CN101857582A - Preparation method of 4-chlorophthalic anhydride - Google Patents
Preparation method of 4-chlorophthalic anhydride Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- BTTRMCQEPDPCPA-UHFFFAOYSA-N 4-chlorophthalic anhydride Chemical compound ClC1=CC=C2C(=O)OC(=O)C2=C1 BTTRMCQEPDPCPA-UHFFFAOYSA-N 0.000 title abstract 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000000047 product Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 20
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004821 distillation Methods 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- PGGASBAOLMMPHM-UHFFFAOYSA-N 5-chloro-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1=CC(Cl)CC2C(=O)OC(=O)C12 PGGASBAOLMMPHM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 10
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims abstract description 7
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- MWUSAETYTBNPDG-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OC(=O)C1=CC=C(Cl)C=C1 MWUSAETYTBNPDG-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 15
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000006254 arylation reaction Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000005899 aromatization reaction Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229950000688 phenothiazine Drugs 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 5
- -1 ether acid anhydride Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- NVLHGZIXTRYOKT-UHFFFAOYSA-N 1-chloro-2,3-dimethylbenzene Chemical group CC1=CC=CC(Cl)=C1C NVLHGZIXTRYOKT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- BCKVHOUUJMYIAN-UHFFFAOYSA-N 5-bromo-2-benzofuran-1,3-dione Chemical compound BrC1=CC=C2C(=O)OC(=O)C2=C1 BCKVHOUUJMYIAN-UHFFFAOYSA-N 0.000 description 1
- SACAJBLZMBDKLR-UHFFFAOYSA-N 7a-chloro-4,5-dihydro-3ah-2-benzofuran-1,3-dione Chemical compound C1=CCCC2C(=O)OC(=O)C21Cl SACAJBLZMBDKLR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 4-chlorophthalic anhydride, which belongs to the field of organic synthesis and is characterized by comprising the following steps: adding a small quantity of phenothiazine or diethylhydroxylamine to maleic anhydride and chloroprene for cyclization to obtain 4-chlorotetrahydrophthalic anhydride; then aromatizing the 4-chlorotetrahydrophthalic anhydride by using liquid bromine as an aromatization reagent, and carrying out reduced pressure distillation or activated carbon decoloring crystallization to obtain the 4-chlorophthalic anhydride. The total yield of the 4-chlorophthalic anhydride is increased to more than 85 percent and the purity thereof is increased to more than 99 percent. The invention avoids the problem of poor reaction selectivity in the traditional production method of the 4-chlorophthalic anhydride, and the whole process can be carried out under solvent-free conditions, and thereby, impurities introduced into the solvent in the reaction process is avoided; time-consuming and labor-consuming reduced pressure rectification is not needed, and thereby, the operation is simplified to a large extend. The invention has the advantages of few reaction byproducts, short process flow, high product yield and purity, mild condition, low cost and the like.
Description
Technical field
The present invention relates to a kind of preparation method of 4-chloro-benzoic anhydride, belong to the organic chemistry synthesis technical field.
Background technology
The 4-chloro-benzoic anhydride is a kind of of many uses, fine chemical product that added value is high, it is the main raw material of compounds such as preparation bibenzene tetracarboxylic dianhydride, diphenyl ether tetraformic dianhydride, diphenyl thio-ether tetrformate dianhydride, bis ether acid anhydride, with these compounds is that the polyimide engineering plastics that monomer prepares have better resistance to elevated temperatures and other specific function than equal benzene type polyimide engineering plastics, is mainly used in high and new technology fields such as Aeronautics and Astronautics, electronics, electromechanics.
