CN101735076A - Method for preparing high-purity cationic monomer diallyl ethylbenzylammonium chloride - Google Patents
Method for preparing high-purity cationic monomer diallyl ethylbenzylammonium chloride Download PDFInfo
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Abstract
The invention relates to a method for preparing high-purity cationic monomer diallyl ethylbenzylammonium chloride. The invention adopts the technical scheme that the method comprises the following steps: performing nucleophilic substitution reaction on ethylamine and allyl chloride used as raw materials under the alkali condition and the action of a phase transfer catalyst, then separating the obtained liquid phase, distilling the oil phase to obtain diallyl ethylamine, directly reacting the diallyl ethylamine and benzyl chloride in the presence of a little amount of water to form high-purity diallyl ethylbenzylammonium chloride crystals, returning the water phase obtained by liquid separation and the low-melting fraction obtained by distilling to a reactor to participate in the next round of reaction, and re-crystallizing and reclaiming the soil separated in the synthesis of the diallyl ethylamine. The method overcomes the defects that the prior art needs to consume a large amount of organic solvent, has long reaction time, lower yield and the like; and the method can obtain the high-purity diallyl ethylbenzylammonium chloride crystals, and has the advantages of shorter reaction time, high conversion rate, simple and convenient operation, low cost, little three wastes discharge, environment-friendly process and easy realization of industrialization. The product of the invention is suitable to be used as a cationic monomer synthesized by macromolecules, and also can be used as an organic synthetic intermediate.
Description
Technical field
The present invention relates to the preparation of Polymer Synthesizing monomer and fine chemical product, especially relate to a kind of preparation method of high-purity cationic monomer diallyl ethylbenzylammonium chloride.
Background technology
Poly (dially dialkyl) based quaternary ammonium salt polymkeric substance is a kind of new type water-solubility polymer that 20th century the fifties American scholar Butler G B and Ingley F L etc. at first succeed in developing, owing to have positive charge density height, good water solubility, high effect nontoxic, cheap with respect to other cation high molecular, and advantage such as the energy that has microbe killing properties, in water treatment, oil production, mechanical workout, plating, papermaking, daily-use chemical industry, textile printing and dyeing, sterilization algae removal and field such as anticorrosion, obtain widespread use.In decades, people to dimethyl dialkylene ammonium chloride (DMDAAC) be representative diallyl quaternary ammonium salt homopolymer and with thiazolinyl class monomer (acrylamide, vinylformic acid, sodium p styrene sulfonate etc.), SO
2Deng multipolymer carried out deep research and development, delivered many papers and patent.Reported the preparation method of monomer DMDAAC and homopolymer thereof as United States Patent (USP) 4151202, United States Patent (USP) 4742134 has been reported the method that improves DMDAAC polymkeric substance relative molecular mass, Chinese patent CN1800146A has disclosed the monomeric method of purification of technical grade DMDAAC of single stage method preparation, and CN101081883A has reported the preparation method of high molecular weight Poly Dimethyl Diallyl Ammonium Chloride etc.
But no matter be abroad or domestic, the research that mainly concentrates on dimethyl diallyl ammonium chloride and polymkeric substance thereof with use, very few to other diallyl quaternary ammonium salt and polymkeric substance research, exploitation.There are following shortcoming in homopolymer or multipolymer based on DMDAAC: what quaternary ammonium N atom connected among the DMDAAC is 2 methyl, and group is little, therefore not strong with the interaction of other lipophilic substance a little less than the lipotropy, causes its some poor-performing.As flocculation agent the time, not strong because the lipotropy of methyl is poor with the effect of organic pollutant, so it removes the limited in one's ability of organic pollutant; During as sterilant,, not have the fat water distribution coefficient that suits because methyl is little, not strong with the effect of microorganism cells, and methyl is too short, can not permeates cell membranes and with the intracellular organic matter effect, therefore, sterilizing ability is not strong yet.In addition, because methyl is saturated group, can not introduces other group molecular structure is transformed to obtain new performance.According to structures shape character, quaternary ammonium group that N connects is changed into other group by methyl, must obtain to be different from the performance and the Application Areas of homopolymer and the multipolymer of DMDAAC.As earlier synthetic diallyl alkylamine, introduce other non-alkyl group by addition on the N atom or substitution reaction again, as introducing benzyl, can adjust the lipophilic wetting ability or the space structure of monomer and polymkeric substance thereof effectively, thereby obtain new performance.About high-purity cationic monomer diallyl ethylbenzylammonium chloride the preparation method have not yet to see pertinent literature and disclose.
