CN106380461A - Preparation method of ethylene carbonate (propylene carbonate) - Google Patents
Preparation method of ethylene carbonate (propylene carbonate) Download PDFInfo
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- CN106380461A CN106380461A CN201610770482.8A CN201610770482A CN106380461A CN 106380461 A CN106380461 A CN 106380461A CN 201610770482 A CN201610770482 A CN 201610770482A CN 106380461 A CN106380461 A CN 106380461A
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- ethylene
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- carbonate
- alkene ester
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 title abstract description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 229920000768 polyamine Polymers 0.000 claims abstract description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 5
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims abstract description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 alkene ester Chemical class 0.000 claims description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 23
- 239000005977 Ethylene Substances 0.000 claims description 23
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 10
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 8
- 150000007517 lewis acids Chemical class 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002841 Lewis acid Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- UAYWVJHJZHQCIE-UHFFFAOYSA-L Zinc iodide Inorganic materials I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 150000001412 amines Chemical class 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000003795 desorption Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 12
- 238000001027 hydrothermal synthesis Methods 0.000 description 12
- 238000003760 magnetic stirring Methods 0.000 description 12
- 239000004417 polycarbonate Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- QQUZYDCFSDMNPX-UHFFFAOYSA-N ethene;4-methyl-1,3-dioxolan-2-one Chemical compound C=C.CC1COC(=O)O1 QQUZYDCFSDMNPX-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007616 round robin method Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of ethylene carbonate (propylene carbonate), and belongs to a novel method for synthesizing cyclic allyl carbonate. According to the method, alkyl polyamine-carbamate prepared in a lab and ethylene oxide (propylene oxide) carry out reactions in the presence of a catalyst to prepare an organic chemical product namely ethylene carbonate (propylene carbonate) with a high additional valve. Moreover, an absorption solvent (alkyl polyamine) can be obtained. The catalyst has a high activity and selectivity, so the yield of ethylene oxide (propylene oxide) is high and can reach more than 90%. The yield of byproduct (alkyl polyamine) can reach more than 95%. The byproduct (alkyl polyamine) can be recovered to cyclically absorb CO2. The fixed C1 resources are converted into an importation chemical product by the preparation method, the greenhouse effect is effectively relieved; at the same time, the problem of large energy consumption for desorption of CO2 in an organic amine solution is solved, and the recovered byproduct can be used to absorb CO2 circularly.
Description
Technical field
The present invention discloses a kind of ethylene（Third）The preparation method of alkene ester, belongs to a kind of new synthesis of cyclic ethylene (propylene) carbonate
Method.
Background technology
CO2A kind of abundant C natural resourcess, nontoxic, good stability, cheap and easy obtain, therefore replacing fossil combustion
Material field is with a wide range of applications；For reply global warming, also there is important strategic importance.Now more ripe
Technology is to utilize CO2As raw material and epoxide synthesizing annular carbonate in the presence of catalyst, it is in secondary cell
Electrolyte, organic synthesis intermediate, the monomer of polycarbonate synthesis, aprotic, polar type solvent, the carrier of alkylated reaction,
The fields such as the carrier of biologically active drug have and are widely applied very much.Wherein utilize CO2With oxirane（EO）And expoxy propane
（PO）There is cycloaddition reaction synthesizing ethylene carbonate（EC）And Allyl carbonate（PC）It is industrial more ripe synthesis road
Line.
EC and PC is a kind of important organic solvent and organic synthesis intermediate, can apply in weaving, battery, cosmetic
The intermediate of product, pharmacy and fine chemical product, gas such as separate at the field.Ethylene（Third）The primary synthetic methods of alkene ester have ester
Exchange process, phosgenation, CO2With epoxy second（Third）Alkane additive reaction method etc..There are a large amount of by-products due in reaction in ester-interchange method
And limited by raw material sources, therefore, it is difficult to industrially it is widely used.Phosgene is poisonous and corrosivity are big, is therefore unfavorable for
Safety in production and environmental pollution.
