CN101357898B - Process for preparing n-butyl isocyanate - Google Patents
Process for preparing n-butyl isocyanate Download PDFInfo
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- CN101357898B CN101357898B CN2008101246751A CN200810124675A CN101357898B CN 101357898 B CN101357898 B CN 101357898B CN 2008101246751 A CN2008101246751 A CN 2008101246751A CN 200810124675 A CN200810124675 A CN 200810124675A CN 101357898 B CN101357898 B CN 101357898B
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- phosgenation reaction
- butyl isocyanate
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Abstract
The invention discloses a preparation method for butyl isocyanate, which includes the following steps: n-butyl amine and m-dichlorobenzene are mixed into solution based on a weight ratio of 1:1.5 to 10, and the solution is fed into a phosgenation reaction tower from the top of tower continuously; the excess phosgenation is fed into the phosgenation reaction tower from the bottom of tower continuously; the phosgenation reaction tower is kept within -5 to 160 DEG C from the top of tower to the bottom of tower; the temperature is controlled by 5 to 10 segments, and the temperature is increased one by one from the top of tower to the bottom of tower; butyl isocyanate is obtained after the distillation of the material which flows from the bottom of the phosgenation reaction tower. The preparation method has the advantages that products with more than 99.0 percent purity can be prepared under the processing condition; industrial production is easily realized; the occurrence of side reactioncan be reduced effectively; the total yield of the invention counting according to n-butyl amine is more than or equal to 96.0 percent.
Description
Technical field
The present invention relates to a kind of synthetic method of organic compound, be specifically related to a kind of preparation method of n-butyl isocyanate.
Background technology
N-butyl isocyanate is a kind of important organic synthesis intermediate, and chemical property is active, can be as products such as synthetic medicine, agricultural chemicals.Traditional technology is that n-Butyl Amine 99, orthodichlorobenzene are added in the reactor, feed excess phosgene at 110～160 ℃, fed phosgene again 20～30 minutes to solution becomes after clear, logical finishing, distillation is collected 160 ℃ with front-end volatiles, collect 106～120 ℃ of cuts and get n-butyl isocyanate through distillation again, this method product content is low, and yield is low.In addition, bibliographical information is arranged, in organic solvent, act on, also can make target product, but do not possess industrial value by n-butyl bromide and potassium cyanate.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of high-quality n-butyl isocyanate.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows:
A kind of preparation method of n-butyl isocyanate: n-Butyl Amine 99 and Meta Dichlorobenzene are pressed mass ratio 1:1.5～10 wiring solution-formings, send into the phosgenation reaction tower continuously from cat head; Excessive phosgene is sent in the phosgenation reaction tower at the bottom of tower continuously; In-5～160 ℃ of scopes, divide 5～10 sections temperature controls at the bottom of keeping the phosgenation reaction tower from cat head to tower, from cat head to tower at the bottom of every section temperature raise successively; The material that the phosgenation reaction tower bottom flow goes out makes the product n-butyl isocyanate through rectifying.
Wherein, the mass ratio of n-Butyl Amine 99 and Meta Dichlorobenzene is preferably 1:2～4.
Wherein, the mol ratio of phosgene and n-Butyl Amine 99 is preferably 1.2～6.0:1, most preferably 1.2～2.8:1.
Wherein, phosgenation reaction tower temperature can be divided into 5～10 sections temperature controls, each section temperature is any, each section is highly any, as long as follow the principle that from the cat head to the column bottom temperature, raises successively, preferred divide 5 sections temperature controls, from cat head to tower at the bottom of every section temperature be preferably :-5 ℃～10 ℃, 10 ℃～30 ℃, 60 ℃～90 ℃, 90 ℃～120 ℃, 120 ℃～160 ℃, most preferably be: 0 ℃～10 ℃, 10 ℃～30 ℃, 80 ℃～90 ℃, 100 ℃～120 ℃, 120 ℃～150 ℃.
Principle of the present invention: the n-Butyl Amine 99 chemical property is active, generates the hydrochloride of acyl chlorides and n-Butyl Amine 99 respectively with phosgene, hcl reaction, simultaneously a large amount of heat releases; Acyl chlorides at high temperature resolves into n-butyl isocyanate, and the hydrochloride of n-Butyl Amine 99 at high temperature decomposes the back and generates n-butyl isocyanate with phosgene reaction.The principal reaction equation is as follows:
Simultaneously, in the reaction there be main side reaction: n-butyl isocyanate and excessive n-Butyl Amine 99 reaction generation ureas by product; The hydrochloride of n-Butyl Amine 99 changes into n-propylcarbinyl chloride under certain condition.
