KR900004552B1 - A process for the preparation of a schifb base surfactants - Google Patents

Abstract

A Schift base of formula (I) is prepd. by reacting an aldehyde or a ketone of formula R1R2C=O with a polyoxyalkylene amine of formula H2N[OH(CH3)CH2O y-[CH2CH2O xR3. In the formulas, R1 and R2 are each H or C9-20 alkyl; R3 is C1-4 alkyl; y is 1-3; x is 4-50. The surfactant comprises 0.1-20 wt.% Schiff base and water.

Description

Method for preparing sif base surfactant

The present invention relates to a process for preparing condensates of aliphatic aldehydes and ketones with amino containing reactants. More specifically, the present invention relates to the preparation of a series of seed bases that are stable to hydrolysis and are water soluble. This class of shipbases are useful as surfactants.

Surfactant refers to a substance that lowers the interfacial tension of a liquid-liquid, liquid-solid, or liquid-gas. Surfactant solutions are widely used alone or in combination with cleaning aids such as additives and enhancers to wet surfaces, remove dirt, pass porous materials, disperse particles, and emulsify oils and oils. It depends on the specific nature of the active agent or the surfactant used.

Preferred surfactants are inexpensive, light colored materials that are applied at low concentrations in aqueous solutions, can be produced in good yields from cheap starting materials, are free of toxic contaminants, are easy to handle and are in the form of free flowing liquids or powders. .

In heavy industrial applications such as metal refining and dishwashing detergent components, these components essentially contain highly alkaline substances such as alkali metal hydroxides, alkali metal alkoxides and alkali metal phosphates. In aqueous media in which these detergents work, the pH of the wash solution is often 10-13.

For this reason, the prerequisite for the strong cleaning component is that it must be stable at high pH in aqueous solution.

The dissolved shipbase obtained by condensing an aliphatic canon with an amine-containing reactant is a dissolved (ethoxylated or sulfated) shipbase prepared by condensing an aliphatic aldehyde or ketone having 6 or more carbon atoms with an aliphatic amine or aminoalcohol. Of particular importance in view of the publication of British Patent No. 414,712 (1933), which produces a detergent which is stable to alkaline and foams well. Unfortunately, dissolution products, as exemplified by the ethoxylated condensates of the shipbase, prepared by reacting a C ₁₁ -C ₁₃ ketone mixture or methyl nathyl ketone with an amino containing reactant such as ethanolamine, have a pH of 5.6- It is extremely unstable in the aqueous solution of 13. Since most washing occurs in this pH range, unstable condensation products according to the British patent are of no practical value as cleaning components.

U.S. Patent No. 3,897,362 (1975) describes a series of chip base surfactants that are more stable than that of British Patent No. 414,712, but as shown in Example VII, the hydrolytic stability is significantly higher than that of the chip bases according to the present invention. little.

The present invention relates to a series of sipebase preparations which have been found to be used as detergents. The seed base according to the present invention is characterized by the following general structural formula.

Wherein R ₁ and R ₂ are each hydrogen or an alkyl radical having 9-20 total carbon atoms in the radical R ₁ -CR ₂ ; R ₃ is alkyl having 1-4 carbons,

or

y is on average 1-3; x is on average 4-60 and the amount of polyoxyethylene in the seed base is 40% by weight or more.

Aminoalkoxylated shipbases are surfactants according to the invention. These surfactants are obtained by condensing aliphatic aldehydes and ketones having 9 to 20 carbon atoms with polyoxyalkyleneamines at high temperatures. Polyoxyalkyleneamines are block copolymers of oxyethylene groups and oxypropylene groups ending with primary amines.

As one example of the present invention, condensation may be accomplished with a class of polyoxyalkylene monoamines of the general formula:

Wherein y is on average 1-3, x is on average 4-50 and preferably 10-30. This class of monoamines has a molecular weight of about 400-1500. These monoamines are derived from oxyethylene groups (-CH ₂ CH ₂ O-) and oxypropylene groups (-CH (CH ₃ ) CH ₂ O-).

It has been found that commercially useful polyoxyalkylene monoamines are suitable for this class and exhibit particularly advantageous properties.

Such monoamines can be used to produce seed bases having at least 40% by weight of polyoxyethylene moieties in the molecule. This polyoxyalkylene monoamine has a molecular weight of about 1000 and is characterized by the following general structural formula.

