CN100391611C - Ullmann condensation reaction catalytic system - Google Patents
Ullmann condensation reaction catalytic system Download PDFInfo
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- CN100391611C CN100391611C CNB2005100140629A CN200510014062A CN100391611C CN 100391611 C CN100391611 C CN 100391611C CN B2005100140629 A CNB2005100140629 A CN B2005100140629A CN 200510014062 A CN200510014062 A CN 200510014062A CN 100391611 C CN100391611 C CN 100391611C
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- ion exchange
- exchange resin
- strong acid
- copper powder
- acid ion
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Abstract
The present invention provides a catalytic system for Ullmann condensation reaction in organic pigment C. I paratonere 177 synthesis, which is prepared from solid strong acid ion exchange resin, organic solvent and copper powders in certain proportion. After reaction, the catalytic system can be recovered and cyclically utilized. The use of the present invention can reduce the discharge of waste water containing acid and deep chroma, reduce environmental pollution, reduce corrosion to equipment, and reduce the production cost. Simultaneously, the yield of a condensation product is obviously higher than that of the traditional sulfuric acid catalytic technology.
Description
Technical field
The present invention relates to a kind of catalysis system of the Ullmann of being used for condensation reaction, particularly be used for the catalysis system of organic pigment C.I paratonere 177 synthetic Ullmann condensation reactions.
Background technology
C.I paratonere 177 is a kind of have good weather-proof, anti-solvent, chemical resistances, the tinting strength, tinting power height, good resistance to migration, the organic dyestuff of anti-plastic shaping temperature, be the main organic red pigment kind of synthetic resin and coloring plastic, have advantages such as bright-coloured, every fastness ability excellence, be widely used in the painted of aspects such as printing ink, coating, cosmetics and printing and dyeing, paint, plastics, synthetic fibers, thought one of high-grade organic red pigment kind by market.But exist inorganic acid sulfate pollution problem of environment when in synthetic C.I paratonere 177 processes, carrying out the Ullmann condensation reaction.
At present, synthetic C.I paratonere 177 is in the following way:
This reaction is initial raw material with bromamine acid (1-amino-4-bromo-anthraquinone-2-sodium), is catalyst with copper powder and 50% sulfuric acid solution, carries out the Ullmann condensation reaction and generates condensation product.The condensation product that is generated carries out the desulfonation reaction and obtains C.I paratonere 177 thick pigment under 80% sulfuric acid system effect.The yield in condensation reaction stage is up to 92%.
In the process of synthetic dyestuff red 177, because the use of a large amount of sulfuric acid, in the last handling process of product, contain acid in a large number and the dark waste water of colourity enters environment, cause severe contamination to environment.If this waste water is handled, then to consume a large amount of energy, the processing cost height.
Solid acid is a large turn of acid catalysis research, and the ion exchange resin type solid acid catalyst is a class wherein, and it has two kinds: a kind of is to introduce highly acid ion-exchange group to form on crosslinked high-molecular copolymer; Another kind be with the common acid catalyst cupport on resin.
Summary of the invention
The invention provides a kind of Ullmann condensation reaction of the C.I of being used for paratonere 177 building-up processes and the catalysis system of recycle and reuse again after reaction.
Catalysis system of the present invention is that the inventor has carried out a large amount of work and gropes to sum up and draw, and use of the present invention not only can reduce the discharging that contains acid and the dark waste water of colourity, reduces environmental pollution; The corrosion of reduction equipment reduces production costs, and the yield of condensation product is apparently higher than the technology of traditional employing sulfuric acid catalysis simultaneously.
Catalysis system of the present invention is made up of solid strong acid ion exchange resin, organic solvent and copper powder, and the mol ratio of these three kinds of components is: strong acid ion exchange resin: copper powder: organic solvent=0.5-2: 5-9: 270-420.
Described solvent can be ethanol, toluene-N, N '-dimethyl formamide, N, N '-dimethyl formamide etc., wherein preferred alcohol.
