DE2523588A1 - POLYGLYCOL ETHERMAL FORMALS AND THEIR USE AS CORROSIVE WETTING, DETERGENT AND CLEANING AGENTS - Google Patents

Description

Polyglycol ether-based formals and their use as caustic alkali- resistant wetting agents, detergents and cleaning agents

The present invention relates to nonionic polyglycol ether thermal formals, and the use of these derivatives in caustic alkali-resistant, low-foam wetting agents, detergents and cleaning agents .

It is known that polyoxyethylated alkylphenols and polyoxyethylated Fatty alcohols have surface-active properties, which make them particularly suitable for use in wetting agents, detergents and cleaning agents or as emulsifiers. at many fields of application, such as B. when used in detergents and detergents for dishwashers and washing machines as well as when cleaning metal surfaces by spraying, However, the strong Scliaumvennögen affects this Connections unfavorable.

Attempts have already been made to reduce the strong foaming tendency of such detergents and cleaning agents by using suitable components, so z. B. of BlockpolyniPrisaten made of polypropylene glycol and Ethylene oxide or other known foam suppression systems, to reduce. However, satisfactory results are not always obtained here. One downside to using it the known nonionic surface-active compounds is also that these products in the presence of strongly alkaline substances, e.g. alkali hydroxides, alkali silicates or alkali phosphates «, are not sufficiently stable. The nonionic products decompose or decompose as a result of the action of the alkalis

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Discoloration.

It has now been found that it is particularly advantageous as a surfactant Surface-active agents that can be used in wetting agents, detergents and cleaning agents Compounds are obtained when the addition products of alkylene oxides with long-lasting, aliphatic ^ A3.kohole or mono-, di- or trialkylphenols - hereinafter referred to as polyglycol ethers - the terminally closed mixed formals manufactures.

The invention relates to nonionic polyglycol ether mixed formals of the general formula I:

R ₁ -O- (X - O) _n - CH ₂ - 0 - R ₂ (I),

in the rule for a lipophilic group, in particular a straight-chain or branched alkyl or alkenyl radical with about 8 to 22, preferably 8 to 18, carbon atoms or a mono- | Di- or trialkylphenol radical with a total of about Ik to 26, preferably 16 to 2k carbon atoms, R ₀ for a straight-chain or branched alkyl radical with 1 to 5j, preferably k carbon atoms, η for 5 to 50, preferably 5 to 30 and, X for an alkylene radical with 2 to 3 carbon atoms, the ether chain (X - 0) consisting entirely of ethoxy units or containing at most n / 5 isopropoxy units.

The polyglycol ether mixed formals of the formula I according to the invention can be prepared by adding 1 mol of an alkyl- _f alkonyl or alkylphenol polyglycol ether of the formula R ₁ -0- (XO) -II in which R ₁ , X and η have the meanings given above, with about 3 to 8 moles, preferably k to 6 moles, of an alcohol of the formula R 0 OH, in which _{R 1 has the abovementioned meaning (} and about 0.5 to 1.0, preferably 0.52 to 0.58 moles of formaldehyde per OH equivalent in Presence of a strong acid such as

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Sulfuric acid or p-toluenesulfonic acid as a catalyst in which heat is converted. Formaldehyde can be used for the reaction in the form of a concentrated aqueous solution or, preferably, as paraformaldehyde; however, it is also possible to use the corresponding amount of trioxane. The strong acid to be used as catalyst is expediently added in such amounts that an acid number of about 2 to 8, preferably 3 to 5 (n> g KOli consumption per g reaction mixture) is established in the reaction mixture. The reaction is expediently carried out with stirring and simultaneous removal of the dialkylforinal formed in the reaction and the water of reaction. In general, the reaction is carried out at temperatures of about 120 to 190 ° C., preferably 160 to 170 ° C., until no more water can be discharged; this is generally the case after a reaction time of about 3 to hours. The reaction mixture is then cooled and neutralized. It is useful here to use a suitable filter aid, such as. B. Kieselguhr in amounts of about 0.5 to 3 wt. % Added. The dialkyl formal still present in the reaction mixture is then separated off from the mixed formal formed by distillation, expediently under reduced pressure. The mixed formal obtained in this way can then be freed from the salts present by filtration. The distilled dialkyl formal of the formula R OCH ₀ OR can be reused for further reactions taking into account the alcohol _{content R 0} CIl, which can be determined from the hydroxyl number of the dialkyl formal.

