CN102627566A - Method for preparing bronopol through catalyzing by solid base - Google Patents
Method for preparing bronopol through catalyzing by solid base Download PDFInfo
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- CN102627566A CN102627566A CN2012100757262A CN201210075726A CN102627566A CN 102627566 A CN102627566 A CN 102627566A CN 2012100757262 A CN2012100757262 A CN 2012100757262A CN 201210075726 A CN201210075726 A CN 201210075726A CN 102627566 A CN102627566 A CN 102627566A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention which belongs to the organic synthesis field discloses a method for preparing bronopol through catalyzing by a solid base. According to the method, nitromethane, a formaldehyde solution and liquid bromine which are used as raw materials are subjected to addition and bromination reactions to synthesize bronopol. Compared with traditional synthetic methods through catalyzing by strong bases, the synthetic method of the invention has the advantages of mild reaction conditions, no generation of organic salts, and convenient post-processing. The yield reaches above 95.0% (by nitromethane), and the product purity reaches above 99.5%. The solid base catalyst has the advantages of easy separation from bronopol, easy regeneration, frequent indiscriminate application, and small corrosion to equipment.
Description
Technical field
The invention belongs to the organic synthesis field, relate to the method that a kind of catalyzed by solid base prepares bronopol particularly.
Background technology
Bronopol chemistry 2-bromo-2-nitro-1 by name, ammediol, English 2-bromo-2-nitro-1 by name, 3-propanediol, external commodity Bronopol by name.It is a kind of wide spectrum, efficient, hypotoxicity fungicidal preservative, in the pH of broad scope, brings into play anti-microbial activity, and yeast, mould are had good inhibitory effect, and the gram-positive microorganism that special antagonism is strong, negative bacterium suppress remarkably productive.To non-stimulated, the no anaphylaxis of human body skin, be one of cosmetics preservative of U.S. FDA approval use simultaneously.It can be prevented and treated because of the sick or bacillary carving rot of the black arm of the caused cotton of cabbage black rot Flavobacterium as the cotton seeds treatment agent.Continuous expansion along with Application Areas is widely used as sterilization, mildew-resistant and algicide in industries such as paper industry, water treatment, coating, washing composition, shoe polish, oil field.
In view of the bigger market demand of bronopol, very active to the research of bronopol synthetic method both at home and abroad, and attempt to explore good industrialized and produce route.The bronopol synthesis technique mainly contains two kinds at present.
Method one, Nitromethane 99Min. and formolite reaction generate 2-nitro-1, ammediol; 2-nitro-1; Ammediol continues and sodium hydroxide (or other alkali) reaction obtains 2-nitro-1, ammediol sodium salt midbody, and this midbody and bromine reaction obtain bronopol (referring to reaction scheme 1).Adopt the patent of this compound method that U.S. Pat 6867336 is arranged, Chinese patent CN1538949 and CN200610130161, Japanese Patent JP57002242 and JP6001756.
Reaction scheme 1:
Method two, Nitromethane 99Min. are dissolved in alkali and generate salt, and reaction generates bromo nitryl methane with bromine again, and the condensation under alkaline condition of bromo nitryl methane and formaldehyde obtains bronopol (referring to route 2).Adopt the patent of this compound method that U.S. Pat 4922030, Japanese Patent JP1132549 are arranged.
Route 2:
Method one is the technology that present domestic industry production bronopol generally adopts.This technology is carried out addition reaction and is prepared 2-nitro-1 under strong alkaline condition, the subsalt midbody of ammediol is strong exothermal reaction, and temperature of reaction is wayward; Midbody poor stability under strong alkaline condition reacts ending phase and must add the excessive alkali of acid neutralization simultaneously, and with producing a large amount of inorganic salt, the operation of increased washing, filtering desalination has influenced quality product; In bromination reaction, must use nonpolar poisonous flammable solvents such as ETHYLE ACETATE, tetracol phenixin or ethylene dichloride; These shortcoming utmost points are unfavorable for suitability for industrialized production.
Bromo nitryl methane and formaldehyde prepared in reaction bronopol under the highly basic condition in the method two; Decompose under the highly basic condition for fear of product, must add the sour excessive alkali that neutralizes, will produce a large amount of salt equally; Increased the operation of washing and filtering desalination; Influence the quality of bronopol product, have only through distillation to obtain bromo nitryl methane, could obtain purer product.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned technology, a kind of method of using catalyzed by solid base to prepare bronopol is provided, the solid base catalyst that the present invention uses has bigger specific surface area, and temperature of reaction is lower, can reduce the generation of side reaction.Solid base catalyst has advantages such as easily separated, reusable simultaneously.
