CN105085536B - A kind of preparation method of tetraphenylporphines - Google Patents
A kind of preparation method of tetraphenylporphines Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of tetraphenylporphines：(1) pyrroles and aromatic aldehyde are made into mixed solution, it is standby；(2) solvent is added into polymer reactor, nitrogen displacement to tail oxygen concentration is less than after 1% to be heated to flowing back by solvent, then start that the mixed solution that step (1) obtains is added dropwise and start to react, stop reaction after continuing reaction after being added dropwise 0.05~0.5 hour；(3) it is passed through the oxygen-containing gas that oxysome fraction is 5~100% into polymer reactor to be aoxidized, oxidation cools down after terminating, filters to obtain filter cake and filtrate, by Washing of Filter Cake, drying to obtain product.The present invention has the advantages of high income, safety and environmental protection, separating-purifying are simple, product quality is stable.
Description
Technical field
The present invention relates to the preparation method of tetraphenylporphines, and in particular to it is a kind of using pyrroles, aromatic aldehyde and oxygen-containing gas as
The safe and efficient method for preparing tetraphenylporphines of reaction raw materials.
Background technology
Tetraphenylporphines (hereinafter referred to as TPP) are important luminescent materials, and the raw material of synthesis metalloporphyrin.Adler
Method is the best way of generally acknowledged synthesis tetraphenylporphines, and the method uses pyrroles and benzaldehyde former for reaction in the lab
Material, in the propionic acid that flow back react synthesized TPP (J.Am.Chem.Soc., 1964,86:3145；J.Org.Chem.,1967,32:
476).But the TPP yields in terms of pyrroles that the method obtains are less than 20%, and wherein contain 5~10% impurity dihydro tetraphenyl
Porphines (hereinafter referred to as TPC).In order to remove the TPC impurity being mixed with TPP, researcher afterwards has been carried out largely to Adler methods
Improvement, be concentrated mainly on both direction：(1) TPP of the impurity containing TPC is dissolved in benzene, dimethyl sulfoxide (DMSO), dichloromethane, three
In the organic solvents such as chloromethanes, TPC is then removed using the method for chromatogram post separation.(2) TPP of the impurity containing TPC is dissolved in
After in certain organic solvent, a certain amount of weak chemical oxidizing agent such as chloro- 5,6- bis- of TCBQ, 2,3- bis- is added
TPC is oxidized to TPP and removes TPC by benzonitrile quinone etc..Due to solubility of the TPP and TPC in organic and inorganic solvent all very littles,
Either chromatogram column technique still adds chemical oxidation agent method, is required for increasing the separation of substantial amounts of solvent, and process is more, solvent damage
Consumption is big, and production cost is high, is not suitable for industrial large-scale production.Moreover, how these laboratory methods are from purifying angle
To consider TPP composition problem, and the rare TPP from the perspective of reaction yield is improved composition problem, cause with pyrroles
The TPP of meter yield is relatively low, and pyrroles is expensive, is cost factor important when producing TPP, this also causes existing experiment
The production cost of room method is high, is not suitable for industrial large-scale production.
China Patent Publication No. CN101550140A, publication date on October 7th, 2009, denomination of invention：Tetaraary porphyrin
Synthetic method and equipment.This application case is disclosed a kind of high for raw material by pyrroles, aromatic aldehyde and air based on Adler methods
The batch process of yield synthesis tetaraary porphyrin (abbreviation TAP).The synthetic method is related to same reactor at ambient pressure
In complete pyrroles simultaneously and aromatic aldehyde is polycondensed into dihydro tetaraary porphyrin (abbreviation TAC) and TAC air oxidation two is reacted.Should
Method reaction time length, causes side reaction more, product yield is low because reaction temperature is relatively low.Moreover, pyrroles, propionic acid or other having
After solvent and air mixing, volatile gas is easily produced, safety problem during industrial production does not also carry in that patent
And.
China Patent Publication No. CN103880852A, publication date 2014 year 06 month 25 days, denomination of invention：Tetaraary porphyrin
Continuous production processes.For this application case based on CN101550140, it is raw material to disclose one kind by pyrroles, aromatic aldehyde and air
The continuous producing method of high yield synthesis tetaraary porphyrin (abbreviation TAP).The solvent used in the present invention be acetic acid, propionic acid, benzene,
One or more in toluene, dimethylbenzene etc., reactant are pyrroles and aromatic aldehyde, and it is anti-that air is continuously passed through in reaction dissolvent
Should.This application case is unaware that continuous operation process is passed through oxygen-containing gas and can bring huge safe operation risk.Described
Great risk existing for air and security are passed through in several solvents, does not refer to any counter-measure.While contain being passed through
In the case of carrier of oxygen, pyrroles and aromatic aldehyde are more easy to be lost by oxygen in system, cause to report in patent in high yield can
Reliability is very low, while generates the gel-like foreign matters for being difficult to separate.
