CN106631899B - A method of isocyanates is prepared using amine and carbonyl fluoride - Google Patents
A method of isocyanates is prepared using amine and carbonyl fluoride Download PDFInfo
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- CN106631899B CN106631899B CN201611121677.6A CN201611121677A CN106631899B CN 106631899 B CN106631899 B CN 106631899B CN 201611121677 A CN201611121677 A CN 201611121677A CN 106631899 B CN106631899 B CN 106631899B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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Abstract
The invention discloses a kind of high-efficient synthesis methods for directly preparing corresponding isocyanates to amine reaction using carbonyl fluoride.This method mainly includes following two step: (1) amine and carbonyl fluoride are preferably to match, and acylation reaction occurs under closed environment, suitable reaction condition, in anhydrous inert organic solvent and generates intermediate carbamyl fluoride；(2) when normal pressure, under suitable reaction condition, intermediate carbamyl fluoride dehydrofluorination obtains target isocyanates.Reaction process is mild without adding catalyst, reaction condition, excessive carbonyl fluoride and used solvent high-efficiency recovery in reaction process, and by-product HF can be with commercial sales after collecting purification.
Description
Technical field
The invention belongs to organic compound compound probability technical fields, and in particular to preparation is directly reacted with amine with carbonyl fluoride
Corresponding isocyanates, while the efficient industrialization for being fluorinated hydrogen retrieval by the realizations excess carbonyl fluorides such as rectifying and by-product, applying
Synthetic method.
Background technique
Isocyanates is the general name of the various esters of isocyanic acid with "-N=C=O " functional group, is mainly used for synthesis of polyurethane
Foamed plastics, elastomer, fiber (spandex), resins for leathers and shoes, coating, sealant, adhesive and imitation wood etc.；It is also used as
The intermediate or raw material that the pesticides such as insecticide, fungicide, herbicide, antidiabetic drug, medical fine chemical product synthesize, it may also be used for
Improve the waterproofness, fast light, weatherability etc. of plastics, fabric, leather etc..Wherein, representative industrial goods are aromatic toluene two
Isocyanates (TDI), methyl diphenylene diisocyanate (MDI) and aliphatic hexa-methylene -1,6- diisocyanate
(HDI), in addition there are some (e.g., paranitroanilinum NA) containing electron-withdrawing group or-NCO functional group is not direct connect with aromatic rings
Special isocyanates (e.g., benzene dimethylene diisocyanate XDI).
Phosgenation is well known most important isocyanates industrial production method in the world at present, can be with according to reaction condition
It is divided into liquid phase phosgenation and gas phase phosgenation.Wherein, liquid phase light phosgenation can be divided into salt phosgenation and direct phosgenation again
Two kinds.There are many disadvantages for this method.It is well known that phosgene has high toxicity (TLV-TWA (ACGIN): 0.1ppm) and strong corruption
Corrosion must use complicated consersion unit, refrigeration system and security protection system in production, and be difficult to amount transport and storage
It deposits, original place production, original place is generally required to use.Direct phosgenation is also easy to generate carbamide compounds, and carbamide compounds are further
The tar compounds that phosgene generates resin-like are consumed, influence the yield of isocyanates, it is also possible to generate monoisocyanates chloride
Equal by-products；Into salt phosgenation before the reaction by aminated compounds and HCl or CO2Reaction, generate its corresponding hydrochloride or
Carbonate, though can preferably inhibit by-product, the reaction time is longer, and complex process degree improves, obtained isocyanates
Through a long time heating easily forms tarry matters, reduces product yield；The a large amount of by-product HCl generated in production process, to work
Skill equipment, the corrosivity of pipeline are serious, and remaining hydrolysis chlorine is difficult to remove in product, may dramatically influence downstream production
Moral character energy；Safe and environment-friendly supervision difficulty is big, at high cost.
Although in addition, phosgenation for the preparation of TDI, MDI, HDI generally have preferable yield (US9024057 B2,
US8921594 B2, US2362648), still, for it is some containing electron-withdrawing group or-NCO functional group it is not direct with it is fragrant
The special isocyanates of ring connection is then difficult to undesirable using phosgenation synthesis or synthetic effect.Such as, Lombardino and
Gerber, by p-trifluoromethylaniline and HCl, phosgene reaction, prepares p-trifluoromethyl phenyl isocyanates in toluene solvant
(TFMPI), yield is only 42% (J.Med.Chem.1964,7,97-101)；2,6- difluoro benzoyl isocyanate (DFBI) work
Oxalyl chloride method (CN103864694, CN103864694A) or triphosgene (CN101906070A), oxalyl chloride are generally used in industry
Method higher cost and exhaust gas and waste liquid amount are larger, and triphosgene is substantially identical as phosgenation；(1- isocyano-the 1- of 1,3- bis-
Methylethyl) benzene (TMXDI) synthesis report be mainly OH-CN, HNCO and related phenyl compound addition process
(EP410169A2, J.Org.Chem., 1964,29,143-145), but this method raw material is not easy to obtain and severe toxicity, catalyst recycling
Difficulty, yield be not high.
Currently, there are many research of the non-phosgene synthetic method for such special isocyanates reports, but because of yield
Lowly, expensive catalyst a variety of different disadvantages such as is not easy to obtain, is with high costs also in laboratory stage, is not suitable for industry metaplasia
It produces.Such as, EP672653A1 uses p-MeC6H4SO3H is catalyst, synthesizes phenylenedimethylidyne by carbamate thermal decomposition method
Diisocyanate (XDI), it is catalyst, solvent difficult separation and recycling, complex process, less economical；Deng et al. is with SnCl4To urge
Agent, in o-dichlorobenzene solution, using Zassol and 2, the reaction of 6- difluoro benzoyl chloride obtains the DFBI of 70% yield
(Tetrahedron, 1988,44 (19), 6079-6086), raw material acquisition are not easy, catalyst, solvent difficult separation and recycling, and are received
Rate is not high；CN1590369A is by CO2With triethylamine, 4,4 '-diamino-dicyclohexyl methanes mix in nitro benzene solvent, are made
Corresponding carbamate anion solutions, then with POCl3Dehydration occurs, obtains 4,4 '-diisocyanate dicyclohexyls
Methane (H12MDI), which has a large amount of reluctant abraum salts to generate.
The preparation early stage that carbonyl fluoride is used for isocyanate compound, there are reports.Patent US3118923 uses phosphinylidyne
Fluorine and alkali metal cyanide, cyanogen halides, inorganic cyanate etc. contain the compound of-CN functional group, are directly using or not direct
Reacted in the case where using catalyst, available corresponding fluorine-containing isocyanates, the raw material cyanide toxicity of this method generally compared with
It by force and is not easy to obtain, while product yield is not high；Patent US3795689 is urged in potassium fluoride, rubidium fluoride RbF plasma type fluoride salt
Under change, perfluor chlorine alkyl imino is reacted in anhydrous aprotic type polarizable medium with carbonyl fluoride, corresponding perfluor chlorine can be made
Alkyl isocyanate, the recycling of this method catalyst is difficult, the reaction time is longer, raw material is not easy to obtain, it is difficult to realize industrialization.Patent
JP5322183 is anti-by 5 kinds of carbonyl fluoride and toluenediamine (TDA), methylene dianiline (MDA) (MDA) etc. the diamines without electron-withdrawing group
It answers, patent CN105837475A reacts carbonyl fluoride with para toluene sulfonamide (pTSA), corresponding isocyanates is made respectively, but
Whether other isocyanates are not suitable for it, especially other containing electron-withdrawing group or-NCO functional group it is not direct with it is fragrant
The synthesis that ring connects the special isocyanates of (in addition to HDI) carries out any verifying experimentally, and the former was not directed to completely
The recycling technique of carbonyl fluoride, organic solvent, by-product HF etc. are measured, environmental pollution is larger, less economical, though the latter mentions
And but be not directed to specific recovery process design and recovering effect example, have to the directive significance of industrialized production very big
Limitation.
