CN100475809C - Method for synthesizing 1,3-propane sultone - Google Patents
Method for synthesizing 1,3-propane sultone Download PDFInfo
- Publication number
- CN100475809C CN100475809C CNB2007100483168A CN200710048316A CN100475809C CN 100475809 C CN100475809 C CN 100475809C CN B2007100483168 A CNB2007100483168 A CN B2007100483168A CN 200710048316 A CN200710048316 A CN 200710048316A CN 100475809 C CN100475809 C CN 100475809C
- Authority
- CN
- China
- Prior art keywords
- preparation
- reaction
- morpholinopropanesulfonic acid
- acid lactone
- hydroxyl
- 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses a new synthesizing method of 1, 3-propane sultone, which comprises the following steps: reacting propanol, sulfite and bisulfite according to certain proportion with pH value at 6-6.5; irradiating through infrared to prepare 3-hydroxy-1-propanesulfonic acid salt; using condensed alcaine to act on 3-hydroxy-1-propanesulfonic acid salt to produce 3-hydroxy-1-propanesulfonic acid; extracting to separate 3-hydroxy-1-propanesulfonic acid through butanol; adopting molecular distilling technique and tail gas buffer device to produce the product.
Description
Technical field
The present invention relates to the preparation method of a kind of sulphur atom as the heterogeneous ring compound of heterocyclic atom, relate in particular to a kind of synthetic 1, the novel method of 3-third sultone.
Background technology
1,3-N-morpholinopropanesulfonic acid lactone (PS) is widely used in fields such as dyestuff, medicine, tensio-active agent, is a good sulfonic acid propylated reagent, with alcohol, phenol, mercaptan, amine etc. stronger reactive behavior is arranged, and alcoholysis and aminolysis take place.The preparation method of PS, though various countries have some patent article reports in succession, as U.S. Pat 3519645, have announced 1,3-hydroxyl-1-propanesulfonic acid carries out intramolecular dehydration and synthesizes 1, the method for 3-N-morpholinopropanesulfonic acid lactone (PS) under the situation of dehydration of chlorine benzene,toluene,xylene do and goods support; U.S. Pat 3117133 has announced that desalination synthesizes 1 in 3-halo-1-propanesulfonic acid sodium (potassium) molecules of salt, the method for 3-N-morpholinopropanesulfonic acid lactone (PS); U.S. Pat 3519646 has announced that 3-halo-1-propanesulfonic acid intramolecularly dehydrochlorination synthesizes 1, the method for 3-N-morpholinopropanesulfonic acid lactone (PS).Method 1 comparatively conveniently is used for the synthetic of laboratory short run; method 2,3 is difficult to actual suitability for industrialized production; a tame factory that has only Germany of practical technique and the production of energy implement scale really can be provided; it mainly uses the rotary flash distillation technology by the synthetic PS of 3-hydroxyl-1-propanesulfonic acid; this method yield is low, the cost height.At present this project still is in blank on the industrial production at home, every profession and trade required 1,3-N-morpholinopropanesulfonic acid lactone (PS) all is directly or indirectly from German import.And monopolized the proprietary manufacturing right of this product abroad, the equal price costliness of its product and derived product, the exploitation and the utilization of many derived product are had a strong impact on, so develop a kind of low cost, environmental protection, be easy to industrializedly 1,3-N-morpholinopropanesulfonic acid lactone (PS) preparation method has crucial meaning.
Summary of the invention
The objective of the invention is to overcome the above-mentioned problems in the prior art, a kind of low cost, environmental protection are provided, are easy to industrialized 1, the preparation method of 3-third sultone, this method makes raw material be converted into the purpose product fully effectively, avoided the generation of by product, make reaction, separate and to become economical, efficient, products obtained therefrom yield height, purity height, are easy to realize industrialization at economy, environmental protection.
The present invention is synthetic intermediate 3-hydroxyl-1-propanesulfonic acid under the situation of infrared rays inducing catalysis reaction, separates this intermediate with n-butanol extraction, utilizes molecular distillation technique to make reaction, is separated in lesser temps, synthesizes 1, the 3-N-morpholinopropanesulfonic acid lactone under the high vacuum condition.
