CN101258181A - Method for manufacturing solid acid catalyst - Google Patents

Abstract

Disclosed is a process for production of a polyether by polymerization or condensation of a raw material compound in the presence of a solid acid catalyst, which is characterized by using a catalyst that is improved in deterioration in catalytic performance with elapse of time to reduce the amount of the catalyst required for the reaction and produce a polyether having a narrow molecular weight distribution with a high conversion rate and in a stable manner for a long period of time. A solid acid catalyst having a hydroxyl group on the surface is allowed to contact with an organic compound other than a polyether and/or an inorganic compound which can react or interact with the hydroxyl group and then subjected to polymerization or condensation reaction. Since a hydrophobic group derived from the organic compound and/or the inorganic compound is bound to the hydroxyl group on the surface of the catalyst, the hydrophobic property of the surface of the catalyst can be improved, any influence of water which may adversely affect the performance of the catalyst can be eliminated, and the deterioration in catalytic performance with elapse of time can be prevented. Further, since a hydrophobic group is already bound to the reactive hydroxyl group on the surface of the catalyst, the binding or interaction of a polyether (i.e., a reaction product) to or with the hydroxyl group on the surface of the catalyst can be prevented, and the deterioration in catalytic performance with elapse of time can be prevented.

Description

The manufacture method of polyethers and the manufacture method of solid acid catalyst

Technical field

The present invention relates to the manufacture method of polyethers.The invention still further relates to the manufacture method of solid acid catalyst and solid acid catalyst.

Background technology

Polyethers is to be used for the raw material of urethane, ammonia ester urea, polyester etc. and to have other polymkeric substance of purposes widely with headed by soft section raw material of spandex fiber, thermoplastic elastomer etc.

As the representative of polyethers, known polyoxyethylene glycol, poly-(1, the 2-propylene glycol), polytetramethylene ether diol etc.Wherein, the synthetic polytetramethylene ether diol receives publicity in aspects such as retractility, elasticity excellence by the ring-opening polymerization of tetrahydrofuran (THF) (THF).

[background of the 1st, the 2nd aspect]

Polyether viscosity is than higher, with it is that raw material is further made under the situation of urethane etc., in its reaction process, need dilution or heating, thereby wish to have the polyethers of a kind of low viscosity (distribution of low molecular weight (molecular weight distribution=weight-average molecular weight (Mw)/number-average molecular weight (Mn))).Make in industrialization under the situation of polyethers, think that the molecular weight distribution of the polyethers that obtains can be subjected to the considerable influence of employed catalyst for polymerization.Certainly, the performance of catalyst for polymerization also can influence the transformation efficiency when making polyethers.

As the catalyzer that uses when making polyethers, the solid acid catalyst that on oxide carriers such as zeolite, silicon-dioxide load has metal oxide is disclosed in the patent documentation 1 and 2.

Patent documentation 1: Japanese kokai publication hei 9-241374 communique

Patent documentation 2: TOHKEMY 2000-327770 communique

According to the inventor's research,, make under the situation of polyethers the polyethers that can't obtain to have the quality that can fully satisfy in industrialization for catalyzer as the existing use of patent documentation 1 and 2 disclosed.Promptly, for existing catalyzer, along with continuing of reaction, the deterioration of catalyst performance strengthens, thereby make active deterioration and generate polyethers molecular weight distribution through the time deterioration become significantly, therefore, a large amount of catalyzer of needs in order stably to make polyethers, and also can only make resulting polyethers is the polyethers with wider molecular weight distribution.

[background of the 3rd aspect]

The soda acid intensity that known metal oxyhydroxide and/or metal oxide have because of himself plays the effect of acid base catalysator.And, can make composite oxides or with a kind of or metal oxide supported on the different kinds of metals oxide carrier more than 2 kinds by compound two or more metal oxide, obtain not second to the independent stronger strength of acid that metal oxide showed, this point is known for people.

In the past, as preparation method with the metal oxide supported solid acid catalyst that on carrier, forms, usually make with the following method: after being carried on metallic salt on the carrier, with alkali etc. the metal-salt on the carrier is hydrolyzed, make metal hydroxides, heating is fired then, and metal hydroxides is converted to metal oxide (patent documentation 3).

As the purposes of such solid acid catalyst, can enumerate the ring-opening polymerization manufacturing polyethers (patent documentation 4) that is used for for example utilizing tetrahydrofuran (THF) cyclic ethers such as (THF).When utilizing this solid acid catalyst to make polyethers, expectation is reacted this point needless to say with high conversion, expect that also the polyethers that produces is a low viscosity in operating aspect, for this reason, preferably produce molecular weight distribution, be weight-average molecular weight (Mw) and the little polyethers of ratio (Mw/Mn) of number-average molecular weight (Mn).

Patent documentation 3: TOHKEMY 2003-113238 communique

Patent documentation 4: TOHKEMY 2004-161893 communique

According to the inventor's research,, be difficult to metal hydroxides and/or the metal oxide state with fine dispersion is loaded on the carrier for patent documentation 3 disclosed methods.And even prepare solid acid catalyst with this method, its soda acid amount is also few sometimes, and also broad of the distribution of strength of acid.It is believed that its reason is, under the situation about being hydrolyzed with alkali after being carried on metallic salt on the carrier, because alkali is supplied with by carrier is outside, the feed rate of alkali can be different because of the position of carrier inside, thereby cause the hydrolysis rate difference, and when metal hydroxides was separated out, metallic salt can be owing to concentration gradient is moved.Promptly, it is believed that, the metal hydroxides of carrier inside can be because of different big part of concentration and the little parts of occurring in the position of carrier inside, the big aggegation of metal hydroxides appears in the big part of concentration, the less aggegation of metal hydroxides appears in the little part of concentration, its result, metal hydroxides loads in the carrier unevenly, and this uneven degree broadens relevant with the minimizing of soda acid amount with the distribution of strength of acid.

It is believed that the strength of acid of this solid acid catalyst distributes to broaden and for example can cause the reduction of transformation efficiency in the ring-opening polymerization of tetrahydrofuran (THF) etc., so cause the polymerization degree to broaden, be that the molecular weight distribution of the polyethers of target broadens.

[background of the 4th aspect]

In the patent documentation 1 and 2, the catalyzer that uses when making polyethers such as polytetramethylene ether diol by the ring-opening polymerization of THF etc. discloses the solid acid catalyst that on oxide carriers such as zeolite, silicon-dioxide load has metal oxide.

For the polyethers that so produces, because necessary molecular-weight average can be according to its purposes and difference, even therefore need the also various polyethers of identical its molecular-weight average of composition of manufacturing polyethers.

The method of the molecular-weight average of resulting polyethers being controlled when making polyethers, past adopts the method for change reaction conditions, promptly changes the method for temperature of reaction, transformation efficiency etc.

Patent documentation 1: Japanese kokai publication hei 9-241374 communique

Patent documentation 2: TOHKEMY 2000-327770 communique

When the molecular-weight average of resulting polyethers being changed, for example, increase under the situation of molecular-weight average according to reaction conditions, reduce temperature of reaction and just can access the big polyethers of molecular-weight average, but by reducing temperature of reaction, reactive behavior is reduced, productivity reduces.And, reduces transformation efficiency and also can access the big polyethers of molecular-weight average, but productivity also reduces in this case.

Also can increase the molecular-weight average of resulting polyethers by reducing the hold concurrently working concentration of terminator of initiators such as diacetyl oxide, but also can cause productivity to reduce because of the reduction of reaction starting velocity in this case.

Conversely, in the time of making the little polyethers of molecular-weight average, improve temperature of reaction just can, but in this case, can cause molecular weight distribution increase (deterioration), polyether viscosity increases, and also is easy to painted.

And, also can reduce the molecular-weight average of resulting polyethers by improving the hold concurrently working concentration of terminator of initiators such as diacetyl oxide, but can increase because of diacetyl oxide content remaining in the reaction solution and in separation circuit thereafter, have a negative impact in this case.

Based on these problems, a kind of molecular-weight average of demand with resulting polyethers be controlled at desired value and can be to the characteristic of reactive behavior, polyethers, handle other performances such as operation and produce dysgenic method.

Summary of the invention

[content of the 1st, the 2nd aspect]

1st, the purpose of the 2nd aspect solid acid catalyst that is to provide following method and is used for this method: in the manufacturing of polyethers, by use catalyst performance through the time deterioration catalyzer that is inhibited, thereby cut down necessary catalytic amount, and can make the method for the little polyethers of molecular weight distribution steadily in the long term with high conversion.

The manufacture method of the polyethers of the 1st aspect is to make starting compound carry out the method that polyethers is made in polyreaction or condensation reaction in the presence of solid acid catalyst, the method is characterized in that, as described solid acid catalyst, using the surface hydroxyl amount is 0.1 μ mol/m ²～2.5 μ mol/m ², the following acid amount of pKa-5.6 is the above solid acid catalysts of 20 μ mol/g.

And the 1st aspect also provides a kind of solid acid catalyst, and the surface hydroxyl amount of this solid acid catalyst is 0.1 μ mol/m ²～2.5 μ mol/m ², the following acid amount of pKa-5.6 is more than the 20 μ mol/g.

The manufacture method of the polyethers of the 2nd aspect is to make starting compound carry out the method that polyethers is made in polyreaction or condensation reaction in the presence of solid acid catalyst, the method is characterized in that, the solid acid catalyst that will have a surface hydroxyl with can use it for described polyreaction or condensation reaction again with after organic compound beyond this surface hydroxyl reaction or interactional, the described polyethers and/or mineral compound contact.

