CN101108816A - Method of synthesizing sulfonation paratope ester - Google Patents
Method of synthesizing sulfonation paratope ester Download PDFInfo
- Publication number
- CN101108816A CN101108816A CNA2007100587311A CN200710058731A CN101108816A CN 101108816 A CN101108816 A CN 101108816A CN A2007100587311 A CNA2007100587311 A CN A2007100587311A CN 200710058731 A CN200710058731 A CN 200710058731A CN 101108816 A CN101108816 A CN 101108816A
- Authority
- CN
- China
- Prior art keywords
- ester
- sulfonation
- filtration
- dilution
- hydrolysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention belongs to the technology field of the reactive dye, in particular to the synthetic method of the sulfonation para-ester. The synthetic method of the sulfonation para-ester comprises sulfonation, hydrolysis, dilution, purification, neutralizing salting-out and filtration and over dry. The difference with the prior art is that the control temperature is always not more than 5 DEG C. in the unit operations of dilution, filtration and neutralizing salting-out; the diatomite with volume of 0.6 to 0.7 per cent of the total volume of the reaction solution is added after dilution, and perform filter processing after stirring evenly; the filter cake is adjusted to pulping by water and the pH value is adjusted equal to 6.0 to 6.5 by 20 per cent to 30 per cent sodium bicarbonate solution; the potassium chloride is added based on 7 per cent to 8 per cent of the total volume of the reaction solution to do salting-out; the filter cake is kept after filtration and is dried under the temperature of 80 DEG C. to 85 DEG C.. The adoption of the synthetic method of the sulfonation para-ester of the invention basically avoids the hydrolysis of the ester, filters the impurities such as the byproduct, improves the product quality and realizes the dryness of the product.
Description
Technical field
The invention belongs to active dye technical field, particularly be the synthetic method of sulfonation para-ester.
Background technology
Sulfonation para-ester is an important intermediate of producing reactive dyestuffs, is mainly used in the synthetic of reactive red 330#, S type reactive dyestuffs such as red 333#, orange 320#.Characteristics such as lovely luster, fastness are good because this structure dyestuff has, exhaustion degree height, solubleness height, so be subjected to user's favorable comment with this intermediate synthetic series dyes.The numerous and confused exploitation of main manufacturing enterprise both domestic and external contains the S type dye of sulfonation para-ester.
The synthetic reaction process complexity of sulfonation para-ester, the product standard of existing producer is not high.
As shown in Figure 2, existing manufacturing technique:
1) sulfonation
In the sulfonation jar, put into oleum, under agitation condition, slowly para-ester is evenly put in the sulfonation jar,, prevent caking to guarantee that raw material evenly adds.Keep temperature≤35 ℃ in the process that feeds intake.
Behind reinforced the finishing, slowly be warming up to about 80 ℃, utilize reaction heat, be warming up to 105 ± 1 ℃, to reacting completely with steam.
2) hydrolysis
The reaction back is cooled to below 59 ℃ with false jacket water, drips water then in jar, and temperature control is no more than 60 ℃ during dropping.Add and be warming up to 105 ± 1 ℃ after water finishes, insulation reaction is complete to hydrolysis reaction.Be cooled to 25 ℃.
3) dilution
In thinning tank, put into Di Shui, start stirring, drop into trash ice, then sulfonated bodies is put in the thinning tank.Constantly add trash ice in the dilution, be controlled at all the time below 15 ℃ to keep temperature.The dilution back that finishes adds Repone K saltout (add-on of Repone K be volume 8%).With continuing agitation and filtration after the salt.
4) refining
Add entry in the jar of pulling an oar, drop into the filter cake making beating, water is adjusted volume, and 7% adding Repone K is by volume saltoutd.
5) filtration is dried
With cake filtration, the wet cake packing
In dilution and treating process, owing to contain a large amount of free acids in the sulfonated bodies, with the water heat release, ester group very easily is hydrolyzed into hydroxylic species in this technology.Following reaction takes place:
Many sulfonated bodiess that generate in the sulfonation reaction and hydrolysis of ester group thing and unreacted para-ester all can not be separated from the sulfonation reaction thing, make that the isomer in the sulfonated bodies is very high, influence the quality of product.