M-1000(텍사코 케미탈 캄파니 제품)이라는 상품명으로 시판되고 있다.The general formula above represents the average structure of the block copolymer monoamine mixture in which y in the formula is an integer from 1 to about 5 and x is in the range of about 7-30. This polyoxyalkylene monoamine

It is marketed under the brand name M-1000 (manufactured by Texco Chemical Corp.).

This class of monoamines is condensed with equimolar amounts of aliphatic aldehydes and / or ketones having 9 to 20 carbon atoms (preferably 10 to 15) in the presence or absence of an inert solvent (eg benzene or toluene) at high temperatures.

The seed base prepared according to the specific example of the present invention is a component of the following general structure.

Wherein R ₁ and R ₂ are selected from the group consisting of hydrogen and alkyl radicals having 9-20 carbon atoms in R ₁ -CR ₂ , R ₃ is alkyl radicals having 1-4 carbon atoms, and y is an average of 1- 3, x is on average 4-50 and preferably 10-30 so that the amount of (CH ₂ CH ₂ O) is at least 40% by weight.

As another example of the present invention, condensation with polyoxyalkylene diamines of the same class can be achieved.

Wherein y is on average 1-3 and x is on average 8-60, with 8-50 being preferred. This class of diamines are derived from oxyethylene groups (-CH ₂ CH ₂ O-) and oxypropylene groups (-CH (CH ₃ ) CH ₂ O-) and have a molecular weight of about 600-3000, which is about 900-2000 desirable.

Three commercially available polyoxyalkylene diamines have been found suitable for this class and exhibit particularly advantageous properties. These diamines can be used to produce seed bases having an intramolecular ethylene oxide content of at least 40% by weight. The first polyoxyalkylene diamine has a molecular weight of about 600 and is characterized by the following structure.

These structural formulas represent a mixture of block copolymer diamines, and it can be seen that the amounts of propylene oxide and ethylene oxide specified in the general formula are only relative molar ratios to the entire mixture.

ED-600(텍사코 케미탈 캄파니 제품)이라는 상품명으로 시판되고 있다.This polyoxyalkylene diamine

It is marketed under the brand name ED-600 (manufactured by Texco Chemical Corp.).

A second polyoxyalkylene diamine having this general structure has been found to exhibit particularly beneficial properties. This polyoxyalkylene diamine has a molecular weight of about 900 and is characterized by the following structure.

ED-900(텍사코 케미탈 캄파니 제품)이라는 상품명으로 시판되고 있다.This polyoxyalkylene diamine

It is marketed under the brand name ED-900 (manufactured by Texco Chemical Corp.).

The third polyoxyalkylene diamine having this general structure has a molecular weight of about 2000 and is characterized by the following structure.

ED-2001(텍사코 케미탈 캄파니 제품)이라는 상품명으로 시판되고 있다.This polyoxyalkylene diamine

It is marketed under the brand name ED-2001 (manufactured by Texco Chemical Corp.).

This class of diamines may be prepared by equimolar or double molar amounts of aliphatic aldehydes and / or ketones having 9-20 (preferably 10-15) carbon atoms in the presence or absence of inert solvents such as benzene or toluene at high temperatures. Condensation.

The seed base prepared according to this another specific example of the present invention is a component of the following general formula.

Wherein R ₁ and R ₂ are selected from the group consisting of hydrogen and alkyl radicals having 9-20 total carbon atoms in R ₁ -CR ₂ ; R ₃ is

A radical selected from the group consisting of; y is on average 1-3; x is on average 8-60 and preferably 8-50 so that the amount of (CH ₂ CH ₂ O) is at least 40% by weight.

; Rohm과 Haas에 의해 시판됨)와 같은 촉매를 이용하여 본 발명의 시프염기를 합성할 수 있다. 이용되는 온도, 촉매 및 용매를 포함하는 시프염기의 일반적인 제조는 기술문헌 및 특허문헌에 완전히 기술되어 있다. 예로써 화학기술백과전서(초판, 제12권, 106페이지 이하 참조; 인터사이언스엔사이클로페디아사 간행)을 들 수 있다. 여기에 수록된 실시예들은 일반적인 것이기는 하나, 당분야에 통상적인 지식을 가진자라면 본 청구범위에 정의된 어떠한 조성물질이라도 합성할 수 있도록 자세히 지시하고 있다.The preparation of the seed base according to the present invention proceeds with the formation and removal of water at high temperatures, in the presence or absence of an inert solvent such as benzene or toluene. The reaction can proceed with or without a catalyst. p-toluenesulfonic acid, sulfuric acid and acid resins (e.g.