Summary of the invention
The purpose of the present invention is to provide a kind of synthesis for directly preparing corresponding isocyanates to amine reaction using carbonyl fluoride
Method, the method overcome deficiency existing for existing synthetic technology in above-mentioned background technique, using corresponding amine under an increased pressure with
Carbonyl fluoride carries out liquid phase reactor, and without adding catalyst, reaction condition is mild, the reaction time is short, by-product is few, high income, together
The design of Shi Jinhang detailed process carries out high efficiente callback to carbonyl fluoride excessive in reaction process and solvent and applies, to by-product HF
It is collected purification, basic three-waste free discharge, environmental-friendly and better economy, reaction equation is shown below.
Wherein R includes being not limited to phenyl, naphthenic base, alkenyl, alkynyl, these groups can also be with other electrophilics herein
Base, aromatic rings or naphthenic base are connected.
The method that carbonyl fluoride method prepares isocyanates described in the invention mainly comprises the steps that (1) amine and carbonyl fluoride
Occur in acylation reaction generation preferably to match under closed environment, suitable reaction condition, in anhydrous inert organic solvent
Mesosome carbamyl fluoride；(2) when normal pressure, under suitable reaction condition, intermediate carbamyl fluoride dehydrofluorination obtains target isocyanide
Acid esters.
The amine molecule is selected from the amine for meeting following general formula,
Wherein, R is selected from halogen, nitro, trifluoromethyl or C1-C6Alkyl, the integer that n is 0 to 5,
R1Selected from key, C1-C6Alkyl, carbonyl or sulfonyl, x are 1 or 2.
The amine is selected from the amine for meeting following general formula
Wherein, R is selected from halogen, nitro, trifluoromethyl or C1-C6Alkyl, the integer that m is 0 to 6,
R2Selected from key or C1-C6Alkyl, x are 1 or 2.
The amine is selected from the amine for meeting following general formula
Wherein, R is selected from halogen, nitro, trifluoromethyl or C1-C6Alkyl, the integer that a is 0 to 4,
R1Selected from key or C1-C6Alkyl,
R3Selected from key, hexafluoroisopropylidenyl, sulfonyl or C1-C6Alkylidene.
The amine is selected from the amine for meeting following general formula
Wherein, R is selected from halogen, nitro, trifluoromethyl or C1-C6Alkyl, the integer that m is 0 to 6,
R2Selected from key or C1-C6Alkyl,
R3Selected from key, sulfonyl or C1-C6Alkylidene.
The amine molecule includes being not limited to: 2,6- difluorobenzamide (DFBA), 5-trifluoromethylaniline (TFMPA), to nitre
Base aniline (NA), 4,4`- sulphonyl diphenyl diamine (BSDA), 4,4`- hexafluoroisopropylidenyl diphenyl diamine (HFPDA), different Buddhist
That ketone diamines (IPDA), dicyclohexyl methyl hydride -4,4'- diamines (H12MDA), phenylenedimethylidyne diamines, 1,4- cyclohexane diamine
(CHDA), cyclohexylamine (CHA), p-chloro benzenesulfonamide (CPSA), trans- -4- methylcyclohexyl amine (HTDA), bis- (alpha-amido of 1,3-
Isopropyl) benzene, parachloroanilinum (CPA), 3,5- dichloroaniline (DCPA).
The inert organic solvents include being not limited to alkyl aromatic, halogenated aryl hydrocarbon, halogenated aliphatic hydrocarbon, aliphatic ester
Close object or aromatic series ester type compound, aliphatic hydrocarbon organic solvent.
The inert organic solvents include being not limited to toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, 1,3,5- trimethylbenzene, two chloroethenes
One of alkane, pentachloroethane are a variety of.
The suitable acylation reaction condition of the step (1) is 25~120 DEG C of temperature, 1~5h of reaction time, each-NH2
Corresponding carbonyl fluoride molar ratio is 1:1.1~1:5；The suitable dehydrofluorination reaction conditions of the step (2) be temperature 60~
260 DEG C, heat 1~5h of reaction time.
It is preferred that 25~80 DEG C of acylation reaction temperature, 1~3h of reaction time；Each-NH2Corresponding carbonyl fluoride molar ratio
For 1:2.2~1:2.7, more preferably 1:2.3~1:2.7；It is preferred that 80~160 DEG C of dehydrofluorination temperature, the reaction time 1~
3h.Wherein each-NH2Corresponding carbonyl fluoride molar ratio can be 1:2.4,1:2.5,1:2.6.
The step (1) recycles excessive raw material carbonyl fluoride and by-product HF afterwards.
After the step (1) recycles excessive carbonyl fluoride and by-product HF, product mixtures are directly entered step (2) and carry out instead
It answers.
Recycle during step (2) reaction carries out or after the completion inert organic solvents and by-product HF.
The method of the recycling inert organic solvents is the distillation when step (2) carry out, or to mixed after step (2) reaction
Object rectifying is closed, or the reaction solution of step (2) is filtered, organic solvent crude product is obtained, is re-used after crude product rectifying is dry.
After the reaction was completed for step (1) and (2), medium-pressure and low-temperature rectification obtains crude product to the method for the recycling by-product HF,
It is refined using multiple rectifying.
Advantages of the present invention:
(1) synthetic route is novel, has no the such synthesis application report of the target product；
(2) reaction condition is mild, can carry out at room temperature or lower than 200 DEG C；And it is not necessarily to catalyst, it advantageously reduces into
Sheet and complex process degree；
(3) carbonyl fluoride reactivity it is stronger than phosgene, when excessive the acylation reaction of first step amine quickly and completely, the pairs such as urea
Product is difficult to be formed；
(4) technological design is reasonable, basic three-waste free discharge, and solvent used in excessive carbonyl fluoride and reaction can be efficient
Recovery, the HF for reacting generation also collect commercial sales after purification, and environmental pressure is small；
(5) toxicity of carbonyl fluoride is equivalent to 1/20 (TLV-TWA (ACGIN): 2ppm) of phosgene, the world Bu Shou " forbidding
Learn weapon pact " limitation, it can be supervised according to general hazardous chemical, can transport for long-distance and quantitatively store, security control difficulty
And cost reduces.
(6) it is based on-NH employed in the present invention2Corresponding carbonyl fluoride molar ratio, in isocyanate product purity and
Unexpected excellent technical effect is achieved in terms of product yield.
