CN105016943A - Preparation methods of nitrile and corresponding amine - Google Patents
Preparation methods of nitrile and corresponding amine Download PDFInfo
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- CN105016943A CN105016943A CN201410156039.2A CN201410156039A CN105016943A CN 105016943 A CN105016943 A CN 105016943A CN 201410156039 A CN201410156039 A CN 201410156039A CN 105016943 A CN105016943 A CN 105016943A
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Abstract
The invention relates to a preparation method of nitrile. Compared with the prior art, the preparation method has the characteristics of obvious reduction of the usage amount of ammonia sources, low environmental pressure, low energy consumption, low production cost, high purity and yields of nitrile products, and the like, and can be used for obtaining nitrile with a more complex structure. The invention also relates to a method for preparing corresponding amine with nitrile.
Description
Technical field
The present invention relates to a kind of manufacture method of nitrile and manufactured the method for corresponding amine by this nitrile.
Background technology
Alicyclic polynitriles such as alicyclic dinitrile is very important chemical intermediate, it and derivative thereof have purposes widely, such as, the cycloalphatic diamine of one of its derivative just has special character, extensive application in dyestuff, medicine, solidifying agent and high molecular polymer etc.
The preparation method of alicyclic dinitrile is substantially all with existing simple nitrile compounds for raw material is obtained by certain reaction, these methods the substrate spectrum that is suitable for very narrow, severe reaction conditions, is not suitable for suitability for industrialized production.
Present stage, the preparation method of aliphatic polybasic nitrile mainly adopts carboxylic acid ammoniation process, but then rarely has report about the technology being manufactured alicyclic polynitriles by carboxylic acid ammoniation process.
But, the present inventor is found by research, prior art is when manufacturing corresponding aliphatic polybasic nitrile by aliphatic polycarboxylic acid's ammoniation process, fully carry out to make aminating reaction, this technology must continue supply (passing into) ammonia source (ammonia) as raw material in the whole ammonifying process of carboxylic acid or within the longer reaction times in reaction system, therefore ammonia usage is huge, cause the actual amount of ammonia considerably beyond the consumption needed for aminating reaction, may be the thousands of times of real reaction requirement, cause the utilization ratio of ammonia extremely low thus.In addition, because the utilization ratio of ammonia is extremely low, this aminating reaction creates a large amount of deposed ammonias but cannot recycle, exerts heavy pressures on, be not inconsistent with the environmental protection production theory followed now after discharge to environment.And, aminating reaction due to this technology have employed overall higher temperature of reaction (such as more than 300 DEG C) and overall longer reaction times, therefore energy consumption is higher, cause production cost higher, and there is the loss of reaction mass in reaction process serious (such as causing reaction mass to be entrained with reaction system because continue to pass into ammonia flow) and side reaction more and cause the quality of nitrile product and yield to be difficult to the problems such as effective raising.In addition, in order to obtain higher nitrile yield, prior art also requires to use the extremely low ammonia of water content as reaction raw materials, and utilizes the ammonia passed into continuously in whole aminating reaction process as entrainment agent, discharges the water of reaction by-product at any time.
Therefore, the current present situation of prior art still needs a kind of manufacture method of alicyclic polynitriles, and its preparation method is simple, is applicable to suitability for industrialized production.
Summary of the invention
The present inventor finds through diligent research on the basis of existing technology, the process transformed from carboxylic acid to nitrile by ammoniation process, need the intermediate steps through forming acid amides, and this intermediate steps only needs can complete in the reaction times under lower temperature of reaction and shorter, and only this intermediate steps just needs the supply in ammonia source, thus the ammoniation process of carboxylic acid is clearly decomposed into two steps of independently carrying out, and find further, by using the nitrile manufacture method with these two particular step, just foregoing problems can be solved, and this completes the present invention.The appearance of this two-step approach novel process, for breaking external monopolization, nitrile compounds and the derived product thereof of development China have very important significance.The invention still further relates to and use this nitrile to manufacture the method for amine.
Specifically, the present invention relates to the content of following aspect.
1. a manufacture method for nitrile, is characterized in that, comprises the following steps:
First step: make carboxylic acid sources and ammonia source at the temperature of reaction T from T1 to T2
alower contact 0.01-2.5 hour (or 0.05-2 hour, or 0.1-1.5 hour, or 0.2-1 hour, or 0.3-0.8 hour) reaction times, obtain acid amides intermediate product, wherein said carboxylic acid sources is selected from the C of alicyclic polycarboxylic acid, described alicyclic polycarboxylic acid
1-4one or more in the acid anhydrides of straight or branched alkyl ester and described alicyclic polycarboxylic acid, the greater in the T1 fusing point that to be described carboxylic acid sources depress at 1 standard atmosphere and temperature value 145 DEG C, T2 is boiling point, the reckling in sublimation temperature Sum decomposition temperature that described alicyclic polycarboxylic acid depresses at 1 standard atmosphere, prerequisite is T2 > T1, preferred T2-T1>=10 DEG C, the ratio in wherein said carboxylic acid sources and described ammonia source makes in the described carboxylic acid sources of carboxyl and with NH
3the mol ratio in described ammonia source of meter reaches 1: 1.1-2.5 (preferably 1: 1.2-2.0, more preferably 1: 1.3-1.6), and second step: by described acid amides intermediate product at the temperature of reaction T from T3 to T4
blower thermal treatment 0.1 to 4.5 hour (or 0.2 to 3 hour, or 0.3 to 2 hour, or 0.4 to 1.2 hour, or 0.4 to 1 hour) reaction times, the greater wherein in the T3 fusing point that to be described acid amides intermediate product depress at 1 standard atmosphere and temperature value 225 DEG C, T4 is boiling point, the reckling in sublimation temperature Sum decomposition temperature that described acid amides intermediate product is depressed at 1 standard atmosphere, and prerequisite is T4 > T3, preferred T4-T3>=10 DEG C.
2. the manufacture method of the nitrile described in any preceding aspect, wherein said temperature of reaction T
afor from T1 ' to T2 ', wherein T1 '=T1+5 DEG C (or T1+10 DEG C or T1+20 DEG C or T1+30 DEG C or T1+40 DEG C or T1+50 DEG C or T1+60 DEG C or T1+70 DEG C or T1+80 DEG C or T1+90 DEG C), T2 '=T2 (or T2-5 DEG C or T2-10 DEG C or T2-20 DEG C or T2-30 DEG C or T2-40 DEG C or T2-50 DEG C or 310 DEG C), prerequisite is T2 ' > T1 '; Described temperature of reaction T
bfor from T3 ' to T4 ', wherein T3 '=T3+5 DEG C (or T3+10 DEG C or T3+20 DEG C or T3+30 DEG C or T3+40 DEG C or T3+50 DEG C or T3+60 DEG C or T3+70 DEG C or T3+80 DEG C), T4 '=T4 (or T4-5 DEG C or T4-10 DEG C or T4-20 DEG C or T4-30 DEG C or T4-40 DEG C or T4-50 DEG C or 350 DEG C), prerequisite is T4 ' > T3 '.
3. the manufacture method of the nitrile described in any preceding aspect, wherein T1 is 145 DEG C (or 150 DEG C, or 160 DEG C, or 170 DEG C, or 180 DEG C, or 190 DEG C, or 200 DEG C, or 210 DEG C, or 220 DEG C, or 230 DEG C, or 240 DEG C, or 250 DEG C, or 260 DEG C, or 270 DEG C, or 280 DEG C, or 290 DEG C, or 300 DEG C), T2 is 310 DEG C (or 300 DEG C, or 290 DEG C, or 280 DEG C, or 270 DEG C, or 260 DEG C, or 250 DEG C, or 240 DEG C, or 230 DEG C, or 220 DEG C, or 210 DEG C, or 200 DEG C, or 190 DEG C, or 180 DEG C), T3 is 225 DEG C (or 230 DEG C, or 240 DEG C, or 250 DEG C, or 260 DEG C, or 270 DEG C, or 280 DEG C, or 290 DEG C, or 300 DEG C, or 310 DEG C), T4 is 350 DEG C (or 340 DEG C, or 330 DEG C, or 320 DEG C, or 310 DEG C, or 300 DEG C, or 290 DEG C, or 280 DEG C, or 270 DEG C).
4. the manufacture method of the nitrile described in any preceding aspect, wherein said first step carries out in closed reaction system, and described second step carries out in open reactive system or closed reaction system.
5. the manufacture method of the nitrile described in any preceding aspect, wherein said first step does not use catalyzer, and described second step carries out in the presence of a catalyst or do not use catalyzer.
6. the manufacture method of the nitrile described in any preceding aspect, wherein said ammonia source be ammonia or produce ammoniacal substance (be preferably selected from urea, cyanic acid, volatile salt, bicarbonate of ammonia and ammonium chloride one or more, be preferably selected from urea and bicarbonate of ammonia one or more, more preferably bicarbonate of ammonia), preferred Industry Waste ammonia, its ammonia content is 60-99.9wt%, preferred 80-99.9wt%.
