WO2025112129A1 - 一种酰基化反应催化剂及其制备方法与应用 - Google Patents

一种酰基化反应催化剂及其制备方法与应用 Download PDF

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WO2025112129A1
WO2025112129A1 PCT/CN2023/140532 CN2023140532W WO2025112129A1 WO 2025112129 A1 WO2025112129 A1 WO 2025112129A1 CN 2023140532 W CN2023140532 W CN 2023140532W WO 2025112129 A1 WO2025112129 A1 WO 2025112129A1
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preparation
acid solution
exchange resin
acylation reaction
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French (fr)
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沈少春
颜青
吴利平
黄旭东
李泽秋
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Petrochina Shanghai Advanced Materials Research Institute Co Ltd
Petrochina Co Ltd
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Petrochina Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
    • C07C49/665—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings a keto group being part of a condensed ring system
    • C07C49/67—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings a keto group being part of a condensed ring system having two rings, e.g. tetralones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/687—Unsaturated compounds containing a keto groups being part of a ring containing halogen
    • C07C49/697—Unsaturated compounds containing a keto groups being part of a ring containing halogen containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/753—Unsaturated compounds containing a keto groups being part of a ring containing ether groups, groups, groups, or groups
    • C07C49/755—Unsaturated compounds containing a keto groups being part of a ring containing ether groups, groups, groups, or groups a keto group being part of a condensed ring system with two or three rings, at least one ring being a six-membered aromatic ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention belongs to the field of fine chemicals, and specifically relates to an acylation reaction resin catalyst and a preparation method and application thereof.
  • Aromatic ketone compounds are important chemical intermediates and are widely used in the fields of medicine, dyes, pesticides, etc.
  • 2-acyl-6-methoxynaphthalene is used to synthesize the anti-inflammatory analgesic drug naproxen
  • o-hydroxybenzophenone compounds are highly efficient and broad-spectrum ultraviolet absorbers and are widely used in industries such as plastics, resins, coatings, synthetic rubber and cosmetics.
  • the Friedel-Crafts reaction is an important method for synthesizing aromatic ketone compounds.
  • Friedel-Crafts reaction is one of the most important reactions in organic chemistry. It refers to the reaction of introducing alkyl or acyl groups into aromatic ring compounds under the catalysis of protonic acid or Lewis acid. The introduction of alkyl is called alkylation reaction, and the introduction of acyl is called acylation reaction. Friedel and Crafts discovered and confirmed that aluminum chloride is an effective catalyst for the acylation reaction of aromatic compounds. Although the reaction was discovered earlier, research in this field is still very active, especially in the research and development of new catalysts.
  • the most widely used acylation catalysts are Lewis acids, such as AlCl 3 and FeCl 3.
  • this type of catalyst will form a complex with the product during the reaction, which increases the amount of catalyst used.
  • the catalyst is difficult to separate from the product and cannot be regenerated.
  • the post-treatment process will produce a large amount of acidic wastewater, which pollutes the environment.
  • the supported catalyst formed by loading Lewis acid on solid acid is another research direction. It overcomes the shortcomings of traditional catalysts such as difficulty in product separation and serious environmental pollution.
  • Some researchers loaded aluminum chloride on carriers such as clay, molecular sieves, and mesoporous silica gel to study the activity and selectivity of the Friedel-Crafts reaction.
  • the purpose of the present invention is to provide an acylation reaction catalyst and a preparation method and application thereof.
  • the acylation reaction catalyst can efficiently realize the acylation catalytic reaction of naphthalene-containing compounds, has good catalytic effect and simple post-treatment.
  • the present invention provides a method for preparing an acylation reaction catalyst, which comprises the following steps:
  • step (2) adding the cation exchange resin obtained in step (1) into a chromatography column, adding 0.01 mol/L-5 mol/L Lewis acid solution for elution, filtering, washing with water, and drying to obtain the acylation reaction catalyst.
  • the cation exchange resin comprises a hydrogen-type strongly acidic styrene-based cation exchange resin and/or a sodium-type strongly acidic styrene-based cation exchange resin.
  • the cation exchange resin includes one or a combination of two or more of 732 cationic resin, 734 cationic resin, D001 cationic resin, Amberlite-113, Amberlyst-15, Amberlyst-35, Amberlyst-16, Amberlyst-36, Amberlyst-45, and Amberlyst-46.
  • the Lewis acid includes one or a combination of two or more of the hydrochloride, hydrobromide and nitrate of Al 3+ , Fe 3+ , Zn 2+ , Cu 2+ and Ni 2+ .