The present invention is achieved by following technical proposals:
A, 1, the preparation of 3-N-morpholinopropanesulfonic acid salt: utilizing vinylcarbinol and hydrosulphite, sulphite is 1: 1.1～1.7: 0.1～0.6 by the mole concentration ratio, have that catalyzer exists, under the infrared light illuminate condition, the pH value maintains under 6～6.5 the solutions of weak acidity and reacted 4～12 hours, temperature of reaction is controlled at 65 ℃-90 ℃, and temperature of reaction is preferably 80 ℃-90 ℃; Be intended to make that material concentration remains on certain scope in the reaction system, the pH value maintains 6～6.5, be convenient to that sulphite and hydrosulphite exist simultaneously in the reaction system, be beneficial to the carrying out of reaction; And catalyst system therefor is the peroxidation type, temperature is too low can't to reach catalytic effect, even reaction hardly, the too high then feasible reaction of temperature is carried out too fast, there are a large amount of by products to generate simultaneously, reaction is can be comparatively gentle and carry out up hill and dale under the condition of 65 ℃～90 ℃ of infrared ray radiations, and transformation efficiency is nearly 100%, yield about 97%.
Described sulphite is any in S-WAT, potassium sulfite, the ammonium sulphite, is preferably potassium sulfite; Described hydrosulphite is any in sodium bisulfite, Potassium hydrogen sulfite, the ammonium bisulfite, is preferably Potassium hydrogen sulfite.
Described catalyzer is any in Cellmic C 121 (ABFN), two tertiary amyl superoxide (DTAP), dicumyl peroxide (DCP), azo diisobutyl nitrile (ABN), t-tutyl cumyl peroxide (TBCP), dibenzoyl peroxide (BPO), two (tert-butyl hydroperoxide sec.-propyl) benzene (BPIB).
The preparation of b, 3-hydroxyl-1-propanesulfonic acid: add a certain amount of technical hydrochloric acid (30%m/m) in the above-mentioned reactant and under 85～90 ℃ of temperature, reacted 1～3 hour, described temperature of reaction is preferably 90 ℃, reaction times is preferably 3 hours, obtain 3-hydroxyl-1-propanesulfonic acid and inorganic salt, reclaim under reduced pressure dilute hydrochloric acid, the thick solids of gained adds wherein 3-hydroxyl-1-propanesulfonic acid of n-butanol extraction, and the gained liquid material adds deionized water 3-hydroxyl-1-propanesulfonic acid wash-out from propyl carbinol is come out; The physico-chemical property (propyl carbinol solubleness in water and saturated brine is little, and 3-hydroxyl-1-propanesulfonic acid is soluble in propyl carbinol) that makes full use of propyl carbinol and 3-hydroxyl-1-propanesulfonic acid herein carries out the separation of science environmental protection.
C, 1, the preparation of 3-N-morpholinopropanesulfonic acid lactone: gained 3-hydroxyl-1-propanesulfonic acid utilization molecular distillation technique is that 140 ℃～150 ℃, pressure are reaction dehydration under 13Pa～266Pa condition in temperature, and reaction, separation are carried out simultaneously, obtains 1,3-third sultone; The used molecular distillation technique of the present invention makes reaction and being separated under the condition of lesser temps, decompression carry out, reduce the reduction of product because of the productive rate that high temperature polymerization, charing, decomposition brought, improved the yield of product, this method makes its transformation efficiency reach 90%, and yield is up to 80%.
Owing to have a certain amount of moisture and sulfur dioxide gas to produce in reaction and the product still-process, in order not influence vacuum tightness and to avoid environment is polluted, so the present invention has done the comparatively processing of science environmental protection to the special drying and the tail gas absorption of vacuum system, described buffered method is successively by the absorption bottle of sodium hydroxide, calcium chloride, whiteruss is housed with tail gas, the absorption bottle of calcium chloride and whiteruss is housed, and three grades of bufferings of surge flask absorption bottle carries out buffered.
