DE2416018A1 - AMPHOTERIC SURFACE-ACTIVE MEDIUM - Google Patents

Description

Amphoteric surfactant putty oil

The present invention relates to novel amphoteric surfactants and quaternary phosphates or sulfates; it relates in particular to ethoxylated amines that are quaternized and then phosphated or partially sulfated and procedures for their use. The new derivatives of certain amphoteric, water-soluble compounds are characterized by the following formula:

, [OCH ₂ (CH ₂ ) _x ] y 0 [Z] _S H _V

M A

^R 1 10CK ₂ (CH ₂ ) _x 3 _y 0 [Z] H _u

'in which R and R are identical or different alkyl chains with 1-2 2 carbon atoms, Z is PO- or SO, χ is an integer from 1 to 3, y is an integer of 1 to 50, t and s each represent numbers with a word from 0, Π5 to 1, u and υ each represent numbers with a value of

409843/1112

0 to ü, yr> -, where the sum of (s + v) and (t + u) respectively must be equal to 1. The sum of s, v, t and ζ must be equal to 2.

Furthermore, f'i stands for hydrogen, a cation, such as, for example, any metal, or amine, and Λ stands for an anion from the group consisting of halogen, sulfate or alkyl sulfate.

There are already many different types of amine phosphoncts sulfonates, phosphates or sulfates and related compounds described. However, none of these compounds have found substantial technical significance, and none have all of them Unusualized properties of the compounds according to the invention.

In the past few years there has been significant research into of phosphates in order to improve the lubricating and rust and corrosion inhibiting properties of the new synthetic ones surface-active preparations are carried out. Most of these surfactants have surfactants as active Part of anionic ions. Research continued to focus on sulphates for the purpose of improving cleaning and cleaning properties Foaming properties of the new synthetic detergent preparations. Most of these synthetic detergent preparations have anionic ions as the active cleaning ingredient. As representative / for the various anionic ones to improve the surface-active cleaning agent and the foam properties in such Additives used in detergent preparations can include alkali metal phosphates, borates, carbonates, sulfates, chlorides, silicates, higher aliphatic alcohols, such as lauryl alcohol, and higher fatty acid anides and alkylolamides, such as lauroyl amide, lauroyl mono- and dialkylamides, lauroylethanolamide and lauroyldiethanolamide,

409843/1112

to be named. The use of the above alkali metal salts, in particular of phosphates and borates resulted in the so-called "structure" - ocjcj: "heavy-duty" detergents. While these preparations partially for Suitable for use in various types of cleaning machines they find limited use for pods in which some type of metal lubrication and cleaning is in question. They also find limited use in areas where substantial skin contact is made and delicate due to them their alkaline reaction and chemical nature. For the latter purposes, 'hoofed' or 'lighter' detergents are not used bziu. Cleaning agent with a practically neutral pH range preferred.

When used for shampooing, the soaps commonly used often form insoluble salts which ^deposit on the hair and thereby give it a dull appearance and usually require acidic rinses to remove them; they are irritating to the eyes, prone to precipitation at a pH of 7 or below, and poor foaming at a pH of 6-7.

Although the amides of these amino acids show better resistance to hard water than usual soaps, they foam Bad in hard water and have poor foam stability: they make the hair dull like the usual soaps Use as shampoo, however, to a lesser extent, and they are precipitated in an aqueous medium at a pH of 4.5.

It has been found that the preparations according to the invention are very valuable Surfactants include, alone or in admixture with other cationic, anionic or non-ionic

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nbejrf l: k; hariaktivon means based on the above mentionedon Areas voruiendct lacrüen künncn.

The preparations according to the invention include their very valuable ones Group of surface-sensitive gowns, din as amphoteric compounds, i.e. chemical agents that are both cationic and anionic Groups contained in a single molecule are known and hence a high degree of stability and remarkable usability show in concentrated electrolytic solutions. These compounds show you an unusual chemical Stability under prolonged contact with alkaline systems. The products made from the compounds of the invention have the following advantages: They have good surface active agents Properties so that they can be used as detergents; furthermore, they can be used as a hair shampoo above or below a pH range of, for example, 3-10; They have the advantage of preventing the accumulation of electrostatic charges; they are well tolerated by the skin and eyes and cause «- things therefore no noticeable irritation or irritation. This property makes the compounds liquid when incorporated into them Foam baths, soaps, fabric softeners or fabric softeners, Lubricants, rust inhibitors, corrosion inhibitors, cleaning agents for hard surfaces, alkaline-soluble cleaning agents, agricultural emulsifiers, hydraulic fluids or emulsion polymerization.

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These Ai;: photoren use the phosphate or sulfate esters as n-ionic Part and thus provide new properties in addition to the creation of a double cationic / anionic functionality, such as metal lubrication and cleaning, improved corrosion inhibition, Alkali solubility or usability in the sulphate form as hot shampoos and soaps.

The phosphate esters according to the invention have the following characteristics Combination of properties: they foam on average every year or hard lass evil; they have good foam stability; they tolerate the presence of chlorine bleaches; you can in Shampoos or cosmetics used at a pH of 4.5-8.5 will and are better foam agents under these conditions: they are better detergents or cleaning agents with average or hard water; they are at a pH up to 4.5 not failed; they are not irritating to the eyes or skin, and they are relatively non-toxic.

