CN105263618B

CN105263618B - Solid catalyst and used the solid catalyst isocyanate compound manufacture method

Info

Publication number: CN105263618B
Application number: CN201480029670.4A
Authority: CN
Inventors: 川口达也; 原田崇司; 德安和也; 山本祥史
Original assignee: Ube Industries Ltd
Current assignee: Ube Corp
Priority date: 2013-05-24
Filing date: 2014-05-22
Publication date: 2018-02-16
Anticipated expiration: 2034-05-22
Also published as: CN105263618A; JP6372484B2; WO2014189120A1; JPWO2014189120A1

Abstract

The problem of the present invention is, repeatability provides well can manufacture isocyanate compound with high selectivity and in high yield and with the easy catalyst of separation of product etc..The present invention relates to containing the solid catalyst that is at least one kind of metallic compound and silica and meeting 2 following conditions simultaneously in alkali metal compound and alkali earth metallic compound, the manufacture method of isocyanate compound for utilizing carbamate compounds to manufacture isocyanate compound in the presence of the catalyst is further related to：(1) it is 0.5~20 using the metallic atom of x-ray photoelectron analytical equipment measure, described metallic compound and the atomic ratio (M/Si) of the silicon atom in the silica.(2) it is 0.01m using the specific surface area of the solid catalyst of nitrogen adsorption methods measure²/ g~50m²/g。

Description

Solid catalyst and used the solid catalyst isocyanate compound system Make method

Technical field

The present invention relates to a kind of at least one kind of metal containing in alkali metal compound and alkali earth metallic compound The solid catalyst of compound and silica.Moreover, it relates to manufactured in the presence of described solid catalyst The method of isocyanate compound.

Background technology

Isocyanate compound is that the manufacture raw material such as carbamate or medical agricultural chemicals is widely used Useful compound.In the past, isocyanate compound was industrially to be manufactured by the reaction of amine and phosgene (referring for example to special Sharp document 1).

As the manufacture method of the isocyanate compound without using phosgene, for example, it is known have make three haloacetyl amines Compound carries out the side of haloform in the presence of the haloid of alkali metal or the catalyst such as haloid of alkaline-earth metal Method (referring for example to patent document 2).

In addition, the manufacture method as the isocyanate compound without using phosgene, it is also known that have amino for example The method of formic acid ester compound thermal decomposition (referring for example to patent document 3).

As the method for manufacturing isocyanate compound by the carbamate compounds using homogeneous catalyst, such as Proposed method (example carbamate compounds decomposed in the liquid phase and with organotin catalysts and solid acid catalyst As with reference to patent document 4).

Thermal decomposition of these the known tin catalysts for carbamate compounds shows suitable reaction achievement.

And on the other hand, it was also proposed that cross and carbamate compounds are thermally decomposed using heterogeneous catalysis and manufacture isocyanide The method of ester compound.

It is known to have following method：As described heterogeneous catalysis, calcium oxide, magnesia, barium monoxide, magnesium gold are used Category etc., toluene diethylamino formic acid esters is thermally decomposed to manufacture isocyanate compound as carbamate compounds (referring for example to patent document 3)；As heterogeneous catalysis, using sodium carbonate, calcium carbonate etc., by N- (isopropenyl-α, α- Dimethyl benzyl) carbamic acid such as carbamic acid isopropyl ester, N- (vinyl-alpha, alpha-dimethylbenzyl) carbamic acid isopropyl ester Ester compounds are thermally decomposed to manufacture isocyanate compound (for example, referring to patent document 5 and patent document 6).

On the other hand, as using heterogeneous catalysis, without using solvent, make carbamate under gas phase condition with urging Agent contacts, and is thermally decomposed to manufacture the method for isocyanate compound, such as known has following method etc.：As catalysis Agent, using at least one kind of in the IB races in periodic table or the transition metal of VIII, lanthanide and actinides The oxidate sintered body of element above or the oxidate sintered body containing alkali metal and/or alkaline-earth metal element, come Manufacture isocyanate compound (referring for example to patent document 7 and patent document 8).

In addition, it further developed and be loaded with being selected from alkali metal compound and alkaline-earth metal on silica supports The isocyanate compound catalyst for producing of at least one kind of metallic compound in compound (referring for example to patent document 9).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 11-310566 publications

Patent document 2：International Publication No. 2011/049023

Patent document 3：Japanese Unexamined Patent Application 54-88201 publications

Patent document 4：Japanese Unexamined Patent Publication 2004-262892 publications

Patent document 5：Japanese Unexamined Patent Publication 2003-012632 publications

Patent document 6：Japanese Unexamined Patent Publication 2004-018507 publications

Patent document 7：Japanese Unexamined Patent Publication 5-186414 publications

Patent document 8：Japanese Unexamined Patent Publication 5-186415 publications

Patent document 9：International Publication No. 2012/111750

The content of the invention

Invent problem to be solved

However, phosgene used in the manufacture method of foregoing patent document 1 is severe toxicity, it is secondary in large quantities to generate hydrogen chloride, The manufacture method of patent document 2 secondary can generate the halide such as chloroform, and the manufacture method of patent document 3 is needed in harsh temperature strip Thermally decomposed under part, therefore easily cause side reaction, the manufacture method of patent document 4 is due to tin catalyst equably to dissolve State exist, therefore poisonous organotin catalysts being mixed into product can be caused cumbersome with catalyst reclaimer operation Change, the activity of reaction in carbamate compounds and the choosing of isocyanate compound in the manufacture method of patent document 5~8 The aspect of selecting property is not abundant enough, from these from the aspect of, it cannot be said that be adapted for the manufacture method actually manufactured.

It is as described above in order to solve the problems, such as, as shown in described in patent document 9, develop and be selected from supported on carriers The isocyanate compound catalyst for producing of at least one kind of metallic compound in alkali metal compound and alkali earth metallic compound Agent, but in order to realize the manufacture method for being more suitable for actually manufacturing, it is desirable to propose repeatability or selective higher catalyst.

For the present invention in view of the situation of foregoing conventional art, its problem are, repeatability provides well can be high Selectivity and in high yield manufacture isocyanate compound and the catalyst easily separated with product.In addition it is of the invention Problem also resides in, there is provided has used the manufacture method of the isocyanate compound of such a catalyst.

For solving the method for problem

For this problem, the parameter of the catalyst impacted so far to selectivity, yield is unclear.Using In the manufacture of the isocyanate compound of the catalyst of patent document 9, be carried on carrier selected from alkali metal compound and At least one kind of metallic compound in alkali earth metallic compound plays a role as alkali, sloughs the nitrogen of carbamate compounds On hydrogen atom, carry out decomposition reaction.

Thus it is expected that by increasing the content of foregoing metallic compound or increasing the specific surface area of catalyst Deng and increase metal and the frequency of exposure of matrix, yield or selectivity can improve.

If however, the research such as the present inventor as a result, the content or catalyst of increase metallic compound Specific surface area, then selectivity or yield can reduce.

The present inventor etc. are studied in further detail, are as a result found, are present in catalyst by control The metallic atom on surface and the specific surface area of the atomic ratio of silicon atom and catalyst, can solve the problem, so as to complete The present invention.

It has further been found that can by the ratio surface of the atomic ratio of the metallic atom of catalyst surface and silicon atom, catalyst Product controls in scope described later, catalyst preparation condition, and excellent catalysis can be provided well with repeatability by completing The manufacture method of the solid catalyst of agent.

Additionally, it is observed that when manufacturing isocyanate compound by carbamate compounds, by using containing metal The catalyst of compound and silica, the new of isocyanate compound can be manufactured with high selectivity and in high yield Industrialization production method, so as to complete the present invention.

The present invention is as follows.

The present invention 1 is related to a kind of solid catalyst, and it contains in alkali metal compound and alkali earth metallic compound At least one kind of metallic compound and silica, while meet 2 following conditions.

(1) metallic atom in the metallic compound of x-ray photoelectron analytical equipment measure and the dioxy are utilized The ratio of number of the atom of silicon atom in SiClx (hereinafter sometimes referred to as atomic ratio, is expressed as M/Si.) it is 0.5~20.

(2) it is 0.01m using the specific surface area of the solid catalyst of nitrogen adsorption methods measure²/ g~50m²/g。

The present invention 2 is related to the solid catalyst described in the present invention 1, wherein, while meet 2 following conditions.

(3) M/Si is 0.8~10.

(4) it is 0.1m using the surface area of the solid catalyst of nitrogen adsorption methods measure²/ g~10m²/g。

The present invention 3 is related to the solid catalyst described in the present invention 1 or 2, wherein, the alkali metal compound closes for sodium Thing or cesium compound.

The present invention 4 is related to the solid catalyst that the present invention any one of 1~3 records, wherein, the alkaline-earth metal chemical combination Thing is magnesium compound or calcium compound.

