CN105503607A - Preparation method of dimethyl carbonate - Google Patents
Preparation method of dimethyl carbonate Download PDFInfo
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- CN105503607A CN105503607A CN201410498055.XA CN201410498055A CN105503607A CN 105503607 A CN105503607 A CN 105503607A CN 201410498055 A CN201410498055 A CN 201410498055A CN 105503607 A CN105503607 A CN 105503607A
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Abstract
The invention relates to a preparation method of dimethyl carbonate, and mainly solves the problems of easy swelling and quick activity decline of resin in the prior art. According to a technical scheme, ethylene carbonate and methanol are adopted as the raw materials, under the conditions of a reaction temperature of 60-160DEG C, a methanol/ethylene carbonate mole ratio of 2-10, and a catalyst/ethylene carbonate weight ratio of 0.005-1, the raw materials and the catalyst contact for reaction so as to generate dimethyl carbonate; and the catalyst is strong alkali composite imidazolyl resin. The method well solves the problems, and can be used for the industrial production of dimethyl carbonate.
Description
Technical field
The present invention relates to a kind of method preparing methylcarbonate.
Background technology
Methylcarbonate (DMC) chemical property is active, physical properties is excellent, and nontoxic, readily biodegradable, a kind of new low stain, environmentally friendly green basic chemical industry raw material, can be used as solvent, gasoline dope, lithium-ion battery electrolytes and carbonylation, methylate and carbomethoxy reagent, be widely used in chemical field, current each state is all in the Green Chemistry process of active research based on this eco-friendly industrial chemicals of DMC.Wherein ester-interchange method is better than reaction conditions gentleness, the high and coproduction ethylene glycol of yield or propylene glycol and become the method having now industrial prospect.
In general, transesterification reaction is mainly with (F.Risseetal., US2011040117 such as alkali metal hydroxide, alkaline carbonate and alkali metal alcohols; C.P.Allaisetal., WO2010063780) as catalyzer, but be homogeneous catalyst because of it, not easily with product separation, reuse difficulty.Conventional heterogeneous catalyst comprises and is carried on basic metal on carrier or an alkali metal salt, metal oxide catalyst, the zeolite of alkali (soil) metal exchange or clay material and ion exchange resin etc.Be carried on the basic metal on carrier or an alkali metal salt, as KF/Al
2o
3, NaOH/ chitosan and Cs
2cO
3/ SiO
2-Al
2o
3deng (H.Zhang, CN101249452; Y.Zhao, CN101121147; C.D.Changetal., WO0156971A1), their shortcoming is easily by water in air and CO
2impact, make activity decrease; Metal oxide catalyst, as Al
2o
3, (B.M.Bhanage, etal.Appl.Catal.A219 (2001) 259-266 such as MgO; J.S.Buchananetal., US2005080287; Z.Z.Jiangetal., US6207850), and the zeolite of alkali (soil) metal exchange or clay material, as (C.D.Changetal., the WO0073256 such as Cs-ZSM-5, Mg-smectite; B.M.Bhanageetal.Catal.Lett.83 (2002) 137-141), the shortcoming of this two classes catalyzer is that activity or selectivity are usually lower; Ion exchange resin, as quaternary ammonium type or tertiary amine resin (J.F.Kniftonetal., J.Mol.Catal.A67 (1991) 389-399; M.Caoetal.React.Kinet.Catal.Lett.88 (2006) 251-259), the usual not swelling resistance of this kind of catalyzer, and long-time activity decrease is than very fast.
