CN103497127B - Synthesis method of para-beta-hydroxyethylsulfonyl sulfate aniline - Google Patents
Synthesis method of para-beta-hydroxyethylsulfonyl sulfate aniline Download PDFInfo
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- CN103497127B CN103497127B CN201310443122.3A CN201310443122A CN103497127B CN 103497127 B CN103497127 B CN 103497127B CN 201310443122 A CN201310443122 A CN 201310443122A CN 103497127 B CN103497127 B CN 103497127B
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- sulfate ester
- hydroxyethyl
- sulfone sulfate
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- 238000001308 synthesis method Methods 0.000 title abstract 4
- NTOLGSSKLPLTDW-UHFFFAOYSA-N hydrogen sulfate;phenylazanium Chemical compound OS(O)(=O)=O.NC1=CC=CC=C1 NTOLGSSKLPLTDW-UHFFFAOYSA-N 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005886 esterification reaction Methods 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 92
- 150000002148 esters Chemical class 0.000 claims description 51
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 42
- 239000006185 dispersion Substances 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 17
- 150000007513 acids Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 230000032050 esterification Effects 0.000 claims description 14
- USHWMIZPVJNJST-UHFFFAOYSA-N C1=CC(=CC=C1CCO)NC(=O)C=S(=O)=O Chemical compound C1=CC(=CC=C1CCO)NC(=O)C=S(=O)=O USHWMIZPVJNJST-UHFFFAOYSA-N 0.000 claims description 13
- 238000010189 synthetic method Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000001935 peptisation Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 abstract 2
- 229960001413 acetanilide Drugs 0.000 abstract 1
- 238000005187 foaming Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- GSUXEDYVOMETRR-UHFFFAOYSA-N 2-(2-hydroxyethylsulfonyl)-n-phenylacetamide Chemical compound OCCS(=O)(=O)CC(=O)NC1=CC=CC=C1 GSUXEDYVOMETRR-UHFFFAOYSA-N 0.000 description 4
- QQNXPCCFPQRLMK-UHFFFAOYSA-N S(O)(O)(=O)=O.OCCS(=O)(=O)CCO Chemical compound S(O)(O)(=O)=O.OCCS(=O)(=O)CCO QQNXPCCFPQRLMK-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001568 sexual effect Effects 0.000 description 2
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of para-beta-hydroxyethylsulfonyl sulfate aniline. The synthesis method comprises the following steps: uniformly mixing para-beta-hydroxyethylsulfonyl acetanilide and a catalytic amount of sulfoacid dispersing agent; adding the mixture into sulfuric acid to carry out esterification reaction for removing acetic acid; after the reaction is ended, treating to obtain the para-beta-hydroxyethylsulfonyl sulfate aniline. The synthesis method has the advantages that the sulfoacid dispersing agent used as a performance additive is added into a reaction system to change the state of a material in the reaction process, so that the material is changed from the original peptization state to a foaming peptization state, the reaction efficiency is increased, the reaction energy consumption is reduced, the material crushing effect is improved, the content of insoluble matters in a product is finally reduced, the final material is changed from the original solid particles to non-solid particles with micro air holes, and the later dye preparation can be more favorably realized.
Description
Technical field
The invention belongs to dyestuff intermediate synthesis field, be specifically related to a kind of synthesis side of p-beta-hydroxyethyl sulfone sulfate ester aniline.
Background technology
P-beta-hydroxyethyl sulfone sulfate ester aniline, have another name called para-ester, No. CAS is 2494-89-5, structure is as shown in formula I, a kind of important intermediate of reactive dyestuff field, be synthesis KN type the indispensable raw material of M type reactive dyestuffs, may be used for preparing active emerald green blue KN-G, tens kinds of reactive dyestuffs such as reactive yellow M-5R, active deep blue M-4G etc.
