CN102516125A - Preparation method of alkyl substitution diphenylmethane diisocyanate - Google Patents
Preparation method of alkyl substitution diphenylmethane diisocyanate Download PDFInfo
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Abstract
The invention discloses a preparation method of alkyl substitution diphenylmethane diisocyanate, which includes the following steps: weighing alkylaniline and urea, placing the alkylaniline and the urea in a reactor, heating the alkylaniline and the urea to the temperature ranging from 100 DEG C to 200 DEG C, stirring the mixture for 10 to 20 minutes, stopping reaction when red liquid is changed to solid, cooling the mixture to the room temperature, washing the mixture for 3 to 6 times through alcohol to obtain dialkyl group diphenyl urea, adding dimethyl carbonate into dialkyl group diphenyl urea, conducting back flowing reaction on the mixture under the temperature ranging from 110 DEG C to 250 DEG C for 6 to 12 hours, adding sodium methoxide into the mixture, conducting filtering after reaction is finished, conducting reduced pressure distillation on filtering liquid, conducting crystallization on normal hexane to obtain alkyl aniline methyl formate, adding lewis acid and methylation agent into the alkyl aniline methyl formate, increasing the temperature to the range from 70 DEG C to 100 DEG C, conducting reaction for 4 to 7 hours, cooling the mixture to the room temperature, conducting filtering on the mixture and washing the mixture through alcohol for 3 to 6 times to obtain alkyl aniline methyl formate and conducting decomposition reaction on the dialkyl group diphenylmethane dicarbamic acid ester. The preparation method of the alkyl substitution diphenylmethane diisocyanate is strong in stability, low in toxicity and controllable in reaction process.
Description
Technical field
The present invention relates to a kind of preparation method of diphenylmethanediisocyanate, is the preparation method of the substituted diphenylmethanediisocyanate of a kind of alkyl specifically.
Background technology
Isocyanic ester is one of starting material of synthesis of polyurethane resin, at civil area or military domain application is very widely arranged all.The domestic main employing of isocyanate-monomer at present is more has these two kinds of toluene-2,4-diisocyanate (TDI) and diphenyl-methane-group diisocyanates (MDI), and its preparation method is main with phosgenation generally then, and this method is to utilize phosgene amino (NH
2) change into isocyanate groups (NCO).Yet phosgenation prepares TDI and MDI exists two significant deficiency.One of which; Phosgene active high with other raw material reaction the time, be difficult to the stability of its reaction of control, and the activity of phosgene can change along with the variation of its content in reaction process; When preparation TDI or MDI, can produce more by product; So when phosgenation prepared TDI or MDI, the usage quantity of phosgene will take excessive at least 50% air flow to reduce the generation of side reaction usually.Its two, phosgene is very big to the toxicity of human body, and is very serious to the pollution of environment, thus its transportation, store and difficulty of using all bigger.In fact, the operational path of synthetic TDI of phosgenation and MDI is longer, technical sophistication, and raw materials cost is expensive, and cost of equipment is high.And, it is applied in all the time can not be on a large scale, and receive strict control because of the high reactivity of phosgene self and strong toxic effect.Therefore, how adopting non-phosgene to prepare TDI and MDI, is the last great technical barrier that remains to be captured of present isocyanic ester industry.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, the preparation method of the substituted diphenylmethanediisocyanate of alkyl that a kind of reaction stability is strong, toxicity is low and reaction process is easy to control is provided.