  • the concentration of the hydrochloric acid solution is 1 mol/L-6 mol/L.
  • the solid-liquid mass ratio of the cation exchange resin to the hydrochloric acid solution is 1:1-1:10, more preferably 1:2-1:5.
  • the ultrasonic time is 10-30 min.
  • the ultrasonic frequency is 60KHz-150KHz, and the ultrasonic temperature is 30-60°C.
  • the Lewis acid solution is a metal salt solution of one or a combination of two or more of the hydrochloride, hydrobromide and nitrate of Al 3+ , Fe 3+ , Zn 2+ , Cu 2+ and Ni 2+ .
  • the concentration of the Lewis acid solution is 0.02-2 mol/L.
  • the volume ratio of the Lewis acid solution to the cation exchange resin is 50:1-2:1, more preferably 20:1-5:1.
  • the flow rate of the Lewis acid solution is 5 mL/min-50 mL/min, more preferably 10 mL/min-20 mL/min.
  • the present invention also provides an acylation reaction catalyst prepared by the preparation method.
  • the present invention also provides application of the acylation reaction catalyst in catalyzing aryl acylation.
  • reaction of the aryl acylation is as follows:
  • A is raw material naphthalene
  • B or C is acylating agent
  • D is acylated naphthalene product
  • R1 is selected from H, C1 - C5 alkyl, C1 - C4 alkoxy, halogen, hydroxyl, and the substitution number of R1 is 0-7
  • R2 is selected from C1 - C5 alkyl, phenyl, phenylmethylene
  • X is Cl or Br.
  • the aryl acylation reaction comprises the following steps:
  • the raw material naphthalene, the acylation agent and the acylation reaction catalyst are added into a solvent, and stirred for reaction at 60-100° C. for 1-24 hours to obtain an acylated naphthalene product, and the acylation reaction catalyst is recovered by filtration.
  • the molar ratio of the raw material naphthalene to the acylating agent is 1:1-1:4, and the mass ratio of the acylation reaction catalyst to the raw material naphthalene is 1:20-1:4.
  • the solvent is one or a combination of two or more of nitrobenzene, chlorobenzene, and dichlorobenzene, and the mass ratio of the solvent to the raw material naphthalene is 2:1-10:1.
  • the acylation reaction catalyst of the present invention can efficiently realize the acylation catalytic reaction of naphthalene-containing compounds by modifying the cationic resin with metal ions, has good catalytic effect, and the post-processing of the reaction system is simple, thus avoiding the problem of product adsorption and separation difficulties caused by the use of AlCl3 catalyst in the prior art;
  • the preparation method of the acylation reaction catalyst of the present invention is simple and economical, and can be widely used.
  • the reagents, methods, instruments and equipment used in the present invention are conventional reagents, methods, instruments and equipment in the art.
  • This preparation example provides an acylation reaction resin catalyst, which is prepared by the following steps:
  • This preparation example provides an acylation reaction resin catalyst, which is prepared by the following steps:
  • This preparation example provides an acylation reaction resin catalyst, which is prepared by the following steps:
  • D001 cationic resin 100 g was added to 500 mL of 3 mol/L hydrochloric acid solution, and filtered after ultrasonication (frequency of 130 Hz, temperature of 55 ° C) for 40 min, and washed with deionized water until the filtrate was neutral.
  • the obtained resin was added to a chromatography column, eluted with 1600 mL of 2 mol/L ZnCl 2 solution at a flow rate of 15 mL/min, and then washed with deionized water until there was no metal ion in the filtrate, and dried to obtain the resin catalyst Cat-3.
  • This preparation example provides an acylation reaction resin catalyst, which is prepared by the following steps:
  • Amberlyst-45 cationic resin 100 g was added to 1000 mL of 5 mol/L hydrochloric acid solution, and filtered after ultrasonication (frequency: 80 Hz, temperature: 50°C) for 30 min. The resin was washed with deionized water until the filtrate was neutral. The obtained resin was added to a chromatography column, and eluted with 1000 mL of 1.5 mol/L AlCl 3 solution at a flow rate of 20 mL/min. The resin was then washed with deionized water until there was no metal ion in the filtrate, and dried to obtain the resin catalyst Cat-4.
  • This preparation example provides an acylation reaction resin catalyst, which is prepared by the following steps:
  • This preparation example provides an acylation reaction resin catalyst, which is prepared by the following steps:
  • 2-methylnaphthalene, propionyl chloride, nitrobenzene and resin catalyst Cat-1 were added into a reactor, wherein the amount of 2-methylnaphthalene was 100 g, the molar ratio of 2-methylnaphthalene to propionyl chloride was 1:2, the mass ratio of Cat-1 to 2-methylnaphthalene was 1:10, and the mass ratio of nitrobenzene to 2-methylnaphthalene was 5:1.