The present invention 5 is related to the solid catalyst that the present invention any one of 1~4 records, wherein, the silica is porous Silica.

The present invention 6 is related to the solid catalyst that the present invention any one of 1~5 records, wherein, the silica is amorphous Matter silica.

The present invention 7 is related to the solid catalyst that the present invention any one of 1~6 records, wherein, the utilization of the silica The intermediate value pore diameter of mercury penetration method measure is 0.1 μm~10 μm.

The present invention 8 be related to the present invention any one of 1~7 record solid catalyst, wherein, by make 700 DEG C~ 1200 DEG C are burnt till silica obtained by 1~20 hour and adsorb the metallic compound, then burn till 1 at 300 DEG C~1200 DEG C ~40 hours and prepare.

The present invention 9 be related to the present invention any one of 1~7 record solid catalyst, wherein, by make 800 DEG C~ 1100 DEG C are burnt till silica obtained by 1~10 hour and adsorb the metallic compound, then burn till 1 at 500 DEG C~1000 DEG C ~20 hours and prepare.

The present invention 10 is related to a kind of manufacture method of isocyanate compound, and it is recorded in the present invention any one of 1~9 In the presence of solid catalyst, isocyanate compound is manufactured using carbamate compounds.

The present invention 11 is related to the manufacture method described in the present invention 10, wherein, the carbamate compounds are following The compound of formula (1) expression is stated,

[changing 1]

In formula, R¹And R²Both can be the same or different, represent can have substituent alkyl, n represent 1~4 it is whole Number.

The isocyanate compound is the compound represented with following formulas (2),

[changing 2]

In formula, n, R¹With it is foregoing synonymous.

The present invention 12 is related to the manufacture method described in the present invention 11, wherein, the n in the formula (1) and (2) is 2.

The present invention 13 is related to the manufacture method that the present invention any one of 10~12 records, wherein, utilize the carbamic acid Reaction temperature when ester compounds manufacture the isocyanate compound is 300 DEG C~500 DEG C.

The present invention 14 is related to the manufacture method that the present invention any one of 10~13 records, wherein, utilize the carbamic acid Reaction pressure during the ester compounds manufacture isocyanate compound is absolute pressure 0.1kPa~101.33kPa.

The present invention 15 is related to the manufacture method that the present invention any one of 10~14 records, wherein, carried out in the form of gas phase The reaction during isocyanate compound is manufactured using the carbamate compounds.

The present invention 16 is related to the manufacture method that the present invention any one of 10~14 records, wherein, carried out in the form of liquid phase The reaction during isocyanate compound is manufactured using the carbamate compounds.

The present invention 17 is related to the solid catalyst of the record of the present invention any one of 1~9 in isocyanate compound is manufactured Application.

Invention effect

According to the solid catalyst of the present invention, in the solid catalyst containing defined metallic compound and silica The metallic compound metallic atom and the silica in silicon atom atomic ratio (M/Si) and the solid Catalyst using nitrogen adsorption methods measure specific surface area this two simultaneously meet foregoing condition when, can with high selectivity, Isocyanate compound is manufactured in high yield.

According to the present invention it is possible to repeatability manufactures such a solid catalyst well, it may, furthermore, provide having used this The manufacture method of the isocyanate compound of kind solid catalyst.

Brief description of the drawings

Fig. 1 is the schematic diagram of the reaction unit of the gas phase fixed bed mode used in embodiment.

Fig. 2 be by the atomic ratio Ca/Si ratios of the specific surface area of the solid catalyst of embodiment, calcium atom and silicon atom and The yield of diisocyanate cpd concentrates figure in the graph (comparative example 1 is not shown).It should be noted that in Fig. 2, " S.A. " represents the specific surface area (m of the solid catalyst using nitrogen adsorption methods measure²/ g), " Ca/Si " represents solid catalysis The atomic ratio of calcium atom and silicon atom on agent surface, " BII yields (BII Yield) " represent the receipts of diisocyanate cpd Rate (%).

Embodiment

Hereinafter, the present invention is described in detail.3 following contents are illustrated.

(A) composition of solid catalyst

(B) preparation method of solid catalyst

(C) manufacture method of isocyanate compound

[composition of (A) solid catalyst]

The solid catalyst of the present invention is containing at least one kind of in alkali metal compound and alkali earth metallic compound Metallic compound and silica, manufacture suitable for isocyanate compound catalyst.The solid catalyst of the present invention It can use with other catalyst combinations, therefore in the solid catalyst of the present invention, also include relative to described containing gold Category compound and silica solid catalyst and be physically mixed with containing with described metallic compound and silica The catalyst of the solid catalyst of different inorganic compounds.

In the solid catalyst of the present invention, in the metallic atom and silica in the metallic compound on its surface The atomic ratio (M/Si) of silicon atom is 0.5~20,0.7~10 is more preferably from the viewpoint of selectivity or yield, further Preferably 0.8~10, particularly preferably 1~6.By like this by the metallic compound (metal compound on the surface of catalyst Thing is considered as the material for mainly helping catalyst reaction) in metallic atom and silica in silicon atom atomicity Ratio be set to certain scope, it is possible to realize excellent selectivity and yield.

It should be noted that in this specification, the atomic ratio (M/Si) on the surface of foregoing solid catalyst is penetrated using X The value of Photoelectron analytical equipment (ESCA) measure.

In addition, the specific surface area using nitrogen adsorption methods measure of the solid catalyst of the present invention is 0.01m²/ g~50m²/ G, 0.1m is more preferably from the viewpoint of selectivity or yield²/ g~10m²/ g, more preferably 0.1m²/ g~5m²/ g, Particularly preferably 0.2m²/ g~3m²/g。

Pore is there are in silica, and the pore is generally divided into this 3 kinds of micropore, mesopore, macropore.Micropore is diameter Pore less than 2nm, mesopore are a diameter of 2nm~50nm pores, macropore be diameter more than 50nm pore (referring for example to Carbon, 2008,850-857.).

Micropore, mesopore are believed to provide catalyst substantial amounts of reflecting point, but on the other hand in the part consumingly Association reaction matrix, it may will not also depart from even if reaction end product at this or non-targeted reaction is carried out.Examined in the present invention Consider, such as silica is handled by using defined method described later, be one by the specific surface area control of solid catalyst Fixed scope and reduce these micropores, mesopore, so as to overcome described drawback.

It should be noted that in the solid catalyst of the present invention, in addition to silica, such as activity can also be used Charcoal；The metal oxides such as aluminum oxide, sial, zirconium oxide, titanium oxide；The composition metals such as titanium silicon, titanium zirconium, zirconium silicon, hydrotalcite aoxidize Thing；The clay minerals such as kaolin, montmorillonite, bentonite, chlorite, illite；The metal silicates such as zeolite；Silica is molten The metal oxide precursors such as glue, alumina sol, containing them and in alkali metal compound and alkali earth metallic compound The solid catalyst of at least one kind of metallic compound can also realize excellent selectivity, yield.

It is preferably metal oxide and metal composite oxide, more preferably aluminum oxide and sial among them.

As the silica used in the present invention, amorphous silica is preferably enumerated.As the noncrystalline titanium dioxide Silicon, any one for synthesizing amorphous silica manufactured using dry process or damp process can be used.In addition, noncrystalline two Silica for example can directly provide the commercially available product containing moisture firing process before (2) with catalyst preparation process described later Or (3) absorption process.In addition it is also possible to suitably use silica gel.

In addition, porous silica can also be used as silica.As its example, Fuji can be enumerated Silysia Chemical company systems CARiACT Q10, CARiACT Q50, CARiACT Q100, CARiACT Q300 etc..It is more Hole silica can also in order to applied in device and sieve after use.

The particle diameter of the silica used in the present invention is not particularly limited, usually 0.5mm~10mm.

In addition, the intermediate value pore diameter using mercury penetration method measure of the silica is usually 8nm~300 μm, Preferably 10nm~50 μm, more preferably 50nm~20 μm, more preferably 0.1 μm~10 μm.It should be noted that dioxy The pore diameter of SiClx can utilize any one method of nitrogen adsorption methods and mercury penetration method measure.

In addition, the pore volume and specific surface area of foregoing porous silica can utilize nitrogen adsorption methods and mercury pressure Enter any one method measure of method.But for pore volume and specific surface area, it is in the pore diameter of porous silica During 0.4nm~200nm, nitrogen adsorption methods can be utilized to determine, when pore diameter is 3.6nm~400 μm, mercury can be utilized Plunging determines.When pore diameter is 3.6nm~200nm, any one of nitrogen adsorption methods and mercury penetration method can be utilized Kind method measure.