Compared with prior art, the invention has the beneficial effects as follows: technology of the present invention is simple, adopted special catalyst and infrared light radiation-induced catalysis to make raw material be converted into the purpose product fully effectively, and avoided the generation of by product, the utilization molecular distillation technique makes reaction, separates the economy that becomes, efficient, products obtained therefrom yield height, purity height, are easy to realize industrialization at economy, environmental protection.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1
With 375 gram (MW126,2.98mol) sodium sulphite anhydrous 99.3,6L water, 20 grams, two tertiary amyl superoxide (DTAP) add in the 20L glass reactor, be warming up under 60～65 ℃, infrared ray radiation by different speed and drip ally alcohol 1392 grams (MW 5824mol) and S-WAT 768 grams (6.1mol), sodium bisulfite 2936 gram (MW 10428.2mol), the formed solution of 10L water simultaneously, make its pH value maintain 6～6.5, dripped off in 2 hours.Drip to finish, be warming up to 90 ℃ and continue illumination half an hour, react after 4 hours and finish, no longer include vinylcarbinol taste (raw material propylene alcohol is not found in the GC detection) this moment.
Above reaction mass is cooled off a little, slowly add concentrated hydrochloric acid (technical grade, about 30%m/m) 4.2L then and maintain 85～90 ℃ of stirring reactions 1 hour.This material is distilled to Rotary Evaporators does not almost have fraction, add hydrochloric acid 1.5L (technical grade, the about 30%m/m of content) and be heated to 85 ℃ the reaction half an hour, add 4L propyl carbinol and heated and stirred again and make its be uniformly dispersed (so that 3-hydroxyl-1-propanesulfonic acid is fully free to propyl carbinol liquid from salt), then material being cooled to 0～5 ℃ kept 3 hours, filter desalination (semi-automatic acidproof supercentrifuge is implemented), the salt thing washs with the 0.8L propyl carbinol in the whizzer, centrifugal till the whizzer outlet absence of liquid, mother liquor adds deionized water 1.5L and stirs half an hour, standing demix is got the lower layer of water liquid layer; And then stir with 1L water and to wash propyl carbinol liquid half an hour, get lower layer of water liquid, propyl carbinol liquid is used for down, and secondary response extracts, merge eluting water liquid, add to underpressure distillation in the 5L Rotary Evaporators, bath temperature is the highest 83 ℃, after 3 hours, almost do not have fraction, about 3259 grams of blush oily matter are arranged approximately, yield about 97% in the reaction flask.
Gained material 3-hydroxyl-1-propanesulfonic acid 3259g is with the 2Kg/hr input speed, adopt KDL10 type short-path distillation (molecular distillation) (Sai Pu Tektronix Ltd. provides) with oily temperature control at about 200 ℃, 140 ℃ of vaporization temperatures, carry out molecular distillation about vacuum tightness 1SPa, get colourless liquid (temperature is a white solid when low) 1, about 2635.2 grams of 3-third sultone (GC detects＞99.5%, collects rate 87.3% with 3-hydroxyl-1-propanesulfonic acid).
Embodiment 2
With 379 gram (MW158,2.4mol) anhydrous potassium sulfite, 6L water, 14 gram Cellmic C 121s (ABFN) add in the 20L glass reactor, be warming up under 60～65 ℃, infrared ray radiation and drip ally alcohol 1392 grams (MW 5824mol) and Potassium hydrogen sulfite 4896 grams (MW12040.8mol) and the formed solution of 10L water simultaneously by different speed, make its pH value maintain 6～6.5, dripped off in about 3 hours.Drip to finish, be warming up to 80 ℃ and continue illumination half an hour, react after about 4 hours and finish, no longer include vinylcarbinol taste (GC detects and do not find raw material propylene alcohol) this moment.
Above reaction mass is cooled off a little, slowly add concentrated hydrochloric acid (technical grade, the about 30%m/m of content) 4.2L then and maintain 85～90 ℃ of stirring reactions 1 hour.This material is distilled to Rotary Evaporators does not almost have fraction, add hydrochloric acid 1.5L (technical grade, the about 30%m/m of content) and be heated to 85 ℃ the reaction half an hour, add 4L propyl carbinol and heated and stirred again and make its be uniformly dispersed (so that 3-hydroxyl-1-propanesulfonic acid is fully free to propyl carbinol liquid from salt), then material being cooled to 0～5 ℃ kept more than 3 hours, filter desalination (semi-automatic acidproof supercentrifuge is implemented), the salt thing washs with the 0.8L propyl carbinol in the whizzer, centrifugal till the whizzer outlet absence of liquid, mother liquor adds deionized water 1.5L and stirs half an hour, standing demix is got the lower layer of water liquid layer; And then stir with 1L water and to wash propyl carbinol liquid half an hour, get lower layer of water liquid, propyl carbinol liquid is used for down, and secondary response extracts, merge eluting water liquid, add to underpressure distillation in the 5L Rotary Evaporators, bath temperature is the highest 83 ℃, after 3 hours, almost do not have fraction, about 3282.7 grams of blush oily matter are arranged approximately, yield about 97.7% in the reaction flask.
