CN102807495A - 3-chlorine-2-hydroxypropyl dimethyl dehydroabietic-base ammonium chloride and preparation method thereof - Google Patents
3-chlorine-2-hydroxypropyl dimethyl dehydroabietic-base ammonium chloride and preparation method thereof Download PDFInfo
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Abstract
The invention relates to 3-chlorine-2-hydroxypropyl dimethyl dehydroabietic-base ammonium chloride and a preparation method thereof. The method comprises the following steps of dehydroabietylamine is used as a raw material to be subjected to Leuckart-Clarke reaction to prepare N, N - dimethyl dehydroabietylamine; utilizing the N, N - dimethyl dehydroabietylamine and epoxy chloropropane to react for 1-68 hours in the presence of hydrochloric acid, then carrying out centrifugation or filtration, ordinary-pressure or decompressed desolventization and composite solvent recrystallization, and finally obtaining a 3-chlorine-2-hydroxypropyl dimethyl dehydroabietic-base ammonium chloride wet-material; and drying the wet-material for 1.0-48.0 hours at the vacuum degree of 0.01-0.1Mpa and the temperature of 10-100 DEG C to obtain a 3-chlorine-2-hydroxypropyl dimethyl dehydroabietic-base ammonium chloride product of which the mass percentage content is larger than 85 percent. The method has the advantages of simple process, high dehydroabietylamine conversion ratio, good water-solubility and emulsifiability of the product and the like.
Description
Technical field
The present invention relates to the preparation method of a kind of forest chemical field tensio-active agent, particularly a kind of preparation method of the novel cats product that contains the dehydroabietylamine structure.
Background technology
Rosin is a kind of natural resource with recyclability, and the staple of the nilox resin that generates after the process disproportionation is a dehydroabietic acid.And dehydroabietic acid can be converted into dehydroabietylamine through amidation, intramolecular dehydration, or obtains containing the rosin derivatives such as alcohol of rosin structure through the direct hydrogenation reduction.Utilize these rosin derivatives to can be used for the product that synthetic a series of character are similar to lipid acid, Fatty Alcohol(C12-C14 and C12-C18) and fatty amine tensio-active agent and show unique characteristics; As utilize dehydroabietic acid to synthesize the dehydroabietic acid sulfonated ester, utilize the alcohol compound or synthetic westvaco rosin polyoxyethylenated alcohol of dehydroabietylamine or the dehydroabietylamine Soxylat A 25-7 etc. that contain the rosin structure.These are the surfactant product that feedstock production obtains with rosin; The demand for development that meets green, environmental protection more; And have good application performance, can be used as the production that emulsifying agent, inhibiter, emulsion splitter, washing composition, pigment dispersing agent, flocculation agent and flotation agent etc. are applied to multiple fine chemicals.Wherein dehydroabietylamine has not only kept rosin inherent good biodegradability properties and environment friendly as one of typical rosin derivative, and the amino that exists in its structure makes it have better reactivity worth and application performance.
Through dehydroabietylamine and oxyethane and the reaction of sulfuric acid dialkyl group fat, can generate with quaternary ammonium structure and the rare chain of polyoxy second cationic surfactant as hydrophilic group; N, N-dimethyl-dehydroabietylamine then can through with halohydrocarbons reaction, directly make the amido in the dehydroabietylamine structure be converted into the quaternary ammonium structure.Under the certain reaction condition, generate N-(3-chloro-2-hydroxypropyl) dehydroabietylamine, and then can generate 3-dehydrogenation fir base-2-hydroxypropyl-trimethyl ammonium chloride through N-(3-chloro-2-hydroxypropyl) dehydroabietylamine and Trimethylamine reaction through dehydroabietylamine and epichlorohydrin reaction; Also can generate the cats product that contains pyridine and dehydroabietylamine structure through N-(3-chloro-2-hydroxypropyl) dehydroabietylamine and pyridine reaction.Numerous application functions such as that these cats products with dehydroabietylamine structure generally all have is antistatic preferably, emulsification, softness and bactericidal.But also exist more deficiency existing the preparation in the method that contains dehydroabietylamine structural cation tensio-active agent; Wang Yan (daily chemical industry; 1997; (4): 16-17) a series of N-dehydrogenation fir base cationic surfactants have been synthesized in modification to dehydroabietylamine, but the dehydroabietylamine transformation efficiency is not high; (fine chemistry industry such as Jiang Fubin; 2007,24 (11): 1074-1079) synthesized two kinds of bis-quaternary ammonium salt cationic surfactants that contain dehydrogenation fir base, the content of quaternary ammonium salt is higher in the product; But the dehydroabietylamine transformation efficiency is not high, and surfactant product is water-soluble relatively poor.