The high-purity diallyl quaternary ammonium salt monomer of preparation need adopt organic solvent at present, for example:
Document 1 is (evergreen, Chen Ye. synthesizing of dimethyl diallyl ammonium chloride. environmental science, 1999,20 (1): 87-90) employing is reacted synthetic DMDAAC by DMAA and chlorallylene under room temperature in acetone, though obtained high-purity DMDAAC crystal, but the reaction times needs 10 days, and yield only reaches 72%.Document 2 (Liu Lihua, Gong Zhuqing. the process modification of two-step approach synthesization of dimethyl diallyl ammonium chloride. fine chemistry industry, 2006,23 (6): 588-592,624), this technology is improved, improve DMAA and chlorallylene quaterisation temperature to 45 ℃, and, having shortened the reaction times with the recrystallisation solvent reuse, yield has improved 20.3% than document 1.And about the preparation method of diethyl diallyl ammonium chloride (DEDAAC), document 3 (Jia Chaoxia, Zheng Yan. the new method of cationic monomer DEDAAC is synthetic. the Southwest Petroleum Institute journal, 1999,21 (3): 60-61,65) adopt the technology for the treatment of different things alike, with ethanol is solvent, diethylamine, chlorallylene and NaOH be raw material in autoclave in 60 ℃ the reaction 2～3h, reaction solution is through activated carbon decolorizing, etoh solvent and water are removed in underpressure distillation, get wax, use acetone recrystallization, vacuum-drying, get the DEDAAC crystal, yield reaches 95%; Document 4 (LIU Li-hua, GONG Zhu-qing, ZHENG Ya-jie.Synthesis and Structure Characterization of Diethyldiallylammonium Chloride.Journal of Central South Universty of Technology, 2003,10 (4): 347-352) adopt two-step process, be medium with water earlier, diethylamine, chlorallylene and NaOH are raw material, the mode that chlorallylene and the employing of NaOH solution alternately drip adds reacts 6h in the reactor, the gained oil phase is after solid NaOH drying, in acetone, descend quaternized 20h with chlorallylene again in 55 ℃, be incubated 4h down at 40 ℃ then, get the DEDAAC colorless prismatic crystal, yield reaches 83.8%, and the total recovery of DEDAAC is 58.41%.
From the above, there is following defective in the method that provides of prior art:
(1) needs to consume a large amount of organic solvents;
(2) reaction times longer, yield is lower;
(3) operation is complicated, and cost is higher.
Summary of the invention
At above-mentioned situation, the purpose of this invention is to provide a kind of preparation method of high-purity cationic monomer diallyl ethylbenzylammonium chloride, this preparation method is simple, reliable, reaction is easy to control, the yield height, and cost is low, three waste discharge is few, is convenient to penetration and promotion and realizes suitability for industrialized production.
A kind of structural formula of high-purity cationic monomer diallyl ethylbenzylammonium chloride is:
Formula 1.
The preparation method of above-mentioned high-purity cationic monomer diallyl ethylbenzylammonium chloride may further comprise the steps:
(1) drip chlorallylene and NaOH solution in being added with the ethylamine solution of phase-transfer catalyst, the mol ratio of ethamine, chlorallylene and NaOH is 1: 2.0～2.4: 2.0～2.2; At 25～45 ℃ of reaction 2～8h, at 50～70 ℃ of reaction 3～9h, separate solid gets liquid phase again, and liquid phase is transferred in the separating funnel, leaves standstill, and separatory gets oil phase;
(2) above-mentioned oil phase is told oil phase and is added stopper and distill through the NaOH drying, collects 129～132 ℃ cut, promptly gets intermediate product diallyl ethylamine;
(3) be to join in reactor at 1～1.2: 1 by diallyl ethylamine and Benzyl Chloride mol ratio, add entry then, the volume ratio of water and diallyl ethylamine is 0.008-0.025: 1; Logical N
2Drive away air in the reactor, at 80～120 ℃ of back flow reaction 3～6h, all be transformed into crystal, washing and filtering gets white crystal, and vacuum-drying gets the product diallyl ethylbenzylammonium chloride.
The mass percentage concentration of NaOH solution is 45% in the step (1).Described phase-transfer catalyst is PEG-400 or PEG-600, and its consumption is 4～10% of an ethamine quality.After separate solid got liquid phase, liquid phase was transferred in the separating funnel, leave standstill 20-40min after, separatory gets oil phase.
Oil phase described in the step (2) is through sheet or granular NaOH drying 8～12h, and the stopper of telling oil phase and adding oil phase quality 0.1～0.2% distills.The consumption that is used for exsiccant sheet or granular NaOH is 1.0～1.1 times of the amount of the required NaOH of reaction.Described stopper comprises Resorcinol, MEHQ or tert-butyl catechol.
The crystal that the middle reaction of step (3) obtains adds washing with acetone and filters, and gets white crystal, be not higher than 60 ℃ of following vacuum-dryings to constant weight, gets the product diallyl ethylbenzylammonium chloride.
Collect 129 ℃ of low boiler cuts of step (1) separatory gained water and step (2) distillation gained, return and participate in the next round reaction in the reactor of step (1), desiccant NaOH adds the NaOH solution that the water wiring solution-forming is done step (1) reaction in the step (2), collect separating obtained solid in the step (1), recrystallization reclaims sodium-chlor.
The preparation method of a kind of high-purity cationic monomer diallyl ethylbenzylammonium chloride of the present invention, it adopts with ethamine and chlorallylene is that raw material under the effect of alkaline condition and phase-transfer catalyst nucleophilic substitution reaction takes place, then the gained liquid phase is carried out separatory, separatory gained oil phase obtains the diallyl ethylamine through distillation, make high-purity diallyl ethylbenzylammonium chloride crystal with Benzyl Chloride direct reaction under the condition that adds less water again, and separatory gained water and distillation gained low boiler cut participated in the next round reaction in the Returning reactor again, isolating solid carried out the technical scheme that recrystallization reclaims sodium-chlor during the diallyl ethylamine was synthetic; It has overcome prior art need consume a large amount of organic solvents, long reaction time, defective such as yield is lower.
