CN105503609B - The method for producing dimethyl carbonate - Google Patents
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- CN105503609B CN105503609B CN201410498142.5A CN201410498142A CN105503609B CN 105503609 B CN105503609 B CN 105503609B CN 201410498142 A CN201410498142 A CN 201410498142A CN 105503609 B CN105503609 B CN 105503609B
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Abstract
The present invention relates to a kind of method for producing 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 hydroxy imidazole 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 producing 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.A219(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.A67 (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 method of new production 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 producing 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 hydroxy imidazole 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 compound imidazoles resin is obtained after imidazoles reaction；
5) added into the compound imidazoles resin and the compound hydroxy imidazole resin of halogen-type is obtained after hydroxyhalide reaction；
6) it is combined in hydroxy imidazole resin to add to the halogen-type and the compound hydroxyl of the strong base is obtained after highly basic is exchanged
Imidazoles resin.
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% imidazoles, reflux state, scrubbed,
The compound imidazoles resin is obtained after drying；Wherein, the organic solvent is selected from acetonitrile, benzonitrile, toluene, tetrahydrofuran, two
At least one of NMF, chloroform or dichloroethanes.
In above-mentioned technical proposal, it is preferable that step 5) course of reaction is：Added into the compound imidazoles resin equivalent to
Under hydroxyhalide X-R-OH, 300~1000% organic solvent of compound imidazoles weight resin 30~300%, reflux state
Reaction 4~30 hours, obtains halogen-type after scrubbed, drying and is combined hydroxy imidazole resin；Wherein, the organic solvent is selected from second
At least one of nitrile, benzonitrile, toluene, tetrahydrofuran, dimethylformamide, chloroform or dichloroethanes；Hydroxyhalide X-
X is Cl, Br or I in R-OH, and R is ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, n-pentyl or n-hexyl.
In above-mentioned technical proposal, it is preferable that step 6) course of reaction is：It is combined to the halogen-type in hydroxy imidazole resin
Highly basic, 200~2000% water that hydroxy imidazole weight resin 20~200% is combined equivalent to halogen-type are added, at room temperature
Stirring 1~20 hour, obtains the compound hydroxy imidazole resin of the strong base after filtering, washing and drying；Wherein, the highly basic
Including 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 hydroxy imidazole resin for catalyst, due to being mixed in resin base material
The nano material of high intensity, so that the resistance to swelling energy of resin is enhanced, further, since hydroxyl can provide hydrogen bond to activate
Reaction substrate, so as to improve catalytic activity.The catalyst of the present invention is used for the ester exchange reaction system of ethylene carbonate and methanol
In standby dimethyl carbonate, in 100 DEG C of reaction temperature, the mol ratio of methanol and ethylene carbonate is 4, catalyst and ethylene carbonate
Weight ratio be under the conditions of 0.1, to react 4 hours, the conversion ratio of ethylene carbonate is 73.5%, the selectivity of dimethyl carbonate is
98.7%, the selectivity of ethylene glycol is 99.2%, and after catalyst is reused 5 times, activity decrease is less than 5%, achieves preferably
Technique effect.
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 of compound chlorine ball：In 500 milliliters of there-necked flasks, 20 grams of compound chlorine ball A of addition, 100 milliliters of tetrahydrofurans,
8 grams of imidazoles, stirring reaction 12 hours at reflux, reaction is filtered to remove mother liquor after terminating, respectively successively with dichloromethane,
Acetone and water washing, imidazoles Resin A 1 must be combined under vacuo by drying.
The reaction of compound imidazoles resin and hydroxyhalide：20 grams of compound imidazoles resins are added in 500 milliliters of there-necked flasks
A1,9.2 grams of ethylene bromohyrins and 200 milliliters of acetonitriles, react 20 hours at reflux, and reaction is filtered to remove mother liquor after terminating,
Use dichloromethane, acetone and water washing successively respectively, the compound hydroxy imidazole Resin A 2 of halogen-type is dried to obtain under vacuo.
Halogen-type is combined the transition of hydroxy imidazole resin：In 200 milliliters of beakers, add 10 grams of halogen-types and be combined hydroxyl miaow
Azoles Resin A 1,3 grams of NaOH and 180 gram of deionized waters, were stirred at room temperature after 2 hours, filtering, after being washed with deionized, in repetition
State process 2 times, filter, be washed with deionized, drying under vacuo obtains strong base and is combined hydroxy imidazole Resin A 3.
