CN104418748B - A kind of o-Xylene Oxidation in Liquid Phase is coupled with esterification and prepares the method for Bisphthalate - Google Patents

A kind of o-Xylene Oxidation in Liquid Phase is coupled with esterification and prepares the method for Bisphthalate Download PDF

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CN104418748B
CN104418748B CN201310374073.2A CN201310374073A CN104418748B CN 104418748 B CN104418748 B CN 104418748B CN 201310374073 A CN201310374073 A CN 201310374073A CN 104418748 B CN104418748 B CN 104418748B
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acid
reaction
esterification
bisphthalate
xylol
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CN104418748A (en
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徐杰
高进
黄义争
苗虹
马红
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/313—Preparation 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 doubly bound oxygen containing functional groups, e.g. carboxyl groups

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention relates to a kind of o-Xylene Oxidation in Liquid Phase to be coupled with esterification and to prepare the method for Bisphthalate.Under catalyzer existence condition, take air or oxygen as oxygen source, o-Xylene Oxidation in Liquid Phase is coupled with esterification and prepares Bisphthalate.The present invention has that reaction conditions gentleness, operational safety, raw material consumption and energy consumption are low, transformation efficiency and selectivity advantages of higher.

Description

A kind of o-Xylene Oxidation in Liquid Phase is coupled with esterification and prepares the method for Bisphthalate
Technical field
The present invention relates to a kind of o-Xylene Oxidation in Liquid Phase to be coupled with esterification and to prepare the method for Bisphthalate.
Background technology
Bisphthalate is important bulk chemical, main as rubber and plastics auxiliaries, its use be improve the product quality such as plastics, rubber and polyester must through approach, effect is to weaken polymer molecule intermolecular forces, increase the movability of molecular chain, reduce the crystallinity of molecular chain, thus improve the plasticity-of polymkeric substance, snappiness, stretchiness and processing characteristics.According to statistics, the annual consumption of global Bisphthalate reaches more than 6,000,000 tons.
The preparation method of current Bisphthalate first changes o-Xylol into phthalic anhydride by gas phase oxidation, then the phthalic anhydride obtained by separating-purifying and alcohol generation esterification obtain Bisphthalate.Wherein there is following shortcoming in gas phase oxidation of o-xylol phthalic anhydride process:
(1) reaction need be carried out under 300 ~ 450 DEG C of high temperature, and need through processes such as rectification under vacuum, crystallization, scraping blades after reaction, complicated operation, energy consumption is high;
(2) easily over oxidation or decarboxylation produce CO 2, raw material consumption is high, environmental influence is large;
(3) reaction is carried out in explosive range, poor stability;
Summary of the invention
In order to solve the subject matter such as raw material consumption and energy consumption is high, poor stability, complicated operation existed in current Bisphthalate preparation process, the object of the invention is: develop a kind of o-Xylene Oxidation in Liquid Phase and be coupled with esterification and prepare the method for Bisphthalate, by o-Xylol direct oxidation esterification, intermediate product directly reacts without separation, obtained product Bisphthalate, has following outstanding advantages:
(1) compared with vapour phase oxidation process, liquid phase oxidation reaction conditions is gentle, raw material consumption and energy consumption is low, security is good, significantly reduce CO 2generate and discharge;
(2) intermediate product does not need separating-purifying, and removes together with the water that generates of oxidising process and esterification process, and operation succinctly facilitates, and significantly can reduce energy consumption.
For achieving the above object, the technical solution used in the present invention is shown below:
In formula, R is C l ~ 18straight or branched alkyl, C 3 ~ 18cycloalkyl or C 6 ~ 18aryl.
In view of air or oxygen is cheap and easy to get, the present invention selects it to be that oxygen source is by o xylene oxidation.But, be that the reaction difficulty of oxygen source is very large with air or oxygen.In o-Xylol, first methyl ratio is easier to be oxidized to carboxyl (-COOH), but because of the strong sucting electronic effect of carboxyl, second methyl on phenyl ring is very difficult to be oxidized to carboxyl.Consider that ester group (-COOR) is more weak than the electron-withdrawing power of carboxyl, near the process that o-toluic acid ester is oxidized to phthalic monoester, to be oxidized to the process of phthalic acid easier for tolyl acid, o-Xylol main oxidation is first o-toluic acid by the present invention, there is esterification again and generate o-toluic acid ester, then phthalic monoester is oxidized to, esterification finally occurs and generates Bisphthalate, all intermediate products all directly react without separation.