7. the manufacture method of the nitrile described in any preceding aspect, wherein said carboxylic acid sources is the carboxylic acid shown in following table, the acid anhydrides of this carboxylic acid or methyl esters, in described first step, temperature of reaction T
aas shown in the table, the reaction times is 0.05-2 hour, or 0.1-1.5 hour, or 0.2-1 hour, or 0.3-0.8 hour, in described second step, and temperature of reaction T
bas shown in the table, the reaction times is 0.2 to 3 hour, or 0.3 to 2 hour, or 0.4 to 1.2 hour, or 0.4 to 1 hour.
| Carboxylic acid | Temperature of reaction T A，℃ | Temperature of reaction T B，℃ |
| Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid | 185 to 225 | 245 to 300 |
| 1,2-cyclohexyl dicarboxylic acid | 200 to 265 | 290 to 315 |
| 4-tetrahydrobenzene-1,2-dioctyl phthalate | 200 to 265 | 290 to 310 |
| 1,1-ring fourth dioctyl phthalate | 185 to 245 | 270 to 300 |
| 5-norbornylene-2,3-dioctyl phthalate | 195 to 240 | 275 to 305 |
| 1,3-adamantane acid | 285 to 300 | 315 to 325 |
| 1,3-ring penta dioctyl phthalate | 150 to 195 | 235 to 285 |
| 1,2,3,4-ring penta tetracarboxylic acid | 205 to 260 | 285 to 315 |
| 1,3,5-hexamethylene tricarboxylic acid | 235 to 270 | 300 to 325 |
| 1,2,4,5-hexamethylene tetracarboxylic acid | 180 to 225 | 255 to 300 |
| 1,2,3,4-ring fourth tetracarboxylic acid | 200 to 245 | 275 to 305 |
| 4-methyl-4-tetrahydrobenzene-1,2-dioctyl phthalate | 235 to 275 | 300 to 325 |
| 1,3,5,7-diamantane tetracarboxylic acid | 300 to 310 | 325 to 350 |
| Isosorbide-5-Nitrae-cyclohexanedione-2,5-dioctyl phthalate | 155 to 200 | 245 to 295 |
| 1，4-cyclohexadiene-Isosorbide-5-Nitrae-dioctyl phthalate | 160 to 205 | 255 to 290 |
| 2,2-nitrogen heterocyclic third dioctyl phthalate | 145 to 185 | 225 to 280 |
| 3,3-oxa-ring fourth dioctyl phthalate | 165 to 200 | 250 to 295 |
| 4,5-isoxazole dioctyl phthalate | 170 to 205 | 250 to 300 |
| 2,3-oxygen Polymorphs dioctyl phthalate | 160 to 200 | 235 to 285 |
| Pyrans-2,6-dioctyl phthalate | 155 to 200 | 240 to 290 |
| DOX-2-methyl-4.5-dioctyl phthalate | 150 to 195 | 245 to 295 |
| 1,3-Pyrimidine-2-methyl-4,5-dioctyl phthalate | 145 to 185 | 235 to 275 |
| 3,4-diamino-2,5-oxygen Polymorphs dioctyl phthalate | 165 to 210 | 240 to 290 |
| 2-methyl-3,4-thiophenedicarboxylic acid | 175 to 225 | 255 to 300 |
| 2,6-thiomorpholine dioctyl phthalate | 145 to 190 | 235 to 280 |
| 3,4-dihydroxyl-2,5-oxygen Polymorphs dioctyl phthalate | 145 to 195 | 240 to 305 |
| 4-acetoxyl heptanaphthenic acid | 185 to 225 | 245 to 300 |
| 4-propionyloxy heptanaphthenic acid | 185 to 225 | 245 to 300 |
| 4-caproyl heptanaphthenic acid | 185 to 225 | 245 to 300 |
| 4-lauric acid base heptanaphthenic acid | 185 to 225 | 245 to 300 |
| 2-nitro-4-caproyl heptanaphthenic acid | 175 to 230 | 245 to 300 |
8. the manufacture method of the nitrile described in any preceding aspect, wherein said alicyclic polycarboxylic acid be selected from the compound with following structural formula one or more:
Wherein, group
for the n valency C optionally replaced
3-20naphthenic hydrocarbon ring, the optional n valency C replaced
3-20cycloolefin ring or the optional n valency C replaced
2-20heterocycle; N-1 group B is singly-bound, the optional divalent C replaced independently of one another
3-20naphthenic hydrocarbon ring, the optional divalent C replaced
3-20cycloolefin ring, the optional divalent C replaced
6-20aromatic ring, the optional divalent C replaced
4-20hetero-aromatic ring, the optional divalent C replaced
2-20heterocycle or the optional divalent combination group replaced are preferably singly-bound independently of one another; When n-1 group B is singly-bound, the optional divalent C replaced independently of one another
3-20naphthenic hydrocarbon ring, the optional divalent C replaced
3-20cycloolefin ring or the optional divalent C replaced
2-20during heterocycle, n-1 radicals R is singly-bound or the optional divalent aliphatics hydrocarbon chain replaced independently of one another; When n-1 group B is the optional divalent C replaced independently of one another
6-20aromatic ring, the optional divalent C replaced
4-20when hetero-aromatic ring or the optional divalent replaced combine group, n-1 radicals R is the optional divalent aliphatics hydrocarbon chain replaced independently of one another; Aliphatics hydrocarbon chain in each definition is selected from C independently of one another
1-15(preferred C
1-9) saturated or undersaturated straight or branched hydrocarbon chain, be preferably selected from C independently of one another
1-15(preferred C
1-9) straight or branched alkane chain, C
2-15(preferred C
2-9) straight or branched alkene chain or C
2-15(preferred C
2-9) straight or branched alkynes chain, be more preferably selected from C independently of one another
1-15(preferred C
1-9) straight or branched alkane chain or C
2-15(preferred C
2-9) straight or branched alkene chain; When the carbonatoms of described aliphatics hydrocarbon chain is more than 2 and comprises C-C singly-bound in its molecular chain, optionally between two carbon atoms of this C-C singly-bound, insert-O-,-S-or-NR
1-(R
1h or C
1-4straight or branched alkyl); N is the integer of 2 to 10, preferably the integer of 2 to 5, more preferably the integer of 2 to 4, further preferably 2 or 3.
9. the manufacture method of the nitrile described in any preceding aspect, wherein said first step also obtains containing ammonia effluent while the described acid amides intermediate product of acquisition, and using described containing in ammonia effluent circulation-supplied to described first step as described ammonia source supplement or a part of, preferably described containing ammonia effluent be fed to through concentrated or dry Posterior circle in described first step as described ammonia source supplement or a part of.
10. a manufacture method for amine, is characterized in that, comprises the following steps:
First step: manufacture nitrile according to the manufacture method described in any preceding aspect; With
Second step: the nitrile that hydrogenation first step obtains manufactures amine.
Technique effect
Compared with prior art, the present invention has the following advantages.
According to nitrile manufacture method of the present invention, only supply ammonia source (such as ammonia etc.) in a first step, and stop the supply in ammonia source in the second step completely, therefore the consumption in ammonia source can significantly reduce, and drastically increases the utilization ratio in ammonia source.
According to nitrile manufacture method of the present invention, because the utilization ratio in ammonia source significantly improves, therefore effectively can reduce the deposed ammonia amount that reaction produces, environmental stress is little, conforms to the environmental protection production theory followed now.
According to nitrile manufacture method of the present invention, strict requirement be there is no to the water content in ammonia source, even directly can use the ammoniacal liquor of ammoniacal liquor or vaporization, do not need the entrainment agent utilizing this ammonia source as water byproduct yet.And, according to nitrile manufacture method of the present invention, find that the deposed ammonia that aminating reaction produces or useless ammonia (being referred to as below containing ammonia effluent) directly can be introduced in the first step of this manufacture method as the supplementary of ammonia source in this area first time, achieve 100% recycle of ammonia-containing water/gas, reduce further the environmental stress of this manufacture method.
According to nitrile manufacture method of the present invention, temperature of reaction and reaction times significantly reduce generally compared to prior art, show energy consumption reduction, production cost reduction and the simple advantage of manufacture method thus.
According to nitrile manufacture method of the present invention, reaction mechanism is simple, and side reaction is less, and aminating reaction is less by impurity effect, and the purity requirement of this manufacture method to ammonia source and carboxylic acid sources is lower thus, can directly use respective thick product as reaction raw materials.Such as, the present invention found in this area first time, this nitrile manufacture method even can directly use containing ammonia industrial waste or byproduct as ammonia source, thus for the various circulation containing ammonia industrial waste or byproduct or recycling open a new way, meets current environmental protection production theory.
According to nitrile manufacture method of the present invention, reaction conditions is simple, even if do not need catalyzer also can carry out (especially first step) smoothly, this not only reduces the manufacturing cost of nitrile, and also reduces the complexity of nitrile product later separation or purifying.
According to nitrile manufacture method of the present invention, first step carries out the shorter reaction times under lower temperature of reaction, and stop the supply in ammonia source in the second step completely, therefore reaction mass loss (carrying secretly) because ammonia source supply etc. causes can greatly be reduced, according to the difference of nitrile product category, the present invention can obtain more than 75%, more than 80%, more than 90%, the nitrile yield of more than 95%, even more than 98% or higher.
According to nitrile manufacture method of the present invention, reaction conditions is gentle, and the less generation of side reaction, can obtain highly purified nitrile product (such as more than 97%) thus.
According to nitrile manufacture method of the present invention, the more complicated nitrile of structure ((polynary) nitrile such as containing various heteroatoms, unsaturated link(age) or ring structure or (mixing) aromatic series (polynary) nitrile) can be produced by carboxylic acid ammoniation process, this is realize first time in the art, thus has greatly expanded the range of application of carboxylic acid ammoniation process.
According to amine manufacture method of the present invention, be raw material owing to employing high purity nitrile constructed in accordance, therefore show that side reaction is few, the corresponding height of product amine purity, advantage that production cost is low.
Embodiment
Below the specific embodiment of the present invention is described in detail, but it is pointed out that protection scope of the present invention not by the restriction of these embodiments, but determined by claims of annex.
All publications, patent application, patent and other reference that this specification sheets is mentioned all draw in this for reference.Unless otherwise defined, all technology that this specification sheets is used and scientific terminology all have the equivalent that in field belonging to the present invention, those skilled in the art understand.In case of conflict, comprise in being defined in, be as the criterion with this specification sheets.
