CN105503607B - The method for preparing dimethyl carbonate - Google Patents
The method for preparing dimethyl carbonate Download PDFInfo
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- CN105503607B CN105503607B CN201410498055.XA CN201410498055A CN105503607B CN 105503607 B CN105503607 B CN 105503607B CN 201410498055 A CN201410498055 A CN 201410498055A CN 105503607 B CN105503607 B CN 105503607B
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Abstract
The present invention relates to a kind of method for preparing dimethyl carbonate, the resin for mainly solving prior art presence is easily swelled, the problem of activity decrease is fast.The present invention is by using using ethylene carbonate and methanol as raw material, it it is 60~160 DEG C in reaction temperature, the mol ratio of methanol and ethylene carbonate is 2~10, the weight ratio of catalyst and ethylene carbonate is under conditions of 0.005~1, raw material is contacted with catalyst, reaction generation dimethyl carbonate;The catalyst is that the technical scheme of the compound imidazole radicals resin of strong base preferably solves the problem, available in the industrial production of dimethyl carbonate.
Description
Technical field
The present invention relates to a kind of method for preparing dimethyl carbonate.
Background technology
Dimethyl carbonate (DMC) chemical property is active, physical property is excellent and nontoxic, easily biological-degradable, is a kind of new
Low stain, environmentally friendly green basic chemical industry raw material, solvent, gasoline additive, lithium-ion battery electrolytes can be used as
And be carbonylated, methylate and carbomethoxy reagent, chemical field is widely used in, current each state is all actively grinding
Study carefully the Green Chemistry process of this environment-friendly industrial chemicals based on DMC.Wherein ester-interchange method is gentle better than reaction condition, receives
Rate is high and coproduction ethylene glycol or propane diols and as the method for present great industrial prospect.
In general, ester exchange reaction is more with alkali metal hydroxide, alkali carbonate and alkali metal alcohol etc.
(F.Risse et al.,US2011040117;C.P.Allais et al., WO2010063780) as catalyst, but because of it
For homogeneous catalyst, it is difficult to separate with product, reuses difficult.Conventional heterogeneous catalyst includes the alkali being carried on carrier
Metal or alkali metal salt, metal oxide catalyst, the zeolite or clay material and amberlite of alkali (soil) metal exchange
Fat etc..It is carried on alkali metal or alkali metal salt on carrier, such as KF/Al2O3, NaOH/ chitosans and Cs2CO3/SiO2-Al2O3
Deng (H.Zhang, CN101249452;Y.Zhao,CN101121147;C.D.Chang et al., WO0156971A1), they
Shortcoming be easily by air reclaimed water and CO2Influence so that activity decrease;Metal oxide catalyst, such as Al2O3, MgO etc.
(B.M.Bhanage,et al.Appl.Catal.A 219(2001)259-266;J.S.Buchanan et al.,
US2005080287;Z.Z.Jiang et al., US6207850), and alkali (soil) metal exchange zeolite or clay material,
Such as Cs-ZSM-5, Mg-smectite (C.D.Chang et al., WO0073256;B.M.Bhanage et
Al.Catal.Lett.83 (2002) 137-141), the shortcoming of this two classes catalyst is active or selectivity is generally than relatively low;
Ion exchange resin, such as quaternary ammonium type or tertiary amine resin (J.F.Knifton et al., J.Mol.Catal.A 67 (1991)
389-399;M.Cao et al.React.Kinet.Catal.Lett.88 (2006) 251-259), this kind of catalyst is generally not
Swelling resistance, and long-time activity decrease is than very fast.