Content of the invention
It is an object of the invention to overcoming the deficiencies in the prior art, provide a kind of ethylene（Third）The preparation method of alkene ester,
Specifically include following steps：
（1）By CO2It is passed into reaction in alkyl polyamine/organic solvent non-aqueous system and obtain mixture（CO2It is passed through to the matter of system
Amount no longer changes）, the solid matter in mixture is separated and obtains carbaminate after being vacuum dried.
（2）Under catalysts conditions, it is 6 by ethylene oxide/propylene oxide and carbaminate mol ratio:1～1:1 ratio
It is placed in reaction kettle for reaction 0.5 h～10 h after example mix homogeneously and obtain ethylene（Third）Alkene ester, reaction temperature 100 DEG C～
160 ℃.
Step of the present invention（1）Described in absorbent alkyl polyamine be ethylenediamine, diethylenetriamine, triethylene tetramine, four
One of ethylene five amine, piperazine, organic solvent is ethanol, diethylene glycol dimethyl ether, N-Methyl pyrrolidone, Allyl carbonate
One of；In alkyl polyamine/organic solvent non-aqueous system, the mass percent concentration of alkyl polyamine is 20%～30%.
Preferably, step of the present invention（2）Described in catalyst be one of potassium halide, lewis acid, potassium halide accounts for
The mole percent of total system is 0.5% mol～1.0% mol, 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、ZnI2One of.
The principle of the present invention is：
The present invention is based on CO2In the presence of a catalyst cyclic carbonate is directly obtained by cycloaddition reaction with alkylene oxide, specifically
Reaction equation is as follows：
Speculate reaction principle taking piperazine carbaminate as a example：Piperazine carbaminate generates carbonic acid with expoxy propane effect
Propylene obtains piperazine simultaneously, and concrete 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 epoxy second
（Third）Alkane reacts preparation ethylene under catalysts conditions（Third）Alkene ester.
The present invention passes through to absorb CO2The carbaminate desorption cycle obtaining absorbs CO2Need a liter high-temperature, therefore consume
Higher energy；By the reaction of carbaminate and alkylene oxide, high value added product ethylene can not only be obtained（Third）Alkene ester,
And the by-product generating is absorbent alkyl polyamine, and yield can reach more than 95%, can continue cycling through absorption by reclaiming
CO2, this not only avoids Amine Solutions and absorb CO2The problem of desorbing high energy consumption, and the ethylene generating（Third）Alkene ester is in work
It is widely used in industry.
The present invention is using the carbaminate preparation ethylene of preparation（Third）Alkene ester, by greenhouse gases CO2This C1 resource
Fixing utilization, and lyosoption can be reclaimed, reach the effect of recycling；This absorption, conversion, utilization, re-absorption utilize
Round-robin method, not only obtain the chemical products of high added value moreover it is possible to effectively reduce greenhouse effect, and solvent can circulate
Use, therefore in the industry on there is very big potential using value.
Beneficial effects of the present invention：
（1）Avoid organic amine system and absorb CO2The problem of desorbing high energy consumption, fixing C1 resource is directly changed into high additional
The chemical products ethylene of value（Third）Alkene ester, and recyclable absorbent alkyl polyamine, continue cycling through absorption CO2, meet greenization
Learn the concept with atom economy benefit, and ethylene（Third）Alkene ester has higher yield.
（2）Selected catalyst activity is high, selectivity is high, cheap, be readily synthesized；Due to CO2First react with amine,
Then react with alkylene oxide again, therefore in body series, reactant carbaminate can substitute promoter, and can be with KX or road
Lewis acid forms good synergic catalytic effect, drastically increases the catalysis activity of catalyst；Selected catalyst can weigh
Again using repeatedly.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited to
Described content.
Using alkyl polyamine/organic solvent non-aqueous system at normal temperatures and pressures with CO2Reaction obtains carbaminate, with
EO, PO prepare the technique of EC, PC in the presence of 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 tri- mouthfuls of 250ml
In flask, CO2Controlled by gas mass flow controller and be passed through in there-necked flask, react 2 h；The liquid-solid mixture of gained leads to
Cross decompression separation and obtain solid and be placed in 40 DEG C of drying 1 h of vacuum drying oven, save backup；Described absorbent alkyl polyamine
For one of ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA, piperazine, organic solvent is ethanol, diethyl two
One of diethylene glycol dimethyl ether, N-Methyl pyrrolidone, Allyl carbonate.
