CN102791679A - Method for producing 4-chlorobenzene sulphonic acid and 4,4'-dichlorodiphenylsulphone - Google Patents
Method for producing 4-chlorobenzene sulphonic acid and 4,4'-dichlorodiphenylsulphone Download PDFInfo
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- CN102791679A CN102791679A CN2011800124916A CN201180012491A CN102791679A CN 102791679 A CN102791679 A CN 102791679A CN 2011800124916 A CN2011800124916 A CN 2011800124916A CN 201180012491 A CN201180012491 A CN 201180012491A CN 102791679 A CN102791679 A CN 102791679A
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- C07—ORGANIC CHEMISTRY
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/39—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing halogen atoms bound to the carbon skeleton
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- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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Abstract
The invention relates to a method for producing 4-chlorobenzene sulphonic acid from 2-chlorobenzene sulphonic acid and/or 3-chlorobenzene sulphonic acid, comprising the reaction of 2-chlorobenzene sulphonic acid and/or 3-chlorobenzene sulphonic acid to form 4-chlorobenzene sulphonic acid in the presence of sulphuric acid at a temperature of 100 to 300 DEG C. The invention further relates to a method for producing 4,4'-dichlorodiphenylsulphone, comprising said method for producing 4-chlorobenzene sulphonic acid.
Description
The present invention relates to a kind ofly prepare the method for 4-chlorobenzenesulfonic acid by 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid, it is included under 100-300 ℃ the temperature and in the presence of sulfuric acid, 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid is changed into the 4-chlorobenzenesulfonic acid.
The invention further relates to a kind of preparation 4, the method for 4 '-dichloro diphenyl sulfone, it comprises the method for the said 4-of preparation chlorobenzenesulfonic acid.
4, the monomer during 4 '-dichloro diphenyl sulfone especially synthesizes as the poly (arylene ether) sulfone.Commercially important instance is a polyethersulfone (4; 4 '-dihydroxy diphenylsulphone and 4, the polymerization of 4 '-dichloro diphenyl sulfone), polysulfones (dihydroxyphenyl propane and 4, the polymerization of 4 '-dichloro diphenyl sulfone) and PPSU (4; 4 '-dihydroxybiphenyl and 4, the polymerization of 4 '-dichloro diphenyl sulfone).4, the center cell that therefore 4 '-dichloro diphenyl sulfone prepares for these industrial copolymers.
The preferred reactant of preparation poly (arylene ether) sulfone is a high purity 4, and 4 '-dichloro diphenyl sulfone has required product property like chemical and the linearity of thermostability, high-dimensional stability and flame retardant resistance, non-angle polymkeric substance because 4,4 ' isomer only forms.
Preparation 4, the method for 4 '-dichloro diphenyl sulfone is known by prior art.Currently known methods especially comprise originate in monochloro benzene and sulphonating agent by the 4-chlorobenzenesulfonic acid as intermediate preparation, said midbody generally is unseparated.
DE 2252571 has described in pressure reactor under 220-260 ℃ temperature, remove simultaneously formation reaction water and by monochloro benzene and the synthetic dichloro diphenyl sulfone of sulfuric acid.
US 2,593, and 001 has described through making the reaction of aromatic sulfonic acid and aromatic hydrocarbons prepare the continuation method of diaryl sulfone, wherein through with the aromatic substance of gas form adverse current adding with reaction water from removing continuously the reaction zone.
US 2,971, and 985 disclose use SO
3, the synthetic dichloro diphenyl sulfone of methyl-sulfate and monochloro benzene.
It is required 4 that preparation dichloro diphenyl sulfone synthetic not only forms, 4 '-dichloro diphenyl sulfone, and always obtain 2,4 ' of different amounts-with 3, and 4 '-isomer, said isomer venue hereinafter is called 4, the incorrect isomer of 4 '-dichloro diphenyl sulfone.For obtaining can be used for 4 in the polymerization, 4 '-dichloro diphenyl sulfone must be with it with very pure isolated in form (usually>99.0 weight %).
Can with the dichloro diphenyl sulfone mixture of isomers for example through with/crystallization and aftertreatment from alcohol, required 4, the 4 '-dichloro diphenyl sulfone of the purity that is improved.EP-A 279387 has described such purification through recrystallize.