China Patent Publication No. CN102952143A, publication date 2013 year 03 month 06 day, denomination of invention：A kind of tetraphenyl porphin
The preparation method of fen.For this application case equally based on Adler methods, it is raw material to disclose one kind by pyrroles, aromatic aldehyde and air
The method of high yield synthesis tetraphenylporphyrin (abbreviation TPP).The synthetic method is related to complete in two different reactors respectively
Dihydro tetraphenylporphyrin (abbreviation TPC) and TPC two reactions of air oxidation are polycondensed into pyrroles and aromatic aldehyde.
The content of the invention
Instant invention overcomes the defects of prior art, there is provided a kind of high income, safety and environmental protection, separating-purifying are simple, production
The preparation method of the stable tetraphenylporphines of quality.
Technical scheme is used by the present invention solves above-mentioned technical problem：A kind of system of safe and efficient tetraphenylporphines
Preparation Method, comprise the following steps：
(1) it is 0.5~1.1 in molar ratio by pyrroles and aromatic aldehyde:1 is made into mixed solution, standby；
(2) solvent is added into polymer reactor, solvent is heated to back by nitrogen displacement to tail oxygen concentration after being less than 1%
Stream, it is 1~5atm to maintain polymer reactor pressure, then starts that the mixed solution that step (1) obtains is added dropwise and starts polymerization instead
Should, maintain molar concentration of the pyrroles in reaction solution to be less than 0.1mol/L during dropwise addition all the time, the pyrroles's being finally added dropwise is total
Molar concentration is 0.1~0.6mol/L, removes the water of reaction generation in course of reaction by distilling with maintenance reaction liquid reclaimed water
Mass percentage concentration is consistently lower than 0.2%, stops reaction after continuing reaction after being added dropwise 0.05~0.5 hour, reaction terminates
When reaction temperature be 125~165 DEG C；
(3) oxygen-containing gas that oxysome fraction is 5~100% is passed through into polymer reactor and carries out oxidation reaction, reaction
During the amount of oxygen-containing gas that is passed through by adjusting control oxygen concentration in tail gas to be less than 2%, oxidization time is 0.1~1.0
Hour, reaction pressure is 1~5atm, and oxidation cools down after terminating, filters to obtain filter cake and filtrate, by Washing of Filter Cake, drying to obtain
Product.
Further：
As the preferred embodiments of the invention, obtained when the water for reacting generation will be removed by distilling in step (2)
After product of distillation condensation layering, upper oil phase and lower floor's aqueous phase are obtained, upper oil phase is recycled back in polymer reactor.
As the preferred embodiments of the invention, the filtrate that step (3) is obtained carries out rectifying with recycling design.
As the preferred embodiments of the invention, the aromatic aldehyde structural formula such as (I) described in step (1) is shown, wherein, take
One kind in hydrogen, alkyl, alkoxy, hydroxyl or halogen is respectively selected from for base R1, R2, R3.
As the preferred embodiments of the invention, described aromatic aldehyde be benzaldehyde, 4-chloro-benzaldehyde, m chlorobenzaldehyde,
O-chlorobenzaldehyde, p-tolyl aldehyde, o-tolualdehyde, a tolyl aldehyde, salicylaldhyde, m-hydroxybenzaldehyde,
Parahydroxyben-zaldehyde, P-methoxybenzal-dehyde, o-methoxybenzaldehyde, m-methoxybenzaldehyde, 4-Fluorobenzaldehyde, adjacent fluorobenzene first
One kind in aldehyde, a fluorobenzaldehyde, p-bromobenzaldehyde, o-bromobenzaldehye, 3-bromobenzaldehyde.
As the preferred embodiments of the invention, solvent propionic acid or propionic acid described in step (2) and hexamethylene, toluene,
A kind of mixture of composition in benzene, ethylbenzene, paraxylene, meta-xylene, ortho-xylene, the volume of propionic acid in the mixture
Fraction is 60~80%.
Kim in 1971 etc. proposes the following four important steps undergone in four aryl porphines building-up processes according to experimental result
Suddenly (Kim J B, Leonard J J, Longo F R.A mechanistic study of the synthesis and
Spectral properties of meso-tetraarylporphyrins [J] .J.Am.Chem.Soc., 1972,94
(11)：3986-3992.)：
(a) benzaldehyde and pyrroles generate single pyrroles's primary alconol (wherein Ar represents aryl, below identical)
(b) propagation process：Single pyrroles's primary alconol and other pyrroles's molecule, the reaction of benzaldehyde molecule
(c) the cyclisation generation porphyrinogen of straight chain tetrapyrrole
(d) Oxidation of porphyrinogen is porphyrin
Lindsey in 1987 thinks there is being N2Protection in the case of, pyrroles and benzaldehyde generate under the catalytic action of acid
Porphyrinogen, this step are reversible, and the rate controlling step entirely reacted, can be by porphyrin when adding the oxidants such as DDQ
Original is oxidized to porphyrin.According to experimental result, reaction mechanism that Lindsey is proposed it is following (Lindesy J S, Scheiman I C,
Hsu H C,et al.Rothemund and Adler-Longo reaction revisited:Synthesis of
tetraphenylporphyrins under equilibrium conditions[J].J.Org.Chem.,1987,52(5):
827-836.)：
According to above reaction mechanism, reaction of the invention is carried out in three steps, as shown in reaction equation (x), (y) and (z)：
In (x) is reacted, four poly-, formation intermediate product porphyrinogen C occur between each other for reactant pyrroles B and benzaldehyde A
(hereinafter referred to as TPPG) and water.The reaction is reversible reaction, and the presence of water can substantially reduce system TPPG yield；Reacting
(y) in, intermediate product TPPG is oxidized to another intermediate product dihydro tetraphenylporphines D (hereinafter referred to as in the presence of oxygen
TPC)；In (z) is reacted, intermediate product TPC is oxidized to target product tetraphenylporphines F (following letters in the presence of oxygen
Claim TPP).TPPG and TPC is the major impurity in TPP.
