CN116768768A - Method for preparing 4,4' -dichlorodiphenyl sulfone by cyclic catalysis - Google Patents
Method for preparing 4,4' -dichlorodiphenyl sulfone by cyclic catalysis Download PDFInfo
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- CN116768768A CN116768768A CN202310754876.4A CN202310754876A CN116768768A CN 116768768 A CN116768768 A CN 116768768A CN 202310754876 A CN202310754876 A CN 202310754876A CN 116768768 A CN116768768 A CN 116768768A
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- dichlorodiphenyl sulfone
- chlorobenzene
- chloride
- preparing
- sulfone
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- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 10
- 125000004122 cyclic group Chemical group 0.000 title claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 105
- ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 4-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(S(Cl)(=O)=O)C=C1 ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000012043 crude product Substances 0.000 claims abstract description 47
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 24
- 239000012452 mother liquor Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 238000001953 recrystallisation Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000000967 suction filtration Methods 0.000 claims description 14
- 239000010413 mother solution Substances 0.000 claims description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 8
- IBRQUKZZBXZOBA-UHFFFAOYSA-N 1-chloro-3-(3-chlorophenyl)sulfonylbenzene Chemical compound ClC1=CC=CC(S(=O)(=O)C=2C=C(Cl)C=CC=2)=C1 IBRQUKZZBXZOBA-UHFFFAOYSA-N 0.000 abstract 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 35
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 30
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 26
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 26
- 239000007789 gas Substances 0.000 description 25
- 238000002474 experimental method Methods 0.000 description 18
- KMVZDSQHLDGKGV-UHFFFAOYSA-N 2-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=CC=C1S(Cl)(=O)=O KMVZDSQHLDGKGV-UHFFFAOYSA-N 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- YKWDWSGYZBURDA-UHFFFAOYSA-N 1-chloro-2-(4-chlorophenyl)sulfonylbenzene Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=CC=C1Cl YKWDWSGYZBURDA-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- RJWBTWIBUIGANW-UHFFFAOYSA-N 4-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C=C1 RJWBTWIBUIGANW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- RKIDDEGICSMIJA-UHFFFAOYSA-N 4-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1 RKIDDEGICSMIJA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing 4,4' -dichlorodiphenyl sulfone by circulating catalysis, which relates to the technical field of dichlorodiphenyl sulfone preparation, chlorobenzene and p-chlorobenzenesulfonyl chloride react in the presence of anhydrous ferric trichloride serving as a catalyst at a first preset temperature to obtain a solution containing 4,4' -dichlorodiphenyl sulfone, the solution is cooled and filtered to obtain a crude product of 4,4' -dichlorodiphenyl sulfone, then the crude product is subjected to alkali treatment, liquid separation, concentrated crystallization and recrystallization to obtain the 4,4' -dichlorodiphenyl sulfone, the purity of the prepared 4,4' -dichlorodiphenyl sulfone reaches more than 99.6%, and mother liquor of the concentrated crystallization can be recycled, so that raw materials and the anhydrous ferric trichloride serving as the catalyst can be reused without waste.
Description
Technical Field
The invention belongs to the technical field of p-chlorobenzenesulfonyl chloride preparation methods, and particularly relates to a method for preparing 4,4' -dichlorodiphenyl sulfone by cyclic catalysis.
Background
4,4 '-dichloro diphenyl sulfone is an important raw material for synthesizing engineering plastics polysulfone, polyether sulfone and polyether ether ketone, and is also a raw material for synthesizing medicine 4,4' -diamino diphenyl sulfone, and along with the wider and wider application and development of special engineering plastics in the high-tech fields of automobiles, electronic appliances, aerospace materials and the like, the demand for the special engineering plastics is rapidly increasing.
At present, a chlorosulfonic acid method, a sulfuryl chloride method and a sulfur trioxide method are mainly adopted for preparing 4,4 '-dichlorodiphenyl sulfone, for example, the publication number is CN102351760A, CN103601659A, CN102304072A, p-chlorobenzenesulfonyl chloride is obtained in the patent, and then the 4,4' -dichlorodiphenyl sulfone is obtained through further catalytic conversion, aluminum trichloride or bismuth tris (trifluoromethyl) sulfonate or antimony pentachloride are used as catalysts, and the catalysts are all disposable and are basically equivalent catalysts, so that a large amount of solid waste and wastewater are generated.
