CN103553946A - Synthetic method of ester tertiary amine by solid acid catalysis on aliphatic acid and ethanol amine - Google Patents
Synthetic method of ester tertiary amine by solid acid catalysis on aliphatic acid and ethanol amine Download PDFInfo
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- CN103553946A CN103553946A CN201310476606.8A CN201310476606A CN103553946A CN 103553946 A CN103553946 A CN 103553946A CN 201310476606 A CN201310476606 A CN 201310476606A CN 103553946 A CN103553946 A CN 103553946A
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Abstract
A synthetic method of ester tertiary amine by solid acid catalysis on aliphatic acid and ethanol amine is as below: according to a molar ratio of fatty acid to ethanolamine of 1.7-2.0:1 and a usage amount of solid acid catalyst accounting for 0.1-1 wt% of the total reactants, adding the aliphatic acid into a reactor; in a N2 atmosphere, stirring and heating until complete melting of the reactants; adding ethanolamine and the solid acid catalyst; conducting an esterification reaction at the operating temperature of 170-200 DEG C in N2 atmosphere; when the acid value of the products reduces to 3 mg KOH / g, stopping the reaction; cooling the system temperature to 70 DEG C; and carrying out hot filtering to separate out the solid acid catalyst, so as to obtain a product ester tertiary amine. The method provided by the invention has the following advantages: the solid acid catalyst has small usage amount, high catalytic activity, good selectivity, easy separation from the products, reusability and no pollution to environment; and the product has performance.
Description
Technical field
The invention belongs to a kind of lipid acid and thanomin esterification synthesizing ester amine, relate to specifically the method for the esterification synthetic ester base tertiary amine of a kind of solid acid catalysis lipid acid and thanomin.
Background technology
In recent years, because the application of softening agent in the fields such as daily use chemicals, weaving, papermaking, leather is increasingly extensive, softening agent market, the world is always in continuing ascendant trend.Traditional softening agent---dialkyl quaternary ammonium salt (being mainly D1821), due to exist biological degradability poor, easily make fabric yellowing, compatibility is poor, raw materials cost is higher, be difficult for the shortcomings such as the highly enriched product of preparation, cannot meet the needs of actual production.The appearance of ester based quaternary ammonium salt type cats product has overcome the shortcoming of D1821, and the linear alkylbenzene sulphonic acid (LAS) that is considered to continue replaces the historical second largest change of side chain ABS rear surface promoting agent.Ester based quaternary ammonium salt is to take a kind of cats product that the grease of natural reproducible synthesizes through series processing as raw material, it not only has good biological degradability, compatibility, static resistance, flexibility, and raw materials cost is low, can not cause the rear yellowing of fabric, product that can production high density, is described as " green surfactant ".
Ester group tertiary amine is the intermediate of preparing ester based quaternary ammonium salt, to obtain ester group tertiary amine by lipid acid and thanomin generation esterification, ester group tertiary amine becomes ester based quaternary ammonium salt by quaterisation again, and the quality of ester group tertiary amine directly has influence on the quality of ester based quaternary ammonium salt product.At present, the esterification catalyzer used of lipid acid and thanomin is homogeneous catalyst (traditional catalyst such as phosphorous acid, tosic acid), these catalyst selectivitys are poor, and dissolve in reaction system, reaction can remain in ester group tertiary amine after finishing not easily separated, and then the performance of subsequent product ester based quaternary ammonium salt is affected.Compare with traditional homogeneous catalyst, solid acid catalyst have acid adjustable, highly selective, easily separated with reactant, without equipment corrosion and environmental pollution, easily reclaim and the advantage such as reuse.With solid acid catalyst, replace traditional catalyzer for the esterification of lipid acid and thanomin, through retrieval, find no prior art.
Summary of the invention
The object of this invention is to provide and a kind ofly with solid acid catalyst, replace traditional catalyzer for the method for the esterification synthetic ester base tertiary amine of lipid acid and thanomin.