Reacted if pyrroles, benzaldehyde are disposably added in the propionic acid solution of reflux state, Typical experimental conditions
Under in obtained reaction system the concentration of reactant pyrroles and benzaldehyde (to react the amount phase of remaining reactant in instantaneous system
The percentage of initial input is represented) relation that changes with time is as shown in Figure 1.
It can be seen that after starting reaction, the concentration of benzaldehyde and pyrroles decline rapidly, show first step reaction (x) quickly, simultaneously
Water can produce rapidly as reaction product.And water is the poisonous substance of reaction, rate-determining steps reaction (x) is affected, to reaction yield
Influence is very big, should be removed in time from reaction system.Fig. 2 gives four benzene obtained during different water contents in maintenance reaction system
The yield of base porphines.It can be seen that the water for reacting generation is timely removed from reaction system, the receipts of target product can be greatly improved
Rate.The water of the invention for especially emphasizing to generate in course of reaction should remove in time to be less than with the mass fraction of the water in maintenance reaction liquid
0.2%, the easy mode for removing water can be passed through solvent and evaporated folder using the side border ring distillation procedure described in claim 1
Take the water of reaction generation out of, the condensate liquid for distilling to obtain is recycled directly back to reaction system by hierarchical operations, organic layer.
Propionic acid and water are azeotropic system, and it is big by the energy consumption for being directly distilled off needing consuming to react the water of generation, therefore,
In the present invention, consider to add hexamethylene, toluene, benzene, ethylbenzene, paraxylene, meta-xylene, ortho-xylene in toward solvent propionic acid
Deng it has been water entrainer effect that it, which is acted on, distillation and tower top organic matter of the more convenient water that will be generated in reaction system by solvent
Flow back and take reaction system out of, relatively low water concentration in maintenance reaction system, in order to avoid water concentration is too high, influence to react (x) generation
Intermediate product TPPG reaction yield.And system must be carried out in acid condition, therefore, the volume fraction of propionic acid in system
It should keep being not less than 60% all the time.
Under the catalytic action of acid, benzaldehyde and pyrroles generate single pyrroles's primary alconol (reaction (a)), and then chain increases generation four
Pyrroles's primary alconol, tetrapyrrole primary alconol can be cyclized generation porphyrinogen C (reaction (c)), can continue to chain and increase generation polypyrrole primary
The process of alcohol, cyclization process and generation polypyrrole primary alconol is vied each other, therefore simple only increase reactant concentration can not
Increase the yield of product, the amount of long-chain polypyrrole accessory substance can be increased on the contrary.Inventors herein have recognized that by controlling pyrroles
B concentration can reduce the speed of pyrroles's B autohemagglutinations in a relatively low scope.Meanwhile by suitably increasing reactant benzaldehyde
With the concentration proportion of pyrroles, it can make it that the conversion of pyrroles is more complete.Therefore, in the present invention, raw material pyrroles and benzaldehyde
Molar ratio control is 0.5~1.1:1, and especially emphasize that pyrroles and substituted benzaldehyde are made into by reaction in proportion before starting
Phase solution, then it is added to by the way of being added dropwise in the reaction dissolvent of reflux state and goes the pyrroles for being reacted, being finally added dropwise
Total mol concentration be 0.1~0.6mol/L, maintain molar concentration of the pyrroles in reaction solution to be less than during dropwise addition all the time
0.1mol/L, to reduce the probability for generating polypyrrole primary alconol, improve the yield of product.