Summary of the invention
The technical problem that solves: contain in order to solve existing preparation that the dehydroabietylamine transformation efficiency that exists in the dehydroabietylamine structure quaternary ammonium salt technology is low, quaternary ammonium salt content is not high in the product, product is water-soluble is not extraordinary problem; The present invention has proposed a kind of preparation method of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride according to the characteristics of dehydroabietylamine.The preparation method who is used for 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride provided by the invention has that technology is simple, feed stock conversion is high, the advantage of product good water solubility.
Technical scheme: 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride, molecular structural formula is as follows:
A kind of preparation method of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride, through the Leuckart-Clarke reaction, order adds formic acid and formaldehyde in dehydroabietylamine, prepares N, N-dimethyl-dehydroabietylamine; Utilize N; N-dimethyl-dehydroabietylamine and hydrochloric acid reaction obtain N, and N-dimethyl-dehydroabietylamine hydrochloride utilizes double solvents dissolving N; With epichlorohydrin reaction, obtain containing the mixture of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride behind the N-dimethyl-dehydroabietylamine hydrochloride; Contain the mixture of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride, remove double solvents, obtain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product through underpressure distillation; 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product is via ethanol and ETHYLE ACETATE (1.0 ~ 10) by volume: double solvents recrystallization, filtration or spinning, vacuum-drying that (1.0 ~ 10) constitute obtain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride product.
Preparation intermediate product N, during N-dimethyl-dehydroabietylamine, formic acid is 1.0 ~ 5.0:1.0 with the amount of substance ratio of dehydroabietylamine, and formaldehyde is 1.0 ~ 4.0:1.0 with dehydroabietylamine amount of substance ratio, and when dripping formic acid and formaldehyde, temperature is controlled at below 40 ℃; After formaldehyde dripped off, temperature of reaction was 40 ~ 80 ℃, and the reaction times is 1 ~ 28h.
Said N, N-dimethyl-dehydroabietylamine is 1.0:2.0 ~ 5.0 with HCl amount of substance ratio.
Dissolving N, the double solvents of N-dimethyl-dehydroabietylamine hydrochloride are that 1 ~ 3:1 constitutes by the second alcohol and water by volume; Epoxy chloropropane and N, N-dimethyl-dehydroabietylamine hydrochloride amount of substance ratio is 1 ~ 4:1, and the temperature of reaction is 30 ~ 80 ℃, and the reaction times is 1 ~ 68h.
The mixture that contains 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride adds solvent ethyl acetate to it thicker product 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride is separated out after underpressure distillation removes double solvents.
The double solvents that is used for 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product recrystallization is by ethanol and ETHYLE ACETATE (1.0 ~ 10) by volume: (1.0 ~ 10) constitute; When recrystallization was handled 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product, double solvents was 1.0 ~ 20.0:1.0 with the mass ratio that contains the crude product of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride.
3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride wet stock vacuum tightness when carrying out vacuum-drying is that 0.01 ~ 0.1MPa, temperature are that 10 ~ 100 ℃, vacuum-drying time are 1.0 ~ 48.0h.
The quality percentage composition of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride in product is greater than 85%.
Specifically, the invention discloses a kind of preparation method of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride, step is:
The first step is used the dissolve with ethanol dehydroabietylamine, then through constant pressure funnel to wherein dripping formic acid, wherein formic acid is 1.0 ~ 5.0:1 with the amount of substance ratio of dehydroabietylamine, dropping temperature is controlled at below 40 ℃, about 25min drips off.After formic acid drips off, continue holding temperature below 40 ℃, and to drip mass percent from same tap funnel be 36% formaldehyde, wherein formaldehyde is 1.0 ~ 4.0:1 with the ratio of dehydroabietylamine amount, and about 30min drips off.After formaldehyde drips off, make material be warming up to 40 ~ 80 ℃, and under agitation react 1 ~ 28h.
