CN110256272A - Utilize the method for solid acid catalyst synthesizing amide class coolant agent - Google Patents
Utilize the method for solid acid catalyst synthesizing amide class coolant agent Download PDFInfo
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- CN110256272A CN110256272A CN201910580875.6A CN201910580875A CN110256272A CN 110256272 A CN110256272 A CN 110256272A CN 201910580875 A CN201910580875 A CN 201910580875A CN 110256272 A CN110256272 A CN 110256272A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/145—Amides; N-substituted amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/06—Preparation of carboxylic acid amides from nitriles by transformation of cyano groups into carboxamide groups
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Abstract
The invention belongs to technical field of compound preparation, disclose a kind of method using solid acid catalyst synthesizing amide class coolant agent, by raw material 2,2- diisopropyl propionitrile, C1‑C6Lower aliphatic alcohols, water be raw material, in fixed bed reactors, solid acid catalyst effect under carry out constant temperature alcoholysis circular response.The present invention replaces liquid acid with solid acid, can avoid leading to the problem of big volume low-concentration acid waste water in tradition coolant agent production, reduces three waste discharge, while can also slow down production equipment corrosion significantly, meet environmentally protective theory；Using fixed bed reactors, with outer circulation type reaction process, under the premise of guaranteeing cyano alcoholysis is that the reaction of N- alkylamide is gone on smoothly, lower aliphatic alcohols are recycled after gas-liquid separator separates, reduce wastage of material, realizes the continuous production of coolant agent.
Description
Technical field
The invention belongs to technical field of compound preparation, are related to a kind of utilization solid acid catalyst synthesizing amide class coolant agent
Method.
Background technique
WS-23(N, 2,3- trimethyl -2- butanamide) it is that a kind of can replace the new of traditional coolant agent menthol
Type coolant agent is compared with menthol, and WS-23 has clear happy, lasting, fresh, nonirritant pungent, without bitter taste, low excellent of dosage
Point, and not strong smell, it is small to eye, mucous membrane and skin irritation, it can be widely applied to chewing gum, toothpaste, candy, fruit
The products such as jelly, jam, starch food, dairy products, meat products, cigarette, drug.
The overwhelming majority inside and outside the producing country of WS-23 is taken using propionitrile and halogenated isopropyl alkane as raw material, by condensation and alcohol
It solves addition two-step reaction and synthesizes WS-23, reaction equation is as follows:
。
The first step is to react to obtain intermediate product 2,2- diisopropyl third using propionitrile and halogenated isopropyl alkane in WS-23 synthesis
Nitrile, second step reaction usually in the presence of methanol or other methylating reagents, are turned cyano using acid catalysis alcoholysis addition mode
Become N- alkylamide.Cyano alcoholysis is that N- alkylamide reaction mechanism is that the hydrogen ion that fatty alcohol and acid catalyst provide is made
With generation carbocationic intermediate attack cyano nitrogen-atoms generates new imines carbonium ion, carbonium ion adds with water rapidly
At, then after sloughing hydrogen ion and isomerization, generate corresponding N- alkylamide.
Cyano alcoholysis is that N- alkylamide reaction step has the head such as numerous studies report, such as Lebedev M Y in 2002
It is raw material first with 2,2- diisopropyl propionitrile and methanol, synthesizes WS-23 under the conditions of sulphuric acid catalysis, then he also found benefit
Methanol is replaced with dimethyl carbonate, can also generate WS-23 in high yield under the conditions of sulphuric acid catalysis；Boden etc. utilizes 2,2- bis-
Isopropyl propionitrile and dimethyl suflfate successfully synthesize WS-23 under glyceryl triacetate existence condition under the conditions of 180 DEG C, but
It is that the method condition is relatively harsh, the cost is relatively high.
The acid catalysis cyano alcoholysis synthesis WS-23 reaction reported at present all uses a large amount of liquid Bronsted acid.Such as Li Jia
When jade etc. is reacted using 2,2- diisopropyl propionitrile and methanol, need to be added the sulfuric acid of 2,2- diisopropyl, 8 times of moles of propionitrile,
The product of higher yields just can be obtained, and the reaction time will be up to 30 hours.It would generally contain in system in the industrial production
A small amount of water, cyano are easy to be hydrolyzed to carboxylic acid under strong acid aqueous conditions, cause target product conversion ratio is low, yield is low to ask
Topic, therefore industrially replace sulfuric acid to be catalyzed using phosphoric acid or polyphosphoric acids, side reaction is reduced, but it is a large amount of to also need consumption
Phosphoric acid also needs that washing is gone to remove acid catalyst using a large amount of water after reaction, and the low-concentration waste acid of generation recycles difficult, pollution
Greatly, pole corrosive equipment is gone back.Therefore, for the synthesis WS-23 of high-efficiency environment friendly green economy, new catalyst is selected to improve catalysis
Efficiency avoids cyano complete hydrolysis at carboxyl, reduces spent acid discharge amount, it is very necessary to reduce environmental pollution.