An essential feature of the process for the preparation of the polyglycol ether thermal formals _{according to the invention is the formation and use of a dialkyl formal R 0 -OCH-OR 0} , which fulfills the function of a dragging agent for removing water and at the same time, however, an aucliv'i ^ reactive component in the equilibrium reaction Formation of the polyglycol etheric formal is included.

The compounds according to the invention show in aqueous solution an extremely weak tendency to foam. You can therefore with special Advantage as a foam suppressor for non-ionic and cationic ones Compounds in wetting agents, detergents and cleaning agents

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can be used. The products according to the invention are also stable in alkaline solution and in the presence of caustic alkali. They have excellent surface-active properties and can therefore be of particular advantage for such uses are used with good cleaning and wetting properties, but little or no foam formation are required.

Because of their good alkali tolerance and their foam-suppressing properties The compounds according to the invention are suitable for properties with advantage for the production of dishwashing detergents and cleaning agents, especially industrial cleaning agents, e.g. for Cleaning of metals, glass, dishes, bottles and the like. The compounds of the formula I or mixtures of the compounds according to the invention Compounds are suitable for the production of liquid or solid detergents and cleaning agents. You can optionally alone or in combination with other known nonionic, cationic or anionic substances, framework substances and other additives or auxiliaries in the washing and detergent formulations can be used.

Suitable anionic detergent raw materials, such as those used as components detergents and cleaning agents containing polyglycol ether mixed formals According to the invention can be used are those of the sulfonate or sulfate type, for example alkylbenzenesulfoiates, especially n-dodecyl benzo sulfonate, olefinsulfonate, how they z. B. by sulfonation of primary or secondary aliphatic Monoolefins with sulfur trioxide and subsequent alkaline or acidic hydrolysis can be obtained, as well as alkanesulf onates, such as those produced by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutral isotion from n-alkanes or by bisulfite addition to olefins. Suitable Anionic detergent raw materials are also oC sulfo fatty acid esters, primary and secondary alkyl sulfates, such as the sulfates of alkoxylated higher-molecular alcohols. More anionic Compounds that may be found in the detergents and cleaning agents that can also be used are the higher molecular ones

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sulfated partial ethers and partial esters of polyvalent ones Alcohols, such as the alkali salts of the monoalkyl ethers or mono fatty acid esters of glycerol monosulfuric acid ester or 1,2-dioxypropanesulfonic acid. Furthermore, the sulfates come from Oxalkylated fatty acid amides or alkylphenols, as well as fatty acid taurides and fatty acid isethionates into consideration. Suitable, optionally to be used anionic detergent raw materials also alkali soaps of fatty acids of natural or synthetic origin, e.g. B. the sodium soaps of coconut, palm kernel fat or Tallow fatty acids.

The anionic detergent raw materials mainly come in their form Sodium, potassium or ammonium salts for use; However, they can also be in the form of their salts with organic bases, such as mono-, Di- or triethanolamine are present. Unless the said anionic Surface-active compounds have an aliphatic hydrocarbon radical, so it should have about 8 to 24 carbon atoms have and preferably be straight-chain. In the compounds with an araliphatic hydrocarbon radical, the alkyl radicals have about 6 to 18 carbon atoms.

Polyglycol ether derivatives of long-chain alcohols, carboxylic acids or alkylphenols, which contain about 3 to 30 glycol ether groups and about 8 to 22 carbon atoms in the hydrocarbon residue, are particularly suitable as nonionic washing raw materials that can be contained in the detergents and cleaning agents according to the invention. Such polyglycol ether derivatives, in which the number of Äthylengl3 koläthergruppen ^r are preferably used from about 5 to 15 and their Kohlenwasserstoffresig from primary, gcradkettigen alcohols having from about 8 to 18 carbon atoms or of alkyl phenols having 6 to Ik carbon atoms having Alkylrestefiv / Burcft * addition of about 3 to 15 moles of propylene oxide to the polyethylene glycol ethers mentioned

detergent raw materials are obtained, which are characterized by a low level of foam distinguish and also in the inventive Detergents may be included.

