CN101538232B - Ureido-ethane sulfinate and preparation method thereof - Google Patents
Ureido-ethane sulfinate and preparation method thereof Download PDFInfo
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- CN101538232B CN101538232B CN200910111582XA CN200910111582A CN101538232B CN 101538232 B CN101538232 B CN 101538232B CN 200910111582X A CN200910111582X A CN 200910111582XA CN 200910111582 A CN200910111582 A CN 200910111582A CN 101538232 B CN101538232 B CN 101538232B
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- ureido
- ethane
- reductive agent
- hyposulfite
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Abstract
The invention provides a ureido-ethane sulfinate and a preparation method thereof, wherein the ureido-ethane sulfinate is white powder and has good chemical stability; and the preparation method comprises the following steps: hyposulphite is used for reacting with oxalic aldehyde and carbamide in alkaline condition to synthesize the ureido-ethane sulfinate. The product of the invention does not generate hazardous and noxious sulfur dioxide, formaldehyde or hydrogen sulphide gas at high temperature and in alkaline condition, and simultaneously has very high negative reduction potential; the chemical property of the prepared product is similar to that of formaldehydesulfoxylate as far as possible; and the product solves the problem of the existing reducing agents such as rongalite C and rongalite that sulfur dioxide, formaldehyde and other hazardous and noxious gases are released at high temperature and in alkaline condition.
Description
Technical field
The invention belongs to field of fine chemical, specially refer to a kind of ureido-ethane sulfinate and preparation method thereof.
Background technology
In chemistry and printing and dyeing industry, reductive agent is that a kind of consumption is very big, uses wider auxiliary chemicals.The reductive agent that uses both at home and abroad at present mainly contains vat powder, sodium sulphite, rongalite and thiourea peroxide.But vat powder can spontaneous combustion, especially after moisture absorption, heats up naturally and burns, and stability in storage is very poor, in air, can decompose, and causes effective constituent constantly to descend; When stripping, also can discharge sulfur dioxide gas, be detrimental to health.Sodium sulphite exceeds standard bio-refractory as sulfide in the reductive agent waste discharge; And thiourea peroxide is difficult to its reductibility of control in practical application, can cause some dyestuff overreduction, and the lighter influences colour fastness, and weight person produces flaw, is difficult to repair.Be difficult to hold the consumption of reductive agent and the ratio of ternary color matching simultaneously, and on the high side, narrow application range is unfavorable for the Economic development of whole dyeing.
As everyone knows;-sulfinic acid is a kind of strong reductant; But very unstable, so-sulfinate all belongs to this type material as reductive agent like vat powder, rongalite, De Gulin and thiourea peroxide usually; RongaliteFD, the Rongal A product of BASF AG's production also belong to this type material in addition, and wherein Rongalite FD composition is about NH (CH
2SO
2Na)
2With N (CH
2SO
2Na)
3Mixture, it once was used for the dyeing of vat dyes, but dye yield is lower; Rongal A is NaN (CH
3CHSO
2)
3, soluble in water, more stable than vat powder at normal temperatures, be prone to moisture absorption, reducing power reduces after the moisture absorption, and it is mainly used in the dyeing of vat dyes.The-sulfinate verivate has been done a lot of researchs as reductive agent abroad, the-sulfinate verivate has been applied to the dyeing of vat dyes and thioxine dyes, obtained preferable dye yield like Schober etc. and Wirth etc.Mulliez etc. have introduced the preparation method of several kinds of-sulfinates, a kind ofly prepare-sulfinate through adding aldehyde by V-Brite B and sodium hydroxide.A kind of is to utilize sulphonate and zinc powder, acetic acid reaction and get.Filby etc. utilize mercaptan under lower temperature, to obtain-sulfinate through the weak oxidant oxidation, and but, Marvel etc. point out that when mercaptan was excessive,-sulfinate can obtain disulphide with thiol reactant, make productive rate reduce.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art; A kind of ureido-ethane sulfinate and preparation method thereof is provided; Utilize hyposulfite under alkaline condition with oxalic dialdehyde, the synthetic a kind of ureido-ethane sulfinate of urea reaction; It can not produce poisonous and hazardous sulfurous gas, formaldehyde and hydrogen sulfide under high temperature and alkaline condition; Very high negative reduction potential is arranged simultaneously, and the chemical property of the product of preparation is similar to the chemical property of formaldehydesulfoxylate as much as possible, and this product has solved existing reductive agent such as vat powder and rongalite discharge toxic and harmfuls such as sulfurous gas, formaldehyde under high temperature, alkaline condition problem.