Disclosure of Invention
In view of the above, the invention provides a method for preparing 4,4' -dichlorodiphenyl sulfone by cyclic catalysis with little solid waste and waste water.
The technical scheme adopted for solving the technical problems is as follows:
a method for preparing 4,4' -dichlorodiphenyl sulfone by cyclic catalysis, comprising the following steps:
s1: at a first preset temperature, chlorobenzene and p-chlorobenzenesulfonyl chloride react in the presence of anhydrous ferric trichloride serving as a catalyst, after the reaction is finished, 4 '-dichlorodiphenyl sulfone solid is cooled and separated out, and a crude product of the 4,4' -dichlorodiphenyl sulfone is obtained through suction filtration; the mother liquor obtained by suction filtration is used for preparing the next batch of crude 4,4' -dichlorodiphenyl sulfone;
s2: and then carrying out liquid alkali treatment, liquid separation, concentration crystallization and recrystallization on the 4,4 '-dichlorodiphenyl sulfone crude product to obtain the 4,4' -dichlorodiphenyl sulfone.
Preferably, the first predetermined temperature is 90 ℃ to 130 ℃.
Preferably, the molar ratio of the p-chlorobenzenesulfonyl chloride to the chlorobenzene, anhydrous ferric chloride is 1:1.5-5:0.01-0.2.
Preferably, when the mother solution is used for preparing the next batch of crude 4,4' -dichlorodiphenyl sulfone, the additional amount of the anhydrous ferric chloride is 1/5-1/4 of the initial addition amount of the anhydrous ferric chloride when the mother solution is prepared.
Preferably, when the mother solution is used for preparing the next batch of crude 4,4' -dichlorodiphenyl sulfone, the additional amount of the chlorobenzene is 1/3-2/3 of the initial adding amount of the chlorobenzene when preparing the mother solution.
Preferably, in the step S1, the reaction is finished as follows: when the content of the residual p-chlorobenzenesulfonyl chloride in the reaction liquid is less than or equal to 3 percent.
Compared with the prior art, the invention has the beneficial effects that:
at a first preset temperature, chlorobenzene and p-chlorobenzenesulfonyl chloride react in the presence of anhydrous ferric trichloride serving as a catalyst, after the reaction is finished, 4 '-dichlorodiphenyl sulfone solid is cooled and separated out, and a crude product of the 4,4' -dichlorodiphenyl sulfone is obtained through suction filtration; the mother liquor obtained by suction filtration is used for preparing the next batch of crude 4,4' -dichlorodiphenyl sulfone; and then 4,4' -dichlorodiphenyl sulfone is obtained by liquid alkali treatment, liquid separation, concentration crystallization and recrystallization of the 4,4' -dichlorodiphenyl sulfone crude, so that the utilization rate of raw materials is greatly improved by recycling the mother liquor, the yield of the product 4,4' -dichlorodiphenyl sulfone is improved, and the mother liquor can be recycled due to less catalyst use, so that solid waste and waste water are reduced, and the requirements of green production are met.
Drawings
Fig. 1 is a gas chromatogram of the first embodiment.
Fig. 2 is a gas chromatogram of the first embodiment.
Fig. 3 is a gas chromatogram of the second embodiment.
FIG. 4 is a gas chromatogram of experiment No. 1 of example three.
Fig. 5 is a gas chromatogram of experiment No. 2 of example three.
FIG. 6 is a gas chromatogram of experiment No. 3 of example three.
FIG. 7 is a gas chromatogram of experiment No. 4 of example three.
FIG. 8 is a gas chromatogram of experiment No. 5 of example three.
Fig. 9 is a gas chromatogram of experiment No. 6 of example three.
FIG. 10 is a gas chromatogram after distillation under reduced pressure in example IV.
FIG. 11 is a gas chromatogram of experiment No. 7 of example four.
FIG. 12 is a gas chromatogram of experiment No. 8 of example four.
Fig. 13 is a gas chromatogram of experiment No. 9 of example four.
Detailed Description
The technical scheme and technical effects of the embodiments of the present invention are further described in detail below with reference to the accompanying drawings.