If produce product bake drying under 80～85 ℃ condition, and since a large amount of free acids that contain, almost 100% hydrolysis of ester group under the catalysis of acid, thus can't dry, can only be as the tide product.And the both unfavorable transportation of tide product, again can't long storage time.
Summary of the invention
The objective of the invention is to overcome the deficiency of existing technology, overcome the side reactions such as hydrolysis of the generation of the many sulfonated bodiess in the building-up process, sulfonic hydrolysis, ester group, and remove the by product of generation by physical method.This product purity that existing processes is produced is low, impurity is many, can not satisfy the needs of producing high-grade reactive dyestuffs.
Technology of the present invention is as follows:
The synthetic method of sulfonation para-ester, comprise sulfonation, hydrolysis, dilution, refining, neutralization is saltoutd and filtration is dried, unlike the prior art be dilute filtration with the unit operation of saltouing that neutralizes in, controlled temperature is all the time≤5 ℃; The dilution back adds the diatomite of reaction solution cumulative volume 0.6～0.7%, after stirring, press filtration, the filter cake water transfers to making beating, sodium hydrogen carbonate solution with 20～30% is adjusted pH=6.0～6.5, add Repone K by 7～8% of reaction solution cumulative volume and saltout, filter back reservation filter cake, filter cake is dry getting final product under 80～85 ℃ of conditions.
Dilute filtration is controlled low temperature with the unit operation that neutralization is saltoutd, and prevents acidic hydrolysis.
Add filtration adjuvant diatomite, can filter, to remove many sulfonated bodiess and impurity such as micro-hydrolysis of ester group thing and unreacted para-ester.
Add sodium bicarbonate, can remove a large amount of free acids, finished product can drying be a dry product, is beneficial to store and transportation, has made things convenient for the use of product.
Select sodium bicarbonate for use, and, prevent alkaline hydrolysis without yellow soda ash or sodium hydroxide.Because ester group also is easy to take place hydrolysis under alkaline medium.React as follows:
And in the ionization equilibrium of sodium bicarbonate and water, medium is neutral substantially, in and in the free acid, the protection ester group is not hydrolyzed.
Effect of the present invention is:
1, avoid the hydrolysis of ester group:
In dilute filtration and the neutralization unit operation of saltouing, issue unboiled water for fear of ester group in the katalysis of acid and separate, controlled temperature is all the time≤5 ℃ in these two unit.
2, filtering isomer:
The inevitable hydrolysis of ester group thing that produces many sulfonated bodiess, sulfonation para-ester in sulfonation and dilution.Novel process adds filtration adjuvant-diatomite in the unit operation of dilute filtration, these by products are removed.
3, the drying of product:
Because sulfonation para-ester when acid medium condition, comparatively high temps hydrolysis reaction can take place, therefore can't make dry product.The present invention neutralization is saltoutd in the unit operation, uses in the sodium bicarbonate and the free acid of sulfonated bodies, to pH=6.2～6.5, and then can be dry under 80～85 ℃ of conditions.The stable with this understanding not hydrolysis of ester group becomes possibility thereby make sulfonation para-ester make the dry product commodity.
Adopt the synthetic method of sulfonation para-ester of the present invention, its effect is the hydrolysis of having avoided ester group substantially, filters the existence of having removed impurity such as by product, has improved the quality of product, has realized the drying of product.
Description of drawings
Fig. 1: preparation technology's schema of the present invention.
Fig. 2: preparation technology's schema of prior art.
Embodiment
According to the batching of existing technical matters method, through oversulfonate, hydrolysis, dilution, refining, neutralization is saltoutd and filtration is dried, in dilute filtration and the unit operation of saltouing that neutralizes, controlled temperature is all the time≤5 ℃; The dilution back adds the diatomite of reaction solution cumulative volume 0.6～0.7%, after stirring, press filtration, the filter cake water transfers to making beating, sodium hydrogen carbonate solution with 20～30% is adjusted pH=6.0～6.5, add Repone K by 7～8% of reaction solution cumulative volume and saltout, filter back reservation filter cake, filter cake is dry getting final product under 80～85 ℃ of conditions.