Ureido-ethane sulfinate of the present invention: described ureido-ethane sulfinate is a white powder, and chemicalstability is good, in the time of 25 ℃: and under the 5.0g/L reductive agent condition, its reduction potential is-38～-13mV; Under 5.0g/L reductive agent+15g/LNaOH condition, its reduction potential is-955～-920mV; In the time of 80 ℃: under 5g/L reductive agent condition, its reduction potential is-85～-26mv; Under 5g/L reductive agent+15g/L NaOH condition, its reduction potential is-1018～-986mV; Its chemical general formula is:
In the formula, M=Na, NH
4, K, Ca, Zn; N is the charge number of M, n=1,2.
The preparing method's of ureido-ethane sulfinate of the present invention step is following: oxalic dialdehyde is slowly joined in the reactor drum that stablizer, hyposulfite, alkaline conditioner and water are housed; Controlled temperature is below 10 ℃; Rotating speed with 25～200r/min stirs; To be warming up to 10～65 ℃ behind reinforced the finishing, add urea and alkaline conditioner again behind reaction 30min～120min, temperature risen to 45～95 ℃ after adding material; Behind reaction 30～210min, vacuum-drying gets white ureido-ethane sulfinate powder with purity of 85%～95%.
The present invention has the following advantages and positively effect:
1. the ureido-ethane sulfinate of developing, at lesser temps or when not having caustic soda to exist, reducing power is very little, be difficult for oxidized, good stability.And nontoxic, use and do not receive season, region limits, be convenient to deposit and transport.
2. the ureido-ethane sulfinate of developing can not discharge toxic and harmfuls such as sulfurous gas, hydrogen sulfide, formaldehyde under high temperature and alkaline condition, very high negative reduction potential is arranged simultaneously.
3. production technique is simple, and raw materials for production are easy to get, and is with short production cycle, reaction temperature with, required equipment is a conventional equipment, whole process flow has basically no waste gas, waste water, waste sludge discharge, is a kind of free of contamination Production Flow Chart that cleans, and is convenient to existing chemical plant and practices midwifery.
Description of drawings
Fig. 1 is the stability experiment of reductive agent reduction potential of the present invention.
Embodiment
The mass percent of the raw material of using in the said preparation process is:
Hyposulfite: 30%～50%
Oxalic dialdehyde: 25%～40%
Urea: 10%～25%
Alkaline conditioner: 0.1%～4.0%
Stablizer: 0.1%～5.0%
H
2O：10％～25％。
Said hyposulfite are one or more mixture of V-Brite B, zinc dithionite, potassium hyposulfite, ammonium hyposulfite or calcium hyposulfite.
Said alkaline conditioner is one or more a mixture of sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, ammoniacal liquor, sodium phosphate, SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate, dibasic.
Said stablizer is one or more a mixture of terepthaloyl moietie, Ucar 35, butyleneglycol, USP Kosher or trihydroxybutane.
Preparation process is: oxalic dialdehyde is slowly added in the reactor drum that contains stablizer, hyposulfite, 0.05%～3.8% alkaline conditioner and water; Controlled temperature is below 10 ℃; Rotating speed with 25～200r/min stirs; To be warming up to 10～65 ℃ behind reinforced the finishing, add the alkaline conditioner of urea and 0.05%～3.8% behind reaction 30min～120min again, temperature risen to 45～95 ℃ after adding material; Behind reaction 30～210min, vacuum-drying gets white ureido-ethane sulfinate powder.
With embodiment the present invention is elaborated below, but the present invention is not limited only to this.
Concrete steps are following:
Raw material and prescription (unit-kilogram):
V-Brite B: 40.5 kilograms
Oxalic dialdehyde (40% content): 33.7 kilograms
Urea: 13 kilograms
Sodium hydroxide: 0.8 kilogram
Terepthaloyl moietie: 0.4 kilogram
H
2The O:11.6 kilogram.
Process step and processing parameter: oxalic dialdehyde is contained in the reactor drum of terepthaloyl moietie, V-Brite B, 0.7 kg of hydrogen sodium oxide, water slow the adding; Controlled temperature is below 10 ℃, and the rotating speed stirring with 50r/min will be warming up to 15 ℃ behind reinforced the finishing; Add urea and 0.1 kg of hydrogen sodium oxide again behind the reaction 30min; After adding material temperature is risen to 50 ℃, behind the reaction 35min, vacuum-drying gets white ureido-ethane-sulfinic acid sodium powder with purity of 86%.In the time of 25 ℃: under the 5.0g/L reductive agent condition, its reduction potential is-14mV; Under 5.0g/L reductive agent+15g/L NaOH condition, its reduction potential is-938mV; In the time of 80 ℃: under 5g/L reductive agent condition, its reduction potential is-53mv; Under 5g/L reductive agent+15g/L NaOH condition, its reduction potential is-1015mV.