Consider that o-Xylol is oxidized by free radical reaction course, and the transition metal salts such as Co, Mn likely accelerate the initiation of free radical reaction medium chain, thus the radical chain oxidizing reaction of catalysis o-Xylol, the acetate of preferred Co and Mn of the present invention or naphthenate mixture are catalyzer.Consider some bromide or basic metal, inductive phase that alkaline-earth metal, transition metal salt likely shorten reaction, the pilot process of accelerated reaction, the inorganic bromides such as the preferred Hydrogen bromide of the present invention, Sodium Bromide, the organic bromides such as tetrabromoethane, carbon tetrabromide, bromine salt, and one or more in the acetate of K, Mg, Ca, Ba, Cu, Fe, V, Zr, T, Ce etc., naphthenate or oxalate are as oxidation promoters.
According to the present invention, esterification process generates most important to the highly selective of product Bisphthalate.Consider that protonic acid or Lewis acid can be had an effect with carboxyl, make the carbon on carboxyl show positive polarity, be conducive to alcohol and nucleophilic attack is carried out to it, thus promote the carrying out of esterification, the mineral acids such as preferably sulfuric acid of the present invention, phosphoric acid, molecular sieve, heteropolyacid, solid super-strong acid, containing-COOH or-SO 3the organic acid of H group, and one or more in the titanic acid ester such as metatitanic acid four methyl esters, tetraethyl titanate, titanium isopropylate, tetrabutyl titanate are as esterifying catalyst.One or more in the described preferred acetic acid of acid containing-COOH group, trifluoroacetic acid, oxalic acid, hexanodioic acid ,-COOH functionalized ion liquid; Described containing-SO 3the preferred Phenylsulfonic acid of acid of H group, naphthene sulfonic acid, trifluoromethanesulfonic acid, alkylsulphonic acid, sulfonic acid ion exchange resin ,-SO 3one or more in H functionalized ion liquid.
According to the present invention, without under extra catalyst existence condition, to react the o-toluic acid of generation, phthalic acid or phthalic monoester from as catalyzer, at relatively high temperatures, esterification process also can carry out, and obtains to higher yields target product Bisphthalate.
According to the present invention, in order to make the mass transfer of conversion process carry out smoothly, adopt excessive alcohol to be solvent, or add described product before the reaction or intermediate product is solvent, reduce the viscosity of reaction system.
According to the present invention, the mol ratio of alcohol and o-Xylol preferably 2: 1 ~ 10: 1; When to add described product or intermediate product before reaction be solvent, the concentration of o-Xylol preferably 25 ~ 50%; Oxide catalyst cobalt or manganese ionic concn difference preferably 100 ~ 500ppm in the reactive mixture; Oxidation promoters metal ion in the reactive mixture or bromine concentration preferably 100 ~ 500ppm; Temperature of reaction preferably 150 ~ 230 DEG C; Oxygen or air pressure preferably 0.1 ~ 3MPa; The oxidizing reaction residence time preferably 0.5 ~ 2h; The mass ratio of esterifying catalyst and o-Xylol preferably 1: 1000 ~ 1: 100; The esterification residence time preferably 0.5 ~ 4h.
Embodiment
The following example contributes to understanding the present invention, but content of the present invention is not limited thereto.
Embodiment 1:
In continuous reaction apparatus, the mixture of o-Xylol, dimethyl phthalate, manganese acetate, Cobaltous diacetate, Potassium ethanoate to be pumped in oxidizing reaction pipe that (in reaction mixture, cobalt, manganese, potassium concentration are respectively 300ppm, o-Xylol concentration is 30%), be filled with 3MPa oxygen, be oxidized at 200 DEG C, reaction time is 2h.The mixture of mixture and methyl alcohol after oxidation is pumped into the esterification pipe that aluminium silicophosphate molecular sieve is housed, and (mol ratio of methyl alcohol and initial o-Xylol is 10: 1, the mass ratio of aluminium silicophosphate molecular sieve and initial o-Xylol is 1: l00), at 150 DEG C, esterification occurs, reaction time is 3h.After esterification, mixture pumps into by second methyl oxidation on phenyl ring in oxidizing reaction pipe, and then pumps in esterification pipe and carry out esterification.After reaction, mixture carries out gas-chromatography and liquid-phase chromatographic analysis, calculates the per pass conversion of o-Xylol and the selectivity of dimethyl phthalate respectively.
Embodiment 2 ~ 18:
The specific practice of embodiment 2 ~ 18 is similar to Example 1, concrete reaction conditions and the results are shown in table 1.
As can be seen from the above embodiments, with o-Xylol and alcohol for raw material, under reaction conditions shown in table 1, liquid-phase oxidation and esterification is adopted to be coupled, namely be first o-toluic acid by o-Xylol main oxidation, making it occur after esterification is carboxyl by second methyl oxidation on phenyl ring again, and then esterification occurs, and can realize process o-Xylol being converted into dimethyl phthalate.Temperature of reaction is 150 ~ 230 DEG C, compared with vapour phase oxidation process, and reaction conditions milder, and significantly reduce CO 2generate and discharge, raw material consumption and energy consumption is low, security is good; Intermediate product does not need separating-purifying, and operation succinctly facilitates, and significantly can reduce energy consumption.

