CN101177408A - Method for preparing isocyanate - Google Patents
Method for preparing isocyanate Download PDFInfo
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- CN101177408A CN101177408A CNA200710191088XA CN200710191088A CN101177408A CN 101177408 A CN101177408 A CN 101177408A CN A200710191088X A CNA200710191088X A CN A200710191088XA CN 200710191088 A CN200710191088 A CN 200710191088A CN 101177408 A CN101177408 A CN 101177408A
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- primary amine
- monoisocyanates
- preparation
- phosgenation reactor
- phosgene
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Abstract
The invention discloses a single-isocyanate preparation method utilizing the primary amine as the raw material. In the suitable solvent, the primary amine continuously passes through the phosgenation reactor with superfluous phosgene and the reacting temperature can be controlled on a plurality of sections; sufficiently mixing up the reactant and then rectifying the reactant to prepare the single-isocyanate. The invention has the advantages that: the additional rectifying step can obtain the product with the purity of 99.9% or above; the industrial production can be easily realized; the secondary reaction can be effectively reduced; and the total yield of the primary amine is not less than 93%.
Description
Technical field
The present invention relates to a kind of preparation method of organic compound, be specifically related to the preparation method of monoisocyanates.
Background technology
Monoisocyanates is important organic synthesis intermediate, and chemical property is active, generates carbamate with the alcohol effect, generates carboxylic acid with the water effect, generates carbamyl amine with the ammonia effect.This compounds can be used for synthetic medicine, agricultural chemicals, synthetic resins, porous plastics, coating, synthon, rubber ingredients etc.
In existing document, with primary amine (RNH
2), orthodichlorobenzene adds in the reactor, feed excess phosgene at 110～160 ℃, fed again 20～30 minutes after clear to solution becomes, logical finishing, distillation is collected 160 ℃ with front-end volatiles, collects 106～120 ℃ of cuts and gets monoisocyanates through distillation again, and this method product content is low, yield is low, generally is not more than 80%.In addition, in organic solvent, act on, also can make target product, but do not possess industrial value by bromine alkane and potassium cyanate.
Summary of the invention
Goal of the invention: technical problem to be solved by this invention provides a kind of preparation method of monoisocyanates, to realize suitability for industrialized production.
Technical scheme: the preparation method of monoisocyanates of the present invention may further comprise the steps:
1, with primary amine and solvent with 1: 2～15 mass ratio, send into phosgenation reactor continuously;
2, excessive phosgene is sent in the phosgenation reactor continuously, the mol ratio of phosgene and primary amine is 1.2～10.5: 1;
3, by regulating phosgenation reactor shell side coolant flow, in-20～200 ℃ scope, divide 2～8 sections control reaction temperature step by step from low temperature to high temperature, and its high temperature is below the boiling point of primary amine, under each section temperature the reaction times of material any, but need to guarantee that the total reaction residence time of material under agitation condition be 1～10 hour;
4, effusive material gets the product monoisocyanates through rectifying in the phosgenation reactor.
Wherein, the primary amine described in the step 1 is aliphatic amide or aromatic amine.
Wherein, the solvent described in the step 1 is benzene and derivative thereof.
Wherein, in the step 1, the mass ratio of primary amine and solvent preferred 1: 3～8.
Wherein, in the step 2, the mol ratio of phosgene and primary amine preferred 2～7: 1.
Wherein, can divide 4 sections control reaction temperature step by step from low temperature to high temperature in the step 3.These 4 sections temperature of reaction can be respectively-10 ℃～15 ℃, 30 ℃～60 ℃, 80 ℃～100 ℃, 120 ℃～150 ℃, and its high temperature is below the boiling point of primary amine.
Wherein, in the step 3, preferred 1～8 hour of material total reaction residence time under agitation condition, the total reaction residence time is 1～7 hour under abundant agitation condition.
Under above-mentioned processing condition, can obtain purity and be the product more than 99.0%, be easy to realize industrialized production, can effectively reduce side reaction and take place, with RNH
2Meter, total recovery of the present invention 〉=93%.
Beneficial effect: the present invention compared with prior art, its remarkable advantage is:
1, the present invention is with primary amine (RNH
2) and the mass ratio of suitable solvent be 1: 2～15, can make primary amine (RNH
2) dispersity in cold reaction increases, side reaction reduces, and reaction develops to favourable direction; Reaction solution residence time in reactor is reduced.
2, phosgene and primary amine (RNH among the present invention
2) mol ratio be 1.2～10.5: 1, can make that cold temperature of reaction reduces, reaction develops to beneficial direction.
3, segmentation control reaction temperature of the present invention can make reaction time reduce, and side reaction is reduced, and improves the transformation efficiency of phosgene.
