A method for synthesizing acryloyloxyethyltrimethyl ammonium chloride based on ordered mesoporous nanocatalyst

Abstract

The application discloses a synthesis method of acryloyloxyethyl trimethyl ammonium chloride based on ordered mesoporous nanocatalysts and belongs to the technical field of chemical product synthesis. MPs grafted with lanthanum, ytterbium or scandium ions are prepared, and the MPs are used as catalysts to catalyze the reaction of acrylate and dimethylaminoethanol to obtain dimethylaminoethyl acrylate; under the condition of an organic solvent, dimethylaminoethyl acrylate and chloromethane are subjected to normal-pressure reaction, and recrystallization is carried out to obtain acryloyloxyethyl trimethyl ammonium chloride. When the catalyst dosage is 1% of the mass of dimethylaminoethanol, the purity of the intermediate can reach 99.3%, the yield is as high as 95%, and the catalyst can be repeatedly used for multiple times. In the application, chloromethane is dissolved in an organic solvent, after the reaction is completed, dry acryloyloxyethyl trimethyl ammonium chloride with a purity higher than 99% can be obtained through recrystallization, DAC synthesis does not need a high-pressure environment, and the operation is safe, which is beneficial to industrialized production.

Description

Technical Field

[0001] This invention belongs to the field of chemical product synthesis technology, specifically relating to a method for synthesizing acryloyloxyethyltrimethylammonium chloride based on an ordered mesoporous nanocatalyst. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Acryloyloxyethyltrimethylammonium chloride (DAC) is an important cationic monomer that can be homopolymerized or copolymerized with other monomers, such as acrylamide, methacrylamide, acrylonitrile, methyl acrylate, methyl methacrylate, styrene, acrylic acid, or methacrylic acid, thereby introducing quaternary ammonium salt groups into the polymer. It can be widely used in the production of fine ionic products such as flocculants for water treatment, antistatic coatings, papermaking additives, chemicals, and fiber additives.

[0004] The chemical structural formula of DAC is:

[0005]

[0006] The mainstream synthesis method of DAC consists of two steps: the synthesis of the intermediate dimethylaminoethyl acrylate (DA) and the preparation of DAC.

[0007] The chemical structural formula of DA is:

[0008]

[0009] The synthesis methods of DA can be broadly classified into the following categories: 1. Esterification: Acrylic acid and dimethylaminoethanol are dehydrated under concentrated sulfuric acid conditions to produce DA. This method has a low yield. 2. Transesterification: Methyl acrylate (or ethyl acrylate and other esters) undergo transesterification with dimethylaminoethanol under catalytic conditions. This method is currently the main synthesis method, and the core of this method is the selection of catalyst. Numerous reports, both domestic and international, have documented various catalysts. For example, the Journal of the American Chemical Society, 1949, vol. 71, p. 3164, reports the use of isopropyl aluminum as a catalyst; patent EP1634866 uses organotin compounds; patent US2008161596 uses titanate compounds; and patent WO2007057120 uses organomagnesium, lithium, zinc, or calcium metal complexes. Other patents have also reported the use of alkali metal phosphate catalysts. All the catalysts reported above are single-use catalysts and cannot be reused, causing significant inconvenience to production. 3. Acyl chloride method: The literature Tetrahedron, 1992, vol. 48, #31, pp. 6371-6384 reports the preparation of acryloyl chloride and dimethylaminoethanol under alkaline conditions. This method has low yield and high cost. 4. Acyl chloride elimination method: The literature Journal Fur Praktische Chemie-Leipzig (Leipzig 1954), 1959 reports the acylation reaction of propane, acyl chloride, and dimethylaminoethanol followed by elimination to obtain the product. This method has low yield and the raw materials are not readily available.

[0010] The preparation of DAC mainly involves DA and chloromethane with water as a solvent, under high pressure. This method not only requires special high-pressure equipment, but also requires auxiliary absorption and treatment equipment for excess toxic chloromethane gas, which not only increases production costs, but also causes extreme waste of resources.