The method of esterification synthetic ester base tertiary amine of the present invention is as follows:
By the mol ratio of lipid acid and thanomin, be 1.7-2.0:1, the 0.1-1wt% that solid acid catalyst consumption is reaction-ure mixture, adds lipid acid in reactor, at N
2under atmosphere, stirring and heat up after it all melts, then add thanomin and solid acid catalyst, is 170-200 ℃ in service temperature, and reaction is at N
2under atmosphere, carry out esterification, when product acid number is down to 3mgKOH/g, stopped reaction, is down to 70 ℃ by system temperature, and heat filtering goes out solid acid catalyst, obtains product ester group tertiary amine.
Thanomin as above is N, N-dimethylethanolamine, N methyldiethanol amine, trolamine.
Lipid acid as above is sad, capric acid, lauric acid, TETRADECONIC ACID, palmitinic acid, stearic acid, oleic acid, coconut oil, tallow acid or behenic acid.
Catalyzer as above is comprised of carrier and active ingredient, and described carrier is mesopore molecular sieve, and the charge capacity of active ingredient is 5-30wt%.
The aperture of mesopore molecular sieve as above is 2-10 nm, comprises MCM-48, MCM-50, SBA-1, SBA-2, SBA-6, SBA-8, SBA-12, SBA-16, FDU-1, KIT-1, JLU-11 or JLU-12.
Active ingredient as above is phospho-molybdic acid, silicotungstic acid, silicomolybdic acid, aluminum chloride, aluminum nitrate, aluminum phosphate, ferric sulfate, copper sulfate, Cadmium Sulfide or zinc sulphide.
The preparation method of solid acid catalyst of the present invention is as follows:
1. normal temperature dipping method
Carrier is greater than under the condition of 0.09 MPa and is impregnated in the active component solution of 5-30 wt% after degassed dehydration in vacuum tightness, at 20-40 ℃, stir after 24 h, active constituent is adsorbed on carrier, then after calcining 3-6h after sample drying at 400-600 ℃, obtains catalyzer.
2. Equilibrium Adsorption Method
The active component solution of 5-30wt% is added in the carrier after appropriate degassed dehydration, more than reflux 5h, makes active ingredient be adsorbed to carrier, incline and liquid, after the sample that will wet is dried and in 400-600 ℃ of calcining 3-6h, obtain catalyzer.
The present invention compared with prior art tool has the following advantages:
The present invention has that solid acid catalyst consumption is few, catalytic activity is high, selectivity is good, easily with the product separation advantages such as also reusable, environmentally safe, product property be good.
Embodiment
Embodiment 1
By mesopore molecular sieve MCM-48 degassed dehydration under vacuum condition, and impregnated in the liquor alumini chloridi of 15wt%, at 30 ℃, stir after 24h, aluminum chloride is adsorbed on MCM-48, then by sample drying, and calcine after 5h at 500 ℃, obtain the AlCl that charge capacity is 10wt%
3/ MCM-48 catalyzer, aperture is 2.9nm.
Take in the four-hole bottle that 284g stearic acid joins 1000mL, at N
2under atmosphere, stir and heat up after it all melts, add AlCl
3/ MCM-48 catalyzer 0.1g, trolamine 75g, under nitrogen atmosphere, be warming up to 190 ℃, increase stirring velocity, after reaction 5h, recording product acid value is 2.6mgKOH/g, now this reaction system is cooled to 70 ℃, and filtered while hot goes out catalyzer, obtain product ester amine, efficient liquid phase chromatographic analysis show that single, double ester amine content is respectively 19.8% and 59.6%.
Embodiment 2
The solution of zinc sulfate of 20wt% is added in the mesopore molecular sieve JLU-11 after the degassed dehydration of 20g, be heated to 105 ℃ of backflow 8h, make zinc sulfate be adsorbed to JLU-11 upper, incline and liquid, the sample that will wet is dried and at 550 ℃ of calcining 4h, obtaining charge capacity is the solid acid catalyst ZnSO of 15wt%
4/ JLU-11, aperture is 4.2nm.