Solvent has a certain impact to the polymerisation of benzaldehyde and pyrroles.Propionic acid or propionic acid and hexamethylene can be selected in solvent
The mixture of a kind of composition in alkane, toluene, benzene, ethylbenzene, paraxylene, meta-xylene, ortho-xylene, third in the mixture
The volume fraction of acid is 60~80%.Into solvent propionic acid add hexamethylene, toluene, benzene, ethylbenzene, paraxylene, meta-xylene,
The effect of ortho-xylene etc. has been water entrainer effect, more convenient by distillation and tower top of the water generated in reaction system by solvent
Organic matter flows back and takes reaction system out of, relatively low water concentration in maintenance reaction system, in order to avoid water concentration is too high, influences to react
(x) the intermediate product TPPG of generation reaction yield.Propionic acid atmospheric boiling point is 141 DEG C, and explosion limit is 2.9~12.1%；Benzene
Atmospheric boiling point is 110.6 DEG C, and explosion limit is 1.2~11.0%；Toluene atmospheric boiling point be 110.6 DEG C, explosion limit be 1.2~
7.0%；Adjacent// atmospheric boiling point of paraxylene is 144.4/139/138.5 DEG C, explosion limit is between 1~7%；Pyrroles
Atmospheric boiling point be 131 DEG C, its normal pressure explosion limit be 3.1~14.8%.For the security of operation, the present invention especially emphasizes,
Before polymer reactor starts to warm up, N need to be used2By the O in reactor2Replace to tail oxygen concentration below 1%, in order to avoid temperature-rise period
After middle solvent or reactant pyrroles evaporation volatile gas-phase space is formed with the air in polymer reactor.Then by system liter
Pyrroles and substituted benzaldehyde are 0.5~1.1 in molar ratio to reaction temperature and reaction pressure by temperature:1 be made into homogeneous phase solution after adopt
Add to obtain in polymer reactor with the mode of dropwise addition, keep the concentration of pyrroles in liquid-phase system to be consistently lower than during dropwise addition
0.1mol/L, it is ensured that concentration of the more volatile pyrroles in gas-phase space is relatively low.
Before polymer reactor starts to warm up, N is used2By the O in reactor2The operation to tail oxygen concentration below 1% is replaced,
Also achieve following unexpected effect.Water concentration is not higher than 0.2% premise in the strict control reaction system of the present invention
Under, before polymer reactor starts to warm up, using N2By the O in reactor2Replace to operation of the tail oxygen concentration below 1%, obtain
To tetraphenylporphines yield and do not use N2By the O in reactor2When replacing the yield of obtained tetraphenylporphines with reaction
Between variation relation such as Fig. 3.It can be seen that, it is generally the case that using N2By the O in reactor2Displacement is to tail oxygen concentration below 1%
After operation, the yield of obtained tetraphenylporphines less uses N2By the O in reactor2Replace the receipts of obtained tetraphenylporphines
Rate is obvious high.Because except reacting in addition to (x) in course of reaction, an also important reaction is exactly benzaldehyde and pyrrole
Cough up the reaction with oxygen.Under high temperature, benzaldehyde be easy to oxygen reaction formed benzoic acid, pyrroles be easy to oxygen reaction and
Consumption.The two reactions are vied each other with goal response (x).In the present invention, N is used2By the O in polymer reactor2After displacement, energy
The reaction of benzaldehyde and pyrroles and oxygen is effectively avoided, so as to improve the selectivity of main reaction, improves the selectivity of target product.
Reaction time is an important factor for influenceing product yield.To reacting (a), experimental result reflects that the kinetics connects
Near is two level, to reactant pyrroles and fragrant aldehyde concentration close to one-level.Phase pyrroles and aromatic aldehyde are in system after the reaction
Concentration decline is very slow, after reacting a period of time, continues to extend yield raising of the reaction time to reaction product less.And anti-
At a temperature of answering, autohemagglutination, the autohemagglutination of the extension meeting addition polymerization pyrroles in reaction time can also occur for pyrroles itself.As shown in Figure 1,15 minutes
Left and right reactant benzaldehyde is reacted complete, is further added by the reaction time, simply increases the autohemagglutination of reactant pyrroles and is lost.
The present inventor through research it has furthermore been found that pyrroles and benzaldehyde reaction speed are very fast, 10 minutes or so products TPPG, TPC and TPP
Total growing amount be more than 75% of growing amount after having reached stable, 30 minutes or so products TPPG, TPC and TPP total generation
Amount i.e. no longer significant changes.The reaction time is further added by, unobvious are influenceed on product TPPG, TPC and TPP total growing amount,
On the contrary, in the presence of high temperature, the autohemagglutination speed of reactant pyrroles is accelerated, and the extension reaction time can only aggravate reactant pyrroles
Autohemagglutination, reduce the total recovery of TPPG, TPC and TPP in terms of reactant pyrroles, simultaneously because autohemagglutination and generate substantial amounts of black and gather
Compound, cause follow-up product separating-purifying difficult.Conventional synthesis TPP method is all reaction more than 0.5 hour, and increase is anti-
Between seasonable, this not but not increase product yield, can also produce substantial amounts of polymeric by-products, cause follow-up separation process to be stranded
It is difficult.And the present inventor adjusts reaction solution by the polymeric reaction temperature after controlling the time of reaction (a) progress and being added dropwise
The concentration and polymerization speed of middle pyrroles, the autohemagglutination of pyrroles can be effectively reduced, therefore, therefore, step (1) reaction time in the present invention
Control was at 0.05~0.5 hour.
Polymeric reaction temperature is an important factor for influenceing product yield.In the presence of high temperature, the autohemagglutination of reactant pyrroles
Speed is accelerated, but reaction speed is simultaneously also obvious to be accelerated, and this is a process vied each other.It is preferable anti-in the present invention
It is 125~165 DEG C to answer temperature.And reaction dissolvent is propionic acid or propionic acid and hexamethylene, toluene, benzene, ethylbenzene, paraxylene, two
A kind of mixture in toluene, ortho-xylene.For maintenance reaction temperature, reaction pressure need to be controlled in 1~5atm.