A method for preparing 4,4' -dichlorodiphenyl sulfone by cyclic catalysis, comprising the following steps:
s1: at a first preset temperature, chlorobenzene and p-chlorobenzenesulfonyl chloride react in the presence of anhydrous ferric trichloride serving as a catalyst, after the reaction is finished, 4 '-dichlorodiphenyl sulfone solid is cooled and separated out, and a crude product of the 4,4' -dichlorodiphenyl sulfone is obtained through suction filtration; the mother liquor obtained by suction filtration is used for preparing the next batch of crude 4,4' -dichlorodiphenyl sulfone;
s2: then the 4,4 '-dichloro diphenyl sulfone crude product is treated by liquid alkali, separated, concentrated, crystallized and recrystallized to obtain the 4,4' -dichloro diphenyl sulfone
Compared with the prior art, the invention has the beneficial effects that:
at a first preset temperature, chlorobenzene and p-chlorobenzenesulfonyl chloride react in the presence of anhydrous ferric trichloride serving as a catalyst, after the reaction is finished, 4 '-dichlorodiphenyl sulfone solid is cooled and separated out, and a crude product of the 4,4' -dichlorodiphenyl sulfone is obtained through suction filtration; the mother liquor obtained by suction filtration is used for preparing the next batch of crude 4,4' -dichlorodiphenyl sulfone; and then 4,4' -dichlorodiphenyl sulfone is obtained by liquid alkali treatment, liquid separation, concentration crystallization and recrystallization of the 4,4' -dichlorodiphenyl sulfone crude, so that the utilization rate of raw materials is greatly improved by recycling the mother liquor, the yield of the product 4,4' -dichlorodiphenyl sulfone is improved, and the mother liquor can be recycled due to less catalyst use, so that solid waste and waste water are reduced, and the requirements of green production are met.
Further, the first predetermined temperature is 90 ℃ to 130 ℃.
Further, the molar ratio of the p-chlorobenzenesulfonyl chloride to the chlorobenzene and anhydrous ferric chloride is 1:1.5-5:0.01-0.2.
Further, when the mother solution is used for preparing the next batch of crude 4,4' -dichlorodiphenyl sulfone, the additional amount of the anhydrous ferric chloride is 1/5-1/4 of the initial addition amount of the anhydrous ferric chloride when the mother solution is prepared.
Further, when the mother solution is used for preparing the next batch of crude 4,4' -dichlorodiphenyl sulfone, the additional amount of the chlorobenzene is 1/3-2/3 of the initial addition amount of the chlorobenzene when the mother solution is prepared.
Further, in the step S1, the reaction is terminated as follows: when the content of the residual p-chlorobenzenesulfonyl chloride in the reaction liquid is less than or equal to 3 percent.
For ease of understanding, the invention is further illustrated by the following examples:
example one (preparation of 4,4' -dichlorodiphenyl sulfone):
4.1g of anhydrous ferric trichloride, 84g of chlorobenzene and 52.6g of p-chlorobenzenesulfonyl chloride prepared in example I were respectively added into a three-necked flask equipped with a stirrer, a reflux and hydrogen chloride gas absorption device and a thermometer; gradually heating the oil bath to the reaction temperature of 110-130 ℃; detecting the content of residual p-chlorobenzenesulfonyl chloride in the reaction liquid by a GC method at fixed time to be less than or equal to 3 percent, and stopping the reaction; cooling to 5 ℃, precipitating 4,4' -dichloro diphenyl sulfone crystal, and carrying out suction filtration to obtain a crude product; the mother liquor (containing chlorobenzene, most of the catalyst, 4' -dichlorodiphenyl sulfone dissolved in chlorobenzene and unreacted p-chlorobenzenesulfonyl chloride) was used for the next batch preparation.
