CN101153014B - 3-(N-nitroso-N-phenyl hydroxylamine) aluminum salt preparation method - Google Patents
3-(N-nitroso-N-phenyl hydroxylamine) aluminum salt preparation method Download PDFInfo
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Abstract
The present invention relates to a preparation method of tri-(N-nitroso - N-phenyl hydroxylamine) aluminum salt as shown in formula (1). In the method, aluminum nitrate and N-nitroso-N-phenyl hydroxylamine ammonium salt are used for the decomposition reaction in the mixed solvent of alcohol; the buffer solution is used for controlling the pH value of the reaction solution to be 5.5 to 5.7; the compound of formula (1) can be prepared at a high collection rate.
Description
Technical field
Content involved in the present invention is the method for preparation three (N-nitroso-group-N-Phenylhydroxylamine) aluminium salt.
Background technology
Three (N-nitroso-group-N-Phenylhydroxylamine) aluminium salt is one of important auxiliary agent of UV curable ink composition product shelf stability.The open JP86-103150A of Japanese Patent has described its result of use: the formulation stability under 80～90 ℃ of temperature can satisfy product use and viscosity performance requirement, and product hydroquinone monomethyl ether's prescription is understood turbidization and gelation under same preparation and working conditions in contrast.Three (N-nitroso-group-N-Phenylhydroxylamine) aluminium salt can be accepted by free radical photo-initiation because be heated, see a little free radical that light and other reasons produce, thereby prevent initiating methacrylates class monomer polymerization and gelation tendency, can effectively prolong the storage validity period of ink product.It has obtained description very early as the complexing assay products that occurs in the analytical chemistry, but it is used the preparation of industrialization carry out as stopper and does not then have bibliographical information.
US2004064336 (A) about the synthetic method of N-nitroso-group-N-Phenylhydroxylamine chromium metal (tetravalence) salt is: two kinds of raw material N-nitroso-group-N-Phenylhydroxylamine ammoniums and four chromium chlorides are soluble in water respectively, mix back regulation and control pH value of water solution 8～9, separate out precipitation, obtain product acetone purifying.EP523965 has used alcoholic solvent to be used for the dissolving of organic amine about the preparation of N-nitroso-group-N-Phenylhydroxylamine organic ammonium salt, optimum is Virahol, and the product of separating out is separated when reducing below the solution temperature to 0 ℃, obtain the organic ammonium salt of purifying, also be used for stopper.
Summary of the invention
The purpose of this invention is to provide a kind of is raw material with N-nitroso-group-N-Phenylhydroxylamine ammonium salt and aluminum nitrate, the method for metathesis preparation three (N-nitroso-group-N-Phenylhydroxylamine) aluminium salt.
Specifically, the invention provides a kind of method of preparation three (N-nitroso-group-N-Phenylhydroxylamine) aluminium salt, this method is included in C
1-4In the mixed solvent system of alcohols and water,, adopt buffered soln that the pH value of reaction solution is controlled at 4.0～7.0, get described aluminium salt aluminum nitrate and N-nitroso-group-N-Phenylhydroxylamine ammonium salt reaction.
In specific embodiment, the inventive method comprises the steps:
1) aluminum nitrate is dissolved in the water, adds C
1-4Alcohols to determining alcohol is 10-30v/v%,
2) add N-nitroso-group-N-Phenylhydroxylamine ammonium salt aqueous solution,
3) with after the reaction solution heating, add damping fluid, 4.0～7.0, stirring reaction obtains aluminium salt with the reacting liquid pH value span of control.
In preferred embodiments, the inventive method comprises the steps:
1) aluminum nitrate is dissolved in the water, adds C
1-4Alcohols to determining alcohol is 15-25v/v%.
2) be added dropwise to N-nitroso-group-N-Phenylhydroxylamine ammonium salt aqueous solution,
3) reaction solution is heated to rises to 40～80 ℃, and to drip the pH value be 6.8 buffered soln, with the pH value stabilization of reaction solution between 5.5～5.7, stirring reaction.
In the methods of the invention, preferably methyl alcohol, ethanol or Virahol etc. of alcohols; Heating temperature is preferably 50-60 ℃; The preferably near neutral damping fluid of damping fluid, acetic acid-sodium acetate buffer solution for example, SODIUM PHOSPHATE, MONOBASIC-disodium hydrogen phosphate buffer solution and boric acid-sodium borate buffer solution etc.SODIUM PHOSPHATE, MONOBASIC-disodium hydrogen phosphate buffer solution most preferably.