Mechanism of the present invention is:
Among the preparation method of A, product diallyl ethylbenzylammonium chloride of the present invention, be phase-transfer catalyst with PEG-600 and PEG-400, it can be folded into the spirane structure of similar crown ether and and Na in reaction system
+Complexing, thus OH carried
-Enter organic phase, produce and phase transfer catalysis like the crown ether-like, promote ethamine and chlorallylene generation nucleophilic substitution reaction to generate the diallyl ethylamine.In preparation process, need the segmentation control reaction temperature, to the having the greatest impact of yield, yield raises with the temperature of low-temperature zone to be increased in the temperature of low-temperature zone, and low-temperature zone must guarantee the enough reaction times, could obtain higher yields.Its major cause is in low-temperature zone, and the long reaction times is beneficial to the chlorallylene solvation and forms some intermediateness with ethamine, though also do not change into the diallyl ethylamine this moment, is beneficial under comparatively high temps and transforms.In addition, in reaction process, exist ethamine only connect an allyl group, chlorallylene easily with side reaction such as NaOH reaction generation allyl alcohol, reactant, intermediate product and diallyl ethylamine have certain solubility in water, therefore, oil phase is distilled gained low boiler cut and the reaction of separatory gained water Returning reactor participation next round, help improving the yield of diallyl ethylamine, reduce the discharging of waste liquid, water saving.
B, the present invention adopt the directly direct reaction in the presence of less water with diallyl ethylamine and Benzyl Chloride, make the diallyl ethylbenzylammonium chloride crystal, and not only speed of response is fast, and the transformation efficiency height; Do not add water and then can only obtain water-soluble very poor and viscous fluid that color is darker; Then speed of response is very slow to add water excess, and the product color is dark, shows that less water plays the polarity and the katalysis of conditioned reaction system in reaction process, so the adding of less water is to implement key of the present invention.
C. product molecule of the present invention contains two diallyls, except that generating by the cyclopolymerization reaction mechanism of alternative intramolecularly Cheng Huan-intermolecular growth the diallyl ethylbenzylammonium chloride polymkeric substance, also can further transform and introduce new group, be easy to oxidized as carbon-carbon double bond, change into epoxide and hydroxyl, can also electrophilic substitution reaction take place with halogen, hydrogen halide, sulfuric acid, hypohalous acid etc., introduce a plurality of halogen atoms, sulfate group and hydroxyl etc.
The beneficial effect that the present invention is had compared to existing technology:
(I) the present invention adopts diallyl ethylamine and Benzyl Chloride under the condition that adds less water, does not add organic solvent direct reaction, can obtain the very high crystal of purity, not only do not need to consume organic solvent, and the reaction times is shorter, the transformation efficiency height, easy and simple to handle, cost is low.And adopt diallyl ethylamine and Benzyl Chloride direct reaction under the condition that does not add water, and can not obtain crystal, what obtain is the darker and water-soluble very poor dope of color; Adopt organic solvent, as in acetone under the acetone boiling point back flow reaction be difficult to carry out, and in ethanol, react, the reaction times is longer, product is separated out with solid form, difficult washing, purity and yield are lower.
(II) the present invention adopts and will be used for oil phase exsiccant NaOH reuse, makes NaOH both play the effect of dry oil phase, can NaOH be fully used, and not produce pollution as reactant again.
(III) among the preparation method of the present invention,, not only reduced the discharging of waste liquid, and improved yield, improved utilization ratio of raw materials, reduced manufacturing cost separatory gained water and the reuse of distillation gained low boiler cut.
(IV) among the preparation method of the present invention, with the solid that is produced carry out recrystallization reclaim sodium-chlor, with separatory gained water and the reuse of distillation gained low boiler cut, desiccant NaOH reuse reactant ligand alkali lye, the pollutent of whole technological process discharging seldom, the process environmental protection.
(V) preparation technology is simple, operation, control easily, three waste discharge seldom, the technological process environmental protection is convenient to penetration and promotion and is realized industrialization.
Product of the present invention contains two allyl groups, except that the monomer as the homopolymer of diallyl ethylbenzylammonium chloride and multipolymer thereof, also can make the intermediate of organic synthesis.
Description of drawings
Fig. 1 is preparation technology's schema of the present invention;
Fig. 2 is the FT-IR spectrogram of product of the present invention;
Fig. 3 is a product of the present invention
1The H-NMR spectrogram.