Solid acid catalyst is due to its highly acid, nontoxic and do not corrode equipment, easily separated and recyclable advantage, through excessive
A kind of year developmental research, it has also become environmentally friendly, effective catalyst of green economy type.Solid acid is many kinds of, probably may be used
It is divided into following a few classes: immobilized liquid acid (such as HF-Al2O3), metal sulfide (such as CdS), metal sulfate/phosphate (such as
AlPO4), metal oxide, zeolite molecular sieve, heteropoly acid, natural clay mine, anion-cation exchange resin and superpower solid acid
Deng.It finds that cyano can be catalyzed by selection particular solid acid in the presence of fatty alcohol by research and is reacted to corresponding N- alkyl acyl
Amine.Xinchen etc., which is just reported, is catalyzed acrylonitrile and isopropanol reaction using H-ZSM-5, has obtained n-isopropyl acrylamide.
But it has been reported and is mostly applied to the cyan-hydrolysis that secondary alcohol and the tertiary alcohol are raw material and reacts, it is higher to obtain corresponding product yield, similar
Primary alconol reaction report it is seldom.
Summary of the invention
It is an object of the invention to not meet for having spent acid discharge in amides coolant agent synthetic method in the prior art
The problem of environmentally protective production, provides a kind of method using solid acid catalyst synthesizing amide class coolant agent.
To achieve the above object, the invention adopts the following technical scheme:
The present invention provides a kind of method using solid acid catalyst synthesizing amide class coolant agent, comprising the following steps:
Step a: by raw material 2,2- diisopropyl propionitrile, C1-C6Lower aliphatic alcohols, water is according to molar ratio 1:(1 ~ 20): (0.01
~ 0.2) it is uniformly mixed through mixer and fixed bed reactors is added, it is anti-that constant temperature alcoholysis circulation is carried out under solid acid catalyst effect
It answers；The solid acid catalyst and 2, the mass ratio of 2- diisopropyl propionitrile are 1:(10 ~ 1000), the constant temperature alcoholysis circulation is anti-
Reaction temperature is 30 ~ 150 DEG C in the reaction condition answered, and the reaction time is 2 ~ 10h；
Step b: sampling analysis detection, when the stable content of target product in reaction solution, by a part of reaction solution through gas-liquid point
C is isolated from device1-C6Lower aliphatic alcohols steam and mother liquor, C1-C6Lower aliphatic alcohols steam enter mixer after cooling
Entrance, mother liquor obtain crude product and unreacted 2,2- diisopropyl propionitrile and C after water washing, distillation, crystallization1-C6It is rudimentary
Fatty alcohol；
Step c: crude product obtains target product after recrystallizing.
Preferably, in the reaction condition of the constant temperature alcoholysis circular response reaction temperature be 70 ~ 80 DEG C, the reaction time be 3 ~
5h。
Preferably, the fixed bed reactors are heated using bushing type.
Preferably, the raw material 2,2- diisopropyl propionitrile, C1-C6Lower aliphatic alcohols, water molar ratio be 1:(6 ~ 8):
(0.05).
Preferably, the solid acid catalyst and 2, the mass ratio of 2- diisopropyl propionitrile are 1:500.
Preferably, the C1-C6Lower aliphatic alcohols be methanol, ethyl alcohol, isopropanol or isoamyl alcohol.
Preferably, the solid acid catalyst is solid selected from heteropoly acid, montmorillonite, perfluorinated sulfonic resin, molecular sieve, profit load type
One of body acid catalyst or superpower solid acid catalyst.
Preferably, carrier is selected from Al in the profit load type solid acid catalyst2O3, molecular sieve, SiO2, diatomite or activity
One of charcoal moistens liquid acid in load type solid acid catalyst and is selected from HF, HClO4、H3PO4, methane sulfonic acid, phosphomolybdic acid, P2O5Or
The molar ratio of one of trifluoromethanesulfanhydride anhydride, the liquid acid and carrier is 1:(0.1 ~ 10).
Preferably, it is super to be selected from the superpower solid acid of zirconium, the superpower solid acid of iron series or titanium system for the superpower solid acid catalyst
One of strong solid acids.