Summary of the invention
It is easily swelling that technical problem to be solved by this invention is that prior art exists resin, and the problem that activity decrease is fast, provides a kind of method preparing methylcarbonate newly.The method has catalyzer swelling resistance, the feature that activity decrease is slow.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method preparing methylcarbonate, with NSC 11801 and methyl alcohol for reaction raw materials, it is 60 ~ 160 DEG C in temperature of reaction, the mol ratio of methyl alcohol and NSC 11801 is 2 ~ 10, the weight ratio of catalyzer and NSC 11801 is under the condition of 0.005 ~ 1, and raw material and catalyst exposure react and obtain methylcarbonate in 1 ~ 8 hour; Described catalyzer is strong base compound imidazolyl resin, and its preparation method comprises the following steps:
1) auxiliary agent one is made into water solution A; By monomer, comonomer, nano material, initiator and auxiliary agent two wiring solution-forming B;
Described monomer is selected from least one in methyl methacrylate, butyl acrylate, vinylbenzene, alpha-methyl styrene, 4-butylstyrene or vinyl cyanide; Described comonomer is selected from least one in ethyleneglycol dimethyacrylate, diallyl benzene, divinyl phenylmethane or Vinylstyrene; Described nano material is selected from least one in multi-walled carbon nano-tubes, Single Walled Carbon Nanotube, C60 or C70 soccerballene; Described initiator is selected from least one in benzoyl peroxide, Diisopropyl azodicarboxylate, lauroyl peroxide or isopropyl benzene hydroperoxide; Described auxiliary agent one is selected from least one in polyvinyl alcohol, gelatin, starch, methylcellulose gum, wilkinite or calcium carbonate; Described auxiliary agent two is selected from least one in aliphatic hydrocarbon, polystyrene, gasoline, lipid acid or paraffin;
Wherein, by weight percentage, the consumption of monomer is 85 ~ 95%, and the consumption of comonomer is 2 ~ 5%, and the consumption of nano material is 0.1 ~ 3%, and the consumption of initiator is 0.1 ~ 10%; The consumption of auxiliary agent one is 150 ~ 400% of monomer consumption, and the consumption of auxiliary agent two is 50 ~ 100% of monomer consumption;
2) solution B is mixed with solution A, be obtained by reacting complex microsphere;
3) in described complex microsphere, add chloromethylation reagents and zinc chloride, obtain compound chlorine ball;
4) chlorine type compound imidazolyl resin is obtained add imdazole derivatives reaction in described compound chlorine ball after; Described imdazole derivatives structural formula is
wherein R is methyl, ethyl, propyl group, sec.-propyl, propenyl, normal-butyl or n-pentyl;
5) add in described chlorine type compound imidazolyl resin after highly basic exchanges and obtain described strong base compound imidazolyl resin.
In technique scheme, preferably, the weight percent concentration of described water solution A is 0.5 ~ 2%.
In technique scheme, preferably, step 2) reaction process is: solution B, 60 ~ 75 DEG C of prepolymerizations 0.5 ~ 2.5 hour, then mixes with solution A by solution B, be warming up to 70 ~ 90 DEG C of reactions 5 ~ 15 hours, then be warming up to 90 ~ 100 DEG C of reactions 5 ~ 15 hours; After reaction terminates, through extracting, washing, filtration, drying, sieve, obtain the complex microsphere of particle size range 0.35 ~ 0.60 millimeter.
In technique scheme, preferably, step 3) reaction process is: in described complex microsphere, add the chloromethylation reagents being equivalent to complex microsphere weight 200 ~ 500%, and be equivalent to the zinc chloride catalyst of complex microsphere weight 20 ~ 70%, react 8 ~ 30 hours at 30 ~ 60 DEG C, after filtration, washing obtain compound chlorine ball, dry to constant weight; Described chloromethylation reagents is selected from least one in chloromethyl ether or Isosorbide-5-Nitrae-dichloro methyl butyl ether.
In technique scheme, preferably, step 4) reaction process is: adds in described compound chlorine ball and is equivalent to the organic solvent of complex microsphere weight 200 ~ 700%, the imdazole derivatives of 30 ~ 300%, react 4 ~ 30 hours under reflux state, after washing, oven dry, obtain described chlorine type compound imidazolyl resin; Wherein, described organic solvent is selected from least one in acetonitrile, cyanobenzene, toluene, tetrahydrofuran (THF), dimethyl formamide, chloroform or ethylene dichloride.