Embodiment
Embodiment 1
(1) mol ratio by ethamine, chlorallylene and NaOH is 1: 2.0: 2.0, in having prolong, constant pressure funnel and churned mechanically 500mL reactor, add mass percentage concentration successively and be 68% ethylamine solution 40mL and 0.90gPEG-600, it is 45% solution that 40gNaOH is made into mass percentage concentration earlier, drip 90mL chlorallylene and NaOH solution by constant pressure funnel, at 42 ℃ of reaction 6h, at 65 ℃ of reaction 5h, separate solid gets liquid phase again;
(2) above-mentioned liquid phase is transferred in the separating funnel, leave standstill 30min after, separatory gets oil phase;
(3) above-mentioned oil phase is told oil phase through 40g sheet or the dry 8h of granular NaOH, adds the 64.4mg Resorcinol and distills, and collects 129～132 ℃ cut 55.2mL, promptly gets intermediate product diallyl ethylamine, yield 67.4%;
(4) be 1: 1 by diallyl ethylamine and Benzyl Chloride mol ratio, step (3) gained diallyl ethylamine and 39.2mL Benzyl Chloride are joined in the reactor of 250mL band mechanical stirring and reflux condensing tube, add 0.4mL water then, logical N
2Air in the expeling reactor at 90 ℃ of following back flow reaction 5h, all is transformed into crystal, adds washing with acetone and filters, and gets white crystal, be not higher than 60 ℃ of following vacuum-dryings to constant weight, gets product diallyl ethylbenzylammonium chloride 72.47g, yield 85.4%;
(5) collect step (2) separatory gained water and step (3) distillation gained low boiler cut, and the desiccant NaOH of step (3);
(6) collect separating obtained solid in the step (1), recrystallization reclaims sodium-chlor.
The infrared spectra of above-mentioned product adopts the KBr compressing tablet, measures at Spectrum One (B) FTIR infrared spectrometer (U.S. PE company), the results are shown in accompanying drawing 2.Wave number (cm wherein
-1) be that 3435.01 broad peak is-the OH stretching vibration peak in the absorption of sample water molecules; Wave number is that 3090.24,3070.54,3054.25,3030.65 peak is CH in the allyl group
2=,=CH-and phenyl ring on=the C-H stretching vibration peak of CH-; Wave number is that 2977.79,2922.84,2896.58,2790.04 peak is respectively CH
3-,-CH
2-asymmetric and symmetrical stretching vibration peak; Wave number is 1631.50 to be the stretching vibration peak of allyl group C=C; Wave number is 1498.36,1474.15 to be C-C stretching vibration in the phenyl ring; Wave number is 1460.42 for CH
3-,-CH
2-the vibration of asymmetric and symmetric curvature; 1404.77 be CH
2=the scissoring vibration peak; Wave number is that 1382.28,1370.68,1348.78 peak is respectively CH
3-,-CH
2-scissoring vibration and face in, the out-of-plane deformation vibration peak; Wave number is 1294.10,1220.89,1050.84,1010.17 etc. to be C-H in-plane bending vibration peak on the phenyl ring; Wave number is that 1178.57,1110.83 and 1083.86 peak is the stretching vibration peak of C-N; 1258.40,1147.10 be=the face internal strain vibration peak of CH-; Wave number is 984.32 to be the outer formation vibration peak of the face of=CH-, the frequency multiplication peak at this peak occurs at 1965.12 places; Wave number is that 942.87,924.81 strong absorption peak is CH
2=the outer formation vibration peak of face; Wave number is that 798.15,764.92,746.53,727.69,707.98 strong absorption peak is C-H out-of-plane deformation vibration peak on the phenyl ring; Wave number is 527.69 can belong to the out-of-plane deformation vibration peak of phenyl ring; Weak peak in appearance such as 1807.30,1886.32,1845.67 and 1926.74 is the complex spectrum band and the frequency multiplication peak of phenyl ring.
Product
1The H-NMR spectrum is with D
2O is a solvent, goes up in AVANCEII NMR spectrometer with superconducting magnet (German Bruker company) and measures, and the results are shown in accompanying drawing 3.δ=4.702nd wherein, the charateristic avsorption band of solvent, the triplet of δ=1.285～1.340 is-C
H 3Absorption peak, the quartet of δ=3.121～3.198 is CH
3-C
H 2-absorption peak, the bimodal of δ=3.698～3.747 is N
+-C
H 2The absorption peak of-CH=, the unimodal of δ=4.342 is Ph-C
H 2Absorption peak, the multiplet of δ=5.544～5.616 is=C
H 2Absorption peak, the multiplet of δ=5.972～6.040 is=C
H-absorption peak, the multiplet of δ=7.396～7.462 is the C-on the Ph
HAbsorption peak.
Above-mentioned product adopts numeral to show that it is 163.5～165 ℃ that micro melting point apparatus (Tyke, Beijing Instr Ltd.) is measured fusing point.The product ultimate analysis adopts Vario EL III type elemental analyser (German Elementar company) to measure down at 950 ℃, and measurement result sees Table 1.
The results of elemental analyses of table 1 product
Results of elemental analyses shows that the element theory calculated value of the measured value of element and diallyl ethylbenzylammonium chloride is very approaching, and the melting range of product is narrow, illustrates that product has very high purity.