[content of the 3rd aspect]

The purpose of the 3rd aspect is to provide a kind of method of making solid acid catalyst, this method loads on the carrier with extremely even and trickle dispersion state by making metal hydroxides, metal oxide, makes more than the soda acid amount and the solid acid catalyst of strength of acid narrowly distributing.

The manufacture method of the solid acid catalyst of the 3rd aspect is the manufacture method with metal hydroxides and/or the metal oxide supported solid acid catalyst that forms on carrier, it is characterized in that this method comprises that the homogeneous precipitator method of utilizing in the carrier pore are in the pore internal burden metal hydroxides of carrier and/or the operation of metal oxide.

[content of the 4th aspect]

The purpose of the 4th aspect is to provide a kind of manufacture method of polyethers, it is by making the cyclic ether ring-opening polymerization make the method for polyethers in the presence of catalyzer, this method can be simply and effectively the molecular-weight average of resulting polyethers is controlled at desired value and can be to the characteristic of reactive behavior, polyethers, handle other performances such as operation and bring detrimentally affect.

The manufacture method of the polyethers of the 4th aspect is by making the cyclic ether ring-opening polymerization make the method for polyethers in the presence of catalyzer, it is characterized in that, as catalyzer, use the following catalyzer that obtains: be selected from by at least a element in the group of periodictable the 1st, 2,4,6,8,9,12,13,14,15,16 and 17 group compositions and can make it contain being selected from of not comprising in this solid acid catalyst with itself solid acid catalyst with the cyclic ether ring-opening polymerization by at least a metallic element in the group of periodictable the 3rd, 5,10 and 11 group compositions for containing.

Embodiment

[explanation of the 1st and the 2nd aspect]

The inventor has carried out deep research in order to solve above-mentioned problem, found that, by the solid acid catalyst with surface hydroxyl being handled with specific organic compound and/or mineral compound, the performance that can suppress catalyzer through the time deterioration, by using described solid acid catalyst through organic compound and/or mineral compound processing, can reduce the catalyst consumption that is used to make polyethers, and can dwindle the molecular weight distribution of polyethers, thereby finish the present invention.

Promptly, have in the method for surface hydroxyl amount of solid acid catalyst of surface hydroxyl in minimizing, comprise the method for at high temperature firing solid acid catalyst, in this case, because the surface-area of solid acid catalyst and acid amount reduce together, so the initial performance of catalyzer can worsen significantly.Relative therewith, under the situation about handling with organic compound and/or mineral compound according to the present invention, can only reduce the surface hydroxyl amount, and can not bring bigger detrimentally affect to the surface-area and the acid amount of solid acid catalyst, its result can utilize the surface hydroxyl amount is low and sour amount is big solid acid catalyst to make the polyethers of narrow molecular weight distribution steadily in the long term with high conversion.

Promptly, the 1st aspect of the present invention is a kind of manufacture method of polyethers, it is to make starting compound carry out the method that polyethers is made in polyreaction or condensation reaction in the presence of solid acid catalyst, the method is characterized in that, as described solid acid catalyst, using the surface hydroxyl amount is 0.1 μ mol/m ²～2.5 μ mol/m ², the following acid amount of pKa-5.6 is the above solid acid catalysts of 20 μ mol/g.

In addition, the 2nd aspect of the present invention is a kind of manufacture method of polyethers, it is to make starting compound carry out the method that polyethers is made in polyreaction or condensation reaction in the presence of solid acid catalyst, the method is characterized in that, the solid acid catalyst that will have a surface hydroxyl with can use it for described polyreaction or condensation reaction again with after organic compound beyond this surface hydroxyl reaction or interactional, the described polyethers and/or mineral compound contact.

1st, in the 2nd aspect, solid acid catalyst is to be selected from least a comparatively suitable in the group of being made up of the catalyzer and the clay catalyst of metal oxide O composite metallic oxide catalyst, load.

1st, in the 2nd aspect, it is comparatively suitable that solid acid catalyst contains at least a metallic element that is selected from by in the group of periodictable the 2nd family, the 3rd family, the 4th family, the 5th family, the 8th family, the 10th family, the 11st family, the 13rd family and the 14th group composition.

In the 2nd aspect, organic compound is that at least a compound that is selected from the group of being made up of alcohols, silanizing agent and carbonates is comparatively suitable.

1st, in the 2nd aspect, preferably make polyethers by making cyclic ether carry out ring-opening polymerization.Especially preferably make polyethers by in the presence of carboxylic acid anhydride and/or carboxylic acid, making cyclic ether carry out ring-opening polymerization.

1st, in the 2nd aspect, solid acid catalyst is made by carry out the homogeneous precipitator method in the carrier pore.

According to the 1st, the 2nd aspect, the solid acid catalyst with surface hydroxyl is handled (with its with can contact with organic compound and/or the mineral compound beyond reaction of this surface hydroxyl or interactional, the polyethers that generated) after, use it for reaction again, the polyethers of narrow molecular weight distribution can be stably produced, and employed catalytic amount can be subdued.That is, when making polyethers since the performance (catalyst activity) of catalyzer through the time deterioration be inhibited, thereby can subdue the catalyst levels that is used to make with the polyethers of amount.And, since molecular weight distribution through the time deterioration also obtained inhibition, so can make the high-quality polyethers of excellents such as thermotolerance.

With the polyethers in the narrow molecular weight distribution of manufacturing aspect the 1st, the 2nd is that raw material is further made under the situation of urethane etc., can reduce the viscosity that is used for facilitating reaction and carries out and adjust the amount of necessary thinner, aspect cost and the productivity aspect also can expect favourable effect.

Embodiment to the 1st, the 2nd aspect is elaborated below, but the explanation of the constitutive requirements of following record only is an example (typical example) of the embodiment of the 1st, the 2nd aspect, and only otherwise exceed its main points, the 1st, the 2nd aspect is not subjected to the restriction of these contents.

[solid acid catalyst]

At first, the solid acid catalyst that uses in the 1st, the 2nd aspect is described.

1st, the solid acid catalyst that uses in the 2nd aspect is that the surface hydroxyl amount is 0.1 μ mol/m ²～2.5 μ mol/m ², the following acid amount of pKa-5.6 is the above solid acid catalysts of 20 μ mol/g, the solid acid catalyst of this low surface hydroxyl amount, peracid amount for example can obtain by solid acid catalyst with surface hydroxyl is contacted with specific organic compound and/or mineral compound.

(solid acid catalyst) with surface hydroxyl

1st, so-called solid acid catalyst with surface hydroxyl is the solid acid catalyst that has hydroxyl (OH yl) on the surface (comprising carrier pore internal surface) at metal and/or carrier in the 2nd aspect.

More particularly, as solid acid catalyst, can enumerate the zeolites of crystalline structure such as for example having MFI, X, Y with surface hydroxyl; Metal oxide-type such as silicon-dioxide, aluminum oxide, titanium dioxide, zirconium white; The complex metal oxides class that two or more oxide-metal combinations such as silica-titania, silica-alumina, silicon-dioxide-zirconium white, aluminum oxide-titanium dioxide form; With metal oxide, gac is that carrier and load have sulfuric acid, heteropolyacid, high fluoride resin (Nafion) etc. to have the compound of acid matter or be different from the loading type acid catalyst class of the metal oxide of carrier; Clay classes such as layered silicate; Load has clay class of compound with acid matter or metal, metal oxide etc.

Wherein, use under the situation of complex metal oxides class, loading type acid catalyst class preferred especially silicon-dioxide-zirconium white, silica-alumina, silicon dioxide carried zirconium white, silicon dioxide carried aluminum oxide.Use under the situation of clay classes such as layered silicate, can enumerate kaolinite, green stone etc. usually, the preferred montmorillonite that uses in the green stone.And the clay class is preferably used with the form of the atlapulgite of pickling, especially preferably uses the atlapulgite that obtains after the montmorillonite pickling.

These solid acid catalysts both can be used alone, and it is two or more also can to mix use.

As this manufacture method with solid acid catalyst of surface hydroxyl, can use technique known and be not particularly limited, specifically, can utilize the manufacture method of record in above-mentioned Japanese kokai publication hei 9-241374 communique, the TOHKEMY 2000-327770 communique etc.

Especially, for the solid acid catalyst that uses in aspect the 1st, the 2nd, preferably in the pore of carrier, carry out the homogeneous precipitator method, metal hydroxides and/or metal oxide are loaded in the pore of carrier and the solid acid catalyst that obtains with even and trickle dispersion state.

Provide an example that utilizes the method for the solid acid catalyst that the manufacturing of the homogeneous precipitator method has surface hydroxyl below.

The following enforcement of the homogeneous precipitator method, for example, infiltrate metal-salt and the precipitation agent precursor that in solution, produces precipitation agent simultaneously in carrier by chemical reactions such as hydrolysis after, this impregnated carrier is carried out heat treated etc. is generated precipitation agent by the precipitation agent precursor processing.Owing to be the homogeneous precipitator method, therefore importantly metal-salt and precipitation agent precursor form liquid phase, promptly form solution.That is, the dipping solution that will contain metal-salt and precipitation agent precursor is infiltrated up in the carrier, then, handles making by precipitation agent precursor generation precipitation agent.

