CN101735064A - Method for catalytically synthesizing di-2-ethyhexyl carbonate by alkali ionic liquid - Google Patents
Method for catalytically synthesizing di-2-ethyhexyl carbonate by alkali ionic liquid Download PDFInfo
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- isooctyl
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000003513 alkali Substances 0.000 title claims abstract description 20
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title abstract description 5
- 230000002194 synthesizing effect Effects 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000007036 catalytic synthesis reaction Methods 0.000 claims abstract description 18
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 23
- 238000004821 distillation Methods 0.000 claims description 19
- 238000009835 boiling Methods 0.000 claims description 10
- 238000005809 transesterification reaction Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000008040 ionic compounds Chemical class 0.000 claims description 2
- -1 ester compounds Chemical class 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000006837 decompression Effects 0.000 abstract 1
- 150000002148 esters Chemical group 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 11
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- RNZTWPUHBBHOEU-UHFFFAOYSA-N C(CCC)N1CN(C=C1)C.N1C=NC=C1 Chemical class C(CCC)N1CN(C=C1)C.N1C=NC=C1 RNZTWPUHBBHOEU-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- HCGMDEACZUKNDY-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCCCN1CN(C)C=C1 HCGMDEACZUKNDY-UHFFFAOYSA-N 0.000 description 2
- WYHCHDAZIXORLN-UHFFFAOYSA-N O(O)O.C(C)N1CN(C=C1)C Chemical compound O(O)O.C(C)N1CN(C=C1)C WYHCHDAZIXORLN-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 description 1
- PFZPMLROUDTELO-UHFFFAOYSA-N 1-methyl-1h-imidazol-1-ium;acetate Chemical compound CC(O)=O.CN1C=CN=C1 PFZPMLROUDTELO-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NSQCYPRUJQTHIJ-UHFFFAOYSA-N N1C=NC=C1.C(C)N1CN(C=C1)C Chemical class N1C=NC=C1.C(C)N1CN(C=C1)C NSQCYPRUJQTHIJ-UHFFFAOYSA-N 0.000 description 1
- NXPZTWODNRJYRJ-UHFFFAOYSA-N O(O)O.C(CCC)N1CN(C=C1)C Chemical compound O(O)O.C(CCC)N1CN(C=C1)C NXPZTWODNRJYRJ-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003845 household chemical Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000006198 methoxylation reaction Methods 0.000 description 1
- 125000005911 methyl carbonate group Chemical class 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a catalytic synthesis method for ionic liquid of di-2-ethyhexyl carbonate and belongs to the technical field of synthesis of ester compounds in organic chemistry. The method comprises the following steps of: performing the two-step ester exchange reaction of isooctanol and methyl carbonate serving as raw materials by alkali ionic liquid serving as a catalyst, and distilling the products by decompression to obtain the di-2-ethyhexyl carbonate, wherein the negative ion in the alkali ionic liquid is one of [OAc]-, Im-, OH-, Br-, Cl- and I- ions or a compound system formed by more of [OAc]-, Im-, OH-, Br-, Cl- and I- ions, the positive ion is 1-alkyl 3-methylimidazole, and the length of the carbon chain of the alkyl group is 1 to 13. The ionic liquid is added in an amount of 1 to 50 percent based on the total mass of the reaction raw materials, and the yield of the di-2-ethyhexyl carbonate is 45 to 85 percent. The alkali ionic liquid is used as the catalyst in the method, so that the method has the advantages of recovery of the catalyst, stable quality and yield of the product, advanced and reasonable process and easy operation.
Description
Technical field
The present invention relates to a kind of ionic liquid-catalyzed synthetic method of carbonic acid di-isooctyl, belong to the catalytic synthetic techniques field of ester compound in the organic chemistry.