From the aspect of reactivity and selectivity, the pore determined using mercury penetration method of the porous silica Volume is preferably 0.01mL/g~2mL/g, more preferably 0.1mL/g~1.5mL/g, more preferably 0.3mL/g~1mL/ g.In addition, the specific surface area determined using the mercury penetration method of porous silica is preferably 0.01m²/ g~100m²/ g, it is more excellent Elect 0.1m as²/ g~80m²/ g, more preferably 0.3m²/ g~50m²/g。

Meanwhile the pore volume of the porous silica determined using nitrogen adsorption methods is preferably 0.0001mL/g~1mL/ G, more preferably 0.0002mL/g~0.8mL/g, more preferably 0.0004mL/g~0.5mL/g.In addition, porous silica The specific surface area using nitrogen adsorption methods measure of silicon is preferably 0.01m²/ g~1000m²/ g, more preferably 0.01m²/ g~ 100m²/ g, more preferably 0.01m²/ g~50m²/ g, particularly preferably 0.1m²/ g~10m²/g。

Silica described above in the present invention, both can be used alone any a kind, can also be applied in combination 2 kinds More than.

The present invention solid catalyst in, using in alkali metal compound and alkali earth metallic compound at least 1 kind of metallic compound.As the alkali metal in the metallic compound, such as lithium, sodium, potassium, rubidium and caesium can be enumerated.In addition, make For the alkaline-earth metal in the metallic compound, such as beryllium, magnesium, calcium, strontium, barium etc. can be enumerated.Among them, it is preferably Sodium, caesium, magnesium, calcium (that is, are preferably sodium compound and cesium compound as alkali metal compound, as alkali earth metallic compound Preferably magnesium compound and calcium compound), more preferably calcium.

As long as in addition, the metallic compound alkali metal or alkaline-earth metal, compound with defined element, just It is not particularly limited, as the metallic compound, such as answering for metal oxide, metal oxide and silica can be enumerated Close oxide etc..

In addition, in the preparation of the solid catalyst of invention described below, silica is set to adsorb alkali metal first Compound or alkali earth metallic compound, are then burnt till.The metallic compound used during as the absorption process, such as can To enumerate：The inorganic acid salt of the alkali metal such as nitrate, carbonate, bicarbonate, silicate or alkaline-earth metal；Fluoride, chlorine The halide of the alkali metal such as compound or alkaline-earth metal；The hydroxide of alkali metal or alkaline-earth metal；And acetate, oxalates Deng alkali metal or the acylate of alkaline-earth metal.In addition, alkali metal compound and alkali earth metallic compound can also be water Compound.

In the solid catalyst of the present invention, relative to the overall quality of solid catalyst, metallic compound described above Content it is total be scaled each metallic atom and preferably 0.01 mass %~50 mass %, more preferably 0.05 mass %~ The mass % of 30 mass %, more preferably 0.1 mass %~20.It should be noted that the metal compound in solid catalyst The content of thing measure such as can use fluorescent X-ray elemental microanalysis method (XRF) or ICP-AES methods.

In addition, the particle diameter of the solid catalyst of the present invention is usually 1mm~10mm, preferably 1mm~5mm.

[preparation method of (B) solid catalyst]

Below, the manufacture method of the solid catalyst of the present invention is illustrated.The solid catalyst of the present invention for example may be used To prepare as follows：Make to be selected from alkali metal compound and alkaline earth in 700 DEG C~1200 DEG C silica for burning till 1~20 hour absorption At least one kind of metallic compound in metal compound, by this adsorbed metallic compound burn till silica 300 DEG C~ 1200 DEG C are burnt till 1~40 hour to prepare.More specifically, such as according to step as follows prepare.

(1) synthesis procedure；Synthetic silica.

(2) firing process before；The silica of gained is burnt till, reduces micropore and mesopore.

(3) absorption process；Using method of impregnation etc., make silica adsorbing metal compound.

(4) drying process；The solid of gained is dried as needed.

(5) firing process；Dried solid is burnt till as needed.

Among this 5 processes, explanation is proceeded by from the process of important (2) and (5).

(2) firing process before

Before the silica adsorbing metal compound used when making the solid catalyst of the preparation present invention, for reduction Foregoing micropore and the purpose of mesopore need to carry out burning till processing.

The described temperature for burning till processing needs the high temperature for 700 DEG C~1200 DEG C, is examined from the viewpoint of selectivity and yield Consider more preferably 800 DEG C~1100 DEG C, more preferably 900 DEG C~1000 DEG C.

It may be considered because of by being set to the scope, it is possible to reduce the micropore and mesopore of silica, it will be passed through The solid catalyst of the invention that each operation afterwards obtains is foregoing using the specific surface area control of nitrogen adsorption methods measure Scope.As a result, matrix easily suitably departs from from the solid catalyst of the present invention after the reaction, so as to reduce the anti-of target Reaction beyond answering.It should be noted that in the stage of the synthesis procedure (1) before the preceding firing process (2), silica Specific surface area be in defined scope, even if not implementing this process (2) then, by the process by (3) described later~(5), Sometimes the scope of the specific surface area of solid catalyst specified in the present invention can also be realized.Thus, in the solid catalysis of the present invention In the manufacture method of agent, this process (2) can also be omitted sometimes.It should be noted that for can also omit process (2), The approximate range of the specific surface area of the silica in the stage of process (1), those skilled in the art can be by implementing this area The experiment for the resonable degree that technical staff is expected and easily grasp.

In addition, to silica burn till the time of processing in the present invention before silica adsorbing metal compound is made It it is 1~20 hour, more preferably 1~10 hour within the scope of foregoing temperature., can be by the present invention's by being set to the scope Solid catalyst is foregoing scope using the specific surface area control of nitrogen adsorption methods measure.

It should be noted that from the viewpoint of uniform burn till, the titanium dioxide preferably to being used in preceding firing process (2) Silicon sieves etc., is burnt till after being unified for 1mm~10mm by its particle diameter, be more preferably unified for 1mm~5mm.

(5) firing process

After being burnt till before being carried out in process (2) to silica, make silica adsorbing metal in process described later (3) Compound, it is necessary to be burnt till again after the solid of gained is dried as desired by process (4).Firing condition can basis Species, form, the content or dry of the inorganic compounds such as metallic compound, silica (foregoing silica, activated carbon etc.) Dry state etc. suitably adjusts.

Firing temperature is preferably 300 DEG C~1200 DEG C, more preferably 500 DEG C~1000 DEG C, more preferably 500 DEG C~ 800℃.By burning till in this range, can by the metallic atom in the metallic compound of the solid catalyst surface of gained with Silicon atom in silica atomic ratio M/Si control be foregoing scope, obtain required catalyst activity (reaction speed, Raising of reaction yield and selectivity etc.).

In addition, as long as firing time is sufficiently carried out the time burnt till, just it is not particularly limited, but preferably 1 is small When~40 hours, more preferably 1 hour~20 hours.By burning till in this range, it is possible to by solid catalyst surface The atomic ratio M/Si controls of the silicon atom in metallic atom and silica in metallic compound are foregoing scope, obtain institute The catalyst activity (raising of reaction speed, reaction yield and selectivity etc.) needed.

Below, the process of (1), (3) and (4) in the preparation to the solid catalyst of the present invention illustrates.

(1) synthesis procedure

Silica can be synthesized according to known method, can also use commercially available product as described above in addition, One of the synthetic method of silica is illustrated herein.By mixing positive silicon with the mixed solvent of polyethylene glycol relative to water Sour tetra-ethyl ester and nitric acid, dried after stirring and cleaning, so as to synthetic silica.

The amount of water used herein is preferably 0.1mL~3mL relative to tetraethyl orthosilicate 1mL, and more preferably 0.5mL~ 2mL.In addition, used polyethylene glycol is preferably 0.01mL~0.2mL relative to tetraethyl orthosilicate 1mL, more preferably 0.02mL~0.1mL.By being set to the scope, it is possible to while good stirring is maintained, prevent the solidification of reaction solution.

Used nitric acid for example concentration be 60% when, relative to tetraethyl orthosilicate 1mL be preferably 0.01mL~ 0.1mL, more preferably 0.02mL~0.08mL.

Drying time after silica gel synthesis is preferably 5 hours~100 hours, more preferably 10 hours~80 hours.In addition, Drying temperature is preferably 90 DEG C~150 DEG C, more preferably 100 DEG C~120 DEG C.By being set to the scope, so as to foregoing Time in the solvent in silica gel is reduced to the amount for not interfering with subsequent processing.

In addition, after the drying, in order to remove the remnant of the material used in the synthesis of the silica such as polyethylene glycol, It can be burnt till in 600 DEG C or so of temperature.

(3) absorption process

After synthesizing silica by process (1), burnt till before being carried out using above-mentioned process (2) to silica.This Afterwards, metallic compound is made to be infiltrated in silica.Used metallic compound is as it was previously stated, be alkali metal or alkaline-earth metal Inorganic acid salt etc..