Goal of the invention of the present invention is achieved in that the preparation method of the substituted diphenylmethanediisocyanate of a kind of alkyl, it is characterized in that: said preparation method may further comprise the steps:
A: take by weighing alkyl benzene amine and urea places in the reactor drum according to suitable proportioning, the mol ratio of alkyl benzene amine and urea is 2-2.6:1;
B: evenly stir and slowly be warming up to 100-200 ℃, continue to stir 10-20 minute after reaching relevant temperature, and feed tail gas in the water and to absorb;
C: question response becomes solid by red liquid and gets final product stopped reaction, and naturally cools to room temperature;
D: the solid in the c step is promptly got the dialkyl group diphenyl urea 3-6 time with the alcohol flushing;
E: add methylcarbonate in the dialkyl group diphenyl urea that in the d step, obtains, and 110-250 ℃ of environment refluxed reaction 6-12 hour, keeping the mol ratio of dialkyl group diphenyl urea and methylcarbonate was 1:4-10;
F: add sodium methylate during back flow reaction in the e step, reaction stops after-filtration;
G: draw flaxen solid to the filtrate decompression distillation that in the f step, draws, can obtain korenyl amido methyl-formiate with the normal hexane recrystallization;
H: add Lewis acid and methylenation reagent in the korenyl amido methyl-formiate that in the g step, draws, and evenly stir, keeping the mol ratio of korenyl amido methyl-formiate and methylenation reagent is 1:2-5;
I: be promoted to 70-100 ℃ to the mixture temperature of h step and reacted 4-7 hour, naturally cool to room temperature after question response stops;
J: filter the reaction product in the i step,, promptly get the dialkyl group diphenyl methane diamino formic ether with 3-6 after drying of alcohol flushing;
L: be added to the dialkyl group diphenyl methane diamino formic ether and carry out decomposition reaction in solvent and the catalyzer, can draw the substituted diphenylmethanediisocyanate of alkyl after separating solvent and catalyzer.
The alkyl of said alkyl benzene amine is that a kind of or mentioned component of methyl, ethyl, propyl group, butyl, amyl group and hexyl mixes by arbitrary proportion.
Alcohol among said steps d and the step j is methyl alcohol and alcoholic acid is a kind of or mentioned component mixes by arbitrary proportion.
Said methylenation reagent is that a kind of or mentioned component of formaldehyde, trioxymethylene and Paraformaldehyde 96 mixes by arbitrary proportion.
Said step h Central Asia methylating reagent is that intermittent type drips.
Said step h Central Asia methylating reagent is that continous way drips.
Catalyzer among the said step l is that a kind of or mentioned component in the inorganic or organic cpds of carbide and oxide compound, antimony, bismuth of quaternary ammonium salt, polynite, five phosphorus oxide, oxidation sulfoxide, boron and oxide compound thereof, copper, zinc, titanium, zirconium, vanadium mixes by arbitrary proportion.
Solvent among the said step l is that a kind of or mentioned component of naphthalane, Witcizer 300, dipropyl phthalate, dimethyl phthalate, certain herbaceous plants with big flowers two dioctyl phthalates, chlorobenzene, dichlorobenzene, toluene, YLENE, trimethylbenzene and phenyl ether mixes by arbitrary proportion.
The present invention has the following advantages:
1, the preparation of the substituted diphenylmethanediisocyanate of alkyl of the present invention adopts decomposition method to carry out; Replace present high reactivity phosgene with SA raw material; Except the stability that makes reaction is able to guarantee; Also improve the productive rate and the yield rate of diphenyl-methane-group diisocyanate (MDI) greatly, reduced the generation of side reaction and sub product, improved its reaction efficiency.Simultaneously, method of the present invention adopts the lower raw material of chemically reactive, and adopts dripping method to prepare, and effectively improves the uncontrollable phenomenon of synthetic reaction process and speed.
2, the preparation method of the substituted diphenylmethanediisocyanate of alkyl of the present invention adopts the hypotoxicity raw material to replace strong toxicity phosgene; Because the toxicity of raw material own is lower; Can effectively reduce the toxic influence of raw material in transportation, storage and the production process, be beneficial to the popularization that diphenylmethanediisocyanate is made.In addition, the hypotoxicity raw material can reduce environmental pollution, reduces the cost of production unit, therefore can significantly reduce production cost.