The amphoteric compounds according to the invention are used as washing, Foam, wetting and emulsifying agents can be used and have a unique combination of properties that are new and improved Supply products for lubricants, pesticide emulsifiers, hard surface cleaners, etc. They can also be used as surfactants Agents used in the treatment of natural and synthetic fibers in the textile and related fields, where they are used as synthetic detergents, dyeing auxiliaries and softeners Find suitability.

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The invented Gulfatesters have the following unnatural combination of f-igones: they irritate the eyes in concentrations at which irritation becomes noticeable; they have a good Gchau: .ibeständigkeiV'j ^s ite tolerate Anuionenheit of chlorine bleaching; When used as a shampoo, they do not dull the hair and therefore do not require any special conditioner; They give hair softness and malleability after shampooing in common and hard water; they can be used in shampoos and other cosmetics at a ·! pH 4.5-8.5 uses aercion and are better foaming agents under these conditions; they are better cleaning or cleaning with more average or hard water. Laundry detergent; they are not precipitated; with a pH word

up to 4.5 they do not irritate eyes or skin, and they are relative non-toxic.

The amphoteric compounds according to the invention are used as washing, Foaming, butchering and emulsifying agents are suitable and are used in the field of shampoos and cosmetics. Furthermore, they are useful as treatment surface active agents natural and synthetic fibers in the textile and related fields, where they are used as synthetic detergents, dyeing auxiliaries and plasticizers can be used.

The amphoterics from which the compounds of the invention are derived are themselves suitable as surface-active agents, have good foaming properties and find use as general purpose detergents, textile treatment agents, Emulsifiers and as components in cosmetics, toilet preparations

advise and shampoos.
/ * and are better foaming agents in ordinary and hard water

409843/1112

_ 7

The experience was surprising?!? j se fRntt ;; Gstnl.lt that non by Quaternisioren oiriF: s alkoxylated amine and subsequent phosphntation or sulfation cioroelber ·. Wnrbindungen heryfcol inn can containing the Arnin-, hydroxyl, quaternary cn Ammoniun ¹ .- and phosphate functions.

These amphoteric surface naUtivcjn V / nrbinc.'ungcn are gogonühnr well-known Uorbinoungen of Uorte.il um! apparently show no significant i äaslcktrischcn point u;. a general oberf lächonaktivo and physical fligünschaftnri as löslichkoit, Jühaunbildung us ¹ Jj. , on a w f- "iηi w uπ.

The present invention relates to photographic chemical preparations, those in aqueous solutions with an acidic, neutral or alkaline one pH can be used. In the former, they serve as cationic surfactants; in the latter as anionic surfactants.

According to the invention, new products, such as surface-active preparations, Rust and corrosion inhibitors, cleaning agents for hard over, flat, agricultural emulsifiers, pesticide emulsifiers, wetting agents, Lubricants, shampoos, soaps, bubble baths, textile treatment agents or fabric softening agents will.

As noted, the present invention provides more photonic compounds of the following formula:

0 9 8 4 3/11 1 ORIGINAL BATHROOM

OCH ₂ (CH ₂ ) _x ] _y 0 [Z

y s ν

M A

OCH ₂ (CH ₂ ) _x ] y 0 [Z

in ωulcher R and R ″ stand for identical or different alkyl chains with 1-22 carbon atoms; Z stands for PO, odor SO-, χ is a number from 1 to 3, y is a number from 1 to 50, t and s each stand for numbers with a value from 0.05 to 1, υ and ν mean numbers with a value from 0 to 0, S ³ S ₅ ujobei the Sun-rae of (s + v) and (t + u) must be equal to 1. The sum of s, v, t and ζ must be equal to 2. M also represents hydrogen, a cation, for example a metal, or amine, and Λ denotes an anion from the group consisting of halogen, sulfate or alkyl sulfate.

R and R preferably have 1-18 carbon atoms, especially 2-12 carbon atoms; χ is preferably 1; and y is preferably 2 to 2o and in particular - 3 to 10. If M is a metal, this can be Wa, K, Mg, Ca, Al, preferably Na or K, be. If M stands for an amine, this can be an alkanolamine or A.lkylaniin, preferably honoathanolarnin? Diethanolamine or triethanolamine, be. If A stands for a halogen, this is chlorine, fluorine, bromine or iodine, preferably chlorine. If Λ stands for a sulfate, this can be an alkyl sulfate, preferably ethyl sulfate. R and R can be different, one for a long alkyl chain and the other is a shorter alkyl chain.

As mentioned, the present invention also encompasses ancestors for the preparation and use of the above compounds.

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The novel compounds of the invention can be prepared from a precursor material be prepared by first having an alkyl anine with 6-22 carbon atoms in its alkyl 'chain in the presence a gas with an alkylene oxide conciensed. To create the quaternized coraponent and a quaternization gno.ttel added, whereupon the ethoxylated amine is quaternized. then the quatern isated to ethoxylated amine to form a quaternary Phosphates or sulfates phosphated or sulfated. the phosphntip.rtcj or sulfated amphoteric prebond is common a mixture with different amounts of monophosphate or Monosulphate, iphosphate or uisulphate and non-phosphated, non-ionic (ethoxylate) phosphoric acid.