Take in the four-hole bottle that 200g lauric acid joins 1000mL, at N
2under atmosphere, stir and heat up after it all melts, add ZnSO
4/ JLU-11 catalyzer 0.2g, trolamine 80g, under nitrogen atmosphere, is warming up to 200 ℃, increase stirring velocity, after reaction 4h, recording product acid value is 2.8mgKOH/g, now, this reaction system is cooled to 70 ℃, and filtered while hot goes out solid acid catalyst, obtain product ester amine, efficient liquid phase chromatographic analysis show that single, double ester amine content is respectively 18.7% and 63.6%.
Embodiment 3
By mesopore molecular sieve SBA-16 degassed dehydration under vacuum condition, and impregnated in the silicotungstic acid solution of 10wt%, at 35 ℃, stir after 24h, silicotungstic acid is adsorbed on SBA-16, then by sample drying, and calcine 3h at 550 ℃ after, obtaining the HSiW/SBA-16 catalyzer that charge capacity is 8wt%, aperture is 6.2nm.
Take in the four-hole bottle that 256g palmitinic acid joins 1000mL, at N
2under atmosphere, stir and heat up after it all melts, add HSiW/SBA-16 catalyzer 0.6g, N methyldiethanol amine 60g, under nitrogen atmosphere, be warming up to 210 ℃, increase stirring velocity, after reaction 6h, recording product acid value is 2.8mgKOH/g, now, this reaction system is cooled to 70 ℃, and filtered while hot goes out solid acid catalyst, obtain product ester amine, efficient liquid phase chromatographic analysis show that single, double ester amine content is respectively 17.9% and 67.3%.
Embodiment 4
The phosphorus molybdenum acid solution of 10wt% is added in the mesopore molecular sieve KIT-1 after the degassed dehydration of 20g, be heated to 105 ℃ of backflow 10h, active ingredient is adsorbed on KIT-1, incline and liquid, the sample that will wet is dried and is calcined 4h at 500 ℃, obtaining charge capacity is the HPM/KIT-1 catalyzer of 15wt%, and aperture is 5.1nm.
Take in the four-hole bottle that 228g TETRADECONIC ACID joins 1000mL, at N
2under atmosphere, stir and heat up after it all melts, add HPM/KIT-1 catalyzer 0.6g, N methyldiethanol amine 60g, under nitrogen atmosphere, be warming up to 210 ℃, increase stirring velocity, after reaction 6h, recording product acid value is 2.1mgKOH/g, now, this reaction system is cooled to 70 ℃, and filtered while hot goes out solid acid catalyst, obtain product ester amine
1h-NMR analyzes and show that the content of single, double ester amine is respectively 0.6% and 97.5%.
Embodiment 5
By mesopore molecular sieve SBA-2 degassed dehydration under vacuum condition, and impregnated in the silicomolybdic acid solution of 10wt%, at 35 ℃, stir after 24h, silicomolybdic acid is adsorbed on SBA-2, then by sample drying, and calcine 3h at 600 ℃ after, obtaining the HSiM/SBA-2 catalyzer that charge capacity is 20wt%, aperture is 5.3nm.
Take in the four-hole bottle that 256g palmitinic acid joins 1000mL, at N
2under atmosphere, stir and heat up after it all melts, add HSiM/SBA-2 catalyzer 0.6g, N methyldiethanol amine 60g, under nitrogen atmosphere, be warming up to 210 ℃, increase stirring velocity, after reaction 6h, recording product acid value is 2.4mgKOH/g, now, this reaction system is cooled to 70 ℃, and filtered while hot goes out solid acid catalyst, obtain product ester amine
1h-NMR analyzes and show that the content of single, double ester amine is respectively 0.7% and 98.1%.
