CN106380461B - A kind of carbonic acid second（Third）The preparation method of enester - Google Patents

A kind of carbonic acid second（Third）The preparation method of enester Download PDF

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CN106380461B
CN106380461B CN201610770482.8A CN201610770482A CN106380461B CN 106380461 B CN106380461 B CN 106380461B CN 201610770482 A CN201610770482 A CN 201610770482A CN 106380461 B CN106380461 B CN 106380461B
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enester
carbonic acid
reaction
preparation
carbaminate
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CN106380461A (en
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赵文波
汪洋
陈媛
李艳红
冯东
赵倩
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Kunming University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • C07D317/38—Ethylene carbonate
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention discloses a kind of carbonic acid second（Third）The preparation method of enester belongs to a kind of method of new synthesis of cyclic ethylene (propylene) carbonate.Alkyl polyamine-carbaminate that the method for the invention is prepared by laboratory under the action of catalyst with epoxy second（Third）Alkane reaction prepares the Organic chemical products carbonic acid second of high added value（Third）Enester, and the solvent alkyl polyamine that can be absorbed, catalyst have higher activity and selectivity, therefore the carbonic acid second prepared（Third）Enester has higher yield, can reach 90% or more；By-product alkyl polyamine yield can reach 95% or more, and recycling can be with cyclic absorption CO2.Greenhouse effects can not only be effectively relieved directly by fixed C1 resource conversions at important chemical products in the present invention, and solve Amine Solutions and absorb CO2The problem of desorbing high energy consumption, the by-product of recycling can be with cyclic absorption CO2。

Description

A kind of carbonic acid second（Third）The preparation method of enester
Technical field
The present invention discloses a kind of carbonic acid second（Third）The preparation method of enester belongs to a kind of new synthesis of cyclic ethylene (propylene) carbonate Method.
Background technology
CO2It is a kind of abundant C natural resources, it is nontoxic, stability is good, cheap and easy acquisition, therefore fossil is being replaced to fire Material field is with a wide range of applications；Also there is important strategic importance for reply global warming.It is now more mature Technology is to utilize CO2As raw material and epoxide synthesizing annular carbonate under the effect of the catalyst, it is in secondary cell Electrolyte, organic synthesis intermediate, the monomer of polycarbonate synthesis, aprotic, polar type solvent, alkylated reaction carrier, The fields such as the carrier of biologically active drug have to be widely applied very much.Wherein utilize CO2With ethylene oxide（EO）And propylene oxide （PO）Cycloaddition reaction synthesizing ethylene carbonate occurs（EC）And propene carbonate（PC）It is industrial more mature synthesis road Line.
EC and PC is a kind of important organic solvent and organic synthesis intermediate, can be applied in weaving, battery, makeup The fields such as product, the intermediate of pharmacy and fine chemical product, gas separation.Carbonic acid second（Third）The primary synthetic methods of enester have ester Exchange process, phosgenation, CO2With epoxy second（Third）Alkane addition reaction method etc..Ester-interchange method is since there are a large amount of by-products in reaction And limited by raw material sources, therefore, it is difficult to industrially be widely used.Phosgene is toxic and corrosivity is big, therefore is unfavorable for Safety in production and environmental pollution.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of carbonic acid second（Third）The preparation method of enester, Specifically include following steps：
（1）By CO2It is passed into alkyl polyamine/organic solvent non-aqueous system and mixture is obtained by the reaction（CO2It is passed through to system Quality no longer change）, carbaminate is obtained after the solid matter in mixture is separated and is dried in vacuo.