Embodiment
The preparation method of the substituted diphenylmethanediisocyanate of alkyl of the present invention mainly may further comprise the steps:
A: take by weighing alkyl benzene amine and urea places in the reactor drum according to suitable proportioning, the mol ratio of alkyl benzene amine and urea is 2-2.6:1;
B: evenly stir and slowly be warming up to 100-200 ℃, continue to stir 10-20 minute after reaching relevant temperature, and feed tail gas in the water and to absorb;
C: question response becomes solid by red liquid and gets final product stopped reaction, and naturally cools to room temperature;
D: the solid in the c step is promptly got the dialkyl group diphenyl urea 3-6 time with the alcohol flushing;
E: add methylcarbonate in the dialkyl group diphenyl urea that in the d step, obtains, and 110-250 ℃ of environment refluxed reaction 6-12 hour, keeping the mol ratio of dialkyl group diphenyl urea and methylcarbonate was 1:4-10;
F: add sodium methylate during back flow reaction in the e step, reaction stops after-filtration;
G: draw flaxen solid to the filtrate decompression distillation that in the f step, draws, can obtain korenyl amido methyl-formiate with the normal hexane recrystallization;
H: add Lewis acid and methylenation reagent in the korenyl amido methyl-formiate that in the g step, draws, and evenly stir, keeping the mol ratio of korenyl amido methyl-formiate and methylenation reagent is 1:2-5;
I: be promoted to 70-100 ℃ to the mixture temperature of h step and reacted 4-7 hour, naturally cool to room temperature after question response stops;
J: filter the reaction product in the i step,, promptly get the dialkyl group diphenyl methane diamino formic ether with 3-6 after drying of alcohol flushing;
L: be added to the dialkyl group diphenyl methane diamino formic ether and carry out decomposition reaction in solvent and the catalyzer, can draw the substituted diphenylmethanediisocyanate of alkyl after separating solvent and catalyzer.
The alkyl of alkyl benzene amine of the present invention is that a kind of or mentioned component of methyl, ethyl, propyl group, butyl, amyl group and hexyl mixes by arbitrary proportion; And alkyl benzene amine can be selected a kind of of an adjacent alkyl benzene amine and an alkyl benzene amine for use; Or the two mixture; An adjacent alkyl benzene amine and an alkyl benzene amine all have higher chemical reaction stability, are not easy to occur side reaction and by product in the reaction process.The alcohol that cleans usefulness can adopt methyl alcohol or ethanol, or both mixtures.Because methyl alcohol or alcoholic acid molecular weight are less, the molecular chain penetrating power is strong, so its cleaning performance is better.Methylenation reagent can adopt formaldehyde, trioxymethylene and Paraformaldehyde 96 or above-mentioned three's mixture.The adding mode of methylenation reagent has intermittent type to drip with continuity to drip two kinds, and dripping method can ensure that methylenation reagent is added to after the reaction system complete reaction rapidly, the productive rate of raising chemical reaction.In the decomposition reaction of dialkyl group diphenyl methane diamino formic ether; The mixture that catalyzer can adopt a kind of or above-mentioned any one-tenth in the inorganic or organic cpds of carbide and oxide compound, antimony, bismuth of quaternary ammonium salt, polynite, five phosphorus oxide, oxidation sulfoxide, boron and oxide compound thereof, copper, zinc, titanium, zirconium, vanadium to be grouped into; Above-mentioned catalyzer only reacts with the chain portion of separating of dialkyl group diphenyl methane diamino formic ether molecular chain; And its chemicalstability is higher, also is easy to decompose.In addition; The solvent of dialkyl group diphenyl methane diamino formic ether can adopt any mixture of a kind of or mentioned component in naphthalane, Witcizer 300, dipropyl phthalate, dimethyl phthalate, certain herbaceous plants with big flowers two dioctyl phthalates, chlorobenzene, dichlorobenzene, toluene, YLENE, trimethylbenzene and the phenyl ether; Above-mentioned solvent can significantly improve the solubleness of dialkyl group diphenyl methane diamino formic ether, and can not disturb carrying out smoothly of decomposition reaction.Temperature of reaction of the present invention is set in 70-250 ℃, and whole chemical reaction can be carried out under the environment of a gentleness, has avoided speed of response too fast or the phenomenon of side reaction occurs.Through test, adopt the substituted diphenylmethanediisocyanate of alkyl of decomposition method preparation of the present invention, productive rate can reach 48-60% in the preparation of korenyl amido methyl-formiate, and productive rate can reach 50%-65% in the preparation of dialkyl group diphenyl methane diamino formic ether.
