CN102397786A - Catalyst for reactive synthesis of carbamate by urea and organic carbonic ester as well as preparation method and application thereof - Google Patents

Catalyst for reactive synthesis of carbamate by urea and organic carbonic ester as well as preparation method and application thereof Download PDF

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CN102397786A
CN102397786A CN2011103939183A CN201110393918A CN102397786A CN 102397786 A CN102397786 A CN 102397786A CN 2011103939183 A CN2011103939183 A CN 2011103939183A CN 201110393918 A CN201110393918 A CN 201110393918A CN 102397786 A CN102397786 A CN 102397786A
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catalyst
ureas
carbamates
organic carbonate
reaction synthesis
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王军威
亢茂青
王心葵
冯月兰
李其峰
赵雨花
殷宁
张清运
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

The invention discloses a catalyst for reactive synthesis of carbamate by urea and organic carbonic ester, which comprises the following components in percentage by weight: 1-20wt% of alkali metal oxide and the balance of carrier, wherein the alkali metal is selected from more than two of Li, Na, K, Rb and Cs; and the carrier is an oxide carrier or a molecular sieve carrier. The catalyst has the advantages of simple preparation process, low raw material cost, high target product yield and no pollution on the environment.

Description

Be used for catalyst and the method for making and the application of ureas and organic carbonate reaction synthesis of carbamates
Technical field
The invention belongs to a kind of Preparation of catalysts methods and applications of synthesis of carbamates, be specifically related to a kind of Catalysts and its preparation method and application that is applicable to ureas and organic carbonate prepared in reaction carbamate compound.
Background of invention
Methyl carbamate is one type of important fine chemicals, and is of many uses, can be used as amino group protection etc. in intermediate and the organic synthesis of agricultural chemicals, medicine, synthetic resin modification, organic synthesis.Carbamate compound is pharmaceutically obtaining application very early as downern, replaces second or propane diols diurethane as antiphlogistic, muscle relaxant, analgestic, antiepileptic etc. with phenyl, has also obtained better curative effect.Carbamate compound as pesticide, acaricide, herbicide and bactericide, has formed a big classification of agricultural chemicals on agricultural chemicals, wide in variety, good drug efficacy, low toxicity.Early stage kind has sevin (Carbaryl, N-methyl 2-naphthyl carbamate), MTMC (Tsumacide, N-methyl-2-tolyl carbamate) and the mould prestige of second (Diethofencarb, N-methyl-3,5-3,5-dimethylphenyl carbamate) etc.The just own ester of carbamic acid is used for STUDY ON THE MODIFICATION OF PENOLIC RESIN, can make phenolic resins have elasticity, the adhesive property that water absorption rate is low and good etc.As organic synthesis intermediate; Can be used for synthesizing isocyanate, nontoxic polyurethane, melamine derivative, dialkyl carbonate and polyvinylamine etc.; Carbamate can with reactions such as unsaturated hydrocarbons, aldehyde ketone, polyalcohol and aromatic ring; Generate the derivative of various uses, also can be used for heterocyclic compounds such as synthetic pyrroles, triazolone, quinazolinone and triazine.
The traditional mode of production of carbamate adopts phosgene route, exists toxicity big, shortcomings such as by-product hydrochloric acid etching apparatus.In recent years, the method for various non-phosgene route synthesis of carbamates constantly occurs, like organic amine and CO, O 2, the oxidization of methanol carbonyl process, the reduction carbonyl process of nitro compound and CO, methyl alcohol, though these routes have been avoided the use of phosgene, there are problems such as poor such as Atom economy, that the process security is lower in the ester-interchange methods of organic amine and carbonic ester etc.Though and the ureas alcoholysis method is able to promote with advantages such as its production security height, reaction condition gentlenesses, the generation of accessory substance amine is difficult to avoid, and Atom economy is relatively poor, and the separation costs of product is high.
With ureas and organic carbonate prepared in reaction carbamate, can reactant be converted into target product fully in theory, Atom economy is high, and reaction condition is gentle, and course of reaction is suc as formula shown in 1.
