CN102816075A - Preparation method of long-chain quaternary ammonium surfactant - Google Patents
Preparation method of long-chain quaternary ammonium surfactant Download PDFInfo
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- CN102816075A CN102816075A CN2012103061686A CN201210306168A CN102816075A CN 102816075 A CN102816075 A CN 102816075A CN 2012103061686 A CN2012103061686 A CN 2012103061686A CN 201210306168 A CN201210306168 A CN 201210306168A CN 102816075 A CN102816075 A CN 102816075A
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Abstract
The invention discloses a preparation method of a long-chain quaternary ammonium surfactant. The method is characterized by: adding long-chain tertiary amine, dimethyl carbonate, a catalyst and a phase transfer agent into a reaction kettle equipped with a stirrer and a thermometer, with the long-chain tertiary amine and the dimethyl carbonate being in a mole ratio of 1:5-10, the dosage of the catalyst being 3.41*10<-4>-2.20*10<-3> mole parts, and the dosage of the phase transfer agent being 5-10% of the weight of the reaction materials, performing a reaction at a temperature of 90-120DEG C and a pressure of 0.2-0.6MPa for 3-10h, conducting evaporation and recovering the solvent, thus obtaining the long-chain quaternary ammonium surfactant. The preparation method has the advantages of short process route, low cost, low energy consumption, and no emission of ''three wastes''.
Description
Technical field
The present invention relates to a kind of preparation method of long chain quaternary tensio-active agent, belong to the preparation field of tensio-active agent.
Technical background
Tensio-active agent has in industrial and agricultural production widely to be used, and is commonly called as " industrial monosodium glutamate ".Quaternary surfactant is one of important cats product.The production of quaternary surfactant is that raw material and quaternizing agent reaction obtain corresponding long carbon chain quaternary ammonium salt to grow the carbochain tertiary amine normally.Season ammonification reagent commonly used has methyl halide (as: methyl chloride, monobromethane, methyl iodide) and methyl-sulfate etc.But above-mentioned season ammonification reagent all has toxicity and the problem of poor stability in various degree.Have higher toxicity like methyl halide, and methyl-sulfate has higher toxicity and bigger reactive behavior, flammable or explosion caused like its chance water, heat, naked light or oxygenant, there is bigger potential safety hazard in transportation, storage with in using.Utilizing the green season ammonification reagent of generally acknowledging in the world---it is to produce a kind of important greenization route of quaternary ammonium salt that methylcarbonate replaces above-mentioned season ammonification reagent and long chain tertiary amine prepared in reaction quaternary ammonium salt.
Chinese patent CN200410012215.1 has described a kind of compound method of ester-amine series quaternary ammonium salt, utilizes methylcarbonate to make season ammonification reagent, has successfully prepared a series of ester-amine series quaternary ammonium salts.Introduce solvent in this method and make that the purifying of product becomes difficulty in the production process, and the recovery of high boiling solvent has improved production cost.
Chinese patent CN200510061094.4 has described a kind of compound method of quaternary ammonium salt, utilizes the reaction of methylcarbonate and ammonium ion to synthesize a series of quaternary ammonium salt.The temperature that this method adopts is higher, and the catalytic amount of introducing is bigger.
Geng Tao etc. are in " methyl carbonic acid ester quat synthetic with characterize " (fine chemistry industry, 2010,27 (6): 537-541) studied the methylation reaction of long chain tertiary amine and methylcarbonate under the condition that does not have catalyzer to exist in the literary composition.This research is only studied methylation reaction itself, and temperature of reaction is higher.
Summary of the invention
The preparation method who the objective of the invention is to be directed against the deficiency of prior art and a kind of long chain quaternary tensio-active agent is provided; Be characterized in the long chain tertiary amine being raw material; Methylcarbonate is a season ammonification reagent, preparation long chain quaternary tensio-active agent in the presence of catalyzer.
The object of the invention is realized that by following technical measures wherein said raw material umber is molfraction except that specified otherwise.
The preparation method of long chain quaternary tensio-active agent may further comprise the steps:
With long chain tertiary amine: the mol ratio of methylcarbonate=1: 5～10, catalyst levels are 3.41 * 10
-4～2. 20 * 10
-3Molar part and consisting of phase-transferring agent consumption are 5～10% of reaction mass weight, add to have in the reaction kettle of whisking appliance, TM, and in temperature 90-120 ℃, pressure 0.2-0.6MPa, reaction 3～10h, evaporation obtains the long chain quaternary tensio-active agent after reclaiming solvent.
