CN101254430B - Capric acid acidamide surfactant and synthetic method thereof - Google Patents

Abstract

A decanamide surfactant and a synthetic method thereof are provided. Based on the summery of research findings by the predecessors, the invention uses decanoic acid, hydroxyethylethylene diamine and chloroacetic acid as raw materials to directly synthesize amide surfactants by a novel vacuum amphoteric method without the ring closing reaction. The decanamide surfactant has the formula as above. The synthetic method includes the following steps: synthesizing an amide surfactant intermediate from decanoic acid and hydroxyethylethylene diamine as raw materials, and then performing amphoteric reaction by 'chloroacetic acid process' to obtain the decanamide surfactant. The inventive decanamide surfactant has good foaming performance, low irritation, and good washing, wetting and penetrating performance; and can be used as a cleaning agent in daily chemical industry and a softening agent in textile industry, as well as a corrosion inhibitor and a foaming agent.

Description

Capric acid acidamide surfactant and synthetic method thereof

[technical field]: the invention belongs to surfactant and preparing technical field thereof.

[background technology]: capric acid acidamide surfactant involved in the present invention is a kind of novel surfactant, and its performance and carboxylic acid type imidazoline amophoteric surface active agent compare favourably.

The imidazoline type amphoteric surfactant of aliphatic group has performances such as excellent washing, wetting, foaming and dispersion ^[1,2], excitant is very low ^[3], low toxicity or nontoxic ^[4], antistatic ^[5], antibiotic ^[6], environmentally friendly.

Amphoteric surfactant is pressed its textural classification: (1) imidazoline amophoteric surface active agent (2) beet alkali ampholytic surface active agent (3) amino acid surfactant (4) lecithin class surfactant.Wherein lecithin class surfactant is natural surfactant, and remaining is artificial synthetic ^[7]

Amphoteric surfactant is the later class of exploitation in surfactant.Nineteen thirty-seven, United States Patent (USP) just had report.Du pont company had been developed this compounds in 1940, and reported first betaine be amphoteric surfactant.It is amphoteric surfactant that German Adolf Schmitz in 1948 has studied amino acid, and begins to use.The U.S. has just produced more than 20 kind of amphoteric surfactant commodity in the eighties in 20th century.Phase late 1980s, the amphoteric surfactant of the U.S. increases with the annual growth of 5%-6%, considerably beyond the annual average rate of increase of industrial surface activity agent 2% at that time.Entered since the nineties in 20th century, the amphoteric surfactant of developed country is still in steady development, and the output of the amphoteric surfactant of developed country accounts for the 2%-3% of surfactant total output, and the kind number of present Japanese amphoteric surfactant is about 200 ^[8]

Domesticly after the seventies in 20th century, begin amphoteric surfactant is conducted a research, have few products to throw people market at present, but kind and quantity are all few, so in amphoteric surface the live research and the application facet of agent, China still is in the starting stage.In China's amphoteric surfactant kind, the still non-betaine type of output maximum does not belong to, and what occupy next is amphoteric imidazoline.The ascendant trend of amido propyl betaine type is very fast in the betaine, and alkyl betaine is the atrophy gesture.Amphoteric imidazoline is not smooth in the development of China, by the leading position of the eighties in 20th century, drops to the subordinate status of the nineties in 20th century, and it is also descending to ratio of cation imidazoline, is to be lower than 50% weak tendency ^[9]

[summary of the invention]: the object of the invention provides a kind of acid amide type surfactant, particularly capric acid acidamide surfactant and synthetic method thereof.

The present invention is on the basis of summing up former achievements, and with capric acid, AEEA and monoxone are raw material, without the ring process that reaches a standard, adopt the vacuum-direct synthesizing amide type of amphoterisation method surfactant innovatively.

Capric acid acidamide surfactant provided by the invention, its structural formula is:

The synthetic route of capric acid acidamide surfactant of the present invention is:

Concrete synthetic method is as follows:

The first, the capric acid acidamide surfactant intermediate is synthetic

With capric acid and AEEA is raw material, synthetic capric acid acidamide surfactant intermediate.Concrete building-up process is as follows:

Mechanical agitation is housed, temperature is taken into account in the four-hole bottle of vacuum distillation apparatus, add capric acid and AEEA (mol ratio is 1: 1～1.5) and begin heating and stirring, slowly reaction temperature is risen to 100 ℃ ± 10 ℃, till when starting vavuum pump conditioned reaction system vacuum to water outlet, in 3-5 hour, make reaction temperature rise to 150 ℃ ± 10 ℃ gradually, complete to water outlet.Stop heating, cooling obtains the capric acid acidamide surfactant intermediate, and structural formula is:

For the structure of capric acid acidamide surfactant intermediate, utilize infrared tracking, can from infrared spectrum, observe, at 1640cm ^-1And 1560cm ^-1Near the very strong acid amides characteristic absorption peak of appearance is at 3300cm ^-1About occur bimodal, at 3100cm ^-1Occur unimodally, illustrate that intermediate is the mixture of secondary amide and teritary amide.Instrument: NICOLET-205 infrared spectrometer.