Purifying a crude product: a) Alkali treatment: grinding the distillation residue crude product into fine particles, transferring into hot 10% liquid alkali for treatment (50 ℃ for 30 min), adding chloroform for dissolving, stirring at 50 ℃ for 30min, separating to obtain an organic layer, and discarding a water layer; b) Concentrating and crystallizing: concentrating the organic layer at 70 ℃ to remove most of chloroform, cooling for crystallization, and carrying out suction filtration to obtain crystals, wherein mother liquor is used for the next crude product treatment; c) And (5) recrystallizing: redissolving the crystals at 50:50 Adding 0.5% active carbon into the chloroform/ethanol mixed solvent of (v/v), further decolorizing at 50deg.C, filtering while the filtrate is hot, cooling the filtrate to 5deg.C, centrifuging, and drying to obtain crystal 4,4' -dichlorodiphenyl sulfone, and detecting product purity, wherein the gas chromatogram is shown in figure 1, and the purity reaches over 99.5%.
The catalyst used in the invention has small dosage of ferric trichloride, can be reused, and can control the reaction. And as ferric trichloride is soluble in chlorobenzene, most of ferric trichloride is left in solution after the catalytic reaction is finished, 4' -dichlorodiphenyl sulfone generated by the reaction precipitates crystals in the cooling process, and only a small amount of ferric trichloride is adsorbed on the surface of the crude product; the separated mother liquor can be recycled for the production process. Therefore, most ferric trichloride catalysts can be recycled, so that the catalyst waste is reduced, the production cost is reduced, the generation of organic waste gas and solid waste is reduced, and the disposable use of the catalysts is avoided.
Example two (4, 4' -dichlorodiphenyl sulfone preparation mother liquor for recycling)
The mother liquor was recycled 5 times as follows, and the amount of anhydrous ferric chloride added each time was 1/4 of the initial addition amount.
In a three-mouth bottle provided with a stirrer, a reflux device, a hydrogen chloride gas absorption device and a thermometer, respectively adding experimental trichlorobenzene mother liquor, 52.8g of p-chlorobenzenesulfonyl chloride, and 0.8g of anhydrous ferric trichloride and 30g of chlorobenzene under stirring; heating to the reaction temperature of 110-130 ℃, and preserving heat for reaction for 6h; and (3) stopping heat preservation, cooling to 5 ℃ and separating out 4,4' -dichloro diphenyl sulfone crystals, performing suction filtration to obtain crude products, performing GC analysis, wherein the patterns of the experiment times 2 and 4 are shown in figures 2 and 3, and the results are shown in table 1:
TABLE 1
The result shows that under the condition that the reaction time and the temperature conditions are consistent, the yield of the 4,4 '-dichlorodiphenyl sulfone is close to 100 percent, the content of the 4,4' -dichlorodiphenyl sulfone in the crude product is high after the crude product is repeatedly used for 5 times, the mother liquor is recycled, the waste of raw materials and other three wastes generated by the residue of the treated raw materials are reduced, the environmental impact of the catalytic preparation process is minimum, the conversion efficiency is high, and the method is suitable for industrial production.
The raw material p-chlorobenzenesulfonyl chloride in the step S1 is prepared by the following steps:
step one: chlorobenzene and chlorosulfonic acid react for a first preset time at a second preset temperature to obtain an intermediate 1;
step two: the intermediate 1 reacts for a second preset time at a third preset temperature under the action of thionyl chloride to obtain a mixed solution containing p-chlorobenzenesulfonyl chloride, and then the mixed solution containing p-chlorobenzenesulfonyl chloride is subjected to extraction, hydrolysis, liquid separation, washing, distillation and recrystallization to obtain the p-chlorobenzenesulfonyl chloride.
And (3) reacting for a preset time at a second preset temperature to obtain an intermediate 1, then generating gas by the intermediate 1 under the catalysis of thionyl chloride, and after the gas is released, promoting the reaction of the intermediate 1 and chlorobenzene to proceed forward, so that the utilization rate of the chlorobenzene reaches more than 90%, and the purity of the product reaches 99%.
Further, in the first step, the chlorosulfonic acid is added dropwise to the chlorobenzene, the yield of p-chlorobenzenesulfonyl chloride is high, and a small amount of by-product 4,4' -dichlorodiphenyl sulfone is produced.
Further, in the first step, the chlorobenzene is added dropwise to the chlorosulfonic acid, so that intermediate 1 is produced with high yield, and further, the yield of p-chlorobenzenesulfonyl chloride is high.