Below in conjunction with concrete operations, describe the present invention in detail, effect of the present invention is made further proof, but the present invention is not limited in the present embodiment.
As shown in Figure 1, concrete grammar is as follows:
1) sulfonation
In 3000L sulfonation jar, put into 104.5 ± 0.1% oleum 2830kg.Under agitation condition, 3 hours times spent were evenly put into para-ester 883.2kg (100%) in the sulfonation jar, kept temperature≤35 ℃ in the process that feeds intake.
Behind reinforced the finishing, slowly be warming up to about 80 ℃, utilize reaction heat, be warming up to 105 ± 1 ℃ with steam.Reacted 4 hours.
2) hydrolysis
The reaction back is cooled to below 59 ℃ with cold water, drips water then in jar, and temperature control is no more than 60 ℃ during dropping.Add about water 195kg about 3 hours of time spent.Add and be warming up to 98 ± 1 ℃ after water finishes, insulation reaction 10 hours.Be cooled to 25 ℃.
3) dilute filtration
In the 10000L thinning tank, put into end water 300L, start stirring, drop into trash ice 1500kg, then sulfonated bodies is put in the thinning tank.Constantly add trash ice in the dilution, be controlled at all the time below 5 ℃ to keep temperature.The dilution back adds diatomite 50kg, after stirring, and press filtration.Filtrate collection is standby in the 10000L jar.
4) refining
Stir adding industrial potassium chloride 500kg in filtrate down, saltout one hour after-filtration.Keep filter cake.
5) neutralization is saltoutd
Add entry 2000L in 10000L making beating jar, 1500kg on the rocks drops into the filter cake making beating, and water is adjusted volume to 6000L, keeps temperature≤5 ℃.Sodium hydrogen carbonate solution with 30% (weight concentration) is adjusted pH=6.0～6.5, and 7% adding Repone K is by volume saltoutd.Saltout 1 hour time spent.
6) filtration is dried
With cake filtration, filter cake is put into baking tray, and is dry under 80～85 ℃ of conditions.
7) pulverize, piece together and mix, pack
Dried material is pulverized, put into jar assembly that is mixed after the pulverizing and mix the qualified back of detection packing.
The contrast of the old and new's explained hereafter quality product
| Operational path | Product batches | Many sulfonated bodiess 3.0min (%) | Sulfonation para-ester 3.7min (%) | Hydrolysis of ester group thing 5.0min (%) | Para-ester 6.3min (%) |
| Former technology | 1 | 1.004 | 91.577 | 4.306 | 1.737 |
| 2 | 1.058 | 91.462 | 4.201 | 1.956 | |
| 3 | 1.123 | 91.741 | 3.932 | 1.740 | |
| 4 | 1.155 | 91.814 | 3.348 | 1.248 | |
| Novel process | 5 | 0.311 | 95.867 | 1.442 | 1.349 |
| 6 | 0.469 | 95.620 | 1.741 | 1.455 | |
| 7 | 0.714 | 96.281 | 1.527 | 0.897 | |
| 8 | 0.647 | 95.372 | 1.480 | 1.641 |
After the sulfonation reaction, by operational path of the present invention, major product content rises significantly, and many sulfonated bodiess, hydrolysis of ester group thing reach the para-ester that does not carry out sulfonation reaction greatly to be reduced.Use indexs such as this raw material synthetic dyestuff enhancing rate, degree of fixation to improve, promoted the quality of derived product.