; The catalysts of the present invention can be synthesized using catalysts such as those sold by Rohm and Haas. General preparation of the seed base, including the temperature, catalyst and solvent employed, is fully described in the technical literature and patent literature. An example is the Encyclopaedia of Chemical Technology (first edition, vol. 12, p. 106); published by Interscience and Cyclopedia. The examples listed here are general, but are directed to those skilled in the art to synthesize any of the compositions defined in the claims.

The aldehydes and ketones used in the preparation of the seed base of the present invention consist of R ₁ and R ₂ (hydrogen or straight and branched chain aliphatic radicals) components. General structural formulas of these aldehydes and ketones are as follows.

Wherein the total number of carbon atoms in the aldehyde or ketone is 9-20. Preferred aldehydes and ketones are mixtures containing 10-15 carbon atoms. Preferred aldehydes are prepared by dehydrogenation of straight and branched chain primary alcohols.

Methylalkyl ketones are one of the preferred ketones. Another class of preferred ketones are mixtures of 10-15 carbon atoms derived by dehydrogenation of secondary alcohols upon boric acid controlled oxidation of straight chain hydrocarbons of 10-15 carbon atoms.

The preparation of these alcohols is described in US Pat. No. 3,410,913 and other references. Ketones derived from these secondary alcohols can be prepared from alcohols at 150 ° -275 ° C. using standard methods of oxidation or catalytic hydrogenation (ie, using cupric chromite). Ketone mixtures prepared by the above methods usually contain at least 1% to 35% by weight of aliphatic ketones, wherein one of the alkyl R ₁ and R ₂ in the ketone is a methyl group.

The alkoxylated sipbases exhibit the properties of long-lasting surfactants at concentrations of 0.01% by weight in aqueous solution and are more prone to depend on the mode of application. The minimum concentration of ethoxylated products used mainly is 0.1% by weight, but the upper concentrations are almost all limited by the price and do not exceed 20% by weight even for special purposes. The concentration range is usually about 1% -15% by weight with the cleaning aids described below. In all instances the lower or minimum concentration (0.01% by weight) is referred to as the "effective amount" of the surfactant. When these stabilized products are used as detergents, they are present in at least minimum concentrations with one or more of the following substances called washing aids.

1. Inorganic salts, acids and bases-these are mainly referred to as "enhancers". These salts usually consist of phosphates and silicates of alkali metals as well as their neutral soluble salts. These materials make up about 40-80% by weight of the composition in which they are used.

2. Organic Enhancers or Additives-These are substances that contribute to properties such as washing, foaming, emulsifying or dirt floating effects. Typical organic enhancers include sodium carboxymethyl cellulose and sequestrants such as ethylenediaminetetraacetic acid and fatty monoethanol amides.

3. Special Purpose Additives-These additives include solubilizing additives such as lower alcohols, glycols and glycol ethers, all of which are dyes, bleaches or varnishes of various structures having a common point in that they do not absorb or reflect light in the visible spectrum. There is.

The present invention includes a class of surfactants having extremely improved hydrolytic stability over a range of pH values.

The composition according to the present invention differs from the chirp base of US Pat. No. 3,897,362 in that the methyl group is attached to C ^α rather than the carbon of a C = N bond. Unexpectedly, this structural change allows the compounds according to the invention to have much more hydrolytic stability than the products of the prior art. Since the detergents in use must be under high temperature conditions, this relative stability is an advantage for detergents. On the other hand, inherent C = N bond hydrolysis instability can increase the rate of primary decomposition of wastewater.

The products according to the invention are useful for improved oil recovery processes of surfactant formulations as well as household wash products.

The product of the present invention is also useful for alkaline surfactants, as a phase transfer accelerator or as an emulsifier for chemical reactions with selective degradability by pH control. Typical formulations are described herein.

Example 1

(A) ED-2001 + 2 moles of 2-undecanone

ED-2001 204g과 2-운데칸온 34g을 채워넣는다. 120℃-230℃에서 2시간동안 용액을 가열하고, 딘-스타아크 트랩내의 응축된 상부 증기(물)을 수거한다. 반응을 완결하기 위해 p-톨루엔설폰산 0.5g을 첨가하고 230℃에서 1시간동안 분해시킨다. 용기내의 물질을 적외선 분석한 결과 C=O 결합이 없어지고 C=N 결합이 생기는 소요의 반응이 이루어졌음을 알았다.In a 1 liter flask equipped with a stirring magnetic rod, N2 bubble tube, Dean-Stark trap, condenser and thermometer

Fill 204g ED-2001 and 34g 2-Undecanone. The solution is heated at 120 ° C.-230 ° C. for 2 hours and the condensed upper vapor (water) in the Dean-Starak trap is collected. To complete the reaction 0.5 g of p-toluenesulfonic acid is added and decomposed at 230 ° C. for 1 hour. Infrared analysis of the material in the vessel revealed that the required reaction was achieved, resulting in the loss of C = O bond and C = N bond.