In technique scheme, preferably, step 5) reaction process is: adds in described chlorine type compound imidazolyl resin and is equivalent to the highly basic of chlorine type compound imidazolyl weight resin 20 ~ 200%, the water of 200 ~ 2000%, at room temperature stir 1 ~ 20 hour, after filtration, wash and obtain described strong base compound imidazolyl resin after oven dry; Wherein, described highly basic comprises NaOH, KOH, LiOH, Ca (OH)
2, Sr (OH)
2or Ba (OH)
2in at least one.
In technique scheme, preferably, described monomer is selected from vinylbenzene.
In technique scheme, preferably, described comonomer is selected from Vinylstyrene.
In technique scheme, preferably, described nano material is selected from multi-walled carbon nano-tubes.
In technique scheme, preferably, described initiator is selected from benzoyl peroxide.
In technique scheme, preferably, described auxiliary agent one is selected from polyvinyl alcohol.
In technique scheme, preferably, described auxiliary agent two is selected from polystyrene.
In technique scheme, preferably, temperature of reaction is 80 ~ 140 DEG C, and the mol ratio of methyl alcohol and NSC 11801 is 2 ~ 8, and the weight ratio of catalyzer and NSC 11801 is 0.01 ~ 0.5, and the reaction times is 1 ~ 6 hour.
The inventive method adopts strong base compound imidazolyl resin to be catalyzer, owing to being mixed with the nano material of high strength in resin base material, thus enhances the swelling resistance performance of resin.The transesterification reaction that catalyzer of the present invention is used for NSC 11801 and methyl alcohol is prepared in methylcarbonate, temperature of reaction 100 DEG C, the mol ratio of methyl alcohol and NSC 11801 is 4, and the weight ratio of catalyzer and NSC 11801 is under 0.1 condition, reacts 4 hours, the transformation efficiency of NSC 11801 is 70.5%, the selectivity of methylcarbonate is 98.3%, and the selectivity of ethylene glycol is 98.1%, after catalyzer reuses 5 times, activity decrease is less than 5%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.Be necessary to herein means out be following examples only for further illustrating of the present invention, can not limiting the scope of the invention be interpreted as.
Embodiment
[embodiment 1]
In 500 milliliters of there-necked flasks, add 58.0 grams of vinylbenzene, 0.6 gram of Vinylstyrene, 30 grams of polystyrene and 0.6 gram of benzoyl peroxide initiator, stir 2.0 hours at 60 DEG C; Then add 2.8 grams of multi-walled carbon nano-tubes, continue stirring and carry out prepolymerization in 1 hour.Add the 260 ml deionized water solution being dissolved with 2.5 grams of polyvinyl alcohol.Regulate stirring velocity, be progressively warming up to 80 DEG C simultaneously, react 5 hours; Be warmed up to 90 DEG C again, react 5 hours, be finally warming up to 98 DEG C, react 6 hours.After reaction terminates, pour out supernatant liquid, with 85 DEG C of hot washes, then use cold water washing, then filter, put into the oven dry of 80 DEG C, baking oven, sieve, the complex microsphere A of collection cut size within the scope of 0.35 ~ 0.60 millimeter.
The chloromethylation of complex microsphere: in the there-necked flask of 500 milliliters, add 50 grams of complex microsphere A and 250 milliliter chloromethyl ethers, room temperature leaves standstill 4 hours, starts to stir, and adding 15 grams of zinc chloride is catalyzer, be warming up to 50 DEG C of reactions 8 hours, be cooled to room temperature after chlorination terminates, leach chlorination mother solution, use methyl alcohol repetitive scrubbing, dry 8 hours at 100 DEG C, obtain compound chlorine ball A.
The imidazoles salinization of compound chlorine ball: in 500 milliliters of there-necked flasks, add 20 grams of compound chlorine ball A, 100 milliliters of tetrahydrofuran (THF)s, 8 grams of N-Methylimidazoles, stirring reaction 12 hours at reflux, reaction terminates rear mistake and filters mother liquor, uses methylene dichloride, acetone and water washing successively respectively, dries to obtain chlorine type compound imidazolyl Resin A 1 under vacuo.
