CN108727192A - The preparation method of dipheryl carbonate esters compound - Google Patents
The preparation method of dipheryl carbonate esters compound Download PDFInfo
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Abstract
The present invention relates to dipheryl carbonate esters compound fields, disclose a kind of preparation method of dipheryl carbonate esters compound, which includes：In the presence of a catalyst, phenol compound shown in formula (II) carries out ester exchange reaction with carbonic acid diester compound shown in structural formula (III), and the catalyst includes imidazoles and potassium carbonate；Wherein, R is hydrogen or C1‑C4Alkyl, R1And R2It is each independently methyl or ethyl.This method can improve the selectivity of dipheryl carbonate esters compound；The catalyst of use, chemical property be stable, safe, inexpensive, not etching apparatus, meanwhile, which is easy to separate and recover and reuse from reaction solution.
Description
Technical field
The present invention relates to dipheryl carbonate esters compound fields, and in particular, to a kind of dipheryl carbonate esters compound
Preparation method.
Background technology
Diphenyl carbonate (DPC) is mainly used for substituting phosgene as a kind of important fine-chemical intermediate, for
Polycondensation reaction polycarbonate synthesis (PC) occurs for bisphenol-A, and makrolon is because of its outstanding shock resistance, optics and Electronic Performance, extensively
It is general to be applied to the fields such as automobile making, building, medical treatment, aerospace.In addition, DPC can be used for synthesizing some other chemical products；
Such as poly- aryl carbonates, monoisocyanates, also act as the plasticizer of polyamide, polyester.In recent years, as makrolon is clear
The popularization and application of clean production technology in the world, the market demand of DPC increase rapidly.Therefore, research and development DPC is green, efficient
Production technology have become the emphasis of laboratory in colleges and universities and enterprises pay attention.
The method for preparing diphenyl carbonate of mainstream mainly has 3 kinds at present：(1) phosgenation；(2) dimethyl carbonate and phenol
Ester-interchange method；(3) phenol oxidation carbonylation method.Wherein, phosgenation production process pollutes greatly, unfriendly to environment；
Phenol oxidation carbonylation method production technology is immature, and production cost is high；In contrast, dimethyl carbonate and phenol ester-interchange method category
In green cleaning, efficient diphenyl carbonate preparation method.
Since the 1970s, the work of diphenyl carbonate is prepared using the ester exchange reaction of dimethyl carbonate and phenol
Skill route, by the extensive concern of researcher, catalyst system and catalyzing can be divided into homogeneous catalyst and heterogeneous catalysis at present
Two major classes.Homogeneous catalyst catalytic activity is higher, but catalyst chemical property is unstable, exists and is detached with product, recycles difficulty,
And the problems such as pollution environment；Heterogeneous catalysis, though have many advantages, such as to be easy to reaction system separation, convenient for recycling, its
Catalytic activity is relatively low, and the selectivity of diphenyl carbonate is low, constrains its process of industrialization significantly.
Currently, many existing homogeneous catalyst systems are further improved.Such as high person of outstanding talent etc. (Journal of Molecular Catalysis,
2001,15:21~24) condition for having studied butyl titanate catalysis of phenol and dimethyl carbonate ester exchange reaction obtains as follows
As a result：Under normal pressure, under the conditions of 175 DEG C, molar feed ratio n (dimethyl carbonate):n(PhOH):N (catalyst)=1.5:1:
The selectivity of 0.05, reaction time 25h, phenol conversion 47.4%, methyl benzol carbonate (MPC) are 90.9%, carbonic acid
Diphenyl ester (DPC) is selectively 9.1%；But such catalyst chemical stability is poor, it is difficult to recycle, when reacting in addition
Between it is long, increase production cost, also, the selectivity of MPC is significantly greater than the selectivity of DPC, and MPC need to further react
DPC can be prepared, processing step and production cost are increased.