4, material reaction time under abundant agitation condition is short among the present invention, about 1～7 hour.
5, product monoisocyanates purity of the present invention is more than 99.0%, with RNH
2Meter, total recovery 〉=93% satisfies need of industrial production fully.
Embodiment
Embodiment 1: the primary amine in this example is an aliphatic amide.
With primary amine (RNH
2) and solvent xylene with 1: 11 mass ratio, send into phosgenation reactor; Send in the phosgenation reactor phosgene and primary amine (RNH by pipeline with excessive phosgene
2) mol ratio be 5: 1; By regulating phosgenation reactor shell side coolant flow, divide four sections control reaction temperature, be respectively-10 ℃～15 ℃, 30 ℃～60 ℃, 80 ℃～100 ℃, 110 ℃～130 ℃ by low temperature to high temperature, its high temperature must be below the boiling point of aliphatic amide, and the material in the phosgenation reactor is about 7 hours of the total reaction residence time under abundant agitation condition; To get purity through rectifying be product monoisocyanates more than 99.0% to effusive material in the phosgenation reactor, with RNH
2Meter, total recovery 〉=95.2%.Embodiment 2: the primary amine in this example is an aliphatic amide.
With primary amine (RNH
2) and the solvent Benzene Chloride with 1: 10 mass ratio, send into phosgenation reactor; Send in the phosgenation reactor phosgene and primary amine (RNH by pipeline with excessive phosgene
2) mol ratio be 4: 1; By regulating phosgenation reactor shell side coolant flow, divide three sections control reaction temperature, be respectively-10 ℃～15 ℃, 30 ℃～60 ℃, 80 ℃～100 ℃ by low temperature to high temperature, its high temperature must be below the boiling point of aliphatic amide, about 6.5 hours of material total reaction residence time under agitation condition in the phosgenation reactor; To get purity through rectifying be product monoisocyanates more than 99.0% to effusive material in the phosgenation reactor, with RNH
2Meter, total recovery 〉=95%.
Embodiment 3: the primary amine in this example is an aliphatic amide.
With primary amine (RNH
2) and solvent toluene with 1: 12 mass ratio, send into phosgenation reactor; Send in the phosgenation reactor phosgene and primary amine (RNH by pipeline with excessive phosgene
2) mol ratio be 5: 1; By regulating phosgenation reactor shell side coolant flow, divide four sections control reaction temperature, be respectively-10 ℃～10 ℃, 20 ℃～35 ℃, 50 ℃～65 ℃ by low temperature to high temperature, 80 ℃～95 ℃, its top temperature must be below the boiling point of aliphatic amide, about 8 hours of material total reaction residence time under agitation condition in the phosgenation reactor; To get purity through rectifying be product monoisocyanates more than 99.0% to effusive material in the phosgenation reactor, with RNH
2Meter, total recovery 〉=93%.
Embodiment 4: the primary amine in this example is an aromatic amine.
With primary amine (ArNH
2) and the solvent orthodichlorobenzene with 1: 9 mass ratio, send into phosgenation reactor; Send in the phosgenation reactor phosgene and primary amine (ArNH by pipeline with excessive phosgene
2) mol ratio be 3: 1; By regulating phosgenation reactor shell side coolant flow, divide three sections control reaction temperature, be respectively-10 ℃～15 ℃, 70 ℃～90 ℃, 120 ℃～150 ℃ by low temperature to high temperature, its high temperature must be below the boiling point of aromatic amine, about 6 hours of the reaction time under abundant agitation condition of the material in the phosgenation reactor; To get purity through rectifying be product monoisocyanates more than 99.0% to effusive material in the phosgenation reactor, with ArNH
2Meter, total recovery 〉=95%.
Embodiment 5: the primary amine in this example is an aromatic amine.
With primary amine (ArNH
2) and solvent xylene with 1: 10 mass ratio, send into phosgenation reactor; Send in the phosgenation reactor phosgene and primary amine (ArNH by pipeline with excessive phosgene
2) mol ratio be 4: 1; By regulating phosgenation reactor shell side coolant flow, divide four sections control reaction temperature, be respectively-10 ℃～15 ℃, 40 ℃～60 ℃, 80 ℃～100 ℃, 120 ℃～150 ℃ by low temperature to high temperature, its high temperature must be below the boiling point of aromatic amine, about 7 hours of the material reaction time under agitation condition in the phosgenation reactor; To get purity through rectifying be product monoisocyanates more than 99.0% to effusive material in the phosgenation reactor, with ArNH
2Meter, total recovery 〉=93%.
Embodiment 6: the primary amine in this example is an aromatic amine.
