CN101328124B - Ester exchange method for synthesizing ethylene diglycol diene propyl carbonic ether - Google Patents
Ester exchange method for synthesizing ethylene diglycol diene propyl carbonic ether Download PDFInfo
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Abstract
The invention provides an ester exchange method for synthesizing diethylene glycol bis (allyl carbonate), belonging to the technical field of preparing carbonate from carboxylic acid ester. The ester exchanger method comprises the following specific steps that: raw materials of diethylene glycol, dimethyl carbonate and allyl alcohol are added into a reactor, wherein the mol ratio of diethylene glycol to dimethyl carbonate to allyl alcohol is 1:2 to 25:2 to 50, a metal oxide catalyst which accounts for 0.1 to 10 percent of the total mass percentage of a reactant system is added, the temperature is raised to react, the reaction temperature is between 85 and 150 DEG C, the reaction lasts for 1 to 20 hours, the reaction pressure is between 399.9 to 90,000Pa, after the reaction is over, the temperature is reduced to the room temperature, the liquid and the solid are separated by filtering, the filter liquor is subjected to further decompression and distillation so that the reaction product of the diethylene glycol bis (allyl carbonate) is obtained, and the filter residue of the metal oxide catalyst is reclaimed and can be used repeatedly after baked simply. The metal oxide catalyst used in the method has high activity and low cost; the reaction process is simple and the industrial application is realized easily; and a product ADC is clear and transparent and has high purity.
Description
Technical field
Technical scheme of the present invention belongs to from organic acid acetic and prepares carbonic ether, specifically a kind of ester-interchange method of synthetic diethylene glycol bis-allyl carbonate.
Background technology
Diethylene glycol bis-allyl carbonate (hereinafter to be referred as ADC) is a kind of important high polymer monomer.
The synthetic method of ADC mainly contains three kinds: phosgenation, CO
2Method and ester-interchange method.
U.S. PPG company developed with phosgene, glycol ether and vinylcarbinol in 1940 be the phosgenation that raw material synthesizes ADC.Because raw material phosgene severe toxicity, the product residual chlorine is difficult to remove, so phosgenation can not obtain Sustainable development.
JP 8102937, JP 8105442 and JP 8105443 disclose with CO
2, glycol ether and propenyl chloride be raw material, triethylamine is made catalyzer, in anhydrous Na
2CO
3There is the CO of synthetic ADC down
2Method; It is catalyst CO that CN 1974528A discloses with the alkyl guanidine compounds
2The method of the synthetic ADC of method.CO
2The subject matter that the synthetic ADC of method exists is that product often has color, is difficult to remove, and has the chloride impurity that is difficult for removing in the product, influences the practical application of ADC.
US 4512930 has disclosed at NaOH, Na
2CO
3, sodium alkoxide and deacidite alkaline catalysts effect under, be the ester-interchange method of the synthetic ADC of raw material with methylcarbonate, vinylcarbinol and glycol ether, the yield of ADC is up to 90%.Though this method has solved phosgenation and CO preferably
2The product that exists among the synthetic ADC of method often has the problem of color, and product is Clear ﹠ Transparent, does not contain any foreign pigment, can directly use, but used NaOH, Na in this method
2CO
3Not easy to be recycled with sodium alkoxide, and deacidite exist can not be high temperature resistant and the shortcoming of easy inactivation, so this method cost is higher, complicated operation.
Metal oxide is the broad-spectrum catalyzer of a class, is used for catalytic oxidation, oxidative dehydrogenation, the alcohol reaction of synthetic fat family, the reaction of Wyler's process synthesizing carbonate ester and reduction reaction more.In addition, metal oxide also can be used as solid acid or solid alkali carries out acid or base catalyzed reactions.As a kind of solid base catalyst, it is simple that metal oxide has preparation process, and the catalytic activity height is easy to after the reaction separate, and be reusable advantage through simple process.
Though metal oxide catalyst is also used in transesterification reaction to some extent, as: (chemical industry journal, 2007,58 (10): 2507) adopt CaO/MgO catalysis grease and methyl alcohol transesterification reaction to prepare biofuel such as Liang Bin; (University Of Tianjin's journal, 2007,40 (3): 286) adopt complex metal oxides catalyzed carbon dimethyl phthalate and the reactions of diethyl carbonate transesterify Catalysts of Preparing Methyl Ethyl Carbonate such as MgO, CaO such as Han Jinyu; (colleges and universities' chemical engineering journal, 2006,20 (3): 374) adopt supported titanium such as Zhao Tiansheng
2Catalysis propylene carbonate and propyl alcohol transesterification reaction; (petrochemical complex, 2003,32 (2): 104) adopt supported titanium such as Ma Xinbin
2, MoO
3Catalysis dimethyl oxalate and the reaction of phenol ester exchange synthesizing diphenyl carbonate, but have not yet to see the report that metal oxide catalyst is used in the synthetic ADC reaction of ester-interchange method.Even if those skilled in the art may expect metal oxide catalyst is used for the reaction of the synthetic ADC of ester-interchange method, yet in view of metal oxide of a great variety, without careful full and accurate and extremely in a large number arduous experiments also be difficult to realize the result of the inventive method, so the inventive method is absolutely not conspicuous.