Figure BSA00000626883400011
According to above-mentioned reaction scheme, Chaudhari etc. adopt the Dibutyltin oxide catalyst, and (Journal of Molecular Catalysis A:Chemical 2004 223:85-92) successfully synthesizes multiple carbamate.Lee can congruence adopt methyl alcohol be contained in 90 ℃ by 1,3-diphenyl urea and dimethyl carbonate synthesize methyl phenyl carbamate (Chinese Chemical Letters 2007,18:149-151).These catalyst all belong to homogeneous catalyst, not only cost an arm and a leg, and are difficult to recycle.Afterwards, Lee understands congruence and again methoxyl group lead is used for this prepared in reaction phenyl urethan (petrochemical industry, 2009,38 (2): 145-148), but the toxicity of plumbous type of catalyst makes its popularization become difficulty.
The reaction of ureas and organic carbonate is a kind of atomic economy reaction of preparation carbamate, and existing at present multiple catalyst comes to light and can promote the carrying out that react, but still there are some above-mentioned problems in these catalyst.
Summary of the invention
The purpose of this invention is to provide that a kind of preparation process is simple, cost of material is low, target product yield is high, and the Catalysts and its preparation method and the application that are used for ureas and organic carbonate prepared in reaction carbamate compound that environment is not polluted.
The present invention is through alkali metal compound being loaded on the oxide carrier, preparing the high activity heterogeneous catalyst that is applicable to ureas and organic carbonate reaction synthesis of carbamates compounds through roasting process.
Catalyst of the present invention consists of: the weight percentage of alkali metal oxide in catalyst is 1～20%, is preferably 5～15%, more preferably 7～12%, and all the other are carrier.
Described alkali metal is Li, Na, K, Rb, Cs and two or more, and preferred alkali metal is Li, Na, K and two kinds.
Described carrier is oxide carrier or molecular sieve carrier, and oxide carrier is SiO 2, Al 2O 3, ZrO 2, TiO 2, ZnO, Fe 2O 3, La 2O 3, CeO 2, Mg-Al hydrotalcite, diatomite, clay or their mixture, preferably SiO 2, Al 2O 3, ZrO 2, TiO 2, La 2O 3Or their mixture.Molecular sieve carrier is Na-Y molecular sieve, Ca-Y molecular sieve, ZSM-5 molecular sieve or their mixture.Na-Y molecular sieve preferably.
Preparation of catalysts method of the present invention comprises following three kinds of methods:
Method 1, infusion process: adopt equi-volume impregnating, alkali metal compound is dissolved in the deionized water, be impregnated on the oxide carrier; Afterwards with drying 1～24h under the macerate room temperature, carry out drying in 90～120 ℃ again, be 6～48h drying time; Be preferably 12～20h; Carry out roasting after the drying, 300～700 ℃ of sintering temperatures are preferably 400～550 ℃; Roasting time is 0.5～10h, is preferably 2～6h; Preferred calcination atmosphere is an air.
Method 2, mechanical mixing: alkali metal compound and oxide carrier is mixed, after grinding, add the entry modulation evenly, compression molding is in 90～120 ℃ of dryings, and be 6～48h drying time, is preferably 12～20h.Carry out roasting after the drying, 350～800 ℃ of sintering temperatures are preferably 400～550 ℃; Roasting time is 0.5～10h, is preferably 2～6h; Preferred calcination atmosphere is an air.
Method 3, ion-exchange: the application of ion-exchange is the carrier of molecular sieve, and alkali metal compound is dissolved in the deionized water, is configured to the solution of 0.1～2.0M; Add molecular sieve carrier, be warming up to 90～100 ℃, 1～6h refluxes; Cooling back is taken out and is filtered, and spends deionised water to 3～6 time, after the filtration with filter cake in 90～120 ℃ of oven dry 2～12h; Transfer to roasting in 350～650 ℃ of scopes in the Muffle furnace again, preferred 450～550 ℃; Roasting time 0.5～10h, preferred 2～6h; Calcination atmosphere is an air, promptly obtains the ion-exchange catalyst of alkali metals modified.
For preparation method's 1 described alkali metal compound is water miscible hydroxide, carbonate, oxalates, nitrate, nitrite, alkoxide or halide.