After described infiltration, solid (original text is utilized：The universe is consolidated) and filtering, solid or filtering, it is possible to obtain in dioxy The solid of metallic compound has been adsorbed in SiClx.As the method for solid filtering, in general method can be used.

In addition, as metallic compound is made in the method for silica, can be using logical in the preparation of solid catalyst Normal method, such as pore filling (pore filling) method, the solid method of evaporation, Equilibrium Adsorption Method, first wet impregnation can be applied (Incipient wetness) method etc..

(4) drying process

The solid obtained in described absorption process generally for the purpose of solvent used in removing, is preferably done It is dry.Drying temperature during the solid catalyst manufacture of the present invention is preferably 50 DEG C~150 DEG C, more preferably 80 DEG C~120 DEG C.It is dry The dry time is preferably 6 hours~36 hours, more preferably 12 hours~24 hours., can be by solid by being set to the scope Solvent be reduced to the amount for not interfering with subsequent processing.

By the way that so obtained solid is burnt till in the firing process (5) of described above, it is possible to obtain this hair Bright solid catalyst.It should be noted that think when the middle inorganic acid salt using alkali metal of absorption process (3), The inorganic acid salt etc. is oxidized because burning till, and is changed into metal oxide or the composite oxides with silica.

If carry out the manufacture of solid catalyst by regulation process described above, based on rated condition, so that it may Manufactured well with repeatability can ground as described later high selectivity and generate in high yield isocyanate compound etc., it is excellent Different solid catalyst.

[manufacture method of (C) isocyanate compound]

The solid catalyst of present invention mentioned above can use as the catalyst of various reactions, especially as profit With carbamate compounds come to manufacture the catalyst of the reaction of isocyanate compound be useful.The isocyanates of the present invention The manufacture method (hereinafter also referred to as " manufacture method of the invention ") of compound is by the solid catalyst in the present invention In the presence of, make carbamate compounds react and implement.The manufacture method of the present invention is implemented preferably by pyrolysis.

As carbamate compounds used in the manufacture method of the present invention, it is adapted to use with following formulas (1) table That shows has at least one amino-formate bond (- NHCO in intramolecular₂-) compound.

[changing 3]

In the formula (1), R¹Represent there can be the alkyl of substituent.

As the alkyl, for example, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, 2- ethylhexyls, The alkyl of the carbon numbers such as nonyl, decyl, dodecyl, octadecyl 1~20；

The alkenyl of the carbon numbers such as acrylic, cyclobutenyl, pentenyl 2~20；

The alkylidene radical of the carbon numbers 1~20 such as methene base, ethidine, propylidene base, butane, pentylidene base, oneself fork base；

Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, methylcyclohexyl, cyclooctyl, methylcyclohexylmethyl, diformazan basic ring Hexyl, isophorone base, norborny, decahydronaphthalene naphthyl, adamantyl, 4,4 '-di-2-ethylhexylphosphine oxide (hexamethylene) base, 2,4 '-Asia The cycloalkyl of the carbon numbers 3~20 such as double (hexamethylene) bases of methyl；

The ring alkylidene radical of the carbon numbers such as Isosorbide-5-Nitrae-cyclohexylidene base 3~20；

Phenyl, tolyl, xylyl, naphthyl, xenyl, anthryl, trimethylphenyl, 4,4 '-methylene diphenylene Deng aryl comprising 1~3 aromatic ring etc..It should be noted that these groups include various isomers.

In the formula (1), R²Represent there can also be the alkyl of substituent.

Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, methylcyclohexyl, cyclooctyl, Dimethylcyclohexyl, isophorone The cycloalkyl of the carbon numbers 3~20 such as base, norborny, decahydronaphthalene naphthyl, adamantyl；

Phenyl, tolyl, xylyl, naphthyl, xenyl, anthryl, trimethylphenyl etc. include 1~3 aromatic ring Aryl etc..It should be noted that these groups include various isomers.

The R of the formula (1)¹And R²In, as the substituent that can have in the alkyl of substituent, such as can be with Enumerate hydroxyl, halogen atom, cyano group, amino, alkyl amino, carboxyl, alkoxy, aryloxy group, alkylthio group, arylthio, (methyl) Acryloxy etc..

In the formula (1), n is 1~4 integer, and this is according to R¹Corresponding bonding valence mumber and the value determined, such as In R¹In the case of group (such as cyclohexyl) for 1 valency, n 1, in R¹For the situation of the group (such as cyclohexylidene) of divalent Under, n 2.In addition, as R¹The example of alkyl can enumerate alkyl, such as in n be 2 (R¹For divalent) in the case of, the hydrocarbon Base is the group (alkylidene) of the divalent corresponding to alkyl.It is the group (chain of similarly corresponding trivalent in the case where n is 3 The base of alkane three).The other groups enumerated for the example as alkyl are also identical.

In addition, from as the various manufacture raw materials of isocyanate compound obtained using manufacture method of the invention etc. From the viewpoint of serviceability, n is preferably 2.

Carbamate compounds used are preferably described above to be represented with formula (1) in the manufacture method of the present invention Compound, as its example, such as fatty family carbamate compounds, alicyclic ring family urethane can be enumerated Compound, fragrant family carbamate compounds etc..

Fatty family carbamate compounds used are, for example, following carbamic acid in the manufacture method of the present invention Ester compounds：In the formula (1), R¹Be can have substituent, the alkyl of carbon number 1~20, carbon number 2~ 20 alkenyl or the alkylidene radical of carbon number 1~20, R²It is can have substituent, carbon number 1~20, preferably carbon former The alkyl or phenyl of subnumber 1~6.As fatty family carbamate compounds used in the manufacture method of the present invention, example It can such as enumerate：Methylhexyl carbamate, Methyl Octyl carbamate, methyl dodecylamino formic acid esters, methyl ten Eight alkyl carbamates, Isosorbide-5-Nitrae-bis- (methyloxycarbonylaminos) butane, Isosorbide-5-Nitrae-bis- (ethoxycarbonylamino group) butane, Isosorbide-5-Nitrae-bis- Double (methyloxycarbonylamino) pentanes of (butoxycarbonylamino group) butane, 1,5-, 1,6- double (methyloxycarbonylamino) hexane, 1, Double (ethoxycarbonylamino group) hexanes of 6-, double (butoxycarbonylamino group) hexanes of 1,6-, 1,8- double (methyloxycarbonylaminos) are pungent Double (butoxycarbonylamino group) octanes of alkane, 1,8-, double (the phenoxycarbonylamino) -4- (phenoxycarbonylamino methyl) of 1,8- are pungent Double (methyloxycarbonylamino) nonanes of alkane, 1,9-, double (butoxycarbonylamino group) nonanes of 1,9-, double (the methoxycarbonyl ammonia of 1,10- Base)-decane, double (the butoxycarbonylamino group)-dodecanes of 1,12-, 1,12- double (methyloxycarbonylamino)-dodecane, 1,12- Double (phenoxycarbonylamino)-dodecanes, 1,3,6- tri- (methyloxycarbonylamino) hexanes, 1,3,6- tri- (phenyloxycarbonyl ammonia Base) hexane etc..

Alicyclic ring family carbamate compounds used are, for example, following carbamic acid in the manufacture method of the present invention Ester compounds：In the formula (1), R¹It is can have substituent, the cycloalkyl of carbon number 3~20, R²It is to have Alkyl or phenyl of substituted base, carbon number 1~6.As alicyclic ring family amino used in the manufacture method of the present invention Formic acid ester compound, such as can enumerate：1,3- or Isosorbide-5-Nitrae-bis- (methyloxycarbonylaminos) hexamethylene, 1,3- or Isosorbide-5-Nitrae-bis- (second Epoxide carbonyl amino) hexamethylene, 1,3- or Isosorbide-5-Nitrae-bis- (butoxycarbonylamino groups) hexamethylene, 1,3- or Isosorbide-5-Nitrae-bis- (methoxyl group carbonyls Base amino methyl) hexamethylene, 1,3- or Isosorbide-5-Nitrae-bis- (ethoxycarbonylamino group methyl) hexamethylene, 1,3- or Isosorbide-5-Nitrae-bis- (butoxy Carbonylamino-methyl) hexamethylene, 2,4 '-or 4,4 '-bis- (methyloxycarbonylamino) dicyclohexyl methyl hydrides, 2,4 '-or 4,4 '-it is bis- (ethoxycarbonylamino group) dicyclohexyl methyl hydride, 2,4 '-or 4,4 '-bis- (butoxycarbonylamino group) dicyclohexyl methyl hydrides, 2,4 '- Or 4,4 '-bis- (phenoxycarbonylamino) dicyclohexyl methyl hydrides, 2,5- double (methyloxycarbonylamino methyl) two rings [2,2,1] heptan Double (Butyloxycarbonylaminomethyl) two ring [2,2, the 1] heptane of alkane, 2,5-, double (methyloxycarbonylamino methyl) two rings of 2,6- [2,2,1] heptane, 2,6- couples of (Butyloxycarbonylaminomethyl) two ring [2,2,1] heptane, 1- (methyloxycarbonylamino) -3,3, 5- trimethyls -5- (methyloxycarbonylamino methyl)-hexamethylene, 1- (butoxycarbonylamino group) -3,3,5- trimethyl -5- (fourths Epoxide carbonyl amino methyl)-hexamethylene, trimethyl -1- (the methoxycarbonyl ammonia of 3- (methyloxycarbonylamino methyl) -3,5,5- Base) hexamethylene, 4,4 '-bis- (methyloxycarbonylamino) -2,2 '-dicyclohexyl propane, 4,4 '-bis- (butoxycarbonylamino groups) - 2,2 '-dicyclohexyl propane etc..