At present, the method that kind more than 20 prepares the monochloro-benzene acid anhydride has been proposed both at home and abroad.Conclusion is got up, mainly containing of industrial application value arranged: the clorox chlorination process of phthalic anhydride (SU1004328, spy open clear 55-20705), phthalic anhydride gas phase catalysis chlorination process (U.S.P2400565), phthalic acid list sodium salt chlorination process (CN1526710), a chloro-o-xylene catalytic gas phase oxidation method (Ger Offen2336875, DE2336875, CN1324793A, CN1257867A) and a chloro-o-xylene liquid phase catalytic oxidation (CN1295999A, CN1560045A).The shortcoming of aforesaid method is that the yield of 4-chloro-benzoic anhydride is low, serious to equipment corrosion, technological process is long etc., the yield problem of 4-chloro-benzoic anhydride particularly, and they are a large amount of 3 position isomers and other impurity of output all.Occidental Chemical Corporation in 1988 has reported that a chloro tetrahydrophthalic anhydride produces the method for monochloro-benzene acid anhydride through aromatization reaction, and 4-chloro-benzoic anhydride yield is 80%.They report in US 4962206, react in solvent with 4-chloro tetrahydrophthalic anhydride and liquid bromine, and be catalyzer with iron or molysite, obtained the mixture of 4-chloro-benzoic anhydride and 4-bromo phthalic anhydride; Reported again that in US5049682 liquid phase virtueization legal system is equipped with the method for single halobenzoyl anhydride, but they do not carry out complete technical study from initial feed yet, at present, the domestic report that yet there are no similar this method.
Summary of the invention
The invention provides a kind of preparation method of 4-chloro-benzoic anhydride, need not any solvent during reaction and participate in (also can add a small amount of solvent), easy and simple to handle, avoided the bad problem of reaction preference in the mode of production of traditional 4-chloro-benzoic anhydride, byproduct of reaction is few, the rectification under vacuum that need not to take time and effort can obtain the 4-chloro-benzoic anhydride of high purity high yield.
The present invention is from initial feed maleic anhydride and chloroprene, add a small amount of thiodiphenylamine or diethyl hydroxylamine, cyclization obtains 4-chloro tetrahydrophthalic anhydride in having heating and internal recycling refrigerative reactor, make virtueization reagent with its aromatize with the liquid bromine again, through underpressure distillation or activated carbon decolorizing crystallization, obtain the 4-chloro-benzoic anhydride, total recovery reaches more than 85%, and purity is more than 99%.Concrete steps are as follows:
The first step, maleic anhydride and chloroprene D-A cyclization prepare 4-chloro tetrahydrophthalic anhydride:
Maleic anhydride and the chloroprene that is equivalent to 0.90～1.18 times of maleic anhydride weight, best 0.94～1.08 times, add thiodiphenylamine or the diethyl hydroxylamine that is equivalent to 0～0.05 times of weight of maleic anhydride weight again, best 0.003～0.026 times, stir, keep temperature of reaction at 45～60 ℃, the best is 50～55 ℃, reflux condensation mode or confined reaction 3～6h.
Second step, the virtue reaction of 4-chloro tetrahydrophthalic anhydride:
Get the first step reaction product, be heated to the virtueization temperature, stir, reflux condensation mode is got the liquid bromine work virtueization reagent that is equivalent to 1.73～1.87 times of step product weight and carry out virtueization, and best liquid bromine weight is 1.77～1.82 times; The drop rate of liquid bromine is 0.017～0.067g (mingD-A cyclization product)-1, best 0.024～0.030g (ming D-A cyclization product)-1.This arylation is in fusion or has under a small amount of solvent condition and carry out, and it is as follows that mode is carried out in reaction,
(a) single temperature or two thermogrades are finished reaction, splash into the liquid bromine at 70～150 ℃, at twice or splash into for three times, for the first time splash into 65～80%, after the liquid bromine consumes greatly, splash into 10～35% once more, after consuming greatly, splash into 0～10% for the third time, keep temperature or temperature is risen to 160～190 ℃ all changing the finished product into until intermediate;
(b) three thermogrades are finished reaction, splash into 65～80% liquid bromine at 70～110 ℃, remain on the temperature in this scope, consume greatly until bromine, temperature is risen to 130～150 ℃ then, splash into 10～35% liquid bromine again, remain on the temperature in this scope, consume greatly until bromine, temperature is upgraded to 160～190 ℃ the most at last, splash into 0～10% liquid bromine at last, remain on the temperature in this scope, all change the finished product into until intermediate.
