. % of a fatty alcohol with a number of carbon atoms of 13 to 15 with 10 moles of oxirane and 7 moles of methyloxirane. 60 wt. % of the concentrate was treated with 20 wt. % of a glycol mixture consisting of 1 part of 1,2 propylene glycol and one part of dipropylene glycol and 20 wt. % of water. The wetting agent prepared in this way had a low foaming property of 148.0%, a wetting time in water of 37.8 sec. and in NaOH of conc. 30 gl ^- ^ 53.8 sec.

The freezing point was minus 13 °C.

Example 7

A surfactant mixture consisting of 60 wt. % nonylphenol with 5 moles of oxirane and 40 wt. % nonylphenol with 9 moles of oxirane and 3 moles of methyloxirane was prepared. 94.9 wt. % of the concentrate was treated with 5 wt. % glycerin and 0.1 wt. % water. The wetting agent prepared in this way had a low foaming capacity of 32.0%, a wetting time in water of 126.9 sec. and in NaOH of conc. 30 g.l 329.2 sec.

The freezing point was minus 5 °C.

Example 8

A wetting agent was prepared according to Example 3, except that instead of the fatty alcohol with 12 to 15 carbon atoms, a fatty alcohol with 12 to 18 carbon atoms was used. The foaming, wetting time and solidification temperature values were at the same level as in Example 3.

Claims (1)

OBJECT OF THE INVENTION Low foaming wetting agent, effective over a wide pH range, characterized in that it contains 60 to 94.9% by weight of a surfactant. % surfactant component consisting of 40 to 80 wt. surfactant formula: % RO (C ₂ H ₄ O) _n H to 20 to 60 wt. surfactant of formula: ^R = ° ^C 2 ^H 4 ^O 'n ^<C 3 ^H 6 ° m ^H 5 to 30 mol. diol and / or triol with mol. weight g.mol 76-94 ^{- "1"} and 0.1 to 20% by weight of water, wherein R is alkyl and / or alkylaryl having 8 to 16 carbon atoms; n is an integer of 5 to 15 m is an integer of 3 to 18.