The Meta Dichlorobenzene solution of n-Butyl Amine 99 enters by low temperature at the bottom of pyritous tower body, the tower from cat head, reacts with the phosgene that enters at the bottom of tower, hydrogenchloride (hydrogenchloride is intermediate reaction product); On the top of tower body, the Meta Dichlorobenzene equal solvent in time shifts out reaction heat, can effectively reduce the generation of side reaction; In the bottom of tower body, provide enough heats that acyl chlorides is decomposed and generate the target product n-butyl isocyanate, make the hydrochloride decomposition back of n-Butyl Amine 99 generate the target product n-butyl isocyanate with phosgene reaction, can effectively improve the transformation efficiency of n-Butyl Amine 99.
Beneficial effect: the present invention compared with prior art, its remarkable advantage is:
1, to adopt Meta Dichlorobenzene be solvent in the present invention, and the reaction heat that n-Butyl Amine 99 and phosgenation reaction are produced is beneficial to and shifts out, and reaction develops to favourable direction; Side reaction is reduced.
2, the present invention is from cat head segmentation control reaction temperature at the bottom of the tower, the Meta Dichlorobenzene solution of n-Butyl Amine 99 enters tower body from cat head, and phosgene enters tower body at the bottom of tower, on the top of tower body, the Meta Dichlorobenzene equal solvent in time shifts out reaction heat, can effectively reduce the generation of side reaction; In the bottom of tower body, provide enough heats that acyl chlorides is decomposed and generate the target product n-butyl isocyanate, make the hydrochloride decomposition back of n-Butyl Amine 99 generate the target product n-butyl isocyanate with phosgene reaction, can effectively improve the transformation efficiency of n-Butyl Amine 99.
3, the present invention adopts excessive phosgene to enter tower body upwards through the laggard row recovery of cat head outflow at the bottom of tower, gained target product n-butyl isocyanate purity is more than 99.0%, in n-Butyl Amine 99, and total recovery 〉=96.0%, compare with traditional technology, the transformation efficiency of n-Butyl Amine 99 effectively improves.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1:
10000 kilograms of n-Butyl Amine 99s slowly are dissolved in wiring solution-forming in 30000 kilograms the Meta Dichlorobenzene, send into the phosgenation reaction tower with 500 kilograms/hour flow continuously from cat head by volume pump; By quantifier with 300 kilograms/hour phosgene from sending into continuously at the bottom of the tower in the phosgenation reaction tower; By regulating phosgenation reaction tower shell side refrigerant or steam flow, dividing 5 sections control reaction temperature from cat head at the bottom of the tower is 0 ℃～5 ℃, 10 ℃～20 ℃, 80 ℃～90 ℃, 110 ℃～120 ℃, 140 ℃～150 ℃; It is 99.2% that the material that goes out from the phosgenation reaction tower bottom flow makes n-butyl isocyanate purity through rectifying, and in n-Butyl Amine 99, total recovery is 96.3%.
Embodiment 2:
10000 kilograms of n-Butyl Amine 99s slowly are dissolved in wiring solution-forming in 40000 kilograms the Meta Dichlorobenzene, send into the phosgenation reaction tower with 500 kilograms/hour flow continuously from cat head by volume pump; By quantifier with 500 kilograms/hour phosgene from sending into continuously at the bottom of the tower in the phosgenation reaction tower; By regulating phosgenation reaction tower shell side refrigerant or steam flow, dividing 5 sections control reaction temperature from cat head at the bottom of the tower is-5 ℃～0 ℃, 20 ℃～30 ℃, 80 ℃～90 ℃, 100 ℃～110 ℃, 120 ℃～130 ℃; It is 99.1% that the material that goes out from the phosgenation reaction tower bottom flow makes n-butyl isocyanate purity through rectifying, and in n-Butyl Amine 99, total recovery is 96.1%.