The present inventor finds, when equivalent raw material N-nitroso-group-N-Phenylhydroxylamine ammonium salt aqueous solution (being weakly alkaline, pH ≈ 7.5) is mixed with aluminum nitrate aqueous solution (be slightly acidic, pH 4.5), the adularescent precipitation produces immediately, reaction rear solution pH value 3.5 (solute is an ammonium nitrate).Under such pH condition, N-nitroso-group-N-Phenylhydroxylamine ammonium salt can hydrolysis be separated out N-nitroso-group-N-Phenylhydroxylamine, and it is water insoluble, together separates out with aluminium complex salt product in the aqueous solution, can't carry out complex reaction again.It is also very unstable simultaneously, very easily decomposes, and discharges nitrogen protoxide, produces by products such as phenylhydroxylamine derivative.But, under the pH value condition of N-nitroso-group-N-Phenylhydroxylamine ammonium salt aqueous solution, carry out complexing the time, also can cause aluminum ions hydrolysis to generate insoluble colloid of aluminium hydroxide and precipitation, make product purity be subjected to very big influence, experimental phenomena and analytical data have also illustrated this point.According to the prompting of organic chemistry document, the complexing condition should be slightly acidic.Through test of many times exploration discovery pH value 5.5～5.7th, optimum span of control.The complexing product purity height that obtains does not almost have toluene insolubles.In order to control such pH value among a small circle, we have used the buffered soln of nearly pH neutral, with in and the acidity of ammonium nitrate solution.The buffered soln that is fit to use in the analytical chemistry can use.What wherein relatively be suitable for has acetic acid-sodium acetate buffer solution, SODIUM PHOSPHATE, MONOBASIC-disodium hydrogen phosphate buffer solution and a boric acid-sodium borate buffer solution etc.SODIUM PHOSPHATE, MONOBASIC-disodium hydrogen phosphate buffer solution most preferably, cost of material cheaply is easy to get, and is suitable for industrialization and uses.
Find in the test, in above preferred pH value scope, still have minor N-nitroso-group-N-Phenylhydroxylamine and complex compound product together to separate out the quality that has influenced product.Study the solvability of N-nitroso-group-N-Phenylhydroxylamine and found, in most of organic solvents, can both dissolve well, considered the characteristics that replacement(metathesis)reaction is carried out in water, selected the water-soluble alcohol kind solvent can make reaction system form uniform solution.When adding an amount of methyl alcohol in the weakly acidic water solution of N-nitroso-group-N-Phenylhydroxylamine white precipitate, white precipitate dissolves immediately, and ethanol and Virahol also have effect same.Under reaction conditions, tested the influence of methanol usage, in 10～30% scopes, can both obtain very good effect, be lower than at 10% o'clock, N-nitroso-group-N-Phenylhydroxylamine is dissolved in scarce capacity in the water, carry this impurity in the complex compound secretly product purity is descended, it is variable color that room temperature is placed a week.When consumption greater than 30% the time, the ratio of alcohol is bigger than normal, and complex compound aluminium salt solubility is increased, yield is lower than 80%, simultaneously, inorganic salt ratio increases in the complexing product.Experiment finds that optimum amount ranges is 15～25%, and product yield reaches 90%, steady quality, and room temperature is deposited six months still for the off-white color solid, does not find variable color.
The inventive method is used C
1-4Alcohols and water mixed solvent system and with method preparation three (N-nitroso-group-N-Phenylhydroxylamine) aluminium salt of buffered soln control reaction solution pH.Wherein the usage ratio of alcohol is preferred 10～30% in alcohol-water mixed solvent, and most preferably 15～25%; C
1-4Alcohols particular methanol, ethanol or Virahol, most preferably methyl alcohol; The reacting liquid pH value span of control is 4.0～7.0, and preferable range is 5.0～6.0, and most preferred range is 5.5～5.7; Used buffered soln can be the buffer solution system of any pH value stabilization about 6.8.Preferred acetic acid-sodium acetate buffer solution and SODIUM PHOSPHATE, MONOBASIC-disodium hydrogen phosphate buffer solution.SODIUM PHOSPHATE, MONOBASIC-disodium hydrogen phosphate buffer solution most preferably.Described alcohols consumption is meant the v/v% with respect to whole solvent system.
Embodiment
Following indefiniteness example will further specify content of the present invention, but the content of claim of the present invention is not limited to cited embodiment.