The transition of chlorine type compound imidazolyl resin: in 200 ml beakers, add 10 grams of chlorine type compound imidazolyl Resin A, 1,3 grams of NaOH and 180 gram deionized waters, stirring at room temperature is after 2 hours, filter, after deionized water wash, repeat said process 2 times, filter, with deionized water wash, dry under vacuo and obtain strong base compound imidazolyl Resin A 2.
[embodiment 2]
In 500 milliliters of there-necked flasks, add the compound chlorine ball A of 20 grams of [embodiment 1] gained, 150 milliliters of toluene, 35.0 grams of N-allyl imidazole, stirring reaction 30 hours at reflux, reaction terminates rear mistake and filters mother liquor, uses methylene dichloride, acetone and water washing successively respectively, dries to obtain chlorine type compound imidazolyl Resin A 3 under vacuo.
The transition of chlorine type compound imidazolyl resin: in 200 ml beakers, add 10 grams of chlorine type compound imidazolyl Resin A, 3,20 grams of Ba (OH)
2with 40 grams of deionized waters, stirring at room temperature, after 18 hours, is filtered, and after deionized water wash, repeats said process 2 times, filters, and with deionized water wash, dries under vacuo and obtains strong base compound imidazolyl Resin A 4.
[embodiment 3]
Monomer mixture solution (60.0 grams of vinylbenzene, 1.7 grams of Vinylstyrenes, the 60 grams of polystyrene containing initiator are added in 500 milliliters of there-necked flasks, 1.6 grams of multi-walled carbon nano-tubes and 1.0 grams of benzoyl peroxides, this solution was prior to 70 DEG C of stirring reactions 0.5 hour), start agitator, add the mixing solutions of 200 ml deionized water and 5 grams of gelatin, be warming up to 85 DEG C, react 3 hours, then be warmed up to 90 DEG C, react 9 hours, finally be warming up to 100 DEG C, react 10 hours.After reaction terminates, pour out supernatant liquid, with 85 DEG C of hot washes, then use cold water washing, then filter, put into the oven dry of 80 DEG C, baking oven, sieve, the complex microsphere B of collection cut size within the scope of 0.35 ~ 0.60 millimeter.
The chloromethylation of complex microsphere: in the there-necked flask of 500 milliliters, add 50 grams of complex microsphere B and 150 milliliter chloromethyl ethers, room temperature leaves standstill 6 hours, starts to stir, and adding 30 grams of zinc chloride is catalyzer, be warming up to 50 DEG C of reactions 24 hours, be cooled to room temperature after chlorination terminates, leach chlorination mother solution, use methyl alcohol repetitive scrubbing, dry 8 hours at 100 DEG C, obtain compound chlorine ball B.
The imidazoles salinization of compound chlorine ball: in 500 milliliters of there-necked flasks, add 20 grams of compound chlorine ball B, 150 milliliters of tetrahydrofuran (THF)s, 30.0 grams of N-propyl imidazoles, stirring reaction 24 hours at reflux, reaction terminates rear mistake and filters mother liquor, uses methylene dichloride, acetone and water washing successively respectively, dries to obtain chlorine type compound imidazolyl resin B 1 under vacuo.
The method of chlorine type compound imidazolyl resin B 1 described in [embodiment 2] is made the transition, obtains strong base compound imidazolyl resin B 2.
[embodiment 4]
In 500 milliliters of there-necked flasks, add the compound chlorine ball B of 15 grams of [embodiment 3] gained, 150 milliliters of tetrahydrofuran (THF)s, 35.0 grams of N-butylimidazolium, stirring reaction 10 hours at reflux, reaction terminates rear mistake and filters mother liquor, uses methylene dichloride, acetone and water washing successively respectively, dries to obtain chlorine type compound imidazolyl resin B 3 under vacuo.
Just the method for chlorine type compound imidazolyl resin B 3 described in [embodiment 2] makes the transition, and obtains strong base compound imidazolyl resin B 4
[embodiment 5]
Change monomer mixture solution (the 76.0 grams of alpha-methyl styrenes in [embodiment 3], 3.5 grams of Vinylstyrenes, 75 grams of gasoline, 2.4 grams of multi-walled carbon nano-tubes and 1.4 grams of benzoyl peroxides), all the other preparation conditions are identical with [embodiment 3], obtain complex microsphere C.
