CN106543036A - A kind of industrial preparative method of tertiary butyl isocyanates - Google Patents
A kind of industrial preparative method of tertiary butyl isocyanates Download PDFInfo
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- CN106543036A CN106543036A CN201610873315.6A CN201610873315A CN106543036A CN 106543036 A CN106543036 A CN 106543036A CN 201610873315 A CN201610873315 A CN 201610873315A CN 106543036 A CN106543036 A CN 106543036A
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- China
- Prior art keywords
- tertiary butyl
- preparative method
- industrial preparative
- cyanate
- butyl isocyanates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/02—Preparation of derivatives of isocyanic acid by reaction of halides with isocyanic acid or its derivatives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of industrial preparative method of tertiary butyl isocyanates, with three-level alkyl halide and metal cyanate salt in catalyst and in the presence of suppressing distintegrant, by unreacted in course of reaction, completely metal cyanate salt and catalyst are continued back in system, reacted again, so as to substantially reduce the unit consumption of metal cyanate salt and catalyst, and the yield of abraum salt is significantly reduced, increased the technique carries out the feasibility of commercial production tertiary butyl isocyanates.
Description
Technical field
The present invention relates to a kind of industrial production process of tertiary butyl isocyanates, more particularly to a kind of suppress making for distintegrant
With and repeated using method to excessive cyanate slag salt.
Background technology
The patented technology with alkali metal cyanate synthesis tertiary butyl isocyanates domestic and international at present is representational mainly to be had
US422423 and CN102548959, as shown in the former, technical method cannot obtain gratifying effect when laboratory synthesizes
Really（Technology example 6：Yield is up to 84.9%, and conversion ratio is 98.1%）, actual Jing test of many times, by technical method which described,
Yield highest only up to 65%.If the technical method as shown in the latter (CN102548959) changes TBIC for dispersant or solvent, also not
Good conversion ratio and the yield described in which can be reached, thus also cannot be adopted in industrialized production.
Tertiary butyl isocyanates are the big weight organic compounds of synthesis, medicine, the useful intermediates of agricultural chemicalses.At this
Before bright, also there is more document to provide more synthetic route, such as reacted by organic amine and phosgene, but because phosgene is severe toxicity
Material, and tert-butylamine price is also relatively expensive, thus more difficult industrialized production.And pass through tert-butyl chloride and cyanic acid reactant salt,
It is representational mainly to have US4224238 and CN102548959, and both has deficiency as above.In consideration of it, of the invention
The method of offer then from for the angle of commercial Application and environmental protection, with more significantly advantage and economic feasibility.
This patent absorbs US4224238 patented technologies, and has carried out on this basis developing and perfect so that industrialization
It is able to complete with amazing yield.
The content of the invention
In view of the foregoing, the invention provides a kind of industrial preparative method of tertiary butyl isocyanates.
To reach above-mentioned purpose, the technical solution adopted for the present invention to solve the technical problems is：
A kind of industrial preparative method of tertiary butyl isocyanates, with metal cyanate salt and tert-butyl chloride, catalyst, suppresses to decompose
Agent, solvent are initiation material, obtain finished product tertiary butyl isocyanates by condensation reaction, distillation, rectification；Wherein condensation reaction
Excessive cyanate Jing after distillation afterwards is once applied mechanically, and continues synthesis tertiary butyl isocyanates.
Its further feature is as follows：
The metal cyanate salt is Sodium cyanate (NaOCN), potassium cyanate or calcium cyanate.
The water content of the metal cyanate salt is less than 0.5%.
Inorganic salt and organic salt of the catalyst for Zn, Fe, Sb, Sn and Co.
The suppression distintegrant is anhydrides thing.
The anhydrides thing is acetic anhydride, propionic andydride or acetic acid.
The solvent is aprotic solvent, and the aprotic solvent is halogenated alkane or halogenated aryl hydrocarbon.
The solvent is ethyl n-butyrate., butyl propionate, ethylene glycol ether acetate, ethohexadiol ethyl ester, butyl second two
Alcohol ethyl ester, 1,2- diethoxyethane, gamma-butyrolacton, phenylacetate, ethylene glycol ether acetate.
The solvent be ethohexadiol MEE, 1,2- Ethoxyethane, diethyl ethylene glycol monomethyl ether, diethyl
Ethylene glycol diethyl ether, dioxanes or methyl phenyl ethers anisole.
The temperature range of the condensation reaction is 60-90 DEG C.
Excessive cyanate Jing after condensation reaction is once applied mechanically.
Due to the utilization of above-mentioned technical proposal, the present invention has following beneficial effect compared with prior art：
A certain amount of suppression distintegrant is added in the reaction, while excessive cyanate is continued reuse once, then is added new
Fresh cyanate, catalyst and suppression distintegrant, can reduce the cost of raw material, and can reduce the abraum salt amount for producing, be conducive to environment
Protection.