Gained material 3-hydroxyl-1-propanesulfonic acid 3259g with the 2Kg/hr input speed adopt KDL10 type short-path distillation (molecular distillation) (Sai Pu Tektronix Ltd. provides) with oily temperature control at about 200 ℃, 145 ℃ of vaporization temperatures, carry out molecular distillation about vacuum tightness 133Pa, get colourless liquid (temperature is a white solid when low) 1, about 2300.5 grams of 3-third sultone (GC detects＞99.5%, collects rate 81% with 3-hydroxyl-1-propanesulfonic acid).
Embodiment 3
1670.4 gram (the total 14.4mol of MW116) anhydrous sodium ammonium sulfate, 6L water, 28 grams, two tertiary amyl superoxide (DTAP) are added in the 20L glass reactor, be warming up under 60～65 ℃, infrared ray radiation and drip ally alcohol 1392 grams (MW 5824mol) and ammonium bisulfite 2613.6 gram (MW 9926.2mol), the formed solution of 10L water simultaneously by different speed, make its pH value maintain 6～6.5, dripped off in about 2～3 hours.Drip to finish, be warming up to 65 ℃ and continue illumination half an hour, react after about 12 hours and finish, no longer include vinylcarbinol taste (GC detects and do not find raw material propylene alcohol) this moment.
Above reaction mass is cooled off a little, slowly add concentrated hydrochloric acid (technical grade, volumn concentration about 30%) 4.2L then and maintain 85～90 ℃ of stirring reactions 1 hour.This material is distilled to Rotary Evaporators does not almost have fraction, add hydrochloric acid 1.5L (technical grade, the about 30%m/m of content) and be heated to 85 ℃ the reaction half an hour, add 4L propyl carbinol and heated and stirred again and make its be uniformly dispersed (so that 3-hydroxyl-1-propanesulfonic acid is fully free to propyl carbinol liquid from salt), then material being cooled to 0～5 ℃ kept more than 3 hours, filter desalination (semi-automatic acidproof supercentrifuge is implemented), the salt thing washs with the 0.8L propyl carbinol in the whizzer, centrifugal till the whizzer outlet absence of liquid, mother liquor adds deionized water 1.5L and stirs half an hour, standing demix is got the lower layer of water liquid layer; And then stir with 1L water and to wash propyl carbinol liquid half an hour, get lower layer of water liquid, propyl carbinol liquid is used for down, and secondary response extracts, merge eluting water liquid, add to underpressure distillation in the 5L Rotary Evaporators, bath temperature is the highest 83 ℃, after 3 hours, almost do not have fraction, the about 3249.1 gram yields about 96.7% of blush oily matter are arranged in the reaction flask approximately.
Gained material 3-hydroxyl-1-propanesulfonic acid 3259g with the 2Kg/hr input speed adopt KDL10 type short-path distillation (molecular distillation) (Sai Pu Tektronix Ltd. provides) with oily temperature control at about 200 ℃, 150 ℃ of vaporization temperatures, carry out molecular distillation about vacuum tightness 266Pa, get colourless liquid (temperature is a white solid when low) 1, the about 2073.3.5 gram of 3-third sultone (GC detects＞99.5%, collects rate 73% with 3-hydroxyl-1-propanesulfonic acid).