Be elaborated in the face of each embodiment down, but therefore do not limit the invention in the said scope of embodiments:
Embodiment 1
The preparation method of the substituted diphenylmethanediisocyanate of alkyl may further comprise the steps:
A: take by weighing monomethylaniline, propyl group aniline and butylaniline mixture and urea places in the reactor drum according to suitable proportioning, the mol ratio of monomethylaniline, propyl group aniline and butylaniline mixture and urea is 2:1;
B: evenly stir and slowly be warming up to 100 ℃, continue to stir 10 minutes after reaching relevant temperature, and feed tail gas in the water and to absorb;
C: question response becomes solid by red liquid and gets final product stopped reaction, and naturally cools to room temperature;
D: the solid in the c step is promptly got the dialkyl group diphenyl urea 3 times with washed with methanol;
E: add methylcarbonate in the dialkyl group diphenyl urea that in the d step, obtains, and 110 ℃ of environment refluxed reactions 6 hours, keeping the mol ratio of dialkyl group diphenyl urea and methylcarbonate was 1:4;
F: add sodium methylate during back flow reaction in the e step, reaction stops after-filtration;
G: draw flaxen solid to the filtrate decompression distillation that in the f step, draws, can obtain korenyl amido methyl-formiate with the normal hexane recrystallization, its productive rate is 48%;
H: add formaldehyde and trioxymethylene mixture and Lewis acid in the korenyl amido methyl-formiate that in the g step, draws; And evenly stir; Keeping the mol ratio of korenyl amido methyl-formiate and formaldehyde and trioxymethylene mixture is 1:2, and formaldehyde and trioxymethylene mixture adopt the intermittent type dripping method to be added in the reaction system;
I: be promoted to 70 ℃ to the mixture temperature of h step and reacted 4 hours, naturally cool to room temperature after question response stops;
J: filter the reaction product in the i step,, promptly get the dialkyl group diphenyl methane diamino formic ether with 3 after drying of washed with methanol;
L: be added to the dialkyl group diphenyl methane diamino formic ether in Witcizer 300, dipropyl phthalate, dimethyl phthalate and certain herbaceous plants with big flowers two dioctyl phthalate mixtures and quaternary ammonium salt, polynite, five phosphorus oxide and the oxidation sulfoxide mixture and carry out decomposition reaction; Can draw the substituted diphenylmethanediisocyanate of alkyl behind the mixture of separation Witcizer 300, dipropyl phthalate, dimethyl phthalate and certain herbaceous plants with big flowers two dioctyl phthalate mixtures and quaternary ammonium salt, polynite, five phosphorus oxide and oxidation sulfoxide, its productive rate is 50%.
Embodiment 2
The preparation method of the substituted diphenylmethanediisocyanate of alkyl may further comprise the steps:
A: take by weighing monomethylaniline, MEA and amyl aniline mixture and urea places in the reactor drum according to suitable proportioning, the mol ratio of monomethylaniline, MEA and amyl aniline mixture and urea is 2.6:1;
B: evenly stir and slowly be warming up to 200 ℃, continue to stir 20 minutes after reaching relevant temperature, and feed tail gas in the water and to absorb;
C: question response becomes solid by red liquid and gets final product stopped reaction, and naturally cools to room temperature;
D: the solid in the c step is promptly got the dialkyl group diphenyl urea 6 times with washed with methanol;
E: add methylcarbonate in the dialkyl group diphenyl urea that in the d step, obtains, and 250 ℃ of environment refluxed reactions 12 hours, keeping the mol ratio of dialkyl group diphenyl urea and methylcarbonate was 1:10;
F: add sodium methylate during back flow reaction in the e step, reaction stops after-filtration;
G: draw flaxen solid to the filtrate decompression distillation that in the f step, draws, can obtain korenyl amido methyl-formiate with the normal hexane recrystallization, its productive rate is 60%;
H: add formaldehyde, trioxymethylene and Paraformaldehyde 96 mixture and Lewis acid in the korenyl amido methyl-formiate that in the g step, draws; And evenly stir; Keeping the mol ratio of korenyl amido methyl-formiate and formaldehyde, trioxymethylene and Paraformaldehyde 96 mixture is 1:5, and formaldehyde, trioxymethylene and Paraformaldehyde 96 mixture adopt the intermittent type dripping method to be added in the reaction system;
I: be promoted to 100 ℃ to the mixture temperature of h step and reacted 7 hours, naturally cool to room temperature after question response stops;
J: filter the reaction product in the i step,, promptly get the dialkyl group diphenyl methane diamino formic ether with 6 after drying of washed with methanol;
L: be added to the dialkyl group diphenyl methane diamino formic ether in the hopcalite of carbide and vanadium of naphthalane, chlorobenzene, dichlorobenzene, toluene, YLENE and phenyl ether mixture and five phosphorus oxide, oxidation sulfoxide, zirconium and carry out decomposition reaction; Can draw the substituted diphenylmethanediisocyanate of alkyl behind the carbide of separation naphthalane, chlorobenzene, dichlorobenzene, toluene, YLENE and phenyl ether mixture and five phosphorus oxide, oxidation sulfoxide, zirconium and the hopcalite of vanadium, its productive rate is 65%.