Specific embodiment
The present invention follows the steps below to implement: (1) after selected amine mixes according to a certain percentage with solvent, squeezing into the first reaction
In kettle, it is passed through a certain amount of carbonyl fluoride, is reacted at a certain temperature, reaction product separates carbonyl fluoride, separation through the first degassing tower
Carbonyl fluoride enter storage tank through compressor, with recycling.The kettle material that first degassing tower flows out is squeezed into the second degassing tower, by fluorine
Change hydrogen separation, into hydrogen fluoride storage tank.(2) reaction product that the second degassing tower flows out is directly entered two reaction kettles, certain temperature
Degree is lower to occur removing hydrogen fluoride reaction, and reaction product enters third degassing tower, hydrogen fluoride is separated, into hydrogen fluoride storage tank, stream
Kettle material out squeezes into solvent recovery tower, if target isocyanates room temperature is solid-state, solvent portion is recycled；If target isocyanic acid
Ester room temperature is liquid, then all recycles solvent, solvent enters solvent tank after recycling.(3) if target isocyanates room temperature is
The kettle material that solvent recovery tower flows out is squeezed into recrystallization kettle and carries out finished product purification by solid-state, and by centrifugal filtration, liquid material is squeezed into
The recycling of second reaction kettle；If target isocyanates room temperature is liquid, the kettle material that solvent recovery tower flows out is squeezed into finished product essence
Tower processed, rectified purified, surplus material enters second reactor and recycles.Production process is realized substantially without " three wastes ", and carbon is reached
The high efficiente callback of acyl fluorides and solvent utilizes, and byproduct hydrogen fluoride can refine as commodity selling.
The carbamyl fluoride intermediate refers to the compound corresponding with above-mentioned amine with-NHC (O) F functional group.
The isocyanate product refers to corresponding with above-mentioned carbamyl fluoride intermediate with-NCO functional group
Compound.
The inert organic solvents main function used of the invention is that diluting reaction object is conducive to realizing homogeneous reaction
The generation of main reaction simultaneously inhibits side reaction, it is desirable that: good to selected amine dissolubility, inert to carbonyl fluoride, preferably boiling point is high
In step (1) reaction temperature, but it is lower than the atent solvent immiscible with carbamyl fluoride intermediate of step (2) reaction temperature,
It is more conducive to solvent recovery and intermediate obtains.The atent solvent includes being not limited to aromatic hydrocarbon, halogenated aryl hydrocarbon, halogenated aliphatic
Hydrocarbon, aliphatic ester compounds or aromatic series ester type compound, aliphatic hydrocarbon organic solvent, can be, but not limited to, first
Benzene, dimethylbenzene, chlorobenzene, dichloro-benzenes, 1,3,5- trimethylbenzenes, dichloroethanes, pentachloroethane etc., it might even be possible to be both the above or more
Kind is with the mixture of arbitrary proportion.
Carbonyl fluoride needs Excess quantities in step (1) of the present invention, and otherwise amine can generate secondary with carbamyl fluoride intermediate reaction
Product, each-NH2Corresponding carbonyl fluoride molar ratio is 1:1.1~1:5, preferably 1:2.2~1:2.7, more preferably 1:2.3
~1:2.7.
Excessive carbonyl fluoride passes through distillation, purification recovery in the first step after reaction in step (1) of the present invention, both
Raw material availability can be improved, reduce cost, and can produce to avoid the isocyanates generated in remaining carbonyl fluoride and step (2)
Object reacts to form by-product.
The acylation reaction temperature of step (1) of the present invention selects 25~120 DEG C, preferably 25~80 DEG C；Reaction time selection 1
~5h, preferably 1~3h.
The dehydrofluorination temperature of step (2) of the present invention selects 60~260 DEG C, preferably 80~160 DEG C；Reaction time choosing
Select 1~5h, preferably 1~3h.
Step (1) of the present invention and (2) can carry out in same reaction kettle, i.e., acyl is first carried out in same reaction kettle
Glycosylation reaction is completed after first step reaction and carries out dehydrofluorination again after pressure release, can also be by dividing kettle to carry out, such as one
Acylation reaction is first carried out in reaction kettle, then dehydrofluorination is carried out in another reaction kettle.
Step (1) acylation reaction of the present invention is to carry out under a certain pressure, and pressure is with reaction in reaction process
It is gradually changed and there are maximum value, maximum pressure and reaction temperature, carbonyl fluoride charge etc. are closely related, anti-by controlling
Maximum pressure is answered to can control reaction process, reaction speed is slow when maximum pressure is smaller, and side reaction easily occurs；Maximum pressure is larger
When reaction speed it is fast, side reaction is few.The maximum pressure that step (1) is reacted in preparation process of the present invention selects 2~5Mpa, excellent
Select 2~3Mpa.
In synthetic reaction of the present invention used solvent step (2) reaction carry out in or and after recycle,
Recovered solvent re-uses after rectification process, realizes the recovery of solvent.
The by-product HF generated in step (1) of the present invention and (2) reaction, obtains crude product by low-temperature atmosphere-pressure rectifying, then pass through
Multiple rectifying is crossed to be refined.
Below based on the basic process and principle of process flow, device is simplified using laboratory, in conjunction with the embodiments to this hair
It is bright to be described in further detail.
Embodiment 1
It is stainless that the 1.50L with blender is added in 161g (1.0mol) 5-trifluoromethylaniline (TFMPA) and 600ml chlorobenzene
In steel reaction kettle, it is filled with closed system after 165g (2.5mol) carbonyl fluoride, 2h is reacted at room temperature, then using reaction kettle as rectifying
Tower tower reactor, direct rectifying adjust bottom temperature, and guarantee system pressure is 1Mpa, and tower top temperature is -40 DEG C, overhead extraction phosphinylidyne
Then tower reactor is warming up to 130 DEG C or so by fluorine 90g, the rate of recovery 91%, guarantee system pressure is 0.5Mpa, and tower top temperature is
20 DEG C, overhead extraction hydrogen fluoride 18g, the rate of recovery 90%.Then 2h is reacted at normal pressure, 130 DEG C of temperature and remove hydrogen fluoride, instead
After answering, tower top refrigerant temperature is 20 DEG C, overhead extraction hydrogen fluoride 19g, and the rate of recovery 95%, kettle liquid is recycled through vacuum distillation
Solvent chlorobenzene 580ml, tower reactor obtain yellow liquid trifluoromethyl phenylisocyanate (TFMPI) crude product 183.8g, and purity 86.8% produces
Object yield 85.3%.The chlorobenzene of recycling returns to solvent tank.
Embodiment 1A
Difference with embodiment 1 is only that the additional amount of carbonyl fluoride is 185g (2.8mol).Gained trifluoromethylbenzene isocyanide
Acid esters (TFMPI) crude product 174.8g, purity 86.0%, product yield 80.4%.
Embodiment 1B
Difference with embodiment 1 is only that the additional amount of carbonyl fluoride is 264g (4mol).Gained trifluoromethylbenzene isocyanic acid
Ester (TFMPI) crude product 201.9g, purity 74.0%, product yield 79.9%.