Another method of removing incorrect isomer is US 4,876, the chromatographic separation of 390 said isomer mixtures.
Under any circumstance all do not mention and be inappropriate for polymeric 4, the incorrect isomer of 4 '-dichloro diphenyl sulfone and the by product isomer of monochloro Phenylsulfonic acid, the i.e. place of 2-chlorobenzenesulfonic acid, 3-chlorobenzenesulfonic acid and 4-chlorobenzenesulfonic acid.
In principle, undesired isomer can be abandoned after from method, discharging.This can be through discharging a part of crystalline mother solution or after from mother liquor, removing incorrect isomer, carrying out.The two has considerably reduced the method yield based on raw material.In addition, processing costs is risen in addition.In this article, can not ignore environment protection aspect (correct handling of chlorinated aromatics).
Therefore to not abandoning from the incorrect isomer of dichloro diphenyl sulfone synthetic, but they are changed into 4,4 '-dichloro diphenyl sulfone is so that therefore improving yield exists suitable interest.
The isomerization reaction itself that originates in aryl sulfone is known by prior art.At Zhurnal Organicheskoi Kimii, in 1976,12 (2), 397 and 1976,13 (6), 1204, people such as V.A.Kozlov have reported tolyl benzene sulfone and the isomerizing of xylyl benzene sulfone in 92.3% sulfuric acid and have separated.Yet, changing into 4 from the incorrect isomer of dichloro diphenyl sulfone synthetic, 4 '-dichloro diphenyl sulfone is impossible by this way.
If the purpose of this invention is to provide the preparation 4 that has above-mentioned shortcoming, the method for 4 '-dichloro diphenyl sulfone with littler degree.
More particularly, preparation 4, the yield of the currently known methods of 4 '-dichloro diphenyl sulfone should through will as by product form 2,4 ' and/or 3,4 '-dichloro diphenyl sulfone changes into 4,4 '-dichloro diphenyl sulfone and improving.
Above-mentioned purpose is through the inventive method and preparation 4 of preparation 4-chlorobenzenesulfonic acid, and the inventive method of 4 '-dichloro diphenyl sulfone realizes.Preferred embodiment can be inferred by following claims and specification sheets.The combination of preferred embodiment can not depart from scope of the present invention.
By monochloro benzene preparation 4, the method for 4 '-dichloro diphenyl sulfone comprises the method that is prepared 4-monochloro Phenylsulfonic acid by 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid.
The inventive method for preparing 4-monochloro Phenylsulfonic acid by 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid is included under 100-300 ℃ and in the presence of sulfuric acid, 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid is changed into the 4-chlorobenzenesulfonic acid.
Explained hereunder is prepared the inventive method of 4-monochloro Phenylsulfonic acid and is prepared 4, each step of the inventive method of 4 '-dichloro diphenyl sulfone by monochloro benzene by 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid.
The method for preparing the 4-chlorobenzenesulfonic acid
The monochloro Phenylsulfonic acid can be with the form of 2-chlorobenzenesulfonic acid, 3-chlorobenzenesulfonic acid or 4-chlorobenzenesulfonic acid, or exists as the mixture of two or three above-claimed cpd.Comprise at least two kinds of above-mentioned mixture of isomers are called the monochloro Phenylsulfonic acid in context of the present invention isomer mixture.
The present invention can originate in the 2-chlorobenzenesulfonic acid or originate in the 3-chlorobenzenesulfonic acid and carry out, and preferably originates in the conversion of 2-chlorobenzenesulfonic acid.Equally preferably originate in the mixture that comprises 2-chlorobenzenesulfonic acid and 3-chlorobenzenesulfonic acid and optional 4-chlorobenzenesulfonic acid, promptly originate in isomer mixture and carry out this method.
This method also can originate in addition 4-chlorobenzenesulfonic acid on the one hand and on the other hand 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid mixture and carry out.The isomer mixture that especially preferably originates in the monochloro Phenylsulfonic acid that comprises the 2-chlorobenzenesulfonic acid transforms.
When conversion originated in the isomer mixture of the monochloro Phenylsulfonic acid that comprises the 4-chlorobenzenesulfonic acid, it carried out along with the increase of 4-chlorobenzenesulfonic acid ratio in the isomer mixture.