Specific embodiment
With reference to specific embodiment, present disclosure is described in further detail：
Embodiment 1（As comparative example）：
The Sodium cyanate (NaOCN) of 0.7 mole 93% of addition, 0.5 mole of tert-butyl chloride in 80ml ethylene glycol ether acetates, 0.055 rubs
That zinc chloride, stirring heat up, and maintain 3 hours at 85 DEG C.After reaction terminates, tertiary butyl isocyanates are steamed, will be steamed
Crude product pass through gas chromatographic analysiss.
Reaction result is as follows：
TBIC（Special fourth isocyanates）Yield：72.1%（Mole）
TBC（Tertiary butyl chloride）Conversion ratio：99.6%（Mole）
This is with reference to US4224238 examples, except that being analyzed after TBIC is steamed, and is able to according to analytical data calculating
Upper result.
Embodiment 2（As comparative example）：
The Sodium cyanate (NaOCN) of 0.7 mole 93% of addition in 60ml ethylene glycol ether acetates, addition tertiary butyl isocyanates 25ml,
0.055 mole of zinc chloride, after stirring 10 minutes, adds 0.5 mole of tert-butyl chloride, heats up, and maintains 4 hours at 85 DEG C.
After reaction terminates, t-butylisocyanate is steamed, the crude product for steaming is passed through into gas chromatographic analysiss.
Reaction result is as follows：
TBIC（Special fourth isocyanates）Yield（The amount of added TBIC is deducted）：68.8%（Mole）
TBC（Tertiary butyl chloride）Conversion ratio：99.6%（Mole）
Embodiment 3（Embodiments of the invention）：
The Sodium cyanate (NaOCN) of 0.7 mole 93% of addition, 0.5 mole of tert-butyl chloride in 80ml ethylene glycol ether acetates, 0.055 rubs
That zinc chloride, 0.015 mole of acetic anhydride, stirring heat up, and maintain 3 hours at 85 DEG C.After reaction terminates, tertiary butyl is steamed
The crude product for steaming is passed through gas chromatographic analysiss by isocyanates.
Reaction result is as follows：
TBIC（Special fourth isocyanates）Yield：75.7%（Mole）
TBC（Tertiary butyl chloride）Conversion ratio：98.6%（Mole）
Add in this example after suppressing distintegrant, yield improves more obvious.
Embodiment 4（Embodiments of the invention）：
Continue example 3, add in the feed liquid after crude product 40ml ethylene glycol ether acetates, add 0.55 mole 93% to steaming
Sodium cyanate (NaOCN), 0.5 mole of tert-butyl chloride, 0.025 mole of zinc chloride, 0.025 mole of acetic anhydride, stirring heat up, and maintain at 85 DEG C
3 hours.After reaction terminates, tertiary butyl isocyanates are steamed, the crude product for steaming is passed through into gas chromatographic analysiss.
Reaction result is as follows：
TBIC（Special fourth isocyanates）Yield：76.5%（Mole）
TBC（Tertiary butyl chloride）Conversion ratio：99.3%（Mole）
This example continues example 3, and slag salt is continued reuse, and after the raw material for adding appropriate amount, gained yield is still preferable.
Embodiment 5（Embodiments of the invention）：
The Sodium cyanate (NaOCN) of 0.75 mole 93% of addition, 0.5 mole of tert-butyl chloride in 80ml ethylene glycol ether acetates, 0.055 rubs
That zinc chloride, 0.025 mole of acetic anhydride, stirring heat up, and maintain 3 hours at 85 DEG C.After reaction terminates, tertiary butyl is steamed
The crude product for steaming is passed through gas chromatographic analysiss by isocyanates.
Reaction result is as follows：
TBIC（Special fourth isocyanates）Yield：82.1%（Mole）
TBC（Tertiary butyl chloride）Conversion ratio：99.6%（Mole）
Embodiment 6（Embodiments of the invention）：
Continue example 5, add in the feed liquid after crude product 40ml ethylene glycol ether acetates, add 0.55 mole 93% to steaming
Sodium cyanate (NaOCN), 0.5 mole of tert-butyl chloride, 0.025 mole of zinc chloride, 0.015 mole of acetic anhydride, stirring heat up, and maintain at 85 DEG C
3 hours.After reaction terminates, tertiary butyl isocyanates are steamed, the crude product for steaming is passed through into gas chromatographic analysiss.
Reaction result is as follows：
TBIC（Special fourth isocyanates）Yield：79.3%（Mole）
TBC（Tertiary butyl chloride）Conversion ratio：97.9%（Mole）
Above-described embodiment technology design only to illustrate the invention and feature, its object is to allow person skilled in the art's energy
Solution present disclosure much of that is simultaneously carried out, and can not be limited the scope of the invention with this, all according to spirit of the invention
Equivalence changes or modification that essence is made, should all cover within the scope of the present invention.