The alkyl portion of the amine can be saturated or unsaturated, substituted or be unsubstituted. A pure source of what to use Alkylamine can be in chain length from 6-22 carbon atoms vary; Examples of pure saturated acids that can be used as precursors for such an amine are Capron, caprylic, caprine, lauric, myristic, palmitic, stearic, Arachidic and behenic acids. Unsaturated pure fatty acid precursors include those of oleic, lauroleic, and palmitoleic acids. A substituted fatty acid suitable according to the invention is e.g. Ricinoleic acid. Mixtures of the above can also be used as precursors Fatty acids, such as those commonly found in vegetable oils and animal fats and marine fats and oils occur., can be used with success. Vegetable suitable as precursors Fatty acids contain mixtures of different proportions of coconut oil, flaxseed oil, olive oil, palm oil, peanut oil, and tung oil and grapeseed oil. Animal and marine sources of fatty

409843/1112

acids with saturated and unsaturated fatty acid substituents are Dlauholzül, tallow and Sardinennl, Erf inciungpgeniäß can as Arainvorlauf er any fatty acid or mixture ν / ο η fatty acids from pure or impure sources can be used as long as they are 6-22 Contain carbon atoms in the chain.

Preferred fatty acids are those in coconut oil. A typical one vegetable coconut oil · may contain fatty acids with different lengths of 8-18 carbon atoms. These fatty acids out Coconut oil can be saturated or unsaturated.

The Alkylar.sine used according to the invention can also be used by the Be derived from esters of fatty acids. The methyl or ethyl esters of the fatty acids can easily be substituted with the polyamines Polyamines are condensed with easy removal of the occurring methanol or ethanol.

The fatty acid amine precursor is prepared by known processes; The reaction and the reaction product are known per se and do not form part of the present invention.

Then the alkylamine obtained in this way is according to known methods, e.g. by reacting the amine with the required number of moles Ethylene oxide to form the ethoxylated used according to the invention Amines, implemented. This oxyethylation is known and e.g., in U.S. Patent 1,970,573 ', among others. the The reaction is preferably carried out at elevated temperatures and pressures and can be catalyzed by quaternary hydroxides, amines, acids and / or coordination compounds, although also strongly alkaline catalysts such as KOH or -TJaCJH etc. due to the lower formation of by-products and easier control

409 8 43/1112

relatable reflection conditions are gcoignot. Because the: reaction is practically 'quantitative, determine the molecular proportions of Ethylanoxid unci amine used the average Oxyäthylenkettenlänqe of the ethoxylated amine obtained, although egg ns Product, of course, a solution from ethoxylated amines with different nylon chain length. VUe mentions there is sufficient ethylene oxide to form nines äthoxyJiorten Λ mi nc wounded that about 25-90 wt .- '.. · contains combined Γ.thyl? noxid. The optimal xyethylene chain length is used in every particular FdI mainly by the special, to oxyäthyliorteruio amine, the special detergent with which it should be mixed, the hardness of the water in which the sedative is used intended to determine the desired effectiveness of the finished product for the particular use, etc.

The present invention is made with reference to both the phosphated quaternized alkoxylated amine as well as the sulfated one quaternized alkoxylated amine described.

The product of the present invention is usually made more appropriate by reaction Ratios of alkoxylated amine in the presence of said hypophosphorous acid and a quaternizing agent, such as diethyl sulfate, the latter in quantities of 5G-100 Hol- / S, preferably 90-100 Hol .- ^, is present.

The alkoxylated products produced by the alkoxylation of primary amines Amine starting materials have the structure

RN - ^ (CH ₂ -CH ₂ O) _n ¹ H /

in which R stands for an alkyl group as defined above and π stands for an integer with a value from 1 to 50, where

A 0 9 8 U 3 / T 11 ')

Compounds in which η = 2 to 15 are preferred.

When the reaction is complete, the alkoxylated amine is treated with a customary Quaternizing agent for quaternizing the tertiary Amino group treated. According to the structural formula above, suitable urination agents are e.g. dialkyl sulfate, such as dimethyl sulfate, diethyl sulfate usu /. ; Alkylsulfonsäuren, such as Methylsu If onsäur.e, Ethyl sulfonic acid, etc. ; Benzyl halides, with benzyl chlorine, Benzyl bromide, benzyl iodide, etc .; Alkyl halides such as methyl chloride usu ;. In the production of the inventively used, Quaternary, alkoxylated amines can therefore be any common quaternizing agent be used.

Then the above quaternized preparation is preferably, but not necessarily, the unreacted quaternizing agent freed and then with a phosphating or sulfating agent implemented to form a quaternized phosphate or sulfate. Suitable phosphating agents include Phosphorus pentoxide, hypophosphorous acid and phosphorus oxychloride, Mixtures of the same, etc. include suitable suIfants Chlorosulfonic acid, sulfur trioxide, sulfamic acid and Sulfuric acid oil.

According to the invention, alkoxylated fatty amine and hypophosphorous acid are mixed together and heated to about 90-100 ° C. under vacuum. The product is then preferably cooled to 30 ⁰ C. 20-90 C; then 50-100 ο1- / ί>, preferably 90-100, of a quaternizing agent are added, and the mixture is heated to quaternize the alkoxylated fatty acid amine. Unreacted quaternizing agent can be used at elevated temperature

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and removed under vacuum. The remaining product is then cooled, whereupon the phosphating or sulfating agent slowly increases in amounts of 10-200 mol, preferably 90-110 Hol-y, at temperatures of 20-110 C, preferably 40-50 C. , is added. If phosphorus hydroxychloride is used as the phosphating agent, nitrogen is passed through the reaction mixture at this temperature until the desired level of chloride ionane, preferably 0.01-1.0 %, is reached. The phosphor oxychloric! is then poured into water and base, whereupon the surface-active solution containing the product according to the invention is obtained.