Said long chain tertiary amine is at least a in carbon 10,12,14,16,18 and the carbon 20.
Said catalyzer is any in 4 bromide, tetraethylammonium bromide, Tetrabutyl amonium bromide, dodecyl dimethyl brometo de amonio, tetradecyl dimethyl-brometo de amonio, hexadecyldimethyl benzyl ammonium brometo de amonio, octadecyl dimethyl-brometo de amonio, bromination 1-butyl-3-Methylimidazole or the 1-butyl-3-methyl imidazolium tetrafluoroborate.
Said consisting of phase-transferring agent is any in methyl alcohol, ethanol, Virahol or the terepthaloyl moietie.
The long chain quaternary tensio-active agent for preparing by the preparation method of long chain quaternary tensio-active agent.
Performance test:
1, adopt the method shown in the QB 1915-93 " cats product fatty alkyl dimethyl-ammonium halide and fatty alkyl dimethyl benzyl ammonium halide " of pressing to measure the active matter content of long chain quaternary.
2, adopt method shown in the GB/T 11276-2007 " mensuration of tensio-active agent micelle-forming concentration " to measure the micelle-forming concentration of long chain quaternary.
The present invention has the following advantages
1, under catalyst action, temperature of reaction is reduced to 90-120 ℃, obtains the product active matter content and reaches 75%-95%, and its active matter content has improved 50% than obtaining product activity thing content under the same reaction conditions that does not add catalyzer.
2, the preparation method of long chain quaternary tensio-active agent provided by the invention, operational path is short, and cost is low, helps suitability for industrialized production.
3, transportation and the hidden danger safe in utilization of having avoided methyl-sulfate to bring adopt methylcarbonate to make season ammonification reagent, in technological process, do not relate to poisonous and hazardous raw material,
4, not having " two is useless " and get rid of, is a kind of reliable green production process.
Embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this present embodiment can only be used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
With the hexadecyldimethyl benzyl ammonium tertiary amine: mol ratio, the 4 bromide 1.43 * 10 of methylcarbonate=1: 6
-3The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 100 ℃ of temperature, pressure 0.26MPa, reaction 6h; After solvent is reclaimed in evaporation, obtain active matter content and be 75.20% long chain quaternary tensio-active agent.
Embodiment 2
With the hexadecyldimethyl benzyl ammonium tertiary amine: mol ratio, the tetraethylammonium bromide 1.05 * 10 of methylcarbonate=1: 6
-3The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 100 ℃ of temperature, pressure 0.60MPa, reaction 6h; After solvent is reclaimed in evaporation, obtain active matter content and be 81.50% long chain quaternary tensio-active agent.
Embodiment 3
With the hexadecyldimethyl benzyl ammonium tertiary amine: mol ratio, the Tetrabutyl amonium bromide 6.82 * 10 of methylcarbonate=1: 6
-4The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 100 ℃ of temperature, pressure 0.47MPa, reaction 6h; After solvent is reclaimed in evaporation, obtain active matter content and be 87.50% long chain quaternary tensio-active agent.
Embodiment 4
With the hexadecyldimethyl benzyl ammonium tertiary amine: mol ratio, the Trimethyllaurylammonium bromide 7.13 * 10 of methylcarbonate=1: 6
-4The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 100 ℃ of temperature, pressure 0.41MPa, reaction 6h; After solvent is reclaimed in evaporation, obtain active matter content and be 81.10% long chain quaternary tensio-active agent.
Embodiment 5
With the hexadecyldimethyl benzyl ammonium tertiary amine: mol ratio, the octadecyl trimethylammonium bromide 5.61 * 10 of methylcarbonate=1: 6
-4The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 100 ℃ of temperature, pressure 0.41MPa, reaction 6h; After solvent is reclaimed in evaporation, obtain active matter content and be 78.90% long chain quaternary tensio-active agent.