The hydroxide, carbonate, oxalates, nitrate, nitrite, alkoxide or the halide that for preparation method's 2 described alkali metal compounds are.
For preparation method's 3 described alkali metal compounds is water miscible hydroxide, carbonate, oxalates or nitrate.
Application of Catalyst method of the present invention comprises the steps:
Ureas, organic carbonate and catalyst by proportion are added in the high-pressure reactor, and closed reactor behind the air in the employing nitrogen replacement reactor is heated to reaction temperature with reactor under stirring condition; 100～220 ℃ of reaction temperatures; Be preferably 120～180 ℃, most preferably be 140～170 ℃, reaction 1～10h; Preferred 1～6h, most preferably 2～4h.
The mol ratio of aforesaid urea and organic carbonate is 0.02～0.2, more preferably 0.03～0.1.Catalyst amount be in the reaction system urea and organic carbonate gross weight 0.5～10%, preferred use amount is 1～7%, more preferably 2～5%;
Aforesaid ureas comprises: urea, 1,3-diphenyl urea, N, N '-dimethyl urea, methyl, ethyl carbamide, thiocarbamide.
Aforesaid organic carbonate class comprises: dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, methyl-ethyl carbonate ester.
The raw material that the present invention compared with prior art has the preparation catalyst is easy to obtain, and the Preparation of catalysts process is simple, and catalyst is prone to separate, be easy to product recycling.In addition, such catalyst has higher carbamate productive rate, and environment is not polluted.
The specific embodiment
Combine the detailed description of embodiment through hereinafter, above-mentioned and other characteristic of the present invention, characteristic will be more readily understood, and these embodiment mode is by way of example illustrated principle of the present invention.These only are in order more clearly to describe the present invention for example, rather than scope of the present invention is limited.
The raw material that is used to prepare catalyst among the present invention be can be easily alkali metal compound and oxide through commercially available acquisition.
Following work embodiment carries out in being equipped with the 100ml high-pressure reactor of thermocouple, magnetic stirring apparatus.Urea, organic carbonate and catalyst are added in this reactor, charge into the air in the nitrogen replacement reactor.Closed reactor is heated to required temperature with reactor afterwards, keeps a period of time as be shown in the examples.Reaction is analyzed products therefrom with liquid chromatograph after accomplishing.With used urea is benchmark, calculates the conversion ratio and the carbamate productive rate of urea.
Embodiment 1
Accurately take by weighing 10.0gZrO 2And 0.6gLi 2CO 3, with Li 2CO 3Be impregnated into ZrO after being dissolved in the 6.0g deionized water 2On, room temperature is dried and is inserted behind the 4h in the baking oven in 110 ℃ of dry 12h, transfers in the Muffle furnace again under air atmosphere, 450 ℃ of roasting 6h, processes Li 2O/ZrO 2Catalyst.
With 30.0g dimethyl carbonate, 3.18g 1,3-diphenyl urea and 0.5g Li 2O/ZrO 2Catalyst is inserted in the 100mL autoclave, logical N 2In the displacement still behind the air, airtight autoclave, under stirring condition, be warming up to 160 ℃ after, keep 4h.Stop reaction afterwards, take out product after reducing to room temperature, carry out chromatography, 1, the conversion ratio of 3-diphenyl urea is 91.3%, the phenyl urethan yield is 74.3%.
Embodiment 2
Accurately take by weighing 10.0gCeO 2And 0.5gLiNO 3, with LiNO 3Be impregnated into CeO after being dissolved in the 5.0g deionized water 2On, room temperature is dried and is inserted behind the 4h in the baking oven in 110 ℃ of dry 12h, transfers in the Muffle furnace again under air atmosphere, 450 ℃ of roasting 4h, processes Li 2O/CeO 2Catalyst.
With 30.0g dimethyl carbonate, 3.18g 1, the above-mentioned Li of 3-diphenyl urea and 0.5g 2O/CeO 2Catalyst is inserted in the 100mL autoclave, under the reaction condition identical with embodiment 1, and 1, the conversion ratio of 3-diphenyl urea is 92.4%, the phenyl urethan yield is 85.8%.
