AIBN Preparation: 2 Steps from Acetone
Preparation of AIBN Azobis(isobutyronitrile)
The virtues of this preparation are simplicity, absence of the use of NH3 and Cl2, and no need for acetone
cyanohydrin.
Dissolve 24 g hydrazine sulfate (0.185 mol) in 175 ml warm water and
place it in a 500 ml Parr shaker bottle. Add 18 g NaCN (0.37 mol) in 50
ml water then 24.5 ml (19.3 g, 0.33 mol) acetone. Stopper the bottle and
mount it in a Parr 3911 or equivalent shaker with a Parr cooling jacket
for cooling water from a recirculating chiller at 20 C as the reaction is
exothermic. (Cooling can be discontinued once reaction subsides as
indicated by thermocouple.)The stopper is fitted with standard Parr T
valve leading to a 100 psi gage, the valve to the onboard gas cylinder is
however closed.
The bottle is shaken intermittently for two days. During that time a
crystalline deposit of Me2(CN)C-NH-NH-C(CN)-Me2 forms.
After 2 days the bottle is vented to hood and the solid separated from
the reaction mixture. It is recrystallized from ether or 95% ethanol.
The yield is 44 g mp 92-93 C.
The product is transferred to a 2 L flask, mixed with 25 ml ethanol and
acidified with dilute hydrochloric acid. The flask is cooled in an ice
bath and stirred vigorously while saturated bromine water (34 g
Br2/liter H2O) is slowly added until a yellow color becomes
permament. Crystalline solid is filtered off and the filtrate again
treated with Br2/water. Product is recrystallized from ether, yield 31.5
g, 71% (56% overall from acetone basis). mp 103-104 C.
Me2-C(CN)-N=N-(CN)C-Me2 (AIBN) 2,2'-azobis(isobutyronitrile)
AIBN is a highly useful free radical initiator for polymerizations and
chlorinations. It is regarded as far safer than dibenzoyl peroxide. It is
however toxic and classified as explosive which makes it difficult and
expensive to ship. Exercise appropriate caution when storing and
handling AIBN.
Dupont sells AIBN under the trademark VAZO and MSDS are
available from them, also Aldrich.
References
Thiele and Heuser, Ann. 290, pp22-23 from larger article pp 1-43.
Dox, JACS 47, 1471 (1925)
Overberger, O'Shaugnessey and Shalit, ibid. 71, 2661 (1949)
These are available in References or from me.
[Edited on 26-3-2008 by Sauron
The following is cortesy of garage chemist. It is the original preparation of hydrazibisisobutyronitrile, the immediate
precursor to AIBN, by Thiele and Heuser. The scale is 1 molar based on hydrazine sulfate, or about 6X that of the
preparation described above.
"Translation of the Hydrazoisobutyronitrile synthesis in Saurons article:
130g hydrazine sulfate are dissolved in just the necessary amount of warm water and mixed with a concentrated
aqueous solution of 130g KCN (2 mol) and with 116g acetone (2 mol). The mixture is vigorously shaken.
In order to prevent excessive evaporation of HCN and acetone from the mixture due to the exotherm, the operation is
done in a round-bottm flask with attached reflux condenser.
After some time, the liquid becomes turbid and an oil layer deposits on its surface.
Now the mixture is intensively stirred with a turbine, and during the slow cooling a large amount of white glistening
leaflets deposit which eventually fill the entire liquid.
After standing for 12 hours, the precipitate is filtered with suction and washed with water.
The nitrile thus obtained is already pure.
Because a significant loss of HCN cannot be prevented in the synthesis, the filtrate, which is kept separate from the
washing waters, is mixed again with 1 mol acetone, 1 mol KCN and an amount of acid equivalent to the KCN. Upon
standing, a good amount of nitrile again separates and the yield is now the theoretical one in regard to the used
hydrazine sulfate.
For analysis, the nitrile is recrystallized from ether, from which it separates in thick, often centimeter-large, glassy
glistening crystals that melt at 92-93°C.
Apparently monoclinic crystals with fissibility (don't know a better translation for Spaltbarkeit) like gypsum.
Easily soluble in alcohol and ether, less in ligroin, insoluble in water and alkalies, soluble in dilute acids.
Upon warming with water, HCN is given off."
Some comments:
1. Note absence of cooling which likely accounts for the noted loss of HCN through reflux condenser. The
subsequent preparations based on this one all advise cooling the reaction mixture and it is clear from the closely
related preps of acetone cyanohydrin that the regulation of the temperature between 0 and 15 C is not an accident in
relation to the boiling point of HCN. This, along with the smaller scale, probably explains why later workers did not
feel obliged to work over the filtrate. Dox, and later Overberger et al, obtained 80% yields without working up the
filtrate. On the scales at which they operated it probably would not have been particularly productive to do so.
A Dewar type condenser would likely also minimize HCN loses. But cooling is IMO still advisible, since the product
loses HCN on warming in water.
2. Efficient stirring can probably replace shaking throughout this procedure. In this case no Parr apparatis is required.
AIBN process:
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for preparing 2,2'-azobis-isobutyronitrile used as a foaming agent for
polymers and an initiating agent in radical polymerization of unsaturated hydrocarbons. Method involves interaction
of acetone cyanohydrin with hydrazine hydrate in an aqueous medium followed by oxidation of intermediate 2,2'-
hydrazobis-isobutyronitrile with hydrogen peroxide in acid medium in the presence of bromine or its compounds
with using tungsten, vanadium and molybdenum compounds as a catalyst. The oxidation process is carried out in the
presence of surface-active substances taken in the amount 0.05-1% of charged acetone cyanohydrin being without
isolation of the intermediate compound. Method provides preparing the end substance with the yield 94-95.3% as
measured for the parent hydrazine.
EFFECT: improved preparing method.
compounds and as catalysts for tungsten, vanadium or molybdenum compounds.