（2）No ethylene under catalysts conditions（Third）The preparation of alkene ester：A certain amount of above-mentioned five kinds of carbaminates and EO,
PO is added in 50ml hydro-thermal reaction crystallizing kettle, using heat collecting type constant-temperature heating magnetic stirring apparatus controlling reaction temperature, reaction knot
Room temperature is naturally cooled to after bundle.No under catalysts conditions, determine that the mol ratio of EO, PO and carbaminate is 6:1～1:1, place
Manage temperature control at 100 DEG C～160 DEG C, response time 0.5h～10h.This example is intended to optimal screening preparation ethylene（Third）Alkene ester
Condition.
（3）There is ethylene under catalysts conditions（Third）The preparation of alkene ester
Embodiment 1
Mol ratio by EO and ethylenediamine-carbaminate is 6:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettle, and addition is urged
Agent ZnO 0.1 %mol (accounts for the mole percent of total system）, at heat collecting type constant-temperature heating magnetic stirring apparatus control
100 DEG C of temperature of reason, response time 0.5 h, reaction naturally cools to room temperature after terminating；EC yield is 92.6%, ethylenediamine yield
For 95.2%.
Embodiment 2
Mol ratio by PO and ethylenediamine-carbaminate is 6:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettle, and addition is urged
Agent KF 0.5% mol (accounts for the mole percent of total system）, using heat collecting type constant-temperature heating magnetic stirring apparatus control process
100 DEG C of temperature, response time 0.5 h, reaction naturally cools to room temperature after terminating；PC yield is 90.2%, and ethylenediamine yield is
96.3%.
Embodiment 3
Mol ratio by EO and diethylenetriamine-carbaminate is 5:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettle, plus
Enter catalyst Z nCl20.11%mol (accounts for the mole percent of total system）, using heat collecting type constant-temperature heating magnetic stirring apparatus
120 DEG C of control process temperature, response time 2.5 h, reaction naturally cools to room temperature after terminating；EC yield is 91.1%, divinyl
Triamine yield is 95.8%.
Embodiment 4
Mol ratio by PO and diethylenetriamine-carbaminate is 5:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettle, plus
Enter catalyst KCl 0.6% mol（Account for the mole percent of total system）, controlled using heat collecting type constant-temperature heating magnetic stirring apparatus
120 DEG C for the treatment of temperature, response time 2.5 h, reaction naturally cools to room temperature after terminating；PC yield is 92.3%, divinyl three
Amine yield is 96.6%.
Embodiment 5
Mol ratio by EO and triethylene tetramine-carbaminate is 4:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettle, plus
Enter catalyst Z nBr20.12%mol (accounts for the mole percent of total system）, using heat collecting type constant-temperature heating magnetic stirring apparatus
140 DEG C of control process temperature, response time 4.5 h；Reaction naturally cools to room temperature after terminating.EC yield is 92.8%, three second
Alkene tetramine yield is 95.5%.
Embodiment 6
Mol ratio by PO and triethylene tetramine-carbaminate is 4:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettle, plus
Enter catalyst KBr 0.7% mol and (account for the mole percent of total system）, controlled using heat collecting type constant-temperature heating magnetic stirring apparatus
140 DEG C for the treatment of temperature, response time 4.5 h, reaction naturally cools to room temperature after terminating；PC yield is 91.9%, triethylene four
Amine yield is 96.9%.
Embodiment 7
Mol ratio by EO and TEPA-carbaminate is 3:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettle, plus
Enter catalyst Z nI20.13%mol (accounts for the mole percent of total system）, using heat collecting type constant-temperature heating magnetic stirring apparatus control
150 DEG C for the treatment of temperature processed, response time 6.5 h, reaction naturally cools to room temperature after terminating；EC yield is 90.7%, four ethylene
Five amine yields are 97.2%.