Background technology
The carbonic acid di-isooctyl is a kind of colourless cleansing oil, have strong polarity ester group, good lubrication performance, lower zero pour and pour point, with good, the higher high thermo-oxidative stability of hydrocarbon-type oil consistency, be one of important industrial chemicals of synthetic base oil.The carbonic acid di-isooctyl is compared with other ester compounds and is difficult for saponification, and biological degradation can take place apace, and the ultraviolet ray between the 200-320nm is had strong sorption, also can be used as the ultraviolet shielding agent in household chemicals field, field of functional materials.It is raw material that the synthetic route of carbonic acid di-isooctyl adopts methylcarbonate and isooctyl alcohol more, uses solid alkali as catalyzer, synthetic through two-step approach.But solid catalyst preparation technology is comparatively complicated, and the selectivity of reaction is relatively poor, very easily by the CO in the atmosphere
2And H
2Contaminating impurities such as O, raw material recycle efficient is low, and the existing shortcoming of solid catalyst has suppressed the industrialization of carbonic acid di-isooctyl and has synthesized.
The solid base catalyst of having reported comprises alkali metal alcoholates, metal oxide, carbonate, potassiumiodide and titanic acid ester etc.For example, Feng Xiuli etc. are by finding relatively that to the catalytic performance of several sylvite potassium titanate has catalytic activity and selectivity preferably, prove that by experiment working as catalyst levels is 1% of raw material total mass, the mol ratio of methylcarbonate and isooctyl alcohol is 1: 3,120 ℃ of temperature of reaction, reaction times 2h, the yield of carbonic acid di-isooctyl are 57.6%.Ren Bo etc. are that the technology that catalyzer is prepared the carbonic acid di-isooctyl by two step transesterification reactions is: the back flow reaction 2h under reactant boiling situation of elder generation with calcium oxide/zirconium dioxide, insert water distilling apparatus then, remove the methyl alcohol of generation, be warming up to 130 ℃ and continue reaction 4h, wherein product yield is up to 62.2% during catalyzer functional quality mark 1.5%.Under same processing condition, Ren Bo etc. utilize calcium oxide/zirconium dioxide-lanthanum solid base catalyst to prepare the carbonic acid di-isooctyl again, and productive rate can reach 66.8%.The oxide compound of human sodium such as Gryglewicz, magnesium, calcium, barium, aluminium, oxyhydroxide and methoxylation compound are catalyzer, methylcarbonate and isooctyl alcohol are reacted at low temperatures, after removing the methyl alcohol and unreacted methylcarbonate of generation, continue reaction 4h down at 120 ℃, the solids removed by filtration catalyzer, can obtain yield through underpressure distillation is 65% carbonic acid di-isooctyl.Use the yield of solid base catalyst catalytic synthesis of C acid di-isooctyl lower.
Ionic liquid can be used as catalyzer and uses in organic synthesis, compares with solid base catalyst, and ionic-liquid catalyst has advantages such as environmental protection, good reaction selectivity, organic efficiency height.For example, 1-butyl-3-Methylimidazole oxyhydroxide, 1-butyl-3-Methylimidazole imidazole salts, the existing reported in literature of 1-butyl-ion liquid synthetic works of glyoxaline cation type such as 3-Methylimidazole acetate, 1-butyl-3-Methylimidazole acetate, 1-butyl-3-Methylimidazole imidazole salts and the 1-butyl-alkalescence of 3-Methylimidazole oxyhydroxide is and increases progressively variation tendency, according to the difference of alkali ionic liquid alkalescence size, it can be used as reaction medium or catalyzer and be used for specific organic synthesis.For example, Chen Xuewei uses 1-butyl-3-Methylimidazole imidazole salts as catalyzer, has realized the Knoevnagel catalyzed reaction between the aromatic aldehyde and active methylene compound under the room temperature condition.Catalyzer has the efficient of recycling height, advantages such as target product yield height.
At present, use acidity or alkali ionic liquid as the catalyst transesterification reaction, the technology of preparation carbonic acid di-isooctyl does not still have report.
Summary of the invention
The alkali ionic liquid process for catalytic synthesis that the purpose of this invention is to provide a kind of carbonic acid di-isooctyl, the reaction conditions gentleness, the reaction efficiency between methylcarbonate and the isooctyl alcohol and the yield of carbonic acid di-isooctyl had both been improved, can guarantee that again reacted raw material and product are able to regeneration, thereby form the new green synthesizing process of carbonic acid di-isooctyl.