Niu Hongying etc. (chemical journal, 2006,64 (12), 1269-1272) has studied Cp2TiCl2It is catalyzed dimethyl carbonate
(DMC) with phenol ester exchange reaction performance, at 150-180 DEG C, n (DMC):n(PhOH):n(Cp2TiCl2)=1:1:0.005,
When reaction time 10h, quantitative analysis is carried out using normalization method, is as a result shown：Phenol conversion 46.8%, methyl benzol carbonate
(MPC) and diphenyl carbonate (DPC) is selectively respectively 43.4% and 54.9%.Tao Zhao it is just equal (HeFei University of Technology's journal,
2004,27:570-574) probe into the catalytic performance of dibutyl tin dilaurate, the results showed that DMC conversion ratios 32.04%,
The yield of DPC, MPC are that 18.00%, 14.04%, DPC is selectively 56.18% respectively.But such catalyst preparation is of high cost,
Also, MPC, which need to further react, could prepare DPC, increase processing step and production cost.
It is studied about heterogeneous catalysis, and Zhou Weiqing etc. (catalysis journal, 2003,10:It is total 760-764) to be utilized respectively cocurrent
The precipitation method and mechanical milling method are prepared for novel oxidized lead-Zinc oxide catalytic, have probed into preparation method, calcination temperature, difference
Parent and parent are with the influence for comparing catalyst catalytic performance；It was found that working as 500 DEG C of calcination temperature, molar ratio n (Pb)/n (Zn) ≈ 2
When, the active highest of catalyst, the conversion ratio 64.6% of phenol, the selectivity 72.0% of diphenyl carbonate (DPC), still, this
The effect that kind catalyst is reused is bad, and toxicity is big, is unfavorable for environmental protection.(the J.Mol.Catal.A such as Fu:
Chem., 1997,118 (3), 293-299) it is prepared for Multimetal oxide catalyst and compares, it finds at 433K,
MoO3/SiO2Transesterification catalytic activity it is best, at n (DMC):N (PhOH)=5:1,MoO3Optimum load mass fraction is
When 17.1%, 4h is reacted, MPC and DPC yields are respectively 17.1% and 0.2%.
Highly selective, the environmental-friendly method for preparing dipheryl carbonate esters compound is found in conclusion preparing, always
It is the Research Challenges using ester-interchange method diphenyl carbonate.
Invention content
The purpose of the invention is to overcome the method choice for preparing dipheryl carbonate esters compound of the prior art it is low,
Raw material availability it is low and not environmentally the problem of, a kind of preparation method of dipheryl carbonate esters compound is provided.
To achieve the goals above, the present invention provides a kind of preparation of the dipheryl carbonate esters compound as shown in formula (I)
Method, wherein the preparation method includes：In the presence of a catalyst, phenol compound shown in formula (II) and formula (III) institute
The carbonic acid diester compound shown carries out ester exchange reaction, and the catalyst includes imidazoles and potassium carbonate；
Wherein, R is hydrogen or C1-C4Alkyl, R1And R2It is each independently methyl or ethyl.
The method for preparing dipheryl carbonate esters compound of the present invention can improve the selection of dipheryl carbonate esters compound
Property；The catalyst of use is compared with the homogeneous catalysts such as butyl titanate for meeting water unstable, chemical property stabilization, safety, valence
Honest and clean, not etching apparatus, meanwhile, which is easy to separate and recover and reuse from reaction solution, will not be generated to environment negative
Face is rung, and is suitable for large-scale industrial production.Therefore, the method for preparing dipheryl carbonate esters compound of the invention can generate very well
Economic benefit and social benefit, have a good application prospect.
Specific implementation mode
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of preparation method of the dipheryl carbonate esters compound as shown in formula (I), wherein the preparation side
Method includes：In the presence of a catalyst, phenol compound shown in formula (II) and carbonic acid diester compound shown in formula (III)
Ester exchange reaction is carried out, the catalyst includes imidazoles and potassium carbonate；
Wherein, R is hydrogen or C1-C4Alkyl, R1And R2It is each independently methyl or ethyl.
In the present invention, under preferable case, R is hydrogen or methyl, further preferably hydrogen；R1And R2For methyl.
In the present invention, in order to further increase the selectivity of dipheryl carbonate esters compound, the dosage and potassium carbonate of imidazoles
Dosage molar ratio be 1.5-2.5：1, preferably 1.8-2.2：1, more preferably 1.9-2.1：1, most preferably 2：1.