(1) mol ratio by ethamine, chlorallylene and NaOH is 1: 2.1: 2.1, in having prolong, constant pressure funnel and churned mechanically 500mL reactor, add mass percentage concentration successively and be 68% ethylamine solution 40mL and 1.13gPEG-600, add water and the low boiler cut collected in embodiment 1 step (5), desiccant NaOH and in addition 2gNaOH to be made into mass percentage concentration earlier be 45% solution, drip 92mL chlorallylene and NaOH solution by constant pressure funnel, at 35 ℃ of reaction 8h, at 60 ℃ of reaction 7h, separate solid gets liquid phase again;
(2) above-mentioned liquid phase is transferred in the separating funnel, leave standstill 20min after, separatory gets oil phase;
(3) above-mentioned oil phase is told oil phase through 42g sheet or the dry 10h of granular NaOH, adds the 79.1mg Resorcinol and distills, and collects 129～132 ℃ cut 56mL, promptly gets intermediate product diallyl ethylamine, yield 68.3%;
(4) be 1.05: 1 by diallyl ethylamine and Benzyl Chloride mol ratio, step (3) gained diallyl ethylamine and 37.8mL Benzyl Chloride are joined in the reactor of 250mL band mechanical stirring and reflux condensing tube, add 0.6mL water then, logical N
2Air in the expeling reactor at 100 ℃ of following back flow reaction 6h, all is transformed into crystal, adds washing with acetone and filters, and gets white crystal, be not higher than 60 ℃ of following vacuum-dryings to constant weight, gets product diallyl ethylbenzylammonium chloride 77.65g, yield 90.3%;
(5) collect step (2) separatory gained water and step (3) distillation gained low boiler cut, and desiccant NaOH;
(6) collect separating obtained solid in the step (1), recrystallization reclaims sodium-chlor.
Embodiment 3
(1) mol ratio by ethamine, chlorallylene and NaOH is 1: 2.2: 2.1, in having prolong, constant pressure funnel and churned mechanically 500mL reactor, add mass percentage concentration successively and be 68% ethylamine solution 40mL and 1.35gPEG-600, add water and the low boiler cut collected in embodiment 2 steps (5), it is 45% solution that desiccant NaOH is made into mass percentage concentration earlier, drip 96.3mL chlorallylene and NaOH solution by constant pressure funnel, at 25 ℃ of reaction 8h, at 70 ℃ of reaction 9h, separate solid gets liquid phase again;
(2) above-mentioned liquid phase is transferred in the separating funnel, leave standstill 30min after, separatory gets oil phase;
(3) above-mentioned oil phase is told oil phase through 42g sheet or the dry 11h of granular NaOH, adds the 88.7mg Resorcinol and distills, and collects 129～132 ℃ cut 50.2mL, promptly gets intermediate product diallyl ethylamine, yield 61.2%;
(4) be 1.1: 1 by diallyl ethylamine and Benzyl Chloride mol ratio, step (3) gained diallyl ethylamine and 35.6mL Benzyl Chloride are joined in the reactor of 250mL band mechanical stirring and reflux condensing tube, add 0.8mL water then, logical N
2Air in the expeling reactor at 110 ℃ of following back flow reaction 4h, all is transformed into crystal, adds washing with acetone and filters, and gets white crystal, be not higher than 60 ℃ of following vacuum-dryings to constant weight, gets product diallyl ethylbenzylammonium chloride 71.43g, yield 92.7%;
(5) collect step (2) separatory gained water and step (3) distillation gained low boiler cut, and desiccant NaOH;
(6) collect separating obtained solid in the step (1), recrystallization reclaims sodium-chlor.
Embodiment 4
(1) mol ratio by ethamine, chlorallylene and NaOH is 1: 2.3: 2.1, in having prolong, constant pressure funnel and churned mechanically 500mL reactor, add mass percentage concentration successively and be 68% ethylamine solution 40mL and 1.58gPEG-600, add water and the low boiler cut collected in embodiment 3 steps (5), it is 45% solution that desiccant NaOH is made into mass percentage concentration earlier, drip 100.7mL chlorallylene and NaOH solution by constant pressure funnel, at 45 ℃ of reaction 2h, at 70 ℃ of reaction 9h, separate solid gets liquid phase again;
(2) above-mentioned liquid phase is transferred in the separating funnel, leave standstill 40min after, separatory gets oil phase;
(3) above-mentioned oil phase is told oil phase through 42g sheet or the dry 12h of granular NaOH, adds the 102mg Resorcinol and distills, and collects 129～132 ℃ cut 48.1mL, promptly gets intermediate product diallyl ethylamine, yield 58.7%;
(4) be 1: 1 by diallyl ethylamine and Benzyl Chloride mol ratio, step (3) gained diallyl ethylamine and 34.1mL Benzyl Chloride are joined in the reactor of 250mL band mechanical stirring and reflux condensing tube, add 1mL water then, logical N
2Air in the expeling reactor at 80 ℃ of following back flow reaction 6h, all is transformed into crystal, adds washing with acetone and filters, and gets white crystal, be not higher than 60 ℃ of following vacuum-dryings to constant weight, gets product diallyl ethylbenzylammonium chloride 61.56g, yield 83.3%;
(5) collect step (2) separatory gained water and step (3) distillation gained low boiler cut, and desiccant NaOH;
(6) collect separating obtained solid in the step (1), recrystallization reclaims sodium-chlor.