Technical scheme of the present invention is following:
The present invention relates to a kind of method of using solid base catalyst catalytic preparation bronopol; With Nitromethane 99Min., formaldehyde solution and liquid bromine is raw material; Solid alkali is a catalyzer; Through addition and the synthetic bronopol of bromination reaction, the steps include: in reaction flask, to add Nitromethane 99Min., formaldehyde solution and solid base catalyst, stirring reaction is 2～5 hours under 10～25 ℃ of conditions.Dropping liquid bromine, temperature of reaction are controlled at 0～15 ℃, keep solution to be liquid bromine color; Reacted 2～3 hours, and added sodium sulfite anhy 96 and eliminate excessive liquid bromine, solids filtered alkaline catalysts; And use the washing with alcohol catalyzer, filtrating uses anhydrous sodium sulfate drying, underpressure distillation to remove ethanol and excessive formaldehyde; To separate out crystal and carry out filtration drying, promptly obtain bronopol.
Its reaction equation is following:
Solid base catalyst of the present invention is a loading type inoganic solids alkali, and its preparation method is: use specific surface area to be 1000m
2The above gac of/g is a carrier, and metal-salt is as presoma.Corresponding metal salt is soluble in water, add isopyknic absorbent charcoal carrier, stirred dipping 3～5 hours; Retort furnace is put in 100～120 ℃ of oven dry, the inflated with nitrogen protection; Speed with 10 ℃/min is warming up to 500 ℃, calcines 2～3 hours, obtains solid base catalyst.
Metal-salt of the present invention is Li
2CO
3, LiF, LiNO
3, Na
2CO
3, CsNO
3, CsF, Ca (NO
3), KNO
3, Mg (NO
3)
2, Sr (NO
3)
2In a kind of.
Of the present inventionly be used to prepare the solid base catalyst that the bronopol filtered and recycled obtains and use alcohol immersion, deionized water wash again, suction filtration; The solid of gained is put into retort furnace; Inflated with nitrogen protection, 500 ℃ of roastings 2～3 hours, the solid base catalyst that obtains regenerating is recycled and reused for the preparation of bronopol.
Compared with prior art, the present invention has the following advantages:
1, use the synthetic bronopol of described solid base catalyst catalysis, make completion in a pot of addition reaction and the bromination reaction, production technique is greatly simplified.
2, compare with the synthetic bronopol of traditional highly basic catalysis, use solid base catalyst not produce inorganic salt, convenient post-treatment, the washing that need not neutralize does not have trade effluent to produce.
3, whole process recovery ratio reaches (in Nitromethane 99Min.) more than 95%, and product purity reaches more than 99.5%.
4, solid base catalyst has separation from product easily, post catalyst reaction is regenerated easily and the advantage little to equipment corrosion.
Embodiment:
Following specific embodiment is used to further specify the present invention, but the present invention only limits to these instances absolutely not, can carry out various conversion according to claim institute restricted portion.The raw material that relates among the embodiment (unless otherwise indicated) is marketable material.
Embodiment one:
Take by weighing the Li of 10g
2CO
3, be dissolved in the 10g deionized water and obtain aqueous metal salt, add and isopyknic gac (the specific surface area 1200m of metal salt solution
2/ g), to stir 3 hours, retort furnace is put in 120 ℃ of oven dry, and inflated with nitrogen protection is warming up to 500 ℃ with the speed of 10 ℃/min, calcines 2～3 hours, obtains solid base catalyst Li
2CO
3/ C, cooling is placed in the moisture eliminator subsequent use.
In three mouthfuls of round-bottomed flasks of 500mL, add 0.4mol Nitromethane 99Min., 1.0mol formaldehyde solution and 0.2mol catalyzer Li
2CO
3/ C is (with Li in the catalyzer
2CO
3Amount of substance represent), stirring reaction is 2～5 hours under 10～25 ℃ of conditions.Dropping liquid bromine, temperature of reaction are controlled at 0～15 ℃, keep solution to be liquid bromine color, react 2～3 hours; Add sodium sulfite anhy 96 and eliminate excessive liquid bromine, the solids filtered alkaline catalysts, and use the washing with alcohol catalyzer; Catalyzer can continue to apply mechanically through regeneration, and filtrating uses anhydrous sodium sulfate drying, underpressure distillation to remove ethanol and excessive formaldehyde; To separate out crystal and carry out filtration drying, obtain bronopol 77.2g, yield 96.0%; Purity 99.8% (performance liquid chromatography normalization method), outward appearance is a light yellow crystalline powder, 125～129 ℃ of fusing points.