With 40 ~ 50 ℃ of reaction solution coolings, adding 30% aqueous sodium hydroxide solution, to be neutralized to pH be 11 ~ 13.Reactant is poured in the separating funnel behind the separatory, and to neutral, lower floor's water is with dichloromethane extraction three times with saturated sodium-chloride water solution washing three times for upper oil phase, and with dichloromethane solution and wash to the neutral upper oil phase and merge.
Oil phase is added in the flask decompression steam ethanol, methylene dichloride and water; Under alkaline condition, in oil phase, drip an amount of Tosyl chloride then; Get the oil phase underpressure distillation after reaction for some time; Collect the cut of 200 ~ 240 ℃/666.61 ~ 1333.22Pa, get little yellow liquid product N, N-dimethyl-dehydroabietylamine.
Second step, get N, N-dimethyl-dehydroabietylamine and aqueous hydrochloric acid back flow reaction 3h, after decompression steamed unnecessary hydrochloric acid, adding by ethanol and water again was the double solvents that 1 ~ 3:1 constitutes by volume; Stir; After treating material dissolution; Press epoxy chloropropane and N, the ratio of N-dimethyl-dehydroabietylamine amount be 1 ~ 4:1 to N, splash into epoxy chloropropane in the N-dimethyl-dehydroabietylamine hydrochloride solution; And under temperature is 30 ~ 80 ℃, react 1 ~ 68h, obtain containing the mixture of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride.
The 3rd step; After second mixture that contains 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride that obtain of step carried out underpressure distillation and remove excessive epoxy chloropropane, ethanol and water; Add ETHYLE ACETATE and stirring, crystallisation by cooling, filtration or spinning again, obtain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product.
The 4th step; Use by ethanol, ETHYLE ACETATE after the organic solvent that constitutes of 1.0 ~ 10:1.0 ~ 10 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product that the 3rd step was obtained carries out recrystallization by volume; Again the solid materials that filters or spinning obtains is carried out vacuum-drying, obtain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride product.During recrystallization, the organic solvent that constitutes of 1.0 ~ 10:1 and the mass ratio of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product are 1.0 ~ 20.0:1 by volume by ethanol, ETHYLE ACETATE.Vacuum tightness is that 0.01 ~ 0.1Mpa, temperature are 10 ~ 100 ℃ during vacuum-drying.
Beneficial effect:
1. when synthesizing 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride through the inventive method, have the advantages that process operation is simple, the dehydroabietylamine transformation efficiency is high, and the content of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride surpasses 85%wt in the product; The 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride product that obtains, with dehydroabietylamine and N, N-dimethyl-dehydroabietylamine is compared has better water solubility; Adopt the pulling-on piece method to measure the surface tension of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride, the cmc value that records product 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride in the time of 25 ℃ is 0.063mmol/L, and corresponding surface tension is 27.6mN/m.Dehydroabietylamine and N, N-dimethyl-dehydroabietylamine is obviously insoluble in water, and product 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride dissolves in water through appearance method visible its relatively more directly perceived.
2. similar with the quaternary cationics that contains the dehydroabietylamine structure of other type; In the molecular structure of the 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride for preparing among the present invention because the group of oleophylic performance is provided is the rosin structure that comes from natural resource; Make its characteristics that can have natural sex and recyclability concurrently, thereby the scope of application is also more extensive.The test of product 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride emulsifying property shows that it has certain emulsifying property.
Description of drawings
Fig. 1 is the structural formula of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride.
The FT-IR figure of Fig. 2 product 3-of the present invention chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride.
Fig. 3 is a product 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride
1H NMR figure.