The invention relates to a method for producing 2,2'-azobisisobutyronitrile, used as a foaming agent of polymers and
initiator of radical polymerization of unsaturated hydrocarbons.
A known method of producing 2,2'-azobisisobutyronitrile by the interaction of acetone cyanohydrin with hydrazine
salts (sulfates, chlorides, phosphates) in an aqueous medium in the presence of caustic alkalis at 15-50 ° C with the
formation of an intermediate 2,2'-hydrazobisisobutyronitrile, which is filtered off, washed with water, dried and then
oxidized with hydrogen peroxide in the presence of bromine and sulfuric acid compounds in an aqueous medium at
a temperature of 15-40 ° C. Product yield 80-92%. (Patent СРР No. 90608, MKI 4 , С 07 С 121/00, 1984; Patent
СРР No. 91258, MKI 4 , С 07 С 121/04, 1985; Patent СРР No. 90607, MKI 4 , С 07 С 121/00, 1984; Patent CPP No.
90708, MKI 4 , C 07 C 121/14, 1985
The disadvantages of the known methods are: a large number of highly concentrated salt wastewater, due to the use
of hydrazine salts and alkalis in the first stage of the process and washing of the intermediate product, the
complexity of the process due to the stages of isolation of the intermediate product and its drying, insufficiently high
yield of the product.
The closest in technical essence and the achieved result is a method for producing 2,2'-azobisisobutyronitrile,
according to which, at the first stage, 2,2'-hydrazobisisobutyronitrile is obtained by known methods from hydrazine
or its adducts and acetone cyanohydrin and then oxidized to the end product by the action of hydrogen peroxide in
aqueous medium in the presence of mineral or organic acid, bromine compounds and as catalysts for molybdenum,
vanadium, tungsten or uranium compounds at 0-50 ° C. The product is filtered off, washed with water and dried in
vacuo at 35 ± 2 ° C. The yield of 2,2'-azobisisobutyronitrile is 91.4-98.2%, counting on 2,2'-
hydrazobisisobutyronitrile (Auth. Certificate Czechoslovakia No. 2323250 MKI 4 , C 07 C 121/16, 1983).
The disadvantages of this method of producing 2,2'-azobisisobutyronitrile are: the complexity of the apparatus
design due to the presence of stages of isolation and preparation of a suspension of intermediate 2,2'-
hydrazobisisobutyronitrile, unfavorable sanitary and environmental characteristics of the process due to additional
contact with cyanide compounds at the stages of isolation, washing and preparing a suspension of an intermediate
product, a large amount of wastewater requiring careful neutralization from cyanide compounds obtained at the
stage of isolation of both the intermediate and the target product.
The objective of the present invention is to develop a technology for producing 2,2'-azobisisobutyronitrile in a
simplified scheme with improved sanitary and environmental characteristics of the production.
The problem is solved by the method of producing 2,2'-azobisisobutyronitrile, which consists in the condensation of
hydrazine hydrate with acetone cyanohydrin in an aqueous medium in the presence of 0.05-1% of a surfactant from
charged acetoncyahydrin followed by oxidation of the resulting intermediate 2,2'-hydrazobisisobutyronitrile its
evolution by hydrogen peroxide in an acidic medium in the presence of bromine or its compounds and as catalysts
for tungsten, vanadium or molybdenum compounds.
The technical result from the implementation of the proposed method, the introduction of a surfactant into the
reaction mass ensures the wettability of the hydrophobic intermediate product, which contributes to its uniform
distribution and improves contact with the oxidizing agent, the process design is simplified and its duration is
reduced, the amount of wastewater is reduced and sanitary and environmental characteristics are improved.
A distinctive feature of the proposed method is the process in the presence of surfactants, without the release of 2,2'-
hydrazobisisobutyronitrile.
Water, a surfactant, acetone cyanohydrin are charged into the reactor, and hydrazine hydrate is dosed at 20-40 ° C.
The mass is kept at 20-45 ° C for 2-8 hours. Then, catalyst, acid, bromine or a compound thereof are sequentially
loaded into it at 10-20 ° C, hydrogen peroxide is held for 4-6 hours. The target product is filtered off, washed with
water and dried. The product yield 94 - 95.3%, counting on the starting hydrazine.
The invention is illustrated by the following examples:
Example 1
In a reaction flask with a capacity of 1 dm 3 equipped with a mechanical stirrer, reflux condenser,
thermometer and dropping funnel, 340 cm 3 of water, 0.06 g of neonol AF 9-10, 116.06 g of 99%
acetone cyanohydrin, 32.68 g 65.6% hydrazine hydrate and incubated for 4 hours at 30-35 ° C.
At the end of the exposure, cool the contents of the flask to 10-15 ° C, load 0.2 g of sodium
tungstate, acidify to pH 1-2 and dose 3 cm 3 of bromine and 88 cm 3 of 34.8% hydrogen peroxide.
It is maintained at 15-20 ° C until a yellow color appears. The target product is filtered off,
washed with water, and dried.
105.2 g of 2,2'-azobisisobutyronitrile are obtained, which is 95% of theory, based on the starting
hydrazine. Melting point 102-103.5 ° C.
Example 2
Under the conditions of Example 1, from 17.2 g of 99% acetoncyanohydrin, 50 cm 3 of water,
0.017 g of syntamide-5, 4.89 g of 65.6% hydrazine hydrate, 0.038 g of sodium tungstate, 9.0 g
40 % hydrobromic acid and 13 cm 3 of 34.8% hydrogen peroxide receive 15.65 g of 2,2'-
azobasisobutyronitrile, which is 95.3% of theory, based on the original hydrazine. Melting point
102-104 ° C.