Further, the second preset temperature is 5 ℃ to 45 ℃, preferably 30 ℃ to 35 ℃, the first preset time is 1h to 2h, the para position is positioned under the low temperature condition in the exothermic reaction of the intermediate 1, the generation of ortho-position products is restrained, the generated para-position intermediate 1 is further reduced, the third preset temperature is 45 ℃ to 65 ℃, preferably 50 ℃ to 55 ℃, the second preset time is 1h to 5h, preferably 2.5h to 3.5h, and the intermediate 1 reacts with chlorobenzene to generate p-chlorobenzenesulfonyl chloride.
Furthermore, the mol ratio of the thionyl chloride to the chlorobenzene is 1:2-5, when the thionyl chloride is not added, the reaction of the intermediate 1 and chlorosulfonic acid reaches equilibrium, the thionyl chloride is added, the activity of the thionyl chloride is stronger than that of the chlorosulfonic acid, the equilibrium is broken, the thionyl chloride reacts with the intermediate 1 to generate p-chlorobenzenesulfonyl chloride and gas under the participation of the thionyl chloride, the reaction is promoted to be carried out forward after the gas is released, because the intermediate 1 can be separated out at low temperature, a pipeline is blocked, the intermediate 1 in waste acid is reduced after the residual intermediate 1 is reacted by the thionyl chloride, and the waste acid treatment is smoother.
In the second step, the thionyl chloride is added after the intermediate 1 reacts for 0.5h to 1.5h at a third preset temperature, and is added after the intermediate 1 and chlorosulfonic acid react to reach equilibrium.
Further, the molar ratio of chlorobenzene to chlorosulfonic acid is 1:2-5, preferably 1:2-3.
In the second step, the extraction step is to add chloroform as an extractant into the mixed solution containing p-chlorobenzenesulfonyl chloride to extract to obtain an extract.
Further, in the second step, the hydrolysis is specifically: and adding hydrochloric acid into the extract to hydrolyze excessive chlorosulfonic acid, wherein the hydrochloric acid is 30% hydrochloric acid, water in the hydrochloric acid reacts with unreacted chlorosulfonic acid to generate hydrogen chloride and sulfuric acid, the reaction releases heat, and in order to prevent local release of heat, the hydrolysis of p-chlorobenzenesulfonyl chloride is caused to generate an intermediate 1, and the generated hydrogen chloride gas brings out the heat of the reaction, so that the yield of the p-chlorobenzenesulfonyl chloride is not influenced.
Example three (p-chlorobenzenesulfonyl chloride):
adding chlorosulfonic acid into a four-neck flask with a stirrer, a reflux and gas absorption device and a thermometer, and dripping 0.5mol of chlorobenzene through a constant-pressure dropping funnel at the temperature of 6-12 ℃; the dripping time is 1h, and the temperature is kept for 30min at 6-12 ℃ after the dripping is finished; then heating to 50-55 ℃, and preserving heat for 1h; then 0.25mol of sulfoxide chloride is added through a dropping funnel, and after the addition is completed for 10 minutes, the temperature is kept at 50-55 ℃ for 3 hours; cooling to room temperature, and adding 150ml of chloroform; 35ml of 30% hydrochloric acid solution is gradually added dropwise through a dropping funnel to decompose excessive chlorosulfonic acid; separating, treating the acid layer with waste acid, and washing the chloroform layer with distilled water once; the chloroform layer after washing was distilled off at normal pressure to remove most of chloroform, and then residual chloroform was distilled off under reduced pressure with a water pump to obtain a crude product, which was sampled for GC analysis.
According to the above experimental method, a method for improving the yield of p-chlorobenzenesulfonyl chloride was investigated.
1. Control groups of 3 were set, 1mol, 1.25mol, 1.5mol chlorosulfonic acid, numbered 1-3, were added respectively, and the results were shown in Table 2 by GC analysis in the same manner as in example one above.