The present invention for achieving the above object, the technical scheme that is adopted is: a kind of process for catalytic synthesis of carbonic acid di-isooctyl is provided, and is raw material with methylcarbonate and isooctyl alcohol, is catalyzer with the alkali ionic liquid, by two step transesterification reactions, obtain the carbonic acid di-isooctyl after the underpressure distillation.
Method one optimal technical scheme according to a kind of alkali ionic liquid catalytic synthesis of C acid di-isooctyl of the present invention: described alkali ionic liquid comprises positively charged ion 1-alkyl 3-Methylimidazole and a kind of negatively charged ion, and its structure is:
Wherein R is the alkyl of 1～13 carbon atom, X-be [OAc]-, one or several ionic compound systems in the middle of Im-, OH-, Br-, Cl-, the I-.
Method one optimal technical scheme according to a kind of alkali ionic liquid catalytic synthesis of C acid di-isooctyl of the present invention: the ionic liquid consumption of described alkaline ionic liquid catalyst is 1～50% of a reaction raw materials total mass per-cent, and alkaline ionic liquid catalyst can reuse.
Method one optimal technical scheme according to a kind of alkali ionic liquid catalytic synthesis of C acid di-isooctyl of the present invention: the mol ratio of described isooctyl alcohol and methylcarbonate is 1: 1～10: 1.
Method one optimal technical scheme according to a kind of alkali ionic liquid catalytic synthesis of C acid di-isooctyl of the present invention: the first step temperature of reaction of described transesterification reaction is controlled between 60～90 ℃, and the reaction times is 0.5～9h.
Method one optimal technical scheme according to a kind of alkali ionic liquid catalytic synthesis of C acid di-isooctyl of the present invention: the second step temperature of reaction of described transesterification reaction is controlled at 100～180 ℃, and the reaction times is 1～10h.
Method one optimal technical scheme according to a kind of alkali ionic liquid catalytic synthesis of C acid di-isooctyl of the present invention: described underpressure distillation condition is 3～10mmHg, collects the colourless liquid carbonic acid di-isooctyl of boiling range between 170～240 ℃.
Beneficial effect of the present invention is:
1, the alkaline ionic liquid catalyst catalytic performance is good, selects then property height, Heat stability is good; Belong to green catalyst, to environment and the basic toxicological harmless effect of daily life, and operating procedure is fairly simple, and product and catalyzer be separate easily relatively, and catalyzer can reuse repeatedly and obvious reduction does not take place catalytic effect.
2, kind by adjusting methylcarbonate and isooctyl alcohol proportioning, alkali ionic liquid and add-on, temperature of reaction, reaction times, can obtain the higher carbonic acid di-isooctyl of purity, carbonic acid di-isooctyl yield is higher than the conventional solid catalyzer.
Embodiment
Embodiment 1
In the 250mL four-hole boiling flask of agitator, thermometer, prolong, constant pressure funnel is housed, add 64.37g isooctyl alcohol and 0.86g1-ethyl-3-Methylimidazole muriate, heat temperature raising to 60 ℃, slowly at the uniform velocity drip the 22.26g methylcarbonate, about 1h drips off, and keeps inserting behind 60 ℃ of reaction 9h methyl alcohol and the unreacted methylcarbonate that water trap will react generation and steams.Be warming up to 110 ℃ of reaction 3h then, reaction finishes after after the cooling, underpressure distillation, standing demix.170 ℃ of colourless liquids are collected in supernatant liquid underpressure distillation under 3mmHg pressure, got product 39.60g, yield is 55.92%.