Example 3
Under the conditions of Example 1, from 17.2 g of 99% acetoncyanohydrin, 50 cm 3 of water,
4.89 g of 65.6% hydrazine hydrate, 0.015 g of neonol AF 9-10, 0.03 g of ammonium
metavanadate, 0 55 g of sodium bromide and 13 cm 3 of 34.8% hydrogen peroxide give 15.55 g of
2,2'-azobisisobutyronitrile, which is 94.5% of theory, based on the starting hydrazine. Melting
point 101.5 ° C.
Process 2:
The invention relates to a method for synthesizing bis-isobutyronitrile hydrazine. Acetone cyanohydrins and
hydrazine hydrate are used as raw materials to carry out condensation reaction by the action of phase transfer
catalyst quaternary ammonium compound. The phase transfer catalyst not only promotes the reaction speed and
enhances the synthesis yield to 98.23 percent to 98.60 percent, but also reduces the addition of water in the reaction,
thus improving the productivity greatly and reducing the production cost as the phase transfer catalyst also takes
effects of dispersing. A product has stable quality, and the purity of the product is more than 98 percent. Therefore,
the method for synthesizing the bis-isobutyronitrile hydrazine is a method fit for industrialized production.
Description
The synthetic method of bis-isobutyronitrile hydrazine
Technical field
The present invention relates to the synthetic method of organic compound bis-isobutyronitrile
hydrazine.
Background technology
Bis-isobutyronitrile hydrazine belongs to a kind of organic chemical industry's product, is mainly used in
the production of initiator Diisopropyl azodicarboxylate.
About the synthetic method of bis-isobutyronitrile hydrazine, mainly be in the preparation technology of
Diisopropyl azodicarboxylate, to be discussed.In disclosed Chinese patent CN1785963 of in June, 2006 "
preparation method of Diisopropyl azodicarboxylate ", just relate to synthesizing as the intermediates
bis-isobutyronitrile hydrazine.This method is the bis-isobutyronitrile hydrazine mother liquor water
(needing to regulate pH value to 4～5) that produces in the primary first-order equation before adding
in acetone cyanohydrin, the clear water that should add when having replaced reaction, carry out
condensation reaction with hydrazine hydrate again, its objective is to utilize and have saturated bis-
isobutyronitrile hydrazine in the mother liquor water, concentration increases after making
condensation reaction, it is slightly more that product is separated out in cooling, reached the effect that
improves yield.But, apply mechanically the method for mother liquor water and brought problem to
production, one, when applying mechanically the mother liquor water jacket with after repeatedly,
because the increase of foreign matter content, the intermediates bis-isobutyronitrile hydrazine product
colour of generation turns to be yellow sometimes, can not guarantee the quality of the finished
product Diisopropyl azodicarboxylate; They are two years old, the intermediates bis-isobutyronitrile
hydrazine preparation method who sets forth among the CN1785963 is similar to classical bis-
isobutyronitrile hydrazine preparation method, all need to add a large amount of water as thinner, play
dissemination, its amount of water is 7～10 times (mol ratios) of acetone cyanohydrin amount, owing to
add big water gaging, the volume of reaction unit is enlarged.If will increase turnout, the bigger reactor
of the essential usefulness of making use of momentum.
Therefore, for the quality that guarantees the bis-isobutyronitrile hydrazine product and improve its throughput,
seeking a kind of new synthesis process of producing bis-isobutyronitrile hydrazine, to satisfy need of industrial
production, is to be badly in need of the realistic problem that solves during enterprise produces.
Summary of invention:
The invention provides a kind of synthetic method of bis-isobutyronitrile hydrazine, it is a kind of bis-
isobutyronitrile hydrazine synthesis technique that is suitable for suitability for industrialized production.Improve
reaction by adding phase-transfer catalyst, phase-transfer catalyst has played dissemination, can reduce the add-on
of clear water in the reaction, has improved throughput.
Bis-isobutyronitrile hydrazine synthetic method of the present invention also is to adopt acetone cyanohydrin and
hydrazine hydrate as reactant, has added the water of dissemination, carries out condensation reaction in the
presence of phase-transfer catalyst, and its reaction equation is as follows:
The interface of accelerating water and organic liquid phase by the interpolation phase-transfer catalyst contacts,
promote reaction to help the minimum bis-isobutyronitrile hydrazine product direction propelling of solubleness in
water, phase-transfer catalyst has played dissemination again, can reduce the consumption of dilution water, under
the state of cooling, can separate out more crystallization, not only improve synthesis yield, but also enlarged
throughput.
The phase-transfer catalyst that adds in reaction is a quaternary ammonium salt compound, and its general formula
is R 4N +X -, wherein four R can be identical or different, and R is C nH 2n+1(n=1～18) or C 6H 5CH 2X is halogen (F,
Cl, Br, I).Preferred quaternary ammonium salt compound is: tetramethyl ammonium chloride, etamon chloride,
tetrabutyl ammonium fluoride, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium
iodide, two octyl alkyl dimethyl ammonium chloride, cetyl trimethylammonium bromide or stearyl dimethyl benzyl
ammonium chloride etc.
The step of bis-isobutyronitrile hydrazine synthetic method of the present invention: add acetone cyanohydrin, the
water of phase-transfer catalyst and dilution usefulness adds hydrazine hydrate under stirring at normal temperature,
carry out condensation reaction.The mol ratio of reactant acetone cyanohydrin and hydrazine hydrate is 1: 0.5～0.6,
the mol ratio of acetone cyanohydrin and diluting water is 1: 1.5～5, the phase-transfer catalyst consumption is
0.0001～0.01 times of acetone cyanohydrin molar weight, temperature of reaction is controlled at 55～85 ℃, and
keeps 2.5～5 hours, reactant is cooled to 5 ℃ then, separate out solid, filter, drying under reduced pressure is 8 ～14
hours at normal temperatures, just obtains white crystals bis-isobutyronitrile hydrazine product.Prove that through
gc analysis its purity is greater than 98%, reaction yield is 98.23%～98.60%.