Embodiment 1
Taking by weighing 42.0 gram (0.11 mole) ANN aluminium nitrate nonahydrate is dissolved in 600 ml waters, drop in 2000 milliliters the reaction flask, add 200 milliliters of methyl alcohol, keep solution temperature at 22～25 ℃. other takes by weighing 50.0 gram (0.32 mole) N-nitroso-group-N-Phenylhydroxylamine ammonium salts and is dissolved in 450 ml waters, be added drop-wise in the reaction flask with 1 hour, very fast adularescent precipitation is separated out. dropwises, rising reacting liquid temperature to 50～60 ℃, and drip 100 milliliters of the SODIUM PHOSPHATE, MONOBASIC-disodium hydrogen phosphate buffer solutions (pH value 6.8) of 3.5% concentration, the pH value stabilization is between 5.5～5.7, stirred 2 hours. be cooled to room temperature then, the suction filtration solid is with 100 ml water washing leaching cakes, obtain the off-white color solid, oven dry is 2 hours in 100 ℃ of baking ovens, must measure 43.0 grams, and yield 91.4%. product fusing point is 167～169 ℃.
Embodiment 2
Take by weighing 42.0 gram (0.11 mole) ANN aluminium nitrate nonahydrate and be dissolved in 600 ml waters, drops in 2000 milliliters the reaction flask, add 200 milliliters of methyl alcohol, the maintenance solution temperature is at 22～25 ℃.Other takes by weighing 50.0 gram (0.32 mole) N-nitroso-group-N-Phenylhydroxylamine ammonium salts and is dissolved in 450 ml waters, is added drop-wise in the reaction flask with 1 hour, and very fast adularescent precipitates separates out.Dropwise, rising reacting liquid temperature to 50～60 ℃, and drip 100 milliliters of the acetate-sodium acetate buffer solutions (pH value 6.8) of 3.5% concentration, the pH value stabilization stirred 2 hours between 5.5～5.7.Be cooled to room temperature then, the suction filtration solid with 100 ml water washing leaching cakes, obtains the off-white color solid, and oven dry is 2 hours in 100 ℃ of baking ovens, must measure 42.1 grams, yield 89.5%.The product fusing point is 167～169 ℃.
Comparative examples 1
Take by weighing 42.0 gram (0.11 mole) ANN aluminium nitrate nonahydrate and be dissolved in 600 ml waters, drops in 2000 milliliters the reaction flask, add 200 milliliters of methyl alcohol, the maintenance solution temperature is at 22～25 ℃.Other takes by weighing 50.0 gram (0.32 mole) N-nitroso-group-N-Phenylhydroxylamine ammonium salts and is dissolved in 450 ml waters, is added drop-wise in the reaction flask with 1 hour, and very fast adularescent precipitates separates out.Dropwise, stirred 2 hours rising reacting liquid temperature to 50～60 ℃, measures pH value 4.8.Be cooled to room temperature then, the suction filtration solid with 100 ml water washing leaching cakes, obtains the off-white color solid, and oven dry is 2 hours in 100 ℃ of baking ovens, must measure 37.7 grams, yield 80%.The product fusing point is 160～162 ℃.
Embodiment 3
The polymerization inhibition effect test
Test recipe table
Testing sequence: by the formulated quantity of sample, test degree of mobilization D under 20 ± 1 ℃ of conditions
0, sample is placed magazine, put into 80 ℃ of baking ovens.Sample after the placement is tested its degree of mobilization D under 20 ± 1 ℃ of conditions
t
Degree of mobilization velocity of variation=(D
0-D
t)/D
0* 100%
Weigh the influence of stopper to thermodynamic stability with the degree of mobilization velocity of variation, velocity of variation is big more unstable more.
The degree of mobilization testing method is referring to GB/T14624.3-93.Table one
| Title | Prescription A | Prescription B | Prescription C | Prescription D | Remarks |
| EB600 | 25g | 25g | 25g | 25g | UCB. S.A. (BE) Bruxelles Belgium |
| EB264 | 25g | 25g | 25g | 25g | UCB. S.A. (BE) Bruxelles Belgium |
| HDDA | 15g | 15g | 15g | 15g | The Tianjin proud son of heaven |
| TMPTA | 15g | 15g | 15g | 15g | The Tianjin proud son of heaven |
| Goth black 250 | 4g | 4g | 4g | 4g | Ciba refines |
| Title | Prescription A | Prescription B | Prescription C | Prescription D | Remarks |
| IHT-910 | 5g | 5g | 5g | 5g | IHT |
| IHT-ITX | 2g | 2g | 2g | 2g | IHT |
| IHT-EDB | 2g | 2g | 2g | 2g | IHT |
| BYK361 | 2g | 2g | 2g | 2g | The Bi Ke chemistry |
| EB110 | 5g | 4.8g | 4.8g | 4.8g | UCB. S.A. (BE) Bruxelles Belgium |
| Embodiment one sample | / | 0.2g | / | / | |
| Phenothiazine | / | / | 0.2g | / | Huge day sea |
| P methoxy phenol | / | / | / | 0.2g | Shanghai chemical reagents corporation |
Test-results
Table two
| The hot storage time | Prescription A | Prescription B | Prescription C | Prescription D |
| 80 ℃, 0 hour | 0％ | 0％ | 0％ | 0％ |
| 80 ℃, 48 hours | 13.9％ | 0％ | 13.9％ | 11.4％ |
| 80 ℃, 72 hours | Completely solidified | 2.9％ | 16.7％ | 14.3％ |
By the result shown in the table two as can be seen: adding stopper in black ink has obvious facilitation to the stability of filling a prescription, and after heat storage in 72 hours, the prescription degree of mobilization velocity of variation minimum of adding stopper of the present invention that is to say that its thermodynamic stability is best.