Embodiment 6
The ferrum sulfuricum oxydatum solutum of 15wt% is added in the mesopore molecular sieve FDU-1 after the degassed dehydration of 20g, is heated to 105 ℃ of backflow 10h, make ferric sulfate be adsorbed to FDU-1 upper, incline and liquid, the sample that will wet is dried and at 500 ℃ of calcining 4h, can be obtained the Fe that charge capacity is 25wt%
2(SO
4)
3/ FDU-1 catalyzer, aperture is 3.8nm.
Take in the four-hole bottle that 200g lauric acid joins 1000mL, at N
2under atmosphere, stir and heat up after it all melts, add Fe
2(SO
4)
3/ FDU-1 catalyzer 0.5g, N, N-dimethylethanolamine 133g, under nitrogen atmosphere, be warming up to 170 ℃, increase stirring velocity, after reaction 10h, recording product acid value is 2.9mgKOH/g, now, this reaction system is cooled to 70 ℃, and filtered while hot goes out solid acid catalyst, obtain product ester amine, monoesters amine content can reach 96.5%.
Embodiment 7
By the degassed dehydration under vacuum condition of SBA-16 mesopore molecular sieve, and impregnated in the Cadmium Sulfide solution of 15wt%, at 30 ℃, stir after 24h, Cadmium Sulfide is adsorbed on SBA-16 molecular sieve, then by sample drying, and calcine 4h at 500 ℃ after, can obtain the CdS/SBA-16 catalyzer that charge capacity is 30wt%, aperture is 9.1nm.
Take in the four-hole bottle that 282g oleic acid joins 1000mL, add CdS/SBA-16 catalyzer 0.1g, trolamine 80g, at N
2under atmosphere, stir and be warming up to 210 ℃, increase stirring velocity, after reaction 4h, recording product acid value is 2.6mgKOH/g, now, this reaction system is cooled to 70 ℃, and filtered while hot goes out solid acid catalyst, obtain product ester amine, efficient liquid phase chromatographic analysis show that single, double ester amine content is respectively 20.9% and 62.1%.
Embodiment 8
By the degassed dehydration under vacuum condition of JLU-11 mesopore molecular sieve, and impregnated in the aluminum phosphate solution of 15wt%, at room temperature stir after 24h, aluminum phosphate is adsorbed on JLU-11 molecular sieve, then by sample drying, and calcine 4h at 550 ℃ after, can to obtain charge capacity be 10% AlPO
4/ JLU-11 catalyzer, aperture is 4.1nm.
Take in the four-hole bottle that 172g capric acid joins 1000mL, add AlPO
4/ JLU-11 catalyzer 0.1g, trolamine 80g, at N
2under atmosphere, stir and be warming up to 190 ℃, increase stirring velocity, after reaction 6h, recording product acid value is 2.7mgKOH/g, now, this reaction system is cooled to 70 ℃, and filtered while hot goes out solid acid catalyst, obtain product ester amine, efficient liquid phase chromatographic analysis show that single, double ester amine content is respectively 21.6% and 65.3%.
Claims (8)
1. a method for solid acid catalysis lipid acid and thanomin synthetic ester base tertiary amine, is characterized in that comprising the steps:
By the mol ratio of lipid acid and thanomin, be 1.7-2.0:1, the 0.1-1wt% that solid acid catalyst consumption is reaction-ure mixture, adds lipid acid in reactor, at N
2under atmosphere, stirring and heat up after it all melts, then add thanomin and solid acid catalyst, is 170-200 ℃ in service temperature, and reaction is at N
2under atmosphere, carry out esterification, when product acid number is down to 3mgKOH/g, stopped reaction, is down to 70 ℃ by system temperature, and heat filtering goes out solid acid catalyst, obtains product ester group tertiary amine.
2. the method for a kind of solid acid catalysis lipid acid as claimed in claim 1 and thanomin synthetic ester base tertiary amine, is characterized in that described thanomin is N, N-dimethylethanolamine, N methyldiethanol amine or trolamine.