In the 3rd step, thick product obtains highly purified 4-chloro-benzoic anhydride through underpressure distillation or activated carbon decolorizing crystallization:
(a) underpressure distillation: the product in second step is directly carried out underpressure distillation, obtain highly purified 4-chloro-benzoic anhydride, can obtain purity is more than 99%, and overall yield is the 4-chloro-benzoic anhydride more than 85%;
(b) activated carbon decolorizing crystallization: in the product in second step, add acetone, the chlorobenzene, 1 that is equivalent to its weight 5～200%, 2, the mixture of one or both of 4-trichlorobenzene, bromobenzene, chloroform, tetracol phenixin and monochloroethane equal solvent, add 0～20% gac again, heating, heat filtering, crystallisation by cooling, can add a kind of a small amount of above-mentioned solvent and promote crystallization, drying, can obtain purity is more than 98%, overall yield is the 4-chloro-benzoic anhydride more than 86%.
Technical process of the present invention is short, product yield and purity is high, by product is few, mild condition, cost are low, easy and simple to handle etc.Product yield of the present invention is a molar yield, and other ratio in the method is part by weight.
Embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme.All embodiment are by above-mentioned 4-chloro-benzoic anhydride preparation method's concrete technical scheme operation.
The first step prepares 4-chloro tetrahydrophthalic anhydride specific embodiment:
Embodiment 1
Add 300g maleic anhydride, 319g chloroprene and 3g thiodiphenylamine in reactor, stir, temperature of reaction remains on 50～55 ℃, and back flow reaction 5h obtains product 545g, single step yield 95%, purity 98%;
Embodiment 2
Add 196g maleic anhydride, 195g chloroprene and 1.5g thiodiphenylamine in reactor, stir, temperature of reaction remains on 50～55 ℃, and confined reaction 4h obtains product 354g, single step yield 95%, purity 98%;
Embodiment 3
Add 300g maleic anhydride, 319g chloroprene and 3g diethyl hydroxylamine in reactor, stir, temperature of reaction remains on 50～55 ℃, and back flow reaction 5h obtains product 514g, single step yield 90%, purity 95%.
The specific embodiment of the second step virtueization reaction and the 3rd step purge process:
Embodiment 1
The reaction product 18.65g that gets the first step embodiment 1 is heated to 105 ℃ in reactor, stir, reflux condensation mode splashes into 25g liquid bromine in 50min, after a complete back keeps 70min, temperature of reaction is risen to 135 ℃ again, in 18min, splash into the liquid bromine of 9g simultaneously, continue reaction 42min, then temperature is risen to 160 ℃ and keep 120min, underpressure distillation obtains product 16.2g, yield 89%, total recovery is 85%, and purity is more than 99%.
Embodiment 2
The reaction product 18.65g that gets the first step embodiment 1 is heated to 105 ℃ in reactor, stir, reflux condensation mode splashes into 25g liquid bromine in 50min, drip to finish back maintenance 70min, temperature of reaction is risen to 135 ℃ again, in 14min, splash into the liquid bromine of 7g simultaneously, keep 46min, temperature is risen to 160 ℃ then, splash into the liquid bromine of 2g simultaneously with same speed once more, keep 120min, underpressure distillation obtains product 16.3g, yield 89%, total recovery is 85%, and purity is more than 99%.
Embodiment 3
The reaction product 18.65g that gets the first step embodiment 1 is heated to 120 ℃ in reactor, stir, reflux condensation mode, in 50min, splash into 25g liquid bromine, after a complete back keeps 50min, splash into the liquid bromine of 9g more once more with same speed, continue reaction 270min, underpressure distillation obtains product 15.8g, yield 87%, total recovery is 83%, and purity is more than 99%.
Embodiment 4
The reaction product 18.65g that gets the first step embodiment 1 is heated to 105 ℃ in reactor, stir, reflux condensation mode, in 50min, splash into 25g liquid bromine, after a complete back keeps 70min, temperature of reaction is risen to 135 ℃ again, in 18min, splash into simultaneously the liquid bromine of 9g, continue reaction 42min, then temperature is risen to 160 ℃ and keep 120min, be cooled to 50 ℃, the acetone, the heat filtering that add 18g, cooling, the tetracol phenixin of adding 4g, crystallization, filter, drying obtains product 16.4g, yield 90%, total recovery is 86%, and purity is 98%.