Embodiment 3
With 30.0g dimethyl carbonate, 2.12g1, the Li among 3-diphenyl urea and the 0.5g embodiment 2 2O/CeO 2Catalyst is inserted in the 100mL autoclave, under the reaction condition identical with embodiment 1, and 1, the conversion ratio of 3-diphenyl urea is 94.5%, the phenyl urethan yield is 87.2%.
Embodiment 4
With 30.0g dimethyl carbonate, 2.12g 1, the Li among 3-diphenyl urea and the 0.5g embodiment 2 2O/CeO 2Catalyst is inserted in the 100mL autoclave, and under the reaction condition identical with embodiment 1, removing reaction temperature is 170 ℃, and 1, the conversion ratio of 3-diphenyl urea is 98.5%, the phenyl urethan yield is 89.6%.
Embodiment 5
With 30.0g dimethyl carbonate, 2.12g1, the Li among 3-diphenyl urea and the 0.5g embodiment 2 2O/CeO 2Catalyst is inserted in the 100mL autoclave, and under the reaction condition identical with embodiment 1, removing the reaction time is 6h, and 1, the conversion ratio of 3-diphenyl urea is 97.8%, the phenyl urethan yield is 91.4%.
Embodiment 6
Accurately take by weighing 10.0gNaY molecular sieve and 0.8gLiNO 3, with LiNO 3Be impregnated on the NaY after being dissolved in the 7.0g deionized water, room temperature is dried and is inserted behind the 6h in the baking oven in 110 ℃ of dry 12h, transfers in the Muffle furnace in 450 ℃ of roasting 4h again, processes Li 2O/NaY infusion process catalyst.
With 30.0g dimethyl carbonate, 3.18g 1, the above-mentioned Li of 3-diphenyl urea and 0.5g 2The O/NaY catalyst is inserted in the 100mL autoclave, under the reaction condition identical with embodiment 1, and 1, the conversion ratio of 3-diphenyl urea is 92.5%, the phenyl urethan yield is 78.4%.
Embodiment 7
Accurately take by weighing 10.0g γ-Al 2O 3And 0.6gLiNO 3, with LiNO 3Be impregnated into γ-Al after being dissolved in the 8.0g deionized water 2O 3On, room temperature is dried and is inserted behind the 4h in the baking oven in 110 ℃ of dry 12h, transfers in the Muffle furnace in 650 ℃ of roasting 4h again, processes Li 2O/Al 2O 3Catalyst.
With 30.0g dimethyl carbonate, 3.18g1, the above-mentioned Li of 3-diphenyl urea and 0.5g 2O/Al 2O 3Catalyst is inserted in the 100mL autoclave, under the reaction condition identical with embodiment 1, and 1, the conversion ratio of 3-diphenyl urea is 94.1%, the phenyl urethan yield is 73.6%.
Embodiment 8
Accurately take by weighing 10.0gTiO 2And 1.0gKNO 3, with KNO 3Be impregnated into TiO after being dissolved in the 6.0g deionized water 2On, room temperature is dried and is inserted behind the 6h in the baking oven in 110 ℃ of dry 12h, transfers in the Muffle furnace in 550 ℃ of roasting 4h again, processes K according to the condition of embodiment 1 2O/TiO 2Catalyst.
With 30.0g dimethyl carbonate, 3.18g1, the above-mentioned K/TiO of 3-diphenyl urea and 0.8g 2Catalyst is inserted in the 100mL autoclave, under the reaction condition identical with embodiment 1, and 1, the conversion ratio of 3-diphenyl urea is 86.5%, the phenyl urethan yield is 72.1%.
Embodiment 9
Accurately take by weighing 10.0gNaY molecular sieve and 6.5gLiNO 3, inserting in the three-neck flask that fills the 100.0mL deionized water, 90 ℃ of backflow 3h carry out ion-exchange, filter afterwards, and 110 ℃ of oven dry filter cake 6h transfer in the Muffle furnace roasting 4h under 450 ℃ of air atmospheres again, process Li 2O/Y ion-exchange catalyst.