Embodiment 6
With the hexadecyldimethyl benzyl ammonium tertiary amine: mol ratio, the bromination 1-butyl-3-Methylimidazole 1.00 * 10 of methylcarbonate=1: 6
-3The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 100 ℃ of temperature, pressure 0.47MPa, reaction 6h; After solvent is reclaimed in evaporation, obtain active matter content and be 83.70% long chain quaternary tensio-active agent.
Embodiment 7
With the hexadecyldimethyl benzyl ammonium tertiary amine: mol ratio, the 1-butyl-3-methyl imidazolium tetrafluoroborate 9.73 * 10 of methylcarbonate=1: 6
-4The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 100 ℃ of temperature, pressure 0.35MPa, reaction 6h; After solvent is reclaimed in evaporation, obtain active matter content and be 84.40% long chain quaternary tensio-active agent.
Embodiment 8
With the hexadecyldimethyl benzyl ammonium tertiary amine: mol ratio, the Tetrabutyl amonium bromide 2.02 * 10 of methylcarbonate=1: 6
-3The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 100 ℃ of temperature, pressure 0.39MPa, reaction 7h; After solvent is reclaimed in evaporation, obtain active matter content and be 86.80% long chain quaternary tensio-active agent.
Embodiment 9
With the hexadecyldimethyl benzyl ammonium tertiary amine: mol ratio, the Tetrabutyl amonium bromide 1.68 * 10 of methylcarbonate=1: 6
-3The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 90 ℃ of temperature, pressure 0.31MPa, reaction 8h; After solvent is reclaimed in evaporation, obtain active matter content and be 60.10% long chain quaternary tensio-active agent.
Embodiment 10
With the hexadecyldimethyl benzyl ammonium tertiary amine: mol ratio, the Tetrabutyl amonium bromide 1.33 * 10 of methylcarbonate=1: 6
-3The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 90 ℃ of temperature, pressure 0.37MPa, reaction 6h; After solvent is reclaimed in evaporation, obtain active matter content and be 60.70% long chain quaternary tensio-active agent.
Embodiment 11
With the hexadecyldimethyl benzyl ammonium tertiary amine: mol ratio, the Tetrabutyl amonium bromide 3.41 * 10 of methylcarbonate=1: 6
-4The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 100 ℃ of temperature, pressure 0.37MPa, reaction 7h; After solvent is reclaimed in evaporation, obtain active matter content and be 80.30% long chain quaternary tensio-active agent.
Embodiment 12
With the hexadecyldimethyl benzyl ammonium tertiary amine: mol ratio, the Tetrabutyl amonium bromide 6.82 * 10 of methylcarbonate=1: 6
-4The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 90 ℃ of temperature, pressure 0.34MPa, reaction 8h; After solvent is reclaimed in evaporation, obtain active matter content and be 62.90% long chain quaternary tensio-active agent.
Embodiment 13
With the hexadecyldimethyl benzyl ammonium tertiary amine: mol ratio, the Tetrabutyl amonium bromide 9.93 * 10 of methylcarbonate=1: 6
-4The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 100 ℃ of temperature, pressure 0.36MPa, reaction 6h; After solvent is reclaimed in evaporation, obtain active matter content and be 79.90% long chain quaternary tensio-active agent.
Embodiment 14
With the dodecyl dimethyl tertiary amine: mol ratio, the Tetrabutyl amonium bromide 1.98 * 10 of methylcarbonate=1: 6
-3The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 120 ℃ of temperature, pressure 0.59MPa, reaction 6h; After solvent is reclaimed in evaporation, obtain active matter content and be 92.50% long chain quaternary tensio-active agent.
Embodiment 15
With the tetradecyl dimethyl tertiary amine: mol ratio, the Tetrabutyl amonium bromide 2.17 * 10 of methylcarbonate=1: 6
-3The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 120 ℃ of temperature, pressure 0.35MPa, reaction 6h; After solvent is reclaimed in evaporation, obtain active matter content and be 91.60% long chain quaternary tensio-active agent.
Embodiment 16
Mix tertiary amine with 12/14: mol ratio, the Tetrabutyl amonium bromide 2.05 * 10 of methylcarbonate=1: 6
-3The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 120 ℃ of temperature, pressure 0.58MPa, reaction 6h; After solvent is reclaimed in evaporation, obtain active matter content and be 95.40% long chain quaternary tensio-active agent.