In the present invention, in order to reduce consumption of raw materials, cost is reduced, under preferable case, the catalyst is by imidazoles and carbonic acid
Potassium forms.
In the present invention, from the selectivity two of raw material availability and dipheryl carbonate esters compound from the aspect of, preferred carbonic acid
The molar ratio of the dosage of potassium and the dosage of phenol compound shown in formula (II) is 0.01-1：1, preferably 0.05-0.5：1,
More preferably 0.1-0.2：1.
In the present invention, in order to further increase the selectivity of dipheryl carbonate esters compound, carbonic acid two shown in formula (III)
The molar ratio of the dosage of ester compounds and the dosage of phenol compound shown in formula (II) is 0.2-5：1, preferably 1-4：1,
More preferably 2-3.5：1.
In the present invention, the condition of the ester exchange reaction can be the existing condition that can carry out ester exchange reaction, excellent
In the case of choosing, the condition of the ester exchange reaction includes：Pressure is 0.1-2MPa, and temperature is 63-200 DEG C, reaction time 9-
11h。
In the present invention, it is preferable that carry out simple distillation or rectifying while the ester exchange reaction.Pass through simple distillation
Or rectifying, the alcohol compound of generation and its azeotropic mixture are removed.
In the present invention, to the reactor of the ester exchange reaction, there is no particular limitation, can be existing in this field
It can be used in the reactor of ester exchange reaction, for example, the reactor can be non-pressurised reactor and pressurized reactor, it is described
Non-pressurised reactor for example can be that conventional glass flask or enamel still, the pressurized reactor for example can be high pressure
Kettle.
When the reactor is non-pressurised reactor, under preferable case, the condition of the ester exchange reaction includes：Pressure
For 0.1-0.2MPa, preferably 0.1-0.11MPa；Temperature is 63-200 DEG C, preferably 87-95 DEG C；Reaction time is 9-11h,
Preferably 9-10h.
When the reactor is pressurized reactor, under preferable case, the condition of the ester exchange reaction includes：Pressure is
0.2-2MPa, preferably 0.8-1.2MPa, further preferably 1MPa；Temperature is 63-200 DEG C, preferably 150-180 DEG C；Instead
It is 9-11h, preferably 9-10h between seasonable.About the ester exchange reaction device and its operating method under pressurized conditions, can also join
Examine the document (doctoral thesis of Wang Shu《Ester-interchange method diphenyl carbonate synthesis technique and catalyst research》, Wuhan：Central China science and technology is big
Learn, 2011) and its citation method.
In the present invention, fluid temperature is with low volatile alcohols material HOR in reactor1And/or HOR2The removing of product and
It increases, therefore, present invention preferably employs heat mediums to provide thermal energy, and " temperature " of the ester exchange reaction refers to " reactor
Heat medium temperature ", for example, when the temperature of heat medium be 100 DEG C when, it can be understood as the temperature of the ester exchange reaction
Degree is 100 DEG C.
In the present invention, the required heat source of reaction temperature of control reaction is not particularly limited, can be this field skill
Various methods well known to art personnel, for example, in the present invention, the heat medium of the reactor can be water-bath or oil bath,
Respectively heat source is obtained from steam or electrical heating.
In the present invention, to the mode of the ester exchange reaction, there is no particular limitation, for example, the ester exchange reaction can be with
For successive reaction or intermittent reaction.
A preferred embodiment of the invention, the preparation method include：First by phenol shown in formula (II)
Compound and catalyst mixing, are heated to the ester exchange reaction required temperature, then again by formula by obtained mixture
(III) carbonic acid diester compound shown in is mixed with the mixture.
According to another preferred method of implementation of the present invention, the preparation method includes：By the catalyst, formula (II) institute
Carbonic acid diester compound shown in the phenol compound and formula (III) shown mixes, and obtained mixture, which is heated to the ester, to be handed over
Reaction required temperature is changed, after reacting 3.5-5 hours, entrainer is added into reaction solution.