TABLE 2
| Experiment number | 1 | 2 | 3 |
| Chlorosulfonic acid to chlorobenzene molar ratio | 2:1 | 2.5:1 | 3:1 |
| Yield g | 87.3 | 92.1 | 92.7 |
| Chlorobenzene utilization/% | 88.02 | 93.31 | 91.51 |
| The ratio of chlorobenzene in the crude product/% | 1.63 | 0.96 | 0.19 |
| P-chlorobenzenesulfonyl chloride in crude product | 79.47 | 79.96 | 88.44 |
| The ratio of O-chlorobenzenesulfonyl chloride in the crude product/% | 1.57 | 2.06 | 2.25 |
| The ratio of 4,4' -dichloro diphenyl sulfone in the crude product/% | 17.13 | 16.92 | 9.09 |
| The ratio of 2,4' -dichloro diphenyl sulfone in the crude product/% | 0.19 | 0.08 | 0.02 |
From the above results, it was found that the higher the yield of p-chlorobenzenesulfonyl chloride produced in the crude product was, the higher the molar ratio of chlorosulfonic acid to chlorobenzene was, the higher the p-chlorobenzenesulfonyl chloride produced in the crude product was 88.44% when the molar ratio of chlorosulfonic acid to chlorobenzene was 3:1, and the o-chlorobenzenesulfonyl chloride, 4' -dichlorodiphenyl sulfone was only 2.25%, 9.09%, and the chlorobenzene utilization rate was 91.51%.
When 4,4' -dichlorodiphenyl sulfone is produced by p-chlorobenzenesulfonyl chloride, the molar ratio of chlorosulfonic acid to chlorobenzene is most preferably 2.5:1, 16.92% of 4,4' -dichlorodiphenyl sulfone is already produced when p-chlorobenzenesulfonyl chloride is produced, and the ratio of o-chlorobenzenesulfonyl chloride to 2,4' -dichlorodiphenyl sulfone is small.
2. The control group 1 was set at a second predetermined temperature (temperature at which chlorobenzene was added dropwise) of 30℃to 35℃and No. 4, and the results of GC analysis, shown in FIG. 7, are shown in Table 3, except for the procedure similar to that in reference number 2.
TABLE 3 Table 3
From the above results, it is apparent that when chlorosulfonic acid reacts with chlorobenzene, the content of p-chlorobenzenesulfonyl chloride is significantly increased and the content of 4,4' -dichlorodiphenyl sulfone is reduced when the first predetermined temperature is increased, which is advantageous for the production of p-chlorobenzenesulfonyl chloride.
3. Control 1 was set, hydrolyzed with water in the hydrolysis step, hydrolyzed without 30% hydrochloric acid, no. 5, and analyzed by GC in the same manner as in reference number 2, as shown in fig. 8, and the results are shown in table 4.
TABLE 4 Table 4
| Experiment number | 2 | 5 |
| Hydrolysis | 30% hydrochloric acid | Pure water |
| The ratio of chlorobenzene in the crude product/% | 0.96 | 0.91 |
| P-chlorobenzenesulfonyl chloride in crude product | 79.96 | 82.46 |
| The ratio of O-chlorobenzenesulfonyl chloride in the crude product/% | 2.06 | 2.32 |
| The ratio of 4,4' -dichloro diphenyl sulfone in the crude product/% | 16.92 | 14.23 |
| The ratio of 2,4' -dichloro diphenyl sulfone in the crude product/% | 0.08 | 0.09 |
| Whether or not solids are present in the waste acid treatment | Without any means for | Has the following components |
From the above results, it was found that, in the case of reacting chlorosulfonic acid with chlorobenzene, hydrolysis using pure water was hardly different from hydrolysis using 30% hydrochloric acid; the main function of the hydrochloric acid is that the heat generated by the reaction is taken away by hydrogen chloride gas, and in the subsequent waste acid treatment process, the waste acid mainly comprises sulfuric acid (concentration is 75-80%) and p-chlorobenzenesulfonic acid, and the p-chlorobenzenesulfonic acid with a certain concentration can be separated out of a concentrated sulfuric acid solution at a low temperature, so that the solid is difficult to separate out and is easy to cause pipeline blockage; on the one hand, 30% hydrochloric acid takes away local heat through hydrogen chloride to prevent generated p-chlorobenzenesulfonyl chloride from being dissolved, and on the other hand, 30% hydrochloric acid dissolves chlorosulfonic acid, so that a pipeline is unobstructed when waste acid is treated.