The content of the invention
The technical problems to be solved by the invention are that prior art has resin and is easily swelled, and the problem of activity decrease is fast carries
For a kind of new method for preparing dimethyl carbonate.This method has catalyst swelling resistance, the characteristics of activity decrease is slow.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:A kind of method for preparing dimethyl carbonate,
It it is 60~160 DEG C in reaction temperature using ethylene carbonate and methanol as reaction raw materials, the mol ratio of methanol and ethylene carbonate is
2~10, the weight ratio of catalyst and ethylene carbonate is that under conditions of 0.005~1, raw material and catalyst haptoreaction 1~8 are small
When obtain dimethyl carbonate;The catalyst is that strong base is combined imidazole radicals resin, and its preparation method comprises the following steps:
1) auxiliary agent one is made into water solution A;Monomer, comonomer, nano material, initiator and auxiliary agent two are made into molten
Liquid B;
The monomer is selected from methyl methacrylate, butyl acrylate, styrene, α-methylstyrene, 4- butyl benzene second
At least one of alkene or acrylonitrile;The comonomer is selected from ethyleneglycol dimethyacrylate, diallyl benzene, divinyl
At least one of base phenylmethane or divinylbenzene;The nano material be selected from multi-walled carbon nanotube, single-walled carbon nanotube,
At least one of C60 or C70 fullerenes;The initiator is selected from benzoyl peroxide, azodiisobutyronitrile, peroxidating bay
At least one of acyl or isopropyl benzene hydroperoxide;The auxiliary agent one is selected from polyvinyl alcohol, gelatin, starch, methylcellulose, swollen
At least one of profit soil or calcium carbonate;The auxiliary agent two is in aliphatic hydrocarbon, polystyrene, gasoline, aliphatic acid or paraffin
It is at least one;
Wherein, by weight percentage, the consumption of monomer is 85~95%, and the consumption of comonomer is 2~5%, nanometer
The consumption of material is 0.1~3%, and the consumption of initiator is 0.1~10%;The consumption of auxiliary agent one for monomer consumption 150~
400%, the consumption of auxiliary agent two is the 50~100% of monomer consumption;
2) solution B is mixed with solution A, reaction obtains complex microsphere;
3) chloromethylation reagents and zinc chloride are added into the complex microsphere, compound chlorine ball is obtained;
4) added into the compound chlorine ball and the compound imidazole radicals resin of chlorine type is obtained after imdazole derivatives reaction;The imidazoles
Derivant structure formula isWherein R is methyl, ethyl, propyl group, isopropyl, acrylic, normal-butyl or n-pentyl;
5) it is combined in imidazole radicals resin to add to the chlorine type and the compound imidazole radicals tree of the strong base is obtained after highly basic is exchanged
Fat.
In above-mentioned technical proposal, it is preferable that the weight percent concentration of the water solution A is 0.5~2%.
In above-mentioned technical proposal, it is preferable that step 2) course of reaction is:Solution B is in 60~75 DEG C of prepolymerizations 0.5~2.5
Hour, then solution B is mixed with solution A, 70~90 DEG C is warming up to and reacts 5~15 hours, then be warming up to 90~100 DEG C of reactions
5~15 hours;After reaction terminates, through extracting, washing, filtering, dry, sieving, 0.35~0.60 millimeter of particle size range is obtained
Complex microsphere.
In above-mentioned technical proposal, it is preferable that step 3) course of reaction is:Added into the complex microsphere equivalent to compound
The chloromethylation reagents of microspheres weight 200~500%, and be catalyzed equivalent to the zinc chloride of complex microsphere weight 20~70%
Agent, is reacted 8~30 hours at 30~60 DEG C, and compound chlorine ball, drying to constant weight are obtained through filtering, washing;The chloromethylation
Reagent is selected from least one of chloromethyl ether or 1,4- dichloro methyl butyl ethers.
In above-mentioned technical proposal, it is preferable that step 4) course of reaction is:Added into the compound chlorine ball equivalent to compound
Reacted 4~30 hours under the organic solvent of microspheres weight 200~700%, 30~300% imdazole derivatives, reflux state, warp
The chlorine type, which is obtained, after washing, drying is combined imidazole radicals resin;Wherein, the organic solvent be selected from acetonitrile, benzonitrile, toluene,
At least one of tetrahydrofuran, dimethylformamide, chloroform or dichloroethanes.