The chloromethylation of complex microsphere: in the there-necked flask of 500 milliliters, add 40 grams of complex microsphere C and 150 milliliter Isosorbide-5-Nitrae-dichloro methyl butyl ether, room temperature leaves standstill 6 hours, start to stir, adding 25 grams of zinc chloride is catalyzer, is warming up to 50 DEG C of reactions 24 hours, is cooled to room temperature after chlorination terminates, leach chlorination mother solution, use methyl alcohol repetitive scrubbing, dry 8 hours at 100 DEG C, obtain compound chlorine ball C.
The imidazoles salinization of compound chlorine ball: in 500 milliliters of there-necked flasks, add 30 grams of compound chlorine ball C, 150 milliliters of tetrahydrofuran (THF)s, 20.0 grams of N-vinyl imidazoles, stirring reaction 12 hours at reflux, reaction terminates rear mistake and filters mother liquor, uses methylene dichloride, acetone and water washing successively respectively, dries to obtain chlorine type compound imidazolyl resin C1 under vacuo.
The method of chlorine type compound imidazolyl resin C1 described in [embodiment 2] is made the transition, obtains strong base compound imidazolyl resin C2.
[embodiment 6]
According to the step of [embodiment 4], imidazoles salinization reaction is carried out to compound chlorine ball C, obtain chlorine type compound imidazolyl resin C3.
The method of chlorine type compound imidazolyl resin C3 described in [embodiment 2] is made the transition, obtains strong base compound imidazolyl resin C4.
[comparative example 1]
The preparation process of catalyzer is identical with [embodiment 1], does not just add multi-walled carbon nano-tubes, obtains chlorine type imidazolyl resin CA1 and strong base imidazolyl resin CA2 respectively.
[embodiment 7]
Strong base compound imidazolyl Resin A 2 prepared by [embodiment 1] is prepared in the reaction of methylcarbonate for NSC 11801 and methyl alcohol transesterify.22.0 grams of NSC 11801,32.0 grams of methyl alcohol and 2.2 grams of A2 catalyzer are placed in 100 milliliters of autoclaves (mol ratio of methyl alcohol and NSC 11801 is 4, and the weight ratio of catalyzer and NSC 11801 is 0.1), and 100 DEG C are reacted 4 hours.After reaction terminates, autoclave is cooled to room temperature, emptying.Get liquid product and carry out gas chromatographic analysis, the transformation efficiency recording NSC 11801 is 70.5%, and the selectivity of methylcarbonate is 98.3%, and the selectivity of ethylene glycol is 98.1%, and the swelling capacity of resin catalyst is S
sWELLbe 4.8%.
[comparative example 2]
Catalyst activity test condition is identical with [embodiment 7], just catalyzer used is strong base imidazolyl resin CA2, and the transformation efficiency obtaining NSC 11801 is 69.8%, and the selectivity of methylcarbonate is 98.5%, the selectivity of ethylene glycol is 98.3%, and the swelling capacity of resin catalyst is S
sWELLbe 20.5%.
[embodiment 8 ~ 12]
Change the strong base compound imidazolyl resin types that uses, identical with described in [embodiment 7] of all the other conditions, the result obtained is as shown in table 1.
Table 1
[embodiment 13]
With [embodiment 7], just temperature of reaction is 120 DEG C.The transformation efficiency obtaining NSC 11801 is 68.3%, and the selectivity of methylcarbonate is 96.2%, and the selectivity of ethylene glycol is 96.5%.
[embodiment 14]
With [embodiment 7], just temperature of reaction is 140 DEG C.The transformation efficiency obtaining NSC 11801 is 64.5%, and the selectivity of NSC 11801 is 92.5%, and the selectivity of ethylene glycol is 91.5%.
[embodiment 15]
With [embodiment 7], just temperature of reaction is 80 DEG C.The transformation efficiency obtaining NSC 11801 is 41.5%, and the selectivity of NSC 11801 is 99.1%, and the selectivity of ethylene glycol is 98.9%.