When this specification sheets with " well known by persons skilled in the art " or " this area conventional known " or similar term describes material, method, parts, device or equipment time, this term represent this specification sheets comprise propose the application time this area routine use those, but also comprise and being also of little use at present, but will become art-recognized for being applicable to those of similar object.
In addition, the various scopes that this specification sheets is mentioned include their end points interior, unless expressly stated otherwise.In addition, when providing scope, one or more preferable range or a lot of preferred upper limit value and preferred lower limit value to amount, concentration or other value or parameter, it should be interpreted as specifically discloses by any all scopes formed any range higher limit or preferred value and any range lower value or preferred value, no matter whether separately disclose these numerical value pair.
In the context of the present specification, unless otherwise defined explicitly, or this implication is beyond the understanding scope of those skilled in the art, hydrocarbon more than 3 carbon atoms or hydrocarbon derivative group (such as propyl group, propoxy-, butyl, butane, butylene, butenyl, hexane etc.) not titled with all have time prefix " just " with titled with implication identical time prefix " just ".Such as, propyl group is generally understood as n-propyl, and butyl is generally understood as normal-butyl.
In the context of the present specification, term " ammonia source " refers to can as any material of ammonia sources (namely providing ammonia) in nitrile manufacture method (first step) of the present invention, comprise the various form goods such as liquid ammonia of ammonia, gaseous ammonia, the ammoniacal liquor of vaporization and ammoniacal liquor etc., under being also included in the reaction conditions of first step (as by hydrolysis or the decomposition reaction such as thermolysis) material (hereinafter referred to as product ammoniacal substance) of ammonia can be produced, such as urea can be enumerated, the ammonium salt (such as volatile salt and bicarbonate of ammonia) etc. of cyanic acid and mineral acid.According to nitrile manufacture method of the present invention, reaction mechanism is simple, and side reaction is less, and aminating reaction is less by impurity effect, and the purity requirement of this manufacture method to ammonia source is lower thus.Given this, in the context of the present specification, term " ammonia source " also comprises containing ammonia or the industrial waste or the industry byproduct that contain aforementioned product ammoniacal substance, comprise various industrial waste or the industry byproduct of gaseous state, liquid state or solid-state form, such as ammonia-containing exhaust (such as from ammonia synthesis process), useless ammonia, deposed ammonia (such as from the nitrile manufacture method of prior art), useless urea water, useless carbon ammonium water etc.Generally speaking, as long as the kind of the impurity in this industrial waste or byproduct except ammonia and water or content do not make a significant impact (such as making the reduction of nitrile yield be no more than 5%) to nitrile manufacture method of the present invention and can directly use, and without the need to carrying out purification process in advance to it.This kind of impurity is generally chemically inert for nitrile manufacture method of the present invention, such as can enumerate hydrogen, nitrogen, air, water vapour or liquid water etc., sometimes be regarded as the inert diluent of this manufacture method.Certainly, those skilled in the art are by simple test (the reduction degree as by measuring nitrile yield), just can confirm whether a certain industrial waste or industry byproduct contain or excessively containing the impurity made a significant impact nitrile manufacture method of the present invention, confirm whether it can directly apply to nitrile manufacture method of the present invention thus.In addition, as required, those skilled in the art also can by conventional known technique means, this kind of impurity contained in a certain industrial waste or industry byproduct is reduced to the level that not remarkably influenced nitrile manufacture method of the present invention is implemented, and as required, the concentration of ammonia in a certain industrial waste or industry byproduct is concentrated into the level (such as the concentration of ammonia or product ammoniacal substance being concentrated into the 10-95wt% accounting for this industrial waste or industry byproduct total amount, preferred 25-95wt%) that nitrile manufacture method of the present invention preferably is implemented.
In the context of the present specification, term " carboxylic acid sources " refers to can as any material of carboxylic acid source (namely providing carboxylic acid) in nitrile manufacture method (first step) of the present invention, comprise carboxylic acid starting material itself and (as by hydrolysis or ammonia solution etc.) can produce free carboxy acid under the reaction conditions of first step material (hereinafter referred to as product carboxylic acid material), such as can enumerate carboxylic acid anhydride and carboxylic acid C
1-4straight or branched alkyl ester etc.According to nitrile manufacture method of the present invention, reaction mechanism is simple, side reaction is less, aminating reaction is less by impurity effect, this manufacture method to the purity requirement of carboxylic acid sources also lower (such as purity is minimum can be 90%) thus, directly can use industrial corresponding thick product, such as (mixing) polycarboxylic acid product etc. of industry (such as oil prodution industry) byproduct.
In the context of the present invention, term " carboxylic acid " uses it to define the most widely, refers to the compound containing free carboxy (i.e.-COOH).
In the context of the present specification, term " polycarboxylic acid " refers to the compound containing multiple (such as 2 to 10, preferably 2 to .5, more preferably 2 to 4, preferably 2 or 3 further) free carboxy.
In the context of the present specification, it is all carbon atoms on aliphatics hydrocarbon chain that term " aliphatic polycarboxylic acid " refers to the carbon atom of each free carboxy Direct Bonding of this polycarboxylic acid, instead of the carbon atom on ring (such as aromatic series or alicyclic ring).
In the context of the present specification, it is carbon atom on alicyclic ring (comprising naphthenic hydrocarbon ring, cycloolefin ring and heterocycle) that term " alicyclic polycarboxylic acid " refers to the carbon atom of at least one free carboxy Direct Bonding of this polycarboxylic acid, but each free carboxy of this polycarboxylic acid all not with the carbon atom Direct Bonding on aromatic ring (comprising aromatic ring and hetero-aromatic ring).
In the context of the present specification, term " aromatic polycarboxylic acid " refers to the carbon atom of at least one free carboxy Direct Bonding of this polycarboxylic acid is carbon atom on aromatic ring (comprising aromatic ring and hetero-aromatic ring).
In the context of the present specification, term " open reactive system " refers to this reaction system outwardly atmosphere opening (use open reactive device) from start to finish, and the reaction now in this reaction system is carried out under the pressure (environmental stress) of (being similar to) ambient atmosphere.
In the context of the present specification, term " closed reaction system " refers to this reaction system and completely cuts off (using closed reactor) with ambient atmosphere from start to finish, and the reaction now in this reaction system is at the pressure (autogenous pressure of such as this reaction system higher than environmental stress; As long as the pressure of safety on producing, with regard to there is no particular limitation) under carry out, but do not get rid of (such as pressure release or discharge a part of by product etc.) as required, this reaction system in whole reaction process outwardly the air short period of time (such as continue 0.05-5 minute, 0.1-4 minute, 0.3-3 minute, 0.5-2 minute or 0.6-1.5 minute etc.) open one or many (such as 1-20 time, 1-10 time, 1-5 time, 1-3 time, 1-2 time or 1 inferior).
In the context of the present specification, term " halogen " refers to fluorine, chlorine, bromine and iodine, preferred chlorine and bromine.
In the context of the present specification, statement " optional replacement " refers to and is optionally selected from halogen, hydroxyl, sulfydryl, amino, aminocarboxyl, nitro, oxo, sulfo-, cyano group, C by one or more (such as 1 to 5,1 to 4,1 to 3,1 to 2 or 1)
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C
2-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C
2-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C
3-20cycloalkyl, C
3-20cycloalkanes (oxygen, sulphur, ammonia) base, C
3-20cycloalkyl C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C
3-20cycloalkyl C
2-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C
3-20cycloalkyl C
2-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C
3-20cycloalkenyl group, C
3-20cyclenes (oxygen, sulphur, ammonia) base, C
3-20cycloalkenyl group C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C
3-20cycloalkenyl group C
2-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C
3-20cycloalkenyl group C
2-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C
6-20aryl, C
6-20virtue (oxygen, sulphur, ammonia) base, C
6-20aryl C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C
6-20aryl C
2-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C
6-20aryl C
2-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C
4-20heteroaryl, C
4-20assorted virtue (oxygen, sulphur, ammonia) base, C
4-20heteroaryl C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C
4-20heteroaryl C
2-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C
4-20heteroaryl C
2-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C
2-20heterocyclic radical, C
2-20heterocycle (oxygen, sulphur, ammonia) base, C
2-20heterocyclic radical C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C
2-20heterocyclic radical C
2-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base and C
2-20heterocyclic radical C
2-6the substituting group (position feasible) of straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base replaces.These substituting groups are when existing multiple, and between two adjacent substituting groups, (such as two substituent molecule chain ends) can bond together and form the substituent structure of divalence.Such as, two adjacent C
1-6straight or branched alkyl can bond together and form corresponding alkylen structures.Or, two adjacent C
1-6straight or branched alkoxyl group such as can form corresponding alkylidene dioxygen based structures, two adjacent C
1-6straight or branched alkylamino such as can form corresponding alkylenediamino structure, two adjacent C
1-5straight or branched alkylthio such as can form corresponding alkylidene group disulfide group structure, etc.As preferred substituting group, such as halogen, hydroxyl, sulfydryl, amino, sulfo-, oxo or C can be enumerated
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base etc.
In the context of the present specification, statement " (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base " implication be: alkyl, haloalkyl, alkoxyl group, alkylthio, alkylamino, alkyl-carbonyl, halogenated alkoxy, halogenated alkylthio, haloalkane amino or halogenated alkyl carbonyl, statement " (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base " implication be: thiazolinyl, haloalkenyl group, alkene oxygen base, alkenylthio group, enamino, alkenyl carbonyl, haloalkene oxygen base, haloalkene sulfenyl, haloalkene amino or haloalkenyl group carbonyl, statement " (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base " implication be: alkynyl, halo alkynyl, alkynyloxy group, alkynes sulfenyl, alkynes is amino, alkynylcarbonyl groups, halo alkynyloxy group, acetylenic halide sulfenyl, acetylenic halide amino or halo alkynylcarbonyl groups, statement " (oxygen, sulphur, ammonia) base " implication be, oxygen base, sulfenyl or amino.At this, described halo comprises a halo, dihalo, three halos or perhalogeno etc.