According to the present invention, the temperature in the conversion process is 100-300 ℃.Temperature of the present invention can be set up in a different manner.More particularly, monochloro Phenylsulfonic acid and sulfuric acid initial compounds can mix under suitable temperature.More particularly, also can prepare mixture being lower than under the temperature of invert point, heat this mixture then.Importantly temperature is remained in the 100-300 ℃ of scope for the purpose of the present invention.
Selectivity and speed that temperature effect 4-chlorobenzenesulfonic acid forms.Invert point is preferably 150 ℃-250 ℃, and especially 170 ℃-210 ℃, more preferably 180-200 ℃.In said scope, the selectivity that the 4-chlorobenzenesulfonic acid forms is high especially.Simultaneously, formation speed is enough high.
The time length that transforms can be during wide in variation.The time length that transforms is to be understood that the time of satisfying condition of the present invention that means.The time length that transforms is preferably 5 minutes to 12 hours, and especially 15 minutes to 3 hours, more preferably 30 minutes to 2 hours.
Used vitriolic amount changes in wide region.Yet the yield to the 4-chlorobenzenesulfonic acid when mol ratio of discovery sulfuric acid and monochloro Phenylsulfonic acid is at least 1 is favourable.The mol ratio of sulfuric acid consumption and monochloro Phenylsulfonic acid consumption is preferably 1-100, especially 2-20, more preferably 3-15.
Used vitriolic concentration is preferably 75-93 weight % based on used vitriolic total amount, especially 80-90 weight %, more preferably 83-87 weight %.Meet these concentration ranges and cause high 4-chlorobenzenesulfonic acid yield and sufficiently high speed of reaction.Usually, the vitriolic weight percentage should be understood with respect to the gross weight of the water that exists in sulfuric acid and the sulfuric acid.With the difference of 100 weight % so by water generates, there is the formation that promotes the 4-chlorobenzenesulfonic acid in water with said scope.
Conversion in the preferred context of the present invention is carried out in sulfuric acid.This conversion is carried out in liquid phase in sulfuric acid.In preferred embodiments, transform not existing under other fluid cpds that is different from sulfuric acid and initial compounds and carry out.This makes avoids unfavorable Dilution of sulphuric acid to reduce with active.
Transform preferably along with intense mixing is carried out.Useful blending means comprises all ordinary methods, especially stirs.Mixing can be before transforming and/or during carry out.In addition, known all methods that in liquid phase, transform of those skilled in the art are useful to transforming, but should select to consider reaction conditions about the material of reactor drum.The preferred embodiment of reacting is stirred tank reactor or the static mixer with downstream time-delay reaction device.
Preparation 4, the method for 4 '-dichloro diphenyl sulfone
In one embodiment of the invention, the said method of preparation 4-chlorobenzenesulfonic acid is attached to originates in monochloro benzene preparation 4, the method for 4 '-dichloro diphenyl sulfone.This has improved preparation 4, the yield of the method for 4 '-dichloro diphenyl sulfone.
Therefore, the present invention provides a kind of monochloro benzene preparation 4 that originates in, the method for 4 '-dichloro diphenyl sulfone, and it comprises the inventive method of preparation 4-chlorobenzenesulfonic acid.Can all preferred embodiments of in the context of the method for preparing the 4-chlorobenzenesulfonic acid, describing advantageously be attached to preparation 4, in the method for 4 '-dichloro diphenyl sulfone.Unique prerequisite is preparation 4, and the method for 4 '-dichloro diphenyl sulfone is carried out as midbody via the 4-chlorobenzenesulfonic acid.
In conversion process; All of carrying out as midbody via the 4-chlorobenzenesulfonic acid are by monochloro benzene preparation 4, the method for 4 '-dichloro diphenyl sulfone form have required 4,4 '-dichloro diphenyl sulfone and at least a incorrect isomer; But common two kinds of incorrect isomer, 2; 4 '-dichloro diphenyl sulfone and 3,4 '-dichloro diphenyl sulfone, and the mixture of common 2-chlorobenzenesulfonic acid, 3-chlorobenzenesulfonic acid and/or 4-chlorobenzenesulfonic acid.