Embodiment 2
In the 250mL four-hole boiling flask of agitator, thermometer, prolong, constant pressure funnel is housed, add 124.04g isooctyl alcohol and 2.91g1-butyl-3-Methylimidazole imidazole salts, heat temperature raising to 70 ℃, slowly at the uniform velocity drip the 21.45g methylcarbonate, about 1h drips off, after keeping 70 ℃ of reaction 8h, the access water trap will react the methyl alcohol and the unreacted methylcarbonate that generate and steam.Be warming up to 140 ℃ of reaction 4h then, reaction finishes after after the cooling, underpressure distillation, standing demix.But lower floor's viscous liquid is the 1-butyl-3-Methylimidazole imidazole salts of second stage employ, and 180 ℃ of colourless liquids are collected in supernatant liquid underpressure distillation under 6mmHg pressure, gets product 49.28g, and yield is 72.23%.
Embodiment 3
In the 250mL four-hole boiling flask of agitator, thermometer, prolong, constant pressure funnel is housed, add 90.20g isooctyl alcohol and 2.23g 1-ethyl-3-Methylimidazole oxyhydroxide, heat temperature raising to 80 ℃, slowly at the uniform velocity drip the 21.42g methylcarbonate, about 1h drips off, and keeps inserting behind 80 ℃ of reaction 6h methyl alcohol and the unreacted methylcarbonate that water trap will react generation and steams.Be warming up to 100 ℃ of reaction 5h then, reaction finishes after after the cooling, underpressure distillation, standing demix.But lower floor's viscous liquid is the 1-ethyl-3-Methylimidazole oxyhydroxide of second stage employ, and 240 ℃ of colourless liquids are collected in supernatant liquid underpressure distillation under 10mmHg pressure, gets product 40.94g, and yield is 49.09%.
Embodiment 4
In the 250mL four-hole boiling flask of agitator, thermometer, prolong, constant pressure funnel is housed, add 89.85g isooctyl alcohol and 3.87g1-butyl-3-Methylimidazole acetate, heat temperature raising to 90 ℃, slowly at the uniform velocity drip the 20.72g methylcarbonate, about 1h drips off, and keeps inserting behind 90 ℃ of reaction 5h methyl alcohol and the unreacted methylcarbonate that water trap will react generation and steams.Be warming up to 180 ℃ of reaction 6h then, reaction finishes after after the cooling, underpressure distillation, standing demix.But lower floor's viscous liquid is the 1-butyl-3-Methylimidazole acetate of second stage employ, and 170 ℃ of colourless liquids are collected in supernatant liquid underpressure distillation under 3mmHg pressure, gets product 56.78g, and yield is 84.15%.
Embodiment 5
In the 1000mL four-hole boiling flask of agitator, thermometer, prolong, constant pressure funnel is housed, add 475.12g isooctyl alcohol and 11.15g1-butyl-3-Methylimidazole imidazole salts, heat temperature raising to 90 ℃, slowly at the uniform velocity drip the 82.16g methylcarbonate, about 3h drips off, and keeps inserting behind 90 ℃ of reaction 3h methyl alcohol and the unreacted methylcarbonate that water trap will react generation and steams.Be warming up to 120 ℃ of reaction 4h then, reaction finishes after after the cooling, underpressure distillation, standing demix.But lower floor's viscous liquid is the 1-butyl-3-Methylimidazole imidazole salts of second stage employ, and 180 ℃ of colourless liquids are collected in supernatant liquid underpressure distillation under 10mmHg pressure, gets product 172.87g, and yield is 66.15%.
Embodiment 6
In the 1000mL four-hole boiling flask of agitator, thermometer, prolong, constant pressure funnel is housed, add 392.60g isooctyl alcohol and 24.15g1-ethyl-3-Methylimidazole imidazole salts, heat temperature raising to 70 ℃, slowly at the uniform velocity drip 90.52 methylcarbonates, about 3h drips off, and keeps inserting behind 70 ℃ of reaction 7h methyl alcohol and the unreacted methylcarbonate that water trap will react generation and steams.Be warming up to 170 ℃ of reaction 3h then, reaction finishes after after the cooling, underpressure distillation, standing demix.But lower floor's viscous liquid is the 1-ethyl-3-Methylimidazole imidazole salts of second stage employ, and 170 ℃ of colourless liquids are collected in supernatant liquid underpressure distillation under 3mmHg pressure, gets product 237.80g, and yield is 82.59%.