  • the reaction was carried out at 80° C. for 12 hours. After filtering, concentrating, separating and purifying, the yield of the propionylation product was 75%.
  • 2-Methoxynaphthalene, acetic anhydride, nitrobenzene and resin catalyst Cat-3 were added into a reactor, wherein the amount of 2-methoxynaphthalene was 100 g, the molar ratio of 2-methoxynaphthalene to acetic anhydride was 1:4, the mass ratio of Cat-3 to 2-methoxynaphthalene was 1:4, and the mass ratio of nitrobenzene to 2-methoxynaphthalene was 10:1.
  • the reaction was carried out at 75° C. for 24 hours. After filtering, concentrating, separating and purifying, the yield of the acetylated product was 81%.
  • 1-bromo-4-ethylnaphthalene, benzoyl chloride, dichlorobenzene and resin catalyst Cat-6 are added into a reactor, wherein the amount of 1-bromo-4-ethylnaphthalene is 100 g, the molar ratio of 1-bromo-4-ethylnaphthalene to benzoyl chloride is 1:2.5, the mass ratio of Cat-6 to 1-bromo-4-ethylnaphthalene is 1:8, and the mass ratio of dichlorobenzene to 1-bromo-4-ethylnaphthalene is 5:1.
  • the reaction is carried out at 100° C. for 20 hours. After filtering, concentrating, separating and purifying, the yield of the benzoylation product is 69%.
  • 1-Ethylnaphthalene, acetyl chloride, chlorobenzene and resin catalyst Cat-1 were added into a reactor, wherein the amount of 1-ethylnaphthalene was 100 g, the molar ratio of 1-ethylnaphthalene to acetyl chloride was 1:1, the mass ratio of Cat-1 to 1-ethylnaphthalene was 1:20, and the mass ratio of chlorobenzene to 1-ethylnaphthalene was 2:1.
  • the reaction was carried out at 85°C for 22 hours. After filtering, concentrating, separating and purifying, the yield of the acetylated product was 71%.
  • 2-isopropylnaphthalene, isobutyric anhydride, nitrobenzene and resin catalyst Cat-1 are added into a reactor, wherein the amount of 2-isopropylnaphthalene is 100 g, the molar ratio of 2-isopropylnaphthalene to isobutyric anhydride is 1:2, the mass ratio of Cat-1 to 2-isopropylnaphthalene is 1:10, and the mass ratio of nitrobenzene to 2-isopropylnaphthalene is 3:1.
  • the reaction is carried out at 85° C. for 18 hours. After filtering, concentrating, separating and purifying, the yield of the acylated product is 82%.
  • 2-methylnaphthalene, propionyl chloride, nitrobenzene and resin catalyst Cat-c1 were added into a reactor, wherein the amount of 2-methylnaphthalene was 100 g, the molar ratio of 2-methylnaphthalene to propionyl chloride was 1:2, the mass ratio of Cat-c1 to 2-methylnaphthalene was 1:10, and the mass ratio of nitrobenzene to 2-methylnaphthalene was 5:1.
  • the reaction was carried out at 80° C. for 12 hours. After filtering, concentrating, separating and purifying, the yield of the propionylation product was 43%.
  • 2-methylnaphthalene, propionyl chloride, nitrobenzene and resin catalyst Cat-c2 are added into a reactor, wherein the amount of 2-methylnaphthalene is 100 g, the molar ratio of 2-methylnaphthalene to propionyl chloride is 1:2, the mass ratio of Cat-c2 to 2-methylnaphthalene is 1:10, and the mass ratio of nitrobenzene to 2-methylnaphthalene is 5:1.
  • the reaction is carried out at 80°C for 12 hours. After filtering, concentrating, separating and purifying, the yield of the propionylation product is 38%.
  • 100g D001 cationic resin was added to 500mL 3mol/L hydrochloric acid solution, and filtered after ultrasonication (frequency of 40Hz, temperature of 25°C) for 40min. The filtrate was washed with deionized water until the filtrate was neutral.
  • the obtained resin was added to a chromatography column, eluted with 1600mL 2mol/L ZnCl2 solution at a flow rate of 15mL/min, and then the resin was washed with deionized water until there was no metal ion in the filtrate.
  • the resin catalyst Cat-c3 was obtained by drying.