In the context of the present specification, term " aliphatics hydrocarbon chain " refers to the saturated of straight or branched or unsaturated hydrocarbons, comprises alkane chain, alkene chain and alkynes chain.
In the context of the present specification, term " n valency " or its similar term refer to the group that n the structure (such as group, hydrocarbon chain or compound ring etc.) limited from this term different carbon atom obtains after each removing (on carbon) hydrogen atom.Such as, term " divalent " refers to the group that the different carbon atom of the structure (such as group, hydrocarbon chain or compound ring etc.) limited from this term 2 obtains after each removing (on carbon) hydrogen atom.Specifically such as, divalent aliphatics hydrocarbon chain refers to aliphatics alkylene or aliphatic hydrocarbon two base.
In the context of the present specification, term " C
3-20naphthenic hydrocarbon ring " refer to monocycle, dicyclo or the polycyclic naphthene hydrocarbon ring with carbon atom on 3-20 ring.As described C
3-20naphthenic hydrocarbon ring, such as can enumerate the single-ring naphthene rings such as cyclopropane ring, cyclohexane ring and pentamethylene ring, and dicyclo penta ring, decahydronaphthalene naphthalene nucleus, diamantane ring, spiral shell [2.4] heptane ring, spiral shell [4.5] decane ring, two rings [3.2.1] octane ring, three ring [2.2.1.0
2,6] octane ring, norbornane ring,
with
on volution, bridged ring or condensed ring formula dicyclo or polycyclic naphthene hydrocarbon ring.As described C
3-20naphthenic hydrocarbon ring, more preferably C
3-15naphthenic hydrocarbon ring.
In the context of the present specification, term " C
3-20cycloolefin ring " refer to aforesaid C
3-20on at least one ring of naphthenic hydrocarbon ring, carbon-carbon single bond (C-C) is by the group after carbon-carbon double bond (C=C) replacement.As described C
3-20cycloolefin ring, such as can enumerate the monocyclic cycloalkenyl hydrocarbon rings such as cyclobutene ring, cyclopentenes ring, cyclopentadiene ring, cyclohexene ring, cyclohexadiene ring, suberene ring, cycloheptadiene ring, cyclooctatetraene ring, and Dicyclopentadiene (DCPD) ring, norbornylene ring, norbornadiene ring,
with
on volution, bridged ring or condensed ring formula dicyclo or multi-ringed cycloolefin hydrocarbon ring.As described C
3-20cycloolefin ring, more preferably C
3-15cycloolefin ring.
In the context of the present specification, term " C
6-20aromatic ring " refer to the aromatic hydrocarbons ring with carbon atom on 6-20 ring.As described C
6-20aromatic ring, such as can enumerate the group that two or more phenyl ring such as phenyl ring, biphenyl and terphenyl condenses with two or more phenyl ring such as group and naphthalene nucleus, anthracene nucleus, phenanthrene ring that singly-bound is directly connected.As described C
6-20aromatic ring, more preferably phenyl ring and biphenyl.
In the context of the present specification, term " C
4-20hetero-aromatic ring " refer to there is heteroatomic aromatic hydrocarbons ring on ring that carbon atom and 1-3 on 4-20 ring be selected from oxygen, sulphur and nitrogen.As described C
4-20hetero-aromatic ring, such as can enumerate furan nucleus, thiphene ring, pyrrole ring, thiazole ring, benzothiazole ring, Thiadiazole, imidazole ring, benzoglyoxaline ring, triazine ring, triazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indole ring, quinoline ring, pteridine ring and acridine ring etc., wherein preferred furan nucleus, thiphene ring, imidazole ring, pyridine ring and indole ring etc.
In the context of the present specification, term " C
2-20heterocycle " refer to aforesaid C
3-20naphthenic hydrocarbon ring or C
3-20on at least one ring of cycloolefin ring, carbon atom is by the group after the replacement of Sauerstoffatom, sulphur atom or nitrogen-atoms.As described C
2-20heterocycle, such as can enumerate piperidine ring, piperazine ring, azepine cyclohexene ring, dioxolane ring, dioxane ring, tetrahydrofuran (THF) ring, trimethylene oxide ring, a word used for translation ring in heptan ring, pyrroline ring, tetrahydro pyridine ring, tetrahydro-pyrazole ring, pyrazoline ring, pyranoid ring, thiapyran ring, Pyrrolidine ring, tetramethylene sulfide ring, aziridine ring, amylene oxide ring, tetrahydric thiapyran ring and morpholine ring etc., wherein preferred piperidine ring, tetrahydrofuran (THF) ring, amylene oxide ring etc.
In the context of the present specification, term " combination group " refers to two or more C
3-20the group that naphthenic hydrocarbon ring bonds together via singly-bound or linking group and formed, two or more C
3-20the group that cycloolefin ring bonds together via singly-bound or linking group and formed, two or more C
6-20the group that aromatic ring bonds together via singly-bound or linking group and formed, two or more C
4-20the group that hetero-aromatic ring bonds together via singly-bound or linking group and formed, two or more C
2-20the group that heterocycle bonds together and formed via singly-bound or linking group or C
3-20naphthenic hydrocarbon ring, C
3-20cycloolefin ring, C
6-20aromatic ring, C
4-20hetero-aromatic ring and C
2-20two or more groups passing through to condense each other or bond together via singly-bound or linking group and formed in heterocycle.As this combination group, such as phenylcyclohexane can be enumerated, tolylthiophene, benzo morpholine, phenylmorpholine, cyclohexenyl pentamethylene, naphthyl norbornane, phenyl diamantane, benzofurane, benzcyclobutane, phenyl pyrazines, phenylpyrrole, cyclohexenyl diamantane, cyclohexyl trimethylene oxide, cyclohexyl morpholine, Huan hexyl isoxazole, phenyl-isoxazole azoles, adamantyl isoxazole, norbornylene butylcyclohexane, norbornene benzene, cyclohexyl ring hexane, cyclohexyl methyl hexanaphthene, thienyl thiophene, pyrryl pyrroles, pyrrolidyl pyrroles, phenmethyl benzene, phenoxy group benzene, thiophenyl benzene, benzyloxy benzene, benzyloxy methylene-benzene, styryl benzene, styryl methylene-benzene, phenyl amino phenyl, phenylaminomethyl benzene, hexamethylene methoxycyclohexyl alkane, benzyloxy benzene,
deng.
In the context of the present specification, term " linking group " refers to any group containing two non-bonding keys (half bond) in structure, can be such as-O-;-S-;-NR
1-, wherein R
1h or C
1-4straight or branched alkyl, preferred hydrogen or methyl; The C of optional replacement
1-6straight or branched alkylene, the preferably optional C replaced
1-4straight or branched alkylidene group, the optional C replaced
2-4straight or branched alkenylene or the optional C replaced
2-4straight or branched alkynylene, the more preferably optional C replaced
1-4straight or branched alkylidene group; Or the arbitrary combination of these linking groups, such as-O-CH
2-,-O-CH
2-O-,-O-CH
2-CH
2-CH
2-,-O-CH
2-CH
2-CH
2-S-,-CH
2-CH
2-CH
2-NH-,-CH
2-CH
2-CH
2-S-,-O-CH=CH-CH
2-,-O-CH=CH-CH
2-O-,-O-CH
2-CH
2-CH
2-NH-,-O-CH
2-O-CH
2-CH
2-,-O-CH
2-O-CH
2-CH
2-O-,-O-CH
2-NH-CH
2-CH
2-O-etc., but-O-,-S-and-NR
1-with the situation of self or Direct Bonding each other except.As described linking group, preferably-O-, the optional C replaced
1-4straight or branched alkylidene group or its arbitrary combination, but except the situation of-O-and self Direct Bonding.
In the context of the present specification, term " containing ammonia effluent " to refer in the manufacture method (especially first step) of nitrile of the present invention the gaseous state containing ammonia or liquid material (such as containing ammonia condensing water, ammonia-containing water and ammonia-containing exhaust etc.) of discharging as by product or unreacted raw material from reaction system after the completion of reaction.
Finally, when clearly not indicating, all percentage ratios, number, ratio etc. mentioned in this specification sheets are all benchmark with weight, unless do not met the routine understanding of those skilled in the art when being benchmark with weight.
The present invention relates to a kind of manufacture method of nitrile, it is characterized in that, comprise first step and the second step of the following stated.
According to first step, make carboxylic acid sources and ammonia source at the temperature of reaction T from T1 to T2
athe lower contact reaction times of 0.01-2.5 hour, obtain acid amides intermediate product, the greater wherein in the T1 fusing point that to be described carboxylic acid sources depress at 1 standard atmosphere and temperature value 145 DEG C, T2 is boiling point, the reckling in sublimation temperature Sum decomposition temperature that described alicyclic polycarboxylic acid depresses at 1 standard atmosphere, and prerequisite is T2 > T1.Preferably, T2-T1 >=10 DEG C.
According to the present invention, described carboxylic acid sources is selected from the C of alicyclic polycarboxylic acid, described alicyclic polycarboxylic acid
1-4the acid anhydrides of straight or branched alkyl ester (preferred methyl esters) or described alicyclic polycarboxylic acid.These carboxylic acid sources can be used alone one, also can two or more combinationally use.