[embodiment 16]
With [embodiment 7], just the quality of methyl alcohol is 48 grams (mol ratio of methyl alcohol and NSC 11801 is 6:1).Obtaining ethylene carbonate ester conversion rate is 72.3%, and the selectivity of methylcarbonate is 99.1%, and the selectivity of ethylene glycol is 97.3%.
[embodiment 17]
With [embodiment 7], just the quality of methyl alcohol is 16.0 grams (mol ratio of methyl alcohol and NSC 11801 is 2:1).Obtaining ethylene carbonate ester conversion rate is 51.2%, and the selectivity of methylcarbonate is 96.3%, and the selectivity of ethylene glycol is 97.8%.
[embodiment 18]
With [embodiment 7], just the quality of catalyzer is 0.55 gram (mass ratio of catalyzer and NSC 11801 is 0.025:1).Obtaining ethylene carbonate ester conversion rate is 60.3%, and the selectivity of methylcarbonate is 98.0%, and the selectivity of ethylene glycol is 97.9%.
[embodiment 19]
With [embodiment 7], just the quality of catalyzer is 1.1 grams (part by weight of catalyzer and NSC 11801 is 0.05:1).Obtaining ethylene carbonate ester conversion rate is 68.1%, and the selectivity of methylcarbonate is 94.8%, and the selectivity of ethylene glycol is 95.7%.
[embodiment 20]
With [embodiment 7], just the quality of catalyzer is 8.8 grams (mass ratio of catalyzer and NSC 11801 is 0.4:1).Obtaining ethylene carbonate ester conversion rate is 72.5%, and the selectivity of methylcarbonate is 96.8%, and the selectivity of ethylene glycol is 96.9%.
[embodiment 21]
Catalyzer after [embodiment 7] reaction being terminated applies mechanically 5 times by same reaction conditions, and activity does not obviously decline.Reaction result is shown in Table 2.
Table 2
[comparative example 3]
Catalyzer after [comparative example 2] reaction being terminated applies mechanically 5 times by same reaction conditions, and activity obviously declines.Reaction result is shown in Table 3.
Table 3
Claims (9)
1. prepare the method for methylcarbonate for one kind, with NSC 11801 and methyl alcohol for reaction raw materials, it is 60 ~ 160 DEG C in temperature of reaction, the mol ratio of methyl alcohol and NSC 11801 is 2 ~ 10, the weight ratio of catalyzer and NSC 11801 is under the condition of 0.005 ~ 1, and raw material and catalyst exposure react and obtain methylcarbonate in 1 ~ 8 hour; Described catalyzer is strong base compound imidazolyl resin, and its preparation method comprises the following steps:
1) auxiliary agent one is made into water solution A; By monomer, comonomer, nano material, initiator and auxiliary agent two wiring solution-forming B;
Described monomer is selected from least one in methyl methacrylate, butyl acrylate, vinylbenzene, alpha-methyl styrene, 4-butylstyrene or vinyl cyanide; Described comonomer is selected from least one in ethyleneglycol dimethyacrylate, diallyl benzene, divinyl phenylmethane or Vinylstyrene; Described nano material is selected from least one in multi-walled carbon nano-tubes, Single Walled Carbon Nanotube, C60 or C70 soccerballene; Described initiator is selected from least one in benzoyl peroxide, Diisopropyl azodicarboxylate, lauroyl peroxide or isopropyl benzene hydroperoxide; Described auxiliary agent one is selected from least one in polyvinyl alcohol, gelatin, starch, methylcellulose gum, wilkinite or calcium carbonate; Described auxiliary agent two is selected from least one in aliphatic hydrocarbon, polystyrene, gasoline, lipid acid or paraffin;
Wherein, by weight percentage, the consumption of monomer is 85 ~ 95%, and the consumption of comonomer is 2 ~ 5%, and the consumption of nano material is 0.1 ~ 3%, and the consumption of initiator is 0.1 ~ 10%; The consumption of auxiliary agent one is 150 ~ 400% of monomer consumption, and the consumption of auxiliary agent two is 50 ~ 100% of monomer consumption;
2) solution B is mixed with solution A, be obtained by reacting complex microsphere;
3) in described complex microsphere, add chloromethylation reagents and zinc chloride, obtain compound chlorine ball;
4) chlorine type compound imidazolyl resin is obtained add imdazole derivatives reaction in described compound chlorine ball after; Described imdazole derivatives structural formula is
wherein R is methyl, ethyl, propyl group, sec.-propyl, propenyl, normal-butyl or n-pentyl;
5) add in described chlorine type compound imidazolyl resin after highly basic exchanges and obtain described strong base compound imidazolyl resin.