The second, adopt " chloroactic acid method " to carry out amphoterisation and obtain capric acid acidamide surfactant

Concrete building-up process is as follows:

In the four-hole bottle that stirring, thermometer, reflux condenser and dropping funel are housed, the capric acid acidamide surfactant intermediate heating that the step obtains in the adding is also stirred, between 50～90 ℃ of temperature, low temperature drips chloroacetic acid solution in the 4h, heat up gradually then and drip NaOH solution, capric acid acidamide surfactant intermediate: monoxone: the NaOH mol ratio is 1: 1～1.3: 2～2.6, and then reacts 1-2 hour, stop reaction, obtain yellow supernatant liquid and be capric acid acidamide surfactant.

Advantage of the present invention and good effect:

The present invention is the acid amides amphoteric surfactant, has high bubble property, low irritant, and preferably, washing, wetting, permeance property.

Capric acid acidamide surfactant provided by the invention can be used for daily use chemicals industry cleaning agent, fabric softener; And can be used as corrosion inhibiter, blowing agent etc.

[specific embodiment]:

Embodiment 1:

Mechanical agitation is housed, temperature is taken into account in the four-hole bottle of vacuum distillation apparatus, add capric acid 105.5g (0.6mol) and AEEA (mol ratio is 1: 1) and begin heating and stirring, slowly reaction temperature is risen to 100 ℃, till when starting vavuum pump conditioned reaction system vacuum to water outlet, in 3 hours, make reaction temperature rise to 150 ℃ gradually, complete to water outlet.Stop heating, cooling obtains the capric acid acidamide surfactant intermediate.

In the four-hole bottle that stirring, thermometer, reflux condenser and dropping funel are housed, capric acid acidamide surfactant intermediate 15.5g (0.06mol) heating that the step obtains in the adding is also stirred, between 50～90 ℃ of temperature, low temperature drips chloroacetic acid solution in 4 hours, heat up gradually then and drip NaOH solution, capric acid acidamide surfactant intermediate: monoxone: the NaOH mol ratio is 1: 1: 2, and then reacted 1 hour, stop reaction, obtain yellow supernatant liquid and be capric acid acidamide surfactant.Surface tension σ (20 ℃, 33.62mNm ^-1) instrument: DP-AW type surface tension instrument.

Embodiment 2:

Mechanical agitation is housed, temperature is taken into account in the four-hole bottle of vacuum distillation apparatus, add capric acid 105.5g (0.6mol) and AEEA (mol ratio is 1: 1.1) and begin heating and stirring, slowly reaction temperature is risen to 110 ℃, till when starting vavuum pump conditioned reaction system vacuum to water outlet, in 4 hours, make reaction temperature rise to 150 ℃ gradually, complete to water outlet.Stop heating, cooling obtains the capric acid acidamide surfactant intermediate.

In the four-hole bottle that stirring, thermometer, reflux condenser and dropping funel are housed, the capric acid reward that the step obtains in the adding is by surfactant intermediate 15.5g (0.06mol) heating and stirring, between 50～90 ℃ of temperature, low temperature drips chloroacetic acid solution in 4 hours, heat up gradually then and drip NaOH solution, capric acid acidamide surfactant intermediate: monoxone: the NaOH mol ratio is 1: 1.3: 2.6, and then reacted 1.5 hours, stop reaction, obtain yellow supernatant liquid and be capric acid acidamide surfactant.

Embodiment 3:

Mechanical agitation is housed, temperature is taken into account in the four-hole bottle of vacuum distillation apparatus, add capric acid 105.5g (0.6mol) and AEEA (mol ratio is 1: 1.2) and begin heating and stirring, slowly reaction temperature is risen to 100 ℃, till when starting vavuum pump conditioned reaction system vacuum to water outlet, in 5 hours, make reaction temperature rise to 150 ℃ gradually, complete to water outlet.Stop heating, cooling obtains the capric acid acidamide surfactant intermediate.

In the four-hole bottle that stirring, thermometer, reflux condenser and dropping funel are housed, capric acid acidamide surfactant intermediate 15.5g (0.06mol) heating that the step obtains in the adding is also stirred, between 50～90 ℃ of temperature, low temperature drips chloroacetic acid solution in 4 hours, heat up gradually then and drip NaOH solution, capric acid acidamide surfactant intermediate: monoxone: the NaOH mol ratio is 1: 1.2: 2.4, and then reacted 1.5 hours, stop reaction, obtain yellow supernatant liquid and be capric acid acidamide surfactant.