According to the present invention, as described alicyclic polycarboxylic acid, the compound of following structure such as can be enumerated.
Wherein, group
for the n valency C optionally replaced
3-20naphthenic hydrocarbon ring, the optional n valency C replaced
3-20cycloolefin ring or the optional n valency C replaced
2-20heterocycle.
According to the present invention, n-1 group B is singly-bound, the optional divalent C replaced independently of one another
3-20naphthenic hydrocarbon ring, the optional divalent C replaced
3-20cycloolefin ring, the optional divalent C replaced
6-20aromatic ring, the optional divalent C replaced
4-20hetero-aromatic ring, the optional divalent C replaced
2-20heterocycle or the optional divalent combination group replaced are preferably singly-bound independently of one another.
According to the present invention, when n-1 group B is singly-bound, the optional divalent C replaced independently of one another
3-20naphthenic hydrocarbon ring, the optional divalent C replaced
3-20cycloolefin ring or the optional divalent C replaced
2-20during heterocycle, n-1 radicals R is singly-bound or the optional divalent aliphatics hydrocarbon chain replaced independently of one another, and when n-1 group B is the optional divalent C replaced independently of one another
6-20aromatic ring, the optional divalent C replaced
4-20when hetero-aromatic ring or the optional divalent replaced combine group, n-1 radicals R is the optional divalent aliphatics hydrocarbon chain replaced independently of one another.
According to the present invention, the aliphatics hydrocarbon chain in each definition is selected from C independently of one another
1-15(preferred C
1-9, such as C
1-3) saturated or undersaturated straight or branched hydrocarbon chain.
According to the present invention, the aliphatics hydrocarbon chain preferably in each definition is selected from C independently of one another
1-15(preferred C
1-9, such as C
1-3) straight or branched alkane chain, C
2-15(preferred C
2-9, such as C
2-3) straight or branched alkene chain or C
2-15(preferred C
2-9, such as C
2-3) straight or branched alkynes chain, be more preferably selected from C independently of one another
1-15(preferred C
1-9, such as C
1-3) straight or branched alkane chain or C
2-15(preferred C
2-9, such as C
2-3) straight or branched alkene chain.
According to the present invention, when the carbonatoms of described aliphatics hydrocarbon chain is more than 2 and comprises C-C singly-bound in its molecular chain, optionally between two carbon atoms of this C-C singly-bound, insert spacer groups :-O-,-S-or-a NR further
1-, wherein R
1h or C
1-4straight or branched alkyl, preferred hydrogen or methyl.The quantity of this C-C singly-bound can be one, also can be multiple, such as 1 to 5,1 to 4,1 to 3,1 to 2 or 1.Such as, described aliphatics hydrocarbon chain is CH
3-CH
2-CH
2-CH
3time (for convenience of description, not showing its valence state), after inserting an O between two carbon atoms of the C-C singly-bound comprised at its molecular chain, CH can be obtained
3-O-CH
2-CH
2-CH
3, CH
3-CH
2-O-CH
2-CH
3and CH
3-CH
2-CH
2-O-CH
3deng, can CH be obtained insert an O respectively between respective two carbon atoms of two C-C singly-bounds after
3-O-CH
2-O-CH
2-CH
3, CH
3-CH
2-O-CH
2-O-CH
3and CH
3-O-CH
2-CH
2-O-CH
3deng, can CH be obtained insert an O respectively between respective two carbon atoms of three C-C singly-bounds after
3-O-CH
2-O-CH
2-O-CH
3.
According to the present invention, n is the integer of 2 to 10, preferably the integer of 2 to 5, more preferably the integer of 2 to 4, further preferably 2 or 3.
According to the present invention, aliphatics hydrocarbon chain, C described here
3-20naphthenic hydrocarbon ring, C
3-20cycloolefin ring, C
6-20aromatic ring, C
4-20hetero-aromatic ring, C
2-20heterocycle and combination group define as mentioned before.
According to the present invention, as described carboxylic acid sources, aforesaid alicyclic polycarboxylic acid can be used alone one, also can two or more combinationally use.
According to the present invention, described carboxylic acid sources can be biogenetic derivation, such as can enumerate natural polycarboxylic acid or (mixing) polycarboxylic acid product etc. as industry (such as oil prodution industry) byproduct, as long as the impurity contained by it or impurity level make the reduction of target nitrile yield be no more than 5%.
According to the present invention, described carboxylic acid sources is at described temperature of reaction T
apreferably be rendered as molten state or liquid state down.Given this, the C of described alicyclic polycarboxylic acid, described alicyclic polycarboxylic acid
1-4the acid anhydrides of straight or branched alkyl ester or described alicyclic polycarboxylic acid preferably has and is equal to or less than described temperature of reaction T
athe fusing point (1 standard atmosphere pressure measures) of (being generally up to 310 DEG C).Those skilled in the art by consulting correlation technique handbook or knowing fusing point that these carboxylic acid sources depress at 1 standard atmosphere (and described alicyclic polycarboxylic acid depress at 1 standard atmosphere boiling point, sublimation temperature Sum decomposition temperature etc.) by conventional determining method, therefore can not repeat them here herein.
According to the present invention, as the described mode making carboxylic acid sources contact with ammonia source, the mode being metered into ammonia source or making the two mixing in the carboxylic acid sources of melting in advance such as can be enumerated.Generally speaking, this contact is carried out according to the mode of interval.
According to the present invention, described ammonia source as mentioned before, but preferred ammonia or produce ammoniacal substance, more preferably Industry Waste ammonia.Now the ammonia content in described ammonia source can be such as 60-99.9wt%, 80-99.9wt%, 85-99.9wt% or 95-99.9wt%, and all the other are then previously described inert diluents etc.
According to the present invention, as described product ammoniacal substance, be preferably selected from urea, cyanic acid, volatile salt, bicarbonate of ammonia and ammonium chloride one or more, be preferably selected from urea and bicarbonate of ammonia one or more, more preferably bicarbonate of ammonia.
According to the present invention, as the consumption in described ammonia source, make in the described carboxylic acid sources of carboxyl and with NH
3the mol ratio in described ammonia source of meter reaches 1: 1.1-2.5, and preferably 1: 1.2-2.0, more preferably 1: 1.3-1.6.
According to the present invention, described first step carries out in closed reaction system (such as closed reactor).As required, this first step can carry out in complete closed reaction system, that is, this reaction system does not need outwardly air opening in any form in whole reaction process.
According to the present invention, after described first step terminates, by reaction system pressure release to external atmospheric pressure, also obtain containing ammonia effluent while acquisition acid amides intermediate product.According to the present invention preferably, using described containing ammonia effluent (preferably through concentrated or dry after) in circulation-supplied to described first step as described ammonia source supplement or a part of.So corresponding minimizing can be supplied to the consumption in the fresh ammonia source of described first step, improve the utilization ratio of ammonia raw material thus, and the Efficient Cycle realized containing ammonia effluent utilizes.
The present inventor finds, even if described first step does not use catalyzer can carry out well yet.Therefore, according to the present invention one preferred embodiment, described first step does not use in this area normally used any catalyzer when carrying out carboxylic acid ammoniation process.
According to the present invention, the reaction times of described first step is preferably 0.05-2 hour, or 0.1-1.5 hour, or 0.2-1 hour, or 0.3-0.8 hour or shorter time.
According to the present invention, after described first step terminates, the acid amides intermediate product obtained directly can carry out second step as raw material, also after temporary grade, can carry out second step again.Or, although and unnecessary, the acid amides intermediate product obtained also can utilize weak ammonia etc. to wash, to remove the unreacted carboxylic acid sources that may remain.
According to the present invention, described first step and second step can carry out in same reaction vessel, also can carry out in different reaction vessels (such as tandem reaction vessel), be not particularly limited.When carrying out in same reaction vessel, after described first step terminates, by reaction system pressure release to external atmospheric pressure, acid amides intermediate product described in not discharging, reaction system is directly changed into the reaction conditions (as described below) of second step, reduce production cost and the production complexity of this manufacture method thus.
According to described second step, the described acid amides intermediate product obtained by first step is at the temperature of reaction T from T3 to T4
bthe reaction times of lower thermal treatment 0.1-4.5 hour, the greater wherein in the T3 fusing point that to be described acid amides intermediate product depress at 1 standard atmosphere and temperature value 225 DEG C, T4 is boiling point, the reckling in sublimation temperature Sum decomposition temperature that described acid amides intermediate product is depressed at 1 standard atmosphere, and prerequisite is T4 > T3.Preferably, T4-T3 >=10 DEG C.
According to the present invention, described acid amides intermediate product is at described temperature of reaction T
bpreferably be rendered as molten state or liquid state down.Given this, described acid amides intermediate product preferably has and is equal to or less than described temperature of reaction T
bthe fusing point (1 standard atmosphere pressure measures) of (being generally up to 350 DEG C).Therefore those skilled in the art can not repeat them here fusing point, boiling point, sublimation temperature Sum decomposition temperature etc. that these acid amides intermediate products are depressed at 1 standard atmosphere herein by consulting correlation technique handbook or being known by conventional determining method.
According to the present invention, preferably 0.2 to the 3 hour reaction times of described second step, or 0.3 to 2 hour, or 0.4 to 1.2 hour, or 0.4 to 1 hour or shorter time.
According to the present invention, do not need to use ammonia source in described second step.
According to the present invention, described second step also can carry out in open reactive system in closed reaction system, preferably carries out in closed reaction system, to reduce production energy consumption.