When using which chlorosulfonic acid is used as a sulfating agent Nitrogen through the reaction mixture at the temperature mentioned passed until the desired level of Chloridior.en, preferably 0.01-1.0 / o is reached. Then the sulfate is in water and base poured, whereupon the product according to the invention containing, surface-active solution obtained.

The following examples illustrate methods of manufacture typical phosphated and sulfated quaternized ethoxylated amphoteric compounds. Unless otherwise stated, all parts, ratios and percentages are parts by weight, Weight ratios and wt .- / o. AO = ethylene oxide

Example 1_

Γη a 1-1 flask provided with a stirrer, thermometer and gas inlet were 320 parts (0.5 moles) coconut amine + 10 AO and 2 parts of 50% hypophosphorous acid were introduced. the Mixture was dried at 80-100 C. under vacuum (10-15 mm), cooled to 40-50 C. under dry nitrogen, whereupon 80 parts

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(θ, 52 moles) · diethyl sulfate were added over won for 2 hours at 40-50 ⁰ C..

Unreacted diethyl sulfate was found under vacuum at 90-100 ° C. stripped. The mixture was then cooled to 30-40 ° C. under a nitrogen blanket, 35.5 parts of phosphorus pentoxide were added and the mixture was stirred for 5 hours at 1 ° C.. Cooling down to 80-85 ° C. and 5 parts of water were added, was stirred for 2 hours. In this way 433 parts of surface-active compound were obtained in a yield of 99 %.

Example 2

According to Example 1, 460 parts (0.4 mol) of tallow amine + 20 AO and 2 parts of 50- ^l , .iige hypophosphorous acid in

given a 1-1 Koiben. The mixture was under vacuum at 90-100 C. dried, cooled to 30-40 C., and then were 60 parts of diethyl sulfate were added over the course of 2 hours. The mixture of the quaternized amine ethoxylate was phosphated as follows: 1 part of 50% hypophosphorous acid was at 40-50 C, added, then at 50-60 ° C. 29 parts of phosphorus pentoxide admitted. The mixture was under a nitrogen blanket 5 Hours heated to 100 C., cooled to 80-85 C., and it 5 parts of water were added. The system was on for 2 hours at 80-85 ° C. touched. 553 parts of a 10% surface-active surface-active were obtained in this way Means.

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VJ -

Bai game

According to Example 1, 460 part o tallow amine + 20

AO, 2 parts of 5Q-yoiger hypophosphorous acid and 60 parts of diethyl sulfate to form 520 parts of quaternized tallowin; + 20 ÄO '-' ■ · implemented. Uiurde to this mixture at 40-60 C. 1 part 50 £ hypophosphorous acid and then at 40-60 ⁰ C. under a nitrogen blanket 170 parts 1i5-) OIGE Polyphcsphorsäure added. The phosphating mixture was heated to 100 ° C. for 5 hours, cooled to 80-85 ° C., and 5 parts of water were added. After 2 hours at 80-85 ° C., 1 part of 35% hydrogen peroxide was added and 697 parts of a 100% surfactant was obtained.

B ice ρ ie 1 4_

According to Example 1, 586 parts of oleylamine ± 7 Ao "and 2 parts of 50% hypophosphorous acid were dried and reacted with 286 parts of oleyl chloride for 10 hours at 60-70 ° C. The quaternized amine ethoxylate mixture was treated with 1 part of 50% under phosphorous acid and 28 parts of water are mixed. Under a nitrogen blanket C. was slowly added 142 parts of phosphorus pentoxide within 2 hours at 40-50 ^0th The. Reaktionsrnischung was heated for 3 hours at 90 C., then 5 parts water were added. The surfactant obtained it was heated to 80-90 ° C. for another 2 hours, cooled to 60 ° C., then 3/4 part of 35% hydrogen peroxide was added, giving 1042 parts of surface-active compound.

Example 5

According to Example 1, 708 parts of stearylamine were used

+ 10 AO, 2 parts 50-, oige hypophosphorous acid and 126 parts Benzyl chloride at 70-80 C. to form the quaternized amine

. U 0 9 8 4 3 / 111V

- 16 -

ätho: c.yl i-cit-DS implemented. Then u / urcie this Rn tori al reacted with 75 parts of phosphorus oxychloride for 1 hour at 4-50 ° C. Dor Chior--

f ujuruß by introducing nitrogen up a con constant chloride content removed. Din phoso-tiorte ÜäurGMixture Ui'urcio in 120 parts of 5tl- ^ igca sodium hydroxide poured and provided 900 file surface-active solution.

Example 6

The 'P ₂ G ₅ Cstcr of talganin + 20 Äü-niäthylsulfat luurde uni'-or ending of 0.1 ^: ' i ohori'li '. ■■ shan-akti.vcn middle in 'ui non-alcoholic alkali at 00 C. for fietallrinigung aoc

Storage tanks tested. The washing lasted 5 minutes. the

The table shows the cleaning power of the i-iaterials according to the invention

compared to a commercially available control sample.