[0011] Addressing the numerous problems existing in current catalytic converter production processes, the inventors have identified the following key issues: 1. The catalyst used for intermediate preparation cannot be recycled and is consumed in large quantities, easily causing pollution; 2. The product yield and purity are relatively low, generally between 95-98%. Obtaining purity above 99% requires specialized distillation equipment, ultimately leading to low yield and high residue tar; 3. The use of chloromethane requires high-pressure conditions, placing high demands on equipment, posing operational hazards, and excess chloromethane cannot be effectively utilized. Therefore, solving these problems while ensuring the quality of DAC products is of great significance for the industrial production of this product. Summary of the Invention

[0012] To address the shortcomings of existing technologies, the present invention aims to provide a method for synthesizing acryloyloxyethyltrimethylammonium chloride based on ordered mesoporous nanocatalysts. The synthesis method provided by the present invention not only solves problems such as catalyst contamination and operational hazards, but also greatly improves the quality and yield of DAC products.

[0013] To achieve the above objectives, the technical solution of the present invention is as follows:

[0014] In a first aspect, the present invention provides a method for preparing an ordered mesoporous nanocatalyst, comprising the following steps:

[0015] (1) Preparation of ordered mesoporous phenolic resins MPs;

[0016] (2) Sulfonate MPs to obtain sulfonic acid group-functionalized HSO3-MPs;

[0017] (3) By impregnating lanthanum, ytterbium or scandium salt solutions, metal ions are grafted onto HSO3-MPs to obtain ordered mesoporous nanocatalysts.

[0018] In some embodiments of the present invention, the sulfonation of MPs includes:

[0019] The MPs were degassed at 100–110 °C for 0.5–1.5 h. After cooling, the system was immersed in an ice-water bath. Dichloromethane was added under the protection of high-purity argon, followed by the addition of sulfonating agent dropwise. The mixture was stirred overnight and then refluxed at 40–60 °C for 10–12 h. After cooling, the mixed solution was slowly added dropwise and dispersed in cold ethanol. The mixture was then filtered to obtain sulfonic acid-functionalized HSO3-MPs.

[0020] The dosage of MPs, dichloromethane and sulfonating agent is 1g:10-15mL:5-15mL; preferably 1g:15mL:10mL.

[0021] In some embodiments of the present invention, the sulfonating agent is chlorosulfonic acid.

[0022] In some embodiments of the present invention, the grafting of metal ions onto the HSO3-MPs includes:

[0023] HSO3-MPs and lanthanum, ytterbium, or scandium salts were placed in anhydrous methanol and stirred at 70–90 °C for 20–25 h. After cooling and filtration, the mixture was washed with anhydrous methanol and dried to obtain an ordered mesoporous nanocatalyst.

[0024] The mass ratio of HSO3-MPs to lanthanum, ytterbium, or scandium salts is 1–1.5:1–1.5, preferably 1:1.

[0025] In some embodiments of the present invention, ordered mesoporous nanocatalysts are obtained by grafting ytterbium ions onto HSO3-MPs through impregnation with ytterbium salt solution.

[0026] Preferably, the ytterbium salt is ytterbium perchlorate.

[0027] In a second aspect, the present invention provides an ordered mesoporous nanocatalyst, which is prepared by the above-described method for preparing ordered mesoporous nanocatalysts.

[0028] A third aspect of the present invention provides the application of the above-described ordered mesoporous nanocatalyst in the synthesis of acryloyloxyethyltrimethylammonium chloride.

[0029] A fourth aspect of the present invention provides a method for synthesizing acryloyloxyethyltrimethylammonium chloride based on an ordered mesoporous nanocatalyst, comprising the following steps:

[0030] Under the catalysis of the above-mentioned ordered mesoporous nanocatalyst, acrylate and dimethylaminoethanol react to obtain the intermediate dimethylaminoethyl acrylate, which is then reacted with chloromethane under normal pressure in an organic solvent and finally recrystallized to obtain acryloyloxyethyltrimethylammonium chloride.

[0031] The ordered mesoporous nanocatalyst contains 1% or more of dimethylaminoethanol by mass;

[0032] Preferably, the molar ratio of acrylate to dimethylaminoethanol is 1 to 3:1, and the reaction temperature of the acrylate and dimethylaminoethanol reaction is 140°C.