In order to obtain better effect, the mol ratio of three kinds of components of catalyst of the present invention is preferably: strong acid ion exchange resin: copper powder: organic solvent=1: 9: 420
Strong acid ion exchange resin described in the present invention can be commercially available 001 * 7,002 * 7,001 * 7 * 7, D001, D061, Amberlite IR-120, the strong acid ion exchange resin of models such as Amberlyst-15.
When using antigravity system of the present invention, in order to obtain preferable reaction effect, the mol ratio of catalyst strong acid ion exchange resin and main initiation material bromamine acid should keep following relation in the reaction system: strong acid ion exchange resin: bromamine acid=1: 1.0-3, preferred molar ratio 1: 1.5.
In this catalyst system and catalyzing, strong acid ion exchange resin and copper powder add with solid form, and after reaction finished, these two kinds of catalyst can be recycled, and strong acid ion exchange resin can be reused more than 10 times after reclaiming; Copper powder reclaims loss 8-12% again, still can continue to use.
Advantage of the present invention and characteristics are:
1) high activity is arranged, chemical stability is good, and consumption is few and repeatedly reusable;
2) reaction speed is accelerated; The productive rate height; Can not introduce impurity, easily separate with product, post processing is simple.
3) etching apparatus not, cost is low.
4) after reaction finishes storng-acid cation exchange resin removed by filter and get final product; Save step such as alkali cleaning, washing in the traditional handicraft, simplified production technology, realized the zero-emission of acid-bearing wastewater substantially.
When preparation catalysis system of the present invention, the preliminary treatment of strong acid ion exchange resin can be undertaken by conventional method.
The specific embodiment
Further specify the present invention with example below, but do not limit the present invention.
Embodiment 1
Strong acid ion exchange resin (001 * 7 type exchanger resin, Chemical Plant of Nankai Univ.)
Strong acid ion exchange resin surface property and active improvement:
Process one: remove the impurity in the strong acid ion exchange resin
Get above-mentioned strong acid ion exchange resin, extremely neutral behind the immersion 10h in the NaOH of 1.0mol/L solution with deionized water rinsing; The HCl solution of then resin being put into 1.0mol/L soaks behind the 10h with deionized water rinsing to neutral again.To remove organic impurities in the resin and iron, copper plasma.
Process two: the exchange of strong acid ion exchange resin
Resin behind the removal impurity at room temperature carries out cation exchange with the HCl solution of 1.0mol/L, and be 12h swap time.After finishing, at every turn with a little top grade pure acetone flushing 3 times.Place 40～50 ℃ of drying boxes dry.Promptly obtain H polystyrene strongly acidic cation-exchange.
Embodiment 2
Thermometer is being housed, add bromamine acid 2.19g in the 100mL four-hole bottle of agitator reflux condensing tube, last gained strong acid ion exchange resin 0.8g in copper powder 1.39g and the example 1,60%-90% ethanolic solution 50mL, behind 68～72 ℃ of following stirring reaction 150min, filter while hot, filtrate is transferred to distillation recovery ethanol in the cucurbit.After treating that ethanol distillation is finished, add after an amount of hot water is heated to boiling, add 15～20g sodium chloride and saltout and filter in 70～80 ℃, with the washing of 10% sodium chloride solution, condensation product is put in the drying box dry.Yield can reach 65.1%.
Embodiment 3
Thermometer is being housed, add bromamine acid 2.19g in the 100mL four-hole bottle of agitator reflux condensing tube, last gained strong acid ion exchange resin 0.8g in copper powder 1.73g and the example 1,60%-90% ethanolic solution 50mL, behind 68～72 ℃ of following stirring reaction 150min, filter while hot, filtrate is transferred to distillation recovery ethanol in the cucurbit.After treating that ethanol distillation is finished, add after an amount of hot water is heated to boiling, add 15～20g sodium chloride and saltout and filter in 70～80 ℃, with the washing of 10% sodium chloride solution, condensation product is put in the drying box dry.Yield can reach 76.5%.