Bis-isobutyronitrile hydrazine synthetic method of the present invention is to make raw material with acetone
cyanohydrin and hydrazine hydrate, carries out condensation reaction in the presence of phase-transfer
catalyst.Adding phase-transfer catalyst in reactant can be so that the interface of organic phase and water fully
contacts, and fast reaction speed helps generating the product bis-isobutyronitrile hydrazine.General its reaction
yield has only 90.23% not with the preparation technology of phase-transfer catalyst, even if adopt the preparation
technology of " applying mechanically condensation waste water ", its reaction yield also has only 90.95%.And the
present invention improves reaction yield greatly, brings up to 98.23%～98.60% from 90.23%.Because phase-
transfer catalyst has played dissemination, can reduce the add-on of clear water in the reaction again, enlarge
throughput widely; And constant product quality, the purity of product is greater than 98%.Therefore, the synthetic
method of bis-isobutyronitrile hydrazine of the present invention is a kind of method that is suitable for suitability
for industrialized production, has the little and big characteristics of throughput of reaction vessel volume, has
improved reaction yield, has reduced production cost.
Expriment 1
In the 500ml flask, add 98.9% acetone cyanohydrin, 129 grams (1.50 moles), 98% Tetrabutyl amonium bromide, 0.2
gram (0.00061 mole) and water 50 grams (2.78 moles), under 25 ℃ of stirrings, the dropping weight concentration
is 80% industrial hydrazine hydrate 47.5 grams (0.76 mole).After dropwising, heat temperature raising to 60 ℃ kept
3 hours.Reactant is cooled to 5 ℃ again, separates out solid, filter, dry 8 hours of decompression (vacuum tightness
is 0.098MPa) at normal temperatures obtains white crystals bis-isobutyronitrile hydrazine product 124.0
grams.Through gc analysis, bis-isobutyronitrile hydrazine purity is 98.7%, and reaction yield is 98.23% (in acetone
cyanohydrin).
EXPRIMENT:2
In the 500ml flask, add 98.9% acetone cyanohydrin, 129 grams (1.50 moles), 98% tetramethyl ammonium chloride,
1 gram (0.00894 mole) and water 45 grams (2.5 moles), under 25 ℃ of stirrings, the dropping weight concentration
is 80% industrial hydrazine hydrate 48 grams (0.767 mole).After dropwising, heat temperature raising to 70 ℃ kept
4 hours.Reactant is cooled to 5 ℃ again, separate out solid, filter, dry 10 hours of decompression (vacuum tightness
is 0.098MPa) at normal temperatures, obtain white crystals bis-isobutyronitrile hydrazine product 124.5 grams,
through gc analysis, bis-isobutyronitrile hydrazine purity is 98.5%, and reaction yield is 98.42% (in acetone
cyanohydrin).
Expriment:3
In the 500ml flask, add 98.9% acetone cyanohydrin, 129 grams (1.50 moles), 98% etamon chloride, 0.5 gram
(0.00296 mole) and water 70 grams (3.89 moles), under 25 ℃ of stirrings, the dropping weight concentration is
40% industrial hydrazine hydrate 99 grams (0.791 mole).After dropwising, heat temperature raising to 65 ℃ kept 5
hours.Reactant is cooled to 5 ℃ again, separate out solid, filter, dry 9 hours of decompression (vacuum tightness is
0.098MPa) at normal temperatures, obtain white crystals bis-isobutyronitrile hydrazine product 123.8 grams,
through gc analysis, bis-isobutyronitrile hydrazine purity is 99.1%, and reaction yield is 98.47% (in acetone
cyanohydrin).
Expriment:4
In the 500ml flask, add 98.9% acetone cyanohydrin, 129 grams (1.50 moles), 98% tetrabutyl ammonium fluoride,
0.5 gram (0.00187 mole) and water 50 grams (2.78 moles), under 25 ℃ of stirrings, the dropping weight
concentration is 80% industrial hydrazine hydrate 48 grams (0.767 mole).After dropwising, heat temperature raising
to 55 ℃ kept 4 hours.Reactant is cooled to 5 ℃ again, separate out solid, filter, dry 11 hours of decompression
(vacuum tightness is 0.098MPa) at normal temperatures, obtain white crystals bis-isobutyronitrile hydrazine product
124.1 grams, through gc analysis, bis-isobutyronitrile hydrazine purity is 99.0%, and reaction yield is 98.60% (in
acetone cyanohydrin).
Expriment:5
In the 500ml flask, add 98.9% acetone cyanohydrin, 129 grams (1.50 moles), 98% tetrabutylammonium chloride,
0.5 gram (0.00176 mole) and water 80 grams (4.44 moles), under 25 ℃ of stirrings, the dropping weight
concentration is 80% industrial hydrazine hydrate 49 grams (0.783 mole).After dropwising, heat temperature raising
to 85 ℃ kept 5 hours.Reactant is cooled to 5 ℃ again, separate out solid, filter, dry 8 hours of decompression
(vacuum tightness is 0.098MPa) at normal temperatures, obtain white crystals bis-isobutyronitrile hydrazine product
124 grams, through gc analysis, bis-isobutyronitrile hydrazine purity is 98.8%, and reaction yield is 98.33% (in
acetone cyanohydrin).
Expriment:6
In the 500ml flask, add 98.9% acetone cyanohydrin, 129 grams (1.50 moles), 98% tetrabutylammonium iodide, 0.1
gram (0.00027 mole) and water 100 grams (5.56 moles), under 25 ℃ of stirrings, the dropping weight concentration
is 40% industrial hydrazine hydrate 97 grams (0.775 mole).After dropwising, heat temperature raising to 60 ℃ kept
3 hours.Reactant is cooled to 5 ℃ again, separate out solid, filter, dry 10 hours of decompression (vacuum tightness
is 0.098MPa) at normal temperatures, obtain white crystals bis-isobutyronitrile hydrazine product 124 grams,
through gc analysis, bis-isobutyronitrile hydrazine purity is 99.0%, and reaction yield is 98.52% (in acetone
cyanohydrin).