（2）It is 6 by ethylene oxide/propylene oxide and carbaminate molar ratio under catalysts conditions:1~1:1 ratio Example, which is uniformly mixed to be placed in reaction kettle, reacts the h of 0.5 h~10 and obtains carbonic acid second（Third）Enester, reaction temperature 100 DEG C~ 160 ℃。
Step of the present invention（1）Described in absorbent alkyl polyamine be ethylenediamine, diethylenetriamine, triethylene tetramine, four One kind in five amine of ethylene, piperazine, organic solvent are ethyl alcohol, diethylene glycol dimethyl ether, N-Methyl pyrrolidone, propene carbonate In one kind；The mass percent concentration of alkyl polyamine is 20%~30% in alkyl polyamine/organic solvent non-aqueous system.
Preferably, step of the present invention（2）Described in catalyst be potassium halide, one kind in lewis acid, potassium halide accounts for The mole percent of total system is the mol of 0.5% mol~1.0%, and the mole percent that lewis acid accounts for total system is 0.1% mol ~0.15% mol.
Preferably, lewis acid of the present invention is ZnO, ZnCl2、ZnBr2、ZnI2In one kind.
The principle of the present invention is：
The present invention is based on CO2Cyclic carbonate is directly obtained by cycloaddition reaction in the presence of a catalyst with alkylene oxide, Specific reaction equation is as follows：
Speculate reaction principle by taking piperazine-carbaminate as an example：Piperazine-carbaminate is generated with propylene oxide effect Propene carbonate obtains piperazine simultaneously, and specific reaction equation is as follows：
The present invention selects alkyl polyamine/organic solvent non-aqueous system liquid-solid-phase changeable to absorb CO2Obtain carbaminate and ring Oxygen second（Third）Alkane reaction under catalysts conditions prepares carbonic acid second（Third）Enester.
The present invention is by absorbing CO2Obtained carbaminate desorption cycle absorbs CO2It needs to increase temperature, therefore consumes Higher energy；By reacting for carbaminate and alkylene oxide, high value added product carbonic acid second can not only be obtained（Third）Enester, And the by-product generated is absorbent alkyl polyamine, and yield can reach 95% or more, and absorption can be continued cycling through by recycling CO2, this not only avoids Amine Solutions to absorb CO2The problem of desorbing high energy consumption, and the carbonic acid second generated（Third）Enester is in work It is widely used in industry.
The present invention prepares carbonic acid second using the carbaminate of preparation（Third）Enester, by greenhouse gases CO2This C1 resources It is fixed to utilize, and lyosoption can be recycled, achieve the effect that recycling；This absorption, utilization, reabsorbs utilization at conversion Round-robin method, not only obtain the chemical products of high added value, moreover it is possible to effectively reduce greenhouse effects, and solvent can recycle It uses, therefore upper with prodigious potential using value in the industry.
Beneficial effects of the present invention：
（1）It avoids organic amine system and absorbs CO2The problem of desorbing high energy consumption, height is directly changed by fixed C1 resources The chemical products carbonic acid second of added value（Third）Enester, and recyclable absorbent alkyl polyamine continue cycling through and absorb CO2, meet green The concept of colour chemistry and atom economy benefit, and carbonic acid second（Third）Enester has higher yield.
（2）Selected catalyst activity height, high selectivity, it is cheap, be readily synthesized；Due to CO2First reacted with amine, Then it is reacted again with alkylene oxide, therefore reactant carbaminate can substitute co-catalyst in this system, and can be with KX or road Lewis acid forms good synergic catalytic effect, greatly improves the catalytic activity of catalyst；Selected catalyst can weigh It is multiple to utilize repeatedly.
Specific implementation mode
With reference to specific embodiment, invention is further described in detail, but protection scope of the present invention is not limited to The content.
Using alkyl polyamine/organic solvent non-aqueous system at normal temperatures and pressures with CO2Carbaminate is obtained by the reaction, with EO, PO prepare the technique of EC, PC under the effect of the catalyst, and concrete operations are as follows：
（1）The preparation of carbaminate：Under normal temperature and pressure, configuration alkyl polyamine/organic solvent mixed solution is placed in 250ml In three-necked flask, CO2It is passed through in three-necked flask by gas mass flow controller control, reacts 2 h；The liquid of gained mixes admittedly Object obtains solid by decompression separation and is placed in 40 DEG C of 1 h of drying of vacuum drying chamber, saves backup；The absorbent alkyl Polyamines is one kind in ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, piperazine, and organic solvent is ethyl alcohol, two One kind in glycol dimethyl ether, N-Methyl pyrrolidone, propene carbonate.