  • 2-methoxynaphthalene, acetic anhydride, nitrobenzene and resin catalyst Cat-c3 are added into a reactor, wherein the amount of 2-methoxynaphthalene is 100 g, the molar ratio of 2-methoxynaphthalene to acetic anhydride is 1:4, the mass ratio of Cat-c3 to 2-methoxynaphthalene is 1:4, and the mass ratio of nitrobenzene to 2-methoxynaphthalene is 10:1.
  • the reaction is carried out at 75°C for 24 hours. After filtering, concentrating, separating and purifying, the yield of the acetylated product is 48%.
  • a nitrobenzene solution of AlCl3 and isobutyric anhydride and a nitrobenzene solution of 2-isopropylnaphthalene (100 g) were prepared at low temperature, wherein the molar ratio of 2-isopropylnaphthalene to isobutyric anhydride was 1:2, the mass ratio of aluminum chloride to 2-isopropylnaphthalene was 1:10, and the mass ratio of nitrobenzene to 2-isopropylnaphthalene was 3:1.
  • the reaction was carried out at 85°C for 18 hours. After the reaction was quenched, filtered, concentrated, separated and purified, the yield of the acylated product was 62%. After the reaction was quenched, flocs were generated, which affected the separation effect and adsorbed the product, resulting in a reduced yield.
  • the present invention can effectively catalyze the acylation reaction of naphthalene compounds, greatly improve the conditions of the acylation reaction, simplify the operation process, and has obvious technical advantages.

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Abstract

一种酰基化反应催化剂及其制备方法与应用，所述的酰基化反应催化剂的制备方法，其包括以下步骤：(1)将阳离子交换树脂加入到0.1mol/L-10mol/L盐酸溶液中，超声1-60min后过滤，用水洗涤至滤液为中性，过滤；(2)将步骤(1)处理得到的阳离子交换树脂加入到层析柱中，加入0.01mol/L-5mol/L的路易斯酸溶液进行淋洗，过滤后水洗、干燥，得到所述酰基化反应催化剂。该酰基化反应催化剂能高效实现含萘化合物的酰基化催化反应，催化效果好，且后处理简单。

Description

一种酰基化反应催化剂及其制备方法与应用 技术领域
本发明属于精细化工领域，具体涉及一种酰基化反应树脂催化剂及其制备方法与应用。
背景技术
芳香酮类化合物是重要的化工中间体，在医药、染料、农药等领域有广泛的应用。例如，2-酰基-6甲氧基萘用于合成消炎镇痛药-萘普生；邻羟基二苯甲酮类化合物作为高效且广谱的紫外线吸收剂，广泛用于塑料、树脂、涂料、合成橡胶及化妆品等行业。而Friedel-Crafts反应是合成芳香酮类化合物的重要方法。