Embodiment 5
(1) presses ethamine, the mol ratio of chlorallylene and NaOH is 1: 2.3: 2.2, having prolong, add mass percentage concentration in constant pressure funnel and the churned mechanically 500mL reactor successively and be 68% ethylamine solution 40mL and 1.13gPEG-400, add water and the low boiler cut collected in embodiment 4 steps (5), desiccant NaOH and in addition 2gNaOH to be made into mass percentage concentration earlier be 45% solution, drip 100.7mL chlorallylene and NaOH solution by constant pressure funnel, at 42 ℃ of reaction 6h, at 60 ℃ of reaction 7h, separate solid gets liquid phase again;
(2) above-mentioned liquid phase is transferred in the separating funnel, leave standstill 30min after, separatory gets oil phase;
(3) above-mentioned oil phase is told oil phase through 44g sheet or the dry 12h of granular NaOH, adds the 162.4mg tert-butyl catechol and distills, and collects 129～132 ℃ cut 68.9mL, promptly gets intermediate product diallyl ethylamine, yield 84.1%;
(4) be 1.2: 1 by diallyl ethylamine and Benzyl Chloride mol ratio, step (3) gained diallyl ethylamine and 40.7mL Benzyl Chloride are joined in the reactor of 250mL band mechanical stirring and reflux condensing tube, add 1.7mL water then, logical N
2Air in the expeling reactor at 120 ℃ of following back flow reaction 3h, all is transformed into crystal, adds washing with acetone and filters, and gets white crystal, be not higher than 60 ℃ of following vacuum-dryings to constant weight, gets product diallyl ethylbenzylammonium chloride 94.66g, yield 89.4%;
(5) collect step (2) separatory gained water and step (3) distillation gained low boiler cut, and desiccant NaOH;
(6) collect separating obtained solid in the step (1), recrystallization reclaims sodium-chlor.
(1) mol ratio by ethamine, chlorallylene and NaOH is 1: 2.4: 2.2, in having prolong, constant pressure funnel and churned mechanically 500mL reactor, add mass percentage concentration successively and be 68% ethylamine solution 40mL and 1.80gPEG-400, add water and the low boiler cut collected in embodiment 5 steps (5), it is 45% solution that desiccant NaOH is made into mass percentage concentration earlier, drip 105.1mL chlorallylene and NaOH solution by constant pressure funnel, at 42 ℃ of reaction 8h, at 70 ℃ of reaction 3h, separate solid gets liquid phase again;
(2) above-mentioned liquid phase is transferred in the separating funnel, leave standstill 30min after, separatory gets oil phase;
(3) above-mentioned oil phase is told oil phase through 44g sheet or the dry 8h of granular NaOH, adds 94.9mg para hydroxybenzene ether and distills, and collects 129～132 ℃ cut 67.1mL, promptly gets intermediate product diallyl ethylamine, yield 81.9%;
(4) be 1.1: 1 by diallyl ethylamine and Benzyl Chloride mol ratio, step (3) gained diallyl ethylamine and 43.3mL Benzyl Chloride are joined in the reactor of 250mL band mechanical stirring and reflux condensing tube, add 0.7mL water then, logical N
2Air in the expeling reactor at 110 ℃ of following back flow reaction 5h, all is transformed into crystal, adds washing with acetone and filters, and gets white crystal, be not higher than 60 ℃ of following vacuum-dryings to constant weight, gets product diallyl ethylbenzylammonium chloride 97.03g, yield 94.1%;
(5) collect step (2) separatory gained water and step (3) distillation gained low boiler cut, and desiccant NaOH;
(6) collect separating obtained solid in the step (1), recrystallization reclaims sodium-chlor.
Embodiment 7
(1) mol ratio by ethamine, chlorallylene and NaOH is 1: 2.1: 2.1, in having prolong, constant pressure funnel and churned mechanically 500mL reactor, add mass percentage concentration successively and be 68% ethylamine solution 40mL and 2.03gPEG-600, add water and the low boiler cut collected in embodiment 6 steps (5), it is 45% solution that desiccant NaOH is made into mass percentage concentration earlier, drip 92mL chlorallylene and NaOH solution by constant pressure funnel, at 42 ℃ of reaction 6h, at 65 ℃ of reaction 5h, separate solid gets liquid phase again;
(2) above-mentioned liquid phase is transferred in the separating funnel, leave standstill 30min after, separatory gets oil phase;
(3) above-mentioned oil phase is told oil phase through 42g sheet or the dry 8h of granular NaOH, adds the 95.5mg Resorcinol and distills, and collects 129～132 ℃ cut 67.5mL, promptly gets intermediate product diallyl ethylamine, yield 82.4%;
(4) be 1.05: 1 by diallyl ethylamine and Benzyl Chloride mol ratio, step (3) gained diallyl ethylamine and 45.6mL Benzyl Chloride are joined in the reactor of 250mL band mechanical stirring and reflux condensing tube, add 0.8mL water then, logical N
2Air in the expeling reactor at 115 ℃ of following back flow reaction 4h, all is transformed into crystal, adds washing with acetone and filters, and gets white crystal, be not higher than 60 ℃ of following vacuum-dryings to constant weight, gets product diallyl ethylbenzylammonium chloride 99.28g, yield 95.7%;
(5) collect step (2) separatory gained water and step (3) distillation gained low boiler cut, and desiccant NaOH;
(6) collect separating obtained solid in the step (1), recrystallization reclaims sodium-chlor.
