CN106215957A - Heterogeneous catalysis system used for preparation of vinyl carboxylate and application method thereof - Google Patents

Heterogeneous catalysis system used for preparation of vinyl carboxylate and application method thereof Download PDF

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CN106215957A
CN106215957A CN201610556220.1A CN201610556220A CN106215957A CN 106215957 A CN106215957 A CN 106215957A CN 201610556220 A CN201610556220 A CN 201610556220A CN 106215957 A CN106215957 A CN 106215957A
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catalyst
acid
palladium
reaction
vinyl
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CN201610556220.1A
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王志光
陈贵夫
李洪峰
姜赟
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巨化集团技术中心
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06Halogens; Compounds thereof
    • B01J27/128Halogens; Compounds thereof with iron group metals or platinum group metals
    • B01J27/13Platinum group metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235Nitrogen containing compounds
    • B01J31/0239Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/30Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/307Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/30Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms

Abstract

The invention discloses a heterogeneous catalysis system used for preparation of vinyl carboxylate. The heterogeneous catalysis system comprises a catalyst and a catalyst aid. The heterogeneous catalysis system is characterized in that the catalyst is a palladium-carbon catalyst in which the mass percentage of palladium is 3.5 to 10%; the catalyst aid is at least one selected from a group consisting of alkali metal halide and quaternary ammonium salt, and a mass ratio of the catalyst to the catalyst aid is (0.5-5): 1. The catalysis system is applied to preparation of vinyl carboxylate and has the advantages of simple process, easy separation of the catalysis system, high yield, low cost, safety and environment friendliness.

Description

一种用于制备羧酸乙烯酯的多相催化体系及其使用方法 A heterogeneous catalytic systems prepared vinyl carboxylate and a method for using

技术领域 FIELD

[0001] 本发明涉及多相催化体系及其使用方法,具体的说,本发明涉及一种用于制备羧酸乙烯酯的多相催化体系及其使用方法。 [0001] The present invention relates to heterogeneous catalytic systems and methods of use, particularly, the present invention relates to heterogeneous catalytic systems used for the preparation of the vinyl carboxylate and methods of use.

背景技术 Background technique

[0002] 羧酸乙烯酯是一类重要的化工原料,因分子中含有活性功能基-双键,能与乙烯、 丙烯酸酯、苯乙烯等具有双键的单体进行共聚提高其共聚物的性能,拓宽其应用范围,是一类优良的改性单体。 [0002] vinyl esters of carboxylic acid is an important chemical raw material, because the molecule contains a reactive functional group - a double bond, a monomer having a double bond can with ethylene, acrylates, styrene copolymers copolymerized to improve the performance of broaden the range of applications, it is a good-quality modifying monomers. 其均聚物或共聚物在粘合剂、涂料、防锈剂等方面均有应用。 Homopolymers or copolymers which are used in adhesives, coatings, rust preventive aspects.

[0003] 羧酸乙烯酯聚合物的性能,按酸种类而异,且差别很大。 [0003] The vinyl carboxylate polymer properties, varies according to the kind of acid, and vary widely. 若进而成为共聚物,则种类更多,性能差别更大而用途非常广泛。 When the copolymer thus become, the more diverse, but larger differences in performance are very versatile. 各种羧酸乙烯酯聚合能力,根据其羧酸烃基而异, 饱和脂肪族羧酸的乙烯酯,随烃基的碳原子数增加,聚合能力减少。 Polymerizing various vinyl carboxylate capacity, which varies according to the hydrocarbon carboxylic acid, vinyl esters of saturated aliphatic carboxylic acids, hydrocarbon group with the number of carbon atoms increases, the ability to reduce the polymerization. 芳香族羧酸乙烯酯,如苯甲酸乙烯酯,由于游离苯核稳定,聚合能力比脂肪族羧酸乙烯酯低。 Aromatic carboxylic acid vinyl esters such as vinyl benzoate, since the stable free benzene nucleus, lower polymerizability than the vinyl esters of aliphatic carboxylic acids. 不饱和羧酸乙烯酯还可用做交联剂,光敏树脂材料。 Vinyl esters of the unsaturated carboxylic acid may also be used as a crosslinking agent, a photosensitive resin material.