Expriment:7
In the 500ml flask, add 98.9% acetone cyanohydrin 129 gram (1.50 moles), 98% pair of octyl alkyl dimethyl
ammonium chloride 1 gram (0.00320 mole) and water 120 and restrain (6.67 moles), under 25 ℃ of stirrings, the
dropping weight concentration is 80% industrial hydrazine hydrate 49 grams (0.783 mole).After dropwising, heat
temperature raising to 85 ℃ kept 3 hours.Reactant is cooled to 5 ℃ again, separate out solid, filter, dry 12 hours of
decompression (vacuum tightness is 0.098MPa) at normal temperatures, obtain white crystals bis-isobutyronitrile
hydrazine product 124.2 grams, through gc analysis, bis-isobutyronitrile hydrazine purity is 98.6%, and reaction
yield is 98.28% (in acetone cyanohydrin).
Expriment:8
In the 500ml flask, add 98.9% acetone cyanohydrin, 129 grams (1.50 moles), 98% cetyl trimethylammonium
bromide, 1.2 grams (0.00323 mole) and water 130 grams (7.22 moles), under 25 ℃ of stirrings, the dropping weight
concentration is 80% industrial hydrazine hydrate 49 grams (0.783 mole).After dropwising, heat temperature raising
to 65 ℃ kept 2.5 hours.Reactant is cooled to 5 ℃ again, separate out solid, filter, dry 14 hours of decompression
(vacuum tightness is 0.098MPa) at normal temperatures, obtain white crystals bis-isobutyronitrile hydrazine product
123.6 grams, through gc analysis, bis-isobutyronitrile hydrazine purity is 99.1%, and reaction yield is 98.31% (in
acetone cyanohydrin).
Expriment:9
In the 500ml flask, add 98.9% acetone cyanohydrin, 129 grams (1.50 moles), 98% stearyl dimethyl benzyl
ammonium chloride, 0.1 gram (0.00023 mole) and water 70 grams (3.89 moles), under 25 ℃ of stirrings, the
dropping weight concentration is 80% industrial hydrazine hydrate 48 grams (0.767 mole).After dropwising, heat
temperature raising to 70 ℃ kept 3.5 hours.Reactant is cooled to 5 ℃ again, separate out solid, filter, dry 10 hours
of decompression (vacuum tightness is 0.098MPa) at normal temperatures, obtain white crystals bis-isobutyronitrile
hydrazine product 124.1 grams, through gc analysis, bis-isobutyronitrile hydrazine purity is 98.8%, and reaction
yield is 98.40% (in acetone cyanohydrin).
Comparing process:1
In the 500ml flask, add 98.9% acetone cyanohydrin, 129 grams (1.5 moles) and water 50 grams, under 25 ℃ of
stirrings, the dropping weight concentration is 80% industrial hydrazine hydrate 47.5 grams (0.756 mole).After
dropwising, heat temperature raising to 60 ℃ is incubated 3 hours.Reactant is cooled to 5 ℃ again, separate out
solid, filter, dry 8 hours of decompression (vacuum tightness is 0.098MPa) at normal temperatures, obtain white
crystals bis-isobutyronitrile hydrazine product 114.6 grams, through gc analysis, bis-isobutyronitrile hydrazine
purity is 98.1%, and reaction yield is 90.23% (in acetone cyanohydrin).
Comparing process :2
In the 500ml flask, add 98.9% acetone cyanohydrin 100 gram (1.17 moles) and pH value and be 4.8 condensation
waste water 150 grams (8.33 moles), under 25 ℃ of stirrings, the dropping weight concentration is that 80%
industrial hydrazine hydrate 36.5 restrains (0.583 mole).After dropwising, heat temperature raising to 60 ℃ is
incubated 3 hours.Reactant is cooled to 5 ℃ again, separate out solid, filter, dry 8 hours of decompression (vacuum
tightness is 0.098MPa) at normal temperatures, obtain little yellow crystal bis-isobutyronitrile hydrazine product
90.1 grams, through gc analysis, bis-isobutyronitrile hydrazine purity is 97.5%, and reaction yield is 90.95% (in
acetone cyanohydrin).
Process description of AIBN
The invention belongs to the technical field of chemical industry, and particularly relates to a method for producing
azobisisobutyronitrile by using hydrobromic acid and hydrogen peroxide under the action of a catalyst. The method
comprises the following steps: adding a hydrobromic acid solution, diisobutyronitrile hydrazine and a catalyst into a
reaction kettle to form two phases; stirring, reacting hydrogen peroxide with hydrobromic acid to generate bromine,
reacting with diisobutyronitrile hydrazine under the action of a catalyst to generate azobisisobutyronitrile and
hydrobromic acid, reacting the hydrobromic acid with the dropwise added hydrogen peroxide to generate bromine,
continuing reacting the bromine with the diisobutyronitrile hydrazine to generate azobisisobutyronitrile and
hydrobromic acid, and terminating the reaction when no diisobutyronitrile hydrazine exists in the solution to finally
form a mixed phase containing the azobisisobutyronitrile and the hydrobromic acid. The method adopts the mother
liquor obtained after the hydrobromic acid reaction, can be recycled, does not precipitate or discharge all
components contained in the mother liquor, and does not generate excessive substances, thereby realizing the
recycling of materials, saving the cost, having excellent economy, shortening the reaction time by half and greatly
saving the energy consumption.
Description
Method for producing azobisisobutyronitrile by using hydrobromic acid and hydrogen peroxide under
action of catalyst
The technical field is as follows:
the invention belongs to the technical field of chemical industry, and particularly relates to a method for
producing azobisisobutyronitrile by using hydrobromic acid and hydrogen peroxide under the action of a
catalyst.