Fragrant family carbamate compounds used are following urethanes in the manufacture method of the present invention Compound：R¹It is can have substituent, the aryl for including aromatic ring of carbon number 6~18, R²It is can have substituent , the alkyl or phenyl of carbon number 1~6.As fragrant family urethane used in the manufacture method of the present invention Compound, such as can enumerate：1,3- or Isosorbide-5-Nitrae-bis- (methyloxycarbonylamino methyl) benzene, 1,3- or Isosorbide-5-Nitrae-bis- (ethoxy carbonyls Amino methyl) benzene, 1,3- or Isosorbide-5-Nitrae-bis- (Butyloxycarbonylaminomethyls) benzene, 1,3- or Isosorbide-5-Nitrae-bis- (methyloxycarbonylaminos) Benzene, 1,3- or Isosorbide-5-Nitrae-bis- (butoxycarbonylamino groups) benzene, 2,2 '-bis- (4- propoxy carbonylaminos phenyl) propane, 2,4 '-or 4, 4 '-bis- (methyloxycarbonylamino) diphenyl methanes, 2,4 '-bis- (ethoxycarbonylamino group) diphenyl methanes, 2,4 '-bis- (fourths Epoxide carbonyl amino) diphenyl methane, 4,4 '-bis- (phenoxycarbonylamino) diphenyl methanes, 1,5- or the double (methoxyl groups of 2,6- Carbonylamino) naphthalene, double (butoxycarbonylamino group) naphthalenes of 1,5- or 2,6-, 4,4 '-bis- (methyloxycarbonylamino) biphenyl, 4,4 '- Double (methyloxycarbonylamino) toluene of double (butoxycarbonylamino group) biphenyl, 2,4- or 2,6-, 2,4- or double (the ethyoxyl carbonyls of 2,6- Base amino) toluene, 2,4- or double (butoxycarbonylamino group) toluene of 2,6- etc..

In the manufacture method of the present invention, such as utilize the carbamate compounds described above represented with formula (1) To manufacture corresponding isocyanate compound, but the isocyanate compound is preferably the compound represented with following formulas (2).

[changing 4]

In formula, R¹And n and the formula (1) R¹And n is synonymous.In addition, in the case where n is more than 2, in foregoing change Beyond compound, obtained sometimes as intermediate by 1, there occurs isocyanation esterification for (n-1) individual carbamate groups Compound.For example, using isophorone dimethylcarbamate (1- (methyloxycarbonylamino) -3,3,5- front threes Base -5- (methyloxycarbonylamino methyl)-hexamethylene) in the case of, it is shown below, beyond diisocyanate body, can also Obtain 2 kinds of monoisocyanates bodies.

[changing 5]

The solid catalyst of the present invention is by by metallic atom/silicon of the metallic compound of catalyst surface and silica The atom ratio of atom is set to defined scope and turns into the suitable catalyst of reactivity, by that nitrogen adsorption methods will be utilized to determine The specific surface area of catalyst be set to certain scope, reaction product is moderately easily separated from.

Therefore, in the reaction of solid catalyst of the present invention has been used, the carbamate of carbamate compounds The major part of key is transformed to NCO, can suppress the generation of the intermediate of above-mentioned shown monoisocyanates etc. In addition it is also possible to suppress the generation of the chlorinated isocyanurates body that is generated when catalyst activity is too high etc..Thus, if made With the solid catalyst of the present invention, it is possible to high selectivity and manufacture isocyanate compound in high yield.

In the manufacture method of the present invention, isocyanate compound is by making carbamic acid in the presence of the catalyst Ester compounds react and manufactured.It is preferred that in the presence of the catalyst, make the carbamate compounds of the formula (1) anti- Answer, manufacture the isocyanate compound of the formula (2).

Reaction form now is not particularly limited, and can be any one in gas phase reaction, liquid phase reactor, but excellent Select gas phase reaction.In addition, reactive mode can use the solid catalysts such as fixed bed mode, fluid bed process, suspension bed mode Reaction mode used.Particularly preferably use fixed bed mode.

The head tank that the gas phase fixed bed mode that preferably uses for example can be as shown in Figure 1 in the manufacture method of the present invention (1), the thermal source (tubular electric furnace etc.) of matrix supply pump (2), the tubular reactor (3) filled with catalyst, heating response device (4), product heat exchanger (6), the chilled product of recovery isocyanate compound receiver (7), for condensed alcohol (by Carbamate compounds manufacture isocyanate compound when generate) heat exchanger (8), the receiver (9) for obtaining alcohol, The vacuum pipeline being connected with vavuum pump (17) is formed, but is not limited to this.It should be noted that for carrying in Fig. 1 The composition of other symbols, illustrate in the embodiment that will be described below.

Relative to the feed speed 1mL/h of the matrix in gas phase fixed bed mode, solid catalyst of the invention preferably with 0.01mL~10mL, more preferably used with 0.02mL~5mL amount.

, then can be with inactive gas such as nitrogen if the state that matrix has been gasified in gas phase fixed bed mode And reacted, it can also be reacted without using inactive gas, can also be carried out under normal or reduced pressure.

In the manufacture method of the present invention, in the case where using solid catalyst in a manner of suspension bed, these catalyst phases For the mass parts of carbamate compounds 100 for example preferably with the scope of the mass parts of 0.1 mass parts~100, more preferably with 0.5 The scope of the mass parts of mass parts~50 uses.

In the manufacture method of the present invention, the reactions of carbamate compounds for example can also be by by urethane Compound and solid catalyst are heated and implemented together with torpescence solvent.The manufacture method of the present invention is preferably by making this anti-in addition The reaction distillation mode that isocyanate compound, the alcoholic compound of middle generation are separated to outside system is answered to implement.Need what is illustrated It is in manufacture method of the invention, to be not necessarily required to together heat torpescence solvent and carbamate compounds, can also It is allowed to react in a manner of without solvent.

In the manufacture method of the present invention, as long as the torpescence solvent is relative to carbamate compounds and generation Isocyanate compound is torpescence, is just not particularly limited, but in order to efficiently implement to react, it is however preferred to have higher than ammonia The solvent of the boiling point of carbamate compound.As such a solvent, such as can enumerate：Dioctyl phthalate, adjacent benzene two The esters such as formic acid didecyl, phthalic acid two (dodecyl) ester, or, such as dibenzyl toluene, triphenyl methane, phenyl Fragrant family hydrocarbon or the fatty family hydrocarbon such as naphthalene, biphenyl, terphenyl, diethyl biphenyl, triethyl group biphenyl, 1,3,5- triisopropylbenzenes Deng.These solvents can be used alone or and with two or more.Its usage amount can according to reaction unit, form and suitably adjust It is whole.

In the manufacture method of the present invention, torpescence solvent for example preferably uses 0.1 relative to carbamate compounds 1mL ~150mL, more preferably using 1~50mL.By being set to the scope, can be prevented anti-while good stirring is maintained Answer the solidification of liquid.

It is excellent relative to the feed speed 1mL/h of carbamate compounds, solid catalyst in the manufacture method of the present invention Select with 0.01mL~10mL, more preferably with 0.02mL~5mL amount use.By being set to the scope, it is possible to industrially to close Suitable reaction speed obtains isocyanate compound.

In the manufacture method of the present invention, the reaction temperature of carbamate compounds is, for example, 80 DEG C~600 DEG C, is preferably 200 DEG C~500 DEG C, more preferably 300 DEG C~500 DEG C.By being set to the scope, reaction (the particularly heat of practicality can be obtained Decompose) speed, the undesirable side reaction such as the polymerization of isocyanate compound can be suppressed.

In the manufacture method of the present invention, reaction pressure is preferably capable the isocyanide of generation relative to above-mentioned reaction temperature Ester compound and the pressure of alcoholic compound gasification, in terms of slave unit and using from the aspect of income, in practical preferably definitely Pressure is 0.1kPa~101.33kPa, and more preferably absolute pressure is 0.5kPa~30kPa.