In preferred embodiments, preparation 4, the method for 4 '-dichloro diphenyl sulfone comprises following steps at least:
(a) monochloro benzene is changed into comprise 4,4 '-dichloro diphenyl sulfone and at least aly be selected from 2,4 '-dichloro diphenyl sulfone and 3, the mixture of the compound of 4 '-dichloro diphenyl sulfone forms the 4-chlorobenzenesulfonic acid as midbody,
(b) from step (a), remove 4 at least in part in the gained mixture, 4 '-dichloro diphenyl sulfone,
(c) in the presence of sulfuric acid, separate 2,4 '-dichloro diphenyl sulfone and/or 3,4 '-dichloro diphenyl sulfone be with optional 4,4 '-dichloro diphenyl sulfone,
(d) simultaneously or subsequently, the inventive method through preparing the 4-chlorobenzenesulfonic acid by 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid with the isomer mixture of gained monochloro Phenylsulfonic acid in the step (c) change into the 4-chlorobenzenesulfonic acid and
(e) make gained 4-chlorobenzenesulfonic acid recycling at least in part in the step (d), and transform again according to step (a).
Above step (a) relates to monochloro benzene is changed into 4,4 '-dichloro diphenyl sulfone and at least aly be selected from 2,4 '-dichloro diphenyl sulfone and 3, the mixture of the compound of 4 '-dichloro diphenyl sulfone.In principle, originate in the monochloro benzo by the 4-chlorobenzenesulfonic acid as intermediate preparation 4, all known means of 4 '-dichloro diphenyl sulfone is used for the context of the inventive method.Correlation method is well known by persons skilled in the art.
Usually, the reaction of monochloro benzene and sulphonating agent forms the 4-chlorobenzenesulfonic acid.Yet this forms the not incorrect isomer of the monochloro Phenylsulfonic acid of ideal by product of conduct inevitably.Make the reaction of 4-chlorobenzenesulfonic acid and 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid isomer and monochloro benzene obtaining 4 subsequently, 4 '-dichloro diphenyl sulfone, it forms the incorrect isomer of said dichloro diphenyl sulfone.The monochloro Phenylsulfonic acid not can be used as yet and can form by isolating midbody.
In preferred first embodiment, 4,4 '-dichloro diphenyl sulfone reacts in counter-current tower through 4-chlorobenzenesulfonic acid and monochloro benzene and forms, wherein with reaction water through the aromatic hydrocarbons that adds at tower bottom with gas form via the top continuously stripping go out.For synthesizing 4,4 '-dichloro diphenyl sulfone can add 4-chlorobenzenesulfonic acid or sulfuric acid at the top of tower.The latter at first reacts to obtain the monochloro Phenylsulfonic acid with monochloro benzene in tower, and said monochloro Phenylsulfonic acid also reacts to obtain dichloro diphenyl sulfone with monochloro benzene then.Correlation method for example is described in US 2,593, in 001, its content is all introduced among this paper.
In second preferred embodiment, dichloro diphenyl sulfone uses SO
3, the preparation of methyl-sulfate and monochloro benzene.This relates at first makes SO
3With methyl-sulfate molar ratio reaction with 2:1 under mild conditions.In this process, a part of SO
3React to form corresponding pyrosulfuric acid ester with methyl-sulfate.All the other SO
3Keep being dissolved in the liquid of formation.Subsequently this mixture is mixed (2 moles of monochloro benzene/2 mole SO under the temperature below 100 ℃ with monochloro benzene
3With 1 mol dimethyl sulfate).Dissolved SO
3, pyrosulfuric acid dimethyl ester and monochloro benzene forms 1 mole of dichloro diphenyl sulfone and 2 mol sulfuric acid, one methyl esters.Reaction mixture is got in the water.Dichloro diphenyl sulfone is settled out.This is filtered and drying.Correlation method for example is described in US 2,971, in 985, its content is all introduced among this paper.
In the process of step (a), can choose the aftertreatment of carrying out one or more reaction product with mode well known by persons skilled in the art wantonly.Aftertreatment is to be understood that and means 4, the recovery of 4 '-dichloro diphenyl sulfone and optional the purification.Correlation method carries out through carrying out step (a) and being similarly method known to those skilled in the art.