Embodiment
The preparation method of a kind of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride that relates in the invention; Its process mainly comprises following components: (1) is added dropwise to formic acid, formaldehyde in the dehydroabietylamine ethanolic soln; Obtain containing N, the mixture of N-dimethyl-dehydroabietylamine after reaction for some time; (2) contain N, the mixture of N-dimethyl-dehydroabietylamine obtains little yellow liquid product N, N-dimethyl-dehydroabietylamine through decompression precipitation, neutralization, extraction, removal of impurities, underpressure distillation; (3) N, revolve again after N-dimethyl-dehydroabietylamine and the aqueous hydrochloric acid back flow reaction steam white-yellowish solid N, N-dimethyl-dehydroabietylamine hydrochloride; N, N-dimethyl-dehydroabietylamine hydrochloride with ethanol and water dissolution after, drip epoxy chloropropane again, obtain containing the mixture of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride after the reaction; (4) mixture that contains 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride is after decompression removes second alcohol and water and unreacted epoxy chloropropane; Add solvent ethyl acetate stirring, cooling, centrifugal or filtering separation again, to obtain containing the crude product of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride; (5) crude product that contains 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride is used the double solvents recrystallization that is made up of ethanol, ETHYLE ACETATE; (6) material behind the recrystallization obtains the wet stock of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride through cooling, crystallization, centrifugal or filtration; (7) 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride wet stock can obtain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride product through vacuum-drying.
The preparation method of a kind of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride that relates in the invention; Its related process parameter is following: (1) N; In the N-dimethyl-dehydroabietylamine building-up process; Formic acid is 1.0 ~ 5.0:1 with the amount of substance ratio of dehydroabietylamine, and formaldehyde is 1.0 ~ 4.0:1 with dehydroabietylamine amount of substance ratio; (2) N, in the N-dimethyl-dehydroabietylamine building-up process, temperature of reaction is 40 ~ 80 ℃; (3) N, in the N-dimethyl-dehydroabietylamine building-up process, the reaction times is 1 ~ 28h; (4) dissolving N, the double solvents of N-dimethyl-dehydroabietylamine hydrochloride are that 1 ~ 3:1 constitutes by ethanol, water by volume; (5) epoxy chloropropane and N, N-dimethyl-dehydroabietylamine hydrochloride amount of substance ratio is 1 ~ 4:1; (6) epoxy chloropropane and N, N-dimethyl-dehydroabietylamine hydrochloride temperature of reaction is 30 ~ 80 ℃; (7) epoxy chloropropane and N, the N-dimethyl-dehydroabietylamine hydrochloride reaction times is 1 ~ 68h; (8) double solvents is to be made up of 1.0 ~ 10:1.0 ~ 10 by volume ethanol, ETHYLE ACETATE during recrystallization; (9) during recrystallization, double solvents is 1.0 ~ 20.0:1 with the mass ratio that contains the crude product of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride; (10) 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride wet stock vacuum tightness when carrying out vacuum-drying is that 0.01 ~ 0.1Mpa, temperature are 10 ~ 100 ℃; (11) the vacuum-drying time is 1.0 ~ 48.0h; (12) in the product after the vacuum-drying 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride quality percentage composition greater than 85%.
Embodiment 1:
It is in 95% ethanol that the 135.7g dehydroabietylamine is dissolved in the 136g mass percent, in above-mentioned solution, drips the 39.2g mass percent then and be 88% formic acid, and dropping temperature is controlled at below 40 ℃.After formic acid dropwises, drip the 62.6g mass percent again and be 36% formaldehyde.After formaldehyde dropwised, heating made material be warming up to 50 ℃, and under agitation reacts 8h.Reaction solution is cooled to 40 ~ 50 ℃, and adding mass percent is that 30% aqueous sodium hydroxide solution neutralizes, to pH be till 11 ~ 13.
Reaction mass after the neutralization is poured in the separating funnel, and with saturated sodium-chloride water solution with upper strata fluid washing three times to neutral, with dichloromethane extraction lower floor water three times.With dichloromethane extraction liquid with wash to the neutral upper strata fluid and merge, and steam ethanol, methylene dichloride and water with the vacuum pump decompression, under alkaline condition, in oil phase, drip the Tosyl chloride of 90.6g then; Get the oil phase underpressure distillation behind the reaction 2h; Collect the cut of 200 ~ 240 ℃/666.61 ~ 1333.22Pa, get little yellow liquid product N, N-dimethyl-dehydroabietylamine; Get little yellow liquid product N, N-dimethyl-dehydroabietylamine 126.9g.