Embodiment 4
With 375 gram (MW126,2.98mol) sodium sulphite anhydrous 99.3,6L water, 70 gram dicumyl peroxides (DCP) add in the 20L glass reactor, be warming up under 60～65 ℃, infrared ray radiation by different speed and drip ally alcohol 1392 grams (MW 5824mol) and S-WAT 768 (6.1mol) gram, sodium bisulfite 2936 gram (MW 10428.2mol), the formed solution of 10L water simultaneously, make its pH value maintain 6～6.5, dripped off in about 2～3 hours.Drip to finish, be warming up to 90 ℃ and continue illumination half an hour, react after about 4 hours and finish, no longer include vinylcarbinol taste (GC detects and do not find raw material propylene alcohol) this moment.
Above reaction mass is cooled off a little, slowly add concentrated hydrochloric acid (technical grade, the about 30%m/m of content) 4.2L then and maintain 85～90 ℃ of stirring reactions 1 hour.This material is distilled to Rotary Evaporators does not almost have fraction, add hydrochloric acid 1.5L (technical grade, the about 30%m/m of content) and be heated to 85 ℃ the reaction half an hour, add 4L propyl carbinol and heated and stirred again and make its be uniformly dispersed (so that 3-hydroxyl-1-propanesulfonic acid is fully free to propyl carbinol liquid from salt), then material being cooled to 0～5 ℃ kept more than 3 hours, filter desalination (semi-automatic acidproof supercentrifuge is implemented), the salt thing washs with the 0.8L propyl carbinol in the whizzer, centrifugal till the whizzer outlet absence of liquid, mother liquor adds deionized water 1.5L and stirs half an hour, standing demix is got the lower layer of water liquid layer; And then stir with 1L water and to wash propyl carbinol liquid half an hour, get lower layer of water liquid, propyl carbinol liquid is used for down, and secondary response extracts, merge eluting water liquid, add to underpressure distillation in the 5L Rotary Evaporators, bath temperature is the highest 83 ℃, after 3 hours, almost do not have fraction, about 3265.9 grams of blush oily matter are arranged approximately, yield about 97.2% in the reaction flask.
Gained material 3-hydroxyl-1-propanesulfonic acid 3259g with the 2Kg/hr input speed adopt KDL10 type short-path distillation (molecular distillation) (Sai Pu Tektronix Ltd. provides) with oily temperature control at about 200 ℃, 150 ℃ of vaporization temperatures, carry out molecular distillation about vacuum tightness 266Pa, get colourless liquid (temperature is a white solid when low) 1, the about 2073.3.5 gram of 3-third sultone (GC detects＞99.5%, collects rate 73% with 3-hydroxyl-1-propanesulfonic acid).
Embodiment 5
Owing to have a certain amount of moisture and sulfur dioxide gas to produce in reaction and the product still-process, in order not influence vacuum tightness and to avoid environment is polluted, so the present invention has done the comparatively processing of science environmental protection to the special drying and the tail gas absorption of vacuum system, specifically implements as follows:
The present invention utilizes whiteruss boiling point height, not volatile characteristic, with sodium hydroxide and Calcium Chloride Powder Anhydrous at the whipped state low suspension in whiteruss, in the absorption system of the second stage, add a certain amount of Calcium Chloride Powder Anhydrous and whiteruss again, the third stage is the empty bottle buffering, prevents that the contaminated vacuum tightness that causes of vacuum machine oil from reducing.
The present invention can fully absorb moisture and the sulfur dioxide gas that produces in the above embodiment process under not influencing vacuum state effectively in the lump, and repeatedly uses back whiteruss and related salts thing thereof can be reused for absorption dehydration usefulness herein again after washing.
Claims (7)
1. one kind prepares 1, and the method for 3-N-morpholinopropanesulfonic acid lactone is characterized in that may further comprise the steps:
A, 1, the preparation of 3-N-morpholinopropanesulfonic acid salt: sulphite, hydrosulphite and vinylcarbinol react under the situation that catalyzer existence, infrared ray radiation inducing catalysis are arranged, temperature of reaction is 65 ℃～90 ℃, the pH value is 6～6.5, reaction times is 4～12 hours, and the reaction molar concentration rate is: vinylcarbinol: hydrosulphite: sulphite=1: 1.1～1.7: 0.1～0.6;
The preparation of b, 3-hydroxyl-1-propanesulfonic acid: add the concentrated hydrochloric acid reaction in above-mentioned reactant, obtain 3-hydroxyl-1-propanesulfonic acid and inorganic salt, filter desalination, filtrate adds n-butanol extraction and separates, and obtains 3-hydroxyl-1-propanesulfonic acid;
C, 1, the preparation of 3-N-morpholinopropanesulfonic acid lactone: gained 3-hydroxyl-1-propanesulfonic acid utilization molecular distillation technique is that 140 ℃～150 ℃, pressure are to dewater under 13Pa～266Pa condition in temperature, and simultaneously with water and 1, the 3-N-morpholinopropanesulfonic acid lactone separates, obtain 1, the 3-N-morpholinopropanesulfonic acid lactone.
