CN109503369A - A kind of preparation method of M-phthalic acid - Google Patents
A kind of preparation method of M-phthalic acid Download PDFInfo
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- CN109503369A CN109503369A CN201811549562.6A CN201811549562A CN109503369A CN 109503369 A CN109503369 A CN 109503369A CN 201811549562 A CN201811549562 A CN 201811549562A CN 109503369 A CN109503369 A CN 109503369A
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- oxidation reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/34—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with ozone; by hydrolysis of ozonides
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Abstract
The invention discloses a kind of preparation methods of M-phthalic acid.The preparation method includes the following steps: meta-xylene carrying out oxidation reaction；Wherein, the oxidant of the oxidation reaction is ozone, and the oxidation reaction carries out under ultraviolet light, and the oxidation reaction carries out in the absence of a solvent.Preparation method of the invention has low energy consumption, and greenhouse gas emission is few, the small feature of equipment investment.
Description
Technical field
The present invention relates to a kind of preparation methods of M-phthalic acid.
Background technique
M-phthalic acid (Iso-phthalic Acid, IPA) is a kind of faster organic chemical industry's intermediate feed of development,
It is mainly used as the modified monomer of PET resin, to improve the processing and product properties of PET resin；It is high-strength for replacing phthalic anhydride to produce
Spend unsaturated-resin resistant to chemical etching；Instead of the alkyd resin of phthalic anhydride production high-performance high solids content.IPA has been obtained in foreign countries
It is widely applied, development prospect is good, and many major companies are prepared for expanding production capacity and creating IPA device.With device
The continuous expansion of scale, cost will be reduced constantly, and application field and the market share will constantly expand.The application of China IPA is
There is certain basis, is applied at present in bottle grade PET resin and polyester cation-dyeable fiber, unsaturated-resin, alkyd resin top grade
Material field all has application, but its source depends on import, and therefore, IPA is wide in China's exploitation prospect.
Industrial MX (meta-xylene) high-temperature S removal process uses Co-Mn-Br three-component compound system for oxidant,
200 DEG C, under 1.5MPa, using Acetic Acid-Water as solvent, air is bubbled in kettle in stirring and carries out as oxidant.Due to reaction temperature
Height, decarboxylic reaction or solvent burning are serious, lead to big energy consumption, high production cost and a large amount of global warming gas of discharge
(CO2), and environmental pollution is serious.Corrosion in order to avoid acetic acid and bromide ion to equipment, reaction kettle need to use titanium alloy,
This more increases the investment of cost.So purifying is mass produced there is an urgent need to develop a kind of alternative techniques of green
IPA reduces energy consumption, solves the problems, such as these correlations, protects environment.
Summary of the invention
The present invention is practical, and the technical problem to be solved is that produce the energy in M-phthalic acid in the prior art to overcome
The defects of consumption is big, greenhouse gas emission is more, equipment corrosion, provides a kind of preparation method of M-phthalic acid.Of the invention
Preparation method has low energy consumption, and greenhouse gas emission is few, the small feature of equipment investment.
The present invention solves above-mentioned technical problem by the following technical programs.
The present invention provides a kind of preparation methods of M-phthalic acid comprising following steps: meta-xylene is carried out oxygen
Change reaction；Wherein, the oxidant of the oxidation reaction is ozone, and the oxidation reaction carries out under ultraviolet light, institute
Oxidation reaction is stated to carry out in the absence of a solvent.
In the present invention, particular determination is not done to the dosage of the oxidant, can be realized oxidation reaction, it is described between two
The molar ratio of toluene and the oxidant can be to be conventional, and may be, for example, (0.8-1): (2-40) can also be 1:(2-10), and can be
1:(3-4).
In the present invention, to carry out the oxidation reaction sufficiently, preferably, being continuously added into institute in the oxidation reaction process
Oxidant is stated, while persistently carrying out ultraviolet light.
In the present invention, the adding manner of the oxidant can be conventional, such as ozone can be passed through in reaction system, institute
The flow velocity that is passed through for stating ozone can be 20-100mL/min, can also be 30-40mL/min.
In the present invention, the wave-length coverage that " ultraviolet light " is covered as known to those skilled in the art may be, for example, 10-400nm,
It can be also 100-320nm, and can be 310nm.