[0033] Preferably, a polymerization inhibitor, namely thiophene, is present during the reaction of acrylate and dimethylaminoethanol.

[0034] In some embodiments of the present invention, the acrylate is one of methyl acrylate, ethyl acrylate or n-butyl acrylate; preferably methyl acrylate.

[0035] In some embodiments of the present invention, the organic solvent is one of dichloromethane, 1,2-dichloroethane, chloroform, or carbon tetrachloride, preferably 1,2-dichloroethane.

[0036] In some embodiments of the present invention, the solvent used for recrystallization is one of petroleum ether, n-heptane, cyclohexane, or n-hexane; preferably n-heptane.

[0037] The beneficial effects of this invention are as follows:

[0038] This invention provides a novel ordered mesoporous nanocatalyst for the reaction of acrylate and dimethylaminoethanol to obtain the intermediate dimethylaminoethyl acrylate. It has a large surface area, high catalytic activity, and can be reused multiple times, solving the problem that the catalyst cannot be recycled when preparing the intermediate. It can effectively avoid the problem of environmental pollution caused by a large amount of catalyst, and at the same time greatly improve the purity and yield of the intermediate. With an addition of 1% of the mass of dimethylaminoethanol, the purity of the intermediate can reach 99.3% and the yield can reach 95%.

[0039] This invention provides a method for synthesizing acryloyloxyethyltrimethylammonium chloride based on an ordered mesoporous nanocatalyst. The method involves reacting acrylate and dimethylaminoethanol under the conditions of an ordered mesoporous nanocatalyst to obtain the intermediate dimethylaminoethyl acrylate. This intermediate is then reacted with chloromethane in an organic solvent under normal pressure. Finally, recrystallization yields acryloyloxyethyltrimethylammonium chloride with a purity >99%. Based on the physicochemical properties of the reaction itself and chloromethane during DAC synthesis, this invention allows for the production of acryloyloxyethyltrimethylammonium chloride with a purity >99% by dissolving chloromethane in an organic solvent and recrystallizing after the reaction. This method eliminates the need for a high-pressure environment during DAC synthesis, allowing for reaction at normal pressure, making the operation safer and facilitating the industrial production of acryloyloxyethyltrimethylammonium chloride. Attached Figure Description

[0040] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0041] Figure 1 The image shows a scanning electron microscope (SEM) image of the Yb(ClO4)3-MPs catalyst prepared in Example 1 of this invention.

[0042] Figure 2 The image shows a transmission electron microscope (TEM) image of the Yb(ClO4)3-MPs catalyst prepared in Example 1 of this invention.

[0043] Figure 3 The GC spectrum of dimethylaminoethyl acrylate prepared in Example 2 of this invention;

[0044] Figure 4 The NMR spectrum of dimethylaminoethyl acrylate prepared in Example 2 of this invention;

[0045] Figure 5 The HPLC spectrum of acryloyloxyethyltrimethylammonium chloride prepared in Example 2 of this invention;

[0046] Figure 6 The HCl spectrum of acryloyloxyethyltrimethylammonium chloride prepared in Example 2 of this invention. Detailed Implementation

[0047] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0048] Example 1

[0049] Preparation of ordered mesoporous nanocatalysts

[0050] The preparation of ordered mesoporous nanocatalysts involves three stages: preparation of ordered mesoporous phenolic resins (MPs), sulfonation of MPs, and metal grafting.

[0051] (1) Preparation process of ordered mesoporous phenolic resins (MPs):

[0052] MPs were prepared using triblock copolymer F127 as a template directing agent via solvent evaporation-induced self-assembly (EISA). In the classic synthesis method: 1.0 g of F127 was added to 20 mL of anhydrous ethanol solution containing 5.0 g of phenolic resin oligomers. After stirring at 40 °C for 0.5 h, a light yellow transparent solution was formed. The mixture was transferred to a petri dish, and the ethanol was evaporated in an oven at 40 °C for 5–8 h. Then, further thermal polymerization was carried out at 100 °C for 24 h to obtain a transparent film material. The obtained material was pulverized and calcined at 350 °C under a nitrogen atmosphere for 6 h. The resulting dark brown powder was dispersed in 98% sulfuric acid solution and refluxed at 95 °C for 24 h. The surfactant F127 was removed by extraction, yielding ordered mesoporous phenolic resin MPs.