Summary of the invention
Technical problem to be solved by this invention is: a kind of ester-interchange method of synthetic diethylene glycol bis-allyl carbonate is provided, and this method is catalyzer with the metal oxide, by the synthetic diethylene glycol bis-allyl carbonate of ester-interchange method.This method had both solved phosgenation and CO
2The product that exists among the synthetic ADC of method often has the problem of color, and product is Clear ﹠ Transparent, does not contain any foreign pigment, can directly use; Overcome used NaOH, Na in US 4512930 methods again
2CO
3Not easy to be recycled with sodium alkoxide, and the deacidite existence can not resistant to elevated temperatures shortcoming.
The present invention solves this technical problem used technical scheme: a kind of ester-interchange method of synthetic diethylene glycol bis-allyl carbonate, having adopted metal oxide in the reaction of synthetic diethylene glycol bis-allyl carbonate is catalyzer, concrete steps are: add the raw material glycol ether in reactor, methylcarbonate and vinylcarbinol, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 2～25: 2～50, add simultaneously that to account for reactant system total mass per-cent be 0.1～10% metal oxide catalyst, heat up then and react, temperature of reaction is 85～150 ℃, reaction times is 1～20 hour, reaction pressure is 399.9Pa～90000Pa, after reaction finishes, reduce to room temperature, carrying out reaction product liquid after filtration separates with the metal oxide catalyst solid, the further underpressure distillation of filtrate promptly obtains the reaction product diethylene glycol bis-allyl carbonate, the filter residue metal oxide catalyst is recovered, and the metal oxide catalyst of recovery is repeated to use after simple roasting.
Underpressure distillation of mentioning in the aforesaid method and simple roasting all are known general technology in the chemical technology field.
In the ester-interchange method of above-mentioned a kind of synthetic diethylene glycol bis-allyl carbonate, the metal oxide catalyst of employing is the oxide compound of Li, Na, K, Ca, Mg, Pb or Zn.
In the ester-interchange method of above-mentioned a kind of synthetic diethylene glycol bis-allyl carbonate, the metal oxide catalyst that adopts is the oxide compound that is carried on Li, Na, K, Ca, Mg, Pb or Zn on the carrier, used carrier is gac, aluminum oxide, silicon oxide or molecular sieve, and the charge capacity of metal oxide is 5～20%.
In the ester-interchange method of above-mentioned a kind of synthetic diethylene glycol bis-allyl carbonate, the metal oxide catalyst that adopts is made up of any 2 kinds of oxide compounds among Li, Na, K, Ca, Mg, Mn, Fe, Pb, Zn, La, Zr and the Al, and the mol ratio of its metal oxide component is not limit.
In the ester-interchange method of above-mentioned a kind of synthetic diethylene glycol bis-allyl carbonate, the metal oxide catalyst that adopts is made up of any 2 kinds of oxide compounds among Li, the Na, K, Ca, Mg, Mn, Fe, Pb, Zn, La, Zr and the Al that are carried on the carrier, wherein used carrier is gac, aluminum oxide, silicon oxide or molecular sieve, the total loading amount of 2 kinds of metal oxides is that the mol ratio of 5～20%, 2 kinds of metal oxide components is not limit.
The preparation method of above-mentioned metal oxide catalyst is known.
The invention has the beneficial effects as follows:
(1) used metal oxide in the synthetic method of the present invention, the catalytic activity height, the preparation method is known, preparation process is simple, cost is lower, be easy to after the reaction separate, promptly reusable after simple process, overcome the deacidite catalyzer cost height that adopts in the synthetic method of existing similar diethylene glycol bis-allyl carbonate, can not be high temperature resistant and easy inactivation, not reproducible use and used NaOH, Na
2CO
3With sodium alkoxide shortcoming not easy to be recycled.
(2) synthetic method of the present invention is catalyzer with the metal oxide, adopts the synthetic ADC of ester-interchange method, and reaction process is simple, and easy handling is realized industrial the amplification easily.
(3) synthetic method synthetic product A DC of the present invention is Clear ﹠ Transparent, and the purity height does not contain any impurity that influences its practical application, has solved phosgenation and CO
2The problem that contains foreign pigment in the synthetic ADC product of method.