In polymerization process, reaction raw materials stop reaction after reacting 0.05~0.5 again after being added dropwise.Then it is polymerizeing
Oxygen-containing gas is passed through in reactor and carries out oxidation reaction, the boiling point of reaction temperature system, reaction pressure is 1~5atm.Reacted
Reaction solution can be stirred continuously in journey to accelerate reaction speed.O in oxygen-containing gas in the present invention2Weight/mass percentage composition be
5%~100%, preferably pure oxygen or oxygen-enriched air or air.For the security of operation, the present invention especially emphasizes, oxidation reaction mistake
The amount for the oxygen being passed through in journey should be controlled strictly, to cause the concentration of oxygen in tail gas to maintain less than 2% all the time.
Oxidation time has a great influence to product purity.To reaction (b) and (c), two are reacted simultaneously in system
Carry out, test result indicates that the kinetics is close to one-level to reactant TPPG and TPC, to reactant oxygen close to zero
Level.Time by extending logical oxygen can reduce impurity TPPG and TPC concentration, improve TPP purity.But experiment is found, in height
Under the conditions of the logical oxygen of temperature, TPP can also be oxidized by oxygen and degrade, and reduce TPP yield.By controlling reaction (b) and (c) to enter
The capable time adjusts the concentration of TPPG and TPC in reaction solution, while controls TPP degraded, can improve the same of TPP purity
Shi Jinliang does not lose TPP yield.Therefore, step (3) reaction time was controlled at 0.1~1 hour in the present invention.
According to the present invention, oxidation time is 0.1~1 hour, and oxidation reaction stops heating after terminating, and stops ventilation,
And normal temperature is cooled to, the product TPP generated in reaction system can crystallize precipitation.Using the separation method of routine as filtered or centrifuging
Method, TPP mixture is separated from system.The TPP that this step obtains is the first product of target product, and the inside still contains
There are a small amount of intermediate product TPPG, TPC and a small amount of azole polymer, oxidation of Benzaldehyde product etc., conventional method can be used
Purified, such as filter cake is washed with again with methanol after hot wash or ethanol, the TPP in terms of reactant pyrroles finally given
Synthetic yield more than 40.1%, reach as high as 59.7%, the content of other impurity is reduced to less than 1.5%, product purity
Reach more than 98.5%.In filtrate in addition to the solvents, also it is mixed with very small amount of water byproduct, a certain amount of undecomposed TPPG,
TPC and TPP, and a certain amount of polymeric impurities to be come by filter cake band.The dosage of solvent is larger, need to recycle and reuse, and leads to
Conventional lock out operation such as distillation operation is crossed, reaction dissolvent can be reclaimed, oxidation can be recirculated back to by reclaiming the reaction dissolvent returned
Reaction is participated in reactor.Outside the water byproduct and residue discharge system of reaction, otherwise processed.
According to the present invention, TPP content liquid-phase chromatographic analysis in product.Because pyrroles is price most expensive in this reaction
Reactant, its autohemagglutination or oxidation product are also the impurity for being most difficult to remove in TPP, therefore, the TPP's in terms of pyrroles in the present invention
As one of good and bad outstanding feature of technical process is weighed, computational methods are synthetic yield：
The present invention has advantages below：
1st, high income, the present invention substantially increase the yield of reaction, with reactant pyrrole by optimizing reaction process and parameter
The synthetic yield of the tetraphenylporphines of meter is coughed up more than 40.1%, up to 59.7%；
2nd, safe operation, product separating-purifying is simple, and after being handled using conventional method, the content of other impurity is reduced to
Less than 1.5%, product purity reaches more than 98.5%, is adapted to industrial-scale production；
3rd, green, three waste discharge is few, filtrate reusable edible.
Brief description of the drawings
Fig. 1 is that pyrroles and benzaldehyde are disposably added in the propionic acid solution of reflux state to react, obtained reactant
The concentration of reactant pyrroles and benzaldehyde changes with time graph of a relation under Typical experimental conditions in system；
Fig. 2 is tetraphenylporphines (R under different water concentrations1=R2=R3=H) yield；
Fig. 3 is before polymer reactor starts to warm up, using N2By the O in reactor2Displacement is to tail oxygen concentration below 1%
Operation after and do not use N2By the O in reactor2Replace obtained tetraphenylporphines (R1=R2=R3=H) yield with the time
Variation relation figure；
Fig. 4 is the craft block-diagram of the present invention.
As illustrated, wherein：
A is aromatic aldehyde, and B is pyrroles, E is solvent that polymerisation uses, and F is target product tetraphenylporphines；
1 is polymer reactor, and 2 be filtration wash unit, and 3 be polymerization solvent recovery tower, and 4 be liquid liquid decker.
Embodiment
The present invention is described in further detail below in conjunction with drawings and examples, but the present invention is not limited to described reality
Apply example.