In the present invention, when reacting carbamate compounds with batch (-type), foregoing solid catalyst is relative to ammonia The mass parts of carbamate compound 100, preferably with the scope of the mass parts of 0.1 mass parts~100, more preferably with 0.5 mass parts~ The scope of 50 mass parts uses.

In addition, though be not necessarily required to together heat torpescence solvent and carbamate compounds, and can also be with Mode without solvent is allowed to react, but in the case of using torpescence solvent, its usage amount is relative to urethane Compound 1g is usually 1~30mL, preferably 1~10mL.

For reaction pressure, temperature as previously described.

Reaction time can suitably be adjusted according to catalytic amount, temperature, the concentration of matrix and pressure etc., and usually 0.5 ~10 hours, preferably 1~5 hour.

, then can be with nitrogen if the state that isocyanate compound has been gasified in the manufacture method of the present invention Reacted, can also be reacted Deng inactive gas without using inactive gas, can also be under normal or reduced pressure Carry out.

The isocyanate compound obtained using the manufacture method of the present invention can utilize such as mistake by reacted solution The operation of the in general such as filter, concentration, extraction, distillation, distillation, recrystallization, column chromatography is separated, purified.As different by obtained by Cyanate esters further purify repeatedly, and the isocyanate compound of high-purity can be made.

In addition, after the reaction of carbamate compounds terminates, can be by residual liquid filtering, the centrifugation point of reaction solution Solid catalyst is easily reclaimed from separation method known to grade, the solid catalyst of recovery directly or can also be utilized Solvent clean, burn till etc. known to method activate again after reuse.

Embodiment

Below, enumerate embodiment and the present invention is specifically described, but the scope of the present invention is not limited by them It is fixed.

[(the Ca/SiO of Production Example 1₂The preparation of catalyst)]

Water 144.0g, polyethylene glycol (PEG, Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity 20000) 9.6g are existed Mix, stir in polyethylene can, homogeneous solution is made.Tetraethyl orthosilicate (TEOS) 120mL, 60% nitric acid are added thereto The aqueous solution (Wako Pure Chemical Industries, Ltd.'s system) 8.4mL, closed container and to be stirred vigorously 1 under room temperature (20 DEG C~30 DEG C) small When.

Then 12 hours are stood at about 50 DEG C, takes out the gel of generation, after being cleaned with purified water, 60 are dried at about 110 DEG C Hour, at about 600 DEG C burn till within 2 hours in atmosphere, at about 1000 DEG C burn till within 3 hours.

Burned material is crushed in mortar, the size for being sieved into particle is 1mm~2mm scope, obtains porous and amorphous The silica gel 25g of matter.Utilize mercury penetration method (measure device：The full-automatic broad pore distribution measure device of Quanta Chrome Co. systems Pore Master 60-GT) measure the silica gel intermediate value pore diameter be 7.5 μm.

On the other hand, calcium nitrate tetrahydrate 0.196g (0.83mmol) and ion exchange water 2.6g are mixed in flask and stirred Mix and obtain calcium nitrate aqueous solution.It will be added using the silica gel 2.0g (33mmol) of the operation preparation in the calcium nitrate aqueous solution (Ca/Si ratio=0.025) afterwards, stand 1 hour.

Dried again at about 110 DEG C 12 hours, about 500 DEG C burn till and obtain catalyst (Ca/ within 5 hours in atmosphere SiO₂)2.1g.Determined using fluorescent X-ray elemental microanalysis method (XRF), as a result, the catalyst (Ca/SiO of gained₂) in, phase It is overall for solid catalyst, be scaled calcium atom and containing 1.8 mass % calcium compound.That is, solid catalyst is overall The atomic ratio of calcium atom and silicon atom (Ca/Si) is 0.027.

In addition, it is 0.3m using the specific surface area of the solid catalyst of nitrogen adsorption methods measure²/ g, utilize X ray photoelectricity The atomic ratio (Ca/Si) of calcium atom and silicon atom that analytical equipment determines, in solid catalyst surface is 5.8.

[(the various Ca/SiO of Production Example 2~11₂The preparation of catalyst)]

In addition to it will be changed shown in various conditions such as following table 1, table 2, operate and prepare identically with Production Example 1 Go out various Ca/SiO₂Solid catalyst.

[table 1]

[table 2]

In table 1, so-called silica gel intermediate value pore diameter is as follows using the value of mercury penetration method measure, condition determination.

As the measure device based on mercury penetration method, the full-automatic broad pore distribution of Quanta Chrome Co. systems has been used Determine device Pore Master 60-GT.In addition, the condition determination as mercury penetration method, boosts from about 7kPa at room temperature It is measured while to 414Mpa.It should be noted that 480dyn/cm has been used as the value of the surface tension of mercury, 140 ° have been used as the value of contact angle.

In table 2, so-called catalyst totality Ca/Si ratios refer to the atomic ratio of calcium atom and silicon atom in solid catalyst, It is the value calculated according to the quality of mixed silica gel and calcium nitrate.It should be noted that the solid after solid catalyst preparation The overall Ca/Si ratios of catalyst can utilize the measure such as fluorescent X-ray elemental microanalysis method (XRF).

In table 2, (the work in foregoing catalyst preparation after so-called solid catalyst specific surface area represents absorption calcium and burnt till Sequence (5)) solid catalyst specific surface area, be using nitrogen adsorption methods measure value.Condition determination is as follows.

This measure is to be carried out using BET formulas powder specific-surface area detection measure device using physisorphtion (nitrogen adsorption method).This In invention, " Japanese Baeyer (strain) is made, BELSORP-miniII ", and adsorbed gas uses nitrogen, carried out BET multipoint mode methods for use Measure.Specifically, powder sample is subjected to heat de-airing at a temperature of 150 DEG C under vacuo, is then cooled to liquid nitrogen temperature Spend and make nitrogen adsorption, determine absorption/desorption isotherm, the specific surface area of sample is calculated according to the absorption/desorption isotherm.

In table 2, atomic ratios of the so-called surface C a/Si than representing calcium atom and silicon atom in solid catalyst surface, it is The value analyzed using x-ray photoelectron analytical equipment.Condition determination is as follows.

(x-ray photoelectron optical spectroscopy (ESCA) condition determination)

Device name：PHI company systems Quantum2000

X-ray source：Monochromatization Al-K α, power output 15kV-20W (X-ray generating surface accumulates 100 μm of φ)

Charged neutralization：Electron gun (20 μ A), ion gun (30V) are used in combination

Beam splitting system：The narrow spectrum (full element) of pulse energy 187.85eV@wide ranges, 46.95eV@

Mensuration region：Point irradiation (340 μm of φ of irradiated area ＜)

Exit angle (takes り to go out angles)：45 ° (relative to surfaces)

[(formula (1) R of embodiment 1¹=1,3,3- trimethyl -1- methylene cyclohexylidenes, R²=methyl, n=2；Based on different Buddhist That ketone dimethylcarbamate (1- (methyloxycarbonylamino) -3,3,5- trimethyl -5- (methyloxycarbonylamino methyl) - Hexamethylene) thermal decomposition IPDI manufacture)]

[changing 6]

As shown in figure 1, using diameter 10mm, long 42cm glass tube (3) as reactor so that the portion filled with catalyst Point (hereinafter referred to as " mode that catalyst layer ") is about 360 DEG C from outside set electric furnace (4).Reactor lower part is set to branch into two The pipeline of series, respectively via the receiver (room temperature) (7) for obtaining isocyanate compound and (13), for cooled product Product heat exchanger (6) and (12), for obtain methanol receiver (with cold ethanol cool down) (9) and (15) (before it Have respectively for condensing the heat exchanger of methanol (8) and (14)), the pipeline of two sides is connected with vavuum pump (17), by vacuum tube Line links.The switching of two pipelines is the pipeline (pipeline of the opposing party by only opening valve (5 and 10 and 11 and 16) side Close) and carry out.

As catalyst, the Ca/SiO that will be prepared in Production Example 1₂Solid catalyst (1.1~2.2mm of particle diameter) 2mL is filled Into above-mentioned glass tube (3) (glass tube (3) is formed using gasification layer (3a) and catalyst layer (3b)), vavuum pump is started (17) absolute pressure 1.33kPa, is depressurized to, opens valve (5), valve (10), valve (11), valve (16) is closed, uses electric furnace (4) temperature of catalyst layer is heated to about 360 DEG C.Will be in about 150 DEG C of molten isophorone dimethylamino first of heating Acid esters (1- (methyloxycarbonylamino) -3,3,5- trimethyl -5- (methyloxycarbonylamino methyl)-hexamethylene) uses syringe pump (2) supplied with 4mL/h to glass tube (3).