Embodiment 3
The preparation method of the substituted diphenylmethanediisocyanate of alkyl may further comprise the steps:
A: take by weighing MEA and butylaniline mixture and urea according to suitable proportioning and place in the reactor drum, the mol ratio of MEA and butylaniline mixture and urea is 2.2:1;
B: evenly stir and slowly be warming up to 120 ℃, continue to stir 17 minutes after reaching relevant temperature, and feed tail gas in the water and to absorb;
C: question response becomes solid by red liquid and gets final product stopped reaction, and naturally cools to room temperature;
D: the solid in the c step is promptly got the dialkyl group diphenyl urea 4 times with washed with methanol;
E: add methylcarbonate in the dialkyl group diphenyl urea that in the d step, obtains, and 130 ℃ of environment refluxed reactions 7 hours, keeping the mol ratio of dialkyl group diphenyl urea and methylcarbonate was 1:6;
F: add sodium methylate during back flow reaction in the e step, reaction stops after-filtration;
G: draw flaxen solid to the filtrate decompression distillation that in the f step, draws, can obtain korenyl amido methyl-formiate with the normal hexane recrystallization, its productive rate is 50%;
H: add trioxymethylene and Paraformaldehyde 96 mixture and Lewis acid in the korenyl amido methyl-formiate that in the g step, draws; And evenly stir; Keeping the mol ratio of korenyl amido methyl-formiate and trioxymethylene and Paraformaldehyde 96 mixture is 1:3, and trioxymethylene and Paraformaldehyde 96 mixture adopt the continous way dripping method to be added in the reaction system;
I: be promoted to 80 ℃ to the mixture temperature of h step and reacted 5 hours, naturally cool to room temperature after question response stops;
J: filter the reaction product in the i step,, promptly get the dialkyl group diphenyl methane diamino formic ether with 5 after drying of washed with methanol;
L: be added to the dialkyl group diphenyl methane diamino formic ether in the hopcalite of carbide and vanadium of naphthalane, chlorobenzene, toluene and phenyl ether mixture and five phosphorus oxide, zirconium and carry out decomposition reaction; Can draw the substituted diphenylmethanediisocyanate of alkyl behind the carbide of separation naphthalane, chlorobenzene, toluene and phenyl ether mixture and five phosphorus oxide, zirconium and the hopcalite of vanadium, its productive rate is 57%.