Get N, after N-dimethyl-dehydroabietylamine 14.3g and 6mL mass percent were 36% hydrochloric acid reflux reaction 3h, unnecessary hydrochloric acid was removed in decompression again, obtains N, N-dimethyl-dehydroabietylamine hydrochloride.Use the mixed solvent dissolving N of 100mL volume ratio as the second alcohol and water of 1.5:1, N-dimethyl-dehydroabietylamine hydrochloride at room temperature to N, splashes into epoxy chloropropane 7.0g in the N-dimethyl-dehydroabietylamine hydrochloride solution; After epoxy chloropropane dropwises, continue to stir and heating, and make material react 8h down at 40 ℃.After reacted material carried out underpressure distillation and remove ethanol, water and unreacted epoxy chloropropane, add solvent ethyl acetate and stirring, cooling, centrifugal or filtering separation again, obtain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product.
To contain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product use by ethanol, ETHYLE ACETATE by volume 2.0:1 constitute the double solvents recrystallization, the mass ratio of double solvents and 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product is 5.0:1 during recrystallization; Material behind the recrystallization is through cooling, crystallization, centrifugal or filter the wet stock that obtains 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride; 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride wet stock is that 0.03Mpa, temperature are dry 10h under 100 ℃ of conditions in vacuum tightness again, promptly obtains 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride quality percentage composition and be 85.3% product.
Embodiment 2:
It is in 95% ethanol that the 135.7g dehydroabietylamine is dissolved in the 136g mass percent, is 88% formic acid then through constant pressure funnel Dropwise 5 2.3g mass percent in above-mentioned solution, and dropping temperature is controlled at below 40 ℃.After formic acid dropwises, drip the 83.5g mass percent again and be 36% formaldehyde.After formaldehyde dropwised, heating made material be warming up to 60 ℃, under agitation reacts 15h.With 40 ~ 50 ℃ of reaction solution coolings, adding mass percent is the neutralization of 30% aqueous sodium hydroxide solution, to pH be till 11 ~ 13.
Reaction mass after the neutralization is poured in the separating funnel, and with saturated sodium-chloride water solution with upper strata fluid washing three times to neutral, with dichloromethane extraction lower floor water three times.With dichloromethane extraction liquid with wash to the neutral upper strata fluid and merge; And steam ethanol, methylene dichloride and water with vacuum pump decompression; Under alkaline condition, in oil phase, drip the Tosyl chloride of 90.6g then, get the oil phase underpressure distillation behind the reaction 2h, collect the cut of 200 ~ 240 ℃/666.61 ~ 1333.22Pa; Get little yellow liquid product N, N-dimethyl-dehydroabietylamine 128.7g.
Get N, after N-dimethyl-dehydroabietylamine 14.3g and 6mL mass percent were 36% hydrochloric acid reflux reaction 3h, unnecessary hydrochloric acid was removed in decompression again, obtains N, N-dimethyl-dehydroabietylamine hydrochloride.Use the mixed solvent dissolving N of 100mL volume ratio as the second alcohol and water of 1.5:1; N-dimethyl-dehydroabietylamine hydrochloride at room temperature to N, splashes into epoxy chloropropane 9.3g in the N-dimethyl-dehydroabietylamine hydrochloride solution; After epoxy chloropropane dropwises; Continue to stir also heating, and make material, after reacted material is carried out underpressure distillation and removes ethanol, water and unreacted epoxy chloropropane at 50 ℃ of reaction 20h down; Add solvent ethyl acetate and stirring, cooling, centrifugal or filtering separation again, obtain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product.
To contain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product use by ethanol, ETHYLE ACETATE by volume 4.0:1 constitute the double solvents recrystallization, double solvents is 7.0:1 with the mass ratio that contains the crude product of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride during recrystallization; Material behind the recrystallization is through cooling, crystallization, centrifugal or filter the wet stock that obtains 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride; 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride wet stock is that 0.05Mpa, drying temperature are dry 8h under 90 ℃ of conditions in vacuum tightness again, promptly obtains 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride quality percentage composition and be 87.8% product.