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Other suitable non-ionic washing raw materials are the water-soluble, about 20 to 25O ethylene glycol ether groups and about Polyethylene oxide adducts containing 10 to 100 propylene glycol ether groups to propylene glycols and alkylpropylene glycols having 1 to 10 carbon atoms in the alkyl radical. The latter compounds usually contain about 1 to 5 ethylene glycol units. As non-ionic washing raw materials In addition, those of the amine oxide and sulfoxide type, which can optionally also be alkoxylated, can also be used

Suitable builders which can also be added to the washing and cleaning agents according to the invention are, in particular, the condensed phosphates such as tripolyphosphates and, in particular, pentasodium dipolyphosphate. The T _r ± polyphosphates can also in a mixture with more highly condensed phosphates, such as "Tetra phosphates or their llydrolyseprodukten such as acidic or neutral Purophosphate _(be employed.

The condensed phosphates can also be wholly or partly replaced by organic, complex-forming aminopolycarboxylic acids will. These include, above all, the alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid. Are also suitable also the salts dex · diethylenetriaminopentaacetic acid, as well as the higher homologues of the aminopolycarboxylic acids mentioned, such as poly (N-succinic acid) ethyleneamines and poly (N-tricarballylic acid) ethyleneimines with average molecular weights of about 500 to

500,000.

Further suitable builders are those which have a complex-forming effect

water-soluble potassium and sodium salts of higher molecular weight

Polycarboxylic acids, e.g. B. Ethylenically unsaturated polymers Mono-, oli- and tricarboxylic acids, ivie acrylic acid, maleic acid, Fumaric acid, itaconic acid, citric acid, aconitic acid, jiesakonic acid and methylenemalonic acid. Copolymers of these, too Carboxylic acids with each other or with other copolymerizable substances, such as. B. Ethylenically unsaturated hydrocarbons, such as ethylene, propylene, isobutylene and styrene, or with ethylenic unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and

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Crotonic acid or other ethylenically unsaturated alcohols, Ethers, esters, amides and nitriles can be used.

In addition, those which act as complexes can also be used as builders polyphosphonic acid salts, e.g. B. the alkali salts of amino polyphosphonic acid, especially aminotri (methylene phosphonic acid), ethylene diphosphonic acid, methylene phosphonic acid and 1-hydroxyethane-1,1-diphosphonic acid be used in detergents and cleaning agents. Finally, mixtures of the. called complex-forming Compounds with each other or with other additives, such as B. alkali salts, especially sodium silicates, also carbonates, bicarbonates, borates and citrates.

The other additives and auxiliaries in detergents and cleaning agents include inorganic per-compounds, as well as activators and stabilizers for these per-compounds, optical brighteners and enzymes from the class of proteases, lipases and analases, as well as neutral salts, in particular sodium sulfate and bacteriostatic substances. Known graying inhibitors, in particular carboxymethyl cellulose, can also be added to increase the wear capacity. If necessary, the detergents and cleaning agents can still be known foam suppressants such. B. saturated fatty acids or their alkali soaps with 20 to 2 ¹ l carbon atoms, as well as higher molecular fatty acid esters.

The amount of the compounds according to the invention in the detergent and cleaning agent formulations can vary within wide limits. It will generally be about 1 to 20 percent by weight, preferably 2 to 10 percent by weight, depending on the intended use and conditions of the washing and cleaning agents. However, amounts which go beyond this range can also be used without further ado. The new compounds of the formula I are also biodegradable and thus meet the legal requirements for detergents in many countries. The washing and cleaning agents can be in a solid, especially powdery, or preferably water-containing liquid consistency. _ g _

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Example 1:

In a 2-liter stirred flask equipped with a stirrer, thermometer and separating apparatus

784 g (1 Hol) of a reaction product of 1 mol of one

C. _{/ 19} fatty alcohol with 1315 moles of ethylene oxide

370 g (5 moles) of n-butanol 9 ^Z * 15 S (3.15 moles) of paraforaldehyde

and 2.5 ml H _rj> SO. presented together and with stirring up to a reaction temperature of 160 ° C., the water of reaction is removed from the system.

The specified amount of paraformaldehyde corresponds to the theoretical amount + 5 % excess.

After no more water can be discharged, the temperature increases to 100 ° C cooled, the catalyst acid contained in the reaction mixture Neutralized with sodium sulfate solution and at the same time kieselguhr added as filter aid.

The excess dibutyl formal is then distilled off from the formed mixed formal on. This happens up to a maximum temperature of approx. Ι4θ C at approx. 20 rabar. The resulting mixed formal is freed from the salts it contains by filtration.

