DE2022342A1 - Process for the production of surface-active phosphate ester compositions - Google Patents

Description

DR. R. ρο:; γ:: ■■. '. ;;: · der

dr. ε. Bü / .iMü * 20223A2

DTPL.-ING. HJ MÜLLER £. υ Δ tone

Pat <? Ntauwj: le

8 Munich 80 Dr .Τ / Dr F / Ww

Lncile - Grahn - Straiia 38 W 14- 6

Teleion 44 37 55 ^

Witco Chemical Corporation, 277 Park Avenue New York , New York 10017 (V.St.A ..)

Process for the production of surface-active phosphate ester compositions

The invention relates to the manufacture of surfactant compositions, and more particularly to an improved method for the production of surface-active compositions with mixtures of primary and secondary phosphate esters organic compounds containing hydroxyl groups.

Consisting of phosphate esters or containing phosphate esters Surfactants are known as well as numerous processes for their preparation and are for example in U.S. Patent 3ehrif "fei 1 944 53o, 2o52 o29, 2656 372, 3oo4 o56, 3oo4 o57, 3o33 889, 3o42 697 and 3o88 917.

Even though many of these known procedures are highly effective it has been shown that the products obtained in this way are somewhat discolored, veiled or look cloudy and not color- and acid-resistant during storage are.

However, clear, light colored products have many uses for surfactants necessary. For example, numerous manufacturers of such masses have strict color specifications for liquid ones Detergents and filterability regulations for dry cleaning formulations. In addition, the acid

109849/1936

BATH ORIGINAL

tendency of the esters to slip during storage lead to serious corrosion problems, which is why here Remedy must be found.

According to the invention, it has now been found that mono- and diphosphate esters and mixtures thereof with surprisingly improved color properties and considerably increased color and pH stability during storage can be produced if 1 mole £ 9 ^ 5 ^m ^ 2-4.5 Reacts moles of a non-ionic surface-active agent under practically anhydrous conditions and then hydrolyzes the phosphate oatsr with at least about 0.5% by weight of water at a temperature below the decomposition temperature of the phosphate ester.

It has also been found that when used as reactants in the process of the invention non-ionic surface-active agents made from alkylene oxide adducts of organic, hydroxyl-containing groups Compounds with at least 6 carbon atoms exist, these adducts in more advantageous Way less than about 0.5 wt. $ Polyglycol by-products with a molecular weight greater than 1,000.

In the case of the nonionic ones suitable for the preparation of the phosphate esters in the context of the process of the invention As a rule, surface-active agents are organic compounds containing hydroxyl groups with at least 6 carbon atoms and one reactive hydrogen atom, preferably around the Alkylene oxide condensation products of these hydroxyl-containing organic compounds.

ORIGINAL BATHROOM

109849/1936

As a respondent in the process the invention used condensation products of alkylene oxide and hydroxyl-containing organic Compounds are known and, as well as suitable processes for their preparation, in numerous patents and other references. As a rule, they can be obtained by condensing an alkylene oxide, for example of propylene oxide, butylene oxide or preferably ethylene oxide with an organic Obtained compound having at least 6 carbon atoms and one reactive hydrogen atom will. Suitable compounds with a reactive hydrogen atom are, for example, straight and branched-chain aliphatic alcohols having at least 6 carbon atoms, especially linear ones and branched chain saturated alcohols having 8-18 carbon atoms, as well as phenols, especially those Mono- or dialkylphenols with about 4 - 2o carbon atoms called in the alkyl radical. The amount of the organic compound containing the hydroxyl groups des The type of condensed alkylene oxide described can vary within wide limits. The amount of alkylene oxide depends mainly on the particular compound with which it is condensed and can be found in the Individual cases can easily be determined by preliminary examination and on the basis of routine examinations. Usually be at least 2 moles of alkylene oxide, preferably ethylene oxide with one mole of the hydroxyl-containing organic Compound of the type described condensed, preferably between about 6 and 14 moles of ethylene oxide to 1 mole of alkylphenol and between about 4 and 12 moles of ethylene oxide to 1 mole of aliphatic alcohol omitted.