Embodiment 3:
It is in 95% ethanol that the 135.7g dehydroabietylamine is dissolved in the 136g mass percent, and dripping the 78.4g mass percent through constant pressure funnel to it then is 88% formic acid, and dropping temperature is controlled at below 40 ℃.After formaldehyde dropwises, drip the 125.2g mass percent again and be 36% formaldehyde.After formaldehyde dropwised, heating made material be warming up to 70 ℃, under agitation reacts 22h.With 40 ~ 50 ℃ of reaction solution coolings, adding mass percent is the neutralization of 30% aqueous sodium hydroxide solution, to pH be till 11 ~ 13.
Reaction mass after the neutralization is poured in the separating funnel, and with saturated sodium-chloride water solution with upper strata fluid washing three times to neutral, with dichloromethane extraction lower floor water three times.With dichloromethane extraction liquid with wash to the neutral upper strata fluid and merge; And steam ethanol, methylene dichloride and water with vacuum pump decompression; Under alkaline condition, in oil phase, drip the Tosyl chloride of 90.6g then, get the oil phase underpressure distillation behind the reaction 2h, collect the cut of 200 ~ 240 ℃/666.61 ~ 1333.22Pa; Get little yellow liquid product N, N-dimethyl-dehydroabietylamine 126.9g.
Get 28.6gN, after N-dimethyl-dehydroabietylamine and 12mL mass percent were 36% hydrochloric acid reflux reaction 3h, unnecessary hydrochloric acid was removed in decompression again, obtains N, N-dimethyl-dehydroabietylamine hydrochloride.Use the mixed solvent dissolving N of 100mL volume ratio as the second alcohol and water of 2:1; N-dimethyl-dehydroabietylamine hydrochloride at room temperature to N, splashes into epoxy chloropropane 18.5g in the N-dimethyl-dehydroabietylamine hydrochloride solution; After epoxy chloropropane dropwises; Continue to stir also heating, and make material, after reacted material is carried out underpressure distillation and removes ethanol, water and unreacted epoxy chloropropane at 60 ℃ of reaction 35h down; Add solvent ethyl acetate and stirring, cooling, centrifugal or filtering separation again, obtain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product.
To contain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product use by ethanol, ETHYLE ACETATE by volume 1.5:1 constitute the double solvents recrystallization, the mass ratio of double solvents and 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product is 10.0:1 during recrystallization; Material behind the recrystallization is through cooling, crystallization, centrifugal or filter the wet stock that obtains 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride; 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride wet stock is that 0.02Mpa, drying temperature are dry 12h under 90 ℃ of conditions in vacuum tightness again, promptly obtains 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride quality percentage composition and be 90.2% product.
Embodiment 4:
It is in 95% ethanol that the 171.3g dehydroabietylamine is dissolved in the 153g mass percent, is 88% formic acid through constant pressure funnel to wherein dripping the 125.4g mass percent then, and dropping temperature is controlled at below 40 ℃.After formaldehyde dropwises, drip the 200g mass percent again and be 36% formaldehyde.After formaldehyde dropwised, heating made material be warming up to 80 ℃, under agitation reacts 25h.With 40 ~ 50 ℃ of reaction solution coolings, adding mass percent is the neutralization of 30% aqueous sodium hydroxide solution, to pH be till 11 ~ 13.
Reaction mass after the neutralization is poured in the separating funnel, and with saturated sodium-chloride water solution with upper strata fluid washing three times to neutral, with dichloromethane extraction lower floor water three times.With dichloromethane extraction liquid with wash to the neutral upper strata fluid and merge; And steam ethanol, methylene dichloride and water with vacuum pump decompression; Under alkaline condition, in oil phase, drip the Tosyl chloride of 115g then, get the oil phase underpressure distillation behind the reaction 2h, collect the cut of 200 ~ 240 ℃/666.61 ~ 1333.22Pa; Get little yellow liquid product N, N-dimethyl-dehydroabietylamine 161.1g.