Friedel-Crafts反应是有机化学反应中最重要的反应之一，它指在质子酸或Lewis酸催化下在芳环化合物上引入烷基或者酰基的反应。其中引入烷基称为烷基化反应，引入酰基称为酰基化反应。Friedel和Crafts发现并证实了氯化铝是芳香化合物酰基化反应的有效催化剂。虽然该反应发现较早，但目前对该领域的研究仍然十分活跃，尤其是在新型催化剂的研究开发上。
目前应用较广的酰基化催化剂是Lewis酸类，如AlCl3，FeCl3等，但这一类催化剂在反应中会与产物形成络合物，增大了催化剂用量，且催化剂与产物分离困难，不能再生，后处理过程会产生大量酸性废水，污染环境。将Lewis酸负载于固体酸上所形成的负载型催化剂是另一个研究方向，它克服了传统催化剂产物分离困难，环境污染严重等缺点。有研究人员将氯化铝负载于黏土、分子筛、中孔硅胶等载体上，研究对Friedel-Crafts反应的活性与选择性，研究结果表明，负载后催化剂的活性及选择性都优于未负载的催化剂。三井公司采用不同的改性分子筛催化合成了高选择性蒽醌。此外，也有研究人员利用沸石分子筛在气-固多相催化条件下合成了蒽醌，但气-固多相催化方法无法精确控制物料配比，反应装置也不利于工业化生产。此外，离子交换树脂、固体超强酸、固体杂多酸、离子液体等都有文献报道用于催化Friedel-Crafts酰基化反应，但存在稳定向差、价格高、难以制备、催化效果差等缺点。
基于上述现状与不足，开发一类环境友好、催化效率高、易于制备的酰基化催化剂是十分必要的。
发明内容
为了解决传统酰基化反应催化体系复杂、产物分离困难、催化效果差等技术问题， 本发明的目的在于提供一种酰基化反应催化剂及其制备方法与应用，该酰基化反应催化剂能高效实现含萘化合物的酰基化催化反应，催化效果好，且后处理简单。
为了达到上述目的，本发明提供了一种酰基化反应催化剂的制备方法，其包括以下步骤：
(1)将阳离子交换树脂加入到0.1mol/L-10mol/L盐酸溶液中，超声1-60min后过滤，用水洗涤至滤液为中性，过滤；
(2)将步骤(1)处理得到的阳离子交换树脂加入到层析柱中，加入0.01mol/L-5mol/L的路易斯酸溶液进行淋洗，过滤后水洗、干燥，得到所述酰基化反应催化剂。
根据本发明的具体实施方案，优选地，所述阳离子交换树脂包括氢型强酸性苯乙烯系阳离子交换树脂和/或钠型强酸性苯乙烯系阳离子交换树脂。
根据本发明的具体实施方案，优选地，所述阳离子交换树脂包括732阳离子树脂、734阳离子树脂、D001阳离子树脂、Amberlite-113、Amberlyst-15、Amberlyst-35、Amberlyst-16、Amberlyst-36、Amberlyst-45、Amberlyst-46中的一种或两种以上的组合。
根据本发明的具体实施方案，优选地，所述路易斯酸包括Al3+、Fe3+、Zn2+、Cu2+、Ni2+的盐酸盐、氢溴酸盐、硝酸盐中的一种或两种以上的组合。
根据本发明的具体实施方案，优选地，步骤(1)中，所述盐酸溶液的浓度为1mol/L-6mol/L。
根据本发明的具体实施方案，优选地，步骤(1)中，阳离子交换树脂与盐酸溶液的固液质量比为1:1-1:10，更优选为1:2-1:5。
根据本发明的具体实施方案，优选地，步骤(1)中，超声时间为10-30min。
根据本发明的具体实施方案，优选地，步骤(1)中，超声频率为60KHz-150KHz，超声温度为30-60℃。
根据本发明的具体实施方案，优选地，步骤(2)中，所述路易斯酸溶液为Al3+、Fe3+、Zn2+、Cu2+、Ni2+的盐酸盐、氢溴酸盐、硝酸盐中的一种或两种以上的组合的金属盐溶液。
根据本发明的具体实施方案，优选地，所述路易斯酸溶液的浓度为0.02-2mol/L。
根据本发明的具体实施方案，优选地，步骤(2)中，路易斯酸溶液与阳离子交换树脂的体积比为50:1-2:1，更优选为20:1-5:1。
根据本发明的具体实施方案，优选地，步骤(2)中，淋洗时，路易斯酸溶液的流速为5mL/min-50mL/min，更优选为10mL/min-20mL/min。
本发明还提供了由上述制备方法制得的酰基化反应催化剂。
本发明还提供了上述酰基化反应催化剂在催化芳基酰基化中的应用。
根据本发明的具体实施方案，优选地，所述芳基酰基化的反应如下反应式：