In the present invention, particular determination is not done to the intensity of the ultraviolet light, as long as being able to achieve oxidation reaction, such as institute
The intensity for stating ultraviolet light can be 1-2000mW/cm2, can also be 100-1000mW/cm2, and can be 200mW/cm2。
In the present invention, particular determination is not done to the temperature of the oxidation reaction, if it is able to achieve oxidation reaction, such as
The temperature of the oxidation reaction can be 0-100 DEG C, can also be 20-40 DEG C, and can be room temperature (20-30 DEG C, such as 25 DEG C).
In the present invention, particular determination is not done to the time of the oxidation reaction, if it is able to achieve oxidation reaction, such as
The time of the oxidation reaction can be 1-60h, can be also 10-40h, and can be 20h.
In the present invention, after the oxidation reaction, it can be filtered and dry.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
Preparation method of the invention has low energy consumption, and greenhouse gas emission is few, the small feature of equipment investment.
Detailed description of the invention
Fig. 1 is the HPLC map for the reaction product that the embodiment of the present invention 1 obtains.
Fig. 2 is the HPLC map for the reaction product that comparative example 1 of the present invention obtains.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
The substance detection of product is surveyed using high-efficient liquid phase chromatogram technique analysis after following embodiment and comparative example reaction of the present invention
Examination, specific instrument and test condition are as follows:
HPLC detection method uses 1120 high performance liquid chromatograph of U.S. Agilent, autosampler, Agilent
1120 type UV/Vis detectors, 2 data processing system of Empower.
Chromatographic condition:
Chromatographic column: Agilent TC-C18 chromatographic column (4.6 × 250mm, 5 μm)；Mobile phase A is 100% acetonitrile, mobile phase
B is+83% water of 17% methanol；Condition of gradient elution: A is from 30% to 100% when 0~20min, and B is from 100% when 20~25min
To 30%, B is from 70% to 0% when 0~20min, and B is from 0% to 70% when 20~25min；Flow velocity: 1mLmin-1；Column temperature: 30
℃；Detection wavelength: 260nm；Sample volume: 20 μ L.
The map obtained for above-mentioned detection method is done as described below:
Firstly, the absorption peak area of different material in product is measured by the standard curve for making different material in experiment, it is right
It should can calculate the concentration of different material.Since the absorption intensity of every kind of substance is different, corresponding absorption peak area is also just different.
Therefore, the peak area size of different material can not directly judge how much is content.
In addition, in the embodiment of the present invention and comparative example, the yield of IPA according to calculation commonly used in the art into
Row, specifically: MX concentration in concentration/raw material of IPA in yield=product.It should be noted that the concentration of IPA refers in product
Concentration in liquid-phase chromatographic analysis, after being configured to sample needed for liquid phase detects.
Embodiment 1
60mLMX (meta-xylene) is added in 100mL round-bottomed flask, with six leaf turbine stirring paddle stirrings, ozone is bubbled logical
Enter in reaction system, ozone flow velocity is 20mL/min, and holding pressure is normal pressure, and temperature is 25 DEG C of room temperature, ultraviolet light prolonged exposure
20h is reacted, ultraviolet lamp power is 100W (200mW/cm2, 310nm).After reaction, measuring meta-xylene surplus is
0.095mol generates M-phthalic acid 0.151mol.The present embodiment meta-xylene conversion ratio is 80%, and M-phthalic acid yield is
30%.
The HPLC map of the present embodiment product after reaction is shown in Fig. 1.The M-phthalic acid main peak under above-mentioned testing conditions
Retention time be 5.3min or so, the retention time of carboxyl benzaldehyde main peak is 6.5min or so, m-methyl benzoic acid master
The retention time at peak is 9.5min or so, and the retention time of tolyl aldehyde main peak is 11.4min or so, meta-xylene main peak
Retention time be 16.8min or so, specifically see Fig. 1.Wherein, peak 1- M-phthalic acid, carboxyl benzaldehyde between peak 2-, peak 3-
Benzoic acid, peak 4- m-methyl benzoic acid, tolyl aldehyde between peak 5-, peak 6- meta-xylene.