Table 1
Per duct % dirt removal (Reiniciunq s' -craft)

ainphoteric phosphate ester 40.0

commercial control sample 53.0

Example 7

According to Example 6, the monophosphate gate was evaluated for metal cleaning. The aiüphoteric material according to the invention showed a scratch distance of 33 / ύ compared to 53 % for the conventional control sample.

Example £ [

The following table shows the solubility and stability in alkali of a 1-; Sigen surface-active solution at 0-100 C. through her look clear.

409843/1 1 1? BATH ORIGINAL

'*> Alkali

amphotoric phosphate ester 5.3

arciphoteric phosphate ester 17.3

ü e i s ρ i el 9

An emulsifiable pesticide concentrate was then used a single surfactant due to the cationic and ionic groups around the molecule. Emulpable concentrate for the agricultural varuenduno.

component C GIU. - / ύ amphoteric phosphate ester 5-10 Alkanolamine 2-4 Pesticide 20-40 inert solvent au.f 1U0

The following surface-active preparations were made for the specified Prepared uses, the quantities given are in parts by weight.

Table 3

liquid waste water vapor cleaning flow cleaner degreaser for

hard upper

1.0 1.0 surfaces Amphoteric phosphate ester 9.0 17.0 1.0 NaOH __ - 2.0- TKPP 90 82.0 10.0 water 100.0 1 00.0 87.0 all in all Rust inhibitor Metal 100.0 cleaning agent 10.0 10.0 ■ amphot. Phosphate ester 20.0 20.0 Triethanolamine _ " 4.0 Sodium nitrite 70.0 66.0 water 100.0 100.0 all in all

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- 10 -

Be.is p'iG3 1 Π until 15

These connections are sine! also a.1s- alkaline detergents for hard surfaces suitable and show, depending on the Hates ethoxylation an excellent resistance to alkali, anionic functionality and are hydrophobic. The alkalinity is shown in Table 4.

Table 4

Beispe. Solubility in alkali: 1 % surface-active agent, at Q-IUO ⁰ C. soluble in [y) y, NaDiI

Example / connection _ ^ _ _: % MaOH _

10 -Matriuin phosphate from coconut arr.in + 5 ACJ-. 9.4

diethyl sulfate

11 Natriu ^ phoaphat of coconut amine + 10 AO- 6.6 diethyl sulfate

12 sodium phosphate and coconut amine + 15 AO-. 4.9 diethyl sulfate

13 sodium phosphate won coconut oil in + 20 eq- 4.25 diethyl sulfate

14 sodium phosphate and coconut amine + 30 -Ä0- 3.2 diethyl sulfate

15 sodium phosphate and coconut amine + 50% - 2.4 diethyl sulfate

Example 1 j6_

The following substances / calibrators and cleaning agents / Fabric softener and disinfectant for use on textiles manufactured:

Geuj. Parts

amphot. surface act. Middle 3-7 10-30 10-30

Distearyl dinethyl ammonium halide - 3-7 3-7

n-Alkyldimethylbenzylammonium, _ "

halide

Sodium acetate 1-2

Water to 100 100 100

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B_ jj i s ρ 'i e 1 1_7

320 parts (Cl, 5 mol) of koskor.amine + 10 A (1 and 2 parts of 50% less ph.ocphorignic acid) were placed in a 1-1 flask equipped with a stirrer, thermometer and casein inlet was dried under vacuum (10-15 mm) at 90-1Π0 ° C. The intestine was cooled to 40-50 ° C. under dry nitrogen and 50 parts (0.52 mol) of diethyl sulfate were added over the course of 2 hours at 40-50 ° C .

The unreacted; Diiithylsulfnt uiurde under vacuum at 90 C3 ~ ^ü C. removed. After cooling to 3CJ ΛLJ C. were fstro with introduction of a nitrogen. it, through the droplets eüspergiorte, introduced 60 parts (.0.52 hol) of chlorosulfonic acid at 30-40 C. The nitrogen supply was ortgeoetzt for 6 hours at 30-40 ° C. up to a Cl content of 0.5 / jf. The sulfate acid was then poured into 150 parts of water, and 51 parts of 50% strength tiatric hydroxide solution were added to a pH of 7.3. This gave 615 g of a surface-active solution with 440 parts of active material, which corresponded to a 98 / JIgBn yield.

Example 1 8

According to Example 17, 430 parts of coconut amine + 15% (0.5 mol), 2 parts of hypophosphorous acid were used and dried under vacuum. At 40-50 ⁰ C. 80 parts (0.52 mole) of diethyl sulfate were added, the temperature of uiorauf 40-5Γ: C. for 2 hours maintained f-iach Abdostillieron unreacted volatile materials at 85-90 C. under a Vacuum of 2 mm was introduced at 40 ° C. 60 parts (0.52 moles) of chlorosulfonic acid under a stream of nitrogen to disperse the acid. The nitrogen supply was continued for 6 hours, then the material became

A 0 9 8 A 3/1 1 1 '-' BATH ORIGINAL

in 150 parts of water and 50 parts of 50 - ;. j.iyo3 liatriur.ihydroxid qognssen. The pH was 7.3. Go, 713 g of amphoteric were obtained. Surface-active solution with 540 g of active material, which corresponded to a 9 8 - / »ig on yield.
Example 19