Embodiment two to embodiment 21:
Take by weighing 10g LiF, be dissolved in the 10g deionized water and obtain aqueous metal salt, add and isopyknic gac (the specific surface area 1500m of metal salt solution
2/ g), stirred 3 hours, retort furnace is put in 120 ℃ of oven dry, inflated with nitrogen protection is warming up to 500 ℃ with the speed of 10 ℃/min, calcine 2～3 hours, obtains solid base catalyst LiF/C, cool off be placed in the moisture eliminator subsequent use.
In three mouthfuls of round-bottomed flasks of 500mL, add 0.4mol Nitromethane 99Min., 1.0 formaldehyde solutions and 0.2mol catalyzer LiF/C (Li in catalyzer
2CO
3Amount of substance represent), stirring reaction is 2～5 hours under 10～25 ℃ of conditions.Dropping liquid bromine, temperature of reaction are controlled at 0～15 ℃, keep solution to be liquid bromine color, react 2～3 hours; Add sodium sulfite anhy 96 and eliminate excessive liquid bromine, the solids filtered alkaline catalysts, and use the washing with alcohol catalyzer; Catalyzer can continue to apply mechanically through regeneration, and filtrating uses anhydrous sodium sulfate drying, underpressure distillation to remove ethanol and excessive formaldehyde; To separate out crystal and carry out filtration drying, obtain bronopol 78.5g, yield 97.7%; Purity 99.8% (performance liquid chromatography normalization method), outward appearance is a light yellow crystalline powder, 125～128 ℃ of fusing points.
The catalyzer that above-mentioned filtration is obtained filters with alcohol immersion 5 hours, and deionized water wash is put into retort furnace, inflated with nitrogen protection, 500 ℃ of roastings 3 hours.Obtain regenerated catalyst and be used to apply mechanically test, (reaction conditions of applying mechanically experiment is constant, and 10% live catalyst is added 5 times in every interval), the yield and the purity that prepare bronopol are seen table 1.
Table 2. embodiment two to embodiment 21 experimental results
| Embodiment | Catalyzer add-on/mol | Yield/% | Purity/% |
| Two | 0.2 | 97.7 | 99.8 |
| Three | 0 | 96.5 | 99.8 |
| Four | 0 | 96.3 | 99.8 |
| Five | 0 | 96.2 | 99.7 |
| Six | 0 | 96.0 | 99.7 |
| Seven | 0.02 | 96.8 | 99.8 |
| Eight | 0 | 96.4 | 99.8 |
| Nine | 0 | 96.3 | 99.7 |
| Ten | 0 | 96.4 | 99.7 |
| 11 | 0 | 95.7 | 99.6 |
| 12 | 0.02 | 96.8 | 99.6 |
| 13 | 0 | 96.5 | 99.5 |
| 14 | 0 | 96.3 | 99.6 |
| 15 | 0 | 95.8 | 99.5 |
| 16 | 0 | 95.7 | 99.5 |
| 17 | 0.02 | 96.7 | 99.7 |
| 18 | 0 | 96.8 | 99.6 |
| 19 | 0 | 96.8 | 99.5 |
| 20 | 0 | 96.7 | 99.5 |
| 21 | 0 | 96.6 | 99.5 |
Embodiment 22 to embodiment 29:
With LiNO
3, Na
2CO
3, CsNO
3, CsF, Ca (NO
3), KNO
3, Mg (NO
3)
2, Sr (NO
3)
2For preparing solid base catalyst as presoma, metal-salt is used to prepare bronopol, other raw material and reaction conditions such as embodiment one.Obtain experimental result and see table 2.