[0004] 目前,合成羧酸乙烯酯的方法主要有乙炔法,乙烯法和乙烯基交换法。 [0004] Currently, methods of synthesizing vinyl carboxylate mainly acetylene, ethylene, and vinyl exchange. 乙烯法气相反应时转化率低,液相反应时腐蚀性大,同时具有爆炸的危险;乙炔法也具有较大的安全风险,同时采用贵金属催化剂,影响了其经济性。 When the conversion is low ethylene gas phase reaction, liquid phase reaction corrosive large, while an explosion hazard; acetylene method also has a large security risk while using a noble metal catalyst, its economic impact. 酯交换法简单易行,反应条件温和,是目前主要的羧酸乙烯酯合成方法。 Transesterification method is simple, mild reaction conditions, is currently the main method for the synthesis of vinyl carboxylates. 乙烯基交换法通常是用醋酸乙烯酯和羧酸,在金属催化下,进行乙烯基的转移,制备相应羧酸的乙烯基酯。 Vinyl exchange method is usually used vinyl acetate and a carboxylic acid, under metal catalysis, transferred vinyl, vinyl esters of the corresponding carboxylic acid was prepared. 由于原料和产物中的双键活性很高,容易发生加成聚合等副反应,所以催化条件的筛选和优化很关键。 Since a side reaction product and the double bond is highly active in the starting material, an addition polymerization easily occurs, so the selection and optimization of catalytic conditions is critical. 该法最典型的催化剂是二价汞的强酸盐。 The most typical method of catalysts is strong acid salt of divalent mercury. 如US2997494报道了由二价汞盐和强酸组成的催化体系。 The catalytic system reported US2997494 divalent mercury salts and acids thereof. 二价汞可以是氧化汞,硫化汞,醋酸汞,硬脂酸汞等,强酸可以是硫酸,磷酸,对甲苯磺酸,三氟醋酸等。 Mercury may be divalent mercury oxide, mercury sulfide, mercury acetate, mercury stearate, strong acid may be sulfuric acid, phosphoric acid, p-toluenesulfonic acid, trifluoroacetic acid and the like. 汞盐和强酸催化体系因为废液中含有大量的汞离子和废酸,后处理成本高,对环境影响大,因此逐渐被淘汰。 Mercury salts and acid catalytic systems because the waste contains large amounts of waste acid and mercuric ions, the high cost of the treatment, a large impact on the environment, thus gradually be eliminated.

[0005] 美国专利US4981973描述了钌基催化剂在乙烯基交换反应中的应用。 [0005] U.S. Patent No. US4981973 describes a ruthenium-based catalyst is applied in the vinyl exchange reaction. 有使用金属铂催化乙烯基交换反应的报道,并能给出非常满意的结果,尽管铂族金属催化性能良好,但是其价格昂贵,并且高活性的均相催化剂容易产生副反应,限制了这类催化剂的广泛应用。 There are metal platinum catalyzed vinyl exchange reaction reports, and can give very satisfactory results, although good platinum group metal catalytic performance, but it is expensive, and the high activity of homogeneous catalysts prone to side reactions, such limits widely used catalyst.

[0006] 钯碳催化剂是一种工业上应用非常广泛的贵金属多相催化剂,具有非常成熟的制备加工技术和市场体系。 [0006] The palladium on carbon catalyst is an industrially widely used noble metal heterogeneous catalysts, prepared with very mature processing technology and market system. 钯金属催化剂能有效地催化乙烯基交换反应,但与均相的钯盐催化剂相比,多相钯催化剂活性降低,容易从反应体系分离,使得贵金属钯能容易回收和重复使用,这样能大大降低发生副反应的可能性,具有较高的反应选择性。 Palladium metal catalyst effective to catalyze the vinyl exchange reaction, but compared with the homogeneous catalyst a palladium salt, a palladium catalyst multiphase activity decreases easily separated from the reaction system, so that the noble metal palladium can be easily recovered and reused, this can greatly reduce the the possibility of side reactions, the reaction with high selectivity. 因此一般采用多相钯催化剂催化乙烯基交换反应。 It is generally catalyzed using a palladium catalyst multiphase vinyl exchange reaction. 多相钯催化剂通常用钯盐为催化剂,以碱金属卤化物为共催化剂,该催化体系反应活性高,副产物少。 Multiphase palladium catalysts are generally palladium salt as catalyst, an alkali metal halide as co-catalyst, the catalytic system, high reactivity, less by-products. 如美国专利US5214172、US5741925使用钯盐与邻菲罗啉配体体系催化合成羧酸乙烯酯,取得了非常好的反应效果,并且向体系中加入强酸能显著提高反应活性。 U.S. Patent No. US5214172, US5741925 using a palladium salt and ligands phenanthroline vinyl carboxylate catalytic synthesis system, the reaction achieved very good results, and a strong acid added to the system can significantly increase the reactivity. 专利CN103025702A公开了使用醋酸钯和邻菲罗啉体系制备羧酸乙烯酯,羧酸转化率在70%左右,并且反应液蒸出产品和溶剂(醋酸乙烯酯)后,反应釜底残渣仍然可以催化多次,羧酸转化率仍然能维持在一个较高的水平。 The patent discloses the use of palladium acetate CN103025702A phenanthroline systems prepared and vinyl carboxylate, carboxylic acid conversion of about 70%, and the reaction products and the solvent was distilled off (vinyl acetate), the reaction can be catalyzed still bottoms residue many times, carboxylic acid conversion rate will remain at a high level.