High purity sulfonation para-ester technical indicator
| Sequence number | Index name | Desired value | |
| High purity product | Usual production | ||
| 1 | Outward appearance | The pale pink crystalline powder | The lightpink crystalline powder |
| 2 | HPLC | ≥95％ | ≈89％ |
| 3 | Amino value | ≥70％ | ≈70％ |
| 4 | Value difference | ≤1.0％ | ≤6％ |
。
The synthetic method of the open and sulfonation para-ester that proposes of the present invention, those skilled in the art can be by using for reference this paper content, and links such as appropriate change raw material, processing parameter, processing step realize.Method of the present invention and technology are described by preferred embodiment, person skilled obviously can be in not breaking away from content of the present invention, spirit and scope to method as herein described with technology is changed or suitably change and combination, realize the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (1)
1. the synthetic method of a sulfonation para-ester, comprise sulfonation, hydrolysis, dilution, refining, neutralization is saltoutd and filtration is dried, and it is characterized in that in dilute filtration and the unit operation of saltouing that neutralizes, controlled temperature is all the time≤5 ℃; The dilution back adds the diatomite of reaction solution cumulative volume 0.6～0.7%, after stirring, press filtration, the filter cake water transfers to making beating, sodium hydrogen carbonate solution with 20～30% is adjusted pH=6.0～6.5, add Repone K by 7～8% of reaction solution cumulative volume and saltout, filter back reservation filter cake, filter cake is dry getting final product under 80～85 ℃ of conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100587311A CN100497304C (en) | 2007-08-14 | 2007-08-14 | Method of synthesizing sulfonation paraposition ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100587311A CN100497304C (en) | 2007-08-14 | 2007-08-14 | Method of synthesizing sulfonation paraposition ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101108816A true CN101108816A (en) | 2008-01-23 |
| CN100497304C CN100497304C (en) | 2009-06-10 |
Family
ID=39041102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100587311A Expired - Fee Related CN100497304C (en) | 2007-08-14 | 2007-08-14 | Method of synthesizing sulfonation paraposition ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100497304C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311372A (en) * | 2011-07-04 | 2012-01-11 | 天津德凯化工股份有限公司 | Preparation process of 4-beta-sulfatoethylsulfonyl aniline-2-sulfonic acid |
| CN102391163A (en) * | 2011-07-04 | 2012-03-28 | 天津德凯化工股份有限公司 | Preparation method of sulfonated para-ester serving as dye intermediate |
| CN101633631B (en) * | 2009-08-17 | 2012-10-03 | 浙江劲光化工有限公司 | Method for synthesizing sulfonated para-ester |
| CN105130858A (en) * | 2015-08-25 | 2015-12-09 | 江苏远征化工有限公司 | Clean production process for dye intermediate sulfonated para-ester |
| CN110066230A (en) * | 2018-08-30 | 2019-07-30 | 内蒙古利元科技有限公司 | A kind of novel sulfonated para-ester production system and technique |
| CN110128306A (en) * | 2019-06-18 | 2019-08-16 | 新乡市锦源化工有限公司 | A kind of preparation method of sulfonated para-ester serving as dye intermediate |
| CN111440098A (en) * | 2020-05-14 | 2020-07-24 | 绍兴上虞联谊化工有限公司 | Preparation process of sulfonated para-ester serving as dye intermediate |
-
2007
- 2007-08-14 CN CNB2007100587311A patent/CN100497304C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101633631B (en) * | 2009-08-17 | 2012-10-03 | 浙江劲光化工有限公司 | Method for synthesizing sulfonated para-ester |
| CN102311372A (en) * | 2011-07-04 | 2012-01-11 | 天津德凯化工股份有限公司 | Preparation process of 4-beta-sulfatoethylsulfonyl aniline-2-sulfonic acid |
| CN102391163A (en) * | 2011-07-04 | 2012-03-28 | 天津德凯化工股份有限公司 | Preparation method of sulfonated para-ester serving as dye intermediate |
| CN105130858A (en) * | 2015-08-25 | 2015-12-09 | 江苏远征化工有限公司 | Clean production process for dye intermediate sulfonated para-ester |
| CN110066230A (en) * | 2018-08-30 | 2019-07-30 | 内蒙古利元科技有限公司 | A kind of novel sulfonated para-ester production system and technique |
| CN110128306A (en) * | 2019-06-18 | 2019-08-16 | 新乡市锦源化工有限公司 | A kind of preparation method of sulfonated para-ester serving as dye intermediate |
| CN111440098A (en) * | 2020-05-14 | 2020-07-24 | 绍兴上虞联谊化工有限公司 | Preparation process of sulfonated para-ester serving as dye intermediate |