Embodiment
Embodiment 1
Metal oxide catalyst is MgO, by Mg (OH)
2Roasting makes.The synthetic reaction process of diethylene glycol bis-allyl carbonate is implemented as follows: add raw material glycol ether 5.3g (0.05mol) in flask, methylcarbonate 27.0g (0.30mol), vinylcarbinol 29.1g (0.5mol) and metal oxide catalyst MgO 1g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 6: 10, it is 1.6% that the metal oxide catalyst MgO that adds accounts for reactant system total mass per-cent, 95 ℃ of temperature of reaction, 15 hours reaction times, react then under the condition of reaction pressure 677Pa, after reaction finishes, reduce to room temperature, carrying out reaction product liquid after filtration separates with metal oxide catalyst MgO solid, filtrate is that further underpressure distillation promptly obtains the reaction product diethylene glycol bis-allyl carbonate under the 399.9Pa at pressure, filter residue metal oxide catalyst MgO is recovered, and the metal oxide catalyst MgO of recovery is repeated to use after simple roasting.
Adopt gas-chromatography that the reaction solution of above-mentioned reaction is analyzed, the gained result is as follows: the glycol ether transformation efficiency is 98.6%, is 86.1% in glycol ether ADC yield, and the selectivity of ADC is 87.3%.
Embodiment 2
Metal oxide catalyst is Na
2O is by NaNO
3Roasting makes.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 1.59g (0.015mol), methylcarbonate 33.8g (0.375mol), vinylcarbinol 43.6g (0.75mol) and metal oxide catalyst Na
2O 0.08g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 25: 50, the metal oxide catalyst Na of adding
2It is 0.1% that O accounts for reactant system total mass per-cent, and reaction conditions is: 85 ℃ of temperature of reaction, 20 hours reaction times, reaction pressure 399.9Pa, the metal oxide catalyst Na of recovery
2O is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 100%, is 83.6% in glycol ether ADC yield, and the selectivity of ADC is 83.6%.
Embodiment 3
Metal oxide catalyst is PbO, by Pb (OAc)
23H
2O makes through roasting.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 3.2g (0.03mol), methylcarbonate 67.6g (0.75mol), vinylcarbinol 3.5g (0.06mol) and metal oxide catalyst PbO 0.5g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 25: 2, it is 0.7% that the metal oxide catalyst PbO that adds accounts for reactant system total mass per-cent, reaction conditions is: 115 ℃ of temperature of reaction, 12 hours reaction times, reaction pressure 90000Pa, the metal oxide catalyst PbO of recovery is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 95.1%, is 49.2% in glycol ether ADC yield, and the selectivity of ADC is 51.7%.
Embodiment 4
Metal oxide catalyst is K
2O is by KNO
3Make through roasting.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 4.2g (0.04mol), methylcarbonate 7.2g (0.08mol), vinylcarbinol 116.2g (2mol) and metal oxide catalyst K
2O 2.1g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 2: 50, the metal oxide catalyst K of adding
2It is 1.6% that O accounts for reactant system total mass per-cent, and reaction conditions is: 140 ℃ of temperature of reaction, 3 hours reaction times, reaction pressure 15333Pa, the metal oxide catalyst K of recovery
2O is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 100%, is 91.3% in glycol ether ADC yield, and the selectivity of ADC is 91.3%.
Embodiment 5
Metal oxide catalyst is ZnO, with Zn (NO
3)
26H
2O is a presoma, adopts precipitator method preparation.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 3.5g (0.033mol), methylcarbonate 54.1g (0.6mol), vinylcarbinol 34.9g (0.6mol) and metal oxide catalyst ZnO 9.25g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 18.2: 18.2, it is 10% that the metal oxide catalyst ZnO that adds accounts for reactant system total mass per-cent, reaction conditions is: 120 ℃ of temperature of reaction, 8 hours reaction times, reaction pressure 2666Pa, the metal oxide catalyst ZnO of recovery is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 97.3%, is 87.5% in glycol ether ADC yield, and the selectivity of ADC is 89.9%.
Embodiment 6
Metal oxide catalyst is Li
2O is by LiOAc2H
2O makes through roasting.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 10.6g (0.1mol), methylcarbonate 27.0g (0.3mol), vinylcarbinol 29.1g (0.5mol) and metal oxide catalyst Li
2O 2.7g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 3: 5, the metal oxide catalyst Li of adding
2It is 4% that O accounts for reactant system total mass per-cent, and reaction conditions is: 125 ℃ of temperature of reaction, 12 hours reaction times, reaction pressure 50000Pa, the metal oxide catalyst Li of recovery
2O is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 95.6%, is 88.3% in glycol ether ADC yield, and the selectivity of ADC is 92.4%.