[0007] 但上述现有技术的不足之处是反应过程中容易析出钯黑,且反应的收率和选择性仍然较低,生产成本较高。 [0007] However, the above-described shortcomings of the prior art is likely to precipitate during the reaction of palladium black, and the reaction selectivity and the yield is still low, higher production costs. 因此,如何保持钯基催化体系的稳定并容易从反应体系分离,同时进一步降低发生副反应的可能性,提高反应的收率和选择性,以降低生产成本,是研究人员迫切需要解决的问题。 Therefore, how to maintain a stable palladium-based catalyst system and are easily separated from the reaction system, and further reduce the possibility of side reactions, increase the yield and selectivity of the reaction, to reduce production costs, researchers urgent problem to be solved.

发明内容 SUMMARY

[0008] 本发明的目的是针对现有技术的缺陷,提供一种工艺简单,催化体系易分离,收率高,成本低,安全环保的用于制备羧酸乙烯酯的多相催化体系及其使用方法。 [0008] The object of the present invention is directed to drawbacks of the prior art, to provide a simple process, easy to separate the catalyst system, high yield, low cost, environmentally safe heterogeneous catalytic systems for preparing the vinyl carboxylate and Instructions.

[0009] 本发明解决上述技术问题采用的方案是:一种用于制备羧酸乙烯酯的多相催化体系,包括催化剂和催化剂助剂,所述催化剂为钯质量百分含量为3.5 %-10 %的钯碳催化剂, 所述催化剂助剂为碱金属卤化物和季铵盐中的至少一种,所述催化剂与催化剂助剂质量比为0.5-5:1 〇 [0009] solve the technical problem of the present invention is employed: A heterogeneous catalytic systems for the preparation of vinyl carboxylate, and a catalyst promoter comprising a catalyst, the catalyst is a palladium content of 3.5 mass% to 10 percent % palladium on carbon catalyst, the catalyst promoter is at least one alkali metal halide and a quaternary ammonium salt, the catalyst and catalyst promoter mass ratio of 0.5-5: 1 billion

[0010] 本发明中碱金属卤化物包括但不限于氯化钠,溴化钠,氟化钠,碘化钠,氯化钾,溴化钾,氟化钾,碘化钾等,所述碱金属卤化物优选为氯化钠、氯化钾、氟化钾、氟化钠、溴化钾、碘化钾中的一种。 [0010] In the present invention, the alkali metal halides include but are not limited to, sodium chloride, sodium bromide, sodium fluoride, sodium iodide, potassium chloride, potassium bromide, potassium fluoride, potassium iodide, the alkali metal halide preferably sodium chloride, potassium chloride, potassium fluoride, sodium fluoride, potassium bromide, potassium iodide, of one.

[0011]本发明中季铵盐包括但不限于苄基三乙基氯化铵(TEBA)、四丁基溴化铵、四丁基氯化铵、四丁基硫酸氢铵(TBAB )、三辛基甲基氯化铵、十二烷基三甲基溴化铵、十四烷基三甲基氯化铵等。 [0011] In the present invention, but are not limited to quaternary ammonium salts include benzyltriethylammonium chloride (of TEBA), tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate (TBAB), three octyl chloride, dodecyl trimethyl ammonium bromide, myristyl trimethyl ammonium chloride and the like. 所述季铵盐优选为四丁基溴化铵、四丁基氯化铵、四丁基硫酸氢铵、三辛基甲基氯化铵中的一种。 Preferably the quaternary ammonium salt is tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride of one.