(1) carrier

Be not particularly limited for carrier, preferable alloy is oxide-based, complex metal oxides class, zeolites, clay class, more preferably silicon-dioxide, aluminum oxide, zirconium white, titanium dioxide, silica-alumina, silicon-dioxide-zirconium white, silica-titania, preferred especially silicon-dioxide, aluminum oxide, zirconium white.

As for particle diameter, fine pore and the pore volume of carrier, can be different because of purposes, use form as solid acid catalyst, cannot treat different things as the same.

These carriers both can be used alone, and also can share two or more.

(2) metal hydroxides and/or metal oxide

Be not particularly limited for above-mentioned metal hydroxides and/or the metal oxide that is carried on like that on the carrier, be generally the oxyhydroxide and/or the oxide compound of the metallic element of periodictable the 2nd～14 family, be preferably and be selected from by periodictable the 2nd family, the 3rd family, the 4th family, the 5th family, the 8th family, the 10th family, the 11st family, the oxyhydroxide of at least a metallic element in the group of the 13rd family and the 14th group composition and/or oxide compound, more preferably be selected from by Ti, Zr, Hf, Nb, Al, Cu, Ni, Ca, the oxyhydroxide and/or the oxide compound of at least a metallic element in the group that Fe and Si form are preferably especially and are selected from by Ti, Zr, Al, Cu, the oxyhydroxide and/or the oxide compound of at least a metallic element in the group that Ni and Nb form.

(3) metal-salt

The metal-salt that is used for the homogeneous precipitator method is to generate the above-mentioned metal hydroxides that is carried on the resulting solid acid catalyst and/or the metal-salt of metal oxide, therefore, be generally the salt of the metallic element of above-mentioned periodictable the 2nd～14 family, be preferably the salt of the metallic element of the 2nd, 3,4,5,8,10,11,13,14 families, more preferably Ti, Zr, Hf, Nb, Al, Si, Cu, Ni, Ca, Fe salt are preferably Ti, Zr, Al, Nb, Cu, Ni salt especially.

Kind for salt is not particularly limited, preferably nitrate, acetate, vitriol, oxynitrate, muriate, oxychloride, more preferably oxynitrate, oxychloride, vitriol.

That is, as nitrate, acetate, vitriol, oxynitrate, muriate, the oxychloride of metal-salt preferred cycle table the 2～14 family's metals, more preferably Zircosol ZN, basic zirconium chloride, zirconium sulfate, titanium chloride, Tai-Ace S 150, niobium oxychloride.

These metal-salts both can be used alone, and also can share two or more.

(4) precipitation agent precursor

The precipitation agent precursor is meant, causes that by processing such as heat in dipping solution hydrolysis or other chemical reactions are to generate the material of precipitation agent.Precipitation agent be meant with dipping solution in reacting metal salt generate the material of precipitate metal hydroxides.In the precipitation agent precursor, be called " alkali precursor " with the sedimentary material of the form of oxyhydroxide or oxide compound by hydrolysis or other chemical reaction with producing the material (that is, in dipping solution, produce alkali, the pH of solution is risen, make metal-salt) of alkali as precipitation agent.

Be not particularly limited for the precipitation agent precursor that is used to carry out the homogeneous precipitator method, but use the alkali precursor usually.

As the alkali precursor, the amide compound that use urea, tricyanic acid, alkyl substituted ureas, thiocarbamide, alkyl substituting thioureido, constitutes by amine and carboxylic acid etc.Preferred urea, tricyanic acid, the alkyl substituted ureas of using is from being easy to obtain and the consideration of cost aspect preferred especially urea, tricyanic acid.These alkali precursors can be used alone, and also can share two or more.

(5) alkaline matter

In dipping solution, not only can add above-mentioned alkali precursor, and the alkaline matter that can be in advance adds predetermined amount in not generating sedimentary scope is to improve pH.By using alkaline matter, consumption, the minimizing that can reduce the alkali precursor generate the precipitation time necessary.

Be not particularly limited for alkaline matter, can enumerate oxyhydroxide, carbonate, supercarbonate, phosphoric acid salt, the acetate of basic metal, alkaline-earth metal and ammonium, ammonia, organic amine etc., preferred ammonia, organic amine, the carbonate of ammonium, supercarbonate, phosphoric acid salt, more preferably volatile salt, bicarbonate of ammonia.

These alkaline matters both can be used alone, and also can share two or more.

(6) dipping solution

Dipping solution prepares by above-mentioned metal-salt, precipitation agent precursor and the alkaline matter that uses as required are dissolved in the water usually.

Concentration to metal-salt in the dipping solution and precipitation agent precursor is not particularly limited, as long as can keep dissolved state and can realize the charge capacity that is fit to the aftermentioned carrier, usually metal salt concentrations is 0.01 weight %～50 weight %, be preferably 0.1 weight %～40 weight %, be preferably 0.5 weight %～30 weight % especially, as described later, the precipitation agent precursor is 0.1～10 times with respect to being enough to make the whole sedimentary theoretical amount of this metal-salt, be preferably 0.2～8 times, be preferably 0.3～5 times especially.

Can suitably use alkaline matter to obtain required pH condition.That is, owing to generate the necessary pH condition of precipitation according to the kind of employed metal-salt and precipitation agent precursor or concentration and different, so can use the alkaline matter of necessary amount according to these conditions.

In addition, in order in carrier, to implement the homogeneous precipitator method, make before the precipitation agent precursor is converted to the processing of precipitation agent, needing at least a metal-salt and precipitation agent precursor is liquid phase in dipping solution, be dissolved state, for the material except this at least a metal-salt and precipitation agent precursor, in dipping solution, exist and all can with random order.

(7) the homogeneous precipitator method

＜dipping solution is to the infiltration method of carrier 〉

Be not particularly limited for the method that above-mentioned dipping solution is infiltrated up in the carrier, load to equably on the carrier, preferably implement with the hole completion method in order to make metal-salt.In this case, the volume that is infiltrated up to the dipping solution in the carrier is preferably 60%～120% of carrier pore volume, and more preferably 70%～110%, be preferably 80%～105% especially.If this hypovolia, then dipping solution can not enter in the carrier pore equably, and causes uneven homogenize.Conversely, if this hypervolia, then steeping fluid still can cause uneven homogenize attached to the carrier outside surface.

In addition, the charge capacity that loads on the metal-salt on the carrier by infiltration can be selected to measure arbitrarily, but be 0.01 weight %～50 weight % with respect to vehicle weight usually, be preferably 0.05 weight %～40 weight %, more preferably 0.1 weight %～30 weight %.Charge capacity for the precipitation agent precursor, if being enough to make the whole sedimentary theoretical amount of the metal-salt that is carried on the carrier is,, in 0.1～10 scope, use the precipitation agent precursor usually at 1 o'clock with molar ratio computing, be preferably 0.2～8 scope, more preferably 0.3～5 scope.

＜sedimentary generation and post-treating method 〉

Dipping solution is infiltrated up in the carrier, the state that makes the metal-salt that is carried on the carrier and precipitation agent precursor in the carrier pore, keep solution thus, implement heating in this state and wait the processing that the precipitation agent precursor is converted to precipitation agent, utilize the precipitation agent that evenly produces in carrier inside that metal-salt is converted to corresponding metal hydroxides.

Usually use the alkali precursor as the precipitation agent precursor, in the processing that the alkali precursor is converted to alkali, utilize the hydrolysis of the alkali precursor that causes by heating.

As mentioned above, in order in the carrier pore, to implement the homogeneous precipitator method, need be before carrying out that the precipitation agent precursor is converted to the processing of precipitation agent, make at least a metal-salt and precipitation agent precursor be solution state, be liquid phase, all can and the material except this at least a metal-salt, precipitation agent precursor is any state.

In based on the hydrolysis reaction that adds thermal initiation, the alkali precursor is converted under the situation of alkali,, adopts 50 ℃～300 ℃ scope usually, preferably adopt 60 ℃～200 ℃ scope as Heating temperature.Heating temperature is changed in time.If Heating temperature is low excessively, the reaction of precipitation agent then might not take place to be generated by the precipitation agent precursor, or need expend the very long time; If Heating temperature is too high, then the necessary moisture of hydrolysis sometimes may all be removed before the reaction that is generated precipitation agent by the precipitation agent precursor finishes.In order to implement the good and stable homogeneous precipitator method, preferably when the sedimentary reaction of generation finished, the moisture entrapment in the dipping solution of infiltration in carrier is more than 5%, and was more preferably residual more than 10%.

As the fixed bed heating unit, can there be the carrier of dipping solution to heat to infiltration at the immobilising state of load carriers, but especially under the situation of a large amount of catalyzer of preparation, more preferably the thermopnore device of working load carrier flow, revolving heating unit etc.It is believed that, when heating, occur under the situation of moisture evaporation, make load carriers mobile method that the water evaporation quantity of every particle loading carrier is changed, thereby further increase uniformity.

In addition, if the moisture evaporation during heating is too fast, then moisture was all removed before the hydrolysis of alkali precursor finishes fully, sometimes can not fully carry out the supply of precipitation agent, therefore it is desirable to usually, by begin heating through precipitation formation reaction finish the back, till removing moisture fully, with more than 1 hour, preferred more than 3 hours, further preferred time more than 6 hours carries out removing fully of moisture.