2. preparation 1 according to claim 1, the method for 3-N-morpholinopropanesulfonic acid lactone is characterized in that described sulphite is any in S-WAT, potassium sulfite, the ammonium sulphite; Described hydrosulphite is any in sodium bisulfite, Potassium hydrogen sulfite, the ammonium bisulfite.
3. preparation 1 according to claim 2, the method for 3-N-morpholinopropanesulfonic acid lactone is characterized in that described sulphite is potassium sulfite, described hydrosulphite is a Potassium hydrogen sulfite.
4. preparation 1 according to claim 1, the method of 3-N-morpholinopropanesulfonic acid lactone is characterized in that described catalyzer is any in Cellmic C 121, two tertiary amyl superoxide, dicumyl peroxide, azo diisobutyl nitrile, t-tutyl cumyl peroxide, dibenzoyl peroxide, two (tert-butyl hydroperoxide sec.-propyl) benzene.
5. preparation 1 according to claim 1, the method for 3-N-morpholinopropanesulfonic acid lactone is characterized in that described catalyst consumption is 1～5% of a vinylcarbinol weight.
6. preparation 1 according to claim 1, the method for 3-N-morpholinopropanesulfonic acid lactone is characterized in that preparing described 1, and the temperature of reaction of 3-N-morpholinopropanesulfonic acid salt is 80 ℃～90 ℃.
7. preparation 1 according to claim 1, the method of 3-N-morpholinopropanesulfonic acid lactone, it is characterized in that described preparation method comprises that also the tail gas that reaction is produced is successively by being equipped with the absorption bottle of sodium hydroxide, calcium chloride, whiteruss, the absorption bottle of calcium chloride and whiteruss is housed, and three grades of bufferings of surge flask absorption bottle carries out the method for buffered.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100483168A CN100475809C (en) | 2007-01-23 | 2007-01-23 | Method for synthesizing 1,3-propane sultone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100483168A CN100475809C (en) | 2007-01-23 | 2007-01-23 | Method for synthesizing 1,3-propane sultone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101012218A CN101012218A (en) | 2007-08-08 |
| CN100475809C true CN100475809C (en) | 2009-04-08 |
Family
ID=38699960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100483168A Expired - Fee Related CN100475809C (en) | 2007-01-23 | 2007-01-23 | Method for synthesizing 1,3-propane sultone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100475809C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456855B (en) * | 2008-11-24 | 2012-02-08 | 张家港市华盛化学有限公司 | Method for preparing 1,3-propanesultone |
| CN103936711B (en) * | 2014-04-15 | 2016-10-05 | 北京蓝海黑石科技有限公司 | A kind of method reducing 1,3-propane sultone moisture |
| CN106117088A (en) * | 2016-06-21 | 2016-11-16 | 宿迁远扬生物科技有限公司 | A kind of 3 rings amine 1 propanesulfonic acid preparation method |
| CN106146453B (en) * | 2016-07-26 | 2018-10-12 | 张家港瀚康化工有限公司 | The preparation method of 1,3- propane sultone |
| CN106397392A (en) * | 2016-08-31 | 2017-02-15 | 湖北吉和昌化工科技有限公司 | 1,4-butane sultone and synthesis process thereof |
| CN106946844A (en) * | 2017-03-24 | 2017-07-14 | 山东瀛寰化工有限公司 | A kind of synthetic method of 1,4 butane sultones |