Embodiment 1
(1) 560mol pyrroles and 560mol benzaldehydes are made into mixed solution, it is standby；
(2) with mechanical agitation and electrical heating chuck, the 2000L titanium reactors for high pressure polymerisation of top tape distilling apparatus
In 1, the solvent E being made up of the hexamethylene of 840L propionic acid and 560L is added, and N is blasted from the bottom of polymer reactor 12To reactor
Push up oxygen concentration in the gas phase of condensator outlet and be less than 1%, then start the electrical heating chuck of polymer reactor 1 switch, it is anti-to polymerizeing
Answer liquid in device 1 to carry out being heated to flowing back, maintain the pressure 5.0atm of polymer reactor 1, while use from the top of polymer reactor 1
Dropwise addition mode adds the mixed solution of step (1) preparation, maintains molar concentration of the pyrroles in reaction solution during dropwise addition all the time
Less than 0.1mol/L.React outside distilling apparatus removal system of the water of generation by the top of polymer reactor 1, through liquid liquid after condensation
Decker 4 is layered, and upper oil phase is recycled back in reaction system.The reflux ratio of constantly regulate destilling tower causes polymer reactor
Water concentration in 1 is consistently lower than 0.05%.After being added dropwise while continue to react, stop reaction after 15min, it is anti-at the end of reaction
It is 157.1 DEG C to answer temperature.Now, the pressure 5atm of polymer reactor 1 is maintained, air is passed through and carries out oxidation reaction, during oxidation reaction
Between be 22 minutes, strictly control oxygen concentration in tail gas to be less than 2% by adjusting the amount of air being passed through in course of reaction.Oxidation
After reaction terminates, cooling is slowly stood.Entered after fluid temperature is down to normal temperature in polymer reactor 1 by filtration wash unit 2
Row filtering, filtrate and filter cake being obtained, filtrate is carried out rectifying and dewatering and reclaimed to obtain solvent by polymerization solvent recovery tower 3,
It is continuing with after recovered solvent is collected in case being recycled back in system, outside the residue discharge system of tower reactor.The filter being filtrated to get
Cake after hot wash repeatedly with filtering, until filtrate is colourless.Then filtered after filter cake is washed with methanol repeatedly again, until filtering
Waste water is colourless.It is product TPP through the washed filter cake of methanol, tetraphenylporphines product is obtained after 80 DEG C of vacuum drying
51.4kg, the product TPP counted using reactant pyrroles synthetic yield is 59.7%, purity 98.7%.
Embodiment 2
Technological process is same as Example 1, and difference is：
(1) 140mol pyrroles and 280mol 4-chloro-benzaldehydes are added；
(2) solvent E is the mixture of 980L propionic acid and 420L toluene；
(3) reaction time in polymer reactor is 9 minutes, and Stress control temperature at the end of 3atm, reaction is 152.4
DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.08%；
(4) gas being passed through during oxidation reaction is pure oxygen, 18 minutes reaction time, reaction pressure 2atm；
By this method, the solid finally obtained obtains product TPP13.8kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 52.2%, purity 99.4%.
Embodiment 3
Technological process is same as Example 1, and difference is：
(1) 840mol pyrroles and 840mol m chlorobenzaldehydes are added；
(2) solvent E is the mixture of 1120L propionic acid and 280L benzene, and Stress control temperature at the end of 2.8atm, reaction is
148.8 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.04%；
(3) reaction time in polymer reactor is 12 minutes；
(4) gas being passed through in oxidation reactor is air, 12 minutes reaction time, reaction pressure normal pressure；
By this method, the solid finally obtained obtains product TPP87.9kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 55.6%, purity 98.5%.
Embodiment 4
Technological process is same as Example 1, and difference is：
(1) 420mol pyrroles and 420mol o-chlorobenzaldehydes are added；
(2) solvent E is 1400L propionic acid；
(3) reaction time in polymer reactor is 30 minutes, and reaction pressure 1atm, reaction temperature exists at the end of reaction
138.1 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.06%；
(4) gas being passed through in oxidation reactor is by N2Oxygen-containing 10% mixed gas being made into pure oxygen, during reaction
Between 60 minutes, reaction pressure normal pressure；
By this method, the solid finally obtained obtains product TPP31.7kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 40.1%, purity 98.7%.
Embodiment 5
Technological process is same as Example 1, and difference is：
(1) 280mol pyrroles and 538mol p-tolyl aldehydes are added；
(2) solvent E is the mixture of 980L propionic acid and 420L ethylbenzene
(3) reaction time in polymer reactor is 10 minutes, and reaction pressure 2.1atm, reaction temperature exists at the end of reaction
159.6 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.1%；
(4) gas being passed through in oxidation reactor is by N2Oxygen-containing 5% mixed gas being made into pure oxygen, reaction time
10 minutes, reaction pressure was normal pressure；
By this method, the solid finally obtained obtains product TPP19.8kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 42.2%, purity 98.8%.