In the present invention, in order to improve reaction-ure conversion-age and selectivity of product, under preferable case, the entrainer divides 3-7
Secondary to be added in reaction solution, the adjacent time interval being added twice is 1.5-2 hours.
In the present invention, the entrainer can be the existing entrainer that can be used in ester exchange reaction, under preferable case,
The entrainer is carbonic acid diester compound shown in formula (III).
In the present invention, it is preferable that each relative to phenol compound, the entrainer shown in 1 mole of formula (II)
Addition be 33-200mL.
Catalyst in the present invention is recyclable, recycling, it is therefore preferable that in the case of, the preparation method is also wrapped
It includes：After the ester exchange reaction, the catalyst in reaction product is recycled.
In the present invention, if dipheryl carbonate esters compound shown in the higher formula of purity (I) is obtained, in reaction terminating
Afterwards, reaction solution is continued into the post-processings such as simple distillation or rectifying, so as to by dipheryl carbonate esters compound shown in formula (I)
From after reaction gained mixture in separate.
Then it is diphenyl carbonate (abbreviation DPC) when R is hydrogen for example, dipheryl carbonate esters compound shown in formula (I).It will
Diphenyl carbonate (DPC) method for separating from gained mixture after reaction includes：By urging in reaction gained mixture
Agent, unreacted phenol, dimethyl carbonate, by-product methyl phenyl ethers anisole and and a small amount of intermediate methyl benzol carbonate,
It is removed from reaction gained mixture.For removing method without particular/special requirement, those skilled in the art, which may be used, to be thought
The each method arrived, in of the invention, the method for preferably first passing through simple distillation or rectifying, methanol, the methyl phenyl ethers anisole etc. that reaction is generated
Volatile compound and unreacted phenol are removed from reaction gained mixture, then pass through the side of washing, filtering or extraction
Method removes a small amount of imidazoles and potassium carbonate from product, finally by the method for recrystallization, by a small amount of intermediate product from production
It is removed in product, diphenyl carbonate shown in purifying formula (I).The method of the extraction and recrystallization can be the choosing of this field routine
It selects, details are not described herein.
The present invention will be described in detail by way of examples below.In following embodiment and comparative example, simple distillation dress
It is set to " dispenser " that upper end is equipped with condenser pipe, " dispenser ", which refers to bottom, the Dean and Stark apparatus of piston switch；
Reactants and products analysis (divides Rayleigh Analytical Instrument Co., Ltd, model by gas chromatograph purchased from Beijing North
For SP-3420) it measures；Using fid detector, quantitative analysis is carried out to reaction solution with external standard method；
The conversion ratio of reactant phenol compound, the selectivity of product calculate in accordance with the following methods：
Conversion ratio (the Z of phenol compoundPhenol)：
Selectivity (the S of product dipheryl carbonate esters compoundDPC)：
Selectivity (the S of product alkylphenyl carbonateMPC)：
In above formula,
MPhenol、MDPC、MMPC、MMethyl phenyl ethers anisolePhenol compound, dipheryl carbonate esters compound, methyl phenyl carbonate are indicated respectively
The molecular weight of ester type compound and methyl phenyl ethers anisole class compound；
CPhenol：Indicate chromatography mass concentration (g/L) of the unreacted benzene phenols compound in liquid-phase product；
CDPC：Indicate chromatography mass concentration (g/L) of the product dipheryl carbonate esters compound in liquid-phase product；
CMPC：Indicate chromatography mass concentration (g/L) of the product MPC class compounds in liquid-phase product；
CMethyl phenyl ethers anisole：Indicate chromatography mass concentration (g/L) of the side reaction product methyl phenyl ethers anisole class compound in liquid-phase product.