Thereafter, water, alkali aqueous solution, aqueous acid, organic solvent etc. clean resulting catalyzer as required, after the drying, under inert gas atmospheres such as nitrogen, argon gas or oxidizing gas atmosphere such as air or dilution oxygen, fire, thus the solid acid catalyst that can obtain having desired performance.Heating firing temperature as this moment is generally 100 ℃～1200 ℃, is preferably 300 ℃～1100 ℃, more preferably 500 ℃～1000 ℃.Fire by carrying out such heating, can make the catalyst activity and the improved stability of resulting solid acid catalyst.

Wherein, above-mentioned operation not all is necessary operation, as long as finally can access the solid acid catalyst with surface hydroxyl, to the not restriction especially of its manufacturing process.

In addition, metal hydroxides and/or metal oxide are preferably 0.05 weight %～40 weight % with respect to the charge capacity of carrier in the solid acid catalyst that is obtained by aforesaid method, are preferably 0.1 weight %～30 weight % especially.

(utilizing the treatment process of organic compound and/or mineral compound)

The organic compound and/or the mineral compound that are used to handle the solid acid catalyst (the preferably solid acid catalyst with surface hydroxyl that obtains by the above-mentioned homogeneous precipitator method) with surface hydroxyl are meant, with the compound of the surface hydroxyl of solid acid catalyst reaction and/or produce interactional compound, can enumerate particularly: alcohols such as methyl alcohol, ethanol; Ethers such as ether; Ester such as methyl acetate, ethyl acetate class; Acylation agents such as acetate, Acetyl Chloride 98Min., diacetyl oxide; Carbonates such as methylcarbonate, diethyl carbonate; Silanizing agents such as trimethylsilyl acetate, chlorotrimethylsilane, tertiary butyl dimethyl chloride silicomethane, hexamethyldisiloxane, trimethyl silane, diethylmethyl silane, triethyl silicane; Metal hydroxides, metal chloride, metal ammonia complex etc.Herein, as the metal of metal hydroxides, metal chloride, metal ammonia complex, can enumerate cupric chloride, nickelous chloride, dichloro four ammonia complex copper, dichloro six amminos and close nickel, four ammino copper dinitrates, hexamine nickel dinitrate etc.Wherein preferred alcohols, ester class, acylation agent, carbonates, silanizing agent; more preferably alcohols, carbonates, silanizing agent; consider special particular methanol, ethanol, methyl acetate, ethyl acetate, methylcarbonate, diethyl carbonate, trimethylsilyl acetate, trimethyl silane, diethylmethyl silane, triethyl silicane from aspects such as reactivity, unreacted organic compound with surface hydroxyl are easy to remove.These organic compound and/or mineral compound both can be used alone, and also can mix two or more uses.

To the restriction especially of treatment process that utilizes the solid acid catalyst that organic compound and/or mineral compound carry out, can adopt in liquid phase, the gas phase any.And, can adopt in batch-type, the flow type any under the situation of liquid phase.

Be under liquid phase, the batch-wise situation, when utilizing organic compound and/or mineral compound to carry out the processing of solid acid catalyst, solid acid catalyst with surface hydroxyl can be added and into be used for the organic compound handled and/or mineral compound itself or organic compound and/or mineral compound diluted the solution that forms, implement to handle by heat treated with inert solvent.

In this case, for the consumption of organic compound and/or mineral compound,, be limited to below 10 times on usually, be limited to down more than 0.1 times with respect to the volume of catalyzer, preferred upper limit is below 8 times, is limited to more than 0.2 times down, is limited to below 5 times on more preferably, is limited to more than 0.3 times down.If the consumption of organic compound and/or mineral compound is too much, then the cost of organic compound and/or mineral compound increases, the burden of removing unreacted organic compound and/or mineral compound also becomes greatly, if described consumption is very few, then undressed catalyzer can occur.

Be not particularly limited for diluting solvent, use hydrocarbon usually, preferably use pentane, hexane, heptane, benzene,toluene,xylene.These solvents both can be used alone, and also can mix two or more uses.Weaker concn suitably determines according to the kind of handling with organic compound and/or mineral compound.

Heating temperature is according to the kind of organic compound and/or mineral compound and difference, be limited under usually more than 10 ℃, on be limited to below 200 ℃ preferred especially 20 ℃～150 ℃.

For the heat treated time, it is according to the kind of organic compound and/or mineral compound and difference, and preferred 0.1 hour～20 hours, preferred especially 0.5 hour～15 hours.

And,, can implement the processing that utilizes organic compound and/or mineral compound to carry out more than twice in order to handle fully.

Under the situation that is liquid phase, flow type, when utilizing organic compound and/or mineral compound to carry out the processing of solid acid catalyst, can in having the solid acid catalyst of surface hydroxyl, circulate to handle organic compound and/or mineral compound are diluted organic compound and/or the mineral compound that forms, implement processing by heating simultaneously with organic compound and/or mineral compound itself or with solvent.

For circulation device, can use in fixed bed and the thermopnore any, consider to be easy to more equably catalyzer be handled the preferred streams movable bed.

Be not particularly limited for solvent, use hydrocarbon usually, preferably use pentane, hexane, heptane, benzene,toluene,xylene.These solvents both can be used alone, and also can mix two or more uses.Weaker concn can suitably determine according to the kind of handling with organic compound and/or mineral compound.

Its flow is not particularly limited preferred SV0.1h ^-1～100h ^-1, preferred especially SV0.5h ^-1～50h ^-1

Heating temperature is different because of the kind of organic compound and/or mineral compound, be limited under usually more than 10 ℃, on be limited to below 300 ℃ preferred especially 20 ℃～200 ℃.

For the heat treated time, it is according to the kind of organic compound and/or mineral compound and difference, and preferred 0.1 hour～20 hours, preferred especially 0.5 hour～15 hours.

And,, can implement the processing that utilizes organic compound and/or mineral compound to carry out more than twice in order to handle fully.

Under the situation that is gas phase, when utilizing organic compound and/or mineral compound to carry out the processing of solid acid catalyst, can be used for handling the organic compound of solid acid catalyst with surface hydroxyl or with inert gas dilution organic compound with vaporized state in solid acid catalyst circulation and heating simultaneously, implement thus to handle.

Circulation device can use any in fixed bed and the thermopnore, considers to be easy to more equably catalyzer be handled the preferred streams movable bed.

As inert dilution gas, use nitrogen, argon gas, carbonic acid gas, helium, air usually, preferred nitrogen, carbonic acid gas, argon gas.These diluent gass both can be used alone, and also can mix two or more uses.

Concentration for organic compound gas in the rare gas element is not particularly limited, and is generally 0.05 mole of %～100 mole %, is preferably 0.1 mole of %～80 mole %, is preferably 0.1 mole of %～50 mole % especially.

The temperature of heating is different because of the kind of organic compound, but preferred 10 ℃～400 ℃, preferred especially 20 ℃～300 ℃.

Flow is not particularly limited preferred SV10h ^-1～5000h ^-1, preferred especially SV30h ^-1～4000h ^-1

The heat treated time is also different because of organic kind, but preferred 0.1 hour～20 hours, preferred especially 0.5 hour～15 hours.

And,, can implement the processing that utilizes organic compound and/or mineral compound to carry out more than twice in order to handle fully.

In addition, in the processing of solid acid catalyst in used organic compound and/or mineral compound and the solvent if contain moisture, can make the catalyst performance deterioration on the contrary.Therefore, be used for the organic compound of processing of solid acid catalyst and/or mineral compound and solvent preferably utilize in advance dewatering agent equal altitudes ground remove moisture be processed into water content be 10 weight % following, be preferably 5 weight % following, be preferably below the 2 weight % especially.

Wherein, organic compound that is used to handle and/or mineral compound can not decompose because of moisture, and the solid acid catalyst after handling can be fired under the temperature more than 300 ℃ before being used to react, the surface hydroxyl amount of the solid acid catalyst after firing remains under the following situation of 2.5 μ mol/g, does not also have problems even contain moisture.

＜the solid acid catalyst handled through organic compound and/or mineral compound 〉

It is believed that the solid acid catalyst by above-mentioned operation manufacturing has characteristic as follows.

Promptly, can think,, can improve the hydrophobicity of catalyst surface by being combined with the hydrophobic group that is derived from organic compound and/or mineral compound on the surface hydroxyl, inhibition may bring the influence of dysgenic moisture to catalyzer, suppress catalyst performance through the time deterioration.And, owing to be combined with hydrophobic group on reactive surface hydroxyl having, thereby think that can suppress polyethers as reaction product combines with surface hydroxyl or interact, the inhibition catalyst performance through the time deterioration.

In addition, for solid acid catalyst through organic compound and/or mineral compound processing, as long as the surface hydroxyl amount remains on below the 2.5 μ mol/g, also can be before being used to react fire, to remove unnecessary reagent treatment and moisture the temperature more than 300 ℃, for example 300 ℃～1000 ℃.

Thus, compare with the solid acid catalyst that does not carry out organic compound and/or mineral compound processing with prior art for preparing, the catalyst performance of solid acid catalyst through handling like this through the time deterioration, catalyst activity through the time deterioration and resulting polyethers molecular weight distribution through the time worsen and be inhibited, can make the polyethers of narrow molecular weight distribution with a spot of catalyzer steadily in the long term.

(solid acid catalyst that is used to react)

Being used for the polyreaction of starting compound or the solid acid catalyst of condensation reaction is that the surface hydroxyl amount is 0.1 μ mol/m ²～2.5 μ mol/m ², the following acid amount of pKa-5.6 is the above solid acid catalysts of 20 μ mol/g.