109849/1 936

BATH ORIGINAL

Are by-products of the alkylene oxide condensation reaction high molecular weight polyglycols. It has been found that the presence of these polyglycols in the phosphate ester product a reason for a veiled, cloudy end product especially when the phosphate ester is in conjunction with organic dry cleaning solvents is used. Consequently, it is highly beneficial in the manufacture of phosphate esters according to the process of the invention, alkylene oxide condensation products to use, which contain practically no polyglycol by-products. Particularly suitable are alkylene oxide condensation products that are no longer than about 0.5% by weight of polyglycols with a molecular weight of greater than 1,000.

Non - ethoxylated, non - ionic surfactants that are used to make phosphate esters Suitable for the process of the invention are organic compounds containing hydroxyl groups with at least 6 carbon atoms and one reactive hydrogen atom. As suitable compounds may be mentioned: aliphatic alcohols, both straight and branched chain aliphatic alcohols, e.g. 2-ethylhexanol, octanol, decanol, dodecanol and octadecanol; cycloaliphatic alcohols such as cyclohexanol and cyoloheptanol; higher fatty alcohols With at least 8 carbon atoms, which are obtained from the various fatty acids of glycerides leave, as well as multi-branched primary alcohols with at least 7th carbon atoms and the Molecular configuration of an "alcohol" as used in the oxo process is obtained from a polyolefin.

109849/1936 ραπ original

20223 ■%

Manufactured by the method according to the invention Phosphate esters can be obtained from the phosphorylation products one or more of the described non-ionic, surfactants or mixtures thereof. Such mixtures are also included the scope of the present invention.

When carrying out the phosphating reaction according to the invention, the phosphating agent used is preferably P ₂ O ₅ . 1 mole of PgOc is reacted with about 2-4.5 moles of the nonionic surfactant described at a temperature not higher than about 100 and preferably at a temperature between about 35 and 65 ° C., and under practically anhydrous conditions.

After the end of phosphorylation, at least about 0.5 and preferably between about 1 and 3 wt and ^{hydrolyze Ho 0} C, whereupon the reaction charge is cooled to about 30 ° C. The hydrolysis stage has the surprising and unexpected effect that the polyphosphates formed during the phosphorylation decompose without the phosphate ester product being hydrolyzed. This makes it possible in the; The problem of the pH value shift, which usually occurs during storage, is practically eliminated and the color of the product is significantly improved.

1 09849/1936

The products obtained according to the invention can be in the form of the free acid or in the form of partially or completely neutralized salts with alkali metals, ' Provide alkaline earth metals, ammonium and organic amines as cations. Use in the form of such Salt is preferred or necessary in some cases, for example when used in alkaline surfactants Masses or in areas of application where thermal stability is required, for example as dry cleaning detergents, use.

Neutralization of the phosphate esters can be accomplished using a number of known neutralizing agents accomplish by known methods. It is particularly suitable for areas of application that require high temperature stability require, expediently, that the water added during the neutralization stage is removed effectively and quickly. A particularly advantageous method for neutralizing the according to the invention produced phosphate ester consists in that one 50 # strength sodium hydroxide solution with vigorous stirring at a temperature (of the batch) between about 4o and 6o ° C in one based on stoichometric considerations and add to the final pH-based amount desired for the hydrolyzed phosphate ester. The ' The neutralized batch is then cooled to about 50 ° C. and fed into a vacuum thin-film evaporator. Here the water is removed quickly at a temperature of 9o ° C, with a product with less than about 0.5 wt. ^ water is obtained.