In above-mentioned technical proposal, it is preferable that step 5) course of reaction is:It is combined in imidazole radicals resin and adds to the chlorine type
Equivalent to highly basic, 200~2000% water that chlorine type is combined imidazole radicals weight resin 20~200%, 1~20 is stirred at room temperature
Hour, the compound imidazole radicals resin of the strong base is obtained after filtering, washing and drying;Wherein, the highly basic include NaOH,
KOH、LiOH、Ca(OH)2、Sr(OH)2Or Ba (OH)2At least one of.
In above-mentioned technical proposal, it is preferable that the monomer is selected from styrene.
In above-mentioned technical proposal, it is preferable that the comonomer is selected from divinylbenzene.
In above-mentioned technical proposal, it is preferable that the nano material is selected from multi-walled carbon nanotube.
In above-mentioned technical proposal, it is preferable that the initiator is selected from benzoyl peroxide.
In above-mentioned technical proposal, it is preferable that the auxiliary agent one is selected from polyvinyl alcohol.
In above-mentioned technical proposal, it is preferable that the auxiliary agent two is selected from polystyrene.
In above-mentioned technical proposal, it is preferable that reaction temperature is 80~140 DEG C, the mol ratio of methanol and ethylene carbonate is 2
~8, the weight ratio of catalyst and ethylene carbonate is 0.01~0.5, and the reaction time is 1~6 hour.
The inventive method uses strong base to be combined imidazole radicals resin for catalyst, due to being mixed with resin base material
The nano material of high intensity, so as to enhance the resistance to swelling energy of resin.The catalyst of the present invention is used for ethylene carbonate and first
The ester exchange reaction of alcohol is prepared in dimethyl carbonate, in 100 DEG C of reaction temperature, and the mol ratio of methanol and ethylene carbonate is 4, is urged
Agent and the weight of ethylene carbonate ratio are under the conditions of 0.1, to react 4 hours, the conversion ratio of ethylene carbonate is 70.5%, carbonic acid
The selectivity of dimethyl ester is 98.3%, and the selectivity of ethylene glycol is 98.1%, and after catalyst is reused 5 times, activity decrease is small
In 5%, preferable technique effect is achieved.
Below by embodiment, the invention will be further elaborated.It is necessarily pointed out that following examples are only used
Further illustrated in the present invention, it is impossible to be interpreted as limiting the scope of the invention.
Embodiment
【Embodiment 1】
58.0 grams of styrene, 0.6 gram of divinylbenzene, 30 grams of polystyrene and 0.6 are added in 500 milliliters of three-necked flasks
Gram benzoyl peroxide initiator, in being stirred 2.0 hours at 60 DEG C;Then 2.8 grams of multi-walled carbon nanotubes are added, continue to stir 1
Hour carries out prepolymerization.Add the 260 ml deionized water solution for being dissolved with 2.5 grams of polyvinyl alcohol.Mixing speed is adjusted, together
When be progressively warming up to 80 DEG C, react 5 hours;90 DEG C are warming up to again, is reacted 5 hours, 98 DEG C are finally warming up to, and are reacted 6 hours.
After reaction terminates, supernatant liquid is poured out, is washed with 85 DEG C of hot washes, then with cold water, is then filtered, be put into baking oven 80 DEG C
Drying, sieving, complex microsphere A of the collection cut size in the range of 0.35~0.60 millimeter.
The chloromethylation of complex microsphere:In 500 milliliters of three-necked flask, 50 grams of complex microsphere A and 250 milliliters of chlorine are added
Methyl ether, is stored at room temperature 4 hours, starts stirring, and it is catalyst to add 15 grams of zinc chloride, is warming up to 50 DEG C and reacts 8 hours, chlorination knot
Room temperature is cooled to after beam, chlorination mother solution is filtered out, methanol cyclic washing is used, dried 8 hours at 100 DEG C, compound chlorine ball A is obtained.
The imidazoles salinization of compound chlorine ball:In 500 milliliters of there-necked flasks, 20 grams of compound chlorine ball A, 100 milliliters of tetrahydrochysene furans are added
Mutter, 8 grams of N- methylimidazoles, stirring reaction 12 hours, react and are filtered to remove mother liquor after terminating, use successively respectively at reflux
Dichloromethane, acetone and water washing, dry to obtain the compound imidazole radicals Resin A 1 of chlorine type under vacuo.