Embodiment 1
Under nitrogen protection, by 7.05g phenol, 1.41g imidazoles and 1.41g potassium carbonate in the three neck round bottoms equipped with dispenser
It is mixed in flask, after oil bath temperature reaches 95 DEG C, 13.5g dimethyl carbonate (phenol, imidazoles, potassium carbonate and carbonic acid diformazan is added
The molar ratio of ester is 1：0.28：0.14：2) it, under the conditions of normal pressure (0.1MPa), reacts 9 hours, in reaction simultaneously by simple
The methanol of generation and its azeotropic mixture are steamed to dispenser and are removed by distillating method.Reaction terminates, and recycles catalyst, solution is carried out
Gas chromatographic analysis, phenol conversion 38.9%, the selectivity 90.5% of diphenyl carbonate, methyl benzol carbonate (MPC) choosing
Selecting property 3.5%.
Embodiment 2
Under nitrogen protection, by 14.12g phenol, 2.04g imidazoles, 2.07g potassium carbonate and 13.51g dimethyl carbonate (benzene
Phenol, imidazoles, potassium carbonate and dimethyl carbonate molar ratio be 1：0.2：0.1：1) in the three neck round bottom equipped with dispenser
Mixing is reacted under the conditions of 95 DEG C of oil bath temperature and normal pressure (0.1MPa), simultaneously will by simple distillation method reacting
The methanol and its azeotropic mixture of generation are steamed to dispenser and are removed, about 6 minutes cooling after reacting 3.5 hours, are mended into round-bottomed flask
Add dimethyl carbonate, it is front and back it is total add 3 times, the adjacent time interval added twice is 1.5 hours, adds 10mL every time, often
It is secondary add dimethyl carbonate after react 1.4 hours and methanol and azeotropic mixture simple distillation gone out into round-bottomed flask simultaneously, wait for reaction solution
Dimethyl carbonate next time is added after cooling 6 minutes, under 95 DEG C of oil bath temperatures, methanol is steamed and dimethyl carbonate is formed
Azeotropic mixture.After reaction, catalyst is recycled, solution is subjected to gas chromatographic analysis, phenol conversion 57.1%, dipheryl carbonate
The selectivity 57% of ester, methyl benzol carbonate (MPC) selectivity 0%.
Embodiment 3
Dipheryl carbonate esters compound is prepared according to the method for embodiment 1, unlike, phenol, imidazoles, potassium carbonate and carbon
The molar ratio of dimethyl phthalate is 1：0.3：0.15：0.5.Gas chromatographic analysis, phenol conversion are carried out to the solution after reaction
10.4%, the selectivity 61.8% of diphenyl carbonate, methyl benzol carbonate (MPC) selectivity 0%.
Comparative example 1
Dipheryl carbonate esters compound is prepared according to the method for embodiment 1, unlike, using the imidazoles of same molar
Instead of potassium carbonate (imidazoles is used alone as catalyst).Reaction terminates, and recycles catalyst, and solution is carried out gas-chromatography point
Analysis, phenol conversion 0.2%, once through yield 0%, the selectivity 0% of diphenyl carbonate, methyl benzol carbonate (MPC) choosing
Selecting property 0%.
Comparative example 2
Dipheryl carbonate esters compound is prepared according to the method for embodiment 1, unlike, using the carbonic acid of same molar
Potassio is for imidazoles (being used alone potassium carbonate as catalyst).Reaction terminates, and recycles catalyst, solution is carried out gas-chromatography
Analysis, phenol conversion 3.8%, the selectivity 0% of diphenyl carbonate, once through yield 0%, methyl benzol carbonate (MPC)
Selectivity 35.5%.
Comparative example 3
Dipheryl carbonate esters compound is prepared according to the method for embodiment 1, unlike, using the pyridine of same molar
Instead of potassium carbonate and imidazoles (pyridine is used alone as catalyst).Reaction terminates, and recycles catalyst, solution is carried out gas phase
Chromatography, phenol conversion 0.1%, the selectivity 0% of diphenyl carbonate, once through yield 0%, methyl benzol carbonate
(MPC) selectivity 100%.
Comparative example 4
Dipheryl carbonate esters compound is prepared according to the method for embodiment 1, unlike, using the pyridine of same molar
Instead of imidazoles (using pyridine and potassium carbonate as catalyst).Reaction terminates, and recycles catalyst, solution is carried out gas-chromatography
Analysis, phenol conversion 7.4%, the selectivity 0% of diphenyl carbonate, once through yield 0%, methyl benzol carbonate (MPC)
Selectivity 0%.