Background art:
at present, the following three methods are mainly adopted for producing azobisisobutyronitrile:
firstly, a chlorine oxidation method: chlorine gas is firstly introduced into a reaction kettle to react with
diisobutyronitrile hydrazine to prepare the azobisisobutyronitrile. The main disadvantages of this
production method are: (1) the process is relatively complex, and the number of control points is large;
the reaction process is not stable, the reaction end point is not easy to control, peroxidation is easy to
cause, and more equipment is used; (2) the utilization rate of chlorine gas is low in the production
process, a part of chlorine gas is wasted due to the fact that the chlorine gas cannot react in time,
nitrogen trichloride byproducts are easily produced, and the danger is high; (3) in the production
process, hydrochloric acid solution is used as a solvent, so that the dissolubility is poor, and the reaction
time is too long; (4) a large amount of liquid caustic soda needs to be consumed to treat the waste tail
gas in the reaction process, and chemical reagents are wasted; (5) the product needs to be washed by
water, 1 ton of product is washed by 20-30 tons of water, water resources are wasted seriously, and a
large amount of waste acid water is generated.
Secondly, sulfuric acid oxidation: preparing 30-40% dilute sulfuric acid, adding diisobutyronitrile
hydrazine, stirring and dissolving in the dilute sulfuric acid, dropwise adding hydrogen peroxide to react
with sodium bromide to generate elemental bromine, and then using the bromine to capture hydrogen
in the diisobutyronitrile hydrazine to prepare the azobisisobutyronitrile. The main disadvantages of this
production method are: (1) the reaction process is not stable, concentrated reaction is easy to cause, a
large amount of heat is generated, the generated azobisisobutyronitrile is decomposed, and production
accidents are caused; (2) the raw materials and the products are mixed together, and the reaction end
point is not easy to control; (3) the utilization rate of the hydrogen peroxide is low, and a part of
hydrogen peroxide is wasted because the hydrogen peroxide cannot react in time; (4) in the production
process, dilute sulfuric acid is used as a solvent, so that the solubility is poor, and the reaction time is too
long; (5) the waste water generated in the reaction process contains a large amount of sulfuric acid solid
salt and dilute sulfuric acid, which are not easy to recover and have higher treatment cost.
Thirdly, bromine oxidation method: adding a bromine solution, an organic solvent and diisobutyronitrile
hydrazine into a reaction kettle to form three phases; the lower layer is a water phase formed by a
bromine solution, the middle layer is an organic phase formed by an organic solvent, and the upper
layer is a solid phase formed by diisobutyronitrile hydrazine; stirring, and reacting diisobutyronitrile
hydrazine with bromine to generate azodiisobutyronitrile and hydrobromic acid. The disadvantages of
this production method are: (1) the reaction time is too long, the generated product is decomposed in
an oxidation environment for too long time, (2) the danger is increased due to the existence of an
organic solvent in the oxidation reaction process, the danger of the organic solvent caused by the
decomposition of the formed material in the long-time oxidation reaction, (3) the reaction between
bromine and diisobutyronitrile hydrazine is too slow, the energy consumption is wasted, (4) the
volatilization of bromine in the excessive mother liquor occurs, and the environmental influence, (5) the
damage to microorganisms and plants is easily caused due to the existence of bromine in the excessive
mother liquor wastewater.
The invention content is as follows:
the invention aims to provide a method for producing azobisisobutyronitrile by using hydrobromic acid and
hydrogen peroxide under the action of a catalyst, the reaction process is moderate, the waste of raw material energy
is avoided, the reacted mother liquor can be recycled, and the surplus mother liquor is simply distilled back to the
mother liquor for recycling.
The invention relates to a method for producing azobisisobutyronitrile by using hydrobromic acid and hydrogen
peroxide under the action of a catalyst, which comprises the following steps: adding a hydrobromic acid solution, a
catalyst and diisobutyronitrile hydrazine into a reaction kettle to form a mixed solid-liquid two phase; stirring,
reacting diisobutyronitrile hydrazine with hydrobromic acid under the action of hydrogen peroxide and a catalyst to
generate azobisisobutyronitrile and hydrobromic acid, finally forming a solid-liquid phase, adding an organic
solvent to completely dissolve the solid, filtering and freezing the organic phase, separating out white crystals,
centrifuging and drying to obtain the azobisisobutyronitrile, and recycling the water phase as a mother solution
containing the hydrobromic acid.
As a further improvement of the invention, the mass ratio of the diisobutyronitrile hydrazine to the hydrobromic acid
solution is 1: 4-6.
As a further improvement of the invention, the mass percentage concentration of the hydrobromic acid solution is 1-
30%; the solvent of the hydrobromic acid solution is water.
As a further improvement of the invention, the mass ratio of the diisobutyronitrile hydrazine to the organic solvent is
1: 3-5.
As a further development of the invention, the organic solvent has a density which is not equal to that of water.
As a further improvement of the invention, the organic solvent is toluene or dichloroethane.
As a further improvement of the invention, the mass ratio of the diisobutyronitrile hydrazine to the hydrogen
peroxide is 1: 0.6-0.8.
As a further improvement of the invention, the reaction temperature is controlled to be between 15 and 30 ℃, and
the reaction time is 1 to 3 hours.
As a further improvement of the method, the mass ratio of the hydrobromic acid solution to the catalyst is 1: 0.0001-
0.002, and the catalyst is dissolved in the hydrobromic acid solution.
As a further improvement of the invention, the catalyst is vanadium pentoxide.
The invention adds the catalyst into the hydrobromic acid solution, which is beneficial to the reaction and increases
the guarantee for the controllability of the reaction process.
The invention is characterized in that the material is white at the initial feeding stage, the mother liquor is red when
hydrogen peroxide is dripped to start reaction, and the mother liquor is blue after the reaction, thus the reaction
process is easy to control.