Heteropoly acid, montmorillonite, perfluorinated sulfonic resin, molecular sieve can be obtained by commercially available in solid acid catalyst in the present invention
, directly or simple activation can be used；Infusion process, calcination method and co-precipitation legal system can be used in profit load type solid acid catalyst
, preferably prepared by infusion process, and general process is as follows: carrier being added in certain density hydrochloric acid or nitric acid solution and is heated back
Stream, the carrier after filter, washing and drying, after being activated；Carrier after activation is added to liquid acid or liquid
In the solution of acid, submergence is loaded, filtration drying, and calcination activation obtains profit load type solid acid catalyst；Superpower solid acid catalyst
The optional SO of the middle superpower solid acid of zirconium4 2-/ZrO2, the optional SO of the superpower solid acid of iron series4 2-/Fe2O3, the superpower solid acid of titanium system is optional
SO4 2-/TiO2, it can be by commercially available acquisition, directly or simple activation can be used.
Compared with prior art, the beneficial effects of the present invention are:
1. the present invention replaces liquid acid catalysis 2,2- diisopropyl propionitrile and lower aliphatic alcohols reaction synthesis coolant agent with solid acid,
Homogeneous reaction is converted into heterogeneous reaction, on the one hand because the catalytic activity of solid acid is relatively stronger, catalytic effect is more preferable, can have
Effect improves the transformation efficiency of reaction, and on the other hand preventing cyano from excessively hydrolyzing becomes carboxyl, improves yield；In addition, with solid acid
Instead of liquid acid, it can avoid leading to the problem of big volume low-concentration acid waste water in tradition coolant agent production, reduce three waste discharge, together
When can also slow down significantly production equipment corrosion, meet environmentally protective theory.
2. the present invention makes full use of solid acid catalyst small spy of dissolubility in Organic Alcohol and 2,2- diisopropyl propionitrile
Point is guaranteeing that cyano alcoholysis is that the reaction of N- alkylamide is gone on smoothly using fixed bed reactors with outer circulation type reaction process
Under the premise of, lower aliphatic alcohols are recycled after gas-liquid separator separates, reduce wastage of material, realize coolant agent
Continuous production；In addition, reaction product does not have to separate with catalyst in the present invention, product also can be easily separated with surplus stock,
Separation costs substantially reduce, and improve coolant agent production efficiency.
3. the present invention uses fixed bed circular response, not only the extent of reaction is high, also effectively prevents asking for catalyst breakage
Topic is easy to operate, it can be achieved that consecutive production, yield is big.
4. it is raw material that different fatty alcohols, which can be used, in the present invention, a variety of amides coolant agents can be prepared, the scope of application is wider,
Application value is high.
Detailed description of the invention
Fig. 1 is the flow diagram of fixed bed reaction system of the present invention.
Numbering in the drawing: 1 is fixed bed reactors, and 2 be mixer, and 3 be inlet valve, and 4 be discharging pump, and 5 be the first valve,
6 be the second valve, and 7 be gas-liquid separator, and 8 be condenser.
Specific embodiment
The following examples are intended to illustrate the invention, but is not used to limit the scope of protection of the present invention.Unless otherwise specified, real
Apply the conventional means that technological means used in example is well known to those skilled in the art.Test method in following embodiments, such as
It is conventional method without special instruction.
Synthetic method of the present invention is realized in fixed bed reaction system, as shown in Figure 1, the fixed bed reaction system includes
Fixed bed reactors 1, mixer 2, inlet valve 3, discharging pump 4, the first valve 5, the second valve 6, gas-liquid separator 7 and condenser
8.The top of fixed bed reactors 1 is provided with spray head, and the lower end of spray head is protruded into fixed bed reactors 1, fixed bed reactors 1
Bottom connects the import of discharging pump 4, and the outlet of discharging pump 4 is divided into two-way, wherein being connected to spray through the second valve 6 and pipeline all the way
The entrance of head, another way connect the side entry of gas-liquid separator 7 through the first valve 5 with pipeline, and the top of gas-liquid separator 7 goes out
Hot stream inlet of the mouth through pipeline connection condenser 8, the hot stream outlet of condenser 8 are mixed through the entrance of pipeline connection mixer 2
The outlet of clutch 2 is connected to the entrance of spray head through inlet valve 3 and pipeline.Fixed bed reactors 1 are heated using bushing type, condenser
8 use recirculated cooling water to cool down for hot logistics.
The diameter of fixed bed reactors used is 40mm, is highly 800mm in embodiment；Raw material is after the mixing of mixer 2
Enter progress constant temperature alcoholysis circular response, the model Tianjin treasure of feed pump in fixed bed reactors 1 through spray head by inlet valve 3
The LS CLASS high pressure infuser constant flow pump of boat Science Court development in science and technology Co., Ltd.
Reaction equation is as follows:
。
Embodiment one
(1) preparation profit load type solid acid catalyst
Take 72g SiO2It is heated to reflux in the HCI solution of 100ml, 0.1mol/L 1 hour, filters, be washed to neutrality, 120 DEG C
It is 2 hours dry.By processed SiO2It is dispersed in dissolved with 100g HClO4Ethyl acetate in, stir evenly, heating concentration, nitrogen
80 ~ 100 DEG C of activation processing 30h, the HClO activated under gas shielded4-SiO2Moisten load type solid acid catalyst.