The main product by this reaction has the following structure.

(B) ED-2001 + 1.5 mol 2-Undecanone

ED-2001 204g과 2-운데칸온 25.5g을 채워넣는다. 휘발물을 제거하면서 170-175℃에서 2시간동안 혼합물을 분해시킨 후, 230℃에서 6시간동안 분해시킨다. 실시예 1-A와 동일한 방법으로 분석한 결과, 생성물을 실시예 1-A의 생성물과 하기 구조를 갖는 물질의 혼합물임이 밝혀졌다.In a 1 liter flask with the same device as Example 1-A

Fill 204g ED-2001 and 25.5g 2-Undecanone. The mixture was decomposed at 170-175 ° C. for 2 hours with volatiles removed and then at 230 ° C. for 6 hours. As a result of analysis in the same manner as in Example 1-A, the product was found to be a mixture of the product of Example 1-A and a substance having the structure shown below.

Example 2

ED-2001 + Isobutylheptylketone

ED-2001 204 및 이소부틸헵틸케톤 36.5g을 사용한다. 180℃-220℃에서 2시간동안 초기 분해를 실시한 후, 220℃-265℃에서 7시간에 걸쳐 상부 휘발물을 제거하면서 가열시킨다.With the method of Example 1-B

ED-2001 204 and 36.5 g of isobutylheptylketone are used. Initial decomposition was carried out at 180 ° C.-220 ° C. for 2 hours and then heated at 220 ° C.-265 ° C. over 7 hours with the upper volatiles removed.

The product was found to be a substance of the following structure.

Example 3

ED-2001 + 2 moles of nonal

ED-2001 204g과 노난알 39g의 혼합물을 자기막대로 교반시키면서 175℃-180℃ 질소하에서 2시간동안 가열하는데, 이때의 휘발물은 제거한다. 적외선 분석 결과, 알데히드의 자체 축합을 나타내는 카르보닐 화합물 또는 C=C가 생성물내에 사실상 존재하지 않음이 밝혀졌다.

A mixture of 204 g of ED-2001 and 39 g of nonal egg was heated under a 175 ° C.-180 ° C. nitrogen for 2 hours while stirring with a magnetic rod, at which time the volatiles were removed. Infrared analysis revealed that there was virtually no carbonyl compound or C═C present in the product, indicating self-condensation of the aldehyde.

Example 4

EDM-1000 + 1 mol 2-Undecanon

M-1000 204g 및 2-운데칸온 34g을 사용한다. 120℃-230℃에서 3 1/2시간에 걸쳐 초기 분해시킨 후, 7 1/2시간에 걸쳐 230℃-280℃로 천천히 가열한다.With the method of Example 1-B

204 g M-1000 and 34 g 2-undecanone are used. Initial decomposition at 120 ° C.-230 ° C. over 3 1/2 hours and then slowly heating to 230 ° C.-280 ° C. over 7 1/2 hours.

The product was found to be a substance of the following structure.

Example 5

M-1000 + 2 moles of C ₁₄ -C ₁₅ ketone mixture

M-1000 150g 및 평균분자량 214의 C₁₄-C₁₅케톤 32g(C₁₄-C₁₅7-파라핀계 화합물을 붕산으로 조절하여 공기산화시킴으로써 제조된 임의의 2차 알콜 혼합물의 촉매적 탈수소화에 의해 합성된 것)을 사용한다. 170℃-225℃에서 2시간동안 초기 분해시킨 후, 225℃-275℃에서 7 1/2시간동안 휘발물을 제거하면서 가열한다.With the method of Example 1-B

By catalytic dehydrogenation of any secondary alcohol mixture prepared by air oxidation of 150 g of M-1000 and 32 g of C ₁₄ -C ₁₅ ketone having an average molecular weight of 214 (C ₁₄ -C ₁₅ 7-paraffinic compound with boric acid). Synthesized). Initial decomposition for 2 hours at 170 ° C.-225 ° C., followed by heating with volatiles removed at 225 ° C.-275 ° C. for 7 1/2 hours.