Chlorine type is combined the transition of imidazole radicals resin:In 200 milliliters of beakers, add 10 grams of chlorine type and be combined imidazole radicals resin
A1,3 grams of NaOH and 180 gram of deionized waters, were stirred at room temperature after 2 hours, filtering, after being washed with deionized, and repeated said process 2
Secondary, filtering is washed with deionized, and drying under vacuo obtains strong base and is combined imidazole radicals Resin A 2.
【Embodiment 2】
In 500 milliliters of there-necked flasks, 20 grams are added【Embodiment 1】The compound chlorine ball A of gained, 150 milliliters of toluene, 35.0 grams
N- allyl imidazoles, stirring reaction 30 hours, react and are filtered to remove mother liquor after terminating, use dichloro successively respectively at reflux
Methane, acetone and water washing, dry to obtain the compound imidazole radicals Resin A 3 of chlorine type under vacuo.
Chlorine type is combined the transition of imidazole radicals resin:In 200 milliliters of beakers, add 10 grams of chlorine type and be combined imidazole radicals resin
A3,20 grams of Ba (OH)2With 40 grams of deionized waters, it is stirred at room temperature after 18 hours, filters, after being washed with deionized, repeats above-mentioned
Process 2 times, filtering, is washed with deionized, and drying under vacuo obtains strong base and is combined imidazole radicals Resin A 4.
【Embodiment 3】
Monomer mixture solution (60.0 grams of styrene, 1.7 grams containing initiator are added in 500 milliliters of three-necked flasks
Divinylbenzene, 60 grams of polystyrene, 1.6 grams of multi-walled carbon nanotubes and 1.0 grams of benzoyl peroxides, the solution are stirred prior to 70 DEG C
Mix reaction 0.5 hour), agitator is started, the mixed solution of 200 ml deionized waters and 5 grams of gelatin is added, is warming up to 85 DEG C,
Reaction 3 hours, then it is warming up to 90 DEG C, react 9 hours, be finally warming up to 100 DEG C, react 10 hours.After reaction terminates, pour out
Supernatant liquid, is washed with 85 DEG C of hot washes, then with cold water, then filters, and is put into 80 DEG C of drying in baking oven, and grain is collected in sieving
Complex microsphere B of the footpath in the range of 0.35~0.60 millimeter.
The chloromethylation of complex microsphere:In 500 milliliters of three-necked flask, 50 grams of complex microsphere B and 150 milliliters of chlorine are added
Methyl ether, is stored at room temperature 6 hours, starts stirring, and it is catalyst to add 30 grams of zinc chloride, is warming up to 50 DEG C and reacts 24 hours, chlorination
Room temperature is cooled to after end, chlorination mother solution is filtered out, methanol cyclic washing is used, dried 8 hours at 100 DEG C, compound chlorine ball is obtained
B。
The imidazoles salinization of compound chlorine ball:In 500 milliliters of there-necked flasks, 20 grams of compound chlorine ball B, 150 milliliters of tetrahydrochysene furans are added
Mutter, 30.0 grams of N- propyl imidazoles, stirring reaction 24 hours at reflux, reaction is filtered to remove mother liquor after terminating, respectively according to
Secondary use dichloromethane, acetone and water washing, dry to obtain the compound imidazole radicals resin B 1 of chlorine type under vacuo.
Chlorine type is combined into imidazole radicals resin B 1 to use【Embodiment 2】Described method is made the transition, and is obtained strong base and is combined miaow
Oxazolyl resin B 2.
【Embodiment 4】
In 500 milliliters of there-necked flasks, 15 grams are added【Embodiment 3】The compound chlorine ball B of gained, 150 milliliters of tetrahydrofurans,
35.0 grams of N- butylimidazoliums, stirring reaction 10 hours, react and mother liquor are filtered to remove after terminating, respectively successively at reflux
With dichloromethane, acetone and water washing, the compound imidazole radicals resin B 3 of chlorine type is dried to obtain under vacuo.