In the synthesis of current p-beta-hydroxyethyl sulfone sulfate ester aniline, main employing be after the drying of p-beta-hydroxyethyl sulfuryl Acetanilide (structure is as shown in formula II), add a certain proportion of sulfuric acid and carry out decompression esterification desacetoxy reaction 8 ~ 12 hours, again to reactant dispersion and fining, obtain qualified p-beta-hydroxyethyl sulfone sulfate ester aniline.Because p-beta-hydroxyethyl sulfuryl Acetanilide is unstable, soluble easy carbonization of being heated, forms insoluble carbide in last product; In reaction process, material is solid-state process by liquid conversion simultaneously, can form the great peptization sexual state of viscosity, can produce great load to equipment, energy consumption is very large, the material extreme hardness finally obtained, and particle is thick, to cause in reaction and all fragile equipment in later stage crushing material refinement.Thus, in traditional p-beta-hydroxyethyl sulfone sulfate ester aniline synthesis, there is insolubles and exceed standard in the p-beta-hydroxyethyl sulfone sulfate ester aniline obtained, and equipment requirements is high.
Publication number is the preparation technology that the Chinese patent application of CN 101633630A discloses a kind of p-beta-hydroxyethyl sulfone sulfate ester aniline, the sulfuric acid being 95 ~ 98% with the p-beta-hydroxyethyl sulfuryl Acetanilide of moisture and content is directly carried out decompression esterification reaction, obtain p-beta-hydroxyethyl sulfone sulfate ester aniline work in-process, p-beta-hydroxyethyl sulfone sulfate ester aniline work in-process are added to the water making beating, then filter, drying is carried out to filter cake, obtains p-beta-hydroxyethyl sulfone sulfate ester aniline.Adopt this preparation technology to shorten the production time, save drying plant, simplify technique and the secondary transferring decreasing material; And sulfuric acid adds without the need to excessive, reduce postprocessing working procedures and expense.But in this preparation process, the viscosity of reaction system is high, energy consumption is high and large to the loss of equipment; In the product obtained, insolubles is more, and product hardness is high, and particle is thick, is unfavorable for that the later stage uses.
Summary of the invention
The invention provides a kind of synthetic method of p-beta-hydroxyethyl sulfone sulfate ester aniline, this synthetic method can reduce the viscosity that system in process is carried out in reaction, thus reduces the loss of energy and equipment; Meanwhile, in the product obtained, insoluble carbide is few, and the hardness of product is little, and particle is thin, is convenient to subsequent operations.
A kind of synthetic method of p-beta-hydroxyethyl sulfone sulfate ester aniline, comprise the steps: even for the sulphonic acids dispersant of p-beta-hydroxyethyl sulfuryl Acetanilide and catalytic amount, join in sulfuric acid and carry out the reaction of esterification desacetoxy, after reacting completely, obtain described p-beta-hydroxyethyl sulfone sulfate ester aniline through process.
Reaction equation is as follows:
In the present invention, by adding sulphonic acids dispersion agent as modified additive in the reaction of p-beta-hydroxyethyl sulfuryl Acetanilide and sulfuric acid, change the state in material reaction process, make material from original peptization sexual state to foaminess peptization state, the generation of bubble improves p-beta-hydroxyethyl sulfuryl Acetanilide and sulfuric acid esterification effect, reduce energy consumption of reaction, improve crushing material effect, eventually reduce the content of insolubles in product, final material is made to change the non-solid particle of the micro-pore of band into by original full particle, more be conducive to the preparation of later stage dyestuff.Meanwhile, because sulphonic acids dispersion agent substantially all will use in further dye preparation, the sulphonic acids dispersion agent added need not be separated, and also can not have influence on follow-up operation.
The sulphonic acids dispersion agent related in the present invention can acid-fast alkali-proof, good tolerance can be had to highly acid reaction conditions, as preferably, described sulphonic acids dispersion agent is Dispersant MF (CAS:9084-06-4), dispersion agent NNO(CAS:26545-58-4), at least one in dispersion agent S, dispersion agent DDA, dispersing agent C S and dispersion agent MS.As further preferably, described sulphonic acids dispersion agent is at least one in Dispersant MF and dispersion agent NNO, and when using this two kinds of dispersion agents, the viscosity of reaction system is less, and the insolubles of the finished product is less, and granularity is better.
Although described sulphonic acids dispersion agent generally needs to add in subsequent applications, but not easily add too much in this reaction system, to prevent the range of application having influence on p-beta-hydroxyethyl sulfone sulfate ester aniline, as preferably, the mass ratio of described sulphonic acids dispersion agent and described p-beta-hydroxyethyl sulfuryl Acetanilide is 0.01% ~ 3%:1, in this amount ranges, good modifying function can be kept, the impact on subsequent step can be avoided again.As further preferred, the mass ratio of described sulphonic acids dispersion agent and described p-beta-hydroxyethyl sulfuryl Acetanilide is 0.2% ~ 0.3%:1.