[0053] (2) Sulfonation process of MPs:

[0054] Weigh 1.0 g of MPs into a round-bottom flask, degas at 105 °C for 1.0 h, cool, immerse the system in an ice-water bath, add 15 mL of CH2Cl2 under high-purity argon protection, then add 10 mL of chlorosulfonic acid dropwise, stir overnight, then transfer to 50 °C and reflux for 12 h. After cooling, slowly add and disperse the mixed solution in 200 mL of cold ethanol, filter to obtain the product, dry, redisperse in 50 mL of deionized water, stir at 80 °C for 3 h, filter to obtain the product, and obtain sulfonic acid-functionalized HSO3-MPs.

[0055] (3) Metal grafting:

[0056] The process of preparing catalyst Yb(ClO4)3-MPs by grafting Yb(ClO4)3 onto HSO3-MPs:

[0057] Weigh 1.0 g HSO3-MPs, 1.0 g Yb(ClO4)3, and 15 mL anhydrous methanol. Stir at 80 °C for 24 h, cool and filter, wash twice with anhydrous methanol, and dry in a vacuum oven to obtain the catalyst Yb(ClO4)3-MPs. (Appendix) Figure 1 , 2 The images are scanning electron microscope (SEM) and transmission electron microscope (TEM) images of the catalyst Yb(ClO4)3-MPs, respectively.

[0058] Example 2

[0059] The preparation of ordered mesoporous nanocatalysts differs from that in Example 1 in that, in “(3) metal grafting”, Sc(OTf)2 is used to replace Yb(ClO4)3 to obtain catalyst Sc(OTf)2-MPs.

[0060] Example 3

[0061] The preparation of the ordered mesoporous nanocatalyst differs from that in Example 1 in that, in “(3) metal grafting”, Sc(ClO4)3 is used to replace Yb(ClO4)3 to obtain the catalyst Sc(ClO4)3-MPs.

[0062] Example 4

[0063] The preparation of the ordered mesoporous nanocatalyst differs from that in Example 1 in that, in “(3) metal grafting”, La(OTf)3 is used to replace Yb(ClO4)3 to obtain the catalyst La(OTf)3-MPs.

[0064] Example 5

[0065] The preparation of ordered mesoporous nanocatalysts differs from that in Example 1 in that, in “(3) metal grafting”, YbCl3 is used to replace Yb(ClO4)3 to obtain catalyst YbCl3-MPs.

[0066] Example 6

[0067] The preparation of ordered mesoporous nanocatalysts differs from that in Example 1 in that, in “(3) metal grafting”, Yb(OTf)3 is used to replace Yb(ClO4)3 to obtain catalyst Yb(OTf)3-MPs.

[0068] The physical parameters of the ordered mesoporous nanocatalysts prepared in Examples 1-6 are shown in Table 1.

[0069] Table 1: Physical parameters of pore structure of ordered mesoporous nanocatalysts

[0070] catalyst <![CDATA[SBET(m 2 / g)]]> Dp(nm) <![CDATA[Sc(OTf)2-MPs]]> 316 3.59 <![CDATA[Sc(ClO4)3-MPs]]> 330 3.35 <![CDATA[La(OTf)3-MPs]]> 305 3.31 <![CDATA[YbCl3-MPs]]> 311 3.20 <![CDATA[Yb(OTf)3-MPs]]> 305 3.00 <![CDATA[Yb(ClO4)3-MPs]]> 372 3.52

[0071] Example 7

[0072] A method for synthesizing acryloyloxyethyltrimethylammonium chloride based on ordered mesoporous nanocatalysts includes the following steps:

[0073] Weigh 189.2 g of methyl acrylate (2.2 mol), 178.2 g of dimethylaminoethanol (2.0 mol), 0.4 g of polymerization inhibitor thiophenezine, and 0.89 g of Yb(OTf)3-MPs into a 250 mL round-bottom flask and heat to 140 °C under reflux. Adjust the reflux ratio of the distillation separator and collect the methyl acrylate and the generated methanol. Monitor the reaction progress by GC. When the residual dimethylaminoethanol is <0.3%, stop the reaction and concentrate the low-boiling-point compound under reduced pressure. After no more fractions are distilled off, heat to 170 °C and collect the fractions to obtain 243.1 g of clear dimethylaminoethyl acrylate (purity 93.7%, yield 85%).

[0074] In a 250 mL round-bottom flask, 100 mL of dichloromethane was added. The chloromethane valve was opened, and dichloromethane was introduced. When the amount of chloromethane introduced reached 5.05 g, the gas flow was stopped. 14.3 g of dimethylaminoethyl acrylate was added, and the stirring speed was adjusted to 350 r / min. As the reaction proceeded, the viscosity increased significantly. At this point, the stirring speed was adjusted to 800 r / min. When the GC test showed that the dimethylaminoethyl acrylate content was <0.5%, the reaction was stopped. The organic solvent and low-boiling-point substances were concentrated, and then 150 mL of petroleum ether was added. The mixture was stirred for 30 minutes, filtered, and the filter cake was washed with petroleum ether. The product was dried under vacuum at 80 °C to obtain 18.3 g of acryloyloxyethyltrimethylammonium chloride (purity 99.0%, yield 95%).

[0075] The effects of different types of acrylates, different reaction temperatures, different types of polymerization inhibitors, and different acrylate / dimethylaminoethanol equivalents on the synthesis of dimethylaminoethyl acrylate were studied. The results are shown in Table 2.

[0076] Table 2. Effects of acrylate, reaction temperature, polymerization inhibitor, and acrylate / dimethylaminoethanol equivalent on the purity and yield of dimethylaminoethyl acrylate.

[0077]

[0078] Note: The basic reaction conditions are as described in Example 7.

[0079] Table 2 shows that different acrylates participate well in the reaction. Considering cost, methyl acrylate was ultimately chosen for further optimization of the conditions. As the reaction temperature increased, the reaction solution became darker, but the yield and purity did not change significantly. Increasing the acrylate equivalent increased the reaction rate, while the yield and purity remained essentially the same. Adding other polymerization inhibitors, such as hydroquinone and p-hydroxyanisole, resulted in a darker product color.

[0080] To further explore the effects of different ordered mesoporous nanocatalysts on the reaction, different catalysts were tested, and the specific data are shown in Table 3.

[0081] Table 3. Effects of different ordered mesoporous nanocatalysts on the reaction.

[0082] catalyst weight purity(%) Yield (%) <![CDATA[Sc(OTf)2-MPs]]> 0.5％ 93.1 83 <![CDATA[Sc(ClO4)3-MPs]]> 0.5％ 95.2 89 <![CDATA[La(OTf)3-MPs]]> 0.5％ 84.0 80 <![CDATA[YbCl3-MPs]]> 0.5％ 90.2 83 <![CDATA[Yb(OTf)3-MPs]]> 0.5％ 97.1 90 <![CDATA[Yb(ClO4)3-MPs]]> 0.5％ 98.0 92 <![CDATA[Yb(ClO4)3-MPs]]> 0.1％ 99.0 50 <![CDATA[Yb(ClO4)3-MPs]]> 1.0％ 99.3 95 <![CDATA[Yb(ClO4)3-MPs]]> 2.0％ 99.1 93 <![CDATA[Yb(ClO4)3-MPs]]> 5.0％ 99.3 93

[0083] Notes: 1. Catalyst weight is based on dimethylaminoethanol weight; 2. Basic reaction conditions: 189.2g methyl acrylate (2.2mol), 178.2g dimethylaminoethanol (2.0mol), 0.4g polymerization inhibitor thiophenezine, ordered mesoporous nanocatalyst, reflux reaction at 140℃.