Embodiment 4
The preparation method of the substituted diphenylmethanediisocyanate of alkyl may further comprise the steps:
A: take by weighing propyl group aniline and hexyl benzene amine mixt and urea according to suitable proportioning and place in the reactor drum, the mol ratio of propyl group aniline and hexyl benzene amine mixt and urea is 2.4:1;
B: evenly stir and slowly be warming up to 140 ℃, continue to stir 18 minutes after reaching relevant temperature, and feed tail gas in the water and to absorb;
C: question response becomes solid by red liquid and gets final product stopped reaction, and naturally cools to room temperature;
D: the solid in the c step is promptly got the dialkyl group diphenyl urea 5 times with washed with methanol;
E: add methylcarbonate in the dialkyl group diphenyl urea that in the d step, obtains, and 160 ℃ of environment refluxed reactions 8 hours, keeping the mol ratio of dialkyl group diphenyl urea and methylcarbonate was 1:5;
F: add sodium methylate during back flow reaction in the e step, reaction stops after-filtration;
G: draw flaxen solid to the filtrate decompression distillation that in the f step, draws, can obtain korenyl amido methyl-formiate with the normal hexane recrystallization, its productive rate is 54%;
H: add trioxymethylene and Paraformaldehyde 96 mixture and Lewis acid in the korenyl amido methyl-formiate that in the g step, draws; And evenly stir; Keeping the mol ratio of korenyl amido methyl-formiate and trioxymethylene and Paraformaldehyde 96 mixture is 1:4, and trioxymethylene and Paraformaldehyde 96 mixture adopt the intermittent type dripping method to be added in the reaction system;
I: be promoted to 90 ℃ to the mixture temperature of h step and reacted 5.5 hours, naturally cool to room temperature after question response stops;
J: filter the reaction product in the i step,, promptly get the dialkyl group diphenyl methane diamino formic ether with 4 after drying of washed with methanol;
L: be added to the dialkyl group diphenyl methane diamino formic ether in the hopcalite of Witcizer 300, chlorobenzene, toluene and phenyl ether mixture and polynite, quaternary ammonium salt and vanadium and carry out decomposition reaction; Can draw the substituted diphenylmethanediisocyanate of alkyl behind the hopcalite of separation Witcizer 300, chlorobenzene, toluene and phenyl ether mixture and polynite, quaternary ammonium salt and vanadium, its productive rate is 58%.
Embodiment 5
The preparation method of the substituted diphenylmethanediisocyanate of alkyl may further comprise the steps:
A: take by weighing MEA and hexyl benzene amine mixt and urea according to suitable proportioning and place in the reactor drum, the mol ratio of MEA and hexyl benzene amine mixt and urea is 2.5:1;
B: evenly stir and slowly be warming up to 170 ℃, continue to stir 19 minutes after reaching relevant temperature, and feed tail gas in the water and to absorb;
C: question response becomes solid by red liquid and gets final product stopped reaction, and naturally cools to room temperature;
D: the solid in the c step is promptly got the dialkyl group diphenyl urea 4 times with washed with methanol;
E: add methylcarbonate in the dialkyl group diphenyl urea that in the d step, obtains, and 220 ℃ of environment refluxed reactions 10 hours, keeping the mol ratio of dialkyl group diphenyl urea and methylcarbonate was 1:8;
F: add sodium methylate during back flow reaction in the e step, reaction stops after-filtration;
G: draw flaxen solid to the filtrate decompression distillation that in the f step, draws, can obtain korenyl amido methyl-formiate with the normal hexane recrystallization, its productive rate is 58%;
H: add trioxymethylene and Lewis acid in the korenyl amido methyl-formiate that in the g step, draws; And evenly stir; Keeping the mol ratio of korenyl amido methyl-formiate and trioxymethylene is 1:3.5, and trioxymethylene adopts the intermittent type dripping method to be added in the reaction system;
I: be promoted to 85 ℃ to the mixture temperature of h step and reacted 5 hours, naturally cool to room temperature after question response stops;
J: filter the reaction product in the i step,, promptly get the dialkyl group diphenyl methane diamino formic ether with 4 after drying of washed with methanol;
L: be added to the dialkyl group diphenyl methane diamino formic ether in the hopcalite of inorganics and vanadium of Witcizer 300, dipropyl phthalate, toluene and phenyl ether mixture and polynite, quaternary ammonium salt, bismuth and carry out decomposition reaction; Can draw the substituted diphenylmethanediisocyanate of alkyl behind the inorganics of separation Witcizer 300, dipropyl phthalate, toluene and phenyl ether mixture and polynite, quaternary ammonium salt, bismuth and the hopcalite of vanadium, its productive rate is 62%.