(1) mol ratio by ethamine, chlorallylene and NaOH is 1: 2.1: 2.1, in having prolong, constant pressure funnel and churned mechanically 500mL reactor, add mass percentage concentration successively and be 68% ethylamine solution 40mL and 2.25gPEG-600, add water and the low boiler cut collected in embodiment 7 steps (5), it is 45% solution that desiccant NaOH is made into mass percentage concentration earlier, drip 92mL chlorallylene and NaOH solution by constant pressure funnel, at 42 ℃ of reaction 4h, at 70 ℃ of reaction 9h, separate solid gets liquid phase again;
(2) above-mentioned liquid phase is transferred in the separating funnel, leave standstill 30min after, separatory gets oil phase;
(3) above-mentioned oil phase is told oil phase through 42g sheet or the dry 8h of granular NaOH, adds the 93.3mg Resorcinol and distills, and collects 129～132 ℃ cut 66mL, promptly gets intermediate product diallyl ethylamine, yield 80.5%;
(4) be 1.05: 1 by diallyl ethylamine and Benzyl Chloride mol ratio, step (3) gained diallyl ethylamine and 44.6mL Benzyl Chloride are joined in the reactor of 250mL band mechanical stirring and reflux condensing tube, add 1mL water then, logical N
2Air in the expeling reactor at 120 ℃ of following back flow reaction 4h, all is transformed into crystal, adds washing with acetone and filters, and gets white crystal, be not higher than 60 ℃ of following vacuum-dryings to constant weight, gets product diallyl ethylbenzylammonium chloride 94.96g, yield 93.7%;
(5) collect step (2) separatory gained water and step (3) distillation gained low boiler cut, and desiccant NaOH;
(6) collect separating obtained solid in the step (1), recrystallization reclaims sodium-chlor.
Embodiment 9
(1) mol ratio by ethamine, chlorallylene and NaOH is 1: 2.1: 2.1, in having prolong, constant pressure funnel and churned mechanically 50L reactor, add mass percentage concentration successively and be 68% ethylamine solution 4L and 180.3gPEG-600,4.2kgNaOH be made into mass percentage concentration earlier and be 45% solution, drip 9.2L chlorallylene and NaOH solution by constant pressure funnel, at 42 ℃ of reaction 6h, at 60 ℃ of reaction 7h, separate solid gets liquid phase again;
(2) above-mentioned liquid phase is transferred in the separating funnel, leave standstill 30min after, separatory gets oil phase;
(3) above-mentioned oil phase is told oil phase through 4.2kg sheet or the dry 8h of granular NaOH, adds the 10.2g Resorcinol and distills, and collects 129～132 ℃ cut 5.77L, promptly gets intermediate product diallyl ethylamine, yield 70.4%;
(4) be 1.05: 1 by diallyl ethylamine and Benzyl Chloride mol ratio, step (3) gained diallyl ethylamine and 3.90L Benzyl Chloride are joined in the reactor of 25L band mechanical stirring and reflux condensing tube, add 69.2mL water then, logical N
2Air in the expeling reactor at 110 ℃ of following back flow reaction 5h, all is transformed into crystal, adds washing with acetone and filters, and gets white crystal, be not higher than 60 ℃ of following vacuum-dryings to constant weight, gets product diallyl ethylbenzylammonium chloride 8.60kg, yield 94.4%;
(5) collect step (2) separatory gained water and step (3) distillation gained low boiler cut, and desiccant NaOH;
(6) collect separating obtained solid in the step (1), recrystallization reclaims sodium-chlor.
(1) mol ratio by ethamine, chlorallylene and NaOH is 1: 2.1: 2.1, in having prolong, constant pressure funnel and churned mechanically 50L reactor, add mass percentage concentration successively and be 68% ethylamine solution 4L and 113gPEG-600, add water and the low boiler cut collected in embodiment 9 steps (5), it is dry that to be made into mass percentage concentration earlier with NaOH be 45% solution, drip 9.2L chlorallylene and NaOH solution by constant pressure funnel, at 42 ℃ of reaction 6h, at 60 ℃ of reaction 7h, separate solid gets liquid phase again;
(2) above-mentioned liquid phase is transferred in the separating funnel, leave standstill 30min after, separatory gets oil phase;
(3) above-mentioned oil phase is told oil phase through 4.2kg sheet or the dry 8h of granular NaOH, adds the 9.35g Resorcinol and distills, and collects 129～132 ℃ cut 6.61L, promptly gets intermediate product diallyl ethylamine, yield 80.7%;
(4) be 1.05: 1 by diallyl ethylamine and Benzyl Chloride mol ratio, step (3) gained diallyl ethylamine and 4.47L Benzyl Chloride are joined in the reactor of 25L band mechanical stirring and reflux condensing tube, add 79.4mL water then, logical N
2Air in the expeling reactor at 110 ℃ of following back flow reaction 5h, all is transformed into crystal, adds washing with acetone and filters, and gets white crystal, be not higher than 60 ℃ of following vacuum-dryings to constant weight, gets product diallyl ethylbenzylammonium chloride 9.671kg, yield 95.3%;
(5) collect step (2) separatory gained water and step (3) distillation gained low boiler cut, and desiccant NaOH;
(6) collect separating obtained solid in the step (1), recrystallization reclaims sodium-chlor.