Pass through 30 minutes confirming that the chilled product containing isocyanate compound starts to have been reclaimed by receiver (7) Afterwards, valve (5), valve (10) are closed, valve (11), valve (16) is opened, contained isocyanates by chilled with 30 minutes The product of compound is recovered in receiver (13), by Methanol Recovery to receiver (15).To what is reclaimed by receiver (13) The chilled product containing isocyanate compound is analyzed with liquid chromatogram, to being condensed and recycled to receiver (15) Methanol is analyzed with gas-chromatography, calculates diamino acid ester conversion rate, the yield of diisocyanate, the receipts of monoisocyanates Rate.

As a result, as product, IPDI is obtained with yield 94% (selection rate 94%), with yield 2% obtains monoisocyanates body.

[embodiment 2~6, comparative example 1~5 (have used various Ca/SiO₂, based on isophorone dimethyl carbamic acid The thermal decomposition of ester (1- (methyloxycarbonylamino) -3,3,5- trimethyl -5- (methyloxycarbonylamino methyl)-hexamethylene) it is different The manufacture of isophorone diisocyanate)]

In addition to it will be changed shown in various conditions such as following table 3, operate and synthesize different same as Example 1ly Isophorone diisocyanate.

[table 3]

From table 1, table 2, table 3, extract out the overall Ca/Si of catalyst than, the specific surface area of solid catalyst, solid catalysis Ca/Si ratios, conversion ratio, the yield on agent surface, by the data recordation summarized in table 4.In addition, the table 4 is subject to pictorialization, The result of gained is shown in Fig. 2 and (does not show comparative example 1).

[table 4]

According to table 4 and Fig. 2, the atomic ratio Ca/Si of calcium atom and silicon atom on solid catalyst surface is met is 0.5 ~20, the specific surface area of solid catalyst is 0.01m²/ g~50m²(embodiment 1~6), two isocyanides during the condition of/g these two aspects The yield of ester compound is more than 85%, and the conversion ratio of diurethane compound is 100%.On the other hand, in solid Catalyst is unsatisfactory for during some foregoing condition (comparative example 1~5), and yield, conversion ratio reduce.

[(the Na/SiO of Production Example 12₂The preparation of catalyst)]

By water 144.0g, polyethylene glycol (PEG, Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity 20,000) 9.6g Mix, stir in polyethylene can, homogeneous solution is made.Tetraethyl orthosilicate (TEOS) 120mL, 60% nitre are added thereto Aqueous acid (Wako Pure Chemical Industries, Ltd.'s system) 8.4mL, closed container are simultaneously stirred vigorously 1 under room temperature (20 DEG C~30 DEG C) Hour.

Burned material is crushed in mortar, the size for being sieved into particle is 2mm~4mm scope, is obtained porous and non- The silica gel 55g of crystalloid.Utilize mercury penetration method (measure device：The full-automatic broad pore distribution measure dress of Quanta Chrome Co. systems Put Pore Master 60-GT) measure the silica gel intermediate value pore diameter be 7.5 μm.

On the other hand, sodium nitrate 0.106g (1.25mmol) and ion exchange water 3.7g are mixed in flask and obtained To sodium nitrate aqueous solution.After silica gel 3.0g (49.9mmol) using the operation preparation is added in the sodium nitrate aqueous solution (Na/Si ratio=0.025), stand 1 hour.

Dried 12 hours at about 110 DEG C again, in atmosphere after about 500 DEG C are burnt till 8 hours, in atmosphere at about 700 DEG C Burn till and obtain solid catalyst (Na/SiO within 8 hours₂)3.03g.Determined using fluorescent X-ray elemental microanalysis method (XRF), As a result, solid catalyst (the Na/SiO of gained₂) in, it is overall relative to solid catalyst, it is scaled sodium atom and contains 0.84 mass % sodium compound.That is, the atomic ratio (Na/Si) of the overall sodium atom of solid catalyst and silicon atom is 0.022. In addition, it is 0.51m using the specific surface area of the solid catalyst of nitrogen adsorption methods measure²/ g, analyzed and filled using x-ray photoelectron Atomic ratio (Na/Si) that put measure, sodium atom on catalyst surface and silicon atom is 0.5.

[(formula (1) R of embodiment 7¹=1,3,3- trimethyl -1- methylene cyclohexylidenes, R²=methyl, n=2；Based on different Buddhist That ketone dimethylcarbamate (1- (methyloxycarbonylamino) -3,3,5- trimethyl -5- (methyloxycarbonylamino methyl) - Hexamethylene) thermal decomposition IPDI manufacture)]

[changing 7]

Except the temperature of catalyst layer is set into 365 DEG C, urged as catalyst using the solid obtained in Production Example 12 Agent (Na/SiO₂：1.1~2.2mm of particle diameter) beyond 3mL, operate same as Example 1ly and produce the isocyanide of isophorone two Acid esters.

The yield of IPDI is 83% (selection rate 84%), and the yield of monoisocyanates is 17%.

[(the Mg/SiO of Production Example 13₂The preparation of catalyst)]

Then 12 hours are stood at about 50 DEG C, takes out the gel of generation, after being cleaned with purified water, 60 are dried at about 110 DEG C Hour, carry out burning till for 2 hours in atmosphere at about 600 DEG C, at about 1000 DEG C burn till within 3 hours.

On the other hand, magnesium nitrate hexahydrate 0.320g (1.25mmol) and ion exchange water 3.5g are mixed in flask and stirred Mix and obtain magnesium nitrate aqueous solution.It is water-soluble that silica gel 3.0g (49.9mmol) using the operation preparation is added to the magnesium nitrate After in liquid (Mg/Si ratio=0.025), 1 hour is stood.

Dried again at about 110 DEG C 12 hours, carry out 8 hours burning till at about 500 DEG C in atmosphere and obtain solid catalyst (Mg/SiO₂)3.03g.Determined using fluorescent X-ray elemental microanalysis method (XRF), as a result, the solid catalyst (Mg/ of gained SiO₂) in, it is overall relative to solid catalyst, be scaled magnesium and containing 1.50 mass % magnesium compound.That is, solid catalyst Overall magnesium atom and the atomic ratio (Mg/Si) of silicon atom are 0.038.In addition, the solid catalysis determined using nitrogen adsorption methods The specific surface area of agent is 0.58m²/ g, magnesium atom determined using x-ray photoelectron analytical equipment, in solid catalyst surface Atomic ratio (Mg/Si) with silicon atom is 1.9.

[(formula (1) R of embodiment 8¹=1,3,3- trimethyl -1- methylene cyclohexylidenes, R²=methyl, n=2；Based on different Buddhist That ketone dimethylcarbamate (1- (methyloxycarbonylamino) -3,3,5- trimethyl -5- (methyloxycarbonylamino methyl) - Hexamethylene) thermal decomposition IPDI manufacture)]

[changing 8]

Except the temperature of catalyst layer is set into 365 DEG C, urged as catalyst using the solid obtained in Production Example 13 Agent (Mg/SiO₂：1.1~2.2mm of particle diameter) beyond 3mL, operate same as Example 1ly and produce the isocyanide of isophorone two Acid esters.

The yield of IPDI is 85% (selection rate 85%), and the yield of monoisocyanates is 12%.

It can be seen from embodiment 7 and 8 more than, the sodium atom or magnesium atom and silicon on solid catalyst surface is met are former The atomic ratio M/Si of son is 0.5~20, the specific surface area of solid catalyst is 0.01m²/ g~50m²The condition of/g these two aspects When, the yield of diisocyanate cpd is more than 83%.

[(the Ca/SiO of Production Example 14₂The preparation of catalyst)]

By water 60g, polyethylene glycol (PEG, Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity 20000) 3.6g poly- Mix, stir in ethene container, homogeneous solution is made.It is water-soluble that tetraethyl orthosilicate (TEOS) 60mL, 60% nitric acid are added thereto Liquid (Wako Pure Chemical Industries, Ltd.'s system) 4.2mL, closed container are simultaneously stirred vigorously 1 hour under room temperature (20 DEG C~30 DEG C).

Then 12 hours are stood at about 50 DEG C, takes out the gel of generation, after being cleaned with purified water, 12 are dried at about 110 DEG C Hour, at about 600 DEG C burn till within 2 hours in atmosphere, at about 1000 DEG C burn till within 3 hours.

A part for burned material is crushed in mortar, the size for being sieved into particle is 1mm~2mm scope, is obtained more Hole and amorphous silica gel 8.0g.Utilize mercury penetration method (measure device：The full-automatic pore of Quanta Chrome Co. systems Distribution measurement device Pore Master 60-GT) measure, the intermediate value pore diameter of the silica gel be 6.1 μm.

On the other hand, calcium nitrate tetrahydrate 0.393g (1.7mmol) and ion exchange water 2.2g are mixed in flask and stirred Mix and obtain calcium nitrate aqueous solution.It will be added using the silica gel 2.0g (33mmol) of the operation preparation in the calcium nitrate aqueous solution (Ca/Si ratio=0.05) afterwards, stand 1 hour.