. list of references

[1]MannheimerH.S，John?JM.Surface-avtive?agents[P].Brit.853441，1960.

[2]Wechsler，Joseph?R，Baber，Tomas?G，Battaglini，George?T，et?al.Imidazolines[P].US?4189593，1980.

[3]Phillips?B.M.，Lambie?A.J.，Thompson?M.E.Aliphatic?Amidoamines[P].Brit.UK?Pat.Appl.2003867，1979.

[4]Mannheimer?H.S.Cycloimidine?detivatives[P].US?2773068，1956.

[5]Sano?Y，Miyamoto?M，Kimura?Y，et?al.Zwitterions?of?1-poly(oxyethylene)-2-imidazoline?derivatives?anti-electrostaticagent?for?polyamide?fiber[J].Polym.Ball.(Berlin)，1982，6(5，6)：343～349.

[6]Ploog?U，Retzold?M，Vphues?G..New?imidazolines?and?their?derivatives?from?fatty?acids?and?hydroxyalkylamines

[J].Fette，Seifen，Ansrichm.，1980，82(2)：57～59.

[7] Lan Yunjun, Bao Lihong, Li Yan. the type of amphoteric surfactant, application performance and general situation of development. Chinese leather, 2003,32 (13): 20～24

[8] Wang Jun, Ge Hong, Zou Wenyuan. the synthetic route general introduction of amphoteric surfactant. daily chemical industry, 2005,35 (1): 45～48

[9] Liang Menglan. the synthetic and application of amphoteric imidazoline surfactant. Speciality Petrochemicals, 1986,2 (5): 14～27

Claims (2)

1. capric acid acidamide surfactant, it consists of:

Described surfactant is to be prepared from through following steps:

The first, the capric acid acidamide surfactant intermediate is synthetic

Building-up process:

Mechanical agitation is housed, temperature is taken into account in the four-hole bottle of vacuum distillation apparatus, according to mol ratio is that 1: 1～1.5 ratio adds capric acid and AEEA, begin heating and stir, slowly reaction temperature is risen to 100 ℃ ± 10 ℃, when starting vavuum pump conditioned reaction system vacuum to water outlet till, in 3-5 hour, make reaction temperature rise to 150 ℃ ± 10 ℃ gradually, complete to water outlet, stop heating, cooling, obtain the capric acid acidamide surfactant intermediate, it consists of:

The second, adopt " chloroactic acid method " to carry out amphoterisation and obtain capric acid acidamide surfactant

Building-up process:

In the four-hole bottle that stirring, thermometer, reflux condenser and dropping funel are housed, the capric acid acidamide surfactant intermediate heating that the step obtains in the adding is also stirred, between 50～90 ℃ of temperature, low temperature drips chloroacetic acid solution in 4 hours, heat up gradually then and drip NaOH solution, capric acid acidamide surfactant intermediate: monoxone: the NaOH mol ratio is 1: 1～1.3: 2～2.6, and then reacts 1-2 hour, stop reaction, obtain yellow supernatant liquid and be capric acid acidamide surfactant.

2. the synthetic method of the described capric acid acidamide surfactant of claim 1 is characterized in that this method comprises:

Synthetic route:

Building-up process:

The first, the capric acid acidamide surfactant intermediate is synthetic

Building-up process:

Mechanical agitation is housed, temperature is taken into account in the four-hole bottle of vacuum distillation apparatus, according to mol ratio is that 1: 1～1.5 ratio adds capric acid and AEEA, begin heating and stir, slowly reaction temperature is risen to 100 ℃ ± 10 ℃, when starting vavuum pump conditioned reaction system vacuum to water outlet till, in 3-5 hour, make reaction temperature rise to 150 ℃ ± 10 ℃ gradually, complete to water outlet, stop heating, cooling, obtain the capric acid acidamide surfactant intermediate, it consists of:

The second, adopt " chloroactic acid method " to carry out amphoterisation and obtain capric acid acidamide surfactant

Building-up process:

In the four-hole bottle that stirring, thermometer, reflux condenser and dropping funel are housed, the capric acid acidamide surfactant intermediate heating that the step obtains in the adding is also stirred, between 50～90 ℃ of temperature, low temperature drips chloroacetic acid solution in 4 hours, heat up gradually then and drip NaOH solution, capric acid acidamide surfactant intermediate: monoxone: the NaOH mol ratio is 1: 1～1.3: 2～2.6, and then reacts 1-2 hour, stop reaction, obtain yellow supernatant liquid and be capric acid acidamide surfactant.