If the surface hydroxyl amount of solid acid catalyst surpasses 2.5 μ mol/m ², then can't obtain polyethers as the narrow molecular weight distribution of purpose of the present invention.

And,, thereby when making polyethers, need use a large amount of catalyzer if the acid amount below the pKa-5.6 of solid acid catalyst then can not obtain sufficient polymerization activity less than 20 μ mol/g.

The surface hydroxyl amount of solid acid catalyst is preferably 0.1 μ mol/m ²～2.0 μ mol/m ², and the following acid amount of pKa-5.6 is preferably more than the 40 μ mol/g, more preferably more than the 60 μ mol/g.

In addition, the following acid amount of the surface hydroxyl amount of solid acid catalyst and pKa-5.6 for example can followingly be measured.

[surface hydroxyl amount]

0.7g takes a sample in U word pipe; under with the condition of the speed of 40cc/min circulation high purity Ar in 300 ℃ of dryings 1 hour; behind the naturally cooling, with under the atmosphere state of contact do not taking off U word pipe, be transferred in the airtight insulation blocking cover (glove bag) of dry gas.

Add sample to the Erlenmeyer flask of putting into airtight insulation blocking cover in advance, again to wherein adding the 20cc dry toluene.Erlenmeyer flask is installed in speed with the 80cc/min N that circulated ₂The titration experiments device on.In the Ar glove box, the ethereal solution of 5cc 1.5M lithium methide-lithiumbromide complex compound is drawn onto in the plastic injector, with rubber seal under the state of needle point with its taking-up, be injected in the Erlenmeyer flask by barrier film.

Capture 10 minutes sweeping gas with capturing bag, with the quantitative methane concentration of GC.Purge gas flow detects with accurate film under meter.Come the surface hydroxyl amount of the catalyzer of Units of Account weight by the methane content of obtaining by methane concentration and purge gas flow that is produced.

Use the HM Model-1201 type of Mountech society manufacturing, utilize the surface-area of the catalyzer of nitrogen absorption BET1 point method analytical unit weight, calculate the surface hydroxyl amount of the per surface area of catalyzer thus.

[the acid amount that pKa-5.6 is following]

With catalyzer in 200 ℃ of vacuum-dryings 3 hours, weighing catalyzer in the glove box under the nitrogen atmosphere.Add 2ml toluene, be installed on the UV determinator, add 0.2 weight % benzylidene acetophenone (pKa≤-5.6 usefulness)/toluene solution 1ml as indicator.As the n-butylamine of titration reagent use 0.01mol/L, by the acid amount below the n-butylamine amount calculating pKa-5.6 that is dripped till disappearing until UV peak with acid sites (sour point) bonded benzylidene acetophenone.

[manufacture method of polyethers]

Be 0.1 μ mol/m to use through manufacture method, the use surface hydroxyl amount of the polyethers of the 2nd aspect of the solid acid catalyst of above-mentioned organic compound and/or mineral compound processing below ²～2.5 μ mol/m ², to be the above solid acid catalyst of 20 μ mol/g describe as the manufacture method of the polyethers of the 1st aspect of catalyst for polymerization the following acid amount of pKa-5.6.

Restriction especially of manufacture method to the polyethers of the 1st, the 2nd aspect, but preferably undertaken, more preferably by being that reaction raw materials makes it carry out the method that ring-opening polymerization is made with the ring-type ethers by the ring-opening polymerization of ring-type ethers or the dehydration condensation of polyvalent alcohol.

Make under the situation of polyethers with the ring-opening polymerization of ring-type ethers, as the cyclic ether as reaction raw materials, the formation carbonatoms that can enumerate ring is 3～10 cyclic ether, and, can use the cyclic ether that replaces with alkyl, halogen radical, acyl group etc.Specifically, can use tetrahydrofuran (THF), trimethylene oxide, oxepane, 1,4-dioxane, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran etc.And, can only use a kind of homopolymerization of ring-type ethers and use any polymerization in the copolymerization of two or more ring-type ethers.

As catalyzer, using as above solid acid catalyst or the surface hydroxyl amount handled through organic compound and/or mineral compound is 0.1 μ mol/m ²～2.5 μ mol/m ², the following acid amount of pKa-5.6 is in the above solid acid catalyst of 20 μ mol/g one or more.

Consider that from the aspect of control molecular weight the ring-opening polymerization of cyclic ether preferably carries out in the presence of carboxylic acid anhydride and/or carboxylic acid.As carboxylic acid anhydride and/or carboxylic acid, generally use aliphatics or aromatic carboxylic acid anhydride and/or carboxylic acid, preferred carboxylic acid anhydride and/or the carboxylic acid that use with 2～8 carbon atoms with 2～12 carbon atoms.These carboxylic acid anhydride and/or carboxylic acid both can be used alone, and also can share two or more.With respect to cyclic ether, carboxylic acid anhydride and/or carboxylic acid add in the scope of 0.01～1.0 (mol ratio) usually and get final product.

Can in reaction, use inert solvent during polyreaction.As this solvent, use the divided ring polyreaction to be in inert aliphatic hydrocarbon, the aromatic hydrocarbon etc. one or more usually.

Reaction formation uses the general form of using such as grooved, tower, can be any of batch mode, continuous mode.Following method etc. is for example arranged: cyclic ether, catalyzer, carboxylic acid anhydride and/or carboxylic acid are under agitation fed intake carry out polymeric method (batch mode); In containing the reactor of catalyzer, supply with cyclic ether, carboxylic acid anhydride and/or carboxylic acid and continuous method (continuous mode) of extracting reaction solution out etc. continuously.Consider preferred continuous mode from the aspect of productivity.

The consumption of solid acid catalyst depends on its kind, be not particularly limited, but for example in the batch-type reactor, if catalytic amount is very few, then polymerization velocity is slack-off, conversely if too much, then be difficult to remove heat of polymerization.And, because the slurry concentration of reaction system uprises, cause stirring difficulty, and be easy to go wrong in the separatory of catalyzer after polyreaction finishes and reaction solution.Therefore, for catalyst consumption, can be generally 0.001～50 times of weight with respect to liquid phase under the condition of the reaction form of considering batch reactions, circulation reaction, be preferably in the scope of 0.01～20 times of weight and select.Wherein, under the situation of circulation reaction, catalyst consumption is represented the amount with respect to the catalyzer of liquid phase feed rate of time per unit.

Temperature of reaction is generally 0 ℃～200 ℃, is preferably 10 ℃～80 ℃.

Reaction pressure is that reaction system can keep the pressure of liquid phase to get final product, usually from normal pressure～10MPa, preferably select from the pressure range of normal pressure～5MPa.

Reaction times is not particularly limited, consider itself and catalytic amount the two, consider yield, economy, the reaction times is 0.1 hour～20 hours scope, is preferably 0.5 hour～15 hours scope.The said herein reaction times is meant, in batch mode, plays the time till reaction finishes to begin to cool down when rising to temperature of reaction by temperature; In continuous mode, the residence time of liquid in reactor formed in reaction.

The molecular weight distribution of the polyethers that is generated depends on the kind of starting compound, but according to the present invention, and solid acid catalyst or the surface hydroxyl amount of utilizing organic compound and/or mineral compound to handle in use are 0.1 μ mol/m ²～2.5 μ mol/m ², the following acid amount of pKa-5.6 is under the situation of the above solid acid catalyst of the 20 μ mol/g ring-opening polymerization that carries out tetrahydrofuran (THF) (THF), can obtain number-average molecular weight (Mn) is 200～80,000, the polyethers of low～middle molecular weight of about 200～40,000 particularly.And then the polyethers that can easily produce narrow molecular weight distribution also is one of feature.Promptly, the Mw/Mn of the polyethers that industrial requirement is bigger is 1.3～2.5, by utilizing solid acid catalyst of the present invention, can access Mw/Mn less than 3, for example Mw/Mn is 1.1～3.0 polytetramethylene ether diol (PTMG), particularly by selecting optimum condition of the present invention for use, can also obtain Mw/Mn and be about 1.4～1.7 the very narrow polyethers of molecular weight distribution.And according to the present invention, the yield that can make product is more than 15%, is preferably more than 20%, further is more than 25%.

And then, since catalyst activity through the time deterioration less, even react the state that also can keep high conversion for a long time.

The polyethers that is produced by the 1st, the 2nd aspect can be used for purposes such as spandex fiber, thermoplastic polyester elastomer, Polyurethane Thermoplastic Elastomer, coating material.

[embodiment and comparative example]

Enumerate synthesis example, embodiment and comparative example below, the 1st, the 2nd aspect is further specifically described, but following embodiment does not limit the scope of the 1st, the 2nd aspect.

In addition, in the content below, the transformation efficiency of polytetramethylene ether diol acetic ester (PTME), number-average molecular weight (Mn), molecular weight distribution (Mw/Mn) utilize following GPC (gel permeation chromatography) to obtain.

The GPC device: Tosoh society makes GPC 8220

Post: TSK-GEL GMHHR-M (30cm) * 4

Detection method: RI

Column temperature: 40 ℃

Mobile phase: THF

Flow velocity: 1ml/min

Sample injection rate: 500 μ L

Sample concentration: the concentration that is adjusted to polyethers is about 0.5 weight %

In addition, the surface hydroxyl amount of solid acid catalyst and following mensuration of acid amount.