4. Control 1 was set up, no thionyl chloride was added to the reaction, and GC analysis was performed in the same manner as in number 6, the other steps described in number 2, as shown in fig. 9, and the results are shown in table 5.
TABLE 5
| Experiment number | 2 | 6 |
| With or without addition of thionyl chloride | Has the following components | Without any means for |
| Yield g | 92.1 | 82.43 |
| Chlorobenzene utilization/% | 93.31 | 85.51 |
| The ratio of chlorobenzene in the crude product/% | 0.96 | 0.09 |
| P-chlorobenzenesulfonyl chloride in crude product | 79.96 | 78.58 |
| The ratio of O-chlorobenzenesulfonyl chloride in the crude product/% | 2.06 | 1.19 |
| The ratio of 4,4' -dichloro diphenyl sulfone in the crude product/% | 16.92 | 19.99 |
| The ratio of 2,4' -dichloro diphenyl sulfone in the crude product/% | 0.08 | 0.15 |
From the above results, when the equivalent of chlorosulfonic acid cannot affect the p-chlorobenzenesulfonyl chloride ratio in the crude product, and thionyl chloride is not added in the reaction, the utilization rate of chlorobenzene is reduced although the p-chlorobenzenesulfonyl chloride ratio in the crude product is also very high, so that the use efficiency of chlorobenzene is reduced, and therefore, thionyl chloride can improve the use efficiency of chlorobenzene, reduce the production cost and facilitate the generation of 4,4' -dichlorodiphenyl sulfone.
Carrying out reduced pressure distillation on the crude product, wherein the distillate is a mixture of p-chlorobenzenesulfonyl chloride and o-chlorobenzenesulfonyl chloride; the distillation residue mainly contains 4,4' -dichloro diphenyl sulfone, the mixture of p-chlorobenzene sulfonyl chloride and o-chlorobenzene sulfonyl chloride is mixed and dissolved with a proper amount of chloroform at 55 ℃, the mixture is stirred and cooled for crystallization to obtain solid, and the obtained crystal is subjected to suction filtration and is analyzed by GC, as shown in figure 10, the following results are obtained: the crystal contains more than 99 percent of p-chlorobenzenesulfonyl chloride, and the purity is suitable for synthesizing 4,4' -dichlorodiphenyl sulfone; while the ortho-isomer remains in the mother liquor.
Purification of 4,4' -dichlorodiphenyl sulfone in the distilled residue was the same as in crude purification of example one.
Example four (p-chlorobenzenesulfonyl chloride):
1. adding 0.5mol of chlorobenzene into a four-neck flask provided with a stirrer, a reflux and gas absorption device and a thermometer, starting to dropwise add 1.25mol of chlorosulfonic acid through a constant pressure dropping funnel at the temperature of 6-12 ℃, wherein the dropwise adding time is 1h, and preserving heat for 30min at the temperature of 6-12 ℃ after the dropwise adding is finished; then heating to 50-55 ℃ and preserving heat for 3h; cooling to room temperature, and adding 150ml of chloroform; through the dropping funnel, 32ml of 30% hydrochloric acid solution is gradually added dropwise to decompose excessive chlorosulfonic acid; separating, treating the acid layer with waste acid, and washing the chloroform layer with distilled water once; the chloroform layer after washing was distilled off under normal pressure to remove most of chloroform, and then residual chloroform was distilled off under reduced pressure with a water pump to obtain a crude product, which was sampled for GC analysis, as shown in FIG. 11, and the results are shown in Table 6, experiment No. 7, and the crude product purification step was the same as in example one.
TABLE 6
As can be seen from comparison of experiment 2 and experiment 7, p-chlorobenzoyl chloride can be generated regardless of the addition, but chlorosulfonic acid is added dropwise to chlorobenzene, the chlorobenzene utilization rate is improved to 96.68%, but the content of p-chlorobenzenesulfonyl chloride in the crude product is reduced to 66.71%, the content of o-chlorobenzenesulfonyl chloride in the crude product is reduced to 0.89%, and 32.04% of 4,4' -dichlorodiphenyl sulfone is generated, and chlorosulfonic acid is added dropwise to chlorobenzene when 4,4' -dichlorodiphenyl sulfone is directly prepared by the reaction, so that the generation of 4,4' -dichlorodiphenyl sulfone is facilitated.