3. the method for a kind of solid acid catalysis lipid acid as claimed in claim 1 and thanomin synthetic ester base tertiary amine, is characterized in that described lipid acid is sad, capric acid, lauric acid, TETRADECONIC ACID, palmitinic acid, stearic acid, oleic acid, coconut oil, tallow acid or behenic acid.
4. the method for a kind of solid acid catalysis lipid acid as claimed in claim 1 and thanomin synthetic ester base tertiary amine, it is characterized in that described catalyzer is comprised of carrier and active ingredient, described carrier is mesopore molecular sieve, and the charge capacity of active ingredient is 5-30wt%.
5. the method for a kind of solid acid catalysis lipid acid as claimed in claim 4 and thanomin synthetic ester base tertiary amine, the aperture that it is characterized in that described mesopore molecular sieve is 2-10 nm, comprises MCM-48, MCM-50, SBA-1, SBA-2, SBA-6, SBA-8, SBA-12, SBA-16, FDU-1, KIT-1, JLU-11 or JLU-12.
6. the method for a kind of solid acid catalysis lipid acid as claimed in claim 4 and thanomin synthetic ester base tertiary amine, is characterized in that described active ingredient is phospho-molybdic acid, silicotungstic acid, silicomolybdic acid, aluminum chloride, aluminum nitrate, aluminum phosphate, ferric sulfate, copper sulfate, Cadmium Sulfide or zinc sulphide.
7. the method for a kind of solid acid catalysis lipid acid as described in claim 4-6 any one and thanomin synthetic ester base tertiary amine, is characterized in that the preparation method of solid acid catalyst is as follows:
Carrier is greater than under the condition of 0.09 MPa and is impregnated in the active component solution of 5-30 wt% after degassed dehydration in vacuum tightness, at 20-40 ℃, stir after 24 h, active constituent is adsorbed on carrier, then after calcining 3-6h after sample drying at 400-600 ℃, obtains catalyzer.
8. the method for a kind of solid acid catalysis lipid acid as described in claim 4-6 any one and thanomin synthetic ester base tertiary amine, is characterized in that the preparation method of solid acid catalyst is as follows:
The active component solution of 5-30wt% is added in the carrier after appropriate degassed dehydration, more than reflux 5h, makes active ingredient be adsorbed to carrier, incline and liquid, after the sample that will wet is dried and in 400-600 ℃ of calcining 3-6h, obtain catalyzer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008460A (en) * | 2017-04-21 | 2017-08-04 | 广州花语精细化工有限公司 | A kind of solid catalyst used in synthesis dual-long-chain ester based quaternary ammonium salt and preparation method thereof |
| CN107033014A (en) * | 2017-04-21 | 2017-08-11 | 广州花语精细化工有限公司 | A kind of synthetic method of dual-long-chain ester based quaternary ammonium salt |
| CN115724754A (en) * | 2022-10-24 | 2023-03-03 | 中国日用化学研究院有限公司 | Diester Gemini quaternary ammonium salt and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008460A (en) * | 2017-04-21 | 2017-08-04 | 广州花语精细化工有限公司 | A kind of solid catalyst used in synthesis dual-long-chain ester based quaternary ammonium salt and preparation method thereof |
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| CN107008460B (en) * | 2017-04-21 | 2020-06-30 | 广州花语精细化工有限公司 | Solid catalyst for synthesizing double-long-chain ester-based quaternary ammonium salt and preparation method thereof |
| CN115724754A (en) * | 2022-10-24 | 2023-03-03 | 中国日用化学研究院有限公司 | Diester Gemini quaternary ammonium salt and preparation method and application thereof |
| CN115724754B (en) * | 2022-10-24 | 2024-03-15 | 中国日用化学研究院有限公司 | Diester-based Gemini quaternary ammonium salt and preparation method and application thereof |
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Application publication date: 20140205 |