Get 42.8gN, after N-dimethyl-dehydroabietylamine and 12mL mass percent were 36% hydrochloric acid reflux reaction 3h, unnecessary hydrochloric acid was removed in decompression again, obtains N, N-dimethyl-dehydroabietylamine hydrochloride.Use the mixed solvent dissolving N of 100mL volume ratio as the second alcohol and water of 3:1; N-dimethyl-dehydroabietylamine hydrochloride at room temperature to N, splashes into epoxy chloropropane 34.7g in the N-dimethyl-dehydroabietylamine hydrochloride solution; After epoxy chloropropane dropwises; Continue to stir also heating, and make material, after reacted material is carried out underpressure distillation and removes ethanol, water and unreacted epoxy chloropropane at 70 ℃ of reaction 45h down; Add solvent ethyl acetate and stirring, cooling, centrifugal or filtering separation again, obtain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product.
To contain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product use by ethanol, ETHYLE ACETATE by volume 6:1 constitute the double solvents recrystallization, the mass ratio of double solvents and 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product is 12.0:1 during recrystallization; Material behind the recrystallization is through cooling, crystallization, centrifugal or filter the wet stock that obtains 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride; 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride wet stock is that 0.06Mpa, drying temperature are dry 20h under 80 ℃ of conditions in vacuum tightness again, promptly obtains 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride quality percentage composition and be 93.2% product.
Embodiment 5:
It is in 95% ethanol that the 171.3g dehydroabietylamine is dissolved in the 153g mass percent; Dripping the 109.7g mass percent through constant pressure funnel to it then is 88% formic acid; Dropping temperature is controlled at below 40 ℃; After formaldehyde dropwises, drip the 175g mass percent again and be 36% formaldehyde, about 30min drips off.After formaldehyde dropwised, heating made material be warming up to 80 ℃, under agitation reacts 28h.With 40 ~ 50 ℃ of reaction solution coolings, adding mass percent is the neutralization of 30% aqueous sodium hydroxide solution, to pH be till 11 ~ 13.
Reaction mass after the neutralization is poured in the separating funnel, and with saturated sodium-chloride water solution with upper strata fluid washing three times to neutral, with dichloromethane extraction lower floor water three times.With dichloromethane extraction liquid with wash to the neutral upper strata fluid and merge; And steam ethanol, methylene dichloride and water with vacuum pump decompression; Under alkaline condition, in oil phase, drip the Tosyl chloride of 115g then, get the oil phase underpressure distillation behind the reaction 2h, collect the cut of 200 ~ 240 ℃/666.61 ~ 1333.22Pa; Get little yellow liquid product N, N-dimethyl-dehydroabietylamine 163.5g.
Get 42.8gN, after N-dimethyl-dehydroabietylamine and 20mL mass percent were 36% hydrochloric acid reflux reaction 3h, unnecessary hydrochloric acid was removed in decompression again, obtains N, N-dimethyl-dehydroabietylamine hydrochloride.Use the mixed solvent dissolving N of 150mL volume ratio as the second alcohol and water of 3:1; N-dimethyl-dehydroabietylamine hydrochloride at room temperature to N, splashes into epoxy chloropropane 41.7g in the N-dimethyl-dehydroabietylamine hydrochloride solution; After epoxy chloropropane dropwises; Continue to stir also heating, and make material, after reacted material is carried out underpressure distillation and removes ethanol, water and unreacted epoxy chloropropane at 80 ℃ of reaction 65h down; Add solvent ethyl acetate and stirring, cooling, centrifugal or filtering separation again, obtain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product.
To contain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product use by ethanol, ETHYLE ACETATE by volume 1.5:1 constitute the double solvents recrystallization, the mass ratio of double solvents and 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product is 15.0:1 during recrystallization; Material behind the recrystallization is through cooling, crystallization, centrifugal or filter the wet stock that obtains 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride; 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride wet stock is that 0.04Mpa, drying temperature are dry 9h under 85 ℃ of conditions in vacuum tightness again, promptly obtains 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride quality percentage composition and be 95.6% product.
Embodiment 6:
Adopt the pulling-on piece method to measure surface tension: product 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride is made into the aqueous solution of a series of concentration, under 25 ℃ with surface tension instrument measure join the surface tension of solution.Do surface tension concentration curve by survey surface tension and corresponding strength of solution, the cmc value that gets 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride is 0.063mmol/L, and this moment, corresponding surface tension was 27.6mN/m.