Embodiment 7
Metal oxide catalyst is CaO, by Ca (NO
3)
26H
2O makes through roasting.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 15.9g (0.15mol), methylcarbonate 27.0g (0.3mol), vinylcarbinol 52.3g (0.9mol) and metal oxide catalyst CaO 2.8g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 2: 6, it is 2.9% that the metal oxide catalyst CaO that adds accounts for reactant system total mass per-cent, reaction conditions is: 130 ℃ of temperature of reaction, 6 hours reaction times, reaction pressure 399.9Pa, the metal oxide catalyst CaO of recovery is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 96.5%, is 90.2% in glycol ether ADC yield, and the selectivity of ADC is 93.5%.
Embodiment 8
Metal oxide catalyst is CaO-ZnO, with Ca (NO
3)
26H
2O and Zn (OAc)
22H
2O is a presoma, makes through grinding roasting, and the mol ratio of component is not limit among the CaO-ZnO.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 8.5g (0.08mol), methylcarbonate 25.2g (0.28mol), vinylcarbinol 48.8g (0.84mol) and metal oxide catalyst CaO-ZnO 1.39g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 3.5: 10.5, it is 1.7% that the metal oxide catalyst CaO-ZnO that adds accounts for reactant system total mass per-cent, reaction conditions is: 110 ℃ of temperature of reaction, 9 hours reaction times, reaction pressure 7999Pa, the metal oxide catalyst CaO-ZnO of recovery is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 99.2%, is 95.3% in glycol ether ADC yield, and the selectivity of ADC is 96.1%.
Embodiment 9
Catalyzer is PbO-MgO, at first by Mg (OH)
2The presoma roasting makes MgO, is carrier impregnation Pb (OAc) then with MgO
23H
2O makes through roasting, and the mol ratio of component is not limit among the PbO-MgO.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 3g (0.028mol), methylcarbonate 15.1g (0.17mol), vinylcarbinol 56.9g (0.98mol) and metal oxide catalyst PbO-MgO 1.3g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 6: 35, it is 1.7% that the metal oxide catalyst PbO-MgO that adds accounts for reactant system total mass per-cent, reaction conditions is: 135 ℃ of temperature of reaction, 5 hours reaction times, reaction pressure 33330Pa, the metal oxide catalyst PbO-MgO of recovery is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 100%, is 89.3% in glycol ether ADC yield, and the selectivity of ADC is 89.3%.
Embodiment 10
Catalyzer is CaO-La
2O
3, with Ca (NO
3)
24H
2O and La (NO
3)
36H
2O is a presoma, adopts the coprecipitation method preparation, CaO-La
2O
3The mol ratio of middle component is not limit.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 10.1g (0.095mol), methylcarbonate 37.8g (0.42mol), vinylcarbinol 24.4g (0.42mol) and metal oxide catalyst CaO-La
2O
31g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 4.4: 4.4, the metal oxide catalyst CaO-La of adding
2O
3Accounting for reactant system total mass per-cent is 1.4%, and reaction conditions is: 135 ℃ of temperature of reaction, 5 hours reaction times, reaction pressure 13330Pa, the metal oxide catalyst CaO-La of recovery
2O
3Promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 98.2%, is 92.0% in glycol ether ADC yield, and the selectivity of ADC is 93.7%.
Embodiment 11
Metal oxide catalyst is Li
2O-ZrO
2, with LiOAc2H
2O and Zr (NO
3)
45H
2O is a presoma, adopts the thermal decomposition method preparation, Li
2O-ZrO
2The mol ratio of middle component is not limit.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 3.7g (0.035mol), methylcarbonate 31.5g (0.35mol), vinylcarbinol 29.1g (0.5mol) and metal oxide catalyst Li
2O-ZrO
23.8g wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 10: 14.3, the metal oxide catalyst Li of adding
2O-ZrO
2Accounting for reactant system total mass per-cent is 5.9%, and reaction conditions is: 120 ℃ of temperature of reaction, 8 hours reaction times, reaction pressure 7999Pa, the metal oxide catalyst Li of recovery
2O-ZrO
2Promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 98.0%, is 91.2% in glycol ether ADC yield, and the selectivity of ADC is 93.1%.
Embodiment 12
Metal oxide catalyst is Na
2O-MnO
2, with NaNO
3With with Mn (OAc)
24H
2O is a presoma, adopts the thermal decomposition method preparation, Na
2O-MnO
2The mol ratio of middle component is not limit.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 10.6g (0.1mol), methylcarbonate 63.1g (0.7mol), vinylcarbinol 40.7g (0.7mol) and metal oxide catalyst Na
2O-MnO
22.8g wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 7: 7, the metal oxide catalyst Na of adding
2O-MnO
2Accounting for reactant system total mass per-cent is 2.4%, and reaction conditions is: 120 ℃ of temperature of reaction, 8 hours reaction times, reaction pressure 21280Pa, the metal oxide catalyst Na of recovery
2O-MnO
2Promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 100%, is 83.5% in glycol ether ADC yield, and the selectivity of ADC is 83.5%.