Chlorine type will be combined into imidazole radicals resin B 3 to use【Embodiment 2】Described method is made the transition, and is obtained strong base and is combined
Imidazole radicals resin B 4
【Embodiment 5】
Change【Embodiment 3】In monomer mixture solution (76.0 grams of α-methylstyrenes, 3.5 grams of divinylbenzenes, 75
Gram gasoline, 2.4 grams of multi-walled carbon nanotubes and 1.4 grams of benzoyl peroxides), remaining preparation condition with【Embodiment 3】It is identical, obtain
Complex microsphere C.
The chloromethylation of complex microsphere:In 500 milliliters of three-necked flask, 40 grams of complex microsphere C and 150 milliliter 1 are added,
4- dichloro methyl butyl ethers, are stored at room temperature 6 hours, start stirring, and it is catalyst to add 25 grams of zinc chloride, is warming up to 50 DEG C of reactions
24 hours, chlorination was cooled to room temperature after terminating, and filters out chlorination mother solution, used methanol cyclic washing, dries 8 hours, obtains at 100 DEG C
To compound chlorine ball C.
The imidazoles salinization of compound chlorine ball:In 500 milliliters of there-necked flasks, 30 grams of compound chlorine ball C, 150 milliliters of tetrahydrochysene furans are added
Mutter, 20.0 grams of N- vinyl imidazoles, stirring reaction 12 hours, react and are filtered to remove mother liquor after terminating, respectively at reflux
Dichloromethane, acetone and water washing are used successively, and the compound imidazole radicals resin C1 of chlorine type is dried to obtain under vacuo.
Chlorine type is combined into imidazole radicals resin C1 to use【Embodiment 2】Described method is made the transition, and is obtained strong base and is combined miaow
Oxazolyl resin C2.
【Embodiment 6】
According to【Embodiment 4】The step of imidazoles salinization reaction is carried out to compound chlorine ball C, obtain chlorine type and be combined imidazole radicals resin
C3。
Chlorine type is combined into imidazole radicals resin C3 to use【Embodiment 2】Described method is made the transition, and is obtained strong base and is combined miaow
Oxazolyl resin C4.
【Comparative example 1】
The preparation process of catalyst with【Embodiment 1】It is identical, multi-walled carbon nanotube is simply added without, chlorine type miaow is respectively obtained
Oxazolyl resin CA1 and strong base imidazole radicals resin CA2.
【Embodiment 7】
Will【Embodiment 1】Prepared strong base, which is combined imidazole radicals Resin A 2, is used for ethylene carbonate and methanol ester exchange system
In the reaction of standby dimethyl carbonate.22.0 grams of ethylene carbonates, 32.0 grams of methanol and 2.2 grams of A2 catalyst are placed in 100 milliliters
(mol ratio of methanol and ethylene carbonate is 4, and the weight ratio of catalyst and ethylene carbonate is 0.1), 100 DEG C anti-in autoclave
Answer 4 hours.After reaction terminates, autoclave is cooled to room temperature, is vented.Take liquid product to carry out gas chromatographic analysis, measure carbon
The conversion ratio of vinyl acetate is 70.5%, and the selectivity of dimethyl carbonate is 98.3%, and the selectivity of ethylene glycol is 98.1%, tree
The swellbility of fat catalyst is SSWELLFor 4.8%.
【Comparative example 2】
Catalyst activity test condition with【Embodiment 7】Identical, simply catalyst used is strong base imidazole radicals resin
CA2, the conversion ratio for obtaining ethylene carbonate is 69.8%, and the selectivity of dimethyl carbonate is 98.5%, the selectivity of ethylene glycol
For 98.3%, the swellbility of resin catalyst is SSWELLFor 20.5%.
【Embodiment 8~12】
Strong base used in changing is combined imidazole radicals resin types, remaining condition with【Embodiment 7】Described is identical, obtains
The result arrived is as shown in table 1.