[surface hydroxyl amount]

The 0.7g that takes a sample in U word pipe in 300 ℃ of dryings 1 hour, behind the naturally cooling, with under the atmosphere state of contact is not taking off U word pipe under with the condition of the speed circulation high purity Ar of 40cc/min, is transferred in the airtight insulation blocking cover of dry gas.

Add sample at the Erlenmeyer flask of putting into airtight insulation blocking cover in advance, again to wherein adding the 20cc dry toluene.Erlenmeyer flask is installed in speed with the 80cc/min N that circulated ₂The titration experiments device on.In the Ar glove box, the ethereal solution of 5cc 1.5M lithium methide-lithiumbromide complex compound is drawn onto in the plastic injector, with rubber seal under the state of needle point with its taking-up, be injected in the Erlenmeyer flask by barrier film.

Capture 10 minutes sweeping gas with capturing bag, with the quantitative methane concentration of GC.Purge gas flow detects with accurate film under meter.Come the surface hydroxyl amount of the catalyzer of Units of Account weight by the methane content of obtaining by methane concentration and purge gas flow that is produced.

Use the HM Model-1201 type of Mountech society manufacturing, utilize the surface-area of the catalyzer of nitrogen absorption BET1 point method analytical unit weight, calculate the surface hydroxyl amount of the per surface area of catalyzer thus.

[the acid amount that pKa-5.6 is following]

With catalyzer in 200 ℃ of vacuum-dryings 3 hours, weighing catalyzer in the glove box under the nitrogen atmosphere.Add 2ml toluene, be installed on the UV determinator, add 0.2 weight % benzylidene acetophenone (pKa≤-5.6 usefulness)/toluene solution 1ml as indicator.As the n-butylamine of titration reagent use 0.01mol/L, by the acid amount below the n-butylamine amount calculating pKa-5.6 that is dripped till disappearing until UV peak with acid sites bonded benzylidene acetophenone.

＜have a preparation of the solid acid catalyst of surface hydroxyl 〉

The synthesis example 1-1 of catalyzer:

(new Japanese metallochemistry society makes ZrO at the 89.66g Zircosol ZN aqueous solution ₂Conversion concentration is 18.12 weight %) middle 18.72g de-salted water and the uniform mixing of adding.To wherein adding 11.84g urea uniform mixing, the preparation dipping solution.In this solution, add 80g SiO ₂(Silysia of Fuji makes, CARiACT Q15, particle diameter 75 μ m～500 μ m, median size 200 μ m, pore volume 1.16ml/g, average fine pore 15nm), vibrate and mixed in about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).

In its 500ml pyriform flask of packing into,, connect thermometer in measurement section at flask top jointing and the bend pipe that is plugged with glass wool.With anchor clamps flask be fixed on the turning axle of rotating dryer on thereafter.Speed rotation turning axle with 10rpm is set at 105 ℃ with the drying machine temperature, carries out 6 hours heating.At this moment, by the moisture entrapment 90% in the changes in weight affirmation dipping solution.Then, unload the bend pipe that is plugged with glass wool on top after, the drying machine temperature is set at 120 ℃, carry out 16 hours heating.

Then, unload the joint on top after, the drying machine temperature is set at 140 ℃, carry out 4 hours heating, moisture is almost completely removed.After 4 hours, stop heating, rotation, take out catalyzer.

Catalyzer is transferred in the beaker of 500ml and naturally cools to room temperature, add the de-salted water of about 300ml then, carry out about 10 minutes suspension cleaning.Next, behind the filtering catalyst, be transferred to once more in the beaker of 500ml, add that the 30g Ammonium Bicarbonate, Food Grade is dissolved in the solution that obtains in the de-salted water of 300ml, carry out about 10 minutes suspension and clean.Next, behind the filtering catalyst, be transferred to once more in the beaker of 500ml, add the 300ml de-salted water, carry out about 10 minutes suspension and clean.After 2 cleanings of this de-salted water repetition, air-dry catalyzer 120 ℃ of dry nights in drying machine, carries out firing in 2 hours in 900 ℃ under airiness then.

Resulting solid acid catalyst is made as " catalyzer 1 ".Obtain by calculating according to the composition of steeping fluid that the zirconic charge capacity with respect to the catalyzer total amount is 16.9 weight % in the catalyzer 1.

And the surface hydroxyl amount of catalyzer 1 is 2.6 μ mol/m ², the following acid amount of pKa-5.6 is 110 μ mol/g.

The synthesis example 1-2 of catalyzer

(new Japanese metallochemistry society makes ZrO at the 89.66g Zircosol ZN aqueous solution ₂Conversion concentration is 18.12 weight %) in add the 0.44g de-salted water and make homogeneous solution, after wherein little by little add 25 weight % ammonium carbonate solution 26.94g, making homogeneous solution, little by little add 7.94g urea under stirring, make dipping solution, in this solution, add 80g SiO ₂(Silysia of Fuji makes, CARiACT Q30, particle diameter 75 μ m～500 μ m, median size 200 μ m, pore volume 1.21ml/g, average fine pore 30nm), vibrate and mixed in about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).

In its 500ml pyriform flask of packing into,, connect thermometer in measurement section at flask top jointing and the bend pipe that is plugged with glass wool.With anchor clamps flask be fixed on the turning axle of rotating dryer on thereafter.Speed rotation turning axle with 10rpm is set at 105 ℃ with the drying machine temperature, carries out 2 hours heating.Then, unload the bend pipe that is plugged with glass wool on top after, the drying machine temperature is set at 120 ℃, carry out 16 hours heating.

Then, unload the joint on top after, the drying machine temperature is set at 140 ℃, carry out 4 hours heating, moisture is removed fully.After 4 hours, stop heating, rotation, take out catalyzer.

Catalyzer is transferred in the beaker of 500ml and naturally cools to room temperature, add the de-salted water of about 300ml then, carry out about 10 minutes suspension cleaning.Next, behind the filtering catalyst, be transferred to once more in the beaker of 500ml, add that the 30g Ammonium Bicarbonate, Food Grade is dissolved in the solution that obtains in the de-salted water of 300ml, carry out about 10 minutes suspension and clean.Next, behind the filtering catalyst, be transferred to once more in the beaker of 500ml, add the 300ml de-salted water, carry out about 10 minutes suspension and clean.After 2 cleanings of this de-salted water repetition, air-dry catalyzer 120 ℃ of dry nights in drying machine, carries out firing in 2 hours in 900 ℃ under the circulation of air then.

Resulting solid acid catalyst is made as " catalyzer 2 ".Obtain by calculating according to the composition of steeping fluid that the zirconic charge capacity with respect to the catalyzer total amount is 16.9 weight % in the catalyzer 2.

And the surface hydroxyl amount of catalyzer 2 is 3.4 μ mol/m ², the following acid amount of pKa-5.6 is 100 μ mol/g.

The synthesis example 1-3 of catalyzer

(new Japanese metallochemistry society makes ZrO at the 88.01g Zircosol ZN aqueous solution ₂Conversion concentration is 18.12 weight %) middle 26.13g de-salted water and the uniform mixing of adding.To wherein adding 11.84g urea uniform mixing, the preparation dipping solution.In this solution, add 80g SiO ₂(Silysia of Fuji make, CARiACT Q30) vibrates and mixed in about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).

In its 500ml pyriform flask of packing into,, connect thermometer in measurement section at flask top jointing and the bend pipe that is plugged with glass wool.With anchor clamps flask be fixed on the turning axle of rotating dryer on thereafter.Speed rotation turning axle with 10rpm is set at 105 ℃ with the drying machine temperature, carries out 2 hours heating.Then, unload the bend pipe that is plugged with glass wool on top after, the drying machine temperature is set at 120 ℃, carry out 16 hours heating.

Then, unload the joint on top after, the drying machine temperature is set at 140 ℃, carry out 4 hours heating, moisture is removed fully.After 4 hours, stop heating, rotation, take out catalyzer.

Catalyzer is transferred in the beaker of 500ml and naturally cools to room temperature, add the de-salted water of about 300ml then, carry out about 10 minutes suspension cleaning.Next, behind the filtering catalyst, be transferred to once more in the beaker of 500ml, add that the 30g Ammonium Bicarbonate, Food Grade is dissolved in the solution that obtains in the de-salted water of 300ml, carry out about 10 minutes suspension and clean.Next, behind the filtering catalyst, be transferred to once more in the beaker of 500ml, add the 300ml de-salted water, carry out about 10 minutes suspension and clean.After 2 cleanings of this de-salted water repetition, air-dry catalyzer 120 ℃ of dry nights in drying machine, carries out firing in 2 hours in 900 ℃ under the circulation of air then.

Resulting solid acid catalyst is made as " catalyzer 3 ".Obtain by calculating according to the composition of steeping fluid that the zirconic charge capacity with respect to the catalyzer total amount is 16.9 weight % in the catalyzer 3.

And the surface hydroxyl amount of catalyzer 3 is 3.3 μ mol/m ², the following acid amount of pKa-5.6 is 100 μ mol/g.

The synthesis example 1-4 of catalyzer

The TonsilOptimumFF that will make as the Sued Chemie society of clay (atlapulgite) catalyzer fired 1 hour in 400 ℃ under airiness, resulting solid acid catalyst was called " catalyzer 4 ".

The surface hydroxyl amount of this catalyzer 4 is 3.5 μ mol/m ², the following acid amount of pKa-5.6 is 190 μ mol/g.