Method using the present invention, which is can be seen that, from embodiment 1-3 prepares dipheryl carbonate esters compound, diphenyl carbonate
The selectivity of class compound is preferable, and phenol conversion is high.
It can be seen that from the comparison of comparative example 1-3 and embodiment 1 and imidazoles, potassium carbonate or pyridine be used alone as catalysis
The selectivity of agent, dipheryl carbonate esters compound is 0%.
From the comparison of comparative example 4 and embodiment 1 as can be seen that the catalyst being grouped as with imidazoles and potassium carbonate group, than with
The catalyst effect that pyridine and potassium carbonate group are grouped as is good.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention
In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, belongs to
Protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the dipheryl carbonate esters compound as shown in formula (I), which is characterized in that the preparation method packet
It includes：In the presence of a catalyst, phenol compound shown in formula (II) is carried out with carbonic acid diester compound shown in formula (III)
Ester exchange reaction, the catalyst include imidazoles and potassium carbonate；
Wherein, R is hydrogen or C1-C4Alkyl, R1And R2It is each independently methyl or ethyl.
2. preparation method according to claim 1, wherein R is hydrogen or methyl, further preferably hydrogen；R1And R2For first
Base.
3. preparation method according to claim 1 or 2, wherein the molar ratio of the dosage of imidazoles and the dosage of potassium carbonate is
1.5-2.5：1, preferably 1.8-2.2：1, more preferably 1.9-2.1：1；
It is further preferred that the catalyst is made of imidazoles and potassium carbonate.
4. preparation method according to claim 1 or 2, wherein the dosage of potassium carbonate and phenol shown in formula (II)
The molar ratio for closing the dosage of object is 0.01-1：1, preferably 0.05-0.5：1, more preferably 0.1-0.2：1.
5. preparation method according to claim 1 or 2, wherein the dosage of carbonic acid diester compound shown in formula (III) with
The molar ratio of the dosage of phenol compound shown in formula (II) is 0.2-5：1, preferably 1-4：1, more preferably 2-3.5：1.
6. preparation method according to claim 1 or 2, wherein the condition of the ester exchange reaction includes：Pressure is 0.1-
2MPa, temperature are 63-200 DEG C, reaction time 9-11h；
Preferably, simple distillation or rectifying are carried out while the ester exchange reaction.
7. preparation method according to claim 1 or 2, wherein the preparation method includes：First by benzene shown in formula (II)
Phenolic compound and catalyst mixing, are heated to the ester exchange reaction required temperature, then again by obtained mixture
Carbonic acid diester compound shown in formula (III) is mixed with the mixture.
8. preparation method according to claim 1 or 2, wherein the preparation method includes：By the catalyst, formula
(II) carbonic acid diester compound shown in phenol compound and formula (III) shown in mixes, and obtained mixture is heated to institute
Ester exchange reaction required temperature is stated, after reacting 3.5-5 hours, entrainer is added into reaction solution；
Preferably, the entrainer divides 3-7 times and is added in reaction solution, and the adjacent time interval being added twice is 1.5-2 hours.
9. preparation method according to claim 8, wherein the entrainer is carbonic diester chemical combination shown in formula (III)
Object；
Preferably, phenol compound shown in the formula (II) relative to 1 mole, each addition of the entrainer are 33-
200mL。
10. preparation method according to claim 1 or 2, wherein the preparation method further includes：The ester exchange reaction
After, recycle the catalyst in reaction product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114011459A (en) * | 2021-11-16 | 2022-02-08 | 沈阳工业大学 | Titanium series double-acid type ionic liquid catalyst, preparation method and application |
| CN116143624A (en) * | 2021-11-16 | 2023-05-23 | 衢州氟瑞医药科技有限公司 | Method for preparing fluorine-containing linear carbonate lithium battery additive by using imidazole as catalyst |
| CN114011459B (en) * | 2021-11-16 | 2023-12-26 | 沈阳工业大学 | Titanium double-acid ionic liquid catalyst and preparation method and application thereof |
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