Embodiment 2
60mLMX (meta-xylene) is added in 100mL round-bottomed flask, with six leaf turbine stirring paddle stirrings, ozone is bubbled logical
Enter in reaction system, ozone flow velocity is 30mL/min, and holding pressure is normal pressure, and temperature is 100 DEG C, the reaction of ultraviolet light prolonged exposure
60h, ultraviolet lamp power are 1W (1mW/cm2, 220nm).After reaction, measuring meta-xylene surplus is 0.402mol, raw
At M-phthalic acid 0.032mol.The present embodiment meta-xylene conversion ratio is 17.45%, and M-phthalic acid yield is 6.57%.
Embodiment 3
60mLMX (meta-xylene) is added in 100mL round-bottomed flask, with six leaf turbine stirring paddle stirrings, ozone is bubbled logical
Enter in reaction system, ozone flow velocity is 40mL/min, and holding pressure is normal pressure, and temperature is 0 DEG C, the reaction of ultraviolet light prolonged exposure
40h, ultraviolet lamp power are 100W (2000mW/cm2, 110nm).After reaction, measuring meta-xylene surplus is
0.243mol generates M-phthalic acid 0.071mol.The present embodiment meta-xylene conversion ratio is 50.1%, M-phthalic acid yield
It is 14.5%.
Embodiment 4
60mLMX (meta-xylene) is added in 100mL round-bottomed flask, with six leaf turbine stirring paddle stirrings, ozone is bubbled logical
Enter in reaction system, ozone flow velocity is 100mL/min, and holding pressure is normal pressure, and temperature is 40 DEG C, the reaction of ultraviolet light prolonged exposure
1h, ultraviolet lamp power are 100W (1000mW/cm2, 10nm).After reaction, measuring meta-xylene surplus is 0.225mol,
Generate M-phthalic acid 0.084mol.The present embodiment meta-xylene conversion ratio is 53.8%, and M-phthalic acid yield is 17.2%.
Embodiment 5
60mLMX is added in 100mL round-bottomed flask, with six leaf turbine stirring paddle stirrings, ozone is bubbled into solution,
Ozone flow velocity is 20mL/min, and holding pressure is normal pressure, and temperature is 100 DEG C, ultraviolet light prolonged exposure 60h, and ultraviolet lamp power is
100W(1000mW/cm2, 220nm).After reaction, meta-xylene surplus is 0.147mol, and M-phthalic acid content is
0.103mol, meta-xylene conversion ratio are 69.81%, and M-phthalic acid yield is 21.15%.
The HPLC map that above embodiments 2-5 is measured is close with embodiment 1.
Comparative example 1
60mLMX (meta-xylene) is added in 100mL round-bottomed flask, with six leaf turbine stirring paddle stirrings, ozone is bubbled logical
Enter in reaction system, ozone flow velocity is 100mL/min, and holding pressure is normal pressure, and temperature is 25 DEG C, reacts 20h in dark, reacts
After, measuring meta-xylene surplus is 0.401mol, generates M-phthalic acid 0mol.The present embodiment meta-xylene conversion ratio
It is 17.6%, M-phthalic acid yield is 0%.HPLC map after reaction is shown in Fig. 2, wherein there is meta-xylene (MX)
Chromatographic peak, but do not occur the chromatographic peak of M-phthalic acid.
Comparative example 2
60mLMX (meta-xylene) is added in 100mL round-bottomed flask, with six leaf turbine stirring paddle stirrings, bubble oxygen is logical
Enter in reaction system, oxygen gas flow rate 100mL/min, holding pressure is normal pressure, and temperature is 25 DEG C, the reaction of ultraviolet light prolonged exposure
60h, ultraviolet lamp power are 100W (1000mW/cm2, 310nm).After reaction, measuring meta-xylene surplus is
0.483mol generates M-phthalic acid 0mol.The present embodiment meta-xylene conversion ratio is 0.82%, and M-phthalic acid yield is
0%.
Comparative example 3
Under not ultraviolet irradiation, using ozone as oxidant, the oxidation reaction of meta-xylene is hardly happened, and is not examined
The generation of M-phthalic acid is measured, only minimal amount of m-methyl benzoic acid generates.
Although specific embodiments of the present invention have been described above, it will be appreciated by those of skill in the art that this is only
For example, protection scope of the present invention is to be defined by the appended claims.Those skilled in the art without departing substantially from
Under the premise of the principle and substance of the present invention, many changes and modifications may be made, but these change and
Modification each falls within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of M-phthalic acid, which is characterized in that it includes the following steps: to carry out meta-xylene to aoxidize anti-
It should；Wherein, the oxidant of the oxidation reaction is ozone, and the oxidation reaction carries out under ultraviolet light, the oxygen
Change reaction to carry out in the absence of a solvent.