【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
Imidazoles, stirring reaction 30 hours, react and mother liquor are filtered to remove after terminating, use dichloromethane, third successively respectively at reflux
Ketone and water washing, imidazoles Resin A 4 must be combined under vacuo by drying.
The reaction of compound imidazoles resin and hydroxyhalide：20 grams of compound imidazoles resins are added in 500 milliliters of there-necked flasks
A1,30.2 grams of ethylene iodohydrins and 200 milliliters of benzonitriles, react 10 hours at reflux, and reaction is filtered to remove mother after terminating
Liquid, uses dichloromethane, acetone and water washing successively respectively, and the compound hydroxy imidazole Resin A 5 of halogen-type is dried to obtain under vacuo.
Halogen-type is combined the transition of hydroxy imidazole resin：In 200 milliliters of beakers, add 10 grams of halogen-types and be combined hydroxyl miaow
Azoles Resin A 5,20 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, weight
Said process 2 times, filtering, are washed with deionized again, and drying under vacuo obtains strong base and is combined hydroxy imidazole Resin A 6.
【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 of compound chlorine ball：In 500 milliliters of there-necked flasks, 20 grams of compound chlorine ball B of addition, 150 milliliters of tetrahydrofurans,
20.0 grams of imidazoles, stirring reaction 24 hours, react and are filtered to remove mother liquor after terminating, use dichloromethane successively respectively at reflux
Alkane, acetone and water washing, imidazoles resin B 1 must be combined under vacuo by drying.
Compound imidazoles resin B 1 is used【Embodiment 2】Described method is reacted and made the transition with hydroxyhalide, is obtained
Halogen-type is combined hydroxy imidazole resin B 2 and strong base is combined hydroxy imidazole resin B 3.
【Embodiment 4】
In 500 milliliters of there-necked flasks, 15 grams are added【Embodiment 3】1,150 milliliters of acetonitriles of compound imidazoles resin B of gained,
20.0 grams of 3- chloropropyl alcohols, stirring reaction 10 hours, react and mother liquor are filtered to remove after terminating, respectively successively with two at reflux
Chloromethanes, acetone and water washing, dry to obtain the compound hydroxy imidazole resin B 4 of halogen-type under vacuo.
Halogen-type is combined into hydroxy imidazole resin B 4 to use【Embodiment 2】Described method is made the transition, and is obtained strong base and is answered
Close hydroxy imidazole resin B 5.
【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 of compound chlorine ball：With【Embodiment 1】Method is identical, obtains compound imidazoles resin C1.
The reaction of compound imidazoles resin and hydroxyhalide：20 grams of compound imidazoles resins are added in 500 milliliters of there-necked flasks
C1,10.5 grams of 5- bromines amylalcohols and 200 milliliters of acetonitriles, react 20 hours at reflux, and reaction is filtered to remove mother liquor after terminating,
Use dichloromethane, acetone and water washing successively respectively, the compound hydroxy imidazole resin C2 of halogen-type is dried to obtain under vacuo.
Halogen-type is combined into hydroxy imidazole resin C2 to use【Embodiment 2】Described method is made the transition, and is obtained strong base and is answered
Close hydroxy imidazole resin C3.
【Embodiment 6】
Catalyst preparation step with【Embodiment 5】The step of it is identical, simply hydroxyhalide used is 6- bromine hexanols, is obtained
Hydroxy imidazole resin C4 is combined to halogen-type and strong base is combined hydroxy imidazole resin C5.
【Comparative example 1】
The preparation process of catalyst with【Embodiment 1】It is identical, multi-walled carbon nanotube is simply added without, compound miaow is respectively obtained
Azoles resin CA1, halogen-type are combined hydroxy imidazole resin CA2 and strong base is combined hydroxy imidazole resin CA3.
【Embodiment 7】
Will【Embodiment 1】Prepared strong base, which is combined hydroxy imidazole Resin A 3, is used for ethylene carbonate and methanol ester exchange
In the reaction for preparing dimethyl carbonate.22.0 grams of ethylene carbonates, 32.0 grams of methanol and 2.2 grams of A3 catalyst are placed in 100 millis
(mol ratio of methanol and ethylene carbonate is 4, and the weight ratio of catalyst and ethylene carbonate is 0.1) 100 DEG C in liter autoclave
Reaction 4 hours.After reaction terminates, autoclave is cooled to room temperature, is vented.Take liquid product to carry out gas chromatographic analysis, measure
The conversion ratio of ethylene carbonate is 73.5%, and the selectivity of dimethyl carbonate is 98.7%, and the selectivity of ethylene glycol is 99.2%,
The swellbility of resin catalyst is SSWELLFor 4.2%.