[0084] As shown in Table 3, the ordered mesoporous nanocatalysts of La, Yb, and Sc can all effectively catalyze the synthesis of dimethylaminoethyl acrylate from methyl acrylate and dimethylaminoethanol. The reaction rate slows down significantly with decreasing catalyst amount, while the yield increases considerably with increasing catalyst amount; however, the yield remains relatively stable beyond 1%. Considering all factors, the optimal conditions currently available for the synthesis of dimethylaminoethyl acrylate are described in Example 8.

[0085] Example 8

[0086] The optimal conditions for synthesizing dimethylaminoethyl acrylate include the following steps:

[0087] Weigh 189.2 g of methyl acrylate (2.2 mol), 178.2 g of dimethylaminoethanol (2.0 mol), 0.4 g of polymerization inhibitor thiophenezine, and 1.78 g of Yb(ClO4)3-MPs into a 250 mL round-bottom flask. Heat to 140 °C under reflux. Adjust the reflux ratio of the distillation separator. Collect methyl acrylate and the generated methanol. Monitor the reaction progress by GC. When the residual dimethylaminoethanol is <0.3%, stop the reaction. Concentrate the low-boiling-point compound under reduced pressure. After no more fractions are distilled, heat to 170 °C and collect the fraction to obtain clear dimethylaminoethyl acrylate with a purity of 99.3% and a yield of 95%.

[0088] Example 9

[0089] Considering the potential for further environmental pollution from the large-scale use of catalysts in mass production, the issue of catalyst reuse is addressed. The reaction rate, purity, and yield of the DA synthesis reaction are investigated as follows:

[0090] 189.2 g of methyl acrylate (2.2 mol), 178.2 g of dimethylaminoethanol (2.0 mol), 0.4 g of polymerization inhibitor thiophenezine, and 1.78 g of Yb(ClO4)3-MPs were added to the concentration flask of the dimethylaminoethyl acrylate reaction. The mixture was heated to 140 °C under reflux. The reflux ratio of the distillation separator was adjusted, and the methyl acrylate and the generated methanol were collected. The reaction progress was monitored by GC. When the residual dimethylaminoethanol was <0.3%, the reaction was stopped. The low-boiling-point compound was concentrated under reduced pressure. After no more fractions were distilled off, the temperature was raised to 170 °C, and the fractions were collected to obtain clear dimethylaminoethyl acrylate.

[0091] The reaction was repeated multiple times, and the reaction time, purity, and yield of dimethylaminoethyl acrylate for each reaction are shown in Table 4.

[0092] Table 4. Reuse of Catalysts

[0093] Number of repetitions Reaction time (h) purity(%) Yield (%) 1 8 99.3 95 2 8.5 98.9 94 3 8.5 98.7 96 4 9 99.0 93 5 9.5 99.4 92 6 10 99.1 91 7 18 98.3 93 8 >24 ---- ----- 9 >72 ---- ----

[0094] As shown in Table 4, the Yb(ClO4)3-MPs catalyst can be recycled up to 6 times with little impact on the reaction. Starting from the 7th recycling, the reaction rate begins to decrease significantly, and by the 9th recycling, the reaction has almost stopped. The specific reasons are still under further investigation, but it is speculated that the enrichment of high-boiling-point impurities may have begun to affect the spatial structure of the catalyst from the 7th recycling, thus affecting the reaction progress.

[0095] For the synthesis of acryloyloxyethyltrimethylammonium chloride, most reported literature uses water as a solvent and conducts the reaction under pressure. This requires a large excess of chloromethane, which inevitably leads to resource waste. In addition, the product is usually sold in an aqueous state with about 80% water content, which greatly inconveniences the application of the product in non-aqueous conditions. Therefore, based on the reaction itself and the physicochemical properties of chloromethane, the inventors found that by dissolving chloromethane in an organic solvent and recrystallizing it after the reaction is complete, a dry product with a purity of >99% can be obtained.