[0012] 本发明还提供该用于制备羧酸乙烯酯的多相催化体系的使用方法,将羧酸、醋酸乙烯酯在多相催化体系作用下进行反应制备羧酸乙烯酯,所述羧酸与醋酸乙烯酯的摩尔比为1:3~15.5,所述多相催化剂体系中催化剂用量为羧酸质量的2.5-40%,反应温度为80-160°C,反应时间为6-48h。 [0012] The present invention further provides a method using heterogeneous catalytic systems of the carboxylic acid vinyl esters for the carboxylic acid, vinyl acetate, vinyl carboxylate prepared in a reaction system under the action of heterogeneous catalysis, the carboxylic acid the molar ratio of vinyl acetate is from 1: 3 to 15.5, the heterogeneous catalyst system in the catalyst in an amount of 2.5-40% by mass of a carboxylic acid, the reaction temperature is 80-160 ° C, the reaction time is 6-48h.

[0013] 在本发明的方法中可使用本领域已知的各种羧酸形成相应的乙烯基酯。 [0013] The corresponding vinyl esters may be formed using various carboxylic acids known in the art in the process of the present invention. 适用于本发明的所述羧酸可包括但不限于如下羧酸:2_乙基己酸、苯甲酸、新癸酸、丙酸、丁酸、戊酸、 庚酸、丙烯酸、甲基丙烯酸、三氟醋酸、月桂酸、硬脂酸和棕榈酸。 Useful in the present invention the carboxylic acid may include, but are not limited to a carboxylic acid: 2_ ethylhexanoic acid, benzoic acid, neodecanoic acid, propionic acid, butyric acid, valeric acid, heptanoic acid, acrylic acid, methacrylic acid, trifluoroacetic acid, lauric acid, stearic acid and palmitic acid. 所述羧酸优选为2-乙基己酸、新癸酸、三氟醋酸、丁酸、棕榈酸、苯甲酸、庚酸、硬脂酸中的一种。 The carboxylic acid is preferably 2-ethylhexanoic acid, neodecanoic acid, trifluoroacetic acid, butyric acid, palmitic acid, benzoic acid, heptanoic acid, stearic of one.

[0014] 本发明用于制备羧酸乙烯酯的多相催化体系以钯碳催化剂为主体,以碱金属卤化物和季铵盐中的至少一种为催化剂助剂,共同组成催化体系。 [0014] The present invention heterogeneous catalytic systems for the preparation of vinyl carboxylates palladium carbon catalyst as the main catalyst at least one alkali metal halide and quaternary ammonium salts aid in the common composition of the catalyst system. 该多相催化体系用于制备羧酸乙烯酯,得到含有相应羧酸乙烯酯的反应液,冷却后过滤分离出钯碳催化剂,可重复使用;微量的催化剂助剂溶于反应液,具有工艺简单,设备投资少,反应条件温和,能耗物耗低等优点,能有效地降低生产成本,羧酸乙烯酯的收率高,生产过程安全环保。 The heterogeneous catalytic systems for preparing vinyl carboxylate, to obtain a reaction liquid containing the corresponding vinyl carboxylates, palladium on carbon catalyst was separated by filtration after cooling, can be reused; minor amounts of auxiliary catalyst dissolved in the reaction solution, having a simple process , less investment in equipment, mild reaction conditions, and low energy and material consumption, can effectively reduce the production cost, a carboxylic acid vinyl ester yield, process safety and environmental protection.