109849/1936

Any suitable compound with the desired metal, ammonium or "organic amine" substituent can be used to prepare the neutral salt of the phosphate esters prepared according to the invention. The use of aqueous sodium hydroxide solutions has proven to be particularly advantageous for this purpose, since the water of the neutralized Phosphatesterlösung be easily ^peeled: I ^{-:.: "■} '. .. ■ '■' ■ ^'': ■■ ^{":: -::} ■

A maximum thermal stability of the phosphate ester can be achieved by practically all of it Water removed from the neutralized product, iPhos-. phatesl ^ 'with more than about 0.5% by weight of water especially when higher temperatures occur Hydrolysis, resulting in a bad color and a Loss of clarity as well as increased health Acidity leads. Various known methods are available by means of which the water can be rapidly removed from the neutralized solutions possible is »The vacuum thin-film evaporator is particularly advantageous. It is essential that the water is removed as quickly as possible in order to hydrolyze the phosphate ester to prevent during this procedural stage.

The products produced according to the invention have largely dependent on the (or those) as Reactants used specific nonionic surfactant (s) surfactants, foaming, emulsifying, wetting agents, and surfactants cleaning properties. These products where

109849/1936

it is calibrated with regard to the phosphate groups present in it to mixtures of primary phosphate?; star with secondary phosphate esters with 2 non - ionic Residues and the like have certain advantages as surfactants.

The products according to the invention can be depending on the intended use with the usual alkaline substances, additives guilders), soap, suspending agents, brighteners, stabilizers and the like mix. In particular, they are suitable for mixing with commercially available organic solvents, e.g. perchlorethylene, Stoddardl exercise agents and carbon tetrachloride, for use in dry cleaning types. The following examples are supposed to do that Explain the method of the invention in more detail. All percentages mean "percent by weight".

example 1

Were approximately in a reaction vessel 5 moles of 7 moles Aethylenoxydaddukts of tridecyl alcohol with about o, c3 $ water and less than about o, 5 introduced i <> polyglycol and heated to about 6o ° C. 1 mol of phosphorus pentoxide was added with vigorous stirring, the temperature being kept at about 60 ° C. When the PgOtj addition was complete, the reaction was allowed to run for about 8 hours, the temperature being maintained at about 60 ° C. A sample of the reaction batch was taken for analysis. Then about $ water, based on the reaction charge, was added with stirring.

109849/1936

and raise the temperature of the batch to about 90 ° C. The hydrolysis reaction airde for about 4 hours run out, the temperature being kept at 90 ° C. during this time. After the Cooling to below 30 ° C, a sample was taken for analysis.

The analysis results are summarized in Table 1 below.

5 Table 1 io) 60 After After 8th hydrolysis Phosphorylation 1 * Water (addition in 9o Temperature in ° C io) 14.8 4th Time in hours 27o Non-ionic surface active 14.4 Medium (addition in 185 Velcro color

It can be seen from the results in the table that an improvement in color was achieved and none Hydrolysis of the phosphate ester product has taken place Has.'

1098 U 9/1936

Example 2

Example 1 was repeated, with the exception that the phosphorylation reaction was carried out for 5 hours a temperature of 55 ° C and 6 hours at a temperature of 6o ° C and the hydrolysis reaction 3 hours at a temperature of 60 ° C with 1 $ water.

The analysis results are summarized in the following table:

Table 2 6th After Hydro 6o Iy se According to the phosphory ι $ lation 2 3 Water (addition in i °) - 12.9 6o 6o Time in hours 3 85 Temperature in ⁰ C 35 2 Non-ionic 12.6 surface active 69 65 Medium (addition in $) 2 Color according to Klett 88 PH value

The results contained in the table clearly show those obtained by the hydrolysis treatment without Hydrolysis of the phosphate ester product caused parboil improvement. pie lower starting temperature in the case of phosphorylation, the color improvement resulted this example in comparison to the one in Example 1

1 09849/1936

sufficient color improvement, immediately after phosphorylation and after hydrolysis and after 90 days Samples of the phosphate ester taken from aging were analyzed for acidity. In the case of the hydrolyzed There was no increase in the sample, whereas the sample taken before hydrolysis was 7.5% Showed an increase in acidity. To that described in the The way obtained, hydrolyzed phosphate ester reaction charge was stirred and under vigorously Maintaining a batch temperature of around 5o ° ■ -. ■■ < a sufficient amount of sodium hydroxide in the form of a 5ο # aqueous solution was added. After all the sodium hydroxide solution had been added, the Batch cooled to about 50 ° C and placed in a, at about 90 ° C working vacuum thin-film evaporator, in which the water to a content of below about o »50 wt. # was removed, fed in. The Velcro (coloring) The value for the neutralized batch was determined to be 77. ·