Embodiment 4
Thermometer is being housed, add bromamine acid 2.19g in the 100mL four-hole bottle of agitator reflux condensing tube, last gained strong acid ion exchange resin 0.8g in copper powder 2.08g and the example 1,60%-90% ethanolic solution 50mL, behind 68～72 ℃ of following stirring reaction 150min, filter while hot, filtrate is transferred to distillation recovery ethanol in the cucurbit.After treating that ethanol distillation is finished, add after an amount of hot water is heated to boiling, add 15～20g sodium chloride and saltout and filter in 70～80 ℃, with the washing of 10% sodium chloride solution, condensation product is put in the drying box dry.Yield can reach 94%.
Embodiment 5
Thermometer is being housed, add bromamine acid 2.19g in the 100mL four-hole bottle of agitator reflux condensing tube, last gained strong acid ion exchange resin 0.4g in copper powder 2.08g and the example 1,60%-90% ethanolic solution 50mL, behind 68～72 ℃ of following stirring reaction 150min, filter while hot, filtrate is transferred to distillation recovery ethanol in the cucurbit.After treating that ethanol distillation is finished, add after an amount of hot water is heated to boiling, add 15～20g sodium chloride and saltout and filter in 70～80 ℃, with the washing of 10% sodium chloride solution, condensation product is put in the drying box dry.Yield is 65.1%.
Embodiment 6
Thermometer is being housed, add bromamine acid 2.19g in the 100mL four-hole bottle of agitator reflux condensing tube, last gained strong acid ion exchange resin 0.6g in copper powder 2.08g and the example 1,60%-90% ethanolic solution 50mL, behind 68～72 ℃ of following stirring reaction 150min, filter while hot, filtrate is transferred to distillation recovery ethanol in the cucurbit.After treating that ethanol distillation is finished, add after an amount of hot water is heated to boiling, add 15～20g sodium chloride and saltout and filter in 70～80 ℃, with the washing of 10% sodium chloride solution, condensation product is put in the drying box dry.Yield is 86.5%.
Embodiment 7
Thermometer is being housed, add bromamine acid 2.19g in the 100mL four-hole bottle of agitator reflux condensing tube, last gained strong acid ion exchange resin 1.0g in copper powder 2.08g and the example 1,60%-90% ethanolic solution 50mL, behind 68～72 ℃ of following stirring reaction 150min, filter while hot, filtrate is transferred to distillation recovery ethanol in the cucurbit.After treating that ethanol distillation is finished, add after an amount of hot water is heated to boiling, add 15～20g sodium chloride and saltout and filter in 70～80 ℃, with the washing of 10% sodium chloride solution, condensation product is put in the drying box dry.Yield can reach 93.8%.
Embodiment 8
Thermometer is being housed, add bromamine acid 2.19g in the 100mL four-hole bottle of agitator reflux condensing tube, last gained strong acid ion exchange resin 0.8g in copper powder 2.08g and the example 1,50mL N, N '-dimethyl formamide, behind 68～72 ℃ of following stirring reaction 150min, filter while hot, filtrate is transferred to distillation recovery N in the cucurbit, N '-dimethyl formamide.Treat N, N '-dimethyl formamide distillation adds an amount of hot water after reclaiming and finishing, be heated to boiling after, in 70～80 ℃, add 15～20g sodium chloride and saltout and filter, with the washing of 10% sodium chloride solution, condensation product is put drying to the drying box.Yield is 70.3%.
Embodiment 9
Thermometer is being housed, add bromamine acid 2.19g in the 100mL four-hole bottle of agitator reflux condensing tube, last gained strong acid ion exchange resin 0.8g in copper powder 2.08g and the example 1,50mL toluene-N, (volume ratio is N '-dimethyl formyl-copper powder: 3-5: 1), behind 68～72 ℃ of following stirring reaction 150min, filter while hot, filtrate is transferred to distillation recovery toluene and N N '-dimethyl formamide-copper powder in the cucurbit.Treat toluene and N, N '-dimethyl formamide-copper powder distillation adds an amount of hot water after reclaiming and finishing, be heated to boiling after, in 70～80 ℃, add 15～20g sodium chloride and saltout and filter, with the washing of 10% sodium chloride solution, condensation product is put drying to the drying box.Yield is 75.1%.