其中，A为原料萘，B或C为酰基化试剂，D为酰基化萘产物；R1选自H、C1-C5烷基、C1-C4烷氧基、卤素、羟基，R1的取代数量为0-7；R2选自C1-C5烷基、苯基、苯基亚甲基；X为Cl或Br。
根据本发明的具体实施方案，优选地，所述芳基酰基化的反应包括以下步骤：
将原料萘、酰基化试剂、所述酰基化反应催化剂加入到溶剂中，在60-100℃下搅拌反应1-24小时，得到酰基化萘产物，所述酰基化反应催化剂经过滤回收。
根据本发明的具体实施方案，优选地，原料萘与酰基化试剂的摩尔比为1:1-1:4，所述酰基化反应催化剂与原料萘的质量比为1:20-1:4。
根据本发明的具体实施方案，优选地，所述溶剂为硝基苯、氯苯、二氯苯中的一种或两种以上的组合，溶剂与原料萘的质量比为2:1-10:1。
本发明具有以下有益效果：
(1)本发明的酰基化反应催化剂通过对阳离子树脂进行金属离子负载改性，能高效实现含萘化合物的酰基化催化反应，催化效果好，且反应体系后处理简单，避免了现有技术利用AlCl3催化剂导致的产物吸附与分离困难的问题；
(2)本发明的酰基化反应催化剂的制备方法简单且经济，可以广泛地应用。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。
除非特别说明，本发明采用的试剂、方法、仪器和设备为本领域常规试剂、方法、仪器和设备。
除非特别说明，以下实施例所用的试剂和材料均为市购，分析纯级。
制备例1
本制备例提供了一种酰基化反应树脂催化剂，其由以下步骤制得：
将100g Amberlyst-15树脂加入到200mL 1mol/L盐酸溶液中，超声(频率为100Hz，温度45℃)30min后过滤，用去离子水洗涤至滤液为中性，将得到的树脂加入到层析柱中，2000mL 0.2mol/L AlCl3溶液，以20mL/min的流速淋洗，而后用去离子水洗树脂至滤液中无金属离子，干燥得到树脂催化剂Cat-1。
制备例2
本制备例提供了一种酰基化反应树脂催化剂，其由以下步骤制得：
将100g 734阳离子树脂加入到150mL 6mol/L盐酸溶液中，超声(频率为120Hz，温度60℃)10min后过滤，用去离子水洗涤至滤液为中性，将得到的树脂加入到层析柱中，800mL 1mol/L ZnCl2溶液，以10mL/min的流速淋洗，而后用去离子水洗树脂至滤液中无金属离子，干燥得到树脂催化剂Cat-2。
制备例3
本制备例提供了一种酰基化反应树脂催化剂，其由以下步骤制得：
将100g D001阳离子树脂加入到500mL 3mol/L盐酸溶液中，超声(频率为130Hz，温度55℃)40min后过滤，用去离子水洗涤至滤液为中性，将得到的树脂加入到层析柱中，1600mL 2mol/L ZnCl2溶液，以15mL/min的流速淋洗，而后用去离子水洗树脂至滤液中无金属离子，干燥得到树脂催化剂Cat-3。
制备例4
本制备例提供了一种酰基化反应树脂催化剂，其由以下步骤制得：
将100g Amberlyst-45阳离子树脂加入到1000mL 5mol/L盐酸溶液中，超声(频率为80Hz，温度50℃)30min后过滤，用去离子水洗涤至滤液为中性，将得到的树脂加入到层析柱中，1000mL 1.5mol/L AlCl3溶液，以20mL/min的流速淋洗，而后用去离子水洗树脂至滤液中无金属离子，干燥得到树脂催化剂Cat-4。
制备例5
本制备例提供了一种酰基化反应树脂催化剂，其由以下步骤制得：
将100g Amberlite-113阳离子树脂加入到700mL 0.2mol/L盐酸溶液中，超声(频率为100Hz，温度35℃)60min后过滤，用去离子水洗涤至滤液为中性，将得到的树脂加入到层析柱中，1400mL 2.5mol/L NiBr2溶液，以10mL/min的流速淋洗，而后用去离子水洗树脂至滤液中无金属离子，干燥得到树脂催化剂Cat-5。
制备例6
本制备例提供了一种酰基化反应树脂催化剂，其由以下步骤制得：
将100g Amberlyst-36阳离子树脂加入到800mL 4mol/L盐酸溶液中，超声(频率为150Hz，温度60℃)25min后过滤，用去离子水洗涤至滤液为中性，将得到的树脂加入到层析柱中，1800mL 2.5mol/L Cu(NO3)2溶液，以16mL/min的流速淋洗，而后用去离子水洗树脂至滤液中无金属离子，干燥得到树脂催化剂Cat-6。
实施例1
将2-甲基萘、丙酰氯、硝基苯以及树脂催化剂Cat-1加入到反应器中，其中2-甲基萘投料量为100g，2-甲基萘与丙酰氯摩尔比为1:2，Cat-1与2-甲基萘质量比为1:10，硝基苯与2-甲基萘质量比为5:1，在80℃下反应12小时，反应经过过滤、浓缩、分离纯化后，丙酰化产物收率为75％。