＜utilize the processing of the solid acid catalyst that organic compound and/or mineral compound carry out and the manufacturing of polyethers 〉

Embodiment 1-1

[utilizing the processing of the solid acid catalyst that organic compound and/or mineral compound carry out]

The 100ml ethanol (water content 50ppm) and 98.3g (832.2mmol) diethyl carbonate (water content 50ppm) that have carried out dewatering with molecular sieve 3a are in advance being mixed in the 500ml flask that has reflux condensing tube under the nitrogen atmosphere.Wherein, under agitation in above-mentioned mixed solution, behind the interpolation 50g catalyzer 1, in oil bath, heat, refluxed 1 hour.Behind the naturally cooling, reflux condensing tube is replaced by still head, in oil bath, heats, slowly heat up, remove ethanol and diethyl carbonate, and then under the nitrogen circulation, in 140 ℃ oil bath, handled 4 hours in 90 ℃～140 ℃ distillations.Behind the naturally cooling, under nitrogen atmosphere, be kept in the encloses container, make to estimate and use catalyzer.

This evaluation is 1.5 μ mol/m with the surface hydroxyl amount of catalyzer ², the following acid amount of pKa-5.6 is 110 μ mol/g.

[polyethers manufacturing reaction evaluating]

This evaluation catalyzer of 22g of in volume is the circulation reaction unit of 520ml, packing into.Mixing solutions (weight ratio is: THF258.6, diacetyl oxide 29.3, acetate 1) with the flow of 87.4ml/h circulation THF, diacetyl oxide, acetate is heated to 35 ℃.Constant time abstraction reaction liquid has at interval carried out the mensuration of yield, number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) by GPC.

The transformation efficiency at initial stage is 34.2%, the Mn at initial stage is 2257, the Mw/Mn at initial stage is 1.81, transformation efficiency behind the reaction 162.5h is that 28.3% (with respect to the initial stage, transformation efficiency is 83% relatively), Mn=2232, Mw/Mn are 1.80 (worsening-0.01 with the preliminary phase ratio).

Comparative example 1-1

Directly use the above-mentioned catalyzer 1 of 22g, similarly carry out polyethers with embodiment 1-1 and make reaction evaluating.

The transformation efficiency at initial stage is 39.7%, the Mn at initial stage is 1851, the Mw/Mn at initial stage is 1.82, transformation efficiency behind the reaction 161.5h is that 28.2% (with respect to the initial stage, transformation efficiency is 71% relatively), Mn=1813, Mw/Mn are 1.85 (worsening+0.03 with the preliminary phase ratio).

Embodiment 1-2

The above-mentioned catalyzer 2 of 40g is filled into fixed bed circulation treatment unit, with the flow circulation nitrogen of 0.8L/min.Then, except circulation nitrogen, also with the flow of 32mg/min with the gaseous phase methyl alcohol (water content 50ppm) that goes into circulation, be heated to 100 ℃ and kept 5 hours.Stop the circulation of methyl alcohol after 5 hours, the nitrogen that only circulates kept 4 hours.Behind the naturally cooling, under nitrogen atmosphere, be kept in the encloses container, make to estimate and use catalyzer.

This evaluation is 2.0 μ mol/m with the surface hydroxyl amount of catalyzer ², the following acid amount of pKa-5.6 is 90 μ mol/g.

Use 22g to estimate and use catalyzer, similarly carry out polyethers with embodiment 1-1 and make reaction evaluating.

The transformation efficiency at initial stage is 34.4%, the Mn at initial stage is 2399, the Mw/Mn at initial stage is 1.76, transformation efficiency behind the reaction 162.0h is that 25.3% (with respect to the initial stage, transformation efficiency is 74% relatively), Mn=2322, Mw/Mn are 1.77 (worsening+0.01 with the preliminary phase ratio).

Embodiment 1-3

The above-mentioned catalyzer 2 of 80g is filled into thermopnore circulation treatment unit, with the flow circulation nitrogen of 1.6L/min.Then, except circulation nitrogen, also with the flow of 88mg/min with the gaseous phase trimethylsilyl acetate that goes into circulation, be heated to 100 ℃ and kept 5 hours.Stop the circulation of trimethylsilyl acetate after 5 hours, be heated to 200 ℃, the nitrogen that only circulates kept 4 hours.Behind the naturally cooling, under nitrogen atmosphere, be kept in the encloses container, make to estimate and use catalyzer.

This evaluation is 1.4 μ mol/m with the surface hydroxyl amount of catalyzer ², the following acid amount of pKa-5.6 is 100 μ mol/g.

Use 22g to estimate and use catalyzer, similarly carry out polyethers with embodiment 1-1 and make reaction evaluating.

The transformation efficiency at initial stage is 33.0%, the Mn at initial stage is 3090, the Mw/Mn at initial stage is 1.80, transformation efficiency behind the reaction 162.0h is that 27.0% (with respect to the initial stage, transformation efficiency is 82% relatively), Mn=2967, Mw/Mn are 1.78 (worsening-0.02 with the preliminary phase ratio).

Comparative example 1-2

Directly use the above-mentioned catalyzer 2 of 22g, similarly carry out polyethers with embodiment 1-1 and make reaction evaluating.

The transformation efficiency at initial stage is 32.0%, the Mn at initial stage is 2287, the Mw/Mn at initial stage is 1.76, transformation efficiency behind the reaction 163.7h is that 23.5% (with respect to the initial stage, transformation efficiency is 73% relatively), Mn=2282, Mw/Mn are 1.81 (worsening+0.05 with the preliminary phase ratio).

Embodiment 1-4

The above-mentioned catalyzer 3 of 80g is filled into thermopnore circulation treatment unit, with the flow circulation nitrogen of 1.6L/min.After being heated to 100 ℃, except circulation nitrogen, also with the flow of 88mg/min with the gaseous phase trimethylsilyl acetate (water content 10ppm is following) that goes into circulation, and kept 5 hours.Stop the circulation of trimethylsilyl acetate after 5 hours, be heated to 200 ℃, the nitrogen that only circulates kept 4 hours.Behind the naturally cooling, under nitrogen atmosphere, be kept in the encloses container, make to estimate and use catalyzer.

This evaluation is 1.6 μ mol/m with the surface hydroxyl amount of catalyzer ², the following acid amount of pKa-5.6 is 100 μ mol/g.

Use 22g to estimate and use catalyzer, similarly carry out polyethers with embodiment 1-1 and make reaction evaluating.

The transformation efficiency at initial stage is 28.8%, the Mn at initial stage is 2022, the Mw/Mn at initial stage is 1.64, transformation efficiency behind the reaction 142.5h is that 23.5% (with respect to the initial stage, transformation efficiency is 82% relatively), Mn=1890, Mw/Mn are 1.66 (worsening+0.02 with the preliminary phase ratio).

Embodiment 1-5

The above-mentioned catalyzer 3 of 80g is filled into thermopnore circulation treatment unit, with the flow circulation nitrogen of 1.6L/min.After being heated to 100 ℃, except circulation nitrogen, also with the flow of 68mg/min with the gaseous phase diethylmethyl silane (water content 10ppm is following) that goes into circulation, and kept 5 hours.Stop the circulation of diethylmethyl silane after 5 hours, be heated to 200 ℃, the nitrogen that only circulates kept 4 hours.Behind the naturally cooling, under nitrogen atmosphere, be kept in the encloses container, make to estimate and use catalyzer.

This evaluation is 2.0 μ mol/m with the surface hydroxyl amount of catalyzer ², the following acid amount of pKa-5.6 is 100 μ mol/g.

Use 22g to estimate and use catalyzer, similarly carry out polyethers with embodiment 1-1 and make reaction evaluating.

The transformation efficiency at initial stage is 31.4%, the Mn at initial stage is 1746, the Mw/Mn at initial stage is 1.64, transformation efficiency behind the reaction 139.7h is that 25.3% (with respect to the initial stage, transformation efficiency is 81% relatively), Mn=1797, Mw/Mn are 1.66 (worsening+0.02 with the preliminary phase ratio).

Embodiment 1-6

The above-mentioned catalyzer 3 of 80g is filled into thermopnore circulation treatment unit, with the flow circulation nitrogen of 1.6L/min.After being heated to 140 ℃, except circulation nitrogen, also with the flow of 23mg/min with the gaseous phase diethylmethyl silane (water content 10ppm is following) that goes into circulation, and kept 5 hours.Stop the circulation of diethylmethyl silane after 5 hours, be heated to 200 ℃, the nitrogen that only circulates kept 4 hours.Behind the naturally cooling, under nitrogen atmosphere, be kept in the encloses container, make to estimate and use catalyzer.

This evaluation is 2.0 μ mol/m with the surface hydroxyl amount of catalyzer ², the following acid amount of pKa-5.6 is 100 μ mol/g.

Use 22g to estimate and use catalyzer, similarly carry out polyethers with embodiment 1-1 and make reaction evaluating.

The transformation efficiency at initial stage is 33.1%, the Mn at initial stage is 2090, the Mw/Mn at initial stage is 1.66, transformation efficiency behind the reaction 161.7h is that 27.4% (with respect to the initial stage, transformation efficiency is 83% relatively), Mn=2108, Mw/Mn are 1.68 (worsening+0.02 with the preliminary phase ratio).

Comparative example 1-3

Directly use the above-mentioned catalyzer 3 of 22g, similarly carry out polyethers with embodiment 1-1 and make reaction evaluating.