In one embodiment, reaction mixture is separated through two kinds of liquid phases that add entry and separation formation.Water comprises unconverted monochloro Phenylsulfonic acid.Vaporize water, and reclaim the monochloro Phenylsulfonic acid as raw material.Can dichloro diphenyl sulfone be separated with the organic phase of mainly being made up of monochloro benzene and dichloro diphenyl sulfone subsequently.Correlation method for example is described in US 4,937, in 387, its content all is incorporated herein.About removing of the incorrect isomer of dichloro diphenyl sulfone, referring to step (b).
It is undesired 2 that the further reaction of 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid and monochloro benzene causes, 4 '-dichloro diphenyl sulfone and/or 3, the formation of 4 '-dichloro diphenyl sulfone isomer.
In step (a) afterwards, in the process of step (b), remove 4,4 '-dichloro diphenyl sulfone.
Need 4, the removing of 4 '-dichloro diphenyl sulfone, because it has constituted most of final product that finally obtains according to the present invention, should be with fully removing in its further conversion from step (c).Step (c)-(e) is particularly useful for improving the yield of step (a).
Remove 4, the correlation method of 4 '-dichloro diphenyl sulfone is well known by persons skilled in the art.As stated, remove and for example to carry out through chromatography.Preferably remove through crystallization, of EP 279387, its content all is incorporated herein.
Preferably will comprise 2; 4 '-dichloro diphenyl sulfone and/or 3; 4 '-dichloro diphenyl sulfone, have or do not have 2-chlorobenzenesulfonic acid, 3-chlorobenzenesulfonic acid and/or 4-chlorobenzenesulfonic acid and do not contain 4 at least in part, the mixture of 4 '-dichloro diphenyl sulfone is further aftertreatment and infeeding in the step (c).Yet; In optional embodiment; Can in intermediate steps, remove 2-chlorobenzenesulfonic acid, 3-chlorobenzenesulfonic acid and/or 4-chlorobenzenesulfonic acid also only with 4, the incorrect isomer of 4 '-dichloro diphenyl sulfone infeeds in the step (c), and the monochloro Phenylsulfonic acid of removing is used further in the method.
Preferably remove chlorobenzene with carrying out before the step (c) afterwards in step (b).The correlation method of removing chlorobenzene is well known by persons skilled in the art, and distillation is especially suitable.This can prevent undesired other chlorobenzenesulfonic acid of being formed by monochloro benzene owing to further transform.
Subsequently, with 2,4 '-dichloro diphenyl sulfone and/or 3,4 '-dichloro diphenyl sulfone separate in the presence of sulfuric acid to form the isomer mixture of monochloro Phenylsulfonic acid in step (c).
Used vitriolic concentration is preferably 90-100 weight % based on used vitriolic gross weight in the step (c), more preferably 93-100 weight %, especially 94-98 weight %, most preferably 96 weight %.In sulfuric acid, transform and preferably in liquid phase, carry out.
Temperature in the step (c) can be through wide variety.Yet, advantageously under at least 100 ℃ temperature, carry out separating, because otherwise isolating speed is too low with sulfuric acid.Step (c) especially 140-250 ℃, is more preferably carried out under 160-230 ℃ the temperature preferably at 100-300 ℃.
In principle, the time length that transforms in the step (c) can change during wide.The time length that transforms is to be understood that the time of satisfying condition of the present invention that means.The time length that transforms is preferably 5 minutes to 12 hours, and especially 15 minutes to 3 hours, more preferably 30 minutes to 2 hours.
Used vitriolic amount can be through wide variety.Yet, find that be favourable when the mol ratio of acid and dichloro diphenyl sulfone is at least 1.The mol ratio of sulfuric acid consumption and dichloro diphenyl sulfone consumption is preferably 1-100, especially 2-20, more preferably 3-15.
The conversion of step (c) preferably in suitable containers and/or reactor drum accompanied by intense mix and to carry out.Correlation method is well known by persons skilled in the art and observes reaction conditions of the present invention.
With step (c) simultaneously or afterwards, in the process of step (d), the present invention who carries out isomer mixture to 4-chlorobenzenesulfonic acid transforms.Above corresponding embodiment has been described in.Can use in principle and be appointed as preferred all embodiments.