Embodiment 7
In the 1000mL four-hole boiling flask of agitator, thermometer, prolong, constant pressure funnel is housed, add 554.47g isooctyl alcohol and 51.78g1-ethyl-3-Methylimidazole acetate, heat temperature raising to 90 ℃, slow Dropwise 5 4.79g methylcarbonate at the uniform velocity, about 2h drips off, and keeps inserting behind 90 ℃ of reaction 4h methyl alcohol and the unreacted methylcarbonate that water trap will react generation and steams.Be warming up to 150 ℃ of reaction 9h then, reaction finishes after after the cooling, underpressure distillation, standing demix.But lower floor's viscous liquid is the 1-ethyl-3-Methylimidazole acetate of second stage employ, and 200 ℃ of colourless liquids are collected in supernatant liquid underpressure distillation under 6mmHg pressure, gets product 137.03g, and yield is 78.63%.
The above; only be the preferable embodiment of the present invention; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to replacement or change according to technical scheme of the present invention and inventive concept thereof, all should be encompassed within protection scope of the present invention.
Claims (7)
1. the process for catalytic synthesis of a carbonic acid di-isooctyl is a raw material with methylcarbonate and isooctyl alcohol, it is characterized in that: be catalyzer with the alkali ionic liquid, by two step transesterification reactions, obtain the carbonic acid di-isooctyl after the underpressure distillation.
2. the process for catalytic synthesis of carbonic acid di-isooctyl according to claim 1 is characterized in that: described alkali ionic liquid comprises positively charged ion 1-alkyl 3-Methylimidazole and a kind of negatively charged ion, and its structure is:
Wherein R is the alkyl of 1～13 carbon atom, X-be [OAc]-, one or several ionic compound systems in the middle of Im-, OH-, Br-, Cl-, the I-.
3. the process for catalytic synthesis of carbonic acid di-isooctyl according to claim 1, it is characterized in that: the ionic liquid consumption of described alkaline ionic liquid catalyst is 1～50% of a reaction raw materials total mass per-cent, and alkaline ionic liquid catalyst can reuse.
4. the process for catalytic synthesis of carbonic acid di-isooctyl according to claim 1, the mol ratio that it is characterized in that described isooctyl alcohol and methylcarbonate is 1: 1～10: 1.
5. the process for catalytic synthesis of carbonic acid di-isooctyl according to claim 1 is characterized in that: the first step temperature of reaction of described transesterification reaction is controlled between 60～90 ℃, and the reaction times is 0.5～9h.
6. the process for catalytic synthesis of carbonic acid di-isooctyl according to claim 1 is characterized in that: the second step temperature of reaction of described transesterification reaction is controlled at 100～180 ℃, and the reaction times is 1～10h.