(2) WS-23 is catalyzed and synthesized
HClO after taking 70g to activate4-SiO2Profit load type solid acid catalyst is uniformly encased in fixed bed reactors 1, then will
140g 2,2- diisopropyl propionitrile, 256g methanol and 1.4g water mixed liquid are uniformly mixed through mixer 2, open inlet valve 3, former
Feed liquid enters in fixed bed reactors 1, after material liquid excludes air in pipeline, opens discharging pump 4 and the second valve 6, makes
Material liquid is obtained in 1 internal circulation flow of fixed bed reactors, opens bushing type heating device, keeps 150 DEG C of constant temperature alcoholysis circulations anti-
Answer 3h.
Sampling analysis, after 2,2- diisopropyl propionitrile content is no longer substantially reduced in reaction solution, the content of target product
When tending towards stability, the first valve 5 is opened, reaction solution is divided into two-way, controls inlet valve 3, the first valve 5 and the second valve 6
Aperture adjusts the flow of two branches and feed inlet, and to keep, fresh material stablizes supplement and product content is stablized.It is a part of anti-
Liquid is answered to isolate methanol steam and mother liquor through gas-liquid separator 7(pressure for 0.1Mpa), methanol steam is laggard through the cooling of condenser 8
Enter the recycling of 2 entrance of mixer, after mother liquor is washed with a small amount, is distilled and crystallization obtains crude product and unreacted 2,2-
Diisopropyl propionitrile and methanol, product yield 85%.
Crude product WS-23 is recrystallized to give net product WS-23(N, 2,3- trimethyl -2- butanamides), through GLC
Testing product purity is that 99.9%, NMR analysis result is as follows:1H NMR (600 MHz, cdcl3) δ7.45 (s, 1H),2.91
(s, 3H), 1.92 (m, 2H), 1.25 (s, 3H), 0.87(d, 12H)。
Embodiment two
(1) preparation profit load type solid acid catalyst
HClO4-SiO2The preparation such as embodiment 1 for moistening load type solid acid catalyst, repeats no more.
(2) N- ethyl -2,3- dimethyl-2-isopropyl butyramide is catalyzed and synthesized
HClO after taking 70g to activate4-SiO2Profit load type solid acid catalyst is uniformly encased in fixed bed reactors 1, then will
140g 2,2- diisopropyl propionitrile, 300g ethyl alcohol and 1.4g water mixed liquid are uniformly mixed through mixer 2, open inlet valve 3, former
Feed liquid enters in fixed bed reactors 1, after material liquid excludes air in pipeline, opens discharging pump 4 and the second valve 6, makes
Material liquid is obtained in 1 internal circulation flow of fixed bed reactors, bushing type heating device is opened, keeps 80 DEG C of constant temperature alcoholysis circular responses
3h。
Sampling analysis, after 2,2- diisopropyl propionitrile content is no longer substantially reduced in reaction solution, the content of target product
When tending towards stability, the first valve 5 is opened, reaction solution is divided into two-way, controls inlet valve 3, the first valve 5 and the second valve 6
Aperture adjusts the flow of two branches and feed inlet, and to keep, fresh material stablizes supplement and product content is stablized.It is a part of anti-
Liquid is answered to isolate alcohol vapour and mother liquor through gas-liquid separator 7(pressure for 0.1Mpa), alcohol vapour is laggard through the cooling of condenser 8
Enter the recycling of 2 entrance of mixer, after mother liquor is washed with a small amount, is distilled and crystallization obtains crude product and unreacted 2,2-
Diisopropyl propionitrile and ethyl alcohol, product yield 92%.
Crude product is recrystallized to give net product N- ethyl -2,3- dimethyl-2-isopropyl butyramide, is detected and is produced through GLC
Product purity is that 99.9%, NMR analysis result is as follows:1H NMR (600 MHz, cdcl3) δ7.95 (s, 1H),3.11 (q,
2H), 1.82 (m, 2H), 1.25 (s, 3H), 1.11(t,3H), 0.87(d, 12H)。
Embodiment three
(1) preparation profit load type solid acid catalyst
Take 72g SiO2It is heated to reflux in the HCI solution of 100ml, 0.1mol/L 1 hour, filters, is washed to neutrality, 120 DEG C
It is 2 hours dry.By processed SiO2It is dispersed in dissolved with 100g H3PO4Ethyl acetate in, stir evenly, heating concentration, nitrogen
80 ~ 100 DEG C of activation processing 30h, the H activated under gas shielded3PO4 -SiO2Moisten load type solid acid catalyst.
