CN100404117C - Preparation method of alpha-alkyl betaine amphoteric surfactant - Google Patents

Preparation method of alpha-alkyl betaine amphoteric surfactant Download PDF

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Publication number
CN100404117C
CN100404117C CNB2005101227935A CN200510122793A CN100404117C CN 100404117 C CN100404117 C CN 100404117C CN B2005101227935 A CNB2005101227935 A CN B2005101227935A CN 200510122793 A CN200510122793 A CN 200510122793A CN 100404117 C CN100404117 C CN 100404117C
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alpha
tertiary amine
low
alkyl
active agent
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CN1803269A (en
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方云
夏咏梅
胡学一
王义友
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Jiangnan University
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Jiangnan University
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Abstract

The present invention relates to a preparation method for an ampholytic surfactant made from alpha-alkyl betaine, which belongs to the technical field of the synthesis of an organic compound. Alpha-halogenated aliphatic carboxylic acid and excessive low-level tertiary amine react in a reactor with normal pressure or a piezocaloric reaction vessel, unreacted tertiary amine is eliminated under the condition of depressurization after reacting for a certain time, and the nreacted tertiary amine is further purified; finally, a crystal refined product with high purity can be obtained. The present invention can directly utilize natural reproducible grease resources to replace expensive tertiary amine with long chains, so the cost of the present invention is lower than that of other similar ampholytic surfactants, and the present invention has the advantages of moderate product performance and wide application. The present invention solves the defect of production and application influenced by the high price of the existing ampholytic surfactant.