【Comparative example 2】
Catalyst activity test condition with【Embodiment 7】Identical, simply catalyst used is combined hydroxyl miaow for strong base
Azoles resin CA3, the conversion ratio for obtaining ethylene carbonate is 71.5%, and the selectivity of dimethyl carbonate is 98.5%, ethylene glycol
Selectivity is 98.9%, and the swellbility of resin catalyst is SSWELLFor 21.5%.
【Embodiment 8-12】
Strong base used in changing is combined hydroxy imidazole resin types, remaining condition with【Embodiment 7】Described is identical,
Obtained result 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 70.3%, carbonic acid two
The selectivity of methyl esters is 96.9%, and the selectivity of ethylene glycol is 97.2%.
【Embodiment 14】
Together【Embodiment 7】, simply reaction temperature is 140 DEG C.The conversion ratio for obtaining ethylene carbonate is 66.5%, ethylene
The selectivity of alkene ester is 97.5%, and the selectivity of ethylene glycol is 93.5%.
【Embodiment 15】
Together【Embodiment 7】, simply reaction temperature is 80 DEG C.The conversion ratio for obtaining ethylene carbonate is 46.5%, ethylene
The selectivity of alkene ester is 99.1%, and the selectivity of ethylene glycol is 98.5%.
【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 74.3%, and the selectivity of dimethyl carbonate is 99.1%, and the selectivity of ethylene glycol is 98.3%.
【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 53.2% to ethylene carbonate ester conversion rate, the selectivity of dimethyl carbonate is 96.4%, the selectivity of ethylene glycol is 97.9%.
【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 63.8% to obtain ethylene carbonate ester conversion rate, and the selectivity of dimethyl carbonate is 98.2%, the selection of ethylene glycol
Property is 97.1%.
【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 68.9% to obtain ethylene carbonate ester conversion rate, and the selectivity of dimethyl carbonate is 95.2%, the selection of ethylene glycol
Property is 95.3%.
【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 75.5% to obtain ethylene carbonate ester conversion rate, and the selectivity of dimethyl carbonate is 97.2%, and the selectivity of ethylene glycol is
95.3%.
【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 producing 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 hydroxyl
Imidazoles 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 compound imidazoles resin is obtained after imidazoles reaction；
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% imidazoles, reflux state, the compound imidazoles resin is obtained after scrubbed, drying；
Wherein, the organic solvent is in acetonitrile, benzonitrile, toluene, tetrahydrofuran, dimethylformamide, chloroform or dichloroethanes
At least one；
5) added into the compound imidazoles resin and the compound hydroxy imidazole resin of halogen-type is obtained after hydroxyhalide reaction；
Step 5) course of reaction is：Added into the compound imidazoles resin equivalent to compound imidazoles weight resin 30~300%
Hydroxyhalide X-R-OH, 300~1000% organic solvent, react 4~30 hours under reflux state, scrubbed, drying
After obtain halogen-type and be combined hydroxy imidazole resin；Wherein, the organic solvent be selected from acetonitrile, benzonitrile, toluene, tetrahydrofuran,
At least one of dimethylformamide, chloroform or dichloroethanes；X is Cl, Br or I in hydroxyhalide X-R-OH, and R is second
Base, propyl group, isopropyl, normal-butyl, isobutyl group, n-pentyl or n-hexyl；
6) it is combined in hydroxy imidazole resin to add to the halogen-type and the compound hydroxy imidazole of the strong base is obtained after highly basic is exchanged
Resin；
Step 6) course of reaction is：It is combined to add in hydroxy imidazole resin to the halogen-type and is combined hydroxyl miaow equivalent to halogen-type
The highly basic of azoles weight resin 20~200%, 200~2000% water, are stirred at room temperature 1~20 hour, through filtering, washing and
The strong base is obtained after drying and is combined hydroxy imidazole resin；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 produced 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 produced 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 produced 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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