Example 3

In a reaction vessel, 3 moles of a 6 mole - ethylene oxide adduct of nonylphenol with about 0.02% water and less than about 0.55% polyglycol were filled and heated to a temperature of about 60 ° C. One mole of ^P 2 ° 5 was added with vigorous stirring while maintaining the temperature at about 60 ° C. When the PgO ₅ addition was complete, the reaction was allowed to proceed for about 4 1/2 hours, the temperature being reduced to about

109849/1936

6o ° C was held. A sample of the reaction batch was taken for analysis. About 1% by weight of water, based on the reaction charge, was then added and the temperature of the charge was increased to about 90.degree. The hydrolysis reaction was allowed to proceed for about 2 hours and then the batch was allowed to cool to below 30 ° C. Here, a sample was used
Analysis taken.

The analysis results are summarized in the following table 3:

Table 3

After the after the
Pho β pho rylation hydrolysis

Water (addition in ^) 4.7 l, o Non-ionic upper 224 area active agent (Addition in 9ί) + 5 1 ° 4.4 Color evaluation according to Klett 157 Acidity (after 90 days ger aging) no increase

The results in the table show that the color improves and no increase in non-ionic components was observed, suggesting that hydrolysis of the phosphate ester did not occur.

BAD ORIGINAL 109849/1 936

" ¹⁵ "■■■■■■; 20223A2

Example 4

a.) Phosphorylation ? ;

It was a mixture of non - ionic components, consisting of 641 g of ethoxylated linear aliphatic alcohol primary (C ^ ₀ -, C ₁₂ - and C ₁₄ - alkyl) with 63 weight 686 g fi branched chain ethylene oxide and γ. , ethoxylated Bbnylphenols with 55 Gew. ^ ethylene oxide provided. This mixture was introduced into the reaction vessel and mixed with 142 g of phosphorus pentoxide while stirring> while a vessel temperature of 40 - 50 ° C was maintained. When the P ₂ Oc addition had ended, the temperature was increased to 60 ° -65 ° C. and the reaction charge was left at this temperature for 6 hours. After this time, the phosphorylation was complete, which corresponds to a P ₂ O ^ analysis (as H ^ PO.) Of about 0.5% by weight and an analysis of the unreacted, non-ionic constituents of about 10% by weight .

b) hydrolysis :

About 1 wt. # Was related to the reaction charge on; the fraction batch, water added, in front the reactor heated to 90 ° C for 2 hours became. The batch was then cooled to 30 ° C calmly. : ■ ::; :

10 9 84 _{9/1936 bä} d ORtGiNAL

o) neutralization :

A sufficient amount of 50% sodium hydroxide solution was added to neutralize the phosphate and bring the pH of the aqueous solution to about 6.5. The NaOH solution was added to the reaction batch over a period of about 10 minutes while stirring, the reaction batch being boiled to maintain a temperature of 40 ° C. During this neutralization, the temperature should not be allowed to drop below 40 ° C., since the mixture has a tendency to gel formation when NaOH is added at lower temperatures. After neutralization, the aqueous solution was immediately fed to a vacuum thin film evaporator (Asco Rota - Film Molecular Still) with an available evaporation area of about 324 cm (o.35 sq. Ft.), Whereupon the water was added within 30 minutes at a temperature of 9o - Ho ⁰ C was driven off. When about 10 parts of neutralized phosphate ester of this example was mixed with 90 parts of perchlorethylene solvent, a clear, almost colorless solution could be obtained.

One after finishing the. ' hosphorylation removed

, __ _m,. _. , _ Phosphate esters and sample aged 12o days at room temperature showed a 13.8% increase in acidity, while a sample taken after hydrolysis showed no acidity increase after 12o days of aging.