Embodiment 13
Metal oxide catalyst is Fe
2O
3-K
2O is with Fe (NO
3)
39H
2O and KNO
3Be presoma, adopt the thermal decomposition method preparation, Fe
2O
3-K
2The mol ratio of component is not limit among the O.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 6.4g (0.06mol), methylcarbonate 27.0g (0.3mol), vinylcarbinol 41.8g (0.72mol) and metal oxide catalyst Fe
2O
3-K
2O 3.0g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 5: 12, the metal oxide catalyst Fe of adding
2O
3-K
2It is 4% that O accounts for reactant system total mass per-cent, and reaction conditions is: 110 ℃ of temperature of reaction, 11 hours reaction times, reaction pressure 7999Pa, the metal oxide catalyst Fe of recovery
2O
3-K
2O is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 100%, is 89.3% in glycol ether ADC yield, and the selectivity of ADC is 89.3%.
Embodiment 14
Metal oxide catalyst is Al
2O
3-K
2O is with Al (NO
3)
39H
2O and KNO
3Be presoma, adopt the thermal decomposition method preparation, Al
2O
3-K
2The mol ratio of component is not limit among the O.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 6.4g (0.06mol), methylcarbonate 27.0g (0.3mol), vinylcarbinol 41.8g (0.72mol) and metal oxide catalyst Al
2O
3-K
2O 3.0g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 5: 12, the metal oxide catalyst Al of adding
2O
3-K
2It is 4% that O accounts for reactant system total mass per-cent, and reaction conditions is: 140 ℃ of temperature of reaction, 12 hours reaction times, reaction pressure 3999Pa, the metal oxide catalyst Al of recovery
2O
3-K
2O is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 90%, is 80.3% in glycol ether ADC yield, and the selectivity of ADC is 89.2%.
Embodiment 15
Metal oxide catalyst is MgO/ carrier A l
2O
3, with Mg (NO
3)
26H
2O is a presoma, adopts immersion process for preparing, and wherein the charge capacity of MgO is 5%.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 5.3g (0.05mol), methylcarbonate 31.5g (0.35mol), vinylcarbinol 40.7g (0.7mol) and metal oxide catalyst MgO/ carrier A l
2O
32.1g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 7: 14, it is 2.7% that the catalyzer that adds accounts for reactant system total mass per-cent, reaction conditions is: 150 ℃ of temperature of reaction, 1 hour reaction times, reaction pressure 26664Pa, the metal oxide catalyst MgO/ carrier A l of recovery
2O
3Promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 100%, is 73.2% in glycol ether ADC yield, and the selectivity of ADC is 73.2%.
Embodiment 16
Metal oxide catalyst is ZnO/ carrier S iO
2, with Zn (OAc)
22H
2O is a presoma, adopts immersion process for preparing, and the ZnO charge capacity is 8%.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 4.1g (0.039mol), methylcarbonate 70.3g (0.78mol), vinylcarbinol 45.3g (0.78mol) and metal oxide supporting catalyst ZnO/ carrier S iO
23.6g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 20: 20, it is 3% that the metal oxide catalyst that adds accounts for reactant system total mass per-cent, reaction conditions is: 125 ℃ of temperature of reaction, 4 hours reaction times, reaction pressure 13330Pa, the metal oxide catalyst ZnO/ carrier S iO of recovery
2Promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 100%, is 82.5% in glycol ether ADC yield, and the selectivity of ADC is 82.5%.
Embodiment 17
Metal oxide catalyst is the active C of CaO/ carrier, with Ca (NO
3)
26H
2O is a precursor, adopts pickling process to make, and wherein the charge capacity of CaO is 5%.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 5.3g (0.05mol), methylcarbonate 31.5g (0.35mol), vinylcarbinol 40.7g (0.7mol) and metal oxide catalyst CaO/C 2.3g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 7: 14, it is 3% that the active C of the metal oxide catalyst CaO/ carrier that adds accounts for reactant system total mass per-cent, reaction conditions is: 130 ℃ of temperature of reaction, 6 hours reaction times, reaction pressure 3999Pa, the active C of the metal oxide catalyst CaO/ carrier of recovery is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 100%, is 90.8% in glycol ether ADC yield, and the selectivity of ADC is 90.8%.