Table 1
【Embodiment 13】
Together【Embodiment 7】, simply reaction temperature is 120 DEG C.The conversion ratio for obtaining ethylene carbonate is 68.3%, carbonic acid two
The selectivity of methyl esters is 96.2%, and the selectivity of ethylene glycol is 96.5%.
【Embodiment 14】
Together【Embodiment 7】, simply reaction temperature is 140 DEG C.The conversion ratio for obtaining ethylene carbonate is 64.5%, ethylene
The selectivity of alkene ester is 92.5%, and the selectivity of ethylene glycol is 91.5%.
【Embodiment 15】
Together【Embodiment 7】, simply reaction temperature is 80 DEG C.The conversion ratio for obtaining ethylene carbonate is 41.5%, ethylene
The selectivity of alkene ester is 99.1%, and the selectivity of ethylene glycol is 98.9%.
【Embodiment 16】
Together【Embodiment 7】, simply the quality of methanol be 48 grams (mol ratio of methanol and ethylene carbonate be 6:1).Obtain
Ethylene carbonate ester conversion rate is 72.3%, and the selectivity of dimethyl carbonate is 99.1%, and the selectivity of ethylene glycol is 97.3%.
【Embodiment 17】
Together【Embodiment 7】, simply the quality of methanol be 16.0 grams (mol ratio of methanol and ethylene carbonate be 2:1).
It is 51.2% to ethylene carbonate ester conversion rate, the selectivity of dimethyl carbonate is 96.3%, the selectivity of ethylene glycol is 97.8%.
【Embodiment 18】
Together【Embodiment 7】, simply the quality of catalyst be 0.55 gram (mass ratio of catalyst and ethylene carbonate be
0.025:1).It is 60.3% to obtain ethylene carbonate ester conversion rate, and the selectivity of dimethyl carbonate is 98.0%, the selection of ethylene glycol
Property is 97.9%.
【Embodiment 19】
Together【Embodiment 7】, simply the quality of catalyst be 1.1 grams (part by weight of catalyst and ethylene carbonate be
0.05:1).It is 68.1% to obtain ethylene carbonate ester conversion rate, and the selectivity of dimethyl carbonate is 94.8%, the selection of ethylene glycol
Property is 95.7%.
【Embodiment 20】
Together【Embodiment 7】, simply the quality of catalyst be 8.8 grams (mass ratio of catalyst and ethylene carbonate be 0.4:
1).It is 72.5% to obtain ethylene carbonate ester conversion rate, and the selectivity of dimethyl carbonate is 96.8%, and the selectivity of ethylene glycol is
96.9%.
【Embodiment 21】
Will【Embodiment 7】Catalyst after reaction terminates is applied mechanically 5 times by same reaction conditions, and activity is not decreased obviously.
Reaction result is shown in Table 2.
Table 2
【Comparative example 3】
Will【Comparative example 2】Catalyst after reaction terminates is applied mechanically 5 times by same reaction conditions, and activity is decreased obviously.Reaction
It the results are shown in Table shown in 3.