According to Example 17, 400 parts of tallow amine were h- 15 Äü ([J, 5 Hol)
mixed with 1 part of 50 "hypophosphorous acid and dried under vacuum. Addition of 63 parts (0.5 f.ol) of denzyl chloride was stirred for 60 hours at 100 ° C., cooled to 30-40 ° C. and passed through at this rate a unit with
A film of liquid Schujtfeltrioxid (sulfane) passed that 40 parts (0.5 Hol) of shoe trioxide were absorbed. The acid was poured into 150 parts of water, then 60 parts of 50% potassium hydroxide to a pH of 7.6 added. Sp
710 parts of surface-active solution with 520 parts were obtained
active material

Be ispiel 20

According to Example 17, 600 parts (0.25 moles) of coconut amine became + 50
ÄO and 2 parts of 50% hypophosphorous acid dried under vacuum. At 40-50 C. 40 parts (0.26 mole) of diethyl sulfate was added "After another 2 hours at this temperature the reaction mixture was stripped at 85-9O ⁰ C. under vacuum over 2 hours, and 30 parts (0 , 26 mol) chlorosulfonic acid with dispersion by means of nitrogen at 40 C ..
added. After 6 hours of nitrogen supply, the Cl content was reduced to 0.07 / j. The crude acid was poured into 150 parts by volume of water and 28.5 parts of 50% sodium hydroxide; thus r.ian received 810 parts of an 80.5% strength surface-active solution with a pH of 7.5.

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BATH ORIGINAL

D q i s; p i e 1 21

According to Example 17, 315 parts of coconut oil + 5 AD ("Ethojvieon C-15" from Arrnark) and 2 parts of 50% hypophosphorous acid were dried and reacted with 125 parts of diethyl sulfate. The quaternary material obtained was reacted with 88 parts of chlorosulfonic acid and to reduce the Cl content
flushed to 0.2 % with an inert gas. The quaternis.-in rto sulfate acid was dissolved in 150 parts of water and 70 parts of SO - '/ uigcos
Sodium hydroxide poured and yielded 653 parts of a 70.8 - /; - strength surface-active solution with a pH of 7.6.

Be i s ρ ie 1 22,

A Schanpon formulation was made as follows:

Components G ew .- / u

Sodium sulfate won Koskosamin + _{on n} / _r . . ~ r. \

_Λ nnn -i · -j L ι ir-i. 20.0 ireStStOrf)

1OAO diethyl sulfate. > \ /

Myristylin oxide (30 % solids) 5.0 water. 75.0

100.0

The above product was evaluated in hard and soft water for Ross Miles foaming, stability (overnight at 0 C.), surface tension and pH. The results of the
amphoteric shampoos are listed in the table below.

Table 5

Foam height - mm 0.25 % at 30 C. in dist. Water: 160 (initially) 140 (after 5 min)

Foam height - mm 0.25 % at 30 C. in ppm CaCO., (Hard water) 175 (initially) 150 (after 5 min)

Clarity - 12 hours at 0 ° C: clear and stable for s Dyn cm - o, 25 % solution at 25 ° C .: 31.6 pH value found: 8.0

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As shown above, irritations that are produced and earthed that foam well in hard or even water, and when stored over night at 0 C. smell freezing (ie the Krafft point is below 0 C.); the l · s (surface tension) of a 0.25% solution is 31.6 dyne / cm at 25 C., which is well within the acceptable value for a high quality shampoo that has the / ■ s value below 40 Dynes / cm at 0.1-0.25-

/ o concentration in water · should decrease. The same Properties have been demonstrated by compounds 5-15 and? U Contained moles of ethylene oxide.

Example 2_3

The lime soap endispersionsindex ("J. Am.Oil. Chem. 3oc."; BrJ. XXVIT-88, (1950)) was determined for various of the above amphoterics and compared with a commercially available control sample ("Hiranol C2M), which is normally found in shampoo. 'and cosmetic products, and the results are shown in Table 6. The lower the number, the better the dispersing properties of

Table 7

product

Soap Dispersion Index

Sodium sulfate of coconut amine + 5 AO diethyl sulfate ¹¹ +

"+10 EO benzyl chloride

"+ 15 EO-diethyl sulfate

conc. "Hiranol C2M" (imidazoline type of fliranol Corp. )

2.5-5.0 2.5-5.0 2.5-5.0 2.5-5.0

U 0 9 8 U 3/11 1 Ι

- / ^ S) -

B e j s -ρ i ο 1 24 to 27

The following concentrates 8 to 11 were produced with different degrees of ethoxylation using the atnphoteric base of Example 20 manufactured and as liquid concentrates for bubble baths orrnuli erungsn evaluated.

Table 7

liquid bubble bath concentrate o

No. constituent 11

In the - !·}

1 2 3

Sodium sulphate from Kokosan. In _{9n f1}
■ f 5 ΛΟ-diethyl sulfate (solid) ^Z '

9 like 8 κι it 10 Λ0 (solid matter) 10 MiXG 8 with 15 ÄO '"

τ - O 20, 0 - 0 - - 0 __ O - 20, - 0 __ "_ - 0 20, 0 5, 5, 0 5, 0 5, 75 75 0 75 75

11 like 8 with 20 EO "coconut diethanolamine (control) Water (control)

100.0 100.0 100.0 100.0

All of the above formulations foamed in u / hard and hard water © Q'iie good in the presence of soap and hard water. The latter is a key criterion for a high quality bubble bath. The results are shown in Table 8.