(2) WS-23 is catalyzed and synthesized
H after taking 65g to activate3PO4 -SiO2Profit load type solid acid catalyst is uniformly encased in fixed bed reactors 1, then will
140g 2,2- diisopropyl propionitrile, 256g methanol and 1.4g water mixed liquid are uniformly mixed through mixer 2, open inlet valve 3, former
Feed liquid enters in fixed bed reactors 1, after material liquid excludes air in pipeline, opens discharging pump 4 and the second valve 6, makes
Material liquid is obtained in 1 internal circulation flow of fixed bed reactors, opens bushing type heating device, keeps 120 DEG C of constant temperature alcoholysis circulations anti-
Answer 3h.
Sampling analysis, after 2,2- diisopropyl propionitrile content is no longer substantially reduced in reaction solution, the content of target product
When tending towards stability, the first valve 5 is opened, reaction solution is divided into two-way, controls inlet valve 3, the first valve 5 and the second valve 6
Aperture adjusts the flow of two branches and feed inlet, and to keep, fresh material stablizes supplement and product content is stablized.It is a part of anti-
Liquid is answered to isolate methanol steam and mother liquor through gas-liquid separator 7(pressure for 0.1Mpa), methanol steam is laggard through the cooling of condenser 8
Enter the recycling of 2 entrance of mixer, after mother liquor is washed with a small amount, is distilled and crystallization obtains crude product and unreacted 2,2-
Diisopropyl propionitrile and methanol, product yield 85%.
Crude product WS-23 is recrystallized to give net product WS-23(N, 2,3- trimethyl -2- butanamides), through GLC
Testing product purity is that 99.8%, NMR analysis result is as follows:1H NMR (600 MHz, cdcl3) δ7.46 (s, 1H),2.90
(s, 3H), 1.92 (m, 2H), 1.26 (s, 3H), 0.88(d, 12H)。
Example IV
(1) solid acid catalyst is prepared
Take 50g montmorillonite in the NaCO of 100ml, 0.2mol/L3It is heated to reflux in solution 1 hour, filters, be washed to neutrality, 120
DEG C dry 2 hours, 200-300 DEG C of 4 ~ 5h of activation processing, the Montmorillonite Solid Acid catalyst activated under nitrogen protection.
(2) WS-23 is catalyzed and synthesized
Montmorillonite Solid Acid catalyst after taking 50g to activate uniformly is encased in fixed bed reactors 1, then by 500g 2,2- bis-
Isopropyl propionitrile, 750g methanol and 5g water mixed liquid are uniformly mixed through mixer 2, open inlet valve 3, material liquid enters fixed bed
In reactor 1, after material liquid excludes air in pipeline, discharging pump 4 and the second valve 6 are opened, so that material liquid is in fixation
Bed 1 internal circulation flow of reactor, opens bushing type heating device, keeps 80 DEG C of constant temperature alcoholysis circular response 3h.
Sampling analysis, after 2,2- diisopropyl propionitrile content is no longer substantially reduced in reaction solution, the content of target product
When tending towards stability, the first valve 5 is opened, reaction solution is divided into two-way, controls inlet valve 3, the first valve 5 and the second valve 6
Aperture adjusts the flow of two branches and feed inlet, and to keep, fresh material stablizes supplement and product content is stablized.It is a part of anti-
Liquid is answered to isolate methanol steam and mother liquor through gas-liquid separator 7(pressure for 0.1Mpa), methanol steam is laggard through the cooling of condenser 8
Enter the recycling of 2 entrance of mixer, after mother liquor is washed with a small amount, is distilled and crystallization obtains crude product and unreacted 2,2-
Diisopropyl propionitrile and methanol, product yield 80%.
Crude product WS-23 is recrystallized to give net product WS-23(N, 2,3- trimethyl -2- butanamides), through GLC
Testing product purity is that 99.9%, NMR analysis result is as follows:1H NMR (600 MHz, cdcl3) δ7.45 (s, 1H),2.90
(s, 3H), 1.91(m, 2H), 1.25 (s, 3H), 0.86(d, 12H)。
Embodiment five
(1) solid acid catalyst is prepared
The preparation of Montmorillonite Solid Acid catalyst such as embodiment 1, repeats no more.
(2) N- isopropyl -2,3- dimethyl-2-isopropyl butyramide is catalyzed and synthesized
Montmorillonite Solid Acid catalyst after taking 50g to activate uniformly is encased in fixed bed reactors 1, then by 500g 2,2- bis-
Isopropyl propionitrile, 600g isopropanol and 5g water mixed liquid are uniformly mixed through mixer 2, open inlet valve 3, material liquid enters fixation
In bed reactor 1, after material liquid excludes air in pipeline, discharging pump 4 and the second valve 6 are opened, so that material liquid is solid
1 internal circulation flow of fixed bed reactor opens bushing type heating device, keeps 80 DEG C of constant temperature alcoholysis circular response 5h.