实施例2
将2-甲氧基萘、乙酸酐、硝基苯以及树脂催化剂Cat-3加入到反应器中，其中2-甲氧基萘投料量为100g，2-甲氧基萘与乙酸酐摩尔比为1:4，Cat-3与2-甲氧基萘质量比为1:4，硝基苯与2-甲氧基萘质量比为10:1，在75℃下反应24小时，反应经过过滤、浓缩、分离纯化后，乙酰化产物收率为81％。
实施例3
将1-溴-4-乙基萘、苯甲酰氯、二氯苯以及树脂催化剂Cat-6加入到反应器中，其中1-溴-4-乙基萘投料量为100g，1-溴-4-乙基萘与苯甲酰氯摩尔比为1:2.5，Cat-6与1-溴-4-乙基萘质量比为1:8，二氯苯与1-溴-4-乙基萘质量比为5:1，在100℃下反应20小时，反应经过过滤、浓缩、分离纯化后，苯甲酰化产物收率为69％。
实施例4
将1-乙基萘、乙酰氯、氯苯以及树脂催化剂Cat-1加入到反应器中，其中1-乙基萘投料量为100g，1-乙基萘与乙酰氯摩尔比为1:1，Cat-1与1-乙基萘质量比为1:20，氯苯与1-乙基萘质量比为2:1，在85℃下反应22小时，反应经过过滤、浓缩、分离纯化后，乙酰化产物收率为71％。
实施例5
将2-异丙基萘、异丁酸酐、硝基苯以及树脂催化剂Cat-1加入到反应器中，其中2-异丙基萘投料量为100g，2-异丙基萘与异丁酸酐摩尔比为1:2，Cat-1与2-异丙基萘质量比为1:10，硝基苯与2-异丙基萘质量比为3:1，在85℃下反应18小时，反应经过过滤、浓缩、分离纯化后，酰化产物收率为82％。
对比例1
将100g Amberlyst-15树脂加入到200mL 1mol/L盐酸溶液中，浸泡30min后过滤，用去离子水洗涤至滤液为中性，将得到的树脂加入到层析柱中，2000mL 0.2mol/L AlCl3溶液，以20mL/min的流速淋洗，而后用去离子水洗树脂至滤液中无金属离子，干燥得到树脂催化剂Cat-c1。
将2-甲基萘、丙酰氯、硝基苯以及树脂催化剂Cat-c1加入到反应器中，其中2-甲基萘投料量为100g，2-甲基萘与丙酰氯摩尔比为1:2，Cat-c1与2-甲基萘质量比为1:10，硝基苯与2-甲基萘质量比为5:1，在80℃下反应12小时，反应经过过滤、浓缩、分离纯化后，丙酰化产物收率为43％。
对比例2
将100g Amberlyst-15树脂加入到200mL 1mol/L盐酸溶液中，超声(频率为100Hz，温度45℃)30min后过滤，用去离子水洗涤至滤液为中性，将得到的树脂加入2000mL 0.2mol/L AlCl3溶液中，浸泡2小时后过滤，而后用去离子水洗树脂至滤液中无金属离子，干燥得到树脂催化剂Cat-c2。
将2-甲基萘、丙酰氯、硝基苯以及树脂催化剂Cat-c2加入到反应器中，其中2-甲基萘投料量为100g，2-甲基萘与丙酰氯摩尔比为1:2，Cat-c2与2-甲基萘质量比为1:10，硝基苯与2-甲基萘质量比为5:1，在80℃下反应12小时，反应经过过滤、浓缩、分离纯化后，丙酰化产物收率为38％。
对比例3
将100g D001阳离子树脂加入到500mL 3mol/L盐酸溶液中，超声(频率为40Hz，温度25℃)40min后过滤，用去离子水洗涤至滤液为中性，将得到的树脂加入到层析柱中，1600mL 2mol/L ZnCl2溶液，以15mL/min的流速淋洗，而后用去离子水洗树脂至滤液中无金属离子，干燥得到树脂催化剂Cat-c3。
将2-甲氧基萘、乙酸酐、硝基苯以及树脂催化剂Cat-c3加入到反应器中，其中2-甲氧基萘投料量为100g，2-甲氧基萘与乙酸酐摩尔比为1:4，Cat-c3与2-甲氧基萘质量比为1:4，硝基苯与2-甲氧基萘质量比为10:1，在75℃下反应24小时，反应经过过滤、浓缩、分离纯化后，乙酰化产物收率为48％。
对比例4
将2-异丙基萘(100g)、异丁酸酐、硝基苯以及Amberlyst-15树脂加入到反应器中，其中2-异丙基萘与异丁酸酐摩尔比为1:2，Amberlyst-15与2-异丙基萘质量比为1:10，硝基苯与2-异丙基萘质量比为3:1，在85℃下反应18小时，反应经过过滤、浓缩、分 离纯化后，酰化产物收率为12％。
对比例5
在低温下分别配制AlCl3与异丁酸酐的硝基苯溶液，以及2-异丙基萘(100g)的硝基苯溶液，其中2-异丙基萘与异丁酸酐摩尔比为1:2，氯化铝与2-异丙基萘质量比为1:10，硝基苯与2-异丙基萘质量比为3:1，在85℃下反应18小时，反应经过淬灭，过滤、浓缩、分离纯化后，酰化产物收率为62％，反应淬灭后有絮状物生成，影响分离效果，且对产物有吸附，导致收率降低。