[0015] 反应式如下: [0015] The reaction is as follows:

Figure CN106215957AD00041

[0017]本发明中碱金属卤化物加入的形式包含但不限于直接添加或者通过浸渍等方法负载到钯碳催化剂上。 [0017] In the present invention, the alkali metal halide is added in the form including but not limited to the direct addition or supported palladium on carbon catalyst is prepared by dipping method. 其中,碱金属卤化物通过浸渍加入到催化体系的方法为:反应瓶中加入钯碳催化剂,碱金属卤化物,高纯水,在一定温度下搅拌浸渍,过滤后150°C下干燥得到Pd/C-碱金属卤化物催化剂。 Wherein the alkali metal halide is added to a catalyst system by impregnation method: The reaction flask was added palladium on carbon catalyst, alkali metal halide, high-pure water, immersed stirred at a certain temperature, filtered and dried to give Pd at 150 ° C / C- an alkali metal halide catalyst. 其中碱金属卤化物为钯碳催化剂质量的10%-50%,高纯水为钯碳催化剂质量的300 %-500%,浸渍温度为20°C_100°C,浸渍时间为2h-10h。 Wherein the alkali metal halide is 10-50% by mass of palladium on carbon catalyst and high water 300% -500% palladium carbon catalyst mass, the immersion temperature is 20 ° C_100 ° C, the immersion time of 2h-10h. 浸渍后过滤干燥,得到Pd/C-碱金属卤化物催化剂。 After impregnation was filtered and dried to give Pd / C- alkali metal halide catalyst.

[0018]与现有技术相比,本发明具有以下优点: [0018] Compared with the prior art, the present invention has the following advantages:

[0019] 1、收率高,本发明的多相催化体系用于羧酸和醋酸乙烯酯制备羧酸乙烯酯时,反应转化率在70 %以上,最高为95 %,选择性在95 %以上,最高为99 % ; [0019] 1, high yield, the present invention heterogeneous catalytic systems for acid and vinyl acetate vinyl carboxylate is prepared, the reaction conversion rate of 70% or more, up to 95%, more than 95% selectivity , up 99%;

[0020] 2、工艺简单,催化体系易分离,该多相催化体系用于制备羧酸乙烯酯,反应液经冷却后过滤分离出钯碳催化剂,可重复使用,微量的催化剂助剂溶于反应液,简化了分离过程; [0020] 2, the process is simple, and easy separation of the catalytic system, the heterogeneous catalytic systems for the preparation of vinyl carboxylate, the reaction liquid was separated by filtration after cooling the palladium on carbon catalyst, can be reused, a trace amount of catalyst promoter is dissolved in the reaction liquid separation process is simplified;

[0021] 3、成本低,本发明的钯碳催化剂、碱金属卤化物和季铵盐原料易得,显著降低了生产成本; [0021] 3, low cost, palladium on carbon catalyst of the present invention, alkali metal halides and quaternary ammonium salts easily available raw materials, significantly reducing the production cost;

[0022] 4、安全环保,本发明的多相催化体系用于羧酸和醋酸乙烯酯制备羧酸乙烯酯时, 稳定性高,无钯黑析出,钯金属流失很少,具有高效,绿色环保的优点。 [0022] 4, safety and environmental protection, heterogeneous catalytic systems of the present invention is used for the preparation of carboxylic acids and carboxylic acid vinyl acetate vinyl acetate, high stability, no precipitate palladium black, palladium metal loss small, highly efficient, green The advantages.

具体实施方式 Detailed ways

[0023]本发明所用的原料羧酸和醋酸乙烯酯为工业级,钯碳催化剂,碱金属卤化物,季铵盐均可市售取得。 [0023] The carboxylic acid starting material used in the present invention and a commercial grade vinyl acetate, palladium on carbon, alkali metal halides, quaternary ammonium salts can be made commercially available. 反应液各物质的浓度用气相色谱仪进行定量分析。 Quantitative analysis of the concentration of each substance was subjected to the reaction by gas chromatography. 所用气相色谱仪为安捷伦GC7890型气相色谱仪,采用面积归一法进行定量。 The gas chromatography Agilent GC7890 Gas Chromatograph, using an area normalization method was quantified.

[0024]下面结合具体实施例对本发明的方法作进一步详细地说明,以下实例仅仅是进一步说明本发明,并不是限制本发明保护的范围。 [0024] The following embodiments in conjunction with the specific embodiments of the method of the present invention will be further described in detail, the following examples are merely to further illustrate the present invention, not to limit the scope of the present invention.