Embodiment 5
The reaction product 18.65g that gets the first step embodiment 1 is heated to 105 ℃ in reactor, stir, reflux condensation mode, in 50min, splash into 25g liquid bromine, after a complete back keeps 70min, temperature of reaction is risen to 135 ℃ again, in 18min, splash into simultaneously the liquid bromine of 9g, continue reaction 42min, then temperature is risen to 160 ℃ and keep 120min, add chlorobenzene, the 0.3g gac of 10g, heat filtering, cooling, the tetracol phenixin of adding 4g, crystallization, filter, drying obtains product 14.2g, yield 78%, total recovery is 74%, and purity is 97%.
Embodiment 6
The reaction product 18.65g that gets the first step embodiment 1 is in reactor, be heated to 105 ℃, stir, reflux condensation mode splashes into 25g liquid bromine in 50min, after a complete back keeps 50min, splash into the liquid bromine of 9g more once more with same speed, continue reaction 270min, know unconverted (gas phase conversion rate 100%, gas phase yield 86% fully after testing, intermediate gas phase ratio is 10%), temperature is elevated to 160 ℃ keeps 60min, intermediate becomes target product, underpressure distillation fully, obtain product 16.3g, yield 89%, total recovery are 85%, and purity is more than 99%.
Embodiment 7
The reaction product 18.65g that gets the first step embodiment 1 is in reactor, add the 2.8g chlorobenzene, be heated to 90 ℃, stir, reflux condensation mode splashes into 25g liquid bromine in 50min, drip to finish back maintenance 70min, temperature of reaction is risen to 135 ℃ again, in 18min, splash into simultaneously the liquid bromine of 9g, continue reaction 42min, then temperature is risen to 160 ℃ and keep 120min, underpressure distillation steams chlorobenzene and derivative thereof, with the remaining solid underpressure distillation, obtain product 15.9g once more, yield 87%, total recovery 83%, purity 99%.
Claims (6)
1. the preparation method of a 4-chloro-benzoic anhydride, with maleic anhydride and chloroprene is raw material, with thiodiphenylamine or diethyl hydroxylamine is stopper, the D-A cyclization obtains 4-chloro tetrahydrophthalic anhydride, make virtueization reagent with its aromatize with the liquid bromine again, obtain the 4-chloro-benzoic anhydride of high purity high yield through underpressure distillation or activated carbon decolorizing crystallization; It is characterized in that step is as follows,
The first step, maleic anhydride and chloroprene D-A cyclization prepare 4-chloro tetrahydrophthalic anhydride:
Maleic anhydride and the chloroprene that is equivalent to 0.90～1.18 times of maleic anhydride weight, add thiodiphenylamine or the diethyl hydroxylamine that is equivalent to 0～0.05 times of weight of maleic anhydride weight again, stir, keep temperature of reaction at 45～60 ℃, reflux condensation mode or confined reaction 3～6h;
Second step, the virtue reaction of 4-chloro tetrahydrophthalic anhydride:
Get the first step reaction product, be heated to the virtueization temperature, stir, reflux condensation mode is got the liquid bromine work virtueization reagent that is equivalent to 1.73～1.87 times of step product weight and carry out virtueization, and the drop rate of liquid bromine is 0.017～0.067g (a mingD-A cyclization product)
-1This arylation is in fusion or has under the solvent condition and carry out, and it is as follows that mode is carried out in reaction,
(a) single temperature or two thermogrades are finished reaction, splash into the liquid bromine at 70～150 ℃, at twice or splash into for three times, for the first time splash into 65～80%, after the liquid bromine consumes greatly, splash into 10～35% once more, after consuming greatly, splash into 0～10% for the third time, keep temperature or temperature is risen to 160～190 ℃ all changing the finished product into until intermediate;
(b) three thermogrades are finished reaction, splash into 65～80% liquid bromine at 70～110 ℃, remain on the temperature in this scope, consume greatly until bromine, temperature is risen to 130～150 ℃ then, splash into 10～35% liquid bromine again, remain on the temperature in this scope, consume greatly until bromine, temperature is upgraded to 160～190 ℃ the most at last, splash into 0～10% liquid bromine at last, remain on the temperature in this scope, all change the finished product into until intermediate;
In the 3rd step, thick product obtains highly purified 4-chloro-benzoic anhydride through underpressure distillation or activated carbon decolorizing crystallization:
(a) underpressure distillation: the product in second step is directly carried out underpressure distillation, obtain highly purified 4-chloro-benzoic anhydride;
(b) activated carbon decolorizing crystallization: in the product in second step, add acetone, the chlorobenzene, 1 that is equivalent to its weight 5～200%, 2, the mixture of one or both of 4-trichlorobenzene, bromobenzene, chloroform, tetracol phenixin and monochloroethane equal solvent, add 0～20% gac again, heating, heat filtering, crystallisation by cooling, drying obtains the 4-chloro-benzoic anhydride.