Description

A kind of preparation method of alpha-alkyl beet alkali ampholytic surface active agent
Technical field
A kind of preparation method of alpha-alkyl beet alkali ampholytic surface active agent, a kind of specifically is the synthetic method that obtains alpha-alkyl beet alkali ampholytic surface active agent of raw material reaction with alpha-halogen aliphatic carboxylic acid and low-grade tertiary amine, belongs to the organic compound synthesis technical field.
Background technology
Alpha-alkyl beet alkali is a kind of carboxylic acid type amphoteric surfactant, contains quaternary nitrogen cation and carboxylic acid group's anion in its molecular structure.
Synthesis of carboxylic acid type betaine is that the carboxylic acid type betaine that obtains is the N-alkyl betaine, works as R=C with long chain tertiary amine and sodium chloroacetate solution effect with most widely used method the earliest 12The time, be the amphoteric surfactant BS-12 of market sale.
Exemplary is:
N-alkyl beet alkali ampholytic surface active agent mature production technology, equipment is simple, of many uses, but owing to carry unreacted long chain tertiary amine and sodium chloroacetate secretly in the product, can make product have offending smell, though while product yield height, but the sodium chloride that will remove in the product is then relatively more difficult.
Summary of the invention
The objective of the invention is to: with alpha-halogen aliphatic carboxylic acid and low-grade tertiary amine is that raw material reaction prepares alpha-alkyl beet alkali ampholytic surface active agent.
The performance of the alpha-alkyl beet alkali ampholytic surface active agent that synthesizes with technology provided by the invention is similar with the N-alkyl beet alkali ampholytic surface active agent, but can substitute expensive long chain tertiary amine with the low price oil resource, reduce the production cost of amphoteric surfactant significantly, and shortened process.
Purpose of the present invention can reach by the following technical solutions: react in normal pressure reactor or pressure thermal response still with alpha-halogen aliphatic carboxylic acid and excessive low-grade tertiary amine, under reduced pressure remove unreacted low-grade tertiary amine behind the reaction certain hour, and be further purified, obtain high-purity crystallized shape purified product at last.Synthetic route is as follows:
Concrete building-up process is as follows:
In normal pressure reactor that has heating, stirring and temperature-controlling system or pressure thermal response still, by the alpha-halogen aliphatic carboxylic acid: the mol ratio of low-grade tertiary amine=1: 2~5 feeds intake, stir 2~12h in 30~90 ℃ of following constant temperature, and under room temperature ageing 18~48h, obtain thick product;
Thick product is adjusted to pH11~12 with NaOH, removes the low-grade tertiary amine that has neither part nor lot in reaction with Rotary Evaporators; Be adjusted to pH1~2 with dense HCl then, moisture content is wherein removed in distillation; Add the ethanol dissolving then, remove by filter inorganic salts wherein; Use acetone recrystallization, obtain white solid through vacuum drying again, this solid is the alpha-alkyl beet alkali of purifying.
In the reaction equation, R is C 0~C 38Saturated or unsaturated, straight or branched, single carbon or mix the hydrocarbon of carbon; Be that general formula is C nH 2n ± 1, n=0~38 wherein.X=F or Cl or Br or I;
R in the low-grade tertiary amine 1, R 2, R 3For alkyl or alcohol saturated or unsaturated, straight or branched, promptly has general formula C nH 2n ± 1O mFatty alcohol, n=1 wherein, 2 or 3, m=0,1,2 or 3.
Beneficial effect of the present invention:
(1) the present invention adopts the reaction of alpha-halogen aliphatic carboxylic acid and low-grade tertiary amine but not with long chain alkyl dimethyl tertiary amine or long-chain amido propyl dimethyl tertiary amine and sodium chloroacetate prepared in reaction betaine type amphoteric surfac-tant, exploitation fat-based amphoteric surfactant new varieties α-long-chain alkyl lycine, so can promote the direct utilization of natural reproducible oil resource, what is more important can substitute expensive long chain tertiary amine with the low price oil resource, reduce the production cost of amphoteric surfactant significantly, and shortened process.
(2) its performance of synthetic product alpha-alkyl beet alkali ampholytic surface active agent of the present invention is relatively gentleer, thickening capabilities to system is strong, acid and alkali-resistance, anti-hard water, this series products can be used for soap composite, produce high-quality cake soap or liquid soap, also can be used in the shampoo series products, or as textile finish, wool fulling agent, foam drilling agent, corrosion inhibitor for metal, disinfectant or gel emulsifying agent.
The specific embodiment
Below the present invention is carried out the description of embodiment, embodiment is as follows:
Synthesizing of embodiment 1 α-butyrobetaine
In the normal pressure reactor that thermometer and magnetic agitation are housed, add the aqueous solution that contains the 0.25mol triethylamine, constant temperature is in 30 ℃.Under fully stirring, drip 0.1mol alpha-fluoro caproic acid, continue to stir 2h and make abundant mixing.Ageing 36h takes out thick product, and conversion ratio reaches 76.6%.
Synthesizing of embodiment 2 alpha-decyl betaines
In the potheater that has heating, stirring and temperature-controlling system, add the alpha-chloro dodecoic acid 0.2mol and the aqueous solution that contains the 0.6mol trimethylamine, stir 10h in 80 ℃ of following constant temperature; Be cooled to ageing 18h after the room temperature, take out thick product, conversion ratio reaches 83.8%.Thick product is adjusted to pH11~12 with NaOH, removes the trimethylamine that has neither part nor lot in reaction with Rotary Evaporators, be adjusted to pH1~2 with dense HCl then, moisture content is wherein removed in distillation; Add the ethanol dissolving then, remove by filter inorganic salts wherein; Use acetone recrystallization, obtain white solid through vacuum drying again, this solid is the alpha-decyl betaine (α-CB) of purifying.
α-CB has very strong dispersion of calcium soap, and foaming properties is superior.α-CB is added in carving board soap powder and the transparent soap with about 30% mass ratio, and the adding of finding α-CB all has improvement to spumescence, wetting power, the washing performance of soap powder, and the wetting power and the detergency of transparent soap made moderate progress, and its foaming properties is decreased.
Synthesizing of embodiment 3 α-empgen BB
In the potheater that has heating, stirring and temperature-controlling system, add the alpha-chloro tetradecylic acid 0.1mol and the aqueous solution that contains the 0.4mol dimethylethanolamine, stir 12h in 70 ℃ of following constant temperature; Be cooled to ageing 24h after the room temperature, take out thick product, conversion ratio reaches 88.6%.Purification step is with embodiment 2.α-empgen BB has good foaming properties and dispersion of calcium soap, can be used in the shampoo series products.
Synthesizing of embodiment 4 α-cetyl betaine
In the potheater that has heating, stirring and temperature-controlling system, elder generation is with the alpha-brominated stearic acid heat fused of 0.1mol, in stirring, slowly add and contain the 0.35mol trimethylamine aqueous solution and maintain 60 ℃ of following continuous stirring reactions about 6 hours, then reactant was left standstill in reactor 24 hours.Thin up in the reactant, remaining trimethylamine and water distillation in the solution is removed in heating, and residue is thick product.Thick product is further purified, and obtains high-purity crystallized shape purified product at last.
α-cetyl betaine has good scourability, at high temperature still demonstrates good wetability, and it has good protective effect to fiber.The surface tension of refining α-cetyl betaine can be hanged down and be reached the 20 dynes per centimeter orders of magnitude, and sample critical micellar concentration (cmc) also has the low characteristics of amphoteric surfactant numerical value, 10 -2~10 -5Between the mol/l, this colloidal nature that manifests surfactant during to low concentration is effective especially.Its Krafft's point (KP) is lower than 42 ℃, has good low-temperature solubility, and this is the unvanquishable shortcoming of fatty acid soaps just.
Synthesizing of embodiment 5 α-hybrid long chain alkyl betaine
In the normal pressure reactor that thermometer and magnetic agitation are housed, add the aqueous solution that contains the 0.35mol trimethylamine, constant temperature is in 40 ℃.Under fully stirring, drip the alpha-brominated coconut oil of 0.1mol, continue to stir 4h and make abundant mixing.Ageing 48h takes out thick product, and conversion ratio reaches 50.6%.If thick product is measured its active matter content without purification process by the ethanol extraction method, and its soap content is 3.3%.Purification step is with embodiment 2.Purified product is because the consonance effect of eutectic effect and surfactant, its KP value is lower, isoelectric zone territory with broad, the characteristics that also promptly in comparatively broad pH scope, all show amphoteric surfactant, and can the low solubility district not appear as common amino acid type surfactant near isoelectric point.This character is extremely important in actual applications, is fit to the kinds of surface activating agent compositely, and can use in various pH environment and does not influence result of use.
Synthesizing of embodiment 6 α-nonacosyl betaine
In the potheater that has heating, stirring and temperature-controlling system, the alpha-iodine of 0.2mol fusing is added in the reactor for melissic acid (alpha-iodine is for myricinic acid), in stirring, slowly add the trimethylamine aqueous solution that contains 1.00mol, 90 ℃ of following continuous stirring reactions about 6 hours; Be cooled to room temperature, take out thick product behind the ageing 48h, conversion ratio reaches 72.8%.