通过上述实施例与对比例结果可知，本发明能有效催化萘类化合物的酰基化反应，且极大地改进了酰基化反应的条件，简化了操作过程，具有明显的技术优势。
虽然，上文中已经用一般性说明、具体实施方式及试验，对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。

Claims (21)

  1. 一种酰基化反应催化剂的制备方法，其包括以下步骤：
    (1)将阳离子交换树脂加入到0.1mol/L-10mol/L盐酸溶液中，超声1-60min后过滤，用水洗涤至滤液为中性，过滤；
    (2)将步骤(1)处理得到的阳离子交换树脂加入到层析柱中，加入0.01mol/L-5mol/L的路易斯酸溶液进行淋洗，过滤后水洗、干燥，得到所述酰基化反应催化剂。
  2. 根据权利要求1所述的制备方法，其中，所述阳离子交换树脂包括氢型强酸性苯乙烯系阳离子交换树脂和/或钠型强酸性苯乙烯系阳离子交换树脂。
  3. 根据权利要求2所述的制备方法，其中，所述阳离子交换树脂包括732阳离子树脂、734阳离子树脂、D001阳离子树脂、Amberlite-113、Amberlyst-15、Amberlyst-35、Amberlyst-16、Amberlyst-36、Amberlyst-45、Amberlyst-46中的一种或两种以上的组合。
  4. 根据权利要求1所述的制备方法，其中，所述路易斯酸包括Al3+、Fe3+、Zn2+、Cu2+、Ni2+的盐酸盐、氢溴酸盐、硝酸盐中的一种或两种以上的组合。
  5. 根据权利要求1所述的制备方法，其中，步骤(1)中，所述盐酸溶液的浓度为1mol/L-6mol/L。
  6. 根据权利要求1所述的制备方法，其中，步骤(1)中，阳离子交换树脂与盐酸溶液的固液质量比为1:1-1:10。
  7. 根据权利要求1所述的制备方法，其中，步骤(1)中，阳离子交换树脂与盐酸溶液的固液质量比为1:2-1:5。
  8. 根据权利要求1所述的制备方法，其中，步骤(1)中，超声时间为10-30min。
  9. 根据权利要求1所述的制备方法，其中，步骤(1)中，超声频率为60KHz-150KHz，超声温度为30-60℃。
  10. 根据权利要求1所述的制备方法，其中，步骤(2)中，所述路易斯酸溶液为Al3+、Fe3+、Zn2+、Cu2+、Ni2+的盐酸盐、氢溴酸盐、硝酸盐中的一种或两种以上的组合的金属盐溶液。
  11. 根据权利要求1所述的制备方法，其中，所述路易斯酸溶液的浓度为0.02-2mol/L。
  12. 根据权利要求1所述的制备方法，其中，步骤(2)中，路易斯酸溶液与阳离子交换树脂的体积比为50:1-2:1。
  13. 根据权利要求1所述的制备方法，其中，步骤(2)中，路易斯酸溶液与阳离子 交换树脂的体积比为20:1-5:1。
  14. 根据权利要求1所述的制备方法，其中，步骤(2)中，淋洗时，路易斯酸溶液的流速为5mL/min-50mL/min。
  15. 根据权利要求1所述的制备方法，其中，步骤(2)中，淋洗时，路易斯酸溶液的流速为10mL/min-20mL/min。
  16. 权利要求1-15任一项所述的制备方法制得的酰基化反应催化剂。
  17. 权利要求16所述的酰基化反应催化剂在催化芳基酰基化中的应用。
  18. 根据权利要求17所述的应用，其中，所述芳基酰基化的反应如下反应式：
    其中，A为原料萘，B或C为酰基化试剂，D为酰基化萘产物；
    R1选自H、C1-C5烷基、C1-C4烷氧基、卤素、羟基，R1的取代数量为0-7；R2选自C1-C5烷基、苯基、苯基亚甲基；X为Cl或Br。
  19. 根据权利要求18所述的应用，其中，所述芳基酰基化的反应包括以下步骤：
    将原料萘、酰基化试剂、所述酰基化反应催化剂加入到溶剂中，在60-100℃下搅拌反应1-24小时，得到酰基化萘产物，所述酰基化反应催化剂经过滤回收。
  20. 根据权利要求19所述的应用，其中，原料萘与酰基化试剂的摩尔比为1:1-1:4，所述酰基化反应催化剂与原料萘的质量比为1:20-1:4。
  21. 根据权利要求19所述的应用，其中，所述溶剂为硝基苯、氯苯、二氯苯中的一种或两种以上的组合，溶剂与原料萘的质量比为2:1-10:1。
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