Embodiment 3:
10000 kilograms of n-Butyl Amine 99s slowly are dissolved in wiring solution-forming in 50000 kilograms the Meta Dichlorobenzene, send into the phosgenation reaction tower with 500 kilograms/hour flow continuously from cat head by volume pump; By quantifier with 800 kilograms/hour phosgene from sending into continuously at the bottom of the tower in the phosgenation reaction tower; By regulating phosgenation reaction tower shell side refrigerant or steam flow, dividing 5 sections control reaction temperature from cat head at the bottom of the tower is-5 ℃～0 ℃, 10 ℃～20 ℃, 60 ℃～80 ℃, 90 ℃～110 ℃, 130 ℃～140 ℃; It is 94.7% that the material that goes out from the phosgenation reaction tower bottom flow makes n-butyl isocyanate purity through rectifying, and in n-Butyl Amine 99, total recovery is 83.9%.
Embodiment 4:
10000 kilograms of n-Butyl Amine 99s slowly are dissolved in wiring solution-forming in 40000 kilograms the Meta Dichlorobenzene, send into the phosgenation reaction tower with 500 kilograms/hour flow continuously from cat head by volume pump; By quantifier with 300 kilograms/hour phosgene from sending into continuously at the bottom of the tower in the phosgenation reaction tower; By regulating phosgenation reaction tower shell side refrigerant or steam flow, dividing 5 sections control reaction temperature from cat head at the bottom of the tower is 0 ℃～5 ℃, 20 ℃～30 ℃, 60 ℃～70 ℃, 90 ℃～100 ℃, 150 ℃～160 ℃; It is 96.8% that the material that goes out from the phosgenation reaction tower bottom flow makes n-butyl isocyanate purity through rectifying, and in n-Butyl Amine 99, total recovery is 89.9%.
Embodiment 5:
10000 kilograms of n-Butyl Amine 99s slowly are dissolved in wiring solution-forming in 15000 kilograms the Meta Dichlorobenzene, send into the phosgenation reaction tower with 500 kilograms/hour flow continuously from cat head by volume pump; By quantifier with 240 kilograms/hour phosgene from sending into continuously at the bottom of the tower in the phosgenation reaction tower; By regulating phosgenation reaction tower shell side refrigerant or steam flow, dividing 7 sections control reaction temperature from cat head at the bottom of the tower is-5 ℃～0 ℃, 10 ℃～20 ℃, 50 ℃～60 ℃, 80～90 ℃, 100 ℃～110 ℃, 130 ℃～140 ℃, 150 ℃～160 ℃; It is 97.3% that the material that goes out from the phosgenation reaction tower bottom flow makes n-butyl isocyanate purity through rectifying, and in n-Butyl Amine 99, total recovery is 91.6%.
Embodiment 6:
10000 kilograms of n-Butyl Amine 99s slowly are dissolved in wiring solution-forming in 80000 kilograms the Meta Dichlorobenzene, send into the phosgenation reaction tower with 500 kilograms/hour flow continuously from cat head by volume pump; By quantifier with 330 kilograms/hour phosgene from sending into continuously at the bottom of the tower in the phosgenation reaction tower; By regulating phosgenation reaction tower shell side refrigerant or steam flow, dividing 10 sections control reaction temperature from cat head at the bottom of the tower is-5 ℃～0 ℃, 10 ℃～20 ℃, 30～40 ℃, 50 ℃～60 ℃, 70 ℃～80 ℃, 80～90 ℃, 90 ℃～100 ℃, 100 ℃～110 ℃, 130 ℃～140 ℃, 150 ℃～160 ℃; It is 98.3% that the material that goes out from the phosgenation reaction tower bottom flow makes n-butyl isocyanate purity through rectifying, and in n-Butyl Amine 99, total recovery is 92.5%.
Claims (6)
1. the preparation method of a n-butyl isocyanate is characterized in that this method is: n-Butyl Amine 99 and Meta Dichlorobenzene are pressed mass ratio 1:1.5～10 wiring solution-formings, send into the phosgenation reaction tower continuously from cat head; Excessive phosgene is sent in the phosgenation reaction tower at the bottom of tower continuously; In-5～160 ℃ of scopes, divide 5～10 sections temperature controls at the bottom of keeping the phosgenation reaction tower from cat head to tower, from cat head to tower at the bottom of every section temperature raise successively; The material that the phosgenation reaction tower bottom flow goes out makes the product n-butyl isocyanate through rectifying.