（2）Without carbonic acid second under catalysts conditions（Third）The preparation of enester：A certain amount of above-mentioned five kinds of carbaminates and EO, PO is added in 50ml hydro-thermal reaction crystallizing kettles, using heat collecting type constant-temperature heating magnetic stirring apparatus controlling reaction temperature, reaction knot Cooled to room temperature after beam.It is 6 without the molar ratio under catalysts conditions, determining EO, PO and carbaminate:1~1:1, place Temperature control is managed at 100 DEG C~160 DEG C, reaction time 0.5h~10h.This example is intended to optimal screening and prepares carbonic acid second（Third）Enester Condition.
（3）There is carbonic acid second under catalysts conditions（Third）The preparation of enester
Embodiment 1
It is 6 by the molar ratio of EO and ethylenediamine-carbaminate:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettles, adds Enter 0.1 %mol of catalyst Z nO and (accounts for the mole percent of total system）, using heat collecting type constant-temperature heating magnetic stirring apparatus control 100 DEG C for the treatment of temperature processed, 0.5 h of reaction time, after reaction cooled to room temperature；EC yields are 92.6%, ethylenediamine Yield is 95.2%.
Embodiment 2
It is 6 by the molar ratio of PO and ethylenediamine-carbaminate:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettles, adds Enter 0.5% mol of catalyst KF and (accounts for the mole percent of total system）, controlled using heat collecting type constant-temperature heating magnetic stirring apparatus 100 DEG C for the treatment of temperature, 0.5 h of reaction time, after reaction cooled to room temperature；PC yields are 90.2%, and ethylenediamine is received Rate is 96.3%.
Embodiment 3
It is 5 by the molar ratio of EO and diethylenetriamine-carbaminate:1 is mixed to join 50ml hydro-thermal reaction crystallizing kettles In, catalyst Z nCl is added20.11%mol (accounts for the mole percent of total system）, stirred using heat collecting type heated at constant temperature magnetic force Mix 120 DEG C of device control process temperature, 2.5 h of reaction time, cooled to room temperature after reaction；EC yields are 91.1%, two Ethylene triamine yield is 95.8%.
Embodiment 4
It is 5 by the molar ratio of PO and diethylenetriamine-carbaminate:1 is mixed to join 50ml hydro-thermal reaction crystallizing kettles In, 0.6% mol of catalyst KCl are added（Account for the mole percent of total system）, using heat collecting type heated at constant temperature magnetic agitation 120 DEG C of device control process temperature, 2.5 h of reaction time, after reaction cooled to room temperature；PC yields are 92.3%, two Ethylene triamine yield is 96.6%.
Embodiment 5
It is 4 by the molar ratio of EO and triethylene tetramine-carbaminate:1 is mixed to join 50ml hydro-thermal reaction crystallizing kettles In, catalyst Z nBr is added20.12%mol (accounts for the mole percent of total system）, stirred using heat collecting type heated at constant temperature magnetic force Mix 140 DEG C of device control process temperature, 4.5 h of reaction time；Cooled to room temperature after reaction.EC yields are 92.8%, Triethylene tetramine yield is 95.5%.
Embodiment 6
It is 4 by the molar ratio of PO and triethylene tetramine-carbaminate:1 is mixed to join 50ml hydro-thermal reaction crystallizing kettles In, 0.7% mol of catalyst KBr are added and (account for the mole percent of total system）, using heat collecting type heated at constant temperature magnetic agitation 140 DEG C of device control process temperature, 4.5 h of reaction time, after reaction cooled to room temperature；PC yields are 91.9%, three Ethylene tetramine yield is 96.9%.