Claims (4)

1. an o-Xylene Oxidation in Liquid Phase is coupled with esterification and prepares the method for Bisphthalate, it is characterized in that: under oxide catalyst existence condition, with one or both in air or oxygen for oxygen source, be coupled with esterification by o-Xylene Oxidation in Liquid Phase and prepare Bisphthalate, process and the intermediate product of reaction experience are as follows:
In formula, R is C 1 ~ 18straight or branched alkyl, C 3 ~ 18cycloalkyl or C 6 ~ 18aryl;
Described reaction for solvent, or adds described product or intermediate product is solvent with alcohol described in reaction formula before the reaction;
Described oxidizing reaction is with the acetate of Co and Mn or naphthenate mixture for catalyzer, and one or more adding in the acetate of bromide or K, Mg, Ca, Ba, Cu, Fe, V, Zr, Ti, Ce, naphthenate or oxalate are promotor;
Described esterification, or to be carried out for catalyzer with one or more in mineral acid, organic acid, titanic acid ester under without extra catalyst existence condition.
2. the method for claim 1, is characterized in that:
Described bromide is one or more in Hydrogen bromide, Sodium Bromide, tetrabromoethane, carbon tetrabromide, bromine salt;
Described mineral acid is one or more in sulfuric acid, phosphoric acid, inorganic solid acid;
Described organic acid is for containing-COOH or-SO 3one or more of H group acid;
Described titanic acid ester is one or more in metatitanic acid four methyl esters, tetraethyl titanate, titanium isopropylate, tetrabutyl titanate.
3. method as claimed in claim 2, is characterized in that:
Described inorganic solid acid is one or more in molecular sieve, heteropolyacid, solid super-strong acid;
The described acid containing-COOH group is one or more in acetic acid, trifluoroacetic acid, oxalic acid, hexanodioic acid ,-COOH functionalized ion liquid;
Described containing-SO 3the acid of H group is Phenylsulfonic acid, naphthene sulfonic acid, trifluoromethanesulfonic acid, alkylsulphonic acid, sulfonic acid ion exchange resin, band-SO 3one or more in H functionalized ion liquid.
4. the method as described in as arbitrary in claims 1 to 3, is characterized in that: the preferred 2:1 ~ 10:1 of mol ratio of alcohol and o-Xylol; When to add described product or intermediate product before reaction be solvent, the concentration of o-Xylol preferably 25 ~ 50%; Oxide catalyst cobalt or manganese ionic concn difference preferably 100 ~ 500ppm in the reactive mixture; Oxidation promoters metal ion in the reactive mixture or bromine concentration preferably 100 ~ 500ppm; Temperature of reaction preferably 150 ~ 230 DEG C; Oxygen or air pressure preferably 0.1 ~ 3MPa; The oxidizing reaction residence time preferably 0.5 ~ 2h; When using esterifying catalyst, the preferred 1:1000 ~ 1:100 of mass ratio of esterifying catalyst and o-Xylol; The esterification residence time preferably 0.5 ~ 4h.
CN201310374073.2A 2013-08-22 2013-08-22 A kind of o-Xylene Oxidation in Liquid Phase is coupled with esterification and prepares the method for Bisphthalate Active CN104418748B (en)

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CN106187750B (en) * 2015-05-06 2019-07-12 中国科学院大连化学物理研究所 A kind of method that dimethylbenzene liquid phase catalytic oxidation prepares phthalic acid
CN108993509B (en) * 2018-08-14 2020-05-15 宿州青果知识产权服务有限公司 Catalyst for improving synthesis conversion rate of dioctyl phthalate plasticizer
CN108997123B (en) * 2018-09-11 2021-04-09 山东元利科技股份有限公司 Method for synthesizing phthalate by catalytic oxidation product of o-xylene or naphthalene
CN109651269A (en) * 2019-01-28 2019-04-19 郭丽 A kind of preparation method of danshensu amide derivatives

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GB1191380A (en) * 1968-10-28 1970-05-13 Shell Int Research Process for the preparation of Diesters of 1,2-Dicarboxylic Acids
US4387243A (en) * 1979-06-20 1983-06-07 Standard Oil Company (Indiana) Continuous production of ortho-phthalic acid product by two-step catalytic neat oxidation of liquid ortho-xylene with air
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US2894978A (en) * 1956-07-02 1959-07-14 Chemische Werke Witten Gmbh Process of producing esters of phthalic acids by oxidation of xylene and toluic acid ester mixtures
GB1191380A (en) * 1968-10-28 1970-05-13 Shell Int Research Process for the preparation of Diesters of 1,2-Dicarboxylic Acids
US4387243A (en) * 1979-06-20 1983-06-07 Standard Oil Company (Indiana) Continuous production of ortho-phthalic acid product by two-step catalytic neat oxidation of liquid ortho-xylene with air
US5534652A (en) * 1994-10-18 1996-07-09 Exxon Chemical Patents Inc. (Ecpi) Preparation of plasticizer esters from phthalic anhydride residue
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