Claims (10)
1. method for preparing three (N-nitroso-group-N-Phenylhydroxylamine) aluminium salt, this method is included in the C that determining alcohol is 15-25v/v%
1-4In the mixed solvent system of alcohols and water,, adopt buffered soln that the pH value of reaction solution is controlled at 5.5-5.7, get described aluminium salt aluminum nitrate and N-nitroso-group-N-Phenylhydroxylamine ammonium salt reaction.
2. according to the method for claim 1, described method comprises the steps:
1) aluminum nitrate is dissolved in the water, adding alcohols to determining alcohol is 15-25v/v%,
2) add N-nitroso-group-N-Phenylhydroxylamine ammonium salt aqueous solution,
3) with after the reaction solution heating, add buffered soln, the pH value of reaction solution is controlled at 5.5-5.7, stirring reaction must the aluminium product salt.
3. according to the method for claim 2, described method comprises the steps:
1) aluminum nitrate is dissolved in the water, adding alcohols to determining alcohol is 15-25v/v%,
2) be added dropwise to N-nitroso-group-N-Phenylhydroxylamine ammonium salt aqueous solution,
3) reaction solution is heated to temperature and rises to 40-80 ℃, dropping pH value is 6.8 buffered soln, and the pH value stabilization that makes reaction solution is at 5.5-5.7, and stirring reaction gets the aluminium product salt.
4. according to arbitrary method of claim 1-3, described alcohols is methyl alcohol, ethanol or Virahol.
5. according to the method for claim 4, described alcohols is a methyl alcohol.
6. according to claim 1-3, arbitrary method of 5, wherein, described buffered soln is acetic acid-sodium acetate buffer solution, SODIUM PHOSPHATE, MONOBASIC-disodium hydrogen phosphate buffer solution or boric acid-sodium borate buffer solution.
7. according to the method for claim 4, wherein, described buffered soln is acetic acid-sodium acetate buffer solution, SODIUM PHOSPHATE, MONOBASIC-disodium hydrogen phosphate buffer solution or boric acid-sodium borate buffer solution.
8. according to the method for claim 6, wherein, described buffered soln is SODIUM PHOSPHATE, MONOBASIC-disodium hydrogen phosphate buffer solution.
9. according to the method for claim 7, wherein, described buffered soln is SODIUM PHOSPHATE, MONOBASIC-disodium hydrogen phosphate buffer solution.
10. according to claim 3,5,7,8, arbitrary method of 9, wherein the Heating temperature in the step 3) is 50-60 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144260A (en) * | 1974-04-30 | 1979-03-13 | Basf Aktiengesellschaft | Production of aluminum salts of N-nitroso-N-alkyl-hydroxylamines |
| EP0523965A1 (en) * | 1991-07-17 | 1993-01-20 | Rohm And Haas Company | Salts of N-nitrosophenylhydroxylamine |
-
2006
- 2006-09-30 CN CN200610113558A patent/CN101153014B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144260A (en) * | 1974-04-30 | 1979-03-13 | Basf Aktiengesellschaft | Production of aluminum salts of N-nitroso-N-alkyl-hydroxylamines |
| EP0523965A1 (en) * | 1991-07-17 | 1993-01-20 | Rohm And Haas Company | Salts of N-nitrosophenylhydroxylamine |
Non-Patent Citations (3)
| Title |
|---|
| ACTA CRYST51.1995,511295-1297. * |
| 佐佐木 与志实.BUNSEKI KAGAKU25 2.1976,25(2),103-107. |
| 佐佐木 与志实.BUNSEKI KAGAKU25 2.1976,25(2),103-107. * |
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