Embodiment 2
207g (1.5mol) paranitroanilinum (NA) and 600ml dimethylbenzene are added to the 1.50L stainless steel for having blender
In reaction kettle, it is filled with closed system after 264g (4.0mol) carbonyl fluoride, after reacting 3h at room temperature, using reaction kettle as rectifying column
Tower reactor, direct rectifying adjust bottom temperature, and guarantee system pressure is 1Mpa, and tower top temperature is -40 DEG C, overhead extraction carbonyl fluoride
Then tower reactor is warming up to 140 DEG C or so by 150g, the rate of recovery 91%, guarantee system pressure is 0.5Mpa, tower top temperature 20
DEG C, overhead extraction hydrogen fluoride 28g, the rate of recovery 93.3%.Then 2h is reacted at normal pressure, 140 DEG C of temperature and remove hydrogen fluoride, instead
After answering, tower top refrigerant temperature is 20 DEG C, overhead extraction hydrogen fluoride 27g, and the rate of recovery 90%, kettle liquid is recycled through vacuum distillation
Solvent xylene 580ml, tower reactor obtain light yellow liquid p-nitrophenyl isocyanate (NPI) crude product 225.6g, and purity 94.0% produces
Product yield 86.2%.The dimethylbenzene of recycling returns to solvent tank.
Embodiment 2A
Difference with embodiment 2 is only that the additional amount of carbonyl fluoride is 138.6g (2.1mol).Gained p-nitrophenyl isocyanide
Acid esters (NPI) crude product 253.3g, purity 77.8%, product yield 80.1%.
Embodiment 2B
Difference with embodiment 2 is only that the additional amount of carbonyl fluoride is 297g (4.5mol).Gained p-nitrophenyl isocyanic acid
Ester (NPI) crude product 264.2g, purity 75.8%, product yield 81.4%.
Embodiment 3
298g (1.2mol) 4,4`- sulphonyl diphenyl diamine (BSDA) and 300ml acetone, 300ml m-dichlorobenzene are added
In 1.50L stainless steel cauldron with blender, it is filled with closed system after 396g (6.0mol) carbonyl fluoride, is reacted at room temperature
After 3h, using reaction kettle as tower bottom of rectifying tower, direct rectifying adjusts bottom temperature, and guarantee system pressure is 1Mpa, tower top temperature
It is -40 DEG C, then tower reactor is warming up to 100 DEG C or so by overhead extraction carbonyl fluoride 219g, the rate of recovery 92.3%, guarantee system
Pressure is 0.6Mpa, and tower top temperature is 20 DEG C, overhead extraction hydrogen fluoride 42g, the rate of recovery 87.5%.Then in normal pressure, temperature
2h is reacted at 140 DEG C and removes hydrogen fluoride, and after reaction, tower top refrigerant temperature is 20 DEG C, overhead extraction hydrogen fluoride 40g, recycling
Rate is 83.3%, after system is down to room temperature, filter to obtain yellow solid 4,4`- sulphonyl diphenyl diisocyanate (BSDI) crude product
364g, purity 96.0%, product yield 97.1%.Recovered solvent crude product through washing, alkali cleaning, distillation obtain 290ml acetone and
287ml m-dichlorobenzene returns to solvent tank.
Embodiment 3A
Difference with embodiment 3 is only that the amount of carbonyl fluoride is 198g (3.0mol).Gained 4,4`- sulphonyl diphenyl two is different
Cyanate (BSDI) crude product 352.5g, purity 82.1%, product yield 80.4%.
Embodiment 3B
Difference with embodiment 3 is only that the amount of carbonyl fluoride is 528g (8.0mol).Gained 4,4`- sulphonyl diphenyl two is different
Cyanate (BSDI) crude product 341.9, purity 83.4%, product yield 79.2%.
Embodiment 4
By 501g (1.5mol) 4,4`- hexafluoroisopropylidenyl diphenyl diamine (HFPDA) and 250ml acetone, 250ml diformazan
Benzene is added in the 1.5L stainless steel cauldron with blender, closed system after 455.4g (6.9mol) carbonyl fluoride is filled with, in room
After the lower reaction 3h of temperature, using reaction kettle as tower bottom of rectifying tower, direct rectifying adjusts bottom temperature, and guarantee system pressure is 1Mpa,
Tower top temperature is -40 DEG C, then tower reactor is warming up to 140 DEG C or so by overhead extraction carbonyl fluoride 220g, the rate of recovery 92.6%,
Guarantee system pressure is 0.5Mpa, and tower top temperature is 20 DEG C, overhead extraction hydrogen fluoride 54g, the rate of recovery 90%.Then normal
It presses, reaction 3h removing hydrogen fluoride at 140 DEG C of temperature, after reaction, tower top refrigerant temperature is 20 DEG C, overhead extraction hydrogen fluoride
56g, the rate of recovery 93.3%, kettle liquid obtain yellow liquid through vacuum distillation recovered solvent acetone 240ml, dimethylbenzene 245ml, tower reactor
4,4`- hexafluoroisopropylidenyl diphenyl diisocyanate (HFPDI) crude product 597.1g, purity 96.0%, product yield 99.0%.
Recovered solvent returns to solvent tank.
Embodiment 4A
Difference with embodiment 4 is only that the amount of carbonyl fluoride is 435.6g (6.6mol).Gained 4,4`- hexafluoroisopropylidenyl
Diphenyl diisocyanate (HFPDI) crude product 547.9g, purity 89.4%, product yield 84.6%.
Embodiment 4B
Difference with embodiment 4 is only that the amount of carbonyl fluoride is 594g (9.0mol).Gained 4,4`- hexafluoroisopropylidenyl two
Phenyl diisocyanate (HFPDI) crude product 591.5g, purity 83.7%, product yield 85.5%.
Embodiment 5
236g (1.5mol) 2,6- difluorobenzamide (DFBA) and 500ml toluene are added to the 1.50L for having blender
In stainless steel cauldron, it is filled with closed system after 237.6g (3.6mol) carbonyl fluoride, 1.5h is reacted at 80 DEG C, after the reaction was completed
It is down to room temperature, using reaction kettle as tower bottom of rectifying tower, direct rectifying adjusts bottom temperature, and guarantee system pressure is 1Mpa, tower top
Temperature is -40 DEG C, overhead extraction carbonyl fluoride 133g, then tower reactor is warming up to 100 DEG C or so by the rate of recovery 96%, guarantees system
System pressure is 0.6Mpa, and tower top temperature is 20 DEG C, overhead extraction hydrogen fluoride 28g, the rate of recovery 93.3%.Then in normal pressure, temperature
Reaction 2h removes hydrogen fluoride at 100 DEG C of degree, and after reaction, tower top refrigerant temperature is 20 DEG C, overhead extraction hydrogen fluoride 25g, returns
Yield is 83.3%, after system is down to room temperature, filter to obtain white solid 2,6- difluoro benzoyl isocyanate (DFBI) crude product
255g, purity 98.2%, product yield 91.2%.Recovered solvent crude product through washing, alkali cleaning, distill to obtain toluene 450ml, return
Solvent tank.
Embodiment 5A
Difference with embodiment 5 is only that the amount of carbonyl fluoride is 198g (3mol).Gained 2,6- difluorobenzoyl isocyanic acid
Ester (DFBI) crude product 272.6g, purity 80.4%, product yield 79.8%.