409843/111

Table 3

Ross Miles Foam Test of Bubble Bath Concentrates - Compounds 8 through 11 of Examples 24-27

Foam height in mm (at fänqlish / after 5 min)

Formuli e runq

8 9 "To i 1

Concentrate. ppm CaLO,
Viasser
hardness Temp. Se if 0.25 0 30th 0 0.25 200 30th 0 0.025 200 37 0 , 5 O
CO
OO
.C-. G, 125 200 37 0 , 5

170/145 "175/155 180/155 135/165

815/160 185/160 19Π / Ί65 190/170

200/170 205/180 215/175 2 ok / i75

200/175 195/165 185/16-J 205/180

All of the above concentrates were stab.il after freezing over power; they were also found to be stable in a freeze / thaw cycle. ?. Q i s ρ i e 1 28 to 33

These compounds are also suitable as alkaline cleaning agents for hard surfaces and show depending on the Measure of their ethoxylation an Eius mark note alkali resistance, anionic functionality and they are hydrophobic. The alkali solubility is shown in Table 9.

Tahe11π 9

Alkaline! Solubility - 1 '!> Oborf laachenakt. Gown, soluble in (x) % NaUM at G-IOP ^{0 C.}

Sample; Jjl.erbin / Jung ^. Na GH_

12 sodium sulfate of coconut amine + 5 EO diethyl sulfate 9.4

13 "+ 10AO" 6.6

14 "+ 15 AG» 4.9

15 »+ 20ÄÜ" 4.25

16 "+ 30ÄÜ" 3.2

17 "+ 50ÄQ« 2,4 Example 34

According to Table 10, soap bars from Syndetseifen- and Syndet type with dispersing, anti-repellent and antibacterial -riellen properties for lime soaps are made.

Λ 0 9 8 Λ 3/1 1 1 V

fable Paraffin wax le IO 2 ! 5 arnphot. obarf lächenakt. middle Geii /. ~ ^C , -j 5-15 5-15 Tallow coconut soap 1 20-50 20-50 Stearic acid __ - - AlkyiriethylbenzylciMmonium- ·
halide
talc 5-15 0-20 0-20 60-80 0.5-1.0
20-60 20-60 0-10 '

Water to 100 100 100 -

Various bulking agents or diluents such as clay, hydrogenated tallow, powdered polyvinyl chloride resin, paraffin wax, starch and stearic acid can be used in the above soap preparation to reduce the cost. Of course, these materials are only used in limited quantities in order to avoid impairment of the properties of the soap, such as foaming power and surface slip. Limited amounts, e.g. below 10 ^, of certain fillers or thinners, such as starch and stearic acid, actually improve the surface lubricity of the soap. Some fillers, such as glycerine, polyglycerine (e.g. with a degree of polymerization of about 6), sugar, pectin, gelatin, finely divided silica, in limited amounts, e.g. below 15%, inhibit the cracking of the soap bars when they dry out after use.

In game 35_

The following fabric softeners, fabric softeners were used and disinfectants for textiles:

0 9 8 £ ■ * / 1 "Μ ν

2 Π- 24 1 601 δ Gοι », -'-. Ί 1 -7 1 3 3 3-7 10- 30th 3-7

ar.iphot. upper smile: = nakt. middle

D i ε * t ear y ld imet hy lamm nniurn halide -

η-Alkyidimethylbbenzylammonium- _ ^ ₁ η

halide

Sodium acetate 1-2

Water to 100 100 100

The compounds of the present invention also show the following Fiorkfiiale: foaming without water pressure; Foam recovery; Show compatibility with soap and soap enscliaum; Release properties; Solution compatibility with very high amounts of Electrodes and / or alkalis, compatibility with quaternary No killings; germicidal, gerinistatic, fungicidal and fungistatic properties; Deodorising properties; and non-drying properties on the skin.

The products according to the invention can also be mixed with other ingredients for the following uses: compounds for the purification of liquid water vapor; Floor care products; Wax remover; Car care products; anhydrous hand cleansers; Degreasers for oil tanks; Aluminum detergent; Hand wash ties; hand disinfectant detergents or "light ¹¹ " detergent compoundsJ shampoos for pets; Carpet and upholstery shampoos; Anti-hot compounds, etc.

0 9 8 L 3/1 1 1 7

Claims (1)