Embodiment 7:
Emulsifying property test: get the 40mL massfraction and be 0.1% the 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride aqueous solution and 40mL benzene and pour in the tool plug graduated cylinder of 100mL; Shake up and down 5 times; Static 1min; Shake 5 times again, repeat 5 times, record obtains the graduated cylinder bottom to tell the time of 10mL water is 412s then.
Claims (9)
1.3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride is characterized in that molecular structural formula is as follows:
2. the preparation method of a 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride is characterized in that: through the Leuckart-Clarke reaction, in dehydroabietylamine, add formic acid and formaldehyde in proper order, prepare N, N-dimethyl-dehydroabietylamine; Utilize N; N-dimethyl-dehydroabietylamine and hydrochloric acid reaction obtain N, and N-dimethyl-dehydroabietylamine hydrochloride utilizes double solvents dissolving N; With epichlorohydrin reaction, obtain containing the mixture of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride behind the N-dimethyl-dehydroabietylamine hydrochloride; Contain the mixture of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride, remove double solvents, obtain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product through underpressure distillation; 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product is via ethanol and ETHYLE ACETATE (1.0 ~ 10) by volume: double solvents recrystallization, filtration or spinning, vacuum-drying that (1.0 ~ 10) constitute obtain 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride product.
3. the preparation method of a kind of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride according to claim 2; It is characterized in that: preparation intermediate product N; During N-dimethyl-dehydroabietylamine, formic acid is 1.0 ~ 5.0:1.0 with the amount of substance ratio of dehydroabietylamine, and formaldehyde is 1.0 ~ 4.0:1.0 with dehydroabietylamine amount of substance ratio; When dripping formic acid and formaldehyde, temperature is controlled at below 40 ℃; After formaldehyde dripped off, temperature of reaction was 40 ~ 80 ℃, and the reaction times is 1 ~ 28h.
4. the preparation method of a kind of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride according to claim 2 is characterized in that: said N, N-dimethyl-dehydroabietylamine is 1.0:2.0 ~ 5.0 with HCl amount of substance ratio.
5. the preparation method of a kind of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride according to claim 2 is characterized in that: dissolving N, the double solvents of N-dimethyl-dehydroabietylamine hydrochloride are that 1 ~ 3:1 constitutes by the second alcohol and water by volume; Epoxy chloropropane and N, N-dimethyl-dehydroabietylamine hydrochloride amount of substance ratio is 1 ~ 4:1, and the temperature of reaction is 30 ~ 80 ℃, and the reaction times is 1 ~ 68h.
6. the preparation method of a kind of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride according to claim 2; It is characterized in that: the mixture that contains 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride adds solvent ethyl acetate to it thicker product 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride is separated out after underpressure distillation removes double solvents.
7. the preparation method of a kind of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride according to claim 2 is characterized in that: the double solvents that is used for 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product recrystallization is by ethanol and ETHYLE ACETATE (1.0 ~ 10) by volume: (1.0 ~ 10) constitute; When recrystallization was handled 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride crude product, double solvents was 1.0 ~ 20.0:1.0 with the mass ratio that contains the crude product of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride.
8. the preparation method of a kind of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride according to claim 2 is characterized in that: 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride wet stock vacuum tightness when carrying out vacuum-drying is that 0.01 ~ 0.1MPa, temperature are that 10 ~ 100 ℃, vacuum-drying time are 1.0 ~ 48.0h.
9. the preparation method of a kind of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride according to claim 2 is characterized in that: the quality percentage composition of 3-chloro-2-hydroxypropyl dimethyl dehydrogenation fir ammonium chloride in product is greater than 85%.
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| CN106220559A (en) * | 2016-07-26 | 2016-12-14 | 南京林业大学 | N 3 pyridine acyl dehydroabietylamine derivatives and its preparation method and application |
| CN114751833A (en) * | 2022-03-25 | 2022-07-15 | 广西大学 | Dehydroabietylamine chiral ionic liquid and preparation method and application thereof |
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| CN114751833A (en) * | 2022-03-25 | 2022-07-15 | 广西大学 | Dehydroabietylamine chiral ionic liquid and preparation method and application thereof |
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