Final weight: 826 g = 95 % of theory

The cloud point of this product in 1% aqueous The solution is> 11.8 ° C ^ the remaining OH number is 12.5.

Formally, at 30 C it is a brownish, clear liquid.

The recovered dibutyl formal is used in further approaches reused tin tor taking into account the butanol contained Part that can be determined from the hydroxyl number of the dibutyl formal leaves.

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Example 2:

Using the same procedure as in Example 1, the apparatus described there

622 g (1 mol) of a reaction product of 1 mol of C ₁ , .. "fatty alcohol with 9 moles of ethylene oxide

320 g dibutylforinal (recovered, (= 0.26

with hydroxyl number '' ± 5) OH equiv.)

7k g (1 mole) of n-butanol

35.6 g (1.185 moles) of paraformaldehyde. 2.5 ml H ₂ SO, conc.

implemented. In order to achieve the necessary dibutyl formal supply only 1 mole of fresh butanol per mole of Fettalkoholoxäthylat needed.

Yield: 655 g = 96 % of theory residual OII number: 12.3,

Cloud point (1% aqueous) 31.5 ⁰ C

Example 3

The following are reacted in the same way as described above: 5 ^ 9 pounds (1 mol) of a reaction product of 1 mol of C ₁

Fatty alcohol with 8 moles of ethylene oxide, 370 g (5 moles) of n-butanol 9 ^, 5 g (3.15 moles) of paraformaldehyde, 2.5 ml of H ₀ SO. conc.

Yield: 613 g = 96.5 % of theory. Residual Oxl number: 17

Cloud point (i% aqueous): 24 ° C

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Example 4:

The following are reacted in the same way as described above: 622 g (1 mol) of a Unisetzurigsproduktes of 1 mol C., ^

alcohol with 9 moles of ethylene oxide 370 g (5 moles) isobutanol 9 ^, 5 g (3.15 moles) paraformaldehyde 2.5 nil H ₉ SO ^ conc.

Yield: 65O g = 95 % of theory residual OH number: 11.5,

Turbidity purict (1 ° o aqueous): 3 ² C

5:

In the same way as described above, the following are reacted: 780 g (1 mol) of an addition compound of 1315 mol

Ethylene oxide on 1 mole of a C ₁ , fatty alcohol

320 g dibutil formal, recover with OH number 90

7k g (1 mol) n-butariol 39 »7 S ( ¹ ^ ² mol) paraformaldehyde 2.5 ml H ₂ SO ^ ₁ conc.

Yield: 830 g = 96 % of theory, residual OH number: 12.

Cloud point (1% aqueous): kl C

Example 6:

The following are implemented in the apparatus of Example 1:

622 g (1 mole) of an addition compound of 9 moles of ethylene oxide and 1 mole of a C _-1 ,., "- fatty alcohol

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43O g (25 mol) dibutyl formal, pure (OH number 2.) 6 g p-toluenesulfonic acid

The reaction components are presented together and at a Bottom temperature of about 160 ° C for 2 hours at reflux. After cooling to 100 ° C., sodium methoxide solution is used again

neutralized and vie in example 1 the excess

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formally removed by distillation.

This is found in the distilled dibutyl formal during reformalization Butanol has become acidified by an OII number of 84.

Mixed formal yield: 65O g = 95 % of theory, residual OH number; 18, cloud point 1%, aqueous: 3 ^, 7 ° C

For the following application examples, the following compounds of the formula I were used (here stands AeO for ethylene oxide). The connections were made according to the procedure described in example 1:

Product A.

C ₁₀ / C ₁₂ alcohol-9Ae0-butyl mixed formal

Product B

C / C ^ alcohol-o ¹ AeO-butyl mixed formal

Product C

C ₁₂ / C _{lZi -alcohol} -lOAeO-Butylmi s chf ormal

Example 7 ^:

Ls becomes eLn alkaline cold cleaner by stirring the following Components manufactured:

23 parts by weight of a dodecylbenzenesulfonatrium

7 parts by weight of product A

30 parts by weight of petroleum from the boiling range I90 - 240 C

5 parts by weight n-butanol

2 parts by weight of oleic acid

1 part by weight of an aqueous sodium hydroxide solution (38 Be)

1 part by weight of sodium tripolyphosphate

2 parts by weight of trisodium phosphate 29 parts by weight of water

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Example 8:

An alkaline detergent for dishwashing detergents consists of the following components: ''

2.0 parts by weight of product A 4l, 5 parts by weight of anhydrous sodium metasilicate 35.0 parts by weight sodium tripolyphosphate

1.5 parts by weight of the sodium salt of dichloroisocyanuric acid

20.0 parts by weight sodium carbonate

The liquid product is sprayed onto the remaining powdery substances during mixing.