[0025] 实施例1 [0025] Example 1

[0026] 向反应瓶中加入5g 2-乙基己酸(0.035mol),50ml醋酸乙烯酯(0.54mol),钯质量百分含量5%的钯碳催化剂lg,0.4g氯化钠,加热到反应温度80°C,反应12小时后,停止反应,冷却后分离出钯碳催化剂,反应液进行色谱分析定量。 [0026] Add 5g 2- ethylhexanoate (0.035mol), 50ml vinyl acetate (0.54 mol), palladium mass percentage of 5% palladium carbon catalyst lg reaction flask, 0.4 g of sodium chloride and heated to the reaction temperature is 80 ° C, after 12 hours, the reaction was stopped, the separation of palladium on carbon catalyst after cooling the reaction liquid chromatographic quantitative analysis. 反应转化率为70%,选择性为98% 〇 The reaction conversion was 70% and the selectivity was 98% square

[0027] 实施例2 [0027] Example 2

[0028]向反应瓶中加入10g新癸酸(0.058mol),50ml醋酸乙稀酯(0.54mol),钯质量百分含量10%的钯碳催化剂2g,0.5g氯化锂,加热到反应温度140 °C,反应48小时后,停止反应, 冷却后分离出钯碳催化剂,反应液进行色谱分析定量。 [0028] neodecanoate was added 10g (0.058 mol) to the reaction flask, 50ml of acetic acid ethylene ester (0.54 mol), palladium mass percentage of 10% palladium on carbon catalyst 2g, 0.5g of lithium chloride and heated to the reaction temperature 140 ° C, after 48 hours, the reaction was stopped, the separation of palladium on carbon catalyst after cooling the reaction liquid chromatographic quantitative analysis. 反应转化率为85%,选择性为96%。 The reaction conversion rate was 85% and the selectivity was 96%. [0029] 实施例3 [0029] Example 3

[0030]向反应瓶中加入20g三氟醋酸(0.175mol),50ml醋酸乙烯酯(0.54mol),钯质量百分含量5 %的钯碳催化剂0.5g,0.5g碘化钾,加热到反应温度80 °C,反应20小时后,停止反应,冷却后分离出钯碳催化剂,反应液进行色谱分析定量。 [0030] The trifluoroacetic acid was added 20g (0.175 mol) to the reaction flask, 50ml vinyl acetate (0.54 mol), mass percent palladium content of 5% palladium on carbon catalyst 0.5g, 0.5g of potassium iodide, to the reaction temperature 80 ° C, will be 20 hours, the reaction was stopped, the separation of palladium on carbon catalyst after cooling the reaction liquid chromatographic quantitative analysis. 反应转化率为82%,选择性为99% 〇 The reaction conversion was 82%, selectivity 99% square

[0031] 实施例4 [0031] Example 4

[0032]向反应瓶中加入5g 丁酸(0.056mol),50ml醋酸乙烯酯(0.54mol),钯质量百分含量10%的钯碳催化剂2g,0. lg溴化钾,加热到反应温度160°C,反应10小时后,停止反应,冷却后分离出钯碳催化剂,反应液进行色谱分析定量。 [0032] butyric acid was added 5g (0.056 mol) to the reaction flask, 50ml vinyl acetate (0.54 mol), palladium mass percentage of 10% palladium on carbon catalyst 2g, 0. Lg of potassium bromide, the reaction was heated to a temperature of 160 ° C, after 10 hours of reaction, the reaction was stopped, the separation of palladium on carbon catalyst after cooling the reaction liquid chromatographic quantitative analysis. 反应转化率为86 %,选择性为99 %。 The reaction conversion was 86% and a selectivity of 99%.

[0033] 实施例5 [0033] Example 5

[0034] 向反应瓶中加入15g棕榈酸(0.058mol),50ml醋酸乙烯酯(0.54mol),钯质量百分含量3.5 %的钯碳催化剂lg,0.2g氟化钠,0.2g四丁基氯化铵,加热到反应温度60°C,反应6 小时后,停止反应,冷却后分离出钯碳催化剂,反应液进行色谱分析定量。 [0034] palmitic acid was added 15g (0.058 mol) to the reaction flask, 50ml vinyl acetate (0.54mol), palladium mass percentage of 3.5% palladium on carbon catalyst lg, 0.2g sodium, 0.2g tetrabutylammonium chloride ammonium hydroxide, heated to the reaction temperature of 60 ° C, after 6 hours, the reaction was stopped, the separation of palladium on carbon catalyst after cooling the reaction liquid chromatographic quantitative analysis. 反应转化率为78%,选择性为95 %。 The reaction conversion was 78%, selectivity of 95%.