[0096] Example 10

[0097] In a 250 mL round-bottom flask, 100 mL of dichloromethane was added. The chloromethane valve was opened, and dichloromethane was introduced. When the amount of chloromethane introduced reached 5.05 g, the gas flow was stopped. 14.3 g of dimethylaminoethyl acrylate was added, and the stirring speed was initially adjusted to 350 r / min. As the reaction proceeded, the viscosity increased significantly. At this point, the stirring speed was adjusted to 800 r / min. When the GC test showed that the dimethylaminoethyl acrylate content was <0.5%, the reaction was stopped. The organic solvent and low-boiling-point substances were concentrated, and then 150 mL of n-heptane was added. The mixture was stirred for 30 minutes, filtered, and the filter cake was washed with petroleum ether. The product was dried under vacuum at 80 °C to obtain 18.3 g of acryloyloxyethyltrimethylammonium chloride (purity 99.0%, yield 95%).

[0098] This invention explored the effects of different organic solvents on the DAC synthesis reaction; specific data are shown in Table 5.

[0099] Table 5. Effects of different solvents on the synthesis of acryloyloxyethyltrimethylammonium chloride

[0100] reaction solvent Crystallization solvent purity(%) Yield (%) dichloromethane petroleum ether 99.1 93 dichloromethane Cyclohexane 99.2 85 dichloromethane n-Hexane 99.0 91 dichloromethane n-Heptane 99.0 95 dichloromethane Toluene 95.0 94 1,2-Dichloroethane n-Heptane 99.5 94 chloroform n-Heptane 96.0 86 Carbon tetrachloride n-Heptane 97.4 90

[0101] As shown in Table 4, when the reaction solvent is 1,2-dichloroethane and the crystallization solvent is n-heptane, the purity of the obtained acryloyloxyethyltrimethylammonium chloride is the highest, reaching 99.5%, and the yield is also high, reaching 94%.

[0102] Analysis of test conditions

[0103] GC detection conditions for dimethylaminoethyl acrylate: Column: Capillary column, Agilent 123-1334DB-624 (30m*0.32mm*1.8um); Column temperature: 40℃ (4min) 10℃ / min 300℃ (4min); Air flow rate: 400mL / min, Hydrogen flow rate: 30mL / min, Make-up flow rate (nitrogen): 25mL / min; Injector: 200℃, Detector: 320℃, Split ratio: 20:1, Column flow rate: 2mL / min; Injection volume: 1uL;

[0104] HPLC test conditions for acryloyloxyethyltrimethylammonium chloride: Column: Wondasil C18-WR (5µm 4.6*250mm)

[0105] Mobile phase:

[0106] Acetonitrile % water% 0min 35 65 17min 90 10 25min 90 10 25.01min 35 65 32min 35 65

[0107] Detection wavelength: 204 nm; Flow rate: 1.0 mL / min; Temperature: 35 °C; Injection volume: 10 μL;

[0108] Preparation of control sample: Weigh 10 mg into a 50 mL volumetric flask, dissolve in a small amount of acetonitrile, then dilute to the mark with 40% acetonitrile.

[0109] Preparation of test sample: Weigh 10 mg into a 50 mL volumetric flask, dissolve in a small amount of acetonitrile, and then dilute to the mark with 40% acetonitrile.

[0110] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for the synthesis of acryloyloxyethyltrimethylammonium chloride based on ordered mesoporous nanocatalysts, characterized by, The method comprises the following steps: The acrylic ester and dimethylaminoethanol are reacted to obtain an intermediate dimethylaminoethyl acrylate under the catalysis of the ordered mesoporous nanocatalyst, then the dimethylaminoethyl acrylate is reacted with chloromethane under the condition of an organic solvent to obtain the trimethylammonium chloride acryloyloxyethyl at normal pressure, and finally the trimethylammonium chloride acryloyloxyethyl is recrystallized to obtain the trimethylammonium chloride acryloyloxyethyl; The mass of the ordered mesoporous nanocatalyst is 1% of the dimethylaminoethanol. The molar ratio of the acrylic ester to the dimethylaminoethanol is 1-3:1, and the reaction temperature of the acrylic ester and the dimethylaminoethanol is 140 DEG C. The polymerization inhibitor is thiophene when the acrylic ester and the dimethylaminoethanol are reacted. The preparation method of the ordered mesoporous nanocatalyst comprises the following steps: (1) preparing ordered mesoporous phenolic resin MP; (2) sulfonating the MP to obtain sulfonic acid group functionalized HSO3-MP; (3) grafting metal ions on the HSO3-MP by immersing a salt solution of lanthanum, ytterbium or scandium to obtain the ordered mesoporous nanocatalyst; The sulfonation of the MP comprises: The MP is degassed at 100-110 DEG C for 0.5-1.5 h, and after cooling, the system is immersed in an ice water bath, dichloromethane is added under the protection of high-purity argon, then the sulfonating agent is added drop by drop, stirred overnight, then transferred to a 40-60 DEG C system to reflux for 10-12 h, after cooling, the mixed solution is slowly added and dispersed in cold ethanol, and the sulfonic acid group functionalized HSO3-MP is obtained by filtration; The dosages of the MP, dichloromethane and sulfonating agent are 1 g:10-15 mL:5-15 mL.