Step (d) is preferably carried out in step (c) afterwards, adjusts reaction conditions simultaneously.Yet, can carry out step (d) and step (c) simultaneously in principle.Under latter event, the condition of set-up procedure (c) has made and has started from the inventive method that 2-monochloro Phenylsulfonic acid and/or 3-monochloro Phenylsulfonic acid prepare 4-monochloro Phenylsulfonic acid simultaneously.In this case, those skilled in the art are through correspondingly selecting the addition of said preferred reaction time the step (c) and the time length (d) of combination.Step (c) and be equivalent to carry out continuously under the same conditions (d) time.In this case, needs are carrying out combination step in the presence of sulfuric acid under 100-300 ℃ the temperature according to the present invention.In the context of the method for preparing the 4-chlorobenzenesulfonic acid, explained preferred embodiment.
Yet, preferably at first carry out step (c), step (d) then, two steps have different reaction conditions.Transformation to step (d) is carried out through changing reaction conditions then.
Therefore, preferably be adjusted to according to the required condition of step (d) and carry out transformation from step (c) to step (d) through the required condition that will originate in step (c).The adjustment of condition preferably relates to vitriolic concentration, and this concentration is preferably 80-90 weight %, especially 82-88 weight %, more preferably 83-87 weight % in step (d).Used vitriolic concentration is preferably 90-100 weight % in the step (c), more preferably 93-100 weight %, especially 94-97 weight %, most preferably 96 weight %.Vitriolic concentration is especially through dilute with water, promptly adds entry and adjusts.
The also separable in principle reaction discharge that is produced by step (c) is used for step (d) with it then.Yet, preferably carry out step (d) afterwards in step (c).
In the process of step (e), make gained 4-chlorobenzenesulfonic acid recycling at least in part in the step (d), preferably after removing, transform again according to step (a).Therefore, gained 4-chlorobenzenesulfonic acid is used to improve 4, the yield of 4 '-dichloro diphenyl sulfone.
The 4-chlorobenzenesulfonic acid preferably passes through extraction or deposition, and more preferably removes through crystallization.
Embodiment
Comparative Examples 1
With 1g (3.5 mmole) 2, the 4-dichloro diphenyl sulfone is suspended in 10ml (18.4g the is equivalent to 180 mmoles) vitriol oil (96 weight %) and at 170 ℃ and stirred 3 hours down.
After 3 hours reaction times, neither there is dichloro diphenyl sulfone in the reaction discharge, there is not any monochloro benzene yet.Analyze according to HPLC, reaction product comprises the mixture of 2-, 3-and 4-chlorobenzenesulfonic acid.Replace isomerizing, only obtain the split product of dichloro diphenyl sulfone.The isomerizing of dichloro diphenyl sulfone is impossible by this way.
Comparative Examples 2
With 1g (3.5 mmole) 2,4-dichloro diphenyl sulfone and 1g (3.5 mmole) 3,4-dichloro diphenyl sulfone are suspended in 4.8g (42 moles) 85% sulfuric acid and at 190 ℃ and stirred 13 hours down.Analyze according to HPLC, obtain, 4 '-dichloro diphenyl sulfone, 94.5 weight %3,4 '-dichloro diphenyl sulfone and 3.3 weight %4, the product mixtures that 4 '-dichloro diphenyl sulfone is formed by 0.5 weight %2.
Therefore principal product is undesired 3,4 '-dichloro diphenyl sulfone.4,4 '-dichloro diphenyl sulfone is very lesser extent ground formation only.
Embodiment 3
Be suspended in 4.8g (42 mmole) the 85 weight % sulfuric acid 1g (5.2 mmole) 2-chlorobenzenesulfonic acid and stirring under 190 ℃.After being reflected at 10,60 and 180 minutes through cooling with use DMSO-D
6The dilution and stop.Through
1H NMR measures and forms (result in the table 1).
Table 1 (about embodiment 3, all numerals are represented with mole %)
Therefore, under 190 ℃ in 3 equivalents, 85% sulfuric acid, originate in the 2-chlorobenzenesulfonic acid, obtain the 4-chlorobenzenesulfonic acid, and do not observe the 3-chlorobenzenesulfonic acid of respective amount in the discharge in reaction.