[0035] 实施例6 [0035] Example 6

[0036] 向反应瓶中加入20g苯甲酸(0.163mol),50ml醋酸乙烯酯(0.54mol),钯质量百分含量5 %的钯碳催化剂0.5g,0.2g氟化钾,加热到反应温度120°C,反应20小时后,停止反应, 冷却后分离出钯碳催化剂,反应液进行色谱分析定量。 [0036] benzoic acid was added 20g (0.163 mol) to the reaction flask, 50ml vinyl acetate (0.54 mol), mass percent palladium content of 5% palladium on carbon catalyst 0.5g, 0.2g of potassium fluoride, heated to the reaction temperature of 120 ° C, after 20 hours, the reaction was stopped, the separation of palladium on carbon catalyst after cooling the reaction liquid chromatographic quantitative analysis. 反应转化率为95%,选择性为99%。 The reaction conversion was 95% and the selectivity 99%. [0037] 实施例7 [0037] Example 7

[0038]向反应瓶中加入20g庚酸(0.152mol),50ml醋酸乙烯酯(0.54mol),钯质量百分含量10 %的钯碳催化剂1 g,三辛基甲基氯化铵0.4g,加热到反应温度120 °C,反应15小时后,停止反应,冷却后分离出钯碳催化剂,反应液进行色谱分析定量。 [0038] heptanoic acid was added 20g (0.152 mol) to the reaction flask, 50ml vinyl acetate (0.54mol), palladium mass percentage of 10% palladium on carbon catalyst 1 g, trioctylmethylammonium chloride 0.4g, the reaction was heated to a temperature of 120 ° C, after 15 hours of reaction, the reaction was stopped, the separation of palladium on carbon catalyst after cooling the reaction liquid chromatographic quantitative analysis. 反应转化率为90 %,选择性为98 %。 The reaction conversion was 90% and a selectivity of 98%.

[0039] 实施例8 [0039] Example 8

[0040]向反应瓶中加入10g硬脂酸(0.035mol),50ml醋酸乙稀酯(0.54mol),lg钯质量百分含量1 〇%的Pd/C,0.2g四丁基溴化铵,加热到反应温度120°C,反应12小时后,停止反应, 冷却后分离出钯碳催化剂,反应液进行色谱分析定量。 [0040] The stearic acid was added 10g (0.035mol), 50ml acetic acid ethylene ester (0.54 mol), palladium LG mass percentage of 1 billion% Pd / C added to the reaction flask, 0.2g of tetrabutylammonium bromide, the reaction was heated to a temperature of 120 ° C, after 12 hours, the reaction was stopped, the separation of palladium on carbon catalyst after cooling the reaction liquid chromatographic quantitative analysis. 反应转化率为88%,选择性为99%。 The reaction conversion was 88% and a selectivity of 99%.

[0041] 对比例1 [0041] Comparative Example 1

[0042] 向反应釜(瓶)中加入5g苯甲酸(0.040mol),50ml醋酸乙烯酯(0.54mol),钯质量百分含量5%的钯碳催化剂0.5g,加热到反应温度80°C,反应10小时后,停止反应,冷却后分离出钯碳催化剂,反应液进行色谱分析定量。 [0042] benzoic acid was added 5g (0.040mol), 50ml vinyl acetate (0.54 mol), palladium mass percentage of 5% palladium carbon catalyst 0.5g to reactor (flask) and heated to the reaction temperature of 80 ° C, after 10 hours, the reaction was stopped, the separation of palladium on carbon catalyst after cooling the reaction liquid chromatographic quantitative analysis. 反应转化率为5%,选择性为98%。 The reaction conversion rate of 5% and a selectivity of 98%.

[0043] 对比例2 [0043] Comparative Example 2

[0044] 向反应釜(瓶)中加入5g苯甲酸(0.040mol),50ml醋酸乙烯酯(0.54mol),钯质量百分含量10%的钯碳催化剂lg,加热到反应温度120°c,反应48小时后,停止反应,冷却后分离出钯碳催化剂,反应液进行色谱分析定量。 [0044] was added to the kettle (flask) benzoic acid in 5g (0.040mol), 50ml vinyl acetate (0.54mol), palladium mass percentage of 10% palladium on carbon catalyst lg, heated to the reaction temperature of 120 ° c, the reaction after 48 hours, the reaction was stopped, palladium on carbon catalyst is separated after cooling, the reaction liquid chromatographic quantitative analysis. 反应转化率为15%,选择性为96%。 The reaction conversion rate was 15% and the selectivity was 96%.