Table 2. embodiment 22 to embodiment 29 experimental results
| Embodiment | Metal-salt | Yield/% | Purity/% |
| 22 | LiNO 3 | 96.3 | 99.4 |
| 23 | Na 2CO 3 | 96.6 | 99.2 |
| 24 | CsNO 3 | 95.8 | 99.6 |
| 25 | CsF | 96.4 | 99.6 |
| 26 | Ca(NO 3) | 96.7 | 99.7 |
| 27 | KNO 3 | 96.3 | 99.4 |
| 28 | Mg(NO 3) 2 | 95.6 | 99.7 |
| 29 | Sr(NO 3) 2 | 96.8 | 99.2 |
Claims (6)
1. a catalyzed by solid base prepares the method for bronopol, the steps include: in reaction flask, to add Nitromethane 99Min., formaldehyde solution, solid base catalyst, and stirring reaction is 2～5 hours under 10～25 ℃ of conditions; Dropping liquid bromine, temperature of reaction are controlled at 0～15 ℃, keep solution to be liquid bromine color; React after 2～3 hours, add sodium sulfite anhy 96 and eliminate excessive liquid bromine, solids filtered alkaline catalysts; And use the washing with alcohol catalyzer, filtrating uses anhydrous sodium sulfate drying, underpressure distillation to remove ethanol and excessive formaldehyde; To separate out crystal and carry out filtration drying, and promptly obtain bronopol, its reaction equation is following:
。
2. according to the described method of claim 1, it is characterized in that solid base catalyst is a loading type inoganic solids alkali, its preparation method is: use specific surface area to be 1000m
2The above gac of/g is a carrier, and metal-salt is as presoma, and corresponding metal salt is soluble in water; Add isopyknic absorbent charcoal carrier, stirred dipping 3～5 hours, 100～120 ℃ of oven dry; Put into retort furnace, inflated with nitrogen protection is warming up to 500 ℃ with the speed of 10 ℃/min; Roasting 2～3 hours obtains solid base catalyst, and cooling drying is subsequent use.
3. according to the described method of claim 2, it is characterized in that metal-salt is Li
2CO
3, LiF, LiNO
3, Na
2CO
3, CsNO
3, CsF, Ca (NO
3), KNO
3, Mg (NO
3)
2, Sr (NO
3)
2In a kind of.
4. according to the described method of claim 1, the mol ratio that it is characterized in that Nitromethane 99Min. and formaldehyde is 1:1.2～1.4.
5. according to the described method of claim 1, the mol ratio that it is characterized in that Nitromethane 99Min. and solid base catalyst is 1:0.5～0.7.
6. according to the described method of claim 1, it is characterized in that being used to preparing the solid base catalyst that the bronopol filtered and recycled obtains and use alcohol immersion, use deionized water wash again; Suction filtration; Put into retort furnace, inflated with nitrogen protection, 500 ℃ of roastings 2～3 hours; Obtain the solid base catalyst of regenerating, can be recycled and reused for the preparation of bronopol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100757262A CN102627566A (en) | 2012-03-21 | 2012-03-21 | Method for preparing bronopol through catalyzing by solid base |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100757262A CN102627566A (en) | 2012-03-21 | 2012-03-21 | Method for preparing bronopol through catalyzing by solid base |
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|---|---|---|---|
| CN2012100757262A Pending CN102627566A (en) | 2012-03-21 | 2012-03-21 | Method for preparing bronopol through catalyzing by solid base |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926661A (en) * | 2015-05-27 | 2015-09-23 | 天津市职业大学 | Synthetic method for bronopol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3711561A (en) * | 1969-10-28 | 1973-01-16 | Henkel & Cie Gmbh | Novel preparation of bromonitro alcohols |
| EP0341466A1 (en) * | 1988-04-30 | 1989-11-15 | Henkel Kommanditgesellschaft auf Aktien | Process for the bromination of Nitroalcohols |
| CN1538949A (en) * | 2001-08-02 | 2004-10-20 | �����ɷ� | Method for cntinuous production of 2-bromo-2-nitro-1, 3-propan ediol |
| CN1903830A (en) * | 2006-08-11 | 2007-01-31 | 南京苏研科创农化有限公司 | Preparation method of 2-bromo-2-nitro-1,3-propylene glycol |
-
2012
- 2012-03-21 CN CN2012100757262A patent/CN102627566A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3711561A (en) * | 1969-10-28 | 1973-01-16 | Henkel & Cie Gmbh | Novel preparation of bromonitro alcohols |
| EP0341466A1 (en) * | 1988-04-30 | 1989-11-15 | Henkel Kommanditgesellschaft auf Aktien | Process for the bromination of Nitroalcohols |
| CN1538949A (en) * | 2001-08-02 | 2004-10-20 | �����ɷ� | Method for cntinuous production of 2-bromo-2-nitro-1, 3-propan ediol |
| CN1903830A (en) * | 2006-08-11 | 2007-01-31 | 南京苏研科创农化有限公司 | Preparation method of 2-bromo-2-nitro-1,3-propylene glycol |
Non-Patent Citations (2)
| Title |
|---|
| 巫建民: "2-溴-2-硝基-1,3-二丙二醇的合成", 《江西化工》 * |
| 李恩博 等: "KF/A12O3催化合成2-溴-2-硝基-1,3-丙二醇", 《河北北方学院学报（自然科学版）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926661A (en) * | 2015-05-27 | 2015-09-23 | 天津市职业大学 | Synthetic method for bronopol |
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Application publication date: 20120808 |