According to the present invention, described second step can carry out in the presence of a catalyst, also can not use catalyzer.As described catalyzer, such as can enumerate in this area conventional those catalyzer used when carrying out carboxylic acid ammoniation process, such as Vanadium Pentoxide in FLAKES, phosphoric acid, phosphoric acid salt, molecular sieve, aluminum oxide, zinc oxide or composite oxide catalysts etc., wherein preferably use Vanadium Pentoxide in FLAKES or phosphoric acid.In use, these catalyzer can use according to the conventional amount used of this area (0.2-10% of to be such as benchmark with weight can be described carboxylic acid sources weight, preferred 1-6%), are not particularly limited.
According to the present invention's further embodiment, described temperature of reaction T
afor from T1 ' to T2 '.Now, described T1 '=T1+5 DEG C or T1+10 DEG C or T1+20 DEG C or T1+30 DEG C or T1+40 DEG C or T1+50 DEG C or T1+60 DEG C or T1+70 DEG C or T1+80 DEG C or T1+90 DEG C.Described T2 '=T2 or T2-5 DEG C or T2-10 DEG C or T2-20 DEG C or T2-30 DEG C or T2-40 DEG C 2 or T2-50 DEG C, but be generally up to 310 DEG C, prerequisite is T2 ' > T1 '.Preferably, T2 '-T1 ' >=10 DEG C.
According to the present invention's further embodiment, described temperature of reaction T
bfor from T3 ' to T4 '.Now, described T3 '=T3+5 DEG C or T3+10 DEG C or T3+20 DEG C or T3+30 DEG C or T3+40 DEG C or T3+50 DEG C or T3+60 DEG C or T3+70 DEG C or T3+80 DEG C.Described T4 '=T4 or T4-5 DEG C or T4-10 DEG C or T4-20 DEG C or T4-30 DEG C or T4-40 DEG C or T4-50 DEG C, but be generally up to 350 DEG C.Prerequisite is T4 ' > T3 '.Preferably, T4 '-T3 ' >=10 DEG C.
According to the present invention one further embodiment, described T1 is 145 DEG C, or 150 DEG C, or 160 DEG C, or 170 DEG C, or 180 DEG C, or 190 DEG C, or 200 DEG C, or 210 DEG C, or 220 DEG C, or 230 DEG C, or 240 DEG C, or 250 DEG C, or 260 DEG C, or 270 DEG C, or 280 DEG C, or 290 DEG C, or 300 DEG C.According to the present invention one further embodiment, described T2 is 310 DEG C, or 300 DEG C, or 290 DEG C, or 280 DEG C, or 270 DEG C, or 260 DEG C, or 250 DEG C, or 240 DEG C, or 230 DEG C, or 220 DEG C, or 210 DEG C, or 200 DEG C, or 190 DEG C, or 180 DEG C.Prerequisite is T2 > T1.Preferably, T2-T1 >=10 DEG C.
According to the present invention one further embodiment, described T3 is 225 DEG C, or 230 DEG C, or 240 DEG C, or 250 DEG C, or 260 DEG C, or 270 DEG C, or 280 DEG C, or 290 DEG C, or 300 DEG C, or 310 DEG C.According to the present invention one further embodiment, described T4 is 350 DEG C, or 340 DEG C, or 330 DEG C, or 320 DEG C, or 310 DEG C, or 300 DEG C, or 290 DEG C, or 280 DEG C, or 270 DEG C.Prerequisite is T4 > T3.Preferably, T4-T3 >=10 DEG C.
The embodiment concrete according to the present invention one, described carboxylic acid sources is the carboxylic acid shown in following table 1, the acid anhydrides of described carboxylic acid or methyl esters (preferred described carboxylic acid), in described first step, temperature of reaction T
aas shown in table 1 below, the reaction times is 0.05-2 hour, or 0.1-1.5 hour, or 0.2-1 hour, or 0.3-0.8 hour, in described second step, and temperature of reaction T
bas shown in table 1 below, the reaction times is 0.2 to 3 hour, or 0.3 to 2 hour, or 0.4 to 1.2 hour, or 0.4 to 1 hour.
Table 1
| Carboxylic acid | Temperature of reaction T A，℃ | Temperature of reaction T B，℃ |
| Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid | 185 to 225 | 245 to 300 |
| 1,2-cyclohexyl dicarboxylic acid | 200 to 265 | 290 to 315 |
| 4-tetrahydrobenzene-1,2-dioctyl phthalate | 200 to 265 | 290 to 310 |
| 1,1-ring fourth dioctyl phthalate | 185 to 245 | 270 to 300 |
| 5-norbornylene-2,3-dioctyl phthalate | 195 to 240 | 275 to 305 |
| 1,3-adamantane acid | 285 to 300 | 315 to 325 |
| 1,3-ring penta dioctyl phthalate | 150 to 195 | 235 to 285 |
| 1,2,3,4-ring penta tetracarboxylic acid | 205 to 260 | 285 to 315 |
| 1,3,5-hexamethylene tricarboxylic acid | 235 to 270 | 300 to 325 |
| 1,2,4,5-hexamethylene tetracarboxylic acid | 180 to 225 | 255 to 300 |
| 1,2,3,4-ring fourth tetracarboxylic acid | 200 to 245 | 275 to 305 |
| 4-methyl-4-tetrahydrobenzene-1,2-dioctyl phthalate | 235 to 275 | 300 to 325 |
| 1,3,5,7-diamantane tetracarboxylic acid | 300 to 310 | 325 to 350 |
| Isosorbide-5-Nitrae-cyclohexanedione-2,5-dioctyl phthalate | 155 to 200 | 245 to 295 |
| 1，4-cyclohexadiene-Isosorbide-5-Nitrae-dioctyl phthalate | 160 to 205 | 255 to 290 |
| 2,2-nitrogen heterocyclic third dioctyl phthalate | 145 to 185 | 225 to 280 |
| 3,3-oxa-ring fourth dioctyl phthalate | 165 to 200 | 250 to 295 |
| 4,5-isoxazole dioctyl phthalate | 170 to 205 | 250 to 300 |
| 2,3-oxygen Polymorphs dioctyl phthalate | 160 to 200 | 235 to 285 |
| Pyrans-2,6-dioctyl phthalate | 155 to 200 | 240 to 290 |
| DOX-2-methyl-4.5-dioctyl phthalate | 150 to 195 | 245 to 295 |
| 1,3-Pyrimidine-2-methyl-4,5-dioctyl phthalate | 145 to 185 | 235 to 275 |
| 3,4-diamino-2,5-oxygen Polymorphs dioctyl phthalate | 165 to 210 | 240 to 290 |
| 2-methyl-3,4-thiophenedicarboxylic acid | 175 to 225 | 255 to 300 |
| 2,6-thiomorpholine dioctyl phthalate | 145 to 190 | 235 to 280 |
| 3,4-dihydroxyl-2,5-oxygen Polymorphs dioctyl phthalate | 145 to 195 | 240 to 305 |
| 4-acetoxyl heptanaphthenic acid | 185 to 225 | 245 to 300 |
| 4-propionyloxy heptanaphthenic acid | 185 to 225 | 245 to 300 |
| 4-caproyl heptanaphthenic acid | 185 to 225 | 245 to 300 |
| 4-lauric acid base heptanaphthenic acid | 185 to 225 | 245 to 300 |
| 2-nitro-4-caproyl heptanaphthenic acid | 175 to 230 | 245 to 300 |
According to the present invention, after described second step terminates, by purifying or the separation method of routine, target nitrile can be isolated as product from the reaction mixture that second step obtains.As described purifying or separation method, such as distillation method and extraction process etc. can be enumerated.
According to the present invention, described distillation method or extraction process can carry out according to the mode of this area routine, are not particularly limited, as long as target nitrile product can be separated from described reaction mixture.
According to the present invention, as described distillation method, such as can enumerate the distillation under vacuum employing rectifying tower, this rectifying tower operational condition is now such as: vacuum tightness is 25-250mbar, column bottom temperature is generally 100-320 DEG C, using the boiling point of target nitrile product under described vacuum tightness (± 2 DEG C) as cut point, be such as generally 80-290 DEG C, but be not limited to this but depend on concrete target nitrile product.As required, the reflux ratio of this rectifying tower can be set as the 1.1-4 of minimum reflux ratio Rmin doubly, and number of actual plates is such as 5-200 block, but is not limited to this but depends on concrete target nitrile product.In addition, the actually operating condition of described rectifying tower is not limited to this, those skilled in the art can select suitable distillation operation condition according to the distillation proterties (such as boiling point and heat decomposition temperature etc.) of target nitrile product, rectifying tower structure (such as plate number etc.) and actual needs (such as predetermined nitrile purity etc.) etc., and this is all conventional known.
According to the present invention, as described extraction process, such as can enumerate and use the good solvent of the target nitrile product such as ethyl acetate, chloroform, hexane described reaction mixture (as required add appropriate 2-5wt% dilute alkaline aqueous solution dilutes or regulates after) to be carried out to the method etc. directly extracted.
According to the present invention, extraction process and distillation method can couplings, extraction process such as first can be utilized to carry out preliminary purifying or separation, then carry out further purifying or separation by distillation method.
According to the present invention, by described purifying or separation, the target nitrile product that can to obtain purity be more than 97% (preferably more than 98%, more preferably more than 99%).Nitrile purity now such as can be measured by vapor-phase chromatography etc. easily.
According to nitrile manufacture method of the present invention, according to the difference of nitrile product category, can realize more than 75%, more than 80%, more than 90%, the nitrile yield of more than 95%, even more than 98% or higher.
According to the present invention, described nitrile can as raw material for the manufacture of corresponding amine.For this reason, the invention still further relates to a kind of manufacture method of amine, this manufacture method manufactures corresponding amine by this nitrile of hydrogenation.