Claims (5)

1. 一种用于制备羧酸乙烯酯的多相催化体系,包括催化剂和催化剂助剂,其特征在于, 所述催化剂为钯质量百分含量为3.5%-10%的钯碳催化剂,所述催化剂助剂为碱金属卤化物和季铵盐中的至少一种,所述催化剂与催化剂助剂质量比为0.5-5:1。 A heterogeneous catalytic systems for the preparation of vinyl carboxylate, and a catalyst promoter comprising a catalyst, wherein the catalyst is a palladium content of 3.5% by mass percentage of 10% palladium on carbon catalyst, the catalyst promoter is at least one alkali metal halide and a quaternary ammonium salt, the catalyst and catalyst promoter mass ratio of 0.5 to 5: 1.
2. 根据权利要求1所述的用于制备羧酸乙烯酯的多相催化体系,其特征在于所述碱金属卤化物为氯化钠、氯化钾、氟化钾、氟化钠、溴化钾、碘化钾中的一种。 The heterogeneous catalytic systems for preparing the vinyl carboxylate according to claim 1, wherein said alkali metal halide is sodium chloride, potassium chloride, potassium fluoride, sodium fluoride, bromide potassium, a potassium iodide.
3. 根据权利要求1所述的用于制备羧酸乙烯酯的多相催化体系,其特征在于所述季铵盐为四丁基溴化铵、四丁基氯化铵、四丁基硫酸氢铵、三辛基甲基氯化铵中的一种。 The heterogeneous catalytic systems for preparing the vinyl carboxylate according to claim 1, wherein said quaternary ammonium salt is tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate ammonium, trioctyl methyl ammonium chloride one.
4. 权利要求1所述的用于制备羧酸乙烯酯的多相催化体系的使用方法,其特征在于将羧酸、醋酸乙烯酯在多相催化体系作用下进行反应制备羧酸乙烯酯,所述羧酸与醋酸乙烯酯的摩尔比为1:3~15.5,所述多相催化剂体系中催化剂用量为羧酸质量的2.5-40%,反应温度为80-160°(:,反应时间为6-4811。 The method of heterogeneous catalytic systems used for preparing the vinyl carboxylate according to claim 1, wherein the carboxylic acid, vinyl acetate, vinyl ester prepared by reacting a carboxylic acid ester Under the effect of heterogeneous catalysis, the said molar ratio of carboxylic acid and vinyl acetate is from 1: 3 to 15.5, the heterogeneous catalyst system in the catalyst in an amount of 2.5-40% by mass of a carboxylic acid, the reaction temperature is 80-160 ° (:, the reaction time was 6 -4811.
5. 根据权利要求4所述的用于制备羧酸乙烯酯的多相催化体系的使用方法,其特征在于所述羧酸为2-乙基己酸、新癸酸、三氟醋酸、丁酸、棕榈酸、苯甲酸、庚酸、硬脂酸中的一种。 The use of heterogeneous catalytic systems for the preparation of vinyl carboxylate according to claim 4, wherein said carboxylic acid is 2-ethylhexanoic acid, neodecanoic acid, trifluoroacetic acid, butyric acid , palmitic acid, benzoic acid, heptanoic acid, stearic of one.
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WO1999059952A1 (en) * 1998-05-15 1999-11-25 Research Triangle Institute Method of preparing alkyl carboxylic acids by carboxylation of lower alkanes methane
CN102643263A (en) * 2012-04-26 2012-08-22 陕西师范大学 Method for preparing glycerol carbonate by liquid-phase oxidation and carbonylation of glycerol
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WO1999059952A1 (en) * 1998-05-15 1999-11-25 Research Triangle Institute Method of preparing alkyl carboxylic acids by carboxylation of lower alkanes methane
CN103025702A (en) * 2010-05-04 2013-04-03 塞拉尼斯国际公司 Process for the continuous transvinylation of carboxylic acids with vinyl acetate
CN102643263A (en) * 2012-04-26 2012-08-22 陕西师范大学 Method for preparing glycerol carbonate by liquid-phase oxidation and carbonylation of glycerol

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