Embodiment 5B
Difference with embodiment 5 is only that the amount of carbonyl fluoride is 495g (7.5mol).Gained 2,6- difluorobenzoyl isocyanide
Acid esters (DFBI) crude product 264.6g, purity 84.7%, product yield 81.6%.
Embodiment 6
169g (1.0mol) isophorone diamine (IPDA) and 500ml chlorobenzene are added to the 1.5L stainless steel for having blender
In reaction kettle, it is filled with closed system after 337g (5.1mol) carbonyl fluoride, 3h is reacted at 50 DEG C, is down to room temperature after the reaction was completed,
Using reaction kettle as tower bottom of rectifying tower, direct rectifying adjusts bottom temperature, and guarantee system pressure is 1Mpa, and tower top temperature is -40
DEG C, then tower reactor is warming up to 140 DEG C or so by overhead extraction carbonyl fluoride 194g, the rate of recovery 94.8%, guarantee that system pressure is
0.5Mpa, tower top temperature are 20 DEG C, overhead extraction hydrogen fluoride 32g, the rate of recovery 80%.Then anti-at normal pressure, 140 DEG C of temperature
3h is answered to remove hydrogen fluoride, after reaction, tower top refrigerant temperature is 20 DEG C, overhead extraction hydrogen fluoride 34g, the rate of recovery 85%,
Kettle liquid obtains light yellow liquid isophorone diisocyanate (IPDI) crude product through vacuum distillation recovered solvent chlorobenzene 489ml
210.5g, purity 92.8%, product yield 88.4%.Recovered solvent returns to solvent tank.
Embodiment 6A
Difference with embodiment 6 is only that the amount of carbonyl fluoride is 198g (3mol).Gained isophorone diisocyanate
(IPDI) crude product 205.0g, purity 81.4%, product yield 75.5%.
Embodiment 6B
Difference with embodiment 6 is only that the amount of carbonyl fluoride is 495g (7.5mol).Gained isophorone diisocyanate
(IPDI) crude product 210.6g, purity 83.2%, product yield 79.3%.
Embodiment 7
315.5g (1.5mol) dicyclohexyl methyl hydride -4,4'- diamines and 500ml dimethylbenzene are added with blender
In 1.5L stainless steel cauldron, it is filled with closed system after 534.6g (8.1mol) carbonyl fluoride, 3h is reacted at 50 DEG C, reaction is completed
After be down to room temperature, using reaction kettle as tower bottom of rectifying tower, direct rectifying, adjust bottom temperature, guarantees system pressure be 1Mpa, tower
Pushing up temperature is -40 DEG C, overhead extraction carbonyl fluoride 324g, then tower reactor is warming up to 150 DEG C or so by the rate of recovery 95.7%, is protected
Card system pressure is 0.5Mpa, and tower top temperature is 20 DEG C, overhead extraction hydrogen fluoride 56g, the rate of recovery 93.3%.Then normal
It presses, reaction 3h removing hydrogen fluoride at 150 DEG C of temperature, after reaction, tower top refrigerant temperature is 20 DEG C, overhead extraction hydrogen fluoride
55g, the rate of recovery 91.7%, kettle liquid obtain light yellow liquid dicyclohexyl first through vacuum distillation recovered solvent dimethylbenzene 476ml
Alkane -4,4'- diisocyanate (H12MDI) crude product 386.4g, purity 94.0%, product yield 92.3%.Recovered solvent returns
Solvent tank.
Embodiment 7A
Difference with embodiment 7 is only that the amount of carbonyl fluoride is 396g (6mol).Gained dicyclohexyl methyl hydride -4,4'- two
Isocyanates (H12MDI) crude product 338.2g, purity 79.6%, product yield 68.4%.
Embodiment 7B
Difference with embodiment 7 is only that the amount of carbonyl fluoride is 561g (8.5mol).Gained dicyclohexyl methyl hydride -4,4'-
Diisocyanate (H12MDI) crude product 392.1g, purity 80.2%, product yield 79.9%.
Embodiment 8
It is stainless that the 1.5L with blender is added in 136g (1.0mol) phenylenedimethylidyne diamines (XDA) and 500ml toluene
In steel reaction kettle, it is filled with closed system after 330g (5mol) carbonyl fluoride, 2h is reacted at 60 DEG C, is down to room temperature after the reaction was completed,
Using reaction kettle as tower bottom of rectifying tower, direct rectifying adjusts bottom temperature, and guarantee system pressure is 1Mpa, and tower top temperature is -40
DEG C, then tower reactor is warming up to 150 DEG C or so by overhead extraction carbonyl fluoride 184g, the rate of recovery 92.9%, guarantee that system pressure is
0.5Mpa, tower top temperature are 20 DEG C, overhead extraction hydrogen fluoride 36.2g, the rate of recovery 90.5%.Then at 150 DEG C of normal pressure, temperature
Lower reaction 3h removes hydrogen fluoride, and after reaction, tower top refrigerant temperature is 20 DEG C, overhead extraction hydrogen fluoride 35.8g, and the rate of recovery is
89.5%, kettle liquid obtains light yellow liquid benzene dimethylene diisocyanate (XDI) through vacuum distillation recovered solvent toluene 481ml
Crude product 181g, purity 95.0%, product yield 91.4%.Recovered solvent returns to solvent tank.
Embodiment 8A
Difference with embodiment 8 is only that the amount of carbonyl fluoride is 198g (3mol).Gained benzene dimethylene diisocyanate
(XDI) crude product 161.3g, purity 74.9%, product yield 64.2%.
Embodiment 8B
Difference with embodiment 8 is only that the amount of carbonyl fluoride is 495g (7.5mol).Gained phenylenedimethylidyne diisocyanate
Ester (XDI) crude product 193.5g, purity 78.1%, product yield 80.3%.
Embodiment 9
137g (1.2mol) 1,4- cyclohexane diamine (CHDA) and 500ml m-dichlorobenzene are added to the 1.5L for having blender
In stainless steel cauldron, it is filled with closed system after 356.4g (5.4mol) carbonyl fluoride, 2h is reacted at 60 DEG C, is dropped after the reaction was completed
To room temperature, using reaction kettle as tower bottom of rectifying tower, direct rectifying adjusts bottom temperature, and guarantee system pressure is 1Mpa, tower top temperature
Degree is -40 DEG C, overhead extraction carbonyl fluoride 179g, then tower reactor is warming up to 140 DEG C or so by the rate of recovery 90.4%, guarantees system
System pressure is 0.5Mpa, and tower top temperature is 20 DEG C, overhead extraction hydrogen fluoride 40.2g, the rate of recovery 83.8%.Then normal pressure,
3h is reacted at 140 DEG C of temperature and removes hydrogen fluoride, and after reaction, tower top refrigerant temperature is 20 DEG C, overhead extraction hydrogen fluoride
42.6g, the rate of recovery 88.8%, kettle liquid obtain Isosorbide-5-Nitrae-hexamethylene diisocyanate through vacuum distillation recovered solvent m-dichlorobenzene 485ml
Ester (CHDI) crude product 188.2g, purity 96.0%, product yield 90.6%.Recovered solvent returns to solvent tank.
Embodiment 9A
Difference with embodiment 9 is only that the amount of carbonyl fluoride is 316.8g (4.8mol).Two isocyanide of gained 1,4- hexamethylene
Acid esters (CHDI) crude product 203.0g, purity 78.8%, product yield 80.2%.