Example 9

A powdery abrasive consists of the following components:

ο parts by weight of a secondary sodium alkanesulfonate

with 13 to 18 carbon atoms in the alkyl radical 1 part by weight of product B 10 parts by weight trisodium phosphate 20 parts by weight sodium pyrophosphate

30 parts by weight of sodium carbonate

31 parts by weight of sodium sulfate

The abrasive is made by simply mixing the components.

Example I Q: __

A liquid disinfectant cleaner is made by mixing the following Components prepares:

10 parts by weight of Rokosfettalkyl-dimethyl-benzyl-ammonium chloride

5 parts by weight of the product C 85 parts by weight of water

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Example H:

For the preparation of a powder disinfectant cleaner

20 parts by weight coconut oil t-alkyl-dimethyl-benzyl-ammonium chloride or id.

35 parts by weight of sodium carbonate

kO parts by weight of sodium tripolyphosphate

5 parts by weight of product C

intensely mixed.

For game 12:

For the production of an alkaline spray cleaner for metal surfaces are in a mixing drum

10 parts by weight sodium hydroxide (powdered)

65 parts by weight of sodium silicate

10 parts by weight of trisodium orthophosphate 10 parts by weight of sodium carbonate

mixed well and thereafter at l ^au f ^"enc * he sprayed drum 5 parts by weight of the product A and mixing is continued for a time.

The spray cleaner shows when spraying and cleaning metal surfaces Good cleaning effects in aqueous solution and no disruptive foam formation. The product is also storage-stable.

Example 1 3:

A liquid, neutral spray cleaner for metal surfaces has the following composition:

30 parts by weight of the trietinolamine salt of coconut fatty acid 1.5 parts by weight of an annealing compound of

8 moles of ethylene oxide to 1 mole of nonlyphenol 2.5 parts by weight of product A

66 parts by weight of water

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When cleaning metal surfaces with a 3% solution With this product, a good degreasing of the surface is achieved without foaming.

Example 3Λ:

The liquid formulation of a rinse aid has the following composition:

11 parts by weight of product C • 3 parts by weight of a reaction product of 1 mol

Isotridecyl alcohol with 5 moles of ethylene oxide and 20 parts by weight of citric acid 66 parts by weight of water

The rinse aid was used in a commercially available automatic dishwasher tested at 80 C and an amount of 0.5 g per liter. Even when hard water was used, no deposits occurred or haze formations on the wash ware. The foaming was low.

Example 1 5:

An alkaline bottle cleaner was prepared by mixing the following components:

25 parts by weight of pentasodium tripolyphosphate

25 parts by weight of sodium metasilicate

32 parts by weight of sodium carbonate

15 parts by weight sodium hydroxide (powdered)

3 parts by weight of product A

When used in a bottle, the bottle cleaning agent shows The cleaning machine does not foam.

At an application concentration of 1.5 percent by weight Beer and milk bottles, some of which still have labels were perfectly cleaned. The labels were good

replaced.

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The disinfectant cleaner described in Example 10 was after DIN 53902 (whipped foam number) comparing to analogous structures Investigated disinfectant cleaners, which instead of the product C according to the invention, the same amount of the following Products contained:

a. Reaction product of 1 mole of 12 moles of oleyl alcohol Ethylene oxide (product U)

b. Reaction product of 1 mole of C., _ - C _{1 r} -oxo alcohol with 9 moles of ethyl dioxide (product V)

c. Dissolution product of 1 mole of C ₁ ^ ₁ - C, - alcohols with 5 moles of ethylene oxide (product W)

The foam cleaners were used in a concentration of 5 g per liter for the tests. The Schauinverhalten was determined at (1O ⁰ C and 60 ° C The results are shown in Table 1 below.:

Table 1

Foaming behavior of disinfectant cleaners according to Example 10 Foam height in cm (DlN 53902)