Embodiment 2:
Concrete steps are following:
Raw material and prescription (unit-kilogram):
Zinc dithionite: 43 kilograms
Oxalic dialdehyde (40% content): 29.5 kilograms
Urea: 12.2 kilograms
Yellow soda ash: 1.9 kilograms
Ucar 35: 0.2 kilogram
H
2The O:13.2 kilogram.
Process step and processing parameter: oxalic dialdehyde slowly added contain in Ucar 35, zinc dithionite, 1.5 kilograms the reactor drum of yellow soda ash, water; Controlled temperature is below 10 ℃, and the rotating speed stirring with 200r/min will be warming up to 20 ℃ behind reinforced the finishing; Reaction adds the yellow soda ash of urea and 0.4 kilogram behind the 50min again; After adding material temperature is risen to 55 ℃, behind the reaction 60min, vacuum-drying gets white ureido-ethane-sulfinic acid zinc powder with purity of 88%.In the time of 25 ℃: under the 5.0g/L reductive agent condition, its reduction potential is-13mV; Under 5.0g/L reductive agent+15g/L NaOH condition, its reduction potential is-955mV; In the time of 80 ℃: under 5g/L reductive agent condition, its reduction potential is-33mV; Under 5g/L reductive agent+15g/LNaOH condition, its reduction potential is-1018mV.
Embodiment 3:
Concrete steps are following:
Raw material and prescription (unit-kilogram):
Potassium hyposulfite: 36.5 kilograms
Oxalic dialdehyde (40% content): 29.7 kilograms
Urea: 13.5 kilograms
Salt of wormwood: 2.2 kilograms
Butyleneglycol: 0.3 kilogram
H
2The O:17.8 kilogram.
Process step and processing parameter: oxalic dialdehyde is contained in the reactor drum of butyleneglycol, potassium hyposulfite, 1.9 kg of potassium carbonate, water slow the adding; Controlled temperature is below 10 ℃, and the rotating speed stirring with 65r/min will be warming up to 25 ℃ behind reinforced the finishing; Add urea and 0.3 kg of potassium carbonate again behind the reaction 60min; After adding material temperature is risen to 60 ℃, behind the reaction 70min, vacuum-drying gets white ureido-ethane-sulfinic acid potassium powder with purity of 86%.In the time of 25 ℃: under the 5.0g/L reductive agent condition, its reduction potential is-18mV; Under 5.0g/L reductive agent+15g/L NaOH condition, its reduction potential is-921mV; In the time of 80 ℃: under 5g/L reductive agent condition, its reduction potential is-56mV; Under 5g/L reductive agent+15g/L NaOH condition, its reduction potential is-965mV.
Embodiment 4:
Concrete steps are following:
Raw material and prescription (unit-kilogram):
Calcium hyposulfite: 35 kilograms
Oxalic dialdehyde (40% content): 28.5 kilograms
Urea: 10 kilograms
Sodium phosphate: 1.5 kilograms
USP Kosher: 1 kilogram
H
2The O:24 kilogram.
Process step and processing parameter: oxalic dialdehyde slowly added contain in USP Kosher, calcium hyposulfite, 1.1 kilograms the reactor drum of sodium phosphate, water; Controlled temperature is below 10 ℃, and the rotating speed stirring with 150r/min will be warming up to 45 ℃ behind reinforced the finishing; Reaction adds the sodium phosphate of urea and 0.4 kilogram behind the 100min again; After adding material temperature is risen to 75 ℃, behind the reaction 180min, vacuum-drying gets white ureido-ethane-sulfinic acid calcium powder with purity of 91%.In the time of 25 ℃: under the 5.0g/L reductive agent condition, its reduction potential is-18mV; Under 5.0g/L reductive agent+15g/L NaOH condition, its reduction potential is-920mV; In the time of 80 ℃: under 5g/L reductive agent condition, its reduction potential is-26mV; Under 5g/L reductive agent+15g/L NaOH condition, its reduction potential is-995mV.
Embodiment 5:
Concrete steps are following:
Raw material and prescription (unit-kilogram):
Ammonium hyposulfite: 33 kilograms
Oxalic dialdehyde (40% content): 30.8 kilograms
Urea: 13.2 kilograms
Ammoniacal liquor (25～28% content): 1.6 kilograms
USP Kosher: 0.4 kilogram
H
2The O:21 kilogram.