With 30.0g dimethyl carbonate, 3.18g 1, the above-mentioned Li/Y catalyst of 3-diphenyl urea and 0.6g is inserted in the 100mL autoclave, under the reaction condition identical with embodiment 1, and 1, the conversion ratio of 3-diphenyl urea is 93.2%, the phenyl urethan yield is 76.1%.
Embodiment 10
Accurately take by weighing 4.0gCeO 2, 6.0g γ-Al 2O 3With 0.6g LiNO 3, in mortar, grind 20min after, add small amount of deionized water, mixed evenly back compressing tablet is put into baking oven again in 110 ℃ of dry 12h, inserts at last in the Muffle furnace in 550 ℃ of roasting 4h, processes mechanical mixing Li 2O/Al 2O 3-CeO 2Catalyst.
With 30.0g dimethyl carbonate, 3.18g1, the above-mentioned catalyst of 3-diphenyl urea and 0.5g is inserted in the 100mL autoclave, under the reaction condition identical with embodiment 1, and 1, the conversion ratio of 3-diphenyl urea is 90.1.2%, the phenyl urethan yield is 75.6%.
Embodiment 11
Accurately take by weighing 4.0gTiO 2, 6.0gSiO 2And 0.5gKNO 3, 0.3gLiNO 3, with KNO 3, LiNO 3Be dissolved in jointly in the 6.0g deionized water, be impregnated into the TiO of even ground and mixed after afterwards 2/ SiO 2On the mixture, room temperature is dried and is inserted behind the 6h in the baking oven in 110 ℃ of dry 18h, transfers in the Muffle furnace in 600 ℃ of roasting 4h again, processes Li according to the condition of embodiment 1 2O-K 2O/TiO 2-SiO 2Catalyst.
With 30.0g dimethyl carbonate, 3.18g1, the above-mentioned catalyst of 3-diphenyl urea and 0.5g is inserted in the 100mL autoclave, under the reaction condition identical with embodiment 1, and 1, the conversion ratio of 3-diphenyl urea is 90.7%, the phenyl urethan yield is 72.6%.
Embodiment 12
Accurately take by weighing 4.0gTiO 2, 6.0gCeO 2And 0.5gLiNO 3, both are mixed, in mortar, grind 20min, add small amount of deionized water, mixed evenly back compressing tablet is put into baking oven in 110 ℃ of oven dry 12h, transfers in the Muffle furnace in 450 ℃ of roasting 4h again, processes mechanical mixing Li/TiO 2-CeO 2Catalyst.
With 30.0g dimethyl carbonate, 2.12g 1, the above-mentioned catalyst of 3-diphenyl urea and 0.5g is inserted in the 100mL autoclave, under the reaction condition identical with embodiment 1, and 1, the conversion ratio of 3-diphenyl urea is 85.4%, the phenyl urethan yield is 77.5%.
Embodiment 13
With 30.0g dimethyl carbonate, 3.5gN, the 0.5g Li among N '-dimethyl urea and the embodiment 2 2O/CeO 2Catalyst is inserted in the 100mL autoclave, with embodiment 1 similar reaction condition under, except reaction temperature is 140 ℃, N, N '-dimethyl urea conversion ratio is 79.3%, the yield of N-methyl carbamate is 71.4%.
Embodiment 14
With 36.0g dibutyl carbonate, 2.1g1, the Li among 3-diphenyl urea and the 0.8g embodiment 2 2O/CeO 2Catalyst is inserted in the 100mL autoclave, under the reaction condition identical with embodiment 1, and 1, the conversion ratio of 3-diphenyl urea is 86.5%, the positive butyl ester yield of carbanilic acid is 78.6%.
Embodiment 15
With 40.0g diphenyl carbonate, 2.1g 1, the Li among 3-diphenyl urea and the 0.8g embodiment 2 2O/CeO 2Catalyst is inserted in the 100mL autoclave, under the reaction condition identical with embodiment 1, and 1, the conversion ratio of 3-diphenyl urea is 78.5%, carbanilic acid phenyl ester yield is 67.6%.