Table 3
Claims (4)
1. a kind of method for preparing dimethyl carbonate, using ethylene carbonate and methanol as reaction raw materials, reaction temperature be 60~
160 DEG C, the mol ratio of methanol and ethylene carbonate is 2~10, and the weight of catalyst and ethylene carbonate is than for 0.005~1
Under the conditions of, raw material obtains dimethyl carbonate in 1~8 hour with catalyst haptoreaction;The catalyst is that strong base is combined imidazoles
Base resin, its preparation method comprises the following steps:
1) auxiliary agent one is made into water solution A;By monomer, comonomer, nano material, initiator and the wiring solution-forming B of auxiliary agent two;
The weight percent concentration of the water solution A is 0.5~2%;
The monomer be selected from methyl methacrylate, butyl acrylate, styrene, α-methylstyrene, 4- butylstyrenes or
At least one of acrylonitrile;The comonomer is selected from ethyleneglycol dimethyacrylate, diallyl benzene, divinylbenzene
At least one of methylmethane or divinylbenzene;The nano material is selected from multi-walled carbon nanotube, single-walled carbon nanotube, C60
At least one of or C70 fullerenes;The initiator is selected from benzoyl peroxide, azodiisobutyronitrile, lauroyl peroxide
At least one of or isopropyl benzene hydroperoxide;The auxiliary agent one is selected from polyvinyl alcohol, gelatin, starch, methylcellulose, swelling
At least one of soil or calcium carbonate;The auxiliary agent two in aliphatic hydrocarbon, polystyrene, gasoline, aliphatic acid or paraffin extremely
Few one kind;
Wherein, by weight percentage, the consumption of monomer is 85~95%, and the consumption of comonomer is 2~5%, nano material
Consumption be 0.1~3%, the consumption of initiator is 0.1~10%;The consumption of auxiliary agent one is the 150~400% of monomer consumption,
The consumption of auxiliary agent two is the 50~100% of monomer consumption;
2) solution B is mixed with solution A, reaction obtains complex microsphere;
Step 2) course of reaction is:Then solution B mixed solution B with solution A in 60~75 DEG C of prepolymerizations 0.5~2.5 hour
Close, be warming up to 70~90 DEG C and react 5~15 hours, then be warming up to 90~100 DEG C and react 5~15 hours;After reaction terminates, through taking out
Carry, wash, filter, dry, sieve, obtain the complex microsphere of 0.35~0.60 millimeter of particle size range;
3) chloromethylation reagents and zinc chloride are added into the complex microsphere, compound chlorine ball is obtained;
Step 3) course of reaction is:The chloromethyl equivalent to complex microsphere weight 200~500% is added into the complex microsphere
Change reagent, and equivalent to the zinc chloride catalyst of complex microsphere weight 20~70%, 8~30 are reacted at 30~60 DEG C small
When, obtain compound chlorine ball, drying to constant weight through filtering, washing;The chloromethylation reagents are selected from chloromethyl ether or 1,4- dichloromethanes
At least one of epoxide butane;
4) added into the compound chlorine ball and the compound imidazole radicals resin of chlorine type is obtained after imdazole derivatives reaction;The imidazole derivatives
Thing structural formula isWherein R is methyl, ethyl, propyl group, isopropyl, acrylic, normal-butyl or n-pentyl;
Step 4) course of reaction is:Added into the compound chlorine ball organic molten equivalent to complex microsphere weight 200~700%
Reacted 4~30 hours under agent, 30~300% imdazole derivatives, reflux state, obtaining the chlorine type after scrubbed, drying answers
Close imidazole radicals resin;Wherein, the organic solvent is selected from acetonitrile, benzonitrile, toluene, tetrahydrofuran, dimethylformamide, chloroform
At least one of or dichloroethanes;
5) it is combined in imidazole radicals resin to add to the chlorine type and the compound imidazole radicals resin of the strong base is obtained after highly basic is exchanged;
Step 5) course of reaction is:It is combined to add in imidazole radicals resin to the chlorine type and is combined imidazole radicals resin weight equivalent to chlorine type
Highly basic, 200~2000% water of amount 20~200%, are stirred at room temperature 1~20 hour, after filtering, washing and drying
Imidazole radicals resin is combined to the strong base;Wherein, the highly basic includes NaOH, KOH, LiOH, Ca (OH)2、Sr(OH)2Or Ba
(OH)2At least one of.
2. the method for dimethyl carbonate is prepared according to claim 1, it is characterised in that the monomer is selected from styrene;It is described
Comonomer is selected from divinylbenzene;The nano material is selected from multi-walled carbon nanotube;The initiator is selected from benzoyl peroxide first
Acyl.
3. the method for dimethyl carbonate is prepared according to claim 1, it is characterised in that the auxiliary agent one is selected from polyvinyl alcohol;
The auxiliary agent two is selected from polystyrene.
4. the method for dimethyl carbonate is prepared according to claim 1, it is characterised in that reaction temperature is 80~140 DEG C, first
The mol ratio of alcohol and ethylene carbonate is 2~8, and the weight ratio of catalyst and ethylene carbonate is 0.01~0.5, and the reaction time is
1~6 hour.
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