Process step and processing parameter: oxalic dialdehyde slowly added contain in stablizer, ammonium hyposulfite, 1.3 kilograms the reactor drum of ammoniacal liquor, water; Controlled temperature is below 10 ℃, and the rotating speed stirring with 90r/min will be warming up to 60 ℃ behind reinforced the finishing; Reaction adds the ammoniacal liquor of urea and 0.3 kilogram behind the 115min again; After adding material temperature is risen to 90 ℃, behind the reaction 200min, vacuum-drying gets white ureido-ethane-sulfinic acid ammonium powder with purity of 92%.In the time of 25 ℃: under the 5.0g/L reductive agent condition, its reduction potential is-38mV; Under 5.0g/L reductive agent+15g/L NaOH condition, its reduction potential is-925mV; In the time of 80 ℃: under 5g/L reductive agent condition, its reduction potential is-85mV; Under 5g/L reductive agent+15g/L NaOH condition, its reduction potential is-986mV.
Choose the above embodiments 1-3 and vat powder, sodium sulfoxylate formaldehyde and carry out stability relatively; Technology is following: at reductive agent 20g/L; Sodium hydroxide 20g/L is under 80 ℃ of conditions, and the reductive agent that makes with potentiometric determination embodiment 1-3, the current potential of vat powder are as shown in Figure 1.Can know by Fig. 1; At 80 ℃; Under the condition of 20g/L sodium hydroxide and 20g/L reductive agent; The reduction potential of embodiment 1-embodiment 3 prepared reductive agents is between vat powder and sodium sulfoxylate formaldehyde, but stability is higher than vat powder and sodium sulfoxylate formaldehyde, and over-all properties is superior to vat powder and sodium sulfoxylate formaldehyde.
Claims (4)
1. ureido-ethane sulfinate, it is characterized in that: described ureido-ethane sulfinate is a white powder, and chemicalstability is good, in the time of 25 ℃: under the 5.0g/L reductive agent condition, its reduction potential is-38～-13mV; Under 5.0g/L reductive agent+15g/L NaOH condition, its reduction potential is-955～-920mV; In the time of 80 ℃: under 5g/L reductive agent condition, its reduction potential is-85～-26mV; Under 5g/L reductive agent+15g/L NaOH condition, its reduction potential is-1018～-986mV; Its chemical general formula is:
In the formula, M=Na, NH
4, K, Ca, Zn; N is the charge number of M, n=1,2.
2. the preparation method of a ureido-ethane sulfinate as claimed in claim 1; It is characterized in that: said preparing method's step is following: oxalic dialdehyde is slowly joined in the reactor drum that stablizer, hyposulfite, alkaline conditioner and water are housed; Controlled temperature is below 10 ℃, and the rotating speed stirring with 25～200r/min will be warming up to 10～65 ℃ behind reinforced the finishing; Add urea and alkaline conditioner again behind reaction 30min～120min; After adding material temperature is risen to 45～95 ℃, behind reaction 30～210min, vacuum-drying gets white ureido-ethane sulfinate powder;
Described hyposulfite are a kind of of V-Brite B, zinc dithionite, potassium hyposulfite, ammonium hyposulfite or calcium hyposulfite;
Said stablizer is one or more a mixture of terepthaloyl moietie, Ucar 35, butyleneglycol, USP Kosher or trihydroxybutane.
3. the preparation method of ureido-ethane sulfinate according to claim 2, it is characterized in that: the mass percent of the raw material of using in the said preparation process is:
Hyposulfite: 30%～50%
Oxalic dialdehyde: 25%～40%
Urea: 10%～25%
Alkaline conditioner: 0.1%～4.0%
Stablizer: 0.1%～5.0%
H
2O：10％～25％。
4. according to the preparation method of claim 2 or 3 described ureido-ethane sulfinates, it is characterized in that: said alkaline conditioner is one or more a mixture of sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, ammoniacal liquor, sodium phosphate, SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate, dibasic.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4515620A (en) * | 1982-01-12 | 1985-05-07 | Ciba Geigy Corporation | Triaza compounds |
| US5001158A (en) * | 1984-04-11 | 1991-03-19 | Centre National De La Recherche Scientifique | Nitrosoureas compounds preparation thereof and utilization thereof in anticancerous |
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2009
- 2009-04-28 CN CN200910111582XA patent/CN101538232B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4515620A (en) * | 1982-01-12 | 1985-05-07 | Ciba Geigy Corporation | Triaza compounds |
| US5001158A (en) * | 1984-04-11 | 1991-03-19 | Centre National De La Recherche Scientifique | Nitrosoureas compounds preparation thereof and utilization thereof in anticancerous |
Non-Patent Citations (2)
| Title |
|---|
| Bodendorf,K.et al.K. Bodendorf und Norbert Senger: Versuche zur Darstellung von Sulfoessigsaure-ureiden.《Berichte der Deutschen Chemischen Gesellschaft》.1939,571-576. * |
| JP昭58118559A 1983.07.14 |
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