Therefore 4, the recycling of the incorrect isomer of 4 '-dichloro diphenyl sulfone is through with 4, the incorrect isomer division of 4 '-dichloro diphenyl sulfone, and subsequently with the isomerizing of monochloro Phenylsulfonic acid, enrichment 4-chlorobenzenesulfonic acid but possible simultaneously.
Claims (13)
1. one kind prepares the method for 4-chlorobenzenesulfonic acid by 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid, and it is included under 100-300 ℃ the temperature and in the presence of sulfuric acid, 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid is changed into the 4-chlorobenzenesulfonic acid.
2. according to the process of claim 1 wherein that the isomer mixture that said conversion originates in the monochloro Phenylsulfonic acid that comprises 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid and optional 4-chlorobenzenesulfonic acid carries out.
3. according to the method for claim 1 or 2, wherein said conversion originates in the isomer mixture of the monochloro Phenylsulfonic acid that comprises the 2-chlorobenzenesulfonic acid and carries out.
4. according to each method among the claim 1-3, wherein said conversion originate in the isomer mixture of the monochloro Phenylsulfonic acid in the presence of the 4-chlorobenzenesulfonic acid and along with isomer mixture in 4-chlorobenzenesulfonic acid ratio increase and carry out.
5. according to each method among the claim 1-4, wherein said invert point is 150-250 ℃, especially 170-210 ℃.
6. according to each method among the claim 1-5, the mol ratio of wherein said vitriolic consumption and monochloro Phenylsulfonic acid consumption is 1-100, especially 2-20.
7. according to each method among the claim 1-6, wherein said vitriolic concentration is 80-90 weight %, especially 83-87 weight %.
8. according to each method among the claim 1-7, wherein said conversion was carried out in 15 minutes to 3 hours.
9. one kind prepares 4, the method for 4 '-dichloro diphenyl sulfone, and it comprises according to each method among the claim 1-8.
10. one kind prepares 4, the method for 4 '-dichloro diphenyl sulfone, and it comprises that order is the following steps of a-b-c-d-e:
(a) monochloro benzene is changed into comprise 4,4 '-dichloro diphenyl sulfone and at least aly be selected from 2,4 '-dichloro diphenyl sulfone and 3, the mixture of the compound of 4 '-dichloro diphenyl sulfone forms the 4-chlorobenzenesulfonic acid as midbody,
(b) from step (a), remove 4 at least in part in the gained mixture, 4 '-dichloro diphenyl sulfone,
(c) in the presence of sulfuric acid, separate 2,4 '-dichloro diphenyl sulfone and/or 3,4 '-dichloro diphenyl sulfone be with optional 4, and 4 '-dichloro diphenyl sulfone to be forming the isomer mixture of monochloro Phenylsulfonic acid,
(d) with step (c) simultaneously or afterwards in step (c), according among the claim 1-8 each with 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid change into the 4-chlorobenzenesulfonic acid and
(e) make gained 4-chlorobenzenesulfonic acid recycling at least in part in the step (d), and transform again according to step (a).
11. according to the method for claim 10, wherein used vitriolic concentration is 90-100 weight %, especially 93-100 weight % in the step (c).
12. according to the method for claim 10 or 11, wherein vitriolic concentration is 80-100 weight %, especially 82-88 weight % in the process of step (d).