| CN111440098B (en) * | 2020-05-14 | 2021-03-16 | 绍兴上虞联谊化工有限公司 | Preparation process of sulfonated para-ester serving as dye intermediate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100497304C (en) | 2009-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100497304C (en) | Method of synthesizing sulfonation paraposition ester | |
| CN101817989A (en) | Method for preparing disperse blue 60 and homologues thereof | |
| CN101439867B (en) | Method for extracting potassium carbonate from cabo and refining carbon | |
| CN101633631B (en) | Method for synthesizing sulfonated para-ester | |
| CN104726705A (en) | Method for extracting chromium from chromite by leaching | |
| CN102320635A (en) | Comprehensive utilization method of waste sulfuric acid of sulfonated products | |
| CN101462985B (en) | Clean production process for azobisformamide | |
| CN109608355A (en) | A kind of synthesis technology of 2- amino -4- acetyl-anisidine | |
| CN104119243A (en) | Iminodiacetic acid energy saving cleaning production method | |
| CN102030625B (en) | Method for synthesizing vanillin | |
| CN101735154B (en) | Method for preparing maleichydrazide | |
| CN102815737A (en) | New method for producing potassium alum | |
| CN101284949A (en) | New process for synthesizing reduced olive T dye | |
| CN105461565B (en) | A kind of method for producing nitro-acetophenone | |
| CN108395381B (en) | Synthesis method of 1, 4-diamino anthraquinone leuco body | |
| CN106809887A (en) | A kind of method for preparing chloro-iridic acid | |
| CN106565621B (en) | A kind of synthetic method of isoxaflutole | |
| CN102516183A (en) | Method for preparing sulfadoxine and its intermediate | |
| CN101591255B (en) | Clean production process of iminodiacetic acid | |
| CN111825565B (en) | Preparation method of naphthol AS-PH | |
| CN107602422A (en) | A kind of clean type product 1,6,1,7 mixes the preparation method of 1-naphthlamine-6-sulfonic acid | |
| CN105567325B (en) | It is a kind of for the catalytic removal of nox of solar energy thermochemical study and the mixture system of carbonate and its preparation and application | |
| CN103687848A (en) | Sustainable chemical process for isolation of naphthalene sulphonic acid compounds with inherent recycle of all acidic streams generated during isolation and washing | |
| CN107868025A (en) | A kind of synthetic method of sulfonation para-ester | |
| CN106810479A (en) | A kind of synthetic method of sulfonation para-ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: TIANJIN DEK CHEMICAL COMPANY LTD. Free format text: FORMER NAME: TIANJIN DEK CHEMICAL CO.,LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 300163 Tianjin city Dongli District ZhangGuiZhuang road Ji'an Road Patentee after: Tianjin Dekai Chemical Industry Co., Ltd. Address before: 300163 Tianjin city Dongli District ZhangGuiZhuang road Ji'an Road Patentee before: Tianjin Dekai Chemical Co., Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for synthesizing sulfonated para-ester Effective date of registration: 20110719 Granted publication date: 20090610 Pledgee: Bank of Dalian Co Tianjin branch Pledgor: Tianjin Dekai Chemical Industry Co., Ltd. Registration number: 2011990000280 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20120711 Granted publication date: 20090610 Pledgee: Bank of Dalian Co Tianjin branch Pledgor: Tianjin Dekai Chemical Industry Co., Ltd. Registration number: 2011990000280 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for synthesizing sulfonated para-ester Effective date of registration: 20120711 Granted publication date: 20090610 Pledgee: Bank of Dalian Co Tianjin branch Pledgor: Tianjin Dekai Chemical Industry Co., Ltd. Registration number: 2012990000366 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20130710 Granted publication date: 20090610 Pledgee: Bank of Dalian Co Tianjin branch Pledgor: Tianjin Dekai Chemical Industry Co., Ltd. Registration number: 2012990000366 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for synthesizing sulfonated para-ester Effective date of registration: 20130710 Granted publication date: 20090610 Pledgee: Bank of Dalian Co Tianjin branch Pledgor: Tianjin Dekai Chemical Industry Co., Ltd. Registration number: 2013990000447 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20140710 Granted publication date: 20090610 Pledgee: Bank of Dalian Co Tianjin branch Pledgor: Tianjin Dekai Chemical Industry Co., Ltd. Registration number: 2013990000447 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090610 Termination date: 20160814 |