Embodiment 10
Solid acid and copper powder utilize again
Process one: the separating of strong acid ion exchange resin and copper powder
After above-mentioned example 2 filtered gained resins and copper powder and soak 10h with watery hydrochloric acid, be washed to neutrality; Dry; Separate copper powder and resin; Calculate the loss late of resin and copper powder.The resin loses rate is 1%, and copper powder is at 8-12%.
Process two: the utilization again of resin after the recovery and copper powder
Copper powder and resin (each all need be added on a small quantity) after reclaiming are joined in the Ullmann condensation reaction system of bromamine acid again, after reaction finishes, continue to reclaim resin and copper powder, find that resin still has catalytic activity in use more than 10 times.
The recovery of embodiment 11 ethanol
After filtering copper powder and resin while hot when reaction finishes, ethanol is reclaimed in distillation in cucurbit.The rate of recovery of ethanol is at 75-80%, and the ethanol after the recovery can continue to use as reaction dissolvent.
Claims (5)
1. catalyst system that is used for the Ullmann condensation reaction, it is characterized in that being made up of solid strong acid ion exchange resin, organic solvent and copper powder, the mol ratio of these three kinds of components is: strong acid ion exchange resin: copper powder: organic solvent=0.5-2: 5-9: 270-420.
2. catalyst system according to claim 1 is characterized in that described solvent is ethanol, toluene-N, N '-dimethyl formamide or N, N '-dimethyl formamide.
3. catalyst system according to claim 1 and 2 is characterized in that the mol ratio of three kinds of components is: strong acid ion exchange resin: copper powder: organic solvent=1: 9: 420.
4. as the application of claim 1, the described Ullmann condensation catalyst of 2 or 3 each claims system, it is characterized in that the mol ratio between the catalyst strong acid ion exchange resin and main initiation material bromamine acid is 1 in the reaction system: 1.0-3.
5. the application of Ullmann condensation catalyst system as claimed in claim 4 is characterized in that the mol ratio between catalyst strong acid ion exchange resin in the reaction system and the main initiation material bromamine acid is 1: 1.5.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100140629A CN100391611C (en) | 2005-06-29 | 2005-06-29 | Ullmann condensation reaction catalytic system |
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| CNB2005100140629A CN100391611C (en) | 2005-06-29 | 2005-06-29 | Ullmann condensation reaction catalytic system |
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| CN1788846A CN1788846A (en) | 2006-06-21 |
| CN100391611C true CN100391611C (en) | 2008-06-04 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102321380A (en) * | 2011-06-22 | 2012-01-18 | 南通市争妍颜料化工有限公司 | Method for preparing high-hiding variety paratonere 2BL of paratonere 177 |
| CN103506138B (en) * | 2013-09-29 | 2015-07-01 | 山东宇虹新颜料股份有限公司 | Preparation method of copper powder carrier catalyst for bromamine acid Ullman condensation reaction |
| CN107459470A (en) * | 2017-08-25 | 2017-12-12 | 天津城建大学 | The method that heterogeneous system catalyzes and synthesizes bromamine acid condensation product |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044417A (en) * | 1989-01-28 | 1990-08-08 | 天津大学 | Be used for the resin-carried copper catalyst and the preparation thereof of itrile group hydration |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044417A (en) * | 1989-01-28 | 1990-08-08 | 天津大学 | Be used for the resin-carried copper catalyst and the preparation thereof of itrile group hydration |
Non-Patent Citations (2)
| Title |
|---|
| 三苯胺及衍生物的合成方法综述. 文利斌等.化工中间体，第11期. 2005 |
| 三苯胺及衍生物的合成方法综述. 文利斌等.化工中间体，第11期. 2005 * |
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Effective date of registration: 20151020 Address after: 253000 Shandong province Dezhou City Tianqu Industrial Park Orchard Road No. 6 Patentee after: Shandong Yuhong New Pigment Co., Ltd. Address before: 300384 No. 26 Jin Jing Road, Xiqing District, Tianjin, Tianjin Institute of Urban Construction Patentee before: Tianjin Urban Construction College |
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Granted publication date: 20080604 Termination date: 20190629 |