Sampling analysis, after 2,2- diisopropyl propionitrile content is no longer substantially reduced in reaction solution, the content of target product
When tending towards stability, the first valve 5 is opened, reaction solution is divided into two-way, controls inlet valve 3, the first valve 5 and the second valve 6
Aperture adjusts the flow of two branches and feed inlet, and to keep, fresh material stablizes supplement and product content is stablized.It is a part of anti-
Liquid is answered to isolate IPA vapor and mother liquor through gas-liquid separator 7(pressure for 0.1Mpa), IPA vapor is cooling through condenser 8
Enter 2 entrance of mixer afterwards to be recycled, after mother liquor is washed with a small amount, is distilled and crystallization obtains crude product and unreacted
2,2- diisopropyl propionitrile and isopropanol, product yield 95%.
(3) crude product is recrystallized to give net product N- isopropyl -2,3- dimethyl-2-isopropyl butyramide, is examined through GLC
Surveying product purity is that 99.8%, NMR analysis result is as follows:1H NMR (600 MHz, cdcl3) δ8.12 (s, 1H),3.78
(m, 1H), 1.76 (m, 2H), 1.25 (s, 3H),0.99(d,6H)0.87(d, 12H)。
Embodiment six
(1) solid acid catalyst is prepared
Take 72g SiO2It is heated to reflux in the HCI solution of 100ml, 0.1mol/L 1 hour, filters, be washed to neutrality, 120 DEG C
It is 2 hours dry.By processed SiO2It is dispersed in the ethyl alcohol dissolved with 1mol phosphomolybdic acid (PMA), stirs evenly, heating concentration,
120 ~ 150 DEG C of activation processing 3 ~ 5h, the PMA-SiO activated under nitrogen protection2Solid acid catalyst.
(2) WS-23 is catalyzed and synthesized
PMA-SiO after taking 70g to activate2Solid acid catalyst is uniformly encased in fixed bed reactors 1, then by 500g 2,2-
Diisopropyl propionitrile, 750g methanol and 5g water mixed liquid are uniformly mixed through mixer 2, open inlet valve 3, material liquid enters fixation
In bed reactor 1, after material liquid excludes air in pipeline, discharging pump 4 and the second valve 6 are opened, so that material liquid is solid
1 internal circulation flow of fixed bed reactor opens bushing type heating device, keeps 90 DEG C of constant temperature alcoholysis circular response 5h.
Sampling analysis, after 2,2- diisopropyl propionitrile content is no longer substantially reduced in reaction solution, the content of target product
When tending towards stability, the first valve 5 is opened, reaction solution is divided into two-way, controls inlet valve 3, the first valve 5 and the second valve 6
Aperture adjusts the flow of two branches and feed inlet, and to keep, fresh material stablizes supplement and product content is stablized.It is a part of anti-
Liquid is answered to isolate methanol steam and mother liquor through gas-liquid separator 7(pressure for 0.1Mpa), methanol steam is laggard through the cooling of condenser 8
Enter the recycling of 2 entrance of mixer, after mother liquor is washed with a small amount, is distilled and crystallization obtains crude product and unreacted 2,2-
Diisopropyl propionitrile and methanol, product yield 94%.
Crude product WS-23 is recrystallized to give net product WS-23(N, 2,3- trimethyl -2- butanamides), through GLC
Testing product purity is that 99.95%, NMR analysis result is as follows:1H NMR (600 MHz, cdcl3) δ7.46 (s, 1H),
2.90 (s, 3H), 1.92 (m, 2H), 1.26 (s, 3H), 0.88(d, 12H)。
Embodiment seven
(1) solid acid catalyst is prepared
Take the commercially available superpower solid acid SO of (traditional Chinese medicines) iron series of 70g4 2-/Fe2O3, impregnated 2 ~ 3 hours with 1mol/L sulfuric acid, 110 DEG C of conditions
Lower drying 12 hours, 500 ~ 600 DEG C of activation processing 4 ~ 5h, the SO activated under nitrogen protection4 2-/Fe2O3Solid acid catalyst.
(2) WS-23 is catalyzed and synthesized
SO after taking 70g to activate4 2-/Fe2O3Solid acid catalyst is uniformly encased in fixed bed reactors 1, then by 500g 2,
2- diisopropyl propionitrile, 750g methanol and 5g water mixed liquid are uniformly mixed through mixer 2, open inlet valve 3, and material liquid enters solid
In fixed bed reactor 1, after material liquid excludes air in pipeline, discharging pump 4 and the second valve 6 are opened, so that material liquid exists
1 internal circulation flow of fixed bed reactors opens bushing type heating device, keeps 80 DEG C of constant temperature alcoholysis circular response 10h.