Embodiment 18
Metal oxide catalyst is K
2O/ carrier S iO
2, with KNO
3Be presoma, adopt immersion process for preparing, wherein K
2The charge capacity of O is 20%.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 3.5g (0.033mol), methylcarbonate 54.1g (0.6mol), vinylcarbinol 34.9g (0.6mol) and metal oxide catalyst K
2O/SiO
25.1g wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 18.2: 18.2, the metal oxide catalyst K of adding
2O/ carrier S iO
2Accounting for reactant system total mass per-cent is 5.5%, and reaction conditions is: 120 ℃ of temperature of reaction, 8 hours reaction times, reaction pressure 7980Pa, the metal oxide catalyst K of recovery
2O/ carrier S iO
2Promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 100%, is 86.6% in glycol ether ADC yield, and the selectivity of ADC is 86.6%.
Embodiment 19
Metal oxide catalyst is Li
2O/ carrier molecule sieve is by LiOAc2H
2O is that presoma adopts pickling process to make, wherein Li
2The charge capacity of O is 8%.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 10.6g (0.1mol), methylcarbonate 27.0g (0.3mol), vinylcarbinol 29.1g (0.5mol) and metal oxide catalyst Li
2O/ molecular sieve 2.7g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 3: 5, the metal oxide catalyst Li of adding
2It is 4% that O/ carrier molecule sieve accounts for reactant system total mass per-cent, and reaction conditions is: 125 ℃ of temperature of reaction, 12 hours reaction times, reaction pressure 29260Pa, the metal oxide catalyst Li of recovery
2O/ carrier molecule sieve is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 98.9%, is 85.1% in glycol ether ADC yield, and the selectivity of ADC is 86.0%.
Embodiment 20
Metal oxide catalyst is PbO/ carrier A l
2O
3, with Pb (NO
3)
2Make for presoma adopts pickling process, wherein the charge capacity of PbO is 15%.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 4.1g (0.039mol), methylcarbonate 70.3g (0.78mol), vinylcarbinol 45.3g (0.78mol) and metal oxide catalyst PbO/Al
2O
33.8g wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 20: 20, the metal oxide catalyst PbO/ carrier A l of adding
2O
3Accounting for reactant system total mass per-cent is 3.2%, and reaction conditions is: 125 ℃ of temperature of reaction, 6 hours reaction times, reaction pressure 11970Pa, the metal oxide catalyst PbO/ carrier A l of recovery
2O
3Promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 100%, is 89.5% in glycol ether ADC yield, and the selectivity of ADC is 89.5%.
Embodiment 21
Metal oxide catalyst is Na
2The active C of O/ carrier is with NaNO
3Be precursor, adopt immersion process for preparing.Na wherein
2The charge capacity of O is 5%.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 1.59g (0.015mol), methylcarbonate 33.8g (0.375mol), vinylcarbinol 43.6g (0.75mol) and metal oxide catalyst Na
2O 0.08g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 25: 50, the metal oxide catalyst Na of adding
2It is 0.1% that the active C of O/ carrier accounts for reactant system total mass per-cent, and reaction conditions is: 85 ℃ of temperature of reaction, 20 hours reaction times, reaction pressure 399.9Pa, the metal oxide catalyst Na of recovery
2The active C of O/ carrier is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 100%, is 83.6% in glycol ether ADC yield, and the selectivity of ADC is 83.6%.
Embodiment 22
Catalyzer is Fe
2O
3-ZnO/ carrier S iO
2, with Fe (NO
3)
39H
2O and Zn (OAc)
22H
2O is a presoma, adopts pickling process to make, wherein, and Fe
2O
3The mol ratio of component is not limit among-the ZnO, and the total loading amount of the two is 15%.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 6.4g (0.06mol), methylcarbonate 27g (0.3mol), vinylcarbinol 41.8g (0.72mol) and metal oxide catalyst Fe
2O
3-ZnO/ carrier S iO
23.8g wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 5: 12, the metal oxide catalyst Fe of adding
2O
3-ZnO/ carrier S iO
2Accounting for reactant system total mass per-cent is 5%, and reaction conditions is: 110 ℃ of temperature of reaction, 11 hours reaction times, reaction pressure 7999Pa, the metal oxide catalyst Fe of recovery
2O
3-ZnO/ carrier S iO
2Promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 100%, is 90.2% in glycol ether ADC yield, and the selectivity of ADC is 90.2%.