2. 1 control group was set, at a first predetermined temperature (temperature at which chlorosulfonic acid was added dropwise) of 30℃to 35℃and No. 8, and the results were shown in Table 6, as shown in FIG. 12, by GC analysis in the same manner as in the step of No. 7.
TABLE 7
From the above results, it is found that raising the first predetermined temperature can increase the chlorobenzene utilization, resulting in a reduction in production cost.
3. Control 1 was set up, no thionyl chloride was added to the reaction, and GC analysis was performed in the same manner as in number 9, the other steps in number 7, as shown in fig. 13, and the results are shown in the table.
TABLE 8
| Experiment number | 7 | 9 |
| With or without addition of thionyl chloride | Has the following components | Without any means for |
| Yield g | 88.6 | 79.3 |
| Chlorobenzene utilization/% | 96.68 | 87.29 |
| The content of chlorobenzene in the crude productRatio/% | 0.11 | 0.12 |
| P-chlorobenzenesulfonyl chloride in crude product | 66.71 | 65.12 |
| The ratio of O-chlorobenzenesulfonyl chloride in the crude product/% | 0.89 | 0.33 |
| The ratio of 4,4' -dichloro diphenyl sulfone in the crude product/% | 32.04 | 33.96 |
| The ratio of 2,4' -dichloro diphenyl sulfone in the crude product/% | 0.24 | 0.47 |
From the above results, it is clear that thionyl chloride can improve the efficiency of chlorobenzene use and reduce the production cost.
The foregoing disclosure is illustrative of the preferred embodiments of the present invention, and is not to be construed as limiting the scope of the invention, as it is understood by those skilled in the art that all or part of the above-described embodiments may be practiced with equivalents thereof, which fall within the scope of the invention as defined by the appended claims.
Claims (6)
1. A method for preparing 4,4' -dichloro diphenyl sulfone by cyclic catalysis, which is characterized by comprising the following steps: the method comprises the following steps:
s1: at a first preset temperature, chlorobenzene and p-chlorobenzenesulfonyl chloride react in the presence of anhydrous ferric trichloride serving as a catalyst, after the reaction is finished, 4 '-dichlorodiphenyl sulfone solid is cooled and separated out, and a crude product of the 4,4' -dichlorodiphenyl sulfone is obtained through suction filtration; the mother liquor obtained by suction filtration is used for preparing the next batch of crude 4,4' -dichlorodiphenyl sulfone;
s2: and then carrying out liquid alkali treatment, liquid separation, concentration crystallization and recrystallization on the 4,4 '-dichlorodiphenyl sulfone crude product to obtain the 4,4' -dichlorodiphenyl sulfone.
2. The process for the cyclical catalytic preparation of 4,4' -dichlorodiphenyl sulfone of claim 1, wherein: the first predetermined temperature is 90 ℃ to 130 ℃.
3. The process for the cyclical catalytic preparation of 4,4' -dichlorodiphenyl sulfone of claim 1, wherein: the mole ratio of the p-chlorobenzenesulfonyl chloride to the chlorobenzene and anhydrous ferric chloride is 1:1.5-5:0.01-0.2.
4. The process for the cyclical catalytic preparation of 4,4' -dichlorodiphenyl sulfone of claim 1, wherein: when the mother solution is used for preparing the next batch of crude 4,4' -dichlorodiphenyl sulfone, the additional amount of the anhydrous ferric chloride is 1/5-1/4 of the initial addition amount of the anhydrous ferric chloride when the mother solution is prepared.
5. The process for the cyclical catalytic preparation of 4,4' -dichlorodiphenyl sulfone of claim 4, wherein: when the mother solution is used for preparing the next batch of crude 4,4' -dichlorodiphenyl sulfone, the adding amount of the chlorobenzene is 1/3-2/3 of the initial adding amount of the chlorobenzene when preparing the mother solution.
6. The process for the cyclical catalytic preparation of 4,4' -dichlorodiphenyl sulfone of claim 1, wherein: in the step S1, after the reaction is finished, the method comprises the following steps: when the content of the residual p-chlorobenzenesulfonyl chloride in the reaction liquid is less than or equal to 3 percent.
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