2. prepare the method for methylcarbonate according to claim 1, it is characterized in that the weight percent concentration of described water solution A is 0.5 ~ 2%.
3. prepare the method for methylcarbonate according to claim 1, it is characterized in that step 2) reaction process is: solution B was 60 ~ 75 DEG C of prepolymerizations 0.5 ~ 2.5 hour, then solution B is mixed with solution A, be warming up to 70 ~ 90 DEG C of reactions 5 ~ 15 hours, then be warming up to 90 ~ 100 DEG C of reactions 5 ~ 15 hours; After reaction terminates, through extracting, washing, filtration, drying, sieve, obtain the complex microsphere of particle size range 0.35 ~ 0.60 millimeter.
4. prepare the method for methylcarbonate according to claim 1, it is characterized in that step 3) reaction process is: in described complex microsphere, add the chloromethylation reagents being equivalent to complex microsphere weight 200 ~ 500%, and be equivalent to the zinc chloride catalyst of complex microsphere weight 20 ~ 70%, react 8 ~ 30 hours at 30 ~ 60 DEG C, after filtration, washing obtain compound chlorine ball, dry to constant weight; Described chloromethylation reagents is selected from least one in chloromethyl ether or Isosorbide-5-Nitrae-dichloro methyl butyl ether.
5. prepare the method for methylcarbonate according to claim 1, it is characterized in that step 4) reaction process is: adds in described compound chlorine ball and is equivalent to the organic solvent of complex microsphere weight 200 ~ 700%, the imdazole derivatives of 30 ~ 300%, react 4 ~ 30 hours under reflux state, after washing, oven dry, obtain described chlorine type compound imidazolyl resin; Wherein, described organic solvent is selected from least one in acetonitrile, cyanobenzene, toluene, tetrahydrofuran (THF), dimethyl formamide, chloroform or ethylene dichloride.
6. prepare the method for methylcarbonate according to claim 1, it is characterized in that step 5) reaction process is: adds in described chlorine type compound imidazolyl resin and is equivalent to the highly basic of chlorine type compound imidazolyl weight resin 20 ~ 200%, the water of 200 ~ 2000%, at room temperature stir 1 ~ 20 hour, after filtration, wash and obtain described strong base compound imidazolyl resin after oven dry; Wherein, described highly basic comprises NaOH, KOH, LiOH, Ca (OH)
2, Sr (OH)
2or Ba (OH)
2in at least one.
7. prepare the method for methylcarbonate according to claim 1, it is characterized in that described monomer is selected from vinylbenzene; Described comonomer is selected from Vinylstyrene; Described nano material is selected from multi-walled carbon nano-tubes; Described initiator is selected from benzoyl peroxide.
8. prepare the method for methylcarbonate according to claim 1, it is characterized in that described auxiliary agent one is selected from polyvinyl alcohol; Described auxiliary agent two is selected from polystyrene.
9. prepare the method for methylcarbonate according to claim 1, it is characterized in that temperature of reaction is 80 ~ 140 DEG C, the mol ratio of methyl alcohol and NSC 11801 is 2 ~ 8, and the weight ratio of catalyzer and NSC 11801 is 0.01 ~ 0.5, and the reaction times is 1 ~ 6 hour.
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| CN110857273A (en) * | 2018-08-21 | 2020-03-03 | 中国石油化工股份有限公司 | Method for preparing carbonic ester from oxalate |
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| CN105503607B (en) | 2017-10-27 |
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