In the present invention, described sulfuric acid is excessive slightly, and as preferably, described p-beta-hydroxyethyl sulfuryl Acetanilide and the mol ratio of sulfuric acid are 1:1 ~ 1.1.
Described sulfuric acid adopts the vitriol oil of 98%.
As preferably, the temperature of described esterification desacetoxy reaction is 110 ~ 130 DEG C, and temperature is too high, and side reaction can be caused to occur, and temperature is too low, and raw material reaction can be made insufficient.Temperature as further preferred, described esterification desacetoxy reaction is 110 ~ 120 DEG C.
As preferably, the reaction times of described esterification desacetoxy reaction is 6 ~ 12 hours, and now, reaction can complete fully.
Compared with the existing technology, beneficial effect of the present invention is embodied in:
(1) sulphonic acids dispersion agent is joined in reaction system, greatly improve p-beta-hydroxyethyl sulfone sulfate ester aniline production efficiency, improve the performance of p-beta-hydroxyethyl sulfone sulfate ester aniline simultaneously.
(2) adding by sulphonic acids dispersion agent, change state during material reaction, the generation of bubble, improves material reaction effect, reduces energy consumption, reduce equipment loss simultaneously, improve plant factor, provide cost savings, the p-beta-hydroxyethyl sulfone sulfate ester aniline HPLC finally obtained reaches more than 97%, ammonia value reaches more than 97% simultaneously, and ester value reaches more than 95%.
Embodiment
Below in conjunction with specific embodiment, further detailed description is done to the present invention.
Embodiment 1
850kg added in blending pot to beta-hydroxyethyl sulfuryl Acetanilide, then additional proportion is the dispersion agent NNO of 2kg, mix after 1 hour, mixture is joined in the p-beta-hydroxyethyl sulfone sulfate ester aniline synthesis pot of the sulfuric acid of band 355kg, heat up 120 DEG C and carry out esterification, react after 6 hours, obtain beta-hydroxyethyl sulfone sulfate ester aniline work in-process; P-beta-hydroxyethyl sulfone sulfate ester aniline work in-process are obtained after pulverizing the acetic acid 210kg of p-beta-hydroxyethyl sulfone sulfate ester aniline 994kg and 94%.Its HPLC purity is 97.23%, and retention time is consistent with commercial standard substance, and ammonia value is 97.5%, and ester value is 95.5%, meets p-beta-hydroxyethyl sulfone sulfate ester aniline quality requirements, simultaneous reactions current load is 12A, hardness is 1.5, insolubles is 0.05%.
Embodiment 2
850kg added in blending pot to beta-hydroxyethyl sulfuryl Acetanilide, then additional proportion is dispersion agent NNO and the Dispersant MF mixed aid of the 1:1 of 1.5kg, mix after 1 hour, mixture is joined in the p-beta-hydroxyethyl sulfone sulfate ester aniline synthesis pot of the sulfuric acid of band 355kg, heat up 110 DEG C and carry out esterification, react after 8 hours, obtain beta-hydroxyethyl sulfone sulfate ester aniline work in-process; P-beta-hydroxyethyl sulfone sulfate ester aniline work in-process are obtained after pulverizing the acetic acid 215kg of p-beta-hydroxyethyl sulfone sulfate ester aniline 992.5kg and 93%.Its HPLC is 97.8%, and retention time is consistent with commercial standard substance, and ammonia value is 97.5%, and ester value is 95.3%, meets p-beta-hydroxyethyl sulfone sulfate ester aniline quality requirements, simultaneous reactions current load is 10A, hardness is 1.2, insolubles is 0.04%.
Embodiment 3
850kg added in blending pot to beta-hydroxyethyl sulfuryl Acetanilide, then additional proportion is the dispersant A PEO of 2kg, mix after 1 hour, mixture is joined in the p-beta-hydroxyethyl sulfone sulfate ester aniline synthesis pot of the sulfuric acid of band 355kg, heat up 110 DEG C and carry out esterification, react after 8 hours, obtain beta-hydroxyethyl sulfone sulfate ester aniline work in-process; P-beta-hydroxyethyl sulfone sulfate ester aniline work in-process are obtained after pulverizing the acetic acid 210kg of p-beta-hydroxyethyl sulfone sulfate ester aniline 993kg and 93.7%.Its HPLC is 96.6%, and retention time is consistent with commercial standard substance, and ammonia value is 96.5%, and ester value is 94.8%, meets p-beta-hydroxyethyl sulfone sulfate ester aniline quality requirements, simultaneous reactions current load is 18A, hardness is 3, insolubles is 0.1%.