Embodiment 11
(1) mol ratio by ethamine, chlorallylene and NaOH is 1: 2.1: 2.1, in having prolong, constant pressure funnel and churned mechanically 50L reactor, add mass percentage concentration successively and be 68% ethylamine solution 4L and 113gPEG-600, add water and the low boiler cut collected in embodiment 10 steps (5), it is dry that to be made into mass percentage concentration earlier with NaOH be 45% solution, drip 9.2L chlorallylene and NaOH solution by constant pressure funnel, at 42 ℃ of reaction 6h, at 60 ℃ of reaction 7h, separate solid gets liquid phase again;
(2) above-mentioned liquid phase is transferred in the separating funnel, leave standstill 30min after, separatory gets oil phase;
(3) above-mentioned oil phase is told oil phase through 4.2kg sheet or the dry 8h of granular NaOH, adds the 9.66g Resorcinol and distills, and collects 129～132 ℃ cut 6.836L, promptly gets intermediate product diallyl ethylamine, yield 83.4%;
(4) be 1.05: 1 by diallyl ethylamine and Benzyl Chloride mol ratio, step (3) gained diallyl ethylamine and 4.62L Benzyl Chloride are joined in the reactor of 25L band mechanical stirring and reflux condensing tube, add 82mL water then, logical N
2Air in the expeling reactor at 120 ℃ of back flow reaction 4h, all is transformed into crystal, adds washing with acetone and filters, and gets white crystal, be not higher than 60 ℃ of following vacuum-dryings to constant weight, gets product diallyl ethylbenzylammonium chloride 9.976kg, yield 95.0%;
(5) collect step (2) separatory gained water and step (3) distillation gained low boiler cut, and desiccant NaOH;
(6) collect separating obtained solid in the step (1), recrystallization reclaims sodium-chlor.
Below only be preferred embodiment of the present invention, according to above-mentioned design of the present invention, those skilled in the art can also make various modifications and conversion to the processing condition of preparation, and similarly these conversion and modification all belong to essence of the present invention.
Claims (9)
1. the preparation method of a high-purity cationic monomer diallyl ethylbenzylammonium chloride is characterized in that, may further comprise the steps:
(1) drip chlorallylene and NaOH solution in being added with the ethylamine solution of phase-transfer catalyst, the mol ratio of ethamine, chlorallylene and NaOH is 1: 2.0～2.4: 2.0～2.2; At 25～45 ℃ of reaction 2～8h, at 50～70 ℃ of reaction 3～9h, separate solid gets liquid phase again, and liquid phase is transferred in the separating funnel, leaves standstill, and separatory gets oil phase;
(2) above-mentioned oil phase is told oil phase and is added stopper and distill through the NaOH drying, collects 129～132 ℃ cut, promptly gets intermediate product diallyl ethylamine;
(3) be to join in reactor at 1～1.2: 1 by diallyl ethylamine and Benzyl Chloride mol ratio, add entry then, the volume ratio of water and diallyl ethylamine is 0.008-0.025: 1; Logical N
2Drive away air in the reactor, at 80～120 ℃ of back flow reaction 3～6h, all be transformed into crystal, washing and filtering gets white crystal, and vacuum-drying gets the product diallyl ethylbenzylammonium chloride.
2. the preparation method of high-purity cationic monomer diallyl ethylbenzylammonium chloride according to claim 1 is characterized in that, the mass percentage concentration of NaOH solution is 45% in the step (1).
3. the preparation method of high-purity cationic monomer diallyl ethylbenzylammonium chloride according to claim 1 is characterized in that, the phase-transfer catalyst described in the step (1) is PEG-400 or PEG-600, and its consumption is 4～10% of an ethamine quality.
4. the preparation method of high-purity cationic monomer diallyl ethylbenzylammonium chloride according to claim 1 is characterized in that, liquid phase is transferred in the separating funnel in the step (1), leave standstill 20-40min after, separatory gets oil phase.
5. the preparation method of high-purity cationic monomer diallyl ethylbenzylammonium chloride according to claim 1, it is characterized in that, oil phase described in the step (2) is through sheet or granular NaOH drying 8～12h, and the stopper of telling oil phase and adding oil phase quality 0.1～0.2% distills.
6. the preparation method of high-purity cationic monomer diallyl ethylbenzylammonium chloride according to claim 1 or 5 is characterized in that described stopper comprises Resorcinol, MEHQ or tert-butyl catechol.
7. the preparation method of high-purity cationic monomer diallyl ethylbenzylammonium chloride according to claim 1 is characterized in that, the consumption that is used for exsiccant sheet or granular NaOH described in the step (2) is 1.0～1.1 times of amount of the required NaOH of reaction.
8. the preparation method of high-purity cationic monomer diallyl ethylbenzylammonium chloride according to claim 1, it is characterized in that, the crystal that reaction obtains in the step (3) adds washing with acetone and filters, get white crystal, be not higher than 60 ℃ of following vacuum-dryings to constant weight, getting the product diallyl ethylbenzylammonium chloride.
9. the preparation method of high-purity cationic monomer diallyl ethylbenzylammonium chloride according to claim 1, it is characterized in that, collect 129 ℃ of low boiler cuts of step (1) separatory gained water and step (2) distillation gained, return and participate in the next round reaction in the reactor of step (1), desiccant NaOH adds the NaOH solution that the water wiring solution-forming is done step (1) reaction in the step (2), collect separating obtained solid in the step (1), recrystallization reclaims sodium-chlor.
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