Embodiment 8
Mol ratio by PO and TEPA-carbaminate is 3:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettle, plus
Enter catalyst KI 0.8% mol and (account for the mole percent of total system）, controlled using heat collecting type constant-temperature heating magnetic stirring apparatus
150 DEG C for the treatment of temperature, response time 6.5 h, reaction naturally cools to room temperature after terminating；PC yield is 90.1%, four ethylene five
Amine yield is 96.3%.
Embodiment 9
Mol ratio by EO and piperazine-carbaminate is 1:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettle, adds catalysis
Agent ZnBr20.15%mol (accounts for the mole percent of total system）, at heat collecting type constant-temperature heating magnetic stirring apparatus control
160 DEG C of temperature of reason, response time 8.5 h；Reaction naturally cools to room temperature after terminating, and EC yield is 94.9%, and piperazine yield is
97.7%.
Embodiment 10
Mol ratio by PO and piperazine-carbaminate is 2:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettle, adds catalysis
Agent KCl 0.9% mol (accounts for the mole percent of total system）, using heat collecting type constant-temperature heating magnetic stirring apparatus control process
160 DEG C of temperature, response time 8.5 h；Reaction naturally cools to room temperature after terminating, and PC yield is 94.6%, and piperazine yield is
98.0%.
Embodiment 11
Mol ratio by PO and piperazine-carbaminate is 1:1 is mixed to join in 50ml hydro-thermal reaction crystallizing kettle, adds catalysis
Agent KI 1.0% mol (accounts for the mole percent of total system）, using heat collecting type constant-temperature heating magnetic stirring apparatus control process temperature
160 DEG C of degree, response time 10 h；Reaction naturally cools to room temperature after terminating, and PC yield is 95.3%, and piperazine yield is 97.6%.
Prepare ethylene for the present invention above（Third）The specific implementation method of alkene ester, but the invention is not restricted to above embodiment party
Formula, can make change in the premise without departing from present inventive concept in experiment condition.
Claims (4)
1. a kind of ethylene（Third）The preparation method of alkene ester is it is characterised in that specifically include following steps：
（1）By CO2It is passed into reaction in alkyl polyamine/organic solvent non-aqueous system and obtain mixture, by the solidss in mixture
Matter is separated and is obtained carbaminate after being vacuum dried；
（2）Under catalysts conditions, it is 6 by ethylene oxide/propylene oxide and carbaminate mol ratio:1～1:1 ratio is mixed
It is placed in reaction kettle for reaction 0.5 h～10 h after closing uniformly and obtain ethylene（Third）Alkene ester, reaction temperature is 100 DEG C～160
℃.
2. ethylene according to claim 1（Third）The preparation method of alkene ester it is characterised in that：Step（1）Described in alkyl
Polyamines be one of ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA, piperazine, organic solvent be ethanol, two
One of glycol dimethyl ether, N-Methyl pyrrolidone, Allyl carbonate.
3. ethylene according to claim 1（Third）The preparation method of alkene ester it is characterised in that：Step（2）Described in urge
Agent is one of potassium halide, lewis acid, and the mole percent that potassium halide accounts for total system is 0.5%～1.0%, lewis acid
The mole percent accounting for total system is 0.1%～0.15%.
4. ethylene according to claim 1 or 3（Third）The preparation method of alkene ester it is characterised in that：Lewis acid be ZnO,
ZnCl2、ZnBr2、ZnI2One of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610770482.8A CN106380461B (en) | 2016-08-31 | 2016-08-31 | A kind of carbonic acid second（Third）The preparation method of enester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610770482.8A CN106380461B (en) | 2016-08-31 | 2016-08-31 | A kind of carbonic acid second（Third）The preparation method of enester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106380461A true CN106380461A (en) | 2017-02-08 |
| CN106380461B CN106380461B (en) | 2018-10-23 |
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ID=57938309
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| JP2019151630A (en) * | 2018-03-02 | 2019-09-12 | 学校法人早稲田大学 | Polyfunctional compound and method for producing the same, amic acid compound and method for producing the same, and method for producing imide compound |
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