Embodiment 23
Catalyzer is MnO
2-Li
2O/ carrier molecule sieve is with Mn (OAc)
24H
2O and with LiOAc2H
2O is a presoma, adopts pickling process to make, wherein, and MnO
2-Li
2The mol ratio of component is not limit among the O, and the total loading amount of the two is 20%.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 8.5g (0.08mol), methylcarbonate 28.8g (0.32mol), vinylcarbinol 27.9g (0.48mol) and metal oxide catalyst MnO
2-Li
2O/ carrier molecule sieve 2.5g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 4: 6, the metal oxide catalyst MnO of adding
2-Li
2It is 3.8% that O/ carrier molecule sieve accounts for reactant system total mass per-cent, and reaction conditions is: 110 ℃ of temperature of reaction, 13 hours reaction times, reaction pressure 23999Pa, the metal oxide catalyst MnO of recovery
2-Li
2O/ carrier molecule sieve is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 93.5%, is 87.1% in glycol ether ADC yield, and the selectivity of ADC is 93.2%.
Embodiment 24
Metal oxide catalyst is CaO-MgO/ carrier A l
2O
3, with Ca (NO
3)
26H
2O and Mg (NO
3)
26H
2O is a presoma, adopts pickling process to make, and wherein, the mol ratio of component is not limit among the CaO-MgO, and the total loading amount of the two is 5%.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 8.5g (0.08mol), methylcarbonate 28.8g (0.32mol), vinylcarbinol 48.8g (0.84mol) and metal oxide catalyst CaO-MgO/ carrier A l
2O
35g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 4: 10.5, the metal oxide catalyst CaO-MgO/ carrier A l of adding
2O
3Accounting for reactant system total mass per-cent is 5.8%, and reaction conditions is: 110 ℃ of temperature of reaction, 9 hours reaction times, reaction pressure 7980Pa, the metal oxide catalyst CaO-MgO/ carrier A l of recovery
2O
3Promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 100%, is 83.5% in glycol ether ADC yield, and the selectivity of ADC is 83.5%.
Embodiment 25
Metal oxide catalyst is PbO-La
2O
3The active C of/carrier is with Pb (OAc)
23H
2O and La (NO
3)
36H
2O is a presoma, adopts pickling process to make, wherein, and PbO-La
2O
3The mol ratio of middle component is not limit, and the total loading amount of the two is 16%.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 8.5g (0.08mol), methylcarbonate 64.9g (0.72mol), vinylcarbinol 46.5g (0.8mol) and metal oxide catalyst PbO-La
2O
3The active C 4.5g of/carrier, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 9: 10, the metal oxide catalyst PbO-La of adding
2O
3It is 3.8% that the active C of/carrier accounts for reactant system total mass per-cent, and reaction conditions is: 100 ℃ of temperature of reaction, 15 hours reaction times, reaction pressure 9310Pa, the metal oxide catalyst PbO-La of recovery
2O
3The active C of/carrier is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 97.5%, is 85.6% in glycol ether ADC yield, and the selectivity of ADC is 87.8%.
Embodiment 26
Metal oxide catalyst is ZrO
2-Na
2O/ carrier molecule sieve is with Zr (NO
3)
45H
2O and NaNO
3Be presoma, adopt pickling process to make, wherein, ZrO
2-Na
2The mol ratio of component is not limit among the O, and the total loading amount of the two is 16%.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 8.5g (0.08mol), methylcarbonate 64.9g (0.72mol), vinylcarbinol 46.5g (0.8mol) and metal oxide catalyst ZrO
2-Na
2O/ carrier molecule sieve 4.5g, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 9: 10, the metal oxide catalyst ZrO of adding
2-Na
2It is 3.8% that O/ carrier molecule sieve accounts for reactant system total mass per-cent, and reaction conditions is: 130 ℃ of temperature of reaction, 12 hours reaction times, reaction pressure 800Pa, the metal oxide catalyst ZrO of recovery
2-Na
2O/ carrier molecule sieve is promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 87.5%, is 75.6% in glycol ether ADC yield, and the selectivity of ADC is 86.4%.
Embodiment 27
Metal oxide catalyst is Al
2O
3-K
2O/ carrier S iO
2, with Al (NO
3)
39H
2O and KNO
3Be presoma, adopt hot dipping stain method to make, wherein, Al
2O
3-K
2The mol ratio of component is not limit among the O, and the total loading amount of the two is 10%.The synthetic reaction process of diethylene glycol bis-allyl carbonate is identical with embodiment 1.Just raw material is glycol ether 6.4g (0.06mol), methylcarbonate 27.0g (0.3mol), vinylcarbinol 41.8g (0.72mol) and metal oxide catalyst Al
2O
3-K
2O/SiO
23.0g wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 5: 12, the metal oxide catalyst Al of adding
2O
3-K
2O/ carrier S iO
2Accounting for reactant system total mass per-cent is 4%, and reaction conditions is: 140 ℃ of temperature of reaction, 12 hours reaction times, reaction pressure 3999Pa, the metal oxide catalyst Al of recovery
2O
3-K
2O/ carrier S iO
2Promptly reusable through simple roasting.