Embodiment 9B
Difference with embodiment 9 is only that the amount of carbonyl fluoride is 475.2g (7.2mol).Two isocyanide of gained 1,4- hexamethylene
Acid esters (CHDI) crude product 217.3g, purity 74.8%, product yield 81.5%.
Embodiment 10
118g (1.2mol) cyclohexylamine (CHA) and 500ml toluene are added to the 1.5L stainless steel cauldron for having blender
In, it is filled with closed system after 213.8g (3.24mol) carbonyl fluoride, 3h is reacted at 50 DEG C, is down to room temperature after the reaction was completed, with anti-
Answer kettle as tower bottom of rectifying tower, direct rectifying adjusts bottom temperature, and guarantee system pressure is 1Mpa, and tower top temperature is -40 DEG C,
Then tower reactor is warming up to 140 DEG C or so by overhead extraction carbonyl fluoride 124g, the rate of recovery 92.1%, guarantee that system pressure is
0.5Mpa, tower top temperature are 20 DEG C, overhead extraction hydrogen fluoride 20g, the rate of recovery 83.3%.Then at normal pressure, 140 DEG C of temperature
It reacts 3h and removes hydrogen fluoride, after reaction, tower top refrigerant temperature is 20 DEG C, overhead extraction hydrogen fluoride 20.3g, and the rate of recovery is
84.6%, kettle liquid obtains cyclohexyl isocyanate (CHI) crude product 148.8g, purity through vacuum distillation recovered solvent toluene 479ml
93.0%, product yield 93.3%.Recovered solvent solvent tank.
Embodiment 10A
Difference with embodiment 10 is only that the amount of carbonyl fluoride is 142.5g (2.16mol).Gained cyclohexyl isocyanate
(CHI) crude product 152g, purity 83.7%, product yield 85.5%.
Embodiment 10B
Difference with embodiment 10 is only that the amount of carbonyl fluoride is 277.2g (4.2mol).Gained cyclohexyl isocyanate
(CHI) crude product 153.9g, purity 84.6%, product yield 87.5%.
Embodiment 11
It is stainless that the 1.5L with blender is added in 287g (1.5mol) p-chloro benzenesulfonamide (CPSA) and 500ml dimethylbenzene
In steel reaction kettle, it is filled with closed system after 227.7g (3.45mol) carbonyl fluoride, 2h is reacted at 80 DEG C, is down to after the reaction was completed
Room temperature, using reaction kettle as tower bottom of rectifying tower, direct rectifying adjusts bottom temperature, and guarantee system pressure is 1Mpa, tower top temperature
It is -40 DEG C, then tower reactor is warming up to 140 DEG C or so by overhead extraction carbonyl fluoride 110g, the rate of recovery 92.6%, guarantee system
Pressure is 0.5Mpa, and tower top temperature is 20 DEG C, overhead extraction hydrogen fluoride 25.6g, the rate of recovery 85.3%.Then in normal pressure, temperature
Reaction 3h removes hydrogen fluoride at 140 DEG C of degree, and after reaction, tower top refrigerant temperature is 20 DEG C, overhead extraction hydrogen fluoride 24.3g,
The rate of recovery is 81%, and kettle liquid is obtained through vacuum distillation recovered solvent dimethylbenzene 484ml to chlorobenzenesulfonyl isocyanates (CPSI) crude product
311.3g, purity 94.0%, product yield 89.7%.Recovered solvent returns to solvent tank.
Embodiment 11A
Difference with embodiment 11 is only that the amount of carbonyl fluoride is 158.4g (2.4mol).Gained is to chlorobenzenesulfonyl isocyanic acid
Ester (CPSI) crude product 330.6g, purity 74.6%, product yield 75.6%.
Embodiment 11B
Difference with embodiment 11 is only that the amount of carbonyl fluoride is 316.8g (4.8mol).Gained is to chlorobenzenesulfonyl isocyanic acid
Ester (CPSI) crude product 338.2g, purity 79.4%, product yield 82.3%.
Embodiment 12
Trans- -4- methylcyclohexyl the amine (HTDA) of 167g (1.5mol) and 500ml dimethylbenzene are added with blender
In 1.5L stainless steel cauldron, it is filled with closed system after 248g (3.75mol) carbonyl fluoride, 3h is reacted at 50 DEG C, reaction is completed
After be down to room temperature, using reaction kettle as tower bottom of rectifying tower, direct rectifying, adjust bottom temperature, guarantees system pressure be 1Mpa, tower
Pushing up temperature is -40 DEG C, overhead extraction carbonyl fluoride 139g, then tower reactor is warming up to 140 DEG C or so by the rate of recovery 93.6%, is protected
Card system pressure is 0.5Mpa, and tower top temperature is 20 DEG C, overhead extraction hydrogen fluoride 26.6g, the rate of recovery 88.7%.Then normal
It presses, reaction 3h removing hydrogen fluoride at 140 DEG C of temperature, after reaction, tower top refrigerant temperature is 20 DEG C, overhead extraction hydrogen fluoride
25.8g, the rate of recovery 86%, kettle liquid obtain trans- -4- methylcyclohexyl isocyanide through vacuum distillation recovered solvent dimethylbenzene 480ml
Acid esters (HTDI) crude product 193.6g, purity 95.0%, product yield 89.5%.Recovered solvent returns to solvent tank.
Embodiment 12A
Difference with embodiment 12 is only that the amount of carbonyl fluoride is 198g (3mol).Trans- -4- the methylcyclohexyl of gained is different
Cyanate (HTDI) crude product 215.1g, purity 74.9%, product yield 78.4%.
Embodiment 12B
Difference with embodiment 12 is only that the amount of carbonyl fluoride is 277.2g (4.2mol).Trans- -4- the methyl cyclohexane of gained
Based isocyanate (HTDI) crude product 221.0g, purity 75.6%, product yield 81.3%.
Embodiment 13
Bis- (alpha-amido isopropyl) benzene of 288g (1.5mol) 1,3- and 500ml dimethylbenzene are added to the 1.5L for having blender
In stainless steel cauldron, it is filled with closed system after 455.4g (6.9mol) carbonyl fluoride, 3h is reacted at 50 DEG C, is dropped after the reaction was completed
To room temperature, using reaction kettle as tower bottom of rectifying tower, direct rectifying adjusts bottom temperature, and guarantee system pressure is 1Mpa, tower top temperature
Degree is -40 DEG C, overhead extraction carbonyl fluoride 240g, then tower reactor is warming up to 140 DEG C or so by the rate of recovery 93.2%, guarantees system
System pressure is 0.5Mpa, and tower top temperature is 20 DEG C, overhead extraction hydrogen fluoride 54.8g, the rate of recovery 91.3%.Then normal pressure,
3h is reacted at 140 DEG C of temperature and removes hydrogen fluoride, and after reaction, tower top refrigerant temperature is 20 DEG C, overhead extraction hydrogen fluoride
53.8g, the rate of recovery 89.7%, kettle liquid obtain the (1- isocyano -1- of 1,3- bis- through vacuum distillation recovered solvent dimethylbenzene 480ml
Methylethyl) benzene (TMXDI) crude product 377.0g, purity 81.6%, product yield 83.8%.Recovered solvent returns to solvent storage
Tank.