Product '10 ° C 60 ° C

C. 120 I70 U 32Ο 350 V 26Ο 250 W. I9O I90

In the same way, the foam behavior of a machine dishwashing detergent according to Example 8 was compared with an aruxlog dishwasher detergent which, instead of product C according to the invention, contained the same amount of a decomposition product of 1 mole of isotridecyl alcohol with 10 moles of ethylene oxide (product J). The tests were carried out in water of 0 and 15 dH at kO C with a concentration of SjjüI-

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carried out by means of 5 g per liter. The results are in Table 2 contain:

Table 2

Foaming behavior of machine dishwashing detergents according to Example 8 Foam height in cnT at 40 ° C (DIN 53902)

Product water 0 ° dll water l5 ° dH

without load with load without load with load immediately after 5 'immediately after 5' immediately after 5 'immediately after 5'

90 70 100 6o 90 60 8o

The foaming behavior of the bottle cleaning agent described in Example 15 tmrde compared to similarly structured bottle cleaning agents which only replace the Product A the same amount

a. a reaction product of 1 mole of isotridecyl alcohol with 10 moles of ethylene oxide (product X) and

bt of an addition compound of 12 moles of ethylene oxide with 1 mole of hexadecyl alcohol, which was further reacted with 1 mole of benzyl chloride (product Y)

contained.

The foam tests were carried out in accordance with DIN 53902 at 20 °, 50 ° and 70 ° C. with solutions that were 5 pi'o liters of each Bottle detergent contained. The compiled in Table 3 Results clearly show the superiority of the Bottle cleaning agent according to the invention compared to the products used for comparison «

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Table 3

Viewing behavior of bottle cleaning agents according to Example 12, foam height in cm

CD O CO OO CTJ

20 ° C

50 ⁰ C

70 ⁰ C

O OO OO

product

0 ° dii

0 ° dii

l5 ° dH

0 ° dII

without B, with B, without B, with B, without B, with B, without B, with B, without B, with B, without B, with B SOf. 5 «SOf 5 'SOf 5' SOf.5 'SOf. 5 'SOf. 5 «SOf. 5 'SOf 5 * SOf. 5' SOf. 5 ¹ SOf. 5 "ROf 5 '

80 60 100 80 So 60 80 70 70 50 8o 60 70 50 3o 60 50 20 70 4to 70 ko 70 '10

60 kO 70

70 (OK 80

10

- 20 10

cn

CO

cn 00 00

Claims (6)

Patent claims: 1. Nonionic polyglycol ether thermal formals of the general formula 1 RO- (X - 0) -CH ₀ -OR ₀ (I), in which R _{1 stands} for a lipophilic alkyl or alkenyl radical with about 8 to 22 carbon atoms, or a mono-, di- or trialkylphenol radical with about 14 to 26 carbon atoms, Rp for an alkyl radical with 1 to 5 carbon atoms, η for 5 to 50 and X stands for an alkylene radical with 2 to 3 carbon atoms, the ether chain (XO) consisting entirely of ethoxy units or at most η - isopropoxy- Contains 5 units. 2. Nonionic polyglycol ether formals of the general ■ formula I according to claim 1, characterized in that R is a butyl radical. 3. Wetting agents, detergents and cleaning agents, characterized by a content of nonionic Polyglykoläthermiscbfornialen der general formula I according to claim 1. 4. Wetting agents, detergents and cleaning agents according to iVnspruch 3, thereby characterized in that their content of nonionic folyglycol ether thermal formals of the general formula 1 about 10 to Weight percent is. 5, · Process for the production of nonionic = poly glycol · - ethereal formals according to claim 1, characterized in that 1 JSoI of an alkyl, alkenyl or alkylphenol polyglycol ether of the formula R "-G- (XG) -H with about " j to £ moles of an alcohol of the formula R ₀ OH, where R .., X, η and R ₁ , have the meanings mentioned in claim 1, and et>: a 0.5 to 1.0 mol of formaldehyde in the presence of a strong Si ' ure SAD ORiQfNAL - 19 - 609851 / 088S HOE 75 / Ρ ^Λ 136 as a catalyst in the heat, with removal of the dialkylformaIs of the formula R ₀ CH ₀ OR and the water of reaction. 6. The method according to claim 5 _t, characterized in that the reaction is carried out at 120 to 190C. 609851 / 088S