According to the present invention, described hydrogenation can be carried out according to this area conventional known any mode when hydrogenated nitrile.Such as, can be 0.6-5.2MPa in reaction total pressure, hydrogen partial pressure is 0.4-5MPa (such as 2-4MPa), temperature of reaction is under the condition of 70-130 DEG C (such as 80-120 DEG C), in the presence of a hydrogenation catalyst, make described nitrile raw material hydrogenation 0.2-3 hour (preferred 0.5-2 hour), but be sometimes not limited to this.
According to the present invention, as described hydrogenation catalyst, directly can use the conventional various catalyzer for hydrogenating nitriles amine in this area, such as Raney's nickel can be enumerated, the Raney's nickel of the doping such as iron or copper, Ni-B or Ni-Co-B amorphous alloy, loading type Ni-B or Ni-Co-B amorphous alloy, carrier loaded precious metal (such as Pb/C, Pd/C or Rh/C etc.) or composite catalyst (such as Raney's nickel/eight cobalt-carbonyl) etc., wherein from the convenient angle implemented of industrialization, preferred Raney's nickel, such as Aladdin Reagent Company is by specification 50 μm or 150 μm of commercially available Raney's nickels.These hydrogenation catalysts can be used alone, and also can two or more combinationally use.
According to the present invention, the 2-10wt% (such as 2-6wt%) of the consumption of described hydrogenation catalyst to take weight as benchmark can be such as described nitrile raw material, but be sometimes not limited to this.
According to the present invention, described hydrogenation preferably carries out under the existence of solvent (or being called thinner), and this is known in the art.As described solvent, such as water can be enumerated; The alcohol such as methyl alcohol, ethanol and 2-propyl alcohol; The esters such as methyl acetate; The aromatic hydrocarbon such as benzene,toluene,xylene; The naphthenic hydrocarbon such as hexanaphthene; The alkane such as heptane; The arbitrary combination of the ethers such as sherwood oil, ether, dioxane and tetrahydrofuran (THF) or these solvents, the wherein mixed solvent (volume ratio of ethanol and water is such as 0.1: 1 to 1: 0.1, but is not limited to this) etc. of preferred alcohol or ethanol and water.These solvents can be used alone, and also can two or more combinationally use.
According to the present invention, as the consumption of described solvent, as long as the heat release situation of reaction effectively can be improved and do not produce excessive burden to follow-up product separation step, with volume be such as benchmark can for the 1-10 of described nitrile raw material doubly, such as 1-5 doubly, 1-4 doubly, 1-3 doubly or 1-2 doubly etc., but be sometimes not limited to this.
According to the present invention, as required, described hydrogenation can also carry out under the existence of hydrogenation auxiliary agent.As described hydrogenation auxiliary agent, such as the alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide can be enumerated.These hydrogenation auxiliary agents can be used alone, and also can two or more combinationally use.
According to the present invention, as the consumption of described hydrogenation auxiliary agent, be such as benchmark with weight can be the 0.3-2wt% (preferred 0.2-1.2wt%) of described nitrile raw material, but sometimes be not limited to this.
According to the present invention, after described hydrogenation terminates, by purifying or the separation method of routine, targeted amine can be isolated as product from reaction mixture.These purifying or separation method are known in the art, and do not repeat them here.
According to the manufacture method of amine of the present invention, according to the difference of nitrile raw material type, can realize more than 85%, more than 90%, the amine yield of more than 95%, even more than 98% or higher, and the purity of amine product can reach more than 97% (preferably more than 98%, more preferably more than 99%).
Embodiment
Below adopt embodiment in further detail the present invention to be described, but the present invention is not limited to these embodiments.
Amide intermediate prepares embodiment
500g carboxylic acid starting material (chemical pure) is added in 1L reactor, and (water content is 0.5wt% to be filled with the ammonia that mole number is carboxylic 1.3 times of this carboxylic acid starting material, industrial goods), or add the bicarbonate of ammonia powder (chemical pure) that ammonium ion mole number is carboxylic 1.4 times of this carboxylic acid starting material, capping still, opens stirring (600r/min).Make reaction at temperature of reaction T
aunder carry out T
cafter hour, the content of reactor is sampled, does nucleus magnetic hydrogen spectrum and ultimate analysis, to characterize amide intermediate.Concrete reaction conditions and characterization result are shown in following Table A-1, Table A-2, Table A-3, Table A-4 and Table A-5.These characterization results show, the amide intermediate obtained has high purity (more than 99%).
Table A-1
Table A-2
Table A-3
Table A-4
Table A-5
Nitrile product prepares embodiment
The amide intermediate that continues prepares embodiment.Close described reactor (when amide intermediate boiling point is at ambient pressure equal to or less than following temperature of reaction T
btime) or keep reactor to be that open state is (when amide intermediate boiling point is at ambient pressure higher than following temperature of reaction T
btime), continue to stir (600r/min), temperature of reaction is changed into T
b, at this temperature of reaction T
blower maintenance T
dafter hour, capping still also connects vacuum pump, makes the vacuum tightness in reactor reach 20-50mbar (according to the difference of nitrile product species and corresponding adjustment), using overhead product as nitrile product.Calculate the yield of this nitrile product, and sampling does nucleus magnetic hydrogen spectrum and ultimate analysis, to characterize obtained nitrile product.Concrete reaction conditions and characterization result are shown in following Table A-6, A-7, A-8, A-9 and A-10.These characterization results show, the nitrile product obtained has high purity (more than 99%).
Prepare in embodiment at these nitrile products, optionally in the stage that reaction starts, in reactor, the disposable 10g Vanadium Pentoxide in FLAKES that adds is as catalyzer.
Table A-6
Table A-7
Table A-8
Table A-9
Table A-10
Amine prepares embodiment
(1) in 1L hydrogenation still, add 100g1,4-hexamethylene dimethoxy nitrile and 3g Raney-Ni, 400mL ethanol, be filled with H continuously
2, make system pressure in reaction process be always maintained at 5MPa.React 0.5h at temperature of reaction 95 DEG C after, cooling.When temperature in question response still is down to room temperature, venting, obtain Isosorbide-5-Nitrae-hexamethylene dimethylamine (purity is more than 99%) by filtration and recrystallization, yield is 90wt%.
1H NMR(300MHz，DMSO)δ2.54-2.50(m，2H)，2.49(d，J＝2.2Hz，2H)，1.94(s，4H)，1.89-1.78(m，4H)，1.20-0.87(m，6H)，ElementalAnalysis：C，67.18；H，12.16；N，19.28。
(2) in 1L hydrogenation still, add 100g4-tetrahydrobenzene-1,2-dimethoxy nitrile and 3g Raney-Ni, 400mL ethanol, be filled with H continuously
2, make system pressure in reaction process be always maintained at 6MPa.React 1h at temperature of reaction 90 DEG C after, cooling.When temperature in question response still is down to room temperature, venting, obtain 4-tetrahydrobenzene-1,2-dimethylamine (purity is more than 99%) by filtration and recrystallization, yield is 91wt%.
1H NMR(300MHz，DMSO)δ5.69(d，J＝11.0Hz，1H)，5.74-5.56(m，2H)，5.64(d，J＝4.5Hz，1H)，2.77-2.59(m，2H)，3.41-2.58(m，2H)，2.53-2.42(m，2H)，2.55-2.32(m，4H)，2.42-2.32(m，2H)，2.07(ddd，J＝12.4，8.3，7.0Hz，2H)，2.07(ddd，J＝12.4，8.3，7.0Hz，2H)，1.95(s，4H)，1.95(s，4H)，1.63-1.50(m，1H)，1.62-1.37(m，2H)，1.50-1.39(m，1H)，Elemental Analysis：C，68.17；H，11.05；N，19.24。
(3) in 1L hydrogenation still, add 100g1,3,5-hexamethylene trimethylsilyl nitrile and 3g Raney-Ni, 400mL ethanol, be filled with H continuously
2, make system pressure in reaction process be always maintained at 6MPa.React 1h at temperature of reaction 100 DEG C after, cooling.When temperature in question response still is down to room temperature, venting, obtain 1,3,5-hexamethylene Trimethylamine 99 (purity is more than 99%) by filtration and recrystallization, yield is 89wt%.
1H NMR(300MHz，DMSO)δ2.50(d，J＝7.2Hz，6H)，1.97-1.90(m，8H)，1.88(s，1H)，1.26-1.18(m，1H)，1.16(s，1H)，1.15-1.06(m，1H)，0.72(d，J＝7.7Hz，2H)，0.68(s，1H)，Elemental Analysis：C，63.01；H，12.14；N，24.19。
(4) in 1L hydrogenation still, add 100g2,3-oxygen Polymorphs dimethoxy nitrile and 3g Raney-Ni, 400mL ethanol, be filled with H continuously
2, make system pressure in reaction process be always maintained at 6MPa.React 1h at temperature of reaction 85 DEG C after, cooling.When temperature in question response still is down to room temperature, venting, obtain 2,3-oxygen Polymorphs dimethylamine (purity is more than 99%) by filtration and recrystallization, yield is 91wt%.
1H NMR(300MHz，DMSO)δ3.99(dt，J＝9.0，7.3Hz，1H)，3.89-3.67(m，2H)，2.88(dd，J＝12.4，7.3Hz，1H)，2.66(ddd，J＝19.4，12.4，7.1Hz，2H)，2.44(dd，J＝124，7.0Hz，1H)，2.15(s，2H)，2.08(s，2H)，1.91(ddd，J＝13.7，11.7，6.7Hz，1H)，1.85-1.73(m，1H)，1.73-1.55(m，1H)，Elemental Analysis：C，55.17；H，10.52；N，21.43。
(5) in 1L hydrogenation still, add 100g1,2,3,4-ring fourth four formonitrile HCN and 3g Raney-Ni, 400mL ethanol, be filled with H continuously
2, make system pressure in reaction process be always maintained at 8MPa.React 1h at temperature of reaction 95 DEG C after, cooling.When temperature in question response still is down to room temperature, venting, obtain 1,2,3,4-ring fourth tetramethylammonium (purity is more than 99%) by filtration and recrystallization, yield is 88wt%.