Dried again at about 110 DEG C 12 hours, carry out 3 hours burning till at about 500 DEG C in atmosphere and obtain solid catalyst (Ca/SiO₂)2.3g.Specific surface area using the solid catalyst of nitrogen adsorption methods measure is 0.8m²/ g, utilize X ray photoelectricity The atomic ratio (Ca/Si) of calcium atom and silicon atom that analytical equipment determines, in solid catalyst surface is 1.1.

[(formula (1) R of embodiment 9¹=hexamethylene -1,3- glycol dimethylene, R²=methyl, n=2；By the double (first of 1,3- Epoxide carbonyl amino methyl) hexamethylene thermal decomposition double (isocyanatomethyl) hexamethylenes of 1,3- manufacture)]

[changing 9]

Except the temperature of catalyst layer is set into 365 DEG C, the solid obtained in Production Example 14 has been used as catalyst Catalyst (Ca/SiO₂：1~2mm of particle diameter) 3mL, as carbamate compounds 1 is used, double (the methoxycarbonyl ammonia of 3- Ylmethyl) beyond hexamethylene, operate same as Example 1ly and produce 1, double (isocyanatomethyl) hexamethylenes of 3-.

The yield of 1,3- double (isocyanatomethyl) hexamethylenes is 95% (selection rate 95%), the yield of monoisocyanates For 1%.

[(the Ca/SiO of Production Example 15₂The preparation of catalyst)]

By water 120g, polyethylene glycol (PEG, Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity 20000) 9.6g poly- Mix, stir in ethene container, homogeneous solution is made.It is water-soluble that tetraethyl orthosilicate (TEOS) 120mL, 60% nitric acid are added thereto Liquid (Wako Pure Chemical Industries, Ltd.'s system) 8.5mL, closed container are simultaneously stirred vigorously 1 hour under room temperature (20 DEG C~30 DEG C).

Then 12 hours are stood at about 50 DEG C, takes out the gel of generation, after being cleaned with purified water, 12 are dried at about 110 DEG C Hour, carry out burning till for 2 hours in atmosphere at about 600 DEG C, at about 1000 DEG C burn till within 3 hours.

A part for burned material is crushed in mortar, the size for being sieved into particle is 1mm~2mm scope, is obtained more Hole and amorphous silica gel 9g.Utilize mercury penetration method (measure device：The full-automatic broad pore distribution of Quanta Chrome Co. systems Determine device Pore Master 60-GT) measure, the intermediate value pore diameter of the silica gel be 1.0 μm.

On the other hand, calcium nitrate tetrahydrate 0.008g (0.03mmol) and ion exchange water 2.5g are mixed in flask and stirred Mix and obtain calcium nitrate aqueous solution.It will be added using the silica gel 2.0g (33mmol) of the operation preparation in the calcium nitrate aqueous solution (Ca/Si ratio=0.001) afterwards, stand 1 hour.

Dried again at about 110 DEG C 12 hours, carry out 3 hours burning till at about 500 DEG C in atmosphere and obtain solid catalyst (Ca/SiO₂)2.0g.Specific surface area using the solid catalyst of nitrogen adsorption methods measure is 1.7m²/ g, utilize X ray photoelectricity The atomic ratio (Ca/Si) of calcium atom and silicon atom that analytical equipment determines, in solid catalyst surface is 0.75.

[(formula (1) R of embodiment 10¹=2,4- tolyl, R²=methyl, n=2；It is double (methyloxycarbonylamino) based on 2,4- The Toluene-2,4-diisocyanate of the thermal decomposition of toluene, the manufacture of 4- diisocyanate)]

[changing 10]

Except the temperature of catalyst layer is set into 375 DEG C, the solid obtained in Production Example 15 has been used as catalyst Catalyst (Ca/SiO₂：1~2mm of particle diameter) 3mL, as carbamate compounds 2 are used, double (the methoxycarbonyl ammonia of 4- Base) beyond toluene, operate same as Example 1ly and produce Toluene-2,4-diisocyanate, 4- diisocyanate.

Toluene-2,4-diisocyanate, the yield of 4- diisocyanate is 95% (selection rate 95%), and the yield of monoisocyanates is 3%.

Industrial applicability

Using the present invention, can provide can high selectivity and manufacture in high yield isocyanate compound and with production Thing is segregative, for example may be used as the solid catalyst of the heterogeneous catalysis of isocyanate compound manufacture.

According to the present invention it is possible to repeatability manufactures such a solid catalyst well, it is furthermore possible to also provide having used such a The manufacture method of the isocyanate compound of solid catalyst.

The explanation of symbol

1 head tank

2 matrix supply pumps

3 are filled with the tubular reactor of catalyst

3a gasification layers (Filled with Quartz)

3b catalyst layers

The thermal source (tubular electric furnace) of 4 heating response devices

5 valves

6 product heat exchangers

The receiver of the isocyanate compound of the 7 chilled products of recovery

8 are used for the heat exchanger of condensed alcohol

9 receiver for obtaining alcohol

10 valves

11 valves

12 product heat exchangers

The receiver of the isocyanate compound of the 13 chilled products of recovery

14 are used for the heat exchanger of condensed alcohol

15 receiver for obtaining alcohol

16 valves

17 vavuum pumps

Claims

1. a kind of solid catalyst, it contains at least one kind of metal in alkali metal compound and alkali earth metallic compound Compound and silica, it meets 2 following conditions simultaneously：

(1) using in surface, the described metallic compound of x-ray photoelectron analytical equipment measure, described solid catalyst Alkali metal atom and/or alkaline-earth metal atom and the silica in the atomic ratio M/Si of silicon atom be 0.8~10；

(2) it is 0.1m using the specific surface area of the solid catalyst of nitrogen adsorption methods measure²/ g~10m²/g。

2. solid catalyst according to claim 1, wherein,

The metallic compound for contributing to catalyst reaction is at least 1 in alkali metal compound and alkali earth metallic compound Kind metallic compound.

3. solid catalyst according to claim 1, wherein,

The alkali metal compound is sodium compound or cesium compound.

4. solid catalyst according to claim 1, wherein,

The alkali earth metallic compound is magnesium compound or calcium compound.

5. solid catalyst according to claim 1, wherein,

The silica is porous silica.

6. solid catalyst according to claim 5, wherein,

The pore volume using mercury penetration method measure of the porous silica is 0.01mL/g~2mL/g, utilizes nitrogen The pore volume of determination of adsorption method is 0.0002mL/g~0.8mL/g, the specific surface area determined using mercury penetration method is 0.1m²/ g~80m²/ g, the specific surface area determined using nitrogen adsorption methods are 0.01m²/ g~50m²/g。

7. solid catalyst according to claim 1, wherein,

The silica is amorphous silica.

8. solid catalyst according to claim 1, wherein,

The intermediate value pore diameter using mercury penetration method measure of the silica is 0.1 μm~10 μm.

9. solid catalyst according to claim 1, wherein,

Relative to the overall quality of solid catalyst, the total of the content of the metallic compound is scaled each metallic atom and is The mass % of 0.05 mass %~30.

10. solid catalyst according to claim 1, wherein,

The particle diameter of solid catalyst is 1mm~5mm.

11. solid catalyst according to claim 1, its two by making to burn till 1~20 hour at 700 DEG C~1200 DEG C Silica adsorbs the metallic compound, then burns till 1~40 hour at 300 DEG C~1200 DEG C and prepares.

12. solid catalyst according to claim 1, its two by making to burn till 1~10 hour at 800 DEG C~1100 DEG C Silica adsorbs the metallic compound, then burns till 1~20 hour at 500 DEG C~1000 DEG C and prepares.

13. a kind of manufacture method of isocyanate compound, in the presence of the solid catalyst described in claim 1, utilize Carbamate compounds manufacture isocyanate compound.

14. manufacture method according to claim 13, wherein,

The carbamate compounds are the compounds represented with following formulas (1),

In formula, R¹And R²Both it can be the same or different, and represented can there is the alkyl of substituent, n represents 1~4 integer；

In formula, n, R¹With it is foregoing synonymous.

15. manufacture method according to claim 14, wherein,

N in the formula (1) and (2) is 2.

16. the manufacture method according to any one of claim 13~15, wherein,

The reaction temperature when isocyanate compound is manufactured using the carbamate compounds is 300 DEG C~500 DEG C.

17. the manufacture method according to any one of claim 13~15, wherein,

The reaction pressure when isocyanate compound is manufactured using the carbamate compounds is absolute pressure 0.1kPa~101.33kPa.

18. the manufacture method according to any one of claim 13~15, wherein,

Carry out manufacturing the reaction during isocyanate compound in the form of gas phase using the carbamate compounds.

19. the manufacture method according to any one of claim 13~15, wherein,

Carry out manufacturing the reaction during isocyanate compound in the form of liquid phase using the carbamate compounds.

20. application of the solid catalyst in isocyanate compound is manufactured described in claim 1.