Claims (24)

1. catalyst that is used for ureas and organic carbonate reaction synthesis of carbamates, it is characterized in that catalyst consists of: the weight percentage of alkali metal oxide in catalyst is 1～20%, all the other are carrier;
Described alkali metal is Li, Na, K, Rb, Cs and two or more;
Described carrier is oxide carrier or molecular sieve carrier.
2. a kind of catalyst that is used for ureas and organic carbonate reaction synthesis of carbamates as claimed in claim 1 is characterized in that the weight percentage of described alkali metal oxide in catalyst is 5～15%.
3. a kind of catalyst that is used for ureas and organic carbonate reaction synthesis of carbamates as claimed in claim 2 is characterized in that the weight percentage of described alkali metal oxide in catalyst is 7～12%.
4. a kind of catalyst that is used for ureas and organic carbonate reaction synthesis of carbamates as claimed in claim 1 is characterized in that described alkali metal is Li, Na, K and two or more.
5. a kind of catalyst that is used for ureas and organic carbonate reaction synthesis of carbamates as claimed in claim 1 is characterized in that described oxide carrier is SiO 2, Al 2O 3, ZrO 2, TiO 2, ZnO, Fe 2O 3, La 2O 3, CeO 2, Mg-Al hydrotalcite, diatomite, clay or their mixture.
6. a kind of catalyst that is used for ureas and organic carbonate reaction synthesis of carbamates as claimed in claim 5 is characterized in that described oxide carrier is SiO 2, Al 2O 3, ZrO 2, TiO 2, La 2O 3Or their mixture.
7. a kind of catalyst that is used for ureas and organic carbonate reaction synthesis of carbamates as claimed in claim 1 is characterized in that described molecular sieve carrier is Na-Y molecular sieve, Ca-Y molecular sieve, ZSM-5 molecular sieve or their mixture.
8. a kind of catalyst that is used for ureas and organic carbonate reaction synthesis of carbamates as claimed in claim 7 is characterized in that described molecular sieve carrier Na-Y molecular sieve.
9. like described each a kind of Preparation of catalysts method that is used for ureas and organic carbonate reaction synthesis of carbamates of claim 1-8, it is characterized in that comprising the steps:
Adopt equi-volume impregnating, alkali metal compound is dissolved in the deionized water, be impregnated on the oxide carrier; Afterwards with drying 1～24h under the macerate room temperature; Carry out drying in 90～120 ℃ again, be 6～48h drying time, carries out roasting after the drying; Sintering temperature is 300～700 ℃, and roasting time is 0.5～10h.
10. a kind of Preparation of catalysts method that is used for ureas and organic carbonate reaction synthesis of carbamates as claimed in claim 9; It is characterized in that be 12～20h described drying time; Sintering temperature is 400～550 ℃, and roasting time is 2～6h, and calcination atmosphere is an air.
11., it is characterized in that described alkali metal compound is water miscible hydroxide, carbonate, oxalates, nitrate, nitrite, alkoxide or halide like claim 9 or 10 described a kind of Preparation of catalysts methods that are used for ureas and organic carbonate reaction synthesis of carbamates.
12., it is characterized in that comprising the steps: like described each a kind of Preparation of catalysts method that is used for ureas and organic carbonate reaction synthesis of carbamates of claim 1-8
Alkali metal compound and oxide carrier is mixed, after grinding, add the entry modulation evenly, compression molding is in 90～120 ℃ of dryings, and be 6～48h drying time.Carry out roasting after the drying, sintering temperature is 350～800 ℃, and roasting time is 0.5～10h.
13. a kind of Preparation of catalysts method that is used for ureas and organic carbonate reaction synthesis of carbamates as claimed in claim 12; It is characterized in that be 12～20h described drying time; Sintering temperature is 400～550 ℃, and roasting time is 2～6h, and calcination atmosphere is an air.
14., it is characterized in that described alkali metal compound is hydroxide, carbonate, oxalates, nitrate, nitrite, alkoxide or halide like claim 12 or 13 described a kind of Preparation of catalysts methods that are used for ureas and organic carbonate reaction synthesis of carbamates.