2. preparation method as described in claim 1, which is characterized in that the molar ratio of the meta-xylene and the oxidant is
(0.8-1): (2-40).
3. preparation method as described in claim 1, which is characterized in that the molar ratio of the meta-xylene and the oxidant is
1:(2-10), preferably 1:(3-4).
4. preparation method as described in claim 1, which is characterized in that be continuously added into the oxidation in the oxidation reaction process
Agent, while persistently carrying out ultraviolet light.
5. preparation method as described in claim 1, which is characterized in that the adding manner of the oxidant is to be passed through ozone instead
It answers in system.
6. preparation method as claimed in claim 5, which is characterized in that the flow velocity that is passed through of the ozone is 20-100mL/min,
Preferably 30-40mL/min.
7. preparation method as described in claim 1, which is characterized in that the wavelength of the ultraviolet light is 10-400nm；
The intensity of the ultraviolet light is 1-2000mW/cm2；
The temperature of the oxidation reaction is 0-100 DEG C；
And/or the time of the oxidation reaction is 1-60h.
8. preparation method as described in claim 1, which is characterized in that the wavelength of the ultraviolet light is 100-320nm；
The intensity of the ultraviolet light is 100-1000mW/cm2；
The temperature of the oxidation reaction is 20-40 DEG C；
And/or the time of the oxidation reaction is 10-40h.
9. preparation method as described in claim 1, which is characterized in that the wavelength of the ultraviolet light is 310nm；
The intensity of the ultraviolet light is 200mW/cm2；
The temperature of the oxidation reaction is 25 DEG C；
And/or the time of the oxidation reaction is 20h.
10. preparation method as described in claim 1, which is characterized in that be filtered and dry after the oxidation reaction.
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| CN201811549562.6A CN109503369A (en) | 2018-12-18 | 2018-12-18 | A kind of preparation method of M-phthalic acid |
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| CN201811549562.6A CN109503369A (en) | 2018-12-18 | 2018-12-18 | A kind of preparation method of M-phthalic acid |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1429471A (en) * | 1970-12-29 | 1976-03-24 | Atlantic Richfield Co | Process for the production of phthalic acids |
| CN101704741A (en) * | 2009-11-06 | 2010-05-12 | 华东理工大学 | Process for producing isophthalic acid |
| CN103288592A (en) * | 2012-02-29 | 2013-09-11 | 中国石油化工股份有限公司 | Toluene oxidation method |
| CN105732356A (en) * | 2014-10-13 | 2016-07-06 | 黄国柱 | Method for preparing carboxylic acid or phenyl ketone by using ozone, singlet oxygen atom free radical or hydroxyl radical |
| CN106631761A (en) * | 2016-09-12 | 2017-05-10 | 华东理工大学 | Method for preparing benzoic acid by oxidizing methylbenzene at atmospheric pressure and low temperature |
-
2018
- 2018-12-18 CN CN201811549562.6A patent/CN109503369A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1429471A (en) * | 1970-12-29 | 1976-03-24 | Atlantic Richfield Co | Process for the production of phthalic acids |
| CN101704741A (en) * | 2009-11-06 | 2010-05-12 | 华东理工大学 | Process for producing isophthalic acid |
| CN103288592A (en) * | 2012-02-29 | 2013-09-11 | 中国石油化工股份有限公司 | Toluene oxidation method |
| CN105732356A (en) * | 2014-10-13 | 2016-07-06 | 黄国柱 | Method for preparing carboxylic acid or phenyl ketone by using ozone, singlet oxygen atom free radical or hydroxyl radical |
| CN106631761A (en) * | 2016-09-12 | 2017-05-10 | 华东理工大学 | Method for preparing benzoic acid by oxidizing methylbenzene at atmospheric pressure and low temperature |
Non-Patent Citations (2)
| Title |
|---|
| E. V. POTAPENKO, ET AL.: "Catalytic Oxidation of Toluene by Ozone in the Acetic Acid–Sulfuric Acid System", 《RUSSIAN JOURNAL OF APPLIED CHEMISTRY》 * |
| 赵志翔 等: "对二甲苯液相催化氧化新工艺", 《应用化工》 * |
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