a t ο η t a η ε: ρ r ü ^ h c • I learned how to make compounds of the formula: 0 [Z] _s H _{v +} M A [OCrI ₂ (CH ₂ ) _x ] _y 0 [Z] _t H _u in lUGlchsr ti and R individually for an ajkyl chain with 1-2? Carbon iitornnn, Z is [ ^J C _V or SO.,>: Is a number from 1 to 3, y is an integer from 1 to> 0, t υ nc ';.> Numbers mii in each case: are led from 0.05 to 1, u and ν are each counters with a value from 0 to 0.95, (s + v) and (tiu) are each equal to 1, the sum of s + v -ι- t + u is 2, M stands for hydrogen, an iron or araincation, and A for an anion from the group consisting of halogen, sulfate or alkylsulfac stands. 2.- 'The method according to claim 1, characterized in that it in the presence of dialkyl sulfate of an alkyl, aryl or alkylaryl halide carried out as a quaternizing agent. 3.- l / experience according to claim 1 and 2, characterized in that ■ Phosphorus pentoxide, hypophosphorous as a phosphating agent Acid or phosphorus oxychloride and diethyl sulfate as dialkyl sulfate is used. 4. - Method according to claim 1 and 2, characterized in that ciuG as a sulphating agent chlorosulphonic acid and as a alkyl sulphite Diethyl sulfate is used. 5, - Method according to claim 1, characterized in that one; Connection is established in the H and Π. each for alkyl. 4098 ^ 3/111 BC stand around.! y α j. non -c-: rt υηη 2 bio 20 has. 6.- traversing Mr! nnch / Wiepruc-h 5. d; .it! urch gckannzoichncit, d;.; ß i: for eino ι ',. _n " _p alkyl group and IΓ for a C" alkyl group Iu-Iu II - I and y has a pin value of 3 to 10. 7.- V / experience according to claim 5, characterized in that dnß y has a tan fourth out of 15. 0. - The method according to claim 5, characterized in that ίί and / or R is a mixture of £ "_ _r alkyl groups and y" has four of 15. 9 .-- The method according to claim 1, characterized in that a Connection is established in which y has a value of 50. 10. Method according to claim 5, characterized in that y has a value of 2. 11 .-- Method according to claims 1 to 10, characterized in that that a connection is made in which M stands for an Arnin stands. 12. - Method according to claim 1 to 10, characterized in that that a connection is established in which M for a Metal katton stands. 13.- The method according to claim 1 to 10, characterized in that a connection is made, in u / elcher M for hydrogen stands. "14. Method according to claim 12, characterized in that ' R stands for Na ° which stands for K. 15.- The method according to claim 1 to 14, characterized in that a vex bond is made, in which A for a 409843/1112 BATH ORIGINAL 11 a 1 η 9 on: ι t.o tn stands. 16.- · The method according to claim 1Iv, "characterized in that A stands for a chloride. 17.- V / experience according to claim 1 to 16, characterized in that that a connection is established in which s a waiting of 1 and t has a fourth of Π. 18.- The method according to claim 1 to 16, characterized in that s has an L'ert won 0, 5 and t has a word of 0.5. 19. - The method according to claims 1-16, characterized in that üa! 3 s has a value of 0.5 and i has a value of ü / 20.- The method according to claim 1-16, characterized in that d aii a connection is established in which s has a value of 1 and t has a value of 1. 409843/111? BATH ORIGINAL 21, - V / orbi ΓΗ youth no. der Fori.-α:: OCH (CH ₂ )] O [Z] H x ^J y ^l - ^J s ν + M A in uiclnhn :: R and R ,, stand individually for vina alkyl chain r., it 1-22 K material grains. Z for Ptl oc! «R Su_stallt, χ a gnr.zfJ number from 1 to 3 is. y πinο gnnzu number from 1 to 50, t and s JGOJGiIs numbers with einoin l.'crt of ^! 'jiJ5 bis ", are, υ and \ / jeui ο ils are numbers with a value from ü to 0.93 _} (s + v) and (t -: - u) jeuicilG are lucky 1, the sum of s + ν + t + u is 2, Ι'Ί stands for hydrogen, a meta] 1 or amine cation, and Λ stands for an anion from a group of halogen, sulfate or alkyl sulfate. 22. Compounds according to claim 21, characterized in that R and R stand for alkyl and y has a value from 2 to 20. 23.- Compounds according to claim 22, characterized in that R for a C alkyl group and R for a C alkyl group and y has a value from 3 to 10. 24. Compounds according to claim 22, characterized in that y has a fourth of 15. 25, - connections according to claim 22, characterized in that, that R and / or R represent a mixture of C alkyl groups • 1 Λ - I tu and y ninfsn has a value of 1 ¹ 3. A 0 9 8 4 3 / 111v 26.- Compounds according to claim 21, characterized in that y has a value of 5G. 2.7.- Compounds according to claim 22, characterized in that y has a value where 2 hnt. 28.- Compounds according to claim 21 to 27, characterized! that M stands for an amine. 29.- Compounds according to claim 21 to 27, characterized in that that M stands for a metal cation. 30, - connections according to claim 21 to 27, characterized in that that M stands for hydrogen. 31.- connections according to claim 29 _? characterized in that M stands for Na or K. 32, - connections according to claim 21 to 31, characterized in that that A stands for a halogen atom. 33.- Compounds according to claim 32, characterized in that A stands for a chloride. 34, - connections according to claim 21 to 33, characterized in that, sat s has a value of 1 and t has a value of 0. 21 to
35.- Compounds according to claim / ^, characterized in that s has a value of 0.5 and t has a value of 0.5. 21. angry
36.- Compounds according to claim / 33, characterized in that s has a value of 0.5 and t has a value of 0. 21 to
37, - connections according to claim / 33, characterized in that s has a fourth of 1 and t has a value of 1. 409843/1112 38.- The use of the compounds according to claim 21 to 37, in which Z is PO, in lubricants, aqueous or solid detergent preparations, liquid drain cleaners, water vapor degreasing, softening preparations for the wet treatment of fibrous materials, rust inhibitors, fabric calibration agents, Metal lubricantsj cleaning agents for hard surfaces, Corrosion inhibitors, pesticide emulsifiers, hydraulic fluids and in surfactants for emulsion polymerization. 39.- The use of compounds according to claims 21 to 37, in which Z stands for SO, in bars of soap, aqueous solutions of detergent preparations, solid detergents, shampoo preparations, Softeners for the wet treatment of fiber-like materials, liquid bubble bath concentrates, fabric softeners or Lubricants. The patent attorney: 409843/1112