The reaction mechanism of the present invention is as follows:
(1)H2O2+2HBr＝Br2+2H2O
(2)C8H14N4+Br2＝C8H12N4+2HBr。
the invention has the following beneficial effects:
(1) the controllability of the reaction is obviously enhanced, the reaction condition of the materials can be
known through the color change of the materials, the materials are white when being fed, the materials
become red in the reaction process, and the materials become blue after the reaction is finished;
(2) in the invention, no excessive acid water which needs to be discharged is left, the excessive hydrobromic
acid solution is simply distilled back to the mother liquor for recycling, and the usable range of the
hydrobromic acid mother liquor is wide by 1-30%;
(3) the catalyst is soluble, can be used in mother liquor in a wide range of 0.01-0.2%, and can be recycled
without precipitation and deterioration in the distillation of excessive mother liquor;
(4) the method has the advantages that no acid-containing wastewater is generated, materials do not need to be
washed, no washing wastewater is generated, the refined mother liquor is recycled, no distillation is
needed, and no distillation residue is generated;
(5) the yield of the azodiisobutyronitrile is more than 99.0 percent, and the purity is more than or equal to 99.5
percent.
Specific implementation mode is as follows
EXPERIMENT :1
A method for producing azobisisobutyronitrile by using hydrobromic acid and hydrogen peroxide under the
action of a catalyst comprises the following steps: adding a hydrobromic acid solution, a catalyst vanadium
pentoxide and diisobutyronitrile hydrazine into a reaction kettle to form a mixed solid-liquid two phase; stirring,
reacting diisobutyronitrile hydrazine with hydrobromic acid under the action of hydrogen peroxide and a
catalyst to generate azobisisobutyronitrile and hydrobromic acid, finally forming a solid-liquid phase, adding an
organic solvent to completely dissolve the solid, filtering and freezing the organic phase, separating out white
crystals, centrifuging and drying to obtain the azobisisobutyronitrile, and recycling the water phase as a mother
solution containing the hydrobromic acid.
The mass ratio of the diisobutyronitrile hydrazine to the hydrobromic acid solution is 1: 4; the mass percentage
concentration of the hydrobromic acid solution is 1 percent; the solvent of the hydrobromic acid solution is
water; the mass ratio of the diisobutyronitrile hydrazine to the organic solvent is 1: 3; the density of the organic
solvent is not equal to that of water; the organic solvent is toluene or dichloroethane; the mass ratio of the
diisobutyronitrile hydrazine to the hydrogen peroxide is 1: 0.6; the reaction temperature is controlled to be 15
℃, and the reaction time is 1 hour; the mass ratio of the hydrobromic acid solution to the catalyst is 1:0.0001,
and the catalyst is dissolved in the hydrobromic acid solution; the catalyst is as follows.
Experiment :2
A method for producing azobisisobutyronitrile by using hydrobromic acid and hydrogen peroxide under the
action of a catalyst comprises the following steps: adding a hydrobromic acid solution, a catalyst vanadium
pentoxide and diisobutyronitrile hydrazine into a reaction kettle to form a mixed solid-liquid two phase; stirring,
reacting diisobutyronitrile hydrazine with hydrobromic acid under the action of hydrogen peroxide and a
catalyst to generate azobisisobutyronitrile and hydrobromic acid, finally forming a solid-liquid phase, adding an
organic solvent to completely dissolve the solid, filtering and freezing the organic phase, separating out white
crystals, centrifuging and drying to obtain the azobisisobutyronitrile, and recycling the water phase as a mother
solution containing the hydrobromic acid.
The mass ratio of the diisobutyronitrile hydrazine to the hydrobromic acid solution is 1: 6; the mass percentage
concentration of the hydrobromic acid solution is 30 percent; the solvent of the hydrobromic acid solution is
water; the mass ratio of the diisobutyronitrile hydrazine to the organic solvent is 1: 5; the density of the organic
solvent is not equal to that of water; the organic solvent is toluene or dichloroethane; the mass ratio of the
diisobutyronitrile hydrazine to the hydrogen peroxide is 1: 0.8; the reaction temperature is controlled to be 30
℃, and the reaction time is 3 hours; the mass ratio of the hydrobromic acid solution to the catalyst is 1:0.002,
and the catalyst is dissolved in the hydrobromic acid solution; the catalyst is as follows.
Expriment :3
A method for producing azobisisobutyronitrile by using hydrobromic acid and hydrogen peroxide under the
action of a catalyst comprises the following steps: adding a hydrobromic acid solution, a catalyst vanadium
pentoxide and diisobutyronitrile hydrazine into a reaction kettle to form a mixed solid-liquid two phase; stirring,
reacting diisobutyronitrile hydrazine with hydrobromic acid under the action of hydrogen peroxide and a
catalyst to generate azobisisobutyronitrile and hydrobromic acid, finally forming a solid-liquid phase, adding an
organic solvent to completely dissolve the solid, filtering and freezing the organic phase, separating out white
crystals, centrifuging and drying to obtain the azobisisobutyronitrile, and recycling the water phase as a mother
solution containing the hydrobromic acid.
The mass ratio of the diisobutyronitrile hydrazine to the hydrobromic acid solution is 1: 5; the mass percentage
concentration of the hydrobromic acid solution is 15 percent; the solvent of the hydrobromic acid solution is
water; the mass ratio of the diisobutyronitrile hydrazine to the organic solvent is 1: 4; the density of the organic
solvent is not equal to that of water; the organic solvent is toluene or dichloroethane; the mass ratio of the
diisobutyronitrile hydrazine to the hydrogen peroxide is 1: 0.7; the reaction temperature is controlled to be 25
℃, and the reaction time is 2 hours; the mass ratio of the hydrobromic acid solution to the catalyst is 1:0.001,
and the catalyst is dissolved in the hydrobromic acid solution; the catalyst is as follows.