Infrared analysis of the material in the vessel confirmed that the required reaction proceeded. This analysis reveals the presence of C═N bonds and the absence of C═O bonds.

Example 6

M-360 + 2 Undecanon

M-360^*365g을 사용한다. 전개된 물을 버리고 상부 유기물을 재순환시키면서, 3 1/2시간동안 180℃에서 혼합물을 분해한다. 온도를 2시간 10분에 걸쳐 180℃에서 250℃로 올린 후, 250℃에서 2시간동안 상부의 모든 물질을 버린다. 적외선 분광법에 의한 분석결과, 생성물은 하기 구조의 물질임이 확인되었다.Example 1-B and 170 g of 2-undecanone and

Use M-360 ^* 365g. Discard the water at 180 ° C. for 3 1/2 hours while discarding the developed water and recycling the upper organics. The temperature is raised from 180 ° C. to 250 ° C. over 2 hours 10 minutes and then discarded all of the material at 250 ° C. for 2 hours. As a result of analysis by infrared spectroscopy, it was confirmed that the product was a substance having the following structure.

It was found that this product, containing only 34% by weight (CH ₂ CH ₂ O), was insoluble in water at 0-100 ° C.

This material, marketed by Texaco Chemical Company, is characterized by the following general formula.

Example 7

Interfacial Tension Measurement of Surfactants for Mineral Oil in Aqueous Solutions

The interfacial tension of several products was measured. The result is as follows.

Example 8

Example 1-A Hydrolysis Stability Study for the Product

The water-soluble stability test of Example 6 in US Pat. No. 3,897,362 was repeated at pH 5.6, 7.7 and 12.2 for 0.6% aqueous solution of this Example 1-A product. After 24 hours, these solutions show no colaudiness at 70 ° C. and maintain their original cloud point temperature of about 100 ° C. This is in stark contrast to the rapid degradation (within 1-30 minutes) exhibited by the seed base surfactants of US Pat. No. 3,897,362.

TABLE 1

The results of similar experiments according to US Pat. No. 3,897,362 are reproduced in Table 7 below.

TABLE 2

Example 9

[Hydrolysis Stability Test]

A 1% aqueous solution of Example 1-A, 2 and 5 products is prepared, left for 17 hours in a 70 ° C. oven and the interfacial tension is measured as in Example 7. The results were 9.4, 6.3 and 2.1 dynes / cm, respectively, indicating that no measurable degradation of the starting material occurred. These results are corroborated by separately measuring anticipated degradation products at equivalent concentrations giving high interfacial tension values.

Claims (5)

Next, a method of preparing a sifbase of the general formula (1) by reacting an aldehyde or a ketone of the general formula (A) with a polyoxyalkylene amine of the general formula (B).

Wherein R ₁ and R ₂ are each hydrogen or alkyl having 9-20 total carbon atoms in R ₁ -CR ₂ ; R ₃ is alkyl having 1-4 carbon atoms,

or

And y is 1-3; x is 4-60 and the amount of (CH ₂ CH ₂ O) in the seed base is at least 40% by weight.)

(Wherein R ₁ and R ₂ are as defined above, y has an average value of 1-3, x has an average value of 4-50, R ₃ is alkyl having 1-4 carbons, or a group of the formula to be.

The method of claim 1 wherein the polyoxyalkylene amine has the structure:

Wherein R ₃ is C ₁ -C ₄ alkyl, x is 1-3 and y is 10-30. The method of claim 1 wherein the polyoxyalkylene amine has the structure:

In which y is 1-3; x is 8-50. Seef base of the general formula (1)

Wherein R ₁ and R ₂ are each hydrogen or alkyl having 9-20 total carbon atoms in R ₁ -CR ₂ ; R ₃ is alkyl having 1-4 carbon atoms,

or

And y is 1-3; x is 4-60 and the amount of (CH ₂ CH ₂ O) in the seed base is at least 40% by weight.) Aqueous detergent solution consisting of 0.1-20 wt% of Schiff base of the general formula (1) and water

Wherein R ₁ and R ₂ are each hydrogen or alkyl having 9-20 total carbon atoms in R ₁ -CR ₂ ; R ₃ is alkyl having 1-4 carbon atoms,

or

y is 1-3; x is 4-60 and the amount of (CH ₂ CH ₂ O) in the seed base is at least 40% by weight).