Embodiment 7
It is 3 by the molar ratio of EO and tetraethylenepentamine-carbaminate:1 is mixed to join 50ml hydro-thermal reaction crystallizing kettles In, catalyst Z nI is added20.13%mol (accounts for the mole percent of total system）, stirred using heat collecting type heated at constant temperature magnetic force Mix 150 DEG C of device control process temperature, 6.5 h of reaction time, cooled to room temperature after reaction；EC yields are 90.7%, Tetraethylenepentamine yield is 97.2%.
Embodiment 8
It is 3 by the molar ratio of PO and tetraethylenepentamine-carbaminate:1 is mixed to join 50ml hydro-thermal reaction crystallizing kettles In, 0.8% mol of catalyst KI are added and (account for the mole percent of total system）, using heat collecting type constant-temperature heating magnetic stirring apparatus 150 DEG C of control process temperature, 6.5 h of reaction time, after reaction cooled to room temperature；PC yields are 90.1%, tetrem Five amine yield of alkene is 96.3%.
Embodiment 9
It is 1 by the molar ratio of EO and piperazine-carbaminate:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettles, is added Catalyst Z nBr20.15%mol (accounts for the mole percent of total system）, using heat collecting type constant-temperature heating magnetic stirring apparatus control 160 DEG C for the treatment of temperature processed, 8.5 h of reaction time；Cooled to room temperature after reaction, EC yields are 94.9%, and piperazine is received Rate is 97.7%.
Embodiment 10
It is 2 by the molar ratio of PO and piperazine-carbaminate:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettles, is added 0.9% mol of catalyst KCl (account for the mole percent of total system）, controlled using heat collecting type constant-temperature heating magnetic stirring apparatus 160 DEG C for the treatment of temperature, 8.5 h of reaction time；Cooled to room temperature after reaction, PC yields are 94.6%, piperazine yield It is 98.0%.
Embodiment 11
It is 1 by the molar ratio of PO and piperazine-carbaminate:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettles, is added 1.0% mol of catalyst KI (account for the mole percent of total system）, at heat collecting type constant-temperature heating magnetic stirring apparatus control Manage 160 DEG C of temperature, 10 h of reaction time；Cooled to room temperature after reaction, PC yields are 95.3%, and piperazine yield is 97.6%。
It is that the present invention prepares carbonic acid second above（Third）The specific implementation method of enester, but the present invention is not limited to the above embodiment party Formula can make variation in the premise for not departing from present inventive concept in experiment condition.

Claims (4)

1. a kind of carbonic acid second（Third）The preparation method of enester, which is characterized in that specifically include following steps：
（1）By CO2It is passed into alkyl polyamine/organic solvent non-aqueous system and mixture is obtained by the reaction, by the solids in mixture Matter is separated and obtains carbaminate after being dried in vacuo；
（2）It is 6 by ethylene oxide/propylene oxide and carbaminate molar ratio under catalysts conditions:1~1:1 ratio is mixed It closes uniformly to be placed in reaction kettle and reacts the h of 0.5 h~10 and obtain carbonic acid second（Third）Enester, reaction temperature is 100 DEG C~160 ℃。
2. carbonic acid second according to claim 1（Third）The preparation method of enester, it is characterised in that：Step（1）Described in alkyl Polyamines is one kind in ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, piperazine, and organic solvent is ethyl alcohol, two One kind in glycol dimethyl ether, N-Methyl pyrrolidone, propene carbonate.
3. carbonic acid second according to claim 1（Third）The preparation method of enester, it is characterised in that：Step（2）Described in urge Agent is potassium halide, and the mole percent that potassium halide accounts for total system is 0.5%~1.0%.
4. carbonic acid second according to claim 1（Third）The preparation method of enester, it is characterised in that：Step（2）Described in urge Agent is ZnO, ZnCl2、ZnBr2、ZnI2In one kind, catalyst account for total system mole percent be 0.1%~0.15%.
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