7. the process for catalytic synthesis of carbonic acid di-isooctyl according to claim 1 is characterized in that: described underpressure distillation condition is 3～10mmHg, collects the colourless liquid carbonic acid di-isooctyl of boiling range between 170～240 ℃.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126957A (en) * | 2011-01-11 | 2011-07-20 | 中国科学院过程工程研究所 | Method for preparing carbonic ester and ethylene alcohol by ionic liquid catalysis |
| CN102351709A (en) * | 2011-10-17 | 2012-02-15 | 上海应用技术学院 | Preparation method for synthesis of dibutyl carbonate under catalysis of alkaline ion liquid |
| CN102372635A (en) * | 2011-11-09 | 2012-03-14 | 上海应用技术学院 | Method for preparing diamyl carbonate by catalyzing and synthesizing alkaline ionized liquid |
| CN102391125A (en) * | 2011-10-17 | 2012-03-28 | 上海应用技术学院 | Method for preparing dipropyl carbonate through catalytic synthesis by using alkaline ionic liquid |
| CN103058873A (en) * | 2013-02-06 | 2013-04-24 | 上海应用技术学院 | Synthesis method of diisooctyl carbonate |
| CN103641720A (en) * | 2013-12-17 | 2014-03-19 | 福州大学 | Method of synthesizing diethyl carbonate by basic ionic liquid as catalyst |
| CN103709032A (en) * | 2013-12-26 | 2014-04-09 | 江西师范大学 | Preparation method for catalytically synthesizing dibutyl carbonate by proline ionic liquid |
| CN105669366A (en) * | 2015-12-31 | 2016-06-15 | 天津中福工程技术有限公司 | Method for synthesizing diethyl carbonate by adopting alkaline ionic liquid as catalyst |
| CN109265344A (en) * | 2017-07-18 | 2019-01-25 | 中国石油化工股份有限公司 | The preparation method of dipheryl carbonate esters compound |
| CN110724255A (en) * | 2019-11-14 | 2020-01-24 | 中国科学院过程工程研究所 | Compound catalyst and application thereof in preparation of bio-based polycarbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102126957A (en) * | 2011-01-11 | 2011-07-20 | 中国科学院过程工程研究所 | Method for preparing carbonic ester and ethylene alcohol by ionic liquid catalysis |
| CN102126957B (en) * | 2011-01-11 | 2013-07-10 | 中国科学院过程工程研究所 | Method for preparing carbonic ester and ethylene alcohol by ionic liquid catalysis |
| CN102351709A (en) * | 2011-10-17 | 2012-02-15 | 上海应用技术学院 | Preparation method for synthesis of dibutyl carbonate under catalysis of alkaline ion liquid |
| CN102391125A (en) * | 2011-10-17 | 2012-03-28 | 上海应用技术学院 | Method for preparing dipropyl carbonate through catalytic synthesis by using alkaline ionic liquid |
| CN102372635A (en) * | 2011-11-09 | 2012-03-14 | 上海应用技术学院 | Method for preparing diamyl carbonate by catalyzing and synthesizing alkaline ionized liquid |
| CN103058873A (en) * | 2013-02-06 | 2013-04-24 | 上海应用技术学院 | Synthesis method of diisooctyl carbonate |
| CN103641720A (en) * | 2013-12-17 | 2014-03-19 | 福州大学 | Method of synthesizing diethyl carbonate by basic ionic liquid as catalyst |
| CN103709032B (en) * | 2013-12-26 | 2015-09-09 | 江西师范大学 | Preparation method for catalytically synthesizing dibutyl carbonate by proline ionic liquid |
| CN103709032A (en) * | 2013-12-26 | 2014-04-09 | 江西师范大学 | Preparation method for catalytically synthesizing dibutyl carbonate by proline ionic liquid |
| CN105669366A (en) * | 2015-12-31 | 2016-06-15 | 天津中福工程技术有限公司 | Method for synthesizing diethyl carbonate by adopting alkaline ionic liquid as catalyst |
| CN109265344A (en) * | 2017-07-18 | 2019-01-25 | 中国石油化工股份有限公司 | The preparation method of dipheryl carbonate esters compound |
| CN109265344B (en) * | 2017-07-18 | 2021-08-03 | 中国石油化工股份有限公司 | Preparation method of diphenyl carbonate compound |
| CN110724255A (en) * | 2019-11-14 | 2020-01-24 | 中国科学院过程工程研究所 | Compound catalyst and application thereof in preparation of bio-based polycarbonate |
| CN111018710A (en) * | 2019-12-09 | 2020-04-17 | 沈阳化工大学 | Preparation method of dimethyl carbonate |
| WO2021114092A1 (en) * | 2019-12-09 | 2021-06-17 | 沈阳化工大学 | Method for preparing dimethyl carbonate |
| CN113563191A (en) * | 2021-09-07 | 2021-10-29 | 中国石油大学(华东) | Method for continuously producing dimethyl carbonate by catalysis of composite alkaline ionic liquid |
| CN113563191B (en) * | 2021-09-07 | 2023-09-15 | 中国石油大学(华东) | Method for continuously producing dimethyl carbonate by catalyzing composite alkaline ionic liquid |
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