Claims (8)
1. the preparation method of the substituted diphenylmethanediisocyanate of alkyl, it is characterized in that: said preparation method may further comprise the steps:
A: take by weighing alkyl benzene amine and urea places in the reactor drum according to suitable proportioning, the molar ratio of alkyl benzene amine and urea is 2-2.6:1;
B: evenly stir and slowly be warming up to 100-200 ℃, continue to stir 10-20 minute after reaching relevant temperature, and feed tail gas in the water and to absorb;
C: question response becomes solid by red liquid and gets final product stopped reaction, and naturally cools to room temperature;
D: the solid in the c step is promptly got the dialkyl group diphenyl urea 3-6 time with the alcohol flushing;
E: add methylcarbonate in the dialkyl group diphenyl urea that in the d step, obtains, and 110-250 ℃ of environment refluxed reaction 6-12 hour, keeping the mol ratio of dialkyl group diphenyl urea and methylcarbonate was 1:4-10;
F: add sodium methylate during back flow reaction in the e step, reaction stops after-filtration;
G: draw flaxen solid to the filtrate decompression distillation that in the f step, draws, can obtain korenyl amido methyl-formiate with the normal hexane recrystallization;
H: add Lewis acid and methylenation reagent in the korenyl amido methyl-formiate that in the g step, draws, and evenly stir, keeping the mol ratio of korenyl amido methyl-formiate and methylenation reagent is 1:2-5;
I: be promoted to 70-100 ℃ to the mixture temperature of h step and reacted 4-7 hour, naturally cool to room temperature after question response stops;
J: filter the reaction product in the i step,, promptly get the dialkyl group diphenyl methane diamino formic ether with 3-6 after drying of alcohol flushing;
L: be added to the dialkyl group diphenyl methane diamino formic ether and carry out decomposition reaction in solvent and the catalyzer, can draw the substituted diphenylmethanediisocyanate of alkyl after separating solvent and catalyzer.
2. according to the preparation method of the substituted diphenylmethanediisocyanate of the said alkyl of claim 1, it is characterized in that: the alkyl of said alkyl benzene amine is that a kind of or mentioned component of methyl, ethyl, propyl group, butyl, amyl group and hexyl mixes by arbitrary proportion.
3. according to the preparation method of the substituted diphenylmethanediisocyanate of the said alkyl of claim 1, it is characterized in that: the alcohol among said steps d and the step j is methyl alcohol and alcoholic acid is a kind of or mentioned component mixes by arbitrary proportion.
4. according to the preparation method of the substituted diphenylmethanediisocyanate of the said alkyl of claim 1, it is characterized in that: said methylenation reagent is that a kind of or mentioned component of formaldehyde, trioxymethylene and Paraformaldehyde 96 mixes by arbitrary proportion.
5. according to the preparation method of the substituted diphenylmethanediisocyanate of the said alkyl of claim 1, it is characterized in that: said step h Central Asia methylating reagent is that intermittent type drips.
6. according to the preparation method of the substituted diphenylmethanediisocyanate of the said alkyl of claim 1, it is characterized in that: said step h Central Asia methylating reagent is that continous way drips.
7. according to the preparation method of the substituted diphenylmethanediisocyanate of the said alkyl of claim 1, it is characterized in that: the catalyzer among the said step l is that a kind of or mentioned component in the inorganic or organic cpds of carbide and oxide compound, antimony, bismuth of quaternary ammonium salt, polynite, five phosphorus oxide, oxidation sulfoxide, boron and oxide compound thereof, copper, zinc, titanium, zirconium, vanadium mixes by arbitrary proportion.
8. according to the preparation method of the substituted diphenylmethanediisocyanate of the said alkyl of claim 1, it is characterized in that: the solvent among the said step l is that a kind of or mentioned component of naphthalane, Witcizer 300, dipropyl phthalate, dimethyl phthalate, certain herbaceous plants with big flowers two dioctyl phthalates, chlorobenzene, dichlorobenzene, toluene, YLENE, trimethylbenzene and phenyl ether mixes by arbitrary proportion.
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| CN110981753A (en) * | 2019-12-19 | 2020-04-10 | 山东华阳农药化工集团有限公司 | Preparation of diphenyl ethane diisocyanate by dimethyl carbonate method and application thereof |
| CN113666845A (en) * | 2021-07-21 | 2021-11-19 | 南京工业大学 | Lignin-based diphenylmethane diisocyanate and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110981753A (en) * | 2019-12-19 | 2020-04-10 | 山东华阳农药化工集团有限公司 | Preparation of diphenyl ethane diisocyanate by dimethyl carbonate method and application thereof |
| CN113666845A (en) * | 2021-07-21 | 2021-11-19 | 南京工业大学 | Lignin-based diphenylmethane diisocyanate and preparation method and application thereof |
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