Embodiment 17
Mix tertiary amine with 14/16: mol ratio, the Tetrabutyl amonium bromide 2.20 * 10 of methylcarbonate=1: 6
-3The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 120 ℃ of temperature, pressure 0.50MPa, reaction 6h; After solvent is reclaimed in evaporation, obtain active matter content and be 94.00% long chain quaternary tensio-active agent.
Embodiment 18
Mix tertiary amine with 16/18: mol ratio, the Tetrabutyl amonium bromide 2.05 * 10 of methylcarbonate=1: 6
-3The consumption of molar part and consisting of phase-transferring agent is that 10% adding of raw material reaction amount has in the reaction kettle of whisking appliance, TM; In 120 ℃ of temperature, pressure 0.40MPa, reaction 6h; After solvent is reclaimed in evaporation, obtain active matter content and be 95.60% long chain quaternary tensio-active agent.
Claims (5)
1. the preparation method of a long chain quaternary tensio-active agent is characterized in that this method may further comprise the steps:
With long chain tertiary amine: the mol ratio of methylcarbonate=1: 5～10, catalyst levels are 3.41 * 10
-4～2. 20 * 10
-3Molar part and consisting of phase-transferring agent consumption are 5～10% of reaction mass weight, add to have in the reaction kettle of whisking appliance, TM, and in temperature 90-120 ℃, pressure 0.2-0.6MPa, reaction 3～10h, evaporation obtains the long chain quaternary tensio-active agent after reclaiming solvent.
2. according to the preparation method of the said long chain quaternary tensio-active agent of claim 1, it is characterized in that long chain tertiary amine is at least a in carbon 10,12,14,16,18 and the carbon 20.
3. according to the preparation method of the said long chain quaternary tensio-active agent of claim 1, it is characterized in that catalyzer is any in 4 bromide, tetraethylammonium bromide, Tetrabutyl amonium bromide, Trimethyllaurylammonium bromide, TTAB, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, bromination 1-butyl-3-Methylimidazole or the 1-butyl-3-methyl imidazolium tetrafluoroborate.
4. according to the preparation method of the said long chain quaternary tensio-active agent of claim 1, it is characterized in that consisting of phase-transferring agent does
In methyl alcohol, ethanol, Virahol or the terepthaloyl moietie any.
5. the long chain quaternary tensio-active agent for preparing according to the preparation method of the said long chain quaternary tensio-active agent of claim 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102806046A (en) * | 2012-08-24 | 2012-12-05 | 四川大学 | Green preparation method of quaternary ammonium salt surfactant |
| CN103111324A (en) * | 2013-01-25 | 2013-05-22 | 中南大学 | Application of bromine or iodine-containing haloid and method for synthesizing methyl three-long-chain aliphatic group quaternary ammonium salt derivative |
| CN109320420A (en) * | 2018-11-16 | 2019-02-12 | 厦门医学院 | A kind of synthetic method of chain alkyl methyl carbonate quaternary ammonium salt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1939889A (en) * | 2006-08-24 | 2007-04-04 | 中国日用化学工业研究院 | Synthesis of fat tertiary amine quaternary ammonium salt derivative |
| CN1948268A (en) * | 2005-10-10 | 2007-04-18 | 浙江师范大学 | Synthesis method of quaternary ammonium salt |
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- 2012-08-24 CN CN2012103061686A patent/CN102816075A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948268A (en) * | 2005-10-10 | 2007-04-18 | 浙江师范大学 | Synthesis method of quaternary ammonium salt |
| CN1939889A (en) * | 2006-08-24 | 2007-04-04 | 中国日用化学工业研究院 | Synthesis of fat tertiary amine quaternary ammonium salt derivative |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102806046A (en) * | 2012-08-24 | 2012-12-05 | 四川大学 | Green preparation method of quaternary ammonium salt surfactant |
| CN103111324A (en) * | 2013-01-25 | 2013-05-22 | 中南大学 | Application of bromine or iodine-containing haloid and method for synthesizing methyl three-long-chain aliphatic group quaternary ammonium salt derivative |
| CN109320420A (en) * | 2018-11-16 | 2019-02-12 | 厦门医学院 | A kind of synthetic method of chain alkyl methyl carbonate quaternary ammonium salt |
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