1H NMR(300MHz，DMSO)δ2.55-2.46(m，8H)，2.24(s，8H)，1.80-1.63(m，4H)，Elemental Analysis：C，55.18；H，11.17；N，32.26。
Although be described in detail the specific embodiment of the present invention above in conjunction with the embodiments, it is pointed out that protection scope of the present invention not by the restriction of these embodiments, but determined by claims of annex.Those skilled in the art can carry out suitable change to these embodiments in the scope not departing from technological thought of the present invention and purport, and the embodiment after these changes is obviously also included within protection scope of the present invention.
Claims (10)
1. a manufacture method for nitrile, is characterized in that, comprises the following steps:
First step: make carboxylic acid sources and ammonia source at the temperature of reaction T from T1 to T2
alower contact 0.01-2.5 hour (or 0.05-2 hour, or 0.1-1.5 hour, or 0.2-1 hour, or 0.3-0.8 hour) reaction times, obtain acid amides intermediate product, wherein said carboxylic acid sources is selected from the C of alicyclic polycarboxylic acid, described alicyclic polycarboxylic acid
1-4one or more in the acid anhydrides of straight or branched alkyl ester and described alicyclic polycarboxylic acid, the greater in the T1 fusing point that to be described carboxylic acid sources depress at 1 standard atmosphere and temperature value 145 DEG C, T2 is boiling point, the reckling in sublimation temperature Sum decomposition temperature that described alicyclic polycarboxylic acid depresses at 1 standard atmosphere, prerequisite is T2 > T1, preferred T2-T1>=10 DEG C, the ratio in wherein said carboxylic acid sources and described ammonia source makes in the described carboxylic acid sources of carboxyl and with NH
3the mol ratio in described ammonia source of meter reaches 1: 1.1-2.5 (preferably 1: 1.2-2.0, more preferably 1: 1.3-1.6), and second step: by described acid amides intermediate product at the temperature of reaction T from T3 to T4
blower thermal treatment 0.1 to 4.5 hour (or 0.2 to 3 hour, or 0.3 to 2 hour, or 0.4 to 1.2 hour, or 0.4 to 1 hour) reaction times, the greater wherein in the T3 fusing point that to be described acid amides intermediate product depress at 1 standard atmosphere and temperature value 225 DEG C, T4 is boiling point, the reckling in sublimation temperature Sum decomposition temperature that described acid amides intermediate product is depressed at 1 standard atmosphere, and prerequisite is T4 > T3, preferred T4-T3>=10 DEG C.
2. the manufacture method of the nitrile of claim 1, wherein said temperature of reaction T
afor from T1 ' to T2 ', wherein T1 '=T1+5 DEG C (or T1+10 DEG C or T1+20 DEG C or T1+30 DEG C or T1+40 DEG C or T1+50 DEG C or T1+60 DEG C or T1+70 DEG C or T1+80 DEG C or T1+90 DEG C), T2 '=T2 (or T2-5 DEG C or T2-10 DEG C or T2-20 DEG C or T2-30 DEG C or T2-40 DEG C or T2-50 DEG C or 310 DEG C), prerequisite is T2 ' > T1 '; Described temperature of reaction T
bfor from T3 ' to T4 ', wherein T3 '=T3+5 DEG C (or T3+10 DEG C or T3+20 DEG C or T3+30 DEG C or T3+40 DEG C or T3+50 DEG C or T3+60 DEG C or T3+70 DEG C or T3+80 DEG C), T4 '=T4 (or T4-5 DEG C or T4-10 DEG C or T4-20 DEG C or T4-30 DEG C or T4-40 DEG C or T4-50 DEG C or 350 DEG C), prerequisite is T4 ' > T3 '.
3. the manufacture method of the nitrile of claim 1, wherein T1 is 145 DEG C (or 150 DEG C, or 160 DEG C, or 170 DEG C, or 180 DEG C, or 190 DEG C, or 200 DEG C, or 210 DEG C, or 220 DEG C, or 230 DEG C, or 240 DEG C, or 250 DEG C, or 260 DEG C, or 270 DEG C, or 280 DEG C, or 290 DEG C, or 300 DEG C), T2 is 310 DEG C (or 300 DEG C, or 290 DEG C, or 280 DEG C, or 270 DEG C, or 260 DEG C, or 250 DEG C, or 240 DEG C, or 230 DEG C, or 220 DEG C, or 210 DEG C, or 200 DEG C, or 190 DEG C, or 180 DEG C), T3 is 225 DEG C (or 230 DEG C, or 240 DEG C, or 250 DEG C, or 260 DEG C, or 270 DEG C, or 280 DEG C, or 290 DEG C, or 300 DEG C, or 310 DEG C), T4 is 350 DEG C (or 340 DEG C, or 330 DEG C, or 320 DEG C, or 310 DEG C, or 300 DEG C, or 290 DEG C, or 280 DEG C, or 270 DEG C).
4. the manufacture method of the nitrile of claim 1, wherein said first step carries out in closed reaction system, and described second step carries out in open reactive system or closed reaction system.
5. the manufacture method of the nitrile of claim 1, wherein said first step does not use catalyzer, and described second step carries out in the presence of a catalyst or do not use catalyzer.
6. the manufacture method of the nitrile of claim 1, wherein said ammonia source be ammonia or produce ammoniacal substance (be preferably selected from urea, cyanic acid, volatile salt, bicarbonate of ammonia and ammonium chloride one or more, be preferably selected from urea and bicarbonate of ammonia one or more, more preferably bicarbonate of ammonia), preferred Industry Waste ammonia, its ammonia content is 60-99.9wt%, preferred 80-99.9wt%.
7. the manufacture method of the nitrile of claim 1, wherein said carboxylic acid sources is the carboxylic acid shown in following table, the acid anhydrides of this carboxylic acid or methyl esters, in described first step, temperature of reaction T
aas shown in the table, the reaction times is 0.05-2 hour, or 0.1-1.5 hour, or 0.2-1 hour, or 0.3-0.8 hour, in described second step, and temperature of reaction T
bas shown in the table, the reaction times is 0.2 to 3 hour, or 0.3 to 2 hour, or 0.4 to 1.2 hour, or 0.4 to 1 hour.
8. the manufacture method of the nitrile of claim 1, wherein said alicyclic polycarboxylic acid be selected from the compound with following structural formula one or more:
Wherein, group
for the n valency C optionally replaced
3-20naphthenic hydrocarbon ring, the optional n valency C replaced
3-20cycloolefin ring or the optional n valency C replaced
2-20heterocycle; N-1 group B is singly-bound, the optional divalent C replaced independently of one another
3-20naphthenic hydrocarbon ring, the optional divalent C replaced
3-20cycloolefin ring, the optional divalent C replaced
6-20aromatic ring, the optional divalent C replaced
4-20hetero-aromatic ring, the optional divalent C replaced
2-20heterocycle or the optional divalent combination group replaced are preferably singly-bound independently of one another; When n-1 group B is singly-bound, the optional divalent C replaced independently of one another
3-20naphthenic hydrocarbon ring, the optional divalent C replaced
3-20cycloolefin ring or the optional divalent C replaced
2-20during heterocycle, n-1 radicals R is singly-bound or the optional divalent aliphatics hydrocarbon chain replaced independently of one another; When n-1 group B is the optional divalent C replaced independently of one another
6-20aromatic ring, the optional divalent C replaced
4-20when hetero-aromatic ring or the optional divalent replaced combine group, n-1 radicals R is the optional divalent aliphatics hydrocarbon chain replaced independently of one another; Aliphatics hydrocarbon chain in each definition is selected from C independently of one another
1-15(preferred C
1-9) saturated or undersaturated straight or branched hydrocarbon chain, be preferably selected from C independently of one another
1-15(preferred C
1-9) straight or branched alkane chain, C
2-15(preferred C
2-9) straight or branched alkene chain or C
2-15(preferred C
2-9) straight or branched alkynes chain, be more preferably selected from C independently of one another
1-15(preferred C
1-9) straight or branched alkane chain or C
2-15(preferred C
2-9) straight or branched alkene chain; When the carbonatoms of described aliphatics hydrocarbon chain is more than 2 and comprises C-C singly-bound in its molecular chain, optionally between two carbon atoms of this C-C singly-bound, insert-O-,-S-or-NR
1-(R
1h or C
1-4straight or branched alkyl); N is the integer of 2 to 10, preferably the integer of 2 to 5, more preferably the integer of 2 to 4, further preferably 2 or 3.
9. the manufacture method of the nitrile of claim 1, wherein said first step also obtains containing ammonia effluent while the described acid amides intermediate product of acquisition, and using described containing in ammonia effluent circulation-supplied to described first step as described ammonia source supplement or a part of, preferably described containing ammonia effluent be fed to through concentrated or dry Posterior circle in described first step as described ammonia source supplement or a part of.
10. a manufacture method for amine, is characterized in that, comprises the following steps:
First step: manufacture nitrile according to the manufacture method of any one of claim 1 to 9; With
Second step: the nitrile that hydrogenation first step obtains manufactures amine.
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| US10906865B2 (en) | 2016-10-04 | 2021-02-02 | Mitsubishi Gas Chemical Company, Inc. | Method for producing 1,4-dicyanocyclohexane, 1,4-bis(aminomethyl)cyclohexane and 1,4-cyclohexanedicarboxylic acid |
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