Embodiment 6
Technological process is same as Example 1, and difference is：
(1) 210mol pyrroles and 375mol o-tolualdehydes are added；
(2) solvent E is the mixture of 980L propionic acid and 420L paraxylene
(3) reaction time in polymer reactor is 12 minutes, and reaction pressure 1.5atm, reaction temperature exists at the end of reaction
148.1 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.08%；
(4) gas being passed through in oxidation reactor is air, and in 6 minutes reaction time, reaction pressure is normal pressure；
By this method, the solid finally obtained obtains product TPP14.7kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 41.8%, purity 98.6%.
Embodiment 7
Technological process is same as Example 1, and difference is：
(1) tolyl aldehyde between 350mol pyrroles and 522mol is added；
(2) solvent E is the mixture of 980L propionic acid and 420L meta-xylenes
(3) reaction time in polymer reactor is 15 minutes, and reaction pressure 2.0atm, reaction temperature exists at the end of reaction
159.6 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.12%；
(4) gas being passed through in oxidation reactor is air, 18 minutes reaction time, reaction pressure normal pressure；
By this method, the solid finally obtained obtains product TPP26.2kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 44.6%, purity 98.7%.
Embodiment 8
Technological process is same as Example 1, and difference is：
(1) 490mol pyrroles and 450mol salicylaldhydes are added；
(2) solvent E is the mixture of 980L propionic acid and 420L ortho-xylenes
(3) reaction time in polymer reactor is 22 minutes, and reaction pressure 1.4atm, reaction temperature exists at the end of reaction
148.5 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.04%；
(4) gas being passed through in oxidation reactor is air, and in 48 minutes reaction time, reaction pressure is normal pressure；
By this method, the solid finally obtained obtains product TPP42.7kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 51.4%, purity 98.5%.
Embodiment 9
Technological process is same as Example 1, and difference is：
(1) 630mol pyrroles and 600mol m-hydroxybenzaldehydes are added；
(2) solvent E is the mixture of 840L propionic acid and 560L hexamethylenes；
(3) reaction time in polymer reactor is 24 minutes, and reaction pressure 4atm, reaction temperature exists at the end of reaction
146.2 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.04%；
(4) gas being passed through in oxidation reactor is air, and in 54 minutes reaction time, reaction pressure is normal pressure；
By this method, the solid finally obtained obtains product TPP49.5kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 46.3%, purity 98.6%.
Embodiment 10
Technological process is same as Example 9, and difference is：
(1) 630mol pyrroles and 600mol parahydroxyben-zaldehydes are added；
(2) reaction time in polymer reactor is 28 minutes, and reaction pressure 3atm, reaction temperature exists at the end of reaction
132.9 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.04%；
(3) gas being passed through in oxidation reactor is air, 60 minutes reaction time；
By this method, the solid finally obtained obtains product TPP72.0kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 55.1%, purity 99.2%.
Embodiment 11
Technological process is same as Example 9, and difference is：
(1) 700mol pyrroles and 1250mol P-methoxybenzal-dehyde are added；
(2) reaction time in polymer reactor is 15 minutes, and reaction pressure 2atm, reaction temperature exists at the end of reaction
126.0 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.02%；
(3) gas being passed through in oxidation reactor is air, 30 minutes reaction time；
By this method, the solid finally obtained obtains product TPP53.3kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 41.5%, purity 99.3%.
Embodiment 12
Technological process is same as Example 9, and difference is：
(1) 448mol pyrroles and 620mol o-methoxybenzaldehydes are added；
(2) reaction time in polymer reactor is 18 minutes, and reaction pressure 5atm, reaction temperature exists at the end of reaction
158.2 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.04%；
(3) gas being passed through in oxidation reactor is air, 22 minutes reaction time；
By this method, the solid finally obtained obtains product TPP38.3kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 46.6%, purity 98.9%.
Embodiment 13
Technological process is same as Example 9, and difference is：
(1) 588mol pyrroles and 670mol m-methoxybenzaldehydes are added；
(2) reaction time in polymer reactor is 22 minutes, and reaction pressure 5atm, reaction temperature exists at the end of reaction
158.2 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.04%；
(3) gas being passed through in oxidation reactor is air, 30 minutes reaction time；
By this method, the solid finally obtained obtains product TPP50.8kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 54.9%, purity 98.9%.
Embodiment 14
Technological process is same as Example 9, and difference is：
(1) 392mol pyrroles and 392mol 4-Fluorobenzaldehydes are added；
(2) reaction time in polymer reactor is 9 minutes, and reaction pressure 5atm, reaction temperature exists at the end of reaction
158.2 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.04%；
(3) gas being passed through in oxidation reactor is air, 30 minutes reaction time；
By this method, the solid finally obtained obtains product TPP38.0kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 56.2%, purity 98.8%.
Embodiment 15
Technological process is same as Example 9, and difference is：
(1) 532mol pyrroles and 918mol o fluorobenzaldehydes are added；
(2) reaction time in polymer reactor is 26 minutes, and reaction pressure 5atm, reaction temperature exists at the end of reaction
158.2 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.04%；
(3) gas being passed through in oxidation reactor is air, 30 minutes reaction time；
By this method, the solid finally obtained obtains product TPP40.84kg after 80 DEG C of vacuum drying.With reactant pyrroles
The product TPP of meter synthetic yield is 44.4%, purity 98.9%.