2. method according to claim 1 is characterized in that, uses maleic anhydride and the chloroprene that is equivalent to 0.94～1.08 times of maleic anhydride weight.
3. method according to claim 1 and 2 is characterized in that, adds the thiodiphenylamine or the diethyl hydroxylamine that are equivalent to 0.003～0.026 times of weight of maleic anhydride weight.
4. method according to claim 1 is characterized in that D-A ring-closure reaction temperature is 50～55 ℃.
5. method according to claim 1 is characterized in that, in the virtue reaction of 4-chloro tetrahydrophthalic anhydride, get the first step reaction product, be heated to the virtueization temperature, stir, reflux condensation mode is got the liquid bromine work virtueization reagent that is equivalent to 1.77～1.82 times of step product weight and carry out virtueization.
6. method according to claim 1 is characterized in that, in the virtue reaction of 4-chloro tetrahydrophthalic anhydride, and the drop rate 0.024～0.030g of liquid bromine (ming D-A cyclization product)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521279A (en) * | 2021-06-25 | 2022-12-27 | 中国石油化工股份有限公司 | Preparation method of 4-halogenated phthalic anhydride and 4-halogenated phthalic anhydride obtained by using method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0338215A2 (en) * | 1988-02-24 | 1989-10-25 | Occidental Chemical Corporation | Process for the preparation of halogen-substituted phthalic anhydride |
| US5049682A (en) * | 1989-09-11 | 1991-09-17 | Occidental Chemical Corporation | Process for the preparation of halophthalic anhydrides |
| US5059697A (en) * | 1990-06-14 | 1991-10-22 | Occidental Chemical Corporation | Preparation of halogenated phthalic anhydrides |
| US5322954A (en) * | 1993-05-28 | 1994-06-21 | Occidental Chemical Corporation | Synthesis of 4-substituted phthalic anhydrides |
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2010
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|---|---|---|---|---|
| EP0338215A2 (en) * | 1988-02-24 | 1989-10-25 | Occidental Chemical Corporation | Process for the preparation of halogen-substituted phthalic anhydride |
| US5049682A (en) * | 1989-09-11 | 1991-09-17 | Occidental Chemical Corporation | Process for the preparation of halophthalic anhydrides |
| US5059697A (en) * | 1990-06-14 | 1991-10-22 | Occidental Chemical Corporation | Preparation of halogenated phthalic anhydrides |
| US5322954A (en) * | 1993-05-28 | 1994-06-21 | Occidental Chemical Corporation | Synthesis of 4-substituted phthalic anhydrides |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521279A (en) * | 2021-06-25 | 2022-12-27 | 中国石油化工股份有限公司 | Preparation method of 4-halogenated phthalic anhydride and 4-halogenated phthalic anhydride obtained by using method |
| CN115521279B (en) * | 2021-06-25 | 2024-03-26 | 中国石油化工股份有限公司 | Preparation method of 4-halophthalic anhydride and 4-halophthalic anhydride obtained by using same |
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