Expriment:4
A method for producing azobisisobutyronitrile by using hydrobromic acid and hydrogen peroxide under the
action of a catalyst comprises the following steps: adding 1000 g of water into a reaction kettle, adding 60 g of
42% hydrobromic acid, adding 1.5 g of catalyst vanadium pentoxide, stirring for dissolving, adding 200 g of
diisobutyronitrile hydrazine, stirring for 5 minutes, adjusting the material temperature to 25 +/-5 ℃, dropwise
adding 140 g of 30% hydrogen peroxide, completing dropwise addition within two hours, keeping the
temperature for 1.5 hours to change the material into blue, adding 1000 g of toluene into the material, heating to
40 ℃, completely dissolving the solid, separating an organic layer from a water layer, filtering the organic
layer, freezing, precipitating white crystals, and performing centrifugal drying to obtain 196 g of white crystal
azodiisobutyronitrile, wherein the yield is 98% and the content is 99.5%. The water layer (mother liquor) is put
into oxidation for continuous recycling, and the organic layer is continuously recycled next time.
Expriment :5
A method for producing azobisisobutyronitrile by using hydrobromic acid and hydrogen peroxide under the
action of a catalyst comprises the following steps: adding 1140 g of hydrobromic acid mother liquor of example
4 into a reaction kettle, adding 200 g of diisobutyronitrile hydrazine, stirring for 5 minutes, adjusting the
material temperature to 25 +/-5 ℃, dropwise adding 140 g of 30% hydrogen peroxide, completing the dropping
within two hours, keeping the temperature for 1.5 hours to change the material into blue, adding 1000 g of
toluene mother liquor of example 4 into the material, heating to 40 ℃, completely dissolving the solid,
separating an organic layer from an aqueous layer, filtering the organic layer, freezing, separating out white
crystals, and centrifugally drying to obtain 198 g of white azodiisobutyronitrile with the yield of 99% and the
content of 99.5%. The water layer is put into oxidation for continuous recycling, and the organic layer is
continuously recycled next time.
Expriment:6
A method for producing azobisisobutyronitrile by using hydrobromic acid and hydrogen peroxide under the
action of a catalyst comprises the following steps: adding 1000 g of hydrobromic acid mother liquor of example
5 into a reaction kettle, adding 200 g of diisobutyronitrile hydrazine, stirring for 5 minutes, adjusting the
material temperature to 25 +/-5 ℃, dropwise adding 140 g of 30% hydrogen peroxide, completing the dropping
within two hours, keeping the temperature for 2 hours until the material turns blue, adding 1200 g of
dichloroethane into the material, heating to 40 ℃ until all solids are dissolved, separating an organic layer from
a water layer, filtering the organic layer, freezing, separating white crystals, and centrifugally drying to obtain
196 g of white crystal azobisisobutyronitrile with the yield of 98% and the content of 99.5%. The water layer is
put into oxidation for continuous recycling, and the organic layer is continuously recycled next time.
Expriment :7
A method for producing azobisisobutyronitrile by using hydrobromic acid and hydrogen peroxide under the
action of a catalyst comprises the following steps: adding residual hydrobromic acid mother liquor of examples
5 and 6 into a reaction kettle, distilling to remove partial water until the volume of the residual mother liquor is
1000 g, cooling to 25 ℃, adding 200 g of diisobutyronitrile hydrazine, stirring for 5 minutes, adjusting the
material temperature to 25 +/-5 ℃, dropwise adding 140 g of 30% hydrogen peroxide, completing dropwise
addition within two hours, keeping the temperature for 1.5 hours to turn the material into blue, adding the
dichloroethane mother liquor of example 6 into the material, heating to 40 ℃ to completely dissolve solids,
separating an organic layer from a water layer, filtering the organic layer, freezing, precipitating white crystals,
centrifugally drying to obtain 198 g of white azodiisobutyronitrile crystals, wherein the yield is 99% and the
content is 99.5%. The water layer is put into oxidation for continuous recycling, and the organic layer is
continuously recycled next time.
Expriment : 8
A method for producing azobisisobutyronitrile by using hydrobromic acid and hydrogen peroxide under the
action of a catalyst comprises the following steps: adding 500 g of hydrobromic acid mother liquor of example
7 into a reaction kettle, adding 500 g of water, adding 200 g of diisobutyronitrile hydrazine, stirring for 5
minutes, adjusting the material temperature to 25 +/-5 ℃, dropwise adding 140 g of 30% hydrogen peroxide,
completing dropping within two hours, keeping the temperature for 2 hours to change the material into blue,
adding the dichloroethane mother liquor of example 7 into the material, heating to 40 ℃, completely dissolving
the solid, separating an organic layer from an aqueous layer, filtering the organic layer, freezing, separating out
white crystals, and centrifugally drying to obtain 198 g of white crystal azobisisobutyronitrile with the yield of
99% and the content of 99.5%. The water layer is put into oxidation for continuous recycling, and the organic
layer is continuously recycled next time.
The invention has the following beneficial effects:
1. compared with the chlorine oxidation reaction, the chlorine oxidation reaction is violent, the decomposition
phenomenon occurs in the later period, the chlorine introducing speed is dangerous, the hydrogen peroxide
method needs to be carried out in a sulfuric acid solution, the oxidizing capability of hydrogen peroxide is
intensified, the danger coefficient of the oxidation reaction is increased, the bromine method is oxidized in
an organic solvent, and the post-treatment difficulty and the danger coefficient are increased once the
danger occurs because of the existence of the organic solvent;
2. in the reaction process, the product is not required to be washed by water, and more than 20 tons of water
are saved for one ton of product; after the oxidation is finished, a large amount of acid exists, a large
amount of clear water is needed for washing, otherwise, the product quality is poor, and a great potential
safety hazard exists in the drying process; meanwhile, the post-treatment of 20 tons of wastewater increases
the consumption and cost of various materials;
3. the process greatly improves the comprehensive yield of the product, the yield can be improved to more
than 99 percent by using the process, and the yield of the products by a chlorine method and a hydrogen
peroxide method is 95 to 97 percent.