15., it is characterized in that comprising the steps: when carrier is molecular sieve, alkali metal compound being dissolved in the deionized water like claim 1,2,3,4,7 or 8 described each a kind of Preparation of catalysts methods that are used for ureas and organic carbonate reaction synthesis of carbamates; Be configured to the solution of 0.1～2.0M, add molecular sieve carrier, be warming up to 90～100 ℃; 1～the 6h that refluxes, the cooling back is taken out and is filtered, and spends deionised water to 3～6 time; After the filtration filter cake is dried 2～12h in 90～120 ℃; Roasting in 350～650 ℃ of scopes again, roasting time 0.5～10h, calcination atmosphere are air.
16. a kind of Preparation of catalysts method that is used for ureas and organic carbonate reaction synthesis of carbamates as claimed in claim 15 is characterized in that described sintering temperature is 450～550 ℃, roasting time is 2～6h.
17., it is characterized in that described alkali metal compound is water miscible hydroxide, carbonate, oxalates or nitrate like claim 15 or 16 described a kind of Preparation of catalysts methods that are used for ureas and organic carbonate reaction synthesis of carbamates.
18., it is characterized in that comprising the steps: like described each a kind of Application of Catalyst that is used for ureas and organic carbonate reaction synthesis of carbamates of claim 1-8
Ureas, organic carbonate and catalyst by proportion are added in the high-pressure reactor, and closed reactor behind the air in the employing nitrogen replacement reactor is heated to reaction temperature with reactor under stirring condition, 100～220 ℃ of reaction temperatures, reaction 1～10h;
The mol ratio of described urea and organic carbonate is 0.02～0.2, catalyst amount be in the reaction system urea and organic carbonate gross weight 0.5～10%.
19. a kind of Application of Catalyst that is used for ureas and organic carbonate reaction synthesis of carbamates as claimed in claim 18 is characterized in that described reaction temperature is 120～180 ℃, the reaction time is 1～6h.
20. a kind of Application of Catalyst that is used for ureas and organic carbonate reaction synthesis of carbamates as claimed in claim 19 is characterized in that described reaction temperature is 140～170 ℃, the reaction time is 2～4h.
21. a kind of Application of Catalyst that is used for ureas and organic carbonate reaction synthesis of carbamates as claimed in claim 18; The mol ratio that it is characterized in that described urea and organic carbonate is 0.03～0.1, catalyst amount be in the reaction system urea and organic carbonate gross weight 1～7%.
22. a kind of Application of Catalyst that is used for ureas and organic carbonate reaction synthesis of carbamates as claimed in claim 21, it is characterized in that described catalyst amount be in the reaction system urea and organic carbonate gross weight 2～5%.
23. like described each a kind of Application of Catalyst that is used for ureas and organic carbonate reaction synthesis of carbamates of claim 18-22; It is characterized in that described ureas is a urea, 1; 3-diphenyl urea, N, N '-dimethyl urea, methyl, ethyl carbamide or thiocarbamide.
24., it is characterized in that described organic carbonate class is dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate or methyl-ethyl carbonate ester like described each a kind of Application of Catalyst that is used for ureas and organic carbonate reaction synthesis of carbamates of claim 18-22.
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CN111971119A (en) * 2018-03-28 2020-11-20 科思创知识产权两合公司 Heterogeneous catalyst for carbamate synthesis

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CN101519390A (en) * 2008-02-28 2009-09-02 中国科学院大连化学物理研究所 Method for preparing propylene oxide

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CN103483224A (en) * 2013-10-14 2014-01-01 中国科学院山西煤炭化学研究所 Substituted urea alcoholysis method for synthesizing carbamate compounds
CN103524381A (en) * 2013-10-14 2014-01-22 中国科学院山西煤炭化学研究所 Synthesis of N-methylmethyl carbamate
CN105367439A (en) * 2015-09-07 2016-03-02 中国科学院福建物质结构研究所 Process method of co-production of oxamide and carbamic acid ester through ammonia ester exchange method
CN111971119A (en) * 2018-03-28 2020-11-20 科思创知识产权两合公司 Heterogeneous catalyst for carbamate synthesis
CN111971119B (en) * 2018-03-28 2023-12-08 科思创知识产权两合公司 Heterogeneous catalyst for carbamate synthesis

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