13. according to each method among the claim 10-12, wherein step (d) is carried out in step (c) afterwards.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10155591 | 2010-03-05 | ||
| EP10155591.0 | 2010-03-05 | ||
| PCT/EP2011/053010 WO2011107465A1 (en) | 2010-03-05 | 2011-03-01 | Method for producing 5-chlorobenzene sulphonic acid and 4,4'-dichlorodiphenylsulphone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102791679A true CN102791679A (en) | 2012-11-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800124916A Pending CN102791679A (en) | 2010-03-05 | 2011-03-01 | Method for producing 4-chlorobenzene sulphonic acid and 4,4'-dichlorodiphenylsulphone |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP2542522A1 (en) |
| JP (1) | JP2013521248A (en) |
| KR (1) | KR20130043620A (en) |
| CN (1) | CN102791679A (en) |
| BR (1) | BR112012021587A2 (en) |
| WO (1) | WO2011107465A1 (en) |
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| CN109369468A (en) * | 2011-12-15 | 2019-02-22 | 索尔维特殊聚合物美国有限责任公司 | For the method from the mixture of dihalo- diaryl sulfone isomers manufacture halogen aryl compound |
| KR102629634B1 (en) | 2015-06-09 | 2024-01-25 | 오로리움 홀딩스 엘엘씨 | Improved process for preparing diaryl sulfones |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3632642A (en) * | 1968-10-07 | 1972-01-04 | Chris Craft Ind Inc | Production of arylsulfonyl chlorides |
| US4873372A (en) * | 1987-02-17 | 1989-10-10 | Basf Aktiengesellschaft | Isolation of 4,4'-dichlorodiphenyl sulfone |
| US4876390A (en) * | 1988-08-19 | 1989-10-24 | Uop | Process for separating dichlorodiphenylsulfone isomers |
| US4983773A (en) * | 1988-10-19 | 1991-01-08 | Basf Aktiengesellschaft | Preparation of bis-(4-chlorophenyl) sulfone |
| EP0592857A2 (en) * | 1992-10-12 | 1994-04-20 | Heidelberger Druckmaschinen Aktiengesellschaft | Device for trouble free transporting products in folding machines |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2593001A (en) | 1950-01-31 | 1952-04-15 | Stauffer Chemical Co | Process for manufacture of a diphenyl sulfone |
| US2971985A (en) | 1958-07-05 | 1961-02-14 | Roussel Uclaf | Process for the preparation of 4, 4'-dichlorodiphenylsulfone |
| GB1393929A (en) | 1972-10-16 | 1975-05-14 | Ici Ltd | Production of di-4-chlorophenyl sulphone |
| US4937387A (en) | 1986-09-05 | 1990-06-26 | Amoco Corporation | Processes for preparing diaryl sulfones |
| JPH06172298A (en) * | 1992-10-06 | 1994-06-21 | Ube Ind Ltd | Production of dichlrodiphenylsulfone |
-
2011
- 2011-03-01 JP JP2012555397A patent/JP2013521248A/en not_active Withdrawn
- 2011-03-01 CN CN2011800124916A patent/CN102791679A/en active Pending
- 2011-03-01 EP EP11708016A patent/EP2542522A1/en not_active Withdrawn
- 2011-03-01 KR KR1020127025928A patent/KR20130043620A/en not_active Application Discontinuation
- 2011-03-01 BR BR112012021587A patent/BR112012021587A2/en not_active IP Right Cessation
- 2011-03-01 WO PCT/EP2011/053010 patent/WO2011107465A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3632642A (en) * | 1968-10-07 | 1972-01-04 | Chris Craft Ind Inc | Production of arylsulfonyl chlorides |
| US4873372A (en) * | 1987-02-17 | 1989-10-10 | Basf Aktiengesellschaft | Isolation of 4,4'-dichlorodiphenyl sulfone |
| US4876390A (en) * | 1988-08-19 | 1989-10-24 | Uop | Process for separating dichlorodiphenylsulfone isomers |
| US4983773A (en) * | 1988-10-19 | 1991-01-08 | Basf Aktiengesellschaft | Preparation of bis-(4-chlorophenyl) sulfone |
| EP0592857A2 (en) * | 1992-10-12 | 1994-04-20 | Heidelberger Druckmaschinen Aktiengesellschaft | Device for trouble free transporting products in folding machines |
Non-Patent Citations (1)
| Title |
|---|
| E. N. KRYLOV等: "Hydrolysis of Aromatic Sulfonic Acids under Thermodynamic Control of the Reaction", 《JOURNAL OF ORGANIC CHEMISTRY OF USSR(ZHURNAL ORGANICCHESKIO KHIMII)》, vol. 19, no. 6, 30 June 1983 (1983-06-30), pages 1263 - 1268, XP008136364 * |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112012021587A2 (en) | 2016-09-13 |
| KR20130043620A (en) | 2013-04-30 |
| WO2011107465A1 (en) | 2011-09-09 |
| JP2013521248A (en) | 2013-06-10 |
| EP2542522A1 (en) | 2013-01-09 |
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