The gained result is as follows: the glycol ether transformation efficiency is 90%, is 80.3% in glycol ether ADC yield, and the selectivity of ADC is 89.2%.
Claims (3)
1. the ester-interchange method of a synthetic diethylene glycol bis-allyl carbonate, it is characterized in that: having adopted metal oxide in the reaction of synthetic diethylene glycol bis-allyl carbonate is catalyzer, concrete steps are: add the raw material glycol ether in reactor, methylcarbonate and vinylcarbinol, wherein material molar ratio is: glycol ether: methylcarbonate: vinylcarbinol=1: 2～25: 2～50, add simultaneously that to account for reactant system total mass per-cent be 0.1～10% metal oxide catalyst, heat up then and react, temperature of reaction is 85～150 ℃, reaction times is 1～20 hour, reaction pressure is 399.9Pa～90000Pa, after reaction finishes, reduce to room temperature, carrying out reaction product liquid after filtration separates with the metal oxide catalyst solid, the further underpressure distillation of filtrate promptly obtains the reaction product diethylene glycol bis-allyl carbonate, the filter residue metal oxide catalyst is recovered, and the metal oxide catalyst of recovery is repeated to use after simple roasting;
Wherein, described metal oxide catalyst is the oxide compound of Li, Na, K, Ca, Mg, Pb or Zn, perhaps be made up of any 2 kinds of oxide compounds among Li, Na, K, Ca, Mg, Mn, Fe, Pb, Zn, La, Zr and the Al, the mol ratio of its metal oxide component is not limit.
2. the ester-interchange method of a kind of synthetic diethylene glycol bis-allyl carbonate according to claim 1, it is characterized in that: the metal oxide catalyst of employing is by the oxide compound that is carried on Li, Na, K, Ca, Mg, Pb or Zn on the carrier, used carrier is gac, aluminum oxide, silicon oxide or molecular sieve, and the charge capacity of metal oxide is 5～20%.
3. the ester-interchange method of a kind of synthetic diethylene glycol bis-allyl carbonate according to claim 1, it is characterized in that: the metal oxide catalyst of employing is made up of any 2 kinds of oxide compounds among Li, the Na, K, Ca, Mg, Mn, Fe, Pb, Zn, La, Zr and the Al that are carried on the carrier, wherein used carrier is gac, aluminum oxide, silicon oxide or molecular sieve, the total loading amount of 2 kinds of metal oxides is that the mol ratio of 5～20%, 2 kinds of metal oxide components is not limit.
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| CN103113231A (en) * | 2013-02-27 | 2013-05-22 | 寿光市鲁源盐化有限公司 | Synthetic method of diallyl diethylene glycol carbonate |
| CN103626663B (en) * | 2013-12-16 | 2016-01-20 | 深圳新宙邦科技股份有限公司 | The preparation method of diallyl carbonate |
| EP3564207B1 (en) * | 2016-12-28 | 2021-09-15 | Kaneka Corporation | Method for producing alcohol compound |
| CN111792995A (en) * | 2020-05-25 | 2020-10-20 | 江苏乾元新材料科技有限公司 | Preparation method of allyl diglycol dicarbonate and special device thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4512930A (en) * | 1981-05-21 | 1985-04-23 | Anic, S.P.A. | Process for synthesizing carbonic acid esters derived from unsaturated alcohols and polyhydric alcohols |
| CN1436162A (en) * | 2000-06-16 | 2003-08-13 | 昭和电工株式会社 | Process for production of alicyclic (meth) allyl esters for plastic lens compositions |
| CN1974528A (en) * | 2006-08-11 | 2007-06-06 | 河北工业大学 | Synthesis process of diethylene glycol diene propyl carbonate |
| WO2007071470A1 (en) * | 2005-12-16 | 2007-06-28 | Evonik Röhm Gmbh | Process for preparing glyceryl carbonate |
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2008
- 2008-08-01 CN CN2008100540254A patent/CN101328124B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4512930A (en) * | 1981-05-21 | 1985-04-23 | Anic, S.P.A. | Process for synthesizing carbonic acid esters derived from unsaturated alcohols and polyhydric alcohols |
| CN1436162A (en) * | 2000-06-16 | 2003-08-13 | 昭和电工株式会社 | Process for production of alicyclic (meth) allyl esters for plastic lens compositions |
| WO2007071470A1 (en) * | 2005-12-16 | 2007-06-28 | Evonik Röhm Gmbh | Process for preparing glyceryl carbonate |
| CN1974528A (en) * | 2006-08-11 | 2007-06-06 | 河北工业大学 | Synthesis process of diethylene glycol diene propyl carbonate |
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