Sampling analysis, after 2,2- diisopropyl propionitrile content is no longer substantially reduced in reaction solution, the content of target product
When tending towards stability, the first valve 5 is opened, reaction solution is divided into two-way, controls inlet valve 3, the first valve 5 and the second valve 6
Aperture adjusts the flow of two branches and feed inlet, and to keep, fresh material stablizes supplement and product content is stablized.It is a part of anti-
Liquid is answered to isolate methanol steam and mother liquor through gas-liquid separator 7(pressure for 0.1Mpa), methanol steam is laggard through the cooling of condenser 8
Enter the recycling of 2 entrance of mixer, after mother liquor is washed with a small amount, is distilled and crystallization obtains crude product and unreacted 2,2-
Diisopropyl propionitrile and methanol, product yield 76%.
Crude product WS-23 is recrystallized to give net product WS-23(N, 2,3- trimethyl -2- butanamides), through GLC
Testing product purity is that 99.9%, NMR analysis result is as follows:1H NMR (600 MHz, cdcl3) δ7.46 (s, 1H),2.90
(s, 3H), 1.92 (m, 2H), 1.26 (s, 3H), 0.88(d, 12H)。
Embodiment eight
(1) preparation profit load type solid acid catalyst
HClO4-SiO2The preparation such as embodiment 1 for moistening load type solid acid catalyst, repeats no more.
(2) WS-23 is prepared
HClO after taking 70g to activate4-SiO2Profit load type solid acid catalyst is uniformly encased in fixed bed reactors 1, then will
140g 2,2- diisopropyl propionitrile, 256g methanol and 1.4g water mixed liquid are uniformly mixed through mixer 2, open inlet valve 3, former
Feed liquid enters in fixed bed reactors 1, after material liquid excludes air in pipeline, opens discharging pump 4 and the second valve 6, makes
Material liquid is obtained in 1 internal circulation flow of fixed bed reactors, bushing type heating device is opened, keeps 30 DEG C of constant temperature alcoholysis circular responses
3h。
Sampling analysis, after 2,2- diisopropyl propionitrile content is no longer substantially reduced in reaction solution, the content of target product
When tending towards stability, the first valve 5 is opened, reaction solution is divided into two-way, controls inlet valve 3, the first valve 5 and the second valve 6
Aperture adjusts the flow of two branches and feed inlet, and to keep, fresh material stablizes supplement and product content is stablized.It is a part of anti-
Answer liquid through gas-liquid separator 7(vacuum degree 0.01pa) methanol steam and mother liquor are isolated, methanol steam is laggard through the cooling of condenser 8
Enter the recycling of 2 entrance of mixer, after mother liquor is washed with a small amount, is distilled and crystallization obtains crude product and unreacted 2,2-
Diisopropyl propionitrile and methanol, product yield 25%.
Crude product WS-23 is recrystallized to give net product WS-23(N, 2,3- trimethyl -2- butanamides), through GLC
Testing product purity is that 99%, NMR analysis result is as follows:1H NMR (600 MHz, cdcl3) δ7.45 (s, 1H),2.91
(s, 3H), 1.92 (m, 2H), 1.25 (s, 3H), 0.87(d, 12H)。
Embodiment nine
(1) preparation profit load type solid acid catalyst
HClO4-SiO2The preparation such as embodiment 1 for moistening load type solid acid catalyst, repeats no more.
(2) N- isopentyl -2,3- dimethyl-2-isopropyl butyramide is prepared
HClO after taking 70g to activate4-SiO2Profit load type solid acid catalyst is uniformly encased in fixed bed reactors 1, then will
140g 2,2- diisopropyl propionitrile, 600g isoamyl alcohol and 1.4g water mixed liquid are uniformly mixed through mixer 2, open inlet valve 3,
Material liquid enters in fixed bed reactors 1, after material liquid excludes air in pipeline, opens discharging pump 4 and the second valve 6,
So that material liquid opens bushing type heating device in 1 internal circulation flow of fixed bed reactors, 150 DEG C of constant temperature alcoholysis circulations are kept
React 3h.
Sampling analysis, after 2,2- diisopropyl propionitrile content is no longer substantially reduced in reaction solution, the content of target product
When tending towards stability, the first valve 5 is opened, reaction solution is divided into two-way, controls inlet valve 3, the first valve 5 and the second valve 6
Aperture adjusts the flow of two branches and feed inlet, and to keep, fresh material stablizes supplement and product content is stablized.It is a part of anti-
Liquid is answered to isolate isoamyl alcohol steam and mother liquor through gas-liquid separator 7(pressure for 0.1Mpa), isoamyl alcohol steam is cooling through condenser 8
Enter 2 entrance of mixer afterwards to be recycled, after mother liquor is washed with a small amount, is distilled and crystallization obtains crude product and unreacted
2,2- diisopropyl propionitrile and isoamyl alcohol, product yield 85%.