With primary amine (ArNH
2) and solvent toluene with 1: 12 mass ratio, send into phosgenation reactor; Send in the phosgenation reactor phosgene and primary amine (ArNH by pipeline with excessive phosgene
2) mol ratio be 5: 1; By regulating phosgenation reactor shell side coolant flow, divide four sections control reaction temperature, be respectively-10 ℃～10 ℃, 40 ℃～60 ℃, 80 ℃～100 ℃, 120 ℃～135 ℃ by low temperature to high temperature, its top temperature must be below the boiling point of aromatic amine, about 8.5 hours of the material reaction time under agitation condition in the phosgenation reactor; To get purity through rectifying be product monoisocyanates more than 99.0% to effusive material in the phosgenation reactor, with ArNH
2Meter, total recovery 〉=93%.
Embodiment 7:
Identical with the method for embodiment 6, the mass ratio of different is primary amine and solvent toluene is 1: 2, and the mol ratio of phosgene and primary amine is 1.2: 1, about 10 hours of material total reaction residence time under agitation condition in the phosgenation reactor.
Embodiment 8:
Identical with the method for embodiment 6, the mass ratio of different is primary amine and solvent toluene is 1: 15, and the mol ratio of phosgene and primary amine is 10.5: 1, about 7 hours of material total reaction residence time under agitation condition in the phosgenation reactor.
Embodiment 9:
Identical with the method for embodiment 6, the mass ratio of different is primary amine and solvent toluene is 1: 3, and the mol ratio of phosgene and primary amine is 2: 1, about 9 hours of material total reaction residence time under agitation condition in the phosgenation reactor.
Embodiment 10:
Identical with the method for embodiment 6, the mass ratio of different is primary amine and solvent toluene is 1: 8, and the mol ratio of phosgene and primary amine is 7: 1, and the material in the phosgenation reactor is about 1 hour of the total reaction residence time under abundant agitation condition.
Claims (9)
1. the preparation method of a monoisocyanates is characterized in that this method may further comprise the steps:
(1) with primary amine and solvent with 1: 2～15 mass ratio, send into phosgenation reactor continuously;
(2) excessive phosgene is sent in the phosgenation reactor continuously, the mol ratio of phosgene and primary amine is 1.2～10.5: 1;
(3) by regulating phosgenation reactor shell side coolant flow, in-20～200 ℃ scope, divide 2～8 sections control reaction temperature step by step from low temperature to high temperature, and its high temperature is below the boiling point of primary amine, the total reaction residence time of material under agitation condition is 1～10 hour;
(4) effusive material gets the product monoisocyanates through rectifying in the phosgenation reactor.
2. the preparation method of monoisocyanates according to claim 1 is characterized in that the primary amine described in the step (1) is aliphatic amide or aromatic amine.
3. the preparation method of monoisocyanates according to claim 1 is characterized in that the solvent described in the step (1) is benzene and derivative thereof.
4. the preparation method of monoisocyanates according to claim 1 is characterized in that in the step (1), the mass ratio of primary amine and solvent is 1: 3～8.
5. the preparation method of monoisocyanates according to claim 1 is characterized in that in the step (2), the mol ratio of phosgene and primary amine is 2～7: 1.
6. the preparation method of monoisocyanates according to claim 1 is characterized in that dividing in the step (3) 4 sections control reaction temperature step by step from low temperature to high temperature.
7. the preparation method of monoisocyanates according to claim 6 it is characterized in that 4 sections temperature of reaction are respectively-10 ℃～15 ℃, 30 ℃～60 ℃, 80 ℃～100 ℃, 120 ℃～150 ℃ in the step (3), and its high temperature is below the boiling point of primary amine.
8. the preparation method of monoisocyanates according to claim 1 is characterized in that in the step (3), and material total reaction residence time under agitation condition is 1～8 hour.
9. the preparation method of monoisocyanates according to claim 8 is characterized in that in the step (3), and material total reaction residence time under abundant agitation condition is 1～7 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710191088XA CN101177408A (en) | 2007-12-07 | 2007-12-07 | Method for preparing isocyanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710191088XA CN101177408A (en) | 2007-12-07 | 2007-12-07 | Method for preparing isocyanate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101177408A true CN101177408A (en) | 2008-05-14 |
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ID=39403854
Family Applications (1)
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|---|---|---|---|
| CNA200710191088XA Pending CN101177408A (en) | 2007-12-07 | 2007-12-07 | Method for preparing isocyanate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357898B (en) * | 2008-08-29 | 2010-12-15 | 江苏安邦电化有限公司 | Process for preparing n-butyl isocyanate |
-
2007
- 2007-12-07 CN CNA200710191088XA patent/CN101177408A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357898B (en) * | 2008-08-29 | 2010-12-15 | 江苏安邦电化有限公司 | Process for preparing n-butyl isocyanate |
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Open date: 20080514 |