ORIGINAL BATHROOM

109849/1936

Example

Following the procedure described in Example 4 were produced phosphate esters using the alcohol mixtures mentioned below as reactants:

A) 64-1 g of the linear, aliphatic alcohol ethorylate? SSd 880 ^P g ^{e of} an ethoxylated, linear nonylphenol with 64% by weight of ethylene oxide;

B) 544 g of ethoxylated, linear, aliphatic, primary alcohol (C ₁₀ - and C ₁₂ - alkyl radicals) with 60 ethylene oxide and 293 g of 2-ethylhexanol;

C) Io52 g of an ethoxylated, linear dodecylphenol with 54% by weight of ethylene oxide and 293 g of 2-ethylhexanol and

D) 489 g of ethoxylated, linear, aliphatic, primary alcohol (C ₁₂ , C ₁₃ , C ₁₄ and C ₁₅ alkyl radicals) with 39% by weight of ethylene oxide and 293 g of 2-ethylhexanol.

When mixed with perchlorethylene, clear, almost colorless, stable solutions of the phosphate esters wet A, B, C and D of this example are obtained. Samples taken immediately after the hydrolysis treatment masses A, B, C and D showed no increase in acidity after aging for 12 days at room temperature.

109849/1936 ORIGINAL BATHROOM

-yt-

Example 6

According to the process described in Example 4, an equimolecular mixture of the 7 mol - ethylene oxide adduct was obtained of tridecyl alcohol and the 9 mol - ethylene oxide adduct of nonylphenol a neutralized phosphate ester manufactured. A liquid sample weighing loo g was poured into a Furnace introduced. This sample had a water content of about 0.5 Grew, # and was tested with samples of the same phosphate ester, however, each of which had the water content given in Table 4 below, compared.

Table 4

To veil education wt »$ Water Days

o, $ 5 43

1.0 I » 18

1.5 I » 16

2, o $> 16

The formation of sole eggs, which indicates instability, is due to the precipitation of sodium phosphate formed as a result of hydrolysis of the phosphate ice.

D ORIGINAL

1 09 SA 9/1936

- patent claims -

Claims (5)

Patent claims Process for the production of a surface-active phosphate residue, characterized in that one a) 1 mole I * 2 ⁰ 5 ^{mi <fc 2} "" ^ ⁹ ^ moles' of a non-ionic surfactant, consisting of a linear or branched-chain, saturated alcohol with 6-18 carbon atoms, a mono- or dialkylphenol, in which the alkyl residue has 4 - 20 carbon atoms, or a 2-14 mol - alkylene oxide adduct of these alcohols and alkylphenols, in which the alkylene oxide consists of ethylene oxide, butylene oxide or propylene oxide, as well as mixtures thereof under practically anhydrous conditions at a temperature of about 25 - Ho ° C and that one b) the phosphate ester reaction charge is hydrolyzed at a temperature between about 6o and Ho ⁰ C with about 0.5-3.0 wt. 2. The method according to claim 1, characterized in that Means that the non - ionic surfactant / off a condensation product of about 4-12 moles of ethylene oxide and 1 mole of aliphatic alcohols B - 18 carbon atoms, a condensation product of 6-14 moles of ethylene oxide and 1 mole of alkylphenols ^ it consists of 4 - 2o carbon atoms in the alkyl radical or mixtures thereof. 109849/1936 3. The method according to claim 2, characterized in that that the ethylene oxide condensation product is less than about 0.5 wt. $ polyglycols having a molecular weight from over looo contains. 4. The method according to claim 1, characterized in that one further comprises the phosphate ester with an alkali metal, Alkaline earth metal, ammonium or organic amine ions containing basic solution neutral A ized and that the neutralized phosphate ester reaction charge quickly removes the water / aass the neutralized product less than about 0.5 wt Contains water. 5. The method according to claim 2, characterized in that one further comprises the phosphate ester with a weight of about 5o #igen aqueous sodium hydroxide solution and that one then from the neutralized phosphate ester reaction charge quickly removes the water, leaving the neutralized product less than about Contains 0.5% by weight of water. 109849/1936