Comparative example 1
Directly joining 850kg in the p-beta-hydroxyethyl sulfone sulfate ester aniline synthesis pot of the sulfuric acid of band 355kg beta-hydroxyethyl sulfuryl Acetanilide, heats up 110 DEG C and carries out esterification, react after 8 hours, obtain beta-hydroxyethyl sulfone sulfate ester aniline work in-process; P-beta-hydroxyethyl sulfone sulfate ester aniline work in-process are obtained after pulverizing the acetic acid 212kg of high-quality p-beta-hydroxyethyl sulfone sulfate ester aniline 993kg and 93.5%.Its HPLC is 96.9%, and retention time is consistent with commercial standard substance, and ammonia value is 96.8%, and ester value is 94.7%, meets p-beta-hydroxyethyl sulfone sulfate ester aniline quality requirements, simultaneous reactions current load is 22A, hardness is 4.0, insolubles is 0.3%.
Claims (7)
1. the synthetic method of a p-beta-hydroxyethyl sulfone sulfate ester aniline, it is characterized in that, comprise the steps: even for the sulphonic acids dispersant of p-beta-hydroxyethyl sulfuryl Acetanilide and catalytic amount, join in sulfuric acid and carry out the reaction of esterification desacetoxy, after reacting completely, obtain described p-beta-hydroxyethyl sulfone sulfate ester aniline through process;
Described sulphonic acids dispersion agent is at least one in Dispersant MF and dispersion agent NNO.
2. the synthetic method of p-beta-hydroxyethyl sulfone sulfate ester aniline according to claim 1, is characterized in that, the mass ratio of described sulphonic acids dispersion agent and described p-beta-hydroxyethyl sulfuryl Acetanilide is 0.01% ~ 3%:1.
3. the synthetic method of p-beta-hydroxyethyl sulfone sulfate ester aniline according to claim 2, is characterized in that, the mass ratio of described sulphonic acids dispersion agent and described p-beta-hydroxyethyl sulfuryl Acetanilide is 0.2% ~ 0.3%:1.
4. the synthetic method of p-beta-hydroxyethyl sulfone sulfate ester aniline according to claim 2, is characterized in that, described p-beta-hydroxyethyl sulfuryl Acetanilide and the mol ratio of sulfuric acid are 1:1 ~ 1.1.
5. the synthetic method of p-beta-hydroxyethyl sulfone sulfate ester aniline according to claim 1, is characterized in that, the temperature of described esterification desacetoxy reaction is 110 ~ 130 DEG C.
6. the synthetic method of p-beta-hydroxyethyl sulfone sulfate ester aniline according to claim 5, is characterized in that, the temperature of described esterification desacetoxy reaction is 110 ~ 120 DEG C.
7. the synthetic method of p-beta-hydroxyethyl sulfone sulfate ester aniline according to claim 1, is characterized in that, the reaction times of described esterification desacetoxy reaction is 6 ~ 12 hours.
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| CN1286920C (en) * | 2004-04-30 | 2006-11-29 | 江苏申新染料化工股份有限公司 | Active red SBE, synthetic method and its composite active red dye |
| CN101323650B (en) * | 2007-06-13 | 2010-11-03 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst and preparation method and application thereof |
| DE102007061969A1 (en) * | 2007-12-21 | 2008-07-17 | Clariant International Limited | Polymers useful in cosmetic, pharmaceutical or dermatological compositions comprise ammonium or metal N-sulfoalkylacrylamide units and organoammonium N-sulfoalkylacrylamide units |
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| CN101633630A (en) * | 2009-08-17 | 2010-01-27 | 浙江劲光化工有限公司 | Preparation process of p-beta-hydroxyethyl sulfone sulfate ester aniline |
| CN101633631B (en) * | 2009-08-17 | 2012-10-03 | 浙江劲光化工有限公司 | Method for synthesizing sulfonated para-ester |
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