Embodiment 13A
Difference with embodiment 13 is only that the amount of carbonyl fluoride is 435.6g (6.6mol).(the 1- isocyanic acid of gained 1,3- bis-
Root -1- Methylethyl) benzene crude product 347.2g, purity 74.1%, product yield 70.2%.
Embodiment 13B
Difference with embodiment 13 is only that the amount of carbonyl fluoride is 561g (8.5mol).(the 1- isocyano-of gained 1,3- bis-
1- Methylethyl) benzene crude product 349.9g, purity 75.3%, product yield 71.9%.
Embodiment 14
It is anti-that the 1.5L stainless steel with blender is added in 191g (1.5mol) parachloroanilinum (CPA) and 500ml dimethylbenzene
It answers in kettle, is filled with closed system after 264g (4.0mol) carbonyl fluoride, 2h is reacted at 50 DEG C, is down to room temperature after the reaction was completed, with
Reaction kettle adjusts bottom temperature as tower bottom of rectifying tower, direct rectifying, and guarantee system pressure is 1Mpa, and tower top temperature is -40
DEG C, then tower reactor is warming up to 140 DEG C or so by overhead extraction carbonyl fluoride 154g, the rate of recovery 93.1%, guarantee that system pressure is
0.5Mpa, tower top temperature are 20 DEG C, overhead extraction hydrogen fluoride 25.6g, the rate of recovery 85.3%.Then at 140 DEG C of normal pressure, temperature
Lower reaction 3h removes hydrogen fluoride, and after reaction, tower top refrigerant temperature is 20 DEG C, overhead extraction hydrogen fluoride 26.4g, and the rate of recovery is
88.0%, kettle liquid obtains chlorophenyl isocyanate (CPI) crude product 246.2g, purity through vacuum distillation recovered solvent dimethylbenzene 475ml
83.7%, product yield 89.5%.Recovered solvent returns to solvent tank.
Embodiment 14A
Difference with embodiment 14 is only that the amount of carbonyl fluoride is 198g (3.0mol).Gained chlorophenyl isocyanate crude product
223.3g, purity 73.3%, product yield 71.1%.
Embodiment 14B
Difference with embodiment 14 is only that the amount of carbonyl fluoride is 297g (4.5mol).Gained chlorophenyl isocyanate crude product
238.4g, purity 81.9%, product yield 84.8%.
Embodiment 15
It is stainless that the 1.5L with blender is added in 243g (1.5mol) 3,5- dichloroaniline (DCPA) and 500ml dimethylbenzene
In steel reaction kettle, it is filled with closed system after 264g (4.0mol) carbonyl fluoride, 2h is reacted at 50 DEG C, is down to room after the reaction was completed
Temperature, using reaction kettle as tower bottom of rectifying tower, direct rectifying adjusts bottom temperature, and guarantee system pressure is 1Mpa, tower top temperature
It is -50 DEG C, then tower reactor is warming up to 160 DEG C or so by overhead extraction carbonyl fluoride 145, the rate of recovery 87.9%, guarantee system pressure
Power is 0.5Mpa, and tower top temperature is 20 DEG C, overhead extraction hydrogen fluoride 25.6g, the rate of recovery 85.3%.Then in normal pressure, temperature
3h is reacted at 140 DEG C and removes hydrogen fluoride, and after reaction, tower top refrigerant temperature is 20 DEG C, overhead extraction hydrogen fluoride 26.9g, is returned
Yield is 89.7%, and kettle liquid obtains 3,5- dichloro phenylisocyanate (DCPI) crude product through vacuum distillation recovered solvent dimethylbenzene 469ml
305.4g, purity 83.1%, product yield 90.0%.Recovered solvent returns to solvent tank.
Embodiment 15A
Difference with embodiment 15 is only that the amount of carbonyl fluoride is 205g (3.1mol).Gained 3,5- dichloro phenylisocyanate
Crude product 262.9g, purity 75.1%, product yield 70.0%.
Embodiment 15B
Difference with embodiment 15 is only that the amount of carbonyl fluoride is 297g (4.5mol).Gained 3,5- dichloro phenylisocyanate
Crude product 274.0g, purity 74.2%, product yield 72.1%.
As it appears from the above, as each-NH2When corresponding carbonyl fluoride molar ratio is 1:2.3~1:2.7, it can obtain more
Excellent purity and product yield.
Unless expressly excluded or otherwise limited, cited herein every document, including any intersection
Reference or relevant patent or patent application, are incorporated by herein hereby.Although having used specific embodiment party
Case illustrate and describes the present invention, but it is obvious for those of skill in the art that, without departing substantially from the present invention
Spirit and scope in the case where can make many other variations and variations.Therefore, it is intended to cover in appended claim
All these changes and modification in the scope of the invention.
Claims (23)
1. a kind of react the method for preparing corresponding isocyanates to amine using carbonyl fluoride, which comprises (1) amine and carbonyl fluoride
Acylation reaction occurs under closed environment, suitable reaction condition, in anhydrous inert organic solvent and generates intermediate carbamyl
Fluorine；(2) when normal pressure, under suitable reaction condition, intermediate carbamyl fluoride dehydrofluorination obtains target isocyanates；
Wherein, each-NH2Corresponding carbonyl fluoride molar ratio is 1:2.3~1:2.7；
Wherein, the amine is selected from: 2,6- difluorobenzamides (DFBA), 5-trifluoromethylaniline (TFMPA), paranitroanilinum
(NA), phenylenedimethylidyne diamines, p-chloro benzenesulfonamide (CPSA), 1,3- bis- (alpha-amido isopropyl) benzene, parachloroanilinum (CPA),
3,5- dichloroaniline (DCPA).
2. according to the method described in claim 1, wherein, inert organic solvents are selected from alkyl aromatic, halogenated aryl hydrocarbon, halogenated rouge
Fat hydrocarbon, aliphatic ester compounds or aromatic series ester type compound, aliphatic hydrocarbon organic solvent.
3. according to the method described in claim 2, the inert organic solvents be selected from toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, 1,
One of 3,5- trimethylbenzene, dichloroethanes, pentachloroethane are a variety of.
4. according to the method described in claim 1, step (1) the suitable acylation reaction condition is 25~120 DEG C of temperature, instead
1~5h between seasonable；Step (2) the suitable dehydrofluorination reaction conditions are 60~260 DEG C of temperature, heat 1~5h of reaction time.
5. method according to any one of claims 1 to 4, preferably 25~80 DEG C of acylation reaction temperature, the reaction time 1~
3h；It is preferred that each-NH2Corresponding carbonyl fluoride molar ratio is 1:2.3~1:2.7；It is preferred that dehydrofluorination temperature 80~160
DEG C, 1~3h of reaction time.
6. a kind of react the method for preparing corresponding isocyanates to amine using carbonyl fluoride, which comprises (1) amine and carbonyl fluoride
Acylation reaction occurs under closed environment, suitable reaction condition, in anhydrous inert organic solvent and generates intermediate carbamyl
Fluorine；(2) when normal pressure, under suitable reaction condition, intermediate carbamyl fluoride dehydrofluorination obtains target isocyanates；
Wherein, each-NH2Corresponding carbonyl fluoride molar ratio is 1:2.3~1:2.7；
Wherein, the amine is selected from the amine for meeting following general formula
Wherein, R is selected from halogen, nitro, trifluoromethyl or C1-C6Alkyl, the integer that m is 0 to 6,
R2Selected from key or C1-C6Alkyl, x are 1 or 2.