Claims (1)

1. the preparation method of an alpha-alkyl beet alkali ampholytic surface active agent, to it is characterized in that with alpha-halogen aliphatic carboxylic acid and low-grade tertiary amine be that raw material reaction is synthetic obtains alpha-alkyl beet alkali ampholytic surface active agent, and synthetic route is as follows:
In the reaction equation, R is C nH 2n+1, n=0~38 wherein;
X=Cl or Br or I;
R in the low-grade tertiary amine 1, R 2, R 3For alkyl saturated or unsaturated, straight or branched, promptly has general formula C nH 2n ± 1, n=1 wherein, 2 or 3;
In having the pressure thermal response still of heating, stirring and temperature-controlling system, by the alpha-halogen aliphatic carboxylic acid: the mol ratio of low-grade tertiary amine=1: 2~5 feeds intake, and stirs 2~12h in 60~90 ℃ of following constant temperature, and under room temperature ageing 18~48h, obtain thick product;
Thick product is adjusted to pH11~12 with NaOH, removes the low-grade tertiary amine that the end participates in reaction with Rotary Evaporators; Be adjusted to pH1~2 with dense HCl then, moisture content is wherein removed in distillation; Add the ethanol dissolving then, remove by filter inorganic salts wherein; Use acetone recrystallization, obtain white solid through vacuum drying again, this solid is the alpha-alkyl beet alkali ampholytic surface active agent of purifying.
CNB2005101227935A 2005-12-01 2005-12-01 Preparation method of alpha-alkyl betaine amphoteric surfactant Expired - Fee Related CN100404117C (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
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CN100446846C (en) * 2006-12-22 2008-12-31 江苏飞翔化工股份有限公司 Cationic Gemini surfactants
CN101250129B (en) * 2008-03-27 2011-04-13 江南大学 Method for preparing alpha-decyl betaine amphoteric surfactant
CN101549266B (en) * 2009-04-13 2011-09-07 江南大学 Preparation of surfactant of double long-chain alkyl lycine and applications thereof
CN102126964A (en) * 2010-12-10 2011-07-20 江南大学 Method for preparing high-content alpha-lauryl betaine by solvent-free quaternization
CN102531971B (en) * 2011-12-28 2014-09-17 江南大学 Preparation method of alpha-N,N-dialkyl oxyamino fatty acid surfactant
CN103524351B (en) * 2013-10-17 2015-07-08 青岛科技大学 Device and method for removing trimethylamine in production process of glycine betaine
CN110354755B (en) * 2019-07-15 2021-04-13 四川轻化工大学 Novel fluorine-containing betaine surfactant and preparation method and application thereof

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