2. The method for synthesis of acryloyloxyethyltrimethylammonium chloride based on ordered mesoporous nanocatalyst according to claim 1, characterized in that, The sulfonation of the MP comprises: The dosages of the MP, dichloromethane and sulfonating agent are 1 g:15 mL:10 mL; The sulfonating agent is chlorosulfonic acid.

3. The method for synthesis of acryloyloxyethyltrimethylammonium chloride based on ordered mesoporous nanocatalyst as claimed in claim 1, wherein, The grafting of metal ions on the HSO3-MP comprises: The HSO3-MP and the lanthanum salt, ytterbium salt or scandium salt are placed in anhydrous methanol, stirred at 70-90 DEG C for 20-25 h, cooled and filtered, washed with anhydrous methanol, and dried to obtain the ordered mesoporous nanocatalyst; The mass ratio of the HSO3-MP to the lanthanum salt, ytterbium salt or scandium salt is 1-1.5:1-1.

5.

4. The method for synthesis of acryloyloxyethyltrimethylammonium chloride based on ordered mesoporous nanocatalysts according to claim 3, characterized in that, The mass ratio of the HSO3-MP to the lanthanum salt, ytterbium salt or scandium salt is 1:

1.

5. The method for synthesis of acryloyloxyethyltrimethylammonium chloride based on ordered mesoporous nanocatalyst as claimed in claim 1, wherein, The ytterbium ions are grafted on the HSO3-MP by immersing a ytterbium salt solution to obtain the ordered mesoporous nanocatalyst.

6. The method for synthesis of acryloyloxyethyltrimethylammonium chloride based on ordered mesoporous nanocatalysts according to claim 5, characterized in that, The ytterbium salt is ytterbium perchlorate.

7. The method for synthesis of acryloyloxyethyltrimethylammonium chloride based on ordered mesoporous nanocatalyst as claimed in claim 1, wherein, The acrylic ester is one of methyl acrylate, ethyl acrylate or n-butyl acrylate.

8. The method for synthesis of acryloyloxyethyltrimethylammonium chloride based on ordered mesoporous nanocatalysts according to claim 7, characterized in that, The acrylic ester is methyl acrylate.

9. The method for synthesis of acryloyloxyethyltrimethylammonium chloride based on ordered mesoporous nanocatalyst as claimed in claim 1, wherein, The organic solvent is one of dichloromethane, 1,2 dichloroethane, chloroform or carbon tetrachloride.

10. The method of synthesis of acryloyloxyethyltrimethylammonium chloride based on ordered mesoporous nanocatalysts according to claim 9, characterized in that, The organic solvent is 1,2 dichloroethane.

11. The method for synthesis of acryloyloxyethyltrimethylammonium chloride based on ordered mesoporous nanocatalyst as claimed in claim 1, wherein, The solvent used for recrystallization is one of petroleum ether, n-heptane, cyclohexane or n-hexane.

12. The method of synthesis of acryloyloxyethyltrimethylammonium chloride based on ordered mesoporous nanocatalysts according to claim 11, characterized in that, The solvent used for recrystallization is n-heptane.

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