7. according to the method described in claim 6, wherein, the amine is selected from: isophorone diamine (IPDA), Isosorbide-5-Nitrae-hexamethylene two
Amine (CHDA), cyclohexylamine (CHA), trans- -4- methylcyclohexyl amine (HTDA).
8. according to the method described in claim 6, wherein, inert organic solvents are selected from alkyl aromatic, halogenated aryl hydrocarbon, halogenated rouge
Fat hydrocarbon, aliphatic ester compounds or aromatic series ester type compound, aliphatic hydrocarbon organic solvent.
9. according to the method described in claim 8, the inert organic solvents be selected from toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, 1,
One of 3,5- trimethylbenzene, dichloroethanes, pentachloroethane are a variety of.
10. according to the method described in claim 6, step (1) the suitable acylation reaction condition be 25~120 DEG C of temperature,
1~5h of reaction time；Step (2) the suitable dehydrofluorination reaction conditions are 60~260 DEG C of temperature, the heating reaction time 1~
5h。
11. according to the described in any item methods of claim 6 to 10, preferred 25~80 DEG C of acylation reaction temperature, the reaction time 1
~3h；It is preferred that each-NH2Corresponding carbonyl fluoride molar ratio is 1:2.3~1:2.7；It is preferred that dehydrofluorination temperature 80~
160 DEG C, 1~3h of reaction time.
12. a kind of react the method for preparing corresponding isocyanates to amine using carbonyl fluoride, which comprises (1) amine and phosphinylidyne
Fluorine occurs acylation reaction under closed environment, suitable reaction condition, in anhydrous inert organic solvent and generates intermediate amino first
Acyl fluorides；(2) when normal pressure, under suitable reaction condition, intermediate carbamyl fluoride dehydrofluorination obtains target isocyanates；
Wherein, each-NH2Corresponding carbonyl fluoride molar ratio is 1:2.3~1:2.7；
Wherein, the amine is selected from the amine for meeting following general formula
Wherein, R is selected from halogen, nitro, trifluoromethyl or C1-C6Alkyl, the integer that a is 0 to 4,
R1Selected from key or C1-C6Alkyl,
R3Selected from key, hexafluoroisopropylidenyl, sulfonyl or C1-C6Alkylidene.
13. according to the method for claim 12, wherein the amine is selected from: 4,4`- sulphonyl diphenyl diamines (BSDA), 4,4
`- hexafluoroisopropylidenyl diphenyl diamine (HFPDA).
14. according to the method for claim 12, wherein inert organic solvents are selected from alkyl aromatic, halogenated aryl hydrocarbon, halogenated
Aliphatic hydrocarbon, aliphatic ester compounds or aromatic series ester type compound, aliphatic hydrocarbon organic solvent.
15. according to the method for claim 14, the inert organic solvents be selected from toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes,
One of 1,3,5- trimethylbenzene, dichloroethanes, pentachloroethane are a variety of.
16. according to the method for claim 12, step (1) the suitable acylation reaction condition is 25~120 DEG C of temperature,
1~5h of reaction time；Step (2) the suitable dehydrofluorination reaction conditions are 60~260 DEG C of temperature, the heating reaction time 1~
5h。
17. 2 to 16 described in any item methods according to claim 1, preferably 25~80 DEG C of acylation reaction temperature, reaction time
1~3h；It is preferred that each-NH2Corresponding carbonyl fluoride molar ratio is 1:2.3~1:2.7；It is preferred that dehydrofluorination temperature 80~
160 DEG C, 1~3h of reaction time.
18. a kind of react the method for preparing corresponding isocyanates to amine using carbonyl fluoride, which comprises (1) amine and phosphinylidyne
Fluorine occurs acylation reaction under closed environment, suitable reaction condition, in anhydrous inert organic solvent and generates intermediate amino first
Acyl fluorides；(2) when normal pressure, under suitable reaction condition, intermediate carbamyl fluoride dehydrofluorination obtains target isocyanates；
Wherein, each-NH2Corresponding carbonyl fluoride molar ratio is 1:2.3~1:2.7；
Wherein, the amine is selected from the amine for meeting following general formula
Wherein, R is selected from halogen, nitro, trifluoromethyl or C1-C6Alkyl, the integer that m is 0 to 6,
R2Selected from key or C1-C6Alkyl,
R3Selected from key, sulfonyl or C1-C6Alkylidene.
19. according to the method for claim 18, wherein the amine are as follows: dicyclohexyl methyl hydride -4,4'- diamines (H12MDA)。
20. according to the method for claim 18, wherein inert organic solvents are selected from alkyl aromatic, halogenated aryl hydrocarbon, halogenated
Aliphatic hydrocarbon, aliphatic ester compounds or aromatic series ester type compound, aliphatic hydrocarbon organic solvent.
21. according to the method for claim 20, the inert organic solvents be selected from toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes,
One of 1,3,5- trimethylbenzene, dichloroethanes, pentachloroethane are a variety of.
22. according to the method for claim 18, step (1) the suitable acylation reaction condition is 25~120 DEG C of temperature,
1~5h of reaction time；Step (2) the suitable dehydrofluorination reaction conditions are 60~260 DEG C of temperature, the heating reaction time 1~
5h。
23. 8 to 22 described in any item methods according to claim 1, preferably 25~80 DEG C of acylation reaction temperature, reaction time
1~3h；It is preferred that each-NH2Corresponding carbonyl fluoride molar ratio is 1:2.3~1:2.7；It is preferred that dehydrofluorination temperature 80~
160 DEG C, 1~3h of reaction time.
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|---|---|---|---|---|
| US3795689A (en) * | 1971-07-09 | 1974-03-05 | Allied Chem | Process for preparing fluoroperhaloalkyl isocyanates |
| US3991108A (en) * | 1973-10-31 | 1976-11-09 | Robert Kenneth Jordan | Carboxylate fluorination process |
| CN102056895A (en) * | 2008-06-09 | 2011-05-11 | 独立行政法人产业技术总合研究所 | Method for producing isocyanate compound |
| CN105837475A (en) * | 2016-05-17 | 2016-08-10 | 北京宇极科技发展有限公司 | Method for preparing p-toluenesulfonyl isocyanate with carbonyl fluoride |
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|---|---|---|---|---|
| US3795689A (en) * | 1971-07-09 | 1974-03-05 | Allied Chem | Process for preparing fluoroperhaloalkyl isocyanates |
| US3991108A (en) * | 1973-10-31 | 1976-11-09 | Robert Kenneth Jordan | Carboxylate fluorination process |
| CN102056895A (en) * | 2008-06-09 | 2011-05-11 | 独立行政法人产业技术总合研究所 | Method for producing isocyanate compound |
| CN105837475A (en) * | 2016-05-17 | 2016-08-10 | 北京宇极科技发展有限公司 | Method for preparing p-toluenesulfonyl isocyanate with carbonyl fluoride |
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