| CN108218828A (en) * | 2018-03-06 | 2018-06-29 | 苏州华新能源科技有限公司 | A kind of preparation method of 1,3- propane sultones |
| CN110483473B (en) * | 2019-09-08 | 2022-12-23 | 江苏瀚康新材料有限公司 | Method for preparing 1, 3-propane sultone |
| CN114292257B (en) * | 2021-12-27 | 2023-10-27 | 湖北吉和昌化工科技有限公司 | Synthesis method of 1, 4-butane sultone |
-
2007
- 2007-01-23 CN CNB2007100483168A patent/CN100475809C/en not_active Expired - Fee Related
Non-Patent Citations (10)
| Title |
|---|
| 丙磺酸内酯的制备. 王迪敏.湘潭师范学院学报，第19卷第6期. 1998 |
| 丙磺酸内酯的制备. 王迪敏.湘潭师范学院学报，第19卷第6期. 1998 * |
| 丙磺酸内酯的合成. 李文遐等.化学试剂，第20卷第3期. 1998 |
| 丙磺酸内酯的合成. 李文遐等.化学试剂，第20卷第3期. 1998 * |
| 分子蒸馏及其在精细化工上的应用. 邓朝霞等.广州化工，第34卷第2期. 2006 |
| 分子蒸馏及其在精细化工上的应用. 邓朝霞等.广州化工，第34卷第2期. 2006 * |
| 新型电镀光亮剂吡啶丙烷磺酸内盐的合成. 张敏等.江苏化工，第31卷第1期. 2003 |
| 新型电镀光亮剂吡啶丙烷磺酸内盐的合成. 张敏等.江苏化工，第31卷第1期. 2003 * |
| 羟基丙烷磺酸内酯的合成工艺. 曾超，吕志.材料保护，第37卷第6期. 2004 |
| 羟基丙烷磺酸内酯的合成工艺. 曾超，吕志.材料保护，第37卷第6期. 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101012218A (en) | 2007-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100475809C (en) | Method for synthesizing 1,3-propane sultone | |
| CN101157681A (en) | Method for preparing 1,3 propane sultone | |
| CN101935276B (en) | Synthetic method of p-phthaloyl chloride | |
| CN100348579C (en) | Methylsulfonic acid preparing process | |
| JP2020522530A (en) | System and process for co-producing dimethyl carbonate and ethylene glycol | |
| CN104549439B (en) | A kind of catalyst of high activity Synthesis of dimethyl carbonate and its preparation method and application | |
| US11214495B2 (en) | Preparation method of phosphotungstic acid | |
| CN102976355A (en) | Production process for ammonia gas and calcium chloride through utilization of ammonium chloride and carbide slag | |
| CN1990460A (en) | Comprehensive treatment of glycine crystallization mother liquid | |
| CN102992268A (en) | Technology for producing hydrogen chloride by using calcium chloride and sulfuric acid | |
| CN104761452A (en) | Purification method for butyl acrylate crude product | |
| CN100545154C (en) | The synthetic method of (methyl) glycidyl acrylate | |
| CN105503513A (en) | Method for catalytically synthesizing 4,4'-bischloromethylbiphenyl by using silicon dioxide-loaded phosphotungstic acid | |
| CN110304639B (en) | Purification method of sodium o-sulfonate benzaldehyde byproduct salt | |
| CN101255100B (en) | Method for synthesizing allyl glycidyl ether | |
| CN1927795A (en) | Method of preparing resorcin by hydrolyzing m-phenylenediamine | |
| CN101704746B (en) | Method for synthesizing levo formyl mandelic acid chloride | |
| CN110452089A (en) | The synthetic method of p-chloromethyl styrene | |
| CN101434539B (en) | Preparation of benzyl acetate | |
| CN110713439A (en) | Preparation method of cyclohexane-1, 2-dicarboxylate environment-friendly plasticizer | |
| CN111153821A (en) | Preparation method of D-p-hydroxyphenylglycine methyl ester | |
| CN102850299B (en) | Preparation method for (methyl)glycidyl acrylate | |
| CN112250600B (en) | Technological method for improving yield of N, N' -diisopropylcarbodiimide product | |
| CN101270077A (en) | Comprehensive process for tail gas in glyphosate production | |
| CN110330428B (en) | Method for preparing diisobutyl phthalate |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090408 Termination date: 20100223 |