Crude product is recrystallized to give net product (N- isopentyl, 2,3- dimethyl-2-isopropyl butyramides), is examined through GLC
Surveying product purity is that 99%, NMR analysis result is as follows:1H NMR (600 MHz, cdcl3) δ8.01 (s, 1H),3.41 (m,
2H), 1.82 (m, 2H), 1.55 (m, 1H), 1.39(m,2H), 1.26(s,3H) ,0.87(d, 18H)。
The embodiment of the above, only presently preferred embodiments of the present invention, is only used to explain the present invention, not limit
The scope of the present invention processed to those of ordinary skill in the art certainly can be according to skill disclosed in this specification
Art content makes other embodiments easily by way of replacing or changing, therefore all made in the principle of the present invention
Changes and improvements etc., should be included in scope of the present invention patent.
Claims (9)
1. a kind of method using solid acid catalyst synthesizing amide class coolant agent, which comprises the following steps:
Step a: by raw material 2,2- diisopropyl propionitrile, C1-C6Lower aliphatic alcohols, water is according to molar ratio 1:(1 ~ 20): (0.01 ~
0.2) it is uniformly mixed through mixer and fixed bed reactors is added, it is anti-that constant temperature alcoholysis circulation is carried out under solid acid catalyst effect
It answers；The solid acid catalyst and 2, the mass ratio of 2- diisopropyl propionitrile are 1:(10 ~ 1000), the constant temperature alcoholysis circulation is anti-
Reaction temperature is 30 ~ 150 DEG C in the reaction condition answered, and the reaction time is 2 ~ 10h；
Step b: sampling analysis detection, when the stable content of target product in reaction solution, by a part of reaction solution through gas-liquid point
C is isolated from device1-C6Lower aliphatic alcohols steam and mother liquor, C1-C6Lower aliphatic alcohols steam enter mixer after cooling
Entrance, mother liquor obtain crude product and unreacted 2,2- diisopropyl propionitrile and C after water washing, distillation, crystallization1-C6It is rudimentary
Fatty alcohol；
Step c: crude product obtains target product after recrystallizing.
2. the method according to claim 1 using solid acid catalyst synthesizing amide class coolant agent, which is characterized in that institute
Stating reaction temperature in the reaction condition of constant temperature alcoholysis circular response is 70 ~ 80 DEG C, and the reaction time is 3 ~ 5h.
3. the method according to claim 1 using solid acid catalyst synthesizing amide class coolant agent, which is characterized in that institute
Fixed bed reactors are stated to heat using bushing type.
4. the method according to claim 1 using solid acid catalyst synthesizing amide class coolant agent, which is characterized in that institute
State raw material 2,2- diisopropyl propionitrile, C1-C6Lower aliphatic alcohols, water molar ratio be 1:(6 ~ 8): (0.05).
5. the method according to claim 1 using solid acid catalyst synthesizing amide class coolant agent, which is characterized in that institute
The mass ratio for stating solid acid catalyst and 2,2- diisopropyl propionitrile is 1:500.
6. the method according to claim 1 using solid acid catalyst synthesizing amide class coolant agent, which is characterized in that institute
State C1-C6Lower aliphatic alcohols be methanol, ethyl alcohol, isopropanol or isoamyl alcohol.
7. the method according to claim 1 using solid acid catalyst synthesizing amide class coolant agent, which is characterized in that institute
It states solid acid catalyst and is selected from heteropoly acid, montmorillonite, perfluorinated sulfonic resin, molecular sieve, profit load type solid acid catalyst or superpower
One of solid acid catalyst.
8. the method according to claim 7 using solid acid catalyst synthesizing amide class coolant agent, which is characterized in that institute
It states carrier in profit load type solid acid catalyst and is selected from Al2O3, molecular sieve, SiO2, one of diatomite or active carbon, moisten load type
Liquid acid is selected from HF, HClO in solid acid catalyst4、H3PO4, methane sulfonic acid, phosphomolybdic acid, P2O5Or one in trifluoromethanesulfanhydride anhydride
Kind, the molar ratio of the liquid acid and carrier is 1:(0.1 ~ 10).
9. the method according to claim 7 using solid acid catalyst synthesizing amide class coolant agent, which is characterized in that institute
It states superpower solid acid catalyst and is selected from one of the superpower solid acid of zirconium, the superpower solid acid of the superpower solid acid of iron series or titanium system.
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| CN113454060A (en) * | 2021-05-28 | 2021-09-28 | 安徽金禾实业股份有限公司 | Preparation method of acetoacetamide-N-sulfonic acid triethylamine salt |
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