Embodiment 16
Technological process is same as Example 9, and difference is：
(1) fluorobenzaldehyde between 616mol pyrroles and 670mol is added；
(2) reaction time in polymer reactor is 22 minutes, and reaction pressure 5atm, reaction temperature exists at the end of reaction
158.2 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.04%；
(3) gas being passed through in oxidation reactor is air, 45 minutes reaction time；
By this method, the solid finally obtained obtains product TPP53.1kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 49.9%, purity 99.0%.
Embodiment 17
Technological process is same as Example 9, and difference is：
(1) 308mol pyrroles and 308mol p-bromobenzaldehydes are added；
(2) reaction time in polymer reactor is 6 minutes, and reaction pressure 5atm, reaction temperature exists at the end of reaction
158.2 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.04%；
(3) gas being passed through in oxidation reactor is air, 30 minutes reaction time；
By this method, the solid finally obtained obtains product TPP33.1kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 46.2%, purity 99.2%.
Embodiment 18
Technological process is same as Example 9, and difference is：
(1) 252mol pyrroles and 286mol o-bromobenzaldehyes are added；
(2) reaction time in polymer reactor is 3 minutes, and reaction pressure 5atm, reaction temperature exists at the end of reaction
158.2 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.04%；
(3) gas being passed through in oxidation reactor is air, 20 minutes reaction time；
By this method, the solid finally obtained obtains product TPP28.8kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 49.1%, purity 99.1%.
Embodiment 19
Technological process is same as Example 9, and difference is：
(1) 672mol pyrroles and 1067mol 3-bromobenzaldehydes are added；
(2) reaction time in polymer reactor is 28 minutes, and reaction pressure 5atm, reaction temperature exists at the end of reaction
158.2 DEG C, the water concentration in polymer reactor is controlled consistently lower than 0.04%；
(3) gas being passed through in oxidation reactor is air, 54 minutes reaction time；
By this method, the solid finally obtained obtains product TPP67.7kg after 80 DEG C of vacuum drying.In terms of reactant pyrroles
Product TPP synthetic yield be 43.3%, purity 99.2%.
Claims (3)
1. a kind of preparation method of tetraphenylporphines, it is characterised in that comprise the following steps：
(1) it is 0.5~1.1 in molar ratio by pyrroles and aromatic aldehyde:1 is made into mixed solution, standby, and described aromatic aldehyde is benzene first
Aldehyde, 4-chloro-benzaldehyde, m chlorobenzaldehyde, o-chlorobenzaldehyde, p-tolyl aldehyde, o-tolualdehyde, a tolyl aldehyde, neighbour
Hydroxy benzaldehyde, m-hydroxybenzaldehyde, parahydroxyben-zaldehyde, P-methoxybenzal-dehyde, o-methoxybenzaldehyde, meta-methoxy benzene
One in formaldehyde, 4-Fluorobenzaldehyde, o fluorobenzaldehyde, a fluorobenzaldehyde, p-bromobenzaldehyde, o-bromobenzaldehye, 3-bromobenzaldehyde
Kind；
(2) added into polymer reactor the volume fraction of propionic acid solvent or propionic acid for 60~80% propionic acid and hexamethylene, toluene,
A kind of admixture solvent of composition in benzene, ethylbenzene, paraxylene, meta-xylene, ortho-xylene, nitrogen displacement to tail oxygen concentration
Solvent is heated to flowing back after less than 1%, it is 1~5atm to maintain polymer reactor pressure, then starts dropwise addition step (1) and obtains
Mixed solution and start polymerisation, maintain molar concentration of the pyrroles in reaction solution to be less than during dropwise addition all the time
0.1mol/L, the total mol concentration for the pyrroles being finally added dropwise is 0.1~0.6mol/L, is reacted in course of reaction by distilling to remove
The water of generation is consistently lower than 0.2% with the mass percentage concentration of maintenance reaction liquid reclaimed water, continue after being added dropwise reaction 0.05~
Stop reaction after 0.5 hour, reaction temperature is 125~165 DEG C at the end of reaction；
(3) oxygen-containing gas that oxysome fraction is 5~100% is passed through into polymer reactor and carries out oxidation reaction, course of reaction
In the amount of oxygen-containing gas that is passed through by adjusting control oxygen concentration in tail gas to be less than 2%, oxidization time is 0.1~1.0 hour,
Reaction pressure is 1~5atm, and oxidation cools down after terminating, filters to obtain filter cake and filtrate, is by Washing of Filter Cake, drying to obtain formula
(I) tetraphenylporphines product, the substituent R led in formula (I)1、R2、R3From aromatic aldehyde,
2. the preparation method of tetraphenylporphines according to claim 1, it is characterised in that will be gone in step (2) by distillation
After the product of distillation condensation layering obtained during except the water for reacting generation, upper oil phase and lower floor's aqueous phase are obtained, upper oil phase is followed
In loopback polymer reactor.
3. the preparation method of tetraphenylporphines according to claim 1, it is characterised in that enter the filtrate that step (3) obtains
Row rectifying is with recycling design.
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