2. the preparation method of n-butyl isocyanate according to claim 1, the mass ratio that it is characterized in that n-Butyl Amine 99 and Meta Dichlorobenzene is 1:2～4.
3. the preparation method of n-butyl isocyanate according to claim 1, the mol ratio that it is characterized in that phosgene and n-Butyl Amine 99 is 1.2～6.0:1.
4. the preparation method of n-butyl isocyanate according to claim 1 is characterized in that 5 sections temperature controls of branch.
5. the preparation method of n-butyl isocyanate according to claim 4, it is characterized in that from cat head to tower at the bottom of every section temperature be respectively :-5 ℃～10 ℃, 10 ℃～30 ℃, 60 ℃～90 ℃, 90 ℃～120 ℃, 120 ℃～160 ℃.
6. the preparation method of n-butyl isocyanate according to claim 5, it is characterized in that from cat head to tower at the bottom of every section temperature be respectively: 0 ℃～10 ℃, 10 ℃～30 ℃, 80 ℃～90 ℃, 100 ℃～120 ℃, 120 ℃～150 ℃.
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| CN2008101246751A CN101357898B (en) | 2008-08-29 | 2008-08-29 | Process for preparing n-butyl isocyanate |
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| CN2008101246751A CN101357898B (en) | 2008-08-29 | 2008-08-29 | Process for preparing n-butyl isocyanate |
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| CN101357898B true CN101357898B (en) | 2010-12-15 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104418773A (en) * | 2013-09-02 | 2015-03-18 | 上海龙翔生物医药开发有限公司 | Synthetic method of 2,4,5-trifluoro-benzene isocyanate and intermediate thereof |
| CN103724229B (en) * | 2013-12-13 | 2015-02-18 | 青岛科技大学 | Dehydration method during production process of toluene diisocynate |
| CN105294498A (en) * | 2015-10-26 | 2016-02-03 | 安徽广信农化股份有限公司 | Production method for n-butyl isocyanate |
| CN105254535A (en) * | 2015-10-26 | 2016-01-20 | 安徽广信农化股份有限公司 | Refining method for n-butyl isocyanate |
| CN105384659A (en) * | 2015-10-26 | 2016-03-09 | 安徽广信农化股份有限公司 | Method for synthesizing n-butyl isocyanate |
| CN110218163A (en) * | 2019-05-20 | 2019-09-10 | 江苏蓝丰生物化工股份有限公司 | The synthetic method of n-butyl isocyanate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163608A (en) * | 1994-11-17 | 1997-10-29 | 拜尔公司 | Process for preparing isocyanates |
| CN1729168A (en) * | 2002-12-19 | 2006-02-01 | 巴斯福股份公司 | Method for the continuous production of isocyanates |
| CN1844091A (en) * | 2006-05-08 | 2006-10-11 | 江苏安邦电化有限公司 | Process for preparing butyl isocyanate |
| CN101177408A (en) * | 2007-12-07 | 2008-05-14 | 江苏安邦电化有限公司 | Method for preparing isocyanate |
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2008
- 2008-08-29 CN CN2008101246751A patent/CN101357898B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163608A (en) * | 1994-11-17 | 1997-10-29 | 拜尔公司 | Process for preparing isocyanates |
| CN1729168A (en) * | 2002-12-19 | 2006-02-01 | 巴斯福股份公司 | Method for the continuous production of isocyanates |
| CN1844091A (en) * | 2006-05-08 | 2006-10-11 | 江苏安邦电化有限公司 | Process for preparing butyl isocyanate |
| CN101177408A (en) * | 2007-12-07 | 2008-05-14 | 江苏安邦电化有限公司 | Method for preparing isocyanate |
Non-Patent Citations (2)
| Title |
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| 姜育田，等.异氰酸正丁酯工艺优化.《化工设计》.2007,第17卷(第6期),16-20. |
| 姜育田等.异氰酸正丁酯工艺优化.《化工设计》.2007,第17卷(第6期),16-20. * |
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Address after: 223002 Huaian City, Jiangsu Province Chemical Qingpu District Road No. 30 Patentee after: Andao mai'anbang (Jiangsu) Co., Ltd Address before: 223002 Huaian City, Jiangsu Province Chemical Qingpu District Road No. 30 Patentee before: JIANGSU ANPON ELECTROCHEMICAL Co.,Ltd. |