Claims (11)
1. a kind of industrial preparative method of tertiary butyl isocyanates, with metal cyanate salt and tert-butyl chloride, catalyst, suppresses to divide
Solution agent, solvent are initiation material, obtain finished product tertiary butyl isocyanates by condensation reaction, distillation, rectification；Wherein it is condensed anti-
The excessive cyanate Jing after distillation after answering once is applied mechanically, and continues synthesis tertiary butyl isocyanates.
2. a kind of industrial preparative method of tertiary butyl isocyanates according to claim 1, it is characterised in that：The metal cyanogen
Hydrochlorate is Sodium cyanate (NaOCN), potassium cyanate or calcium cyanate.
3. the industrial preparative method of a kind of tertiary butyl isocyanates according to claim 1 or claim 2, it is characterised in that：The gold
The water content of category cyanate is less than 0.5%.
4. a kind of industrial preparative method of tertiary butyl isocyanates according to claim 1, it is characterised in that：The catalyst
For the inorganic salt and organic salt of Zn, Fe, Sb, Sn and Co.
5. a kind of industrial preparative method of tertiary butyl isocyanates according to claim 1, it is characterised in that：It is described to suppress to divide
Solution agent is anhydrides thing.
6. a kind of industrial preparative method of tertiary butyl isocyanates according to claim 5, it is characterised in that：The anhydrides
Thing is acetic anhydride, propionic andydride or acetic acid.
7. a kind of industrial preparative method of tertiary butyl isocyanates according to claim 1, it is characterised in that：The solvent is
Aprotic solvent, the aprotic solvent are halogenated alkane or halogenated aryl hydrocarbon.
8. a kind of industrial preparative method of tertiary butyl isocyanates according to claim 1, it is characterised in that：The solvent is
Ethyl n-butyrate., butyl propionate, ethylene glycol ether acetate, ethohexadiol ethyl ester, butyl glycol ethyl ester, 1,2- diethoxies
Base ethane, gamma-butyrolacton, phenylacetate, ethylene glycol ether acetate.
9. a kind of industrial preparative method of tertiary butyl isocyanates according to claim 1, it is characterised in that：The solvent is
Ethohexadiol MEE, 1,2- Ethoxyethane, diethyl ethylene glycol monomethyl ether, diethyl ethylene glycol diethyl ether, dioxanes
Or methyl phenyl ethers anisole.
10. a kind of industrial preparative method of tertiary butyl isocyanates according to claim 1, it is characterised in that：The condensation
The temperature range of reaction is 60-90 DEG C.
A kind of 11. industrial preparative methods of tertiary butyl isocyanates according to claim 1, it is characterised in that：Condensation reaction
Excessive cyanate Jing afterwards is once applied mechanically.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610873315.6A CN106543036A (en) | 2016-10-08 | 2016-10-08 | A kind of industrial preparative method of tertiary butyl isocyanates |
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| CN201610873315.6A CN106543036A (en) | 2016-10-08 | 2016-10-08 | A kind of industrial preparative method of tertiary butyl isocyanates |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382777A (en) * | 2017-07-12 | 2017-11-24 | 黄河三角洲京博化工研究院有限公司 | A kind of method of chlorinated derivative content in reduction isocyanates |
| CN115819284A (en) * | 2022-12-12 | 2023-03-21 | 浙江丽水有邦新材料有限公司 | Preparation method of tert-butyl isocyanate by using byproduct hydrochloric acid as raw material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4224238A (en) * | 1978-04-18 | 1980-09-23 | Showa Denko K.K. | Process for preparing tertiary alkyl isocyanates |
| CN102548959A (en) * | 2009-09-28 | 2012-07-04 | Ks试验研究株式会社 | Production method for an alkyl isocyanate |
-
2016
- 2016-10-08 CN CN201610873315.6A patent/CN106543036A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4224238A (en) * | 1978-04-18 | 1980-09-23 | Showa Denko K.K. | Process for preparing tertiary alkyl isocyanates |
| CN102548959A (en) * | 2009-09-28 | 2012-07-04 | Ks试验研究株式会社 | Production method for an alkyl isocyanate |
Non-Patent Citations (1)
| Title |
|---|
| R.FUCK ET AL.: "New Syntheses of Aliphatic Isocyanates via Cyanogen Chloride", 《TETRAHEDRON》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382777A (en) * | 2017-07-12 | 2017-11-24 | 黄河三角洲京博化工研究院有限公司 | A kind of method of chlorinated derivative content in reduction isocyanates |
| CN107382777B (en) * | 2017-07-12 | 2020-06-26 | 山东益丰生化环保股份有限公司 | Method for reducing content of chloro-derivative in isocyanate |
| CN115819284A (en) * | 2022-12-12 | 2023-03-21 | 浙江丽水有邦新材料有限公司 | Preparation method of tert-butyl isocyanate by using byproduct hydrochloric acid as raw material |
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