The transformation efficiency at initial stage is 29.6%, the Mn at initial stage is 1582, the Mw/Mn at initial stage is 1.68, transformation efficiency behind the reaction 139.5h is that 23.0% (with respect to the initial stage, transformation efficiency is 78% relatively), Mn=1567, Mw/Mn are 1.74 (worsening+0.06 with the preliminary phase ratio).

Embodiment 1-7

The above-mentioned catalyzer 4 of 80g is filled into thermopnore circulation treatment unit, with the flow circulation nitrogen of 1.6L/min.Then, except circulation nitrogen, also with the flow of 88mg/min with the gaseous phase trimethylsilyl acetate that goes into circulation, be heated to 100 ℃ and kept 5 hours.Stop the circulation of trimethylsilyl acetate after 5 hours, be heated to 200 ℃, the nitrogen that only circulates kept 4 hours.Behind the naturally cooling, under nitrogen atmosphere, be kept in the encloses container, make to estimate and use catalyzer.

This evaluation is 2.4 μ mol/m with the surface hydroxyl amount of catalyzer ², the following acid amount of pKa-5.6 is 190 μ mol/g.

Use 22g to estimate and use catalyzer, similarly carry out polyethers with embodiment 1-1 and make reaction evaluating.

The transformation efficiency at initial stage is 29.0%, the Mn at initial stage is 3500, the Mw/Mn at initial stage is 1.84, transformation efficiency behind the reaction 165.4h is that 12.2% (with respect to the initial stage, transformation efficiency is 42% relatively), Mn=3470, Mw/Mn are 1.85 (worsening+0.01 with the preliminary phase ratio).

Comparative example 1-4

Directly use the above-mentioned catalyzer 4 of 22g, similarly carry out polyethers with embodiment 1-1 and make reaction evaluating.

The transformation efficiency at initial stage is 28.1%, the Mn at initial stage is 2668, the Mw/Mn at initial stage is 1.85, transformation efficiency behind the reaction 165.4h is that 10.1% (with respect to the initial stage, transformation efficiency is 36% relatively), Mn=2794, Mw/Mn are 2.00 (worsening+0.15 with the preliminary phase ratio).

Above-mentioned evaluation result provides with showing to gather among the 1-2 in following table 1-1.

[table 1-1]

[table 1-2]

	Initial stage transformation efficiency (%)	Initial stage Mn	Initial stage Mw/Mn	The reaction elapsed time (h)	Through the time transformation efficiency (%)	Through the time Mn	Through the time Mw/Mn	Relative transformation efficiency (%)	Mw/Mn worsens
										Comparative example 1-1	39.7	1851	1.82	161.5	28.2	1813	1.85	71	+0.03
Embodiment 1-1	34.2	2257	1.81	162.5	28.3	2232	1.80	83	-0.01
										Comparative example 1-2	32.0	2287	1.76	142.5	23.5	2282	1.81	73	+0.05
Embodiment 1-2	34.4	2399	1.76	162.0	25.3	2322	1.77	74	+0.01
										Embodiment 1-3	33.0	3090	1.80	163.7	27.0	2967	1.78	82	-0.02
Comparative example 1-3	29.6	1582	1.68	139.5	23.0	1567	1.74	78	+0.06
										Embodiment 1-4	28.8	2022	1.64	142.5	23.5	1890	1.66	82	+0.02
Embodiment 1-5	31.4	1746	1.64	139.7	25.3	1797	1.66	81	+0.02
										Embodiment 1-6	33.1	2090	1.66	161.7	27.4	2108	1.68	83	+0.02
Comparative example 1-4	28.1	2668	1.85	165.4	10.1	2794	2.00	36	+0.15
										Embodiment 1-7	29.0	3500	1.84	165.4	12.2	3470	1.85	42	+0.01

By table 1-1, table 1-2 as can be known, by handling solid acid catalyst with organic compound and/or mineral compound in advance, can obtain the solid acid catalyst of low surface hydroxyl amount and peracid amount, by use this solid acid catalyst can prevent transformation efficiency through the time reduce, and, can also prevent resulting polyethers molecular weight distribution (Mw/Mn) through the time worsen, can obtain the polyethers of narrow molecular weight distribution.

[explanation of the 3rd aspect]

The inventor finds, by in the pore of carrier, carrying out the homogeneous precipitator method (it is to generate sedimentary reaction from uniform solution), metal hydroxides and/or metal oxide can be loaded in the carrier with even and trickle dispersion state, thereby finish the 3rd aspect of the present invention.

It is believed that, under the situation of the homogeneous precipitator method, the precipitation agent (for example alkali) that is used for metallic salt is made metal hydroxides can generate equably in carrier pore inside, thereby the concentration difference of the metal hydroxides on the different positions of carrier inside becomes minimum, can generate trickle and uniform aggegation and the big aggegation of metal hydroxides can in carrier, not occur, its result can access more than the soda acid amount and the solid acid catalyst of strength of acid narrowly distributing.

The main points of the 3rd aspect are a kind of manufacture method of solid acid catalyst, it is the manufacture method with metal hydroxides and/or the metal oxide supported solid acid catalyst that forms on carrier, it is characterized in that this method comprises that the homogeneous precipitator method of utilizing in the carrier pore are in the pore internal burden metal hydroxides of carrier and/or the operation of metal oxide.

In the 3rd aspect, the described homogeneous precipitator method are to have utilized the homogeneous precipitator method of precipitation agent precursor comparatively suitable.

This precipitation agent precursor is that the alkali precursor is comparatively suitable.

Metal hydroxides and/or metal oxide be selected from by the oxyhydroxide and/or the oxide compound of at least a metallic element in the group of periodictable the 3rd family, the 4th family, the 5th family, the 13rd family and the 14th group composition comparatively suitable.

The alkali precursor is that urea is comparatively suitable.

According to the 3rd aspect, by in the pore of carrier, carrying out the homogeneous precipitator method (it is to generate sedimentary reaction from uniform solution), metal hydroxides and/or metal oxide can be loaded in the carrier with even and trickle dispersion state, its result can access that the soda acid amount is many, the solid acid catalyst of strength of acid narrowly distributing.

By utilizing such solid acid catalyst, can in the ring-opening polymerization of for example tetrahydrofuran (THF), make the polyethers of narrow molecular weight distribution with high conversion.

Embodiment to the 3rd aspect is elaborated below, but the explanation of the constitutive requirements of following record only is an example (typical example) of the embodiment of the 3rd aspect, and only otherwise exceed its main points, the 3rd aspect is not subjected to the restriction of these contents.

Solid acid catalyst with the method manufacturing of the 3rd aspect is by carry out the homogeneous precipitator method in the pore of carrier metal hydroxides and/or metal oxide to be loaded on the catalyzer that obtains in the pore of carrier with homogeneous and trickle dispersion state.

The following enforcement of these homogeneous precipitator method, for example, infiltrate metal-salt and the precipitation agent precursor that in solution, produces precipitation agent simultaneously in carrier by chemical reactions such as hydrolysis after, this impregnated carrier is carried out heat treated etc. is generated precipitation agent by the precipitation agent precursor processing.Owing to be the homogeneous precipitator method, therefore importantly metal-salt and precipitation agent precursor form liquid phase, promptly form solution.That is, the dipping solution that will contain metal-salt and precipitation agent precursor is infiltrated up in the carrier, then, carries out being generated by the precipitation agent precursor processing of precipitation agent.

[manufacture method of solid acid catalyst]

At first, manufacture method based on the solid acid catalyst of the 3rd aspect of the homogeneous precipitator method is described, and as mentioned above, the described homogeneous precipitator method are, the dipping solution that will contain metal-salt and precipitation agent precursor infiltrates in carrier, carries out being generated by the precipitation agent precursor processing of precipitation agent then.

(1) carrier

The carrier that uses for the 3rd aspect is not particularly limited, preferable alloy is oxide-based, complex metal oxides class, zeolites, clay class, more preferably silicon-dioxide, aluminum oxide, zirconium white, titanium dioxide, silica-alumina, silicon-dioxide-zirconium white, silica-titania, preferred especially silicon-dioxide, aluminum oxide, zirconium white.

As for particle diameter, fine pore and the pore volume of carrier, can be different because of purposes, use form as solid acid catalyst, cannot treat different things as the same.

These carriers both can be used alone, and also can share two or more.

(2) metal hydroxides and/or metal oxide

Be not particularly limited for above-mentioned metal hydroxides and/or the metal oxide that is carried on like that on the carrier, be generally the oxyhydroxide and/or the oxide compound of the metallic element of periodictable the 2nd～14 family, be preferably and be selected from by periodictable the 3rd family, the 4th family, the 5th family, the oxyhydroxide of at least a metallic element in the group of the 13rd family and the 14th group composition and/or oxide compound, more preferably be selected from by Ti, Zr, Hf, Nb, the oxyhydroxide and/or the oxide compound of at least a metallic element in the group that Al and Si form are preferably especially and are selected from by Ti, Zr, the oxyhydroxide and/or the oxide compound of at least a metallic element in the group that Al and Nb form.

(3) metal-salt

The metal-salt that is used for the homogeneous precipitator method is to generate the above-mentioned metal hydroxides that is carried on the resulting solid acid catalyst and/or the metal-salt of metal oxide, therefore, be generally the salt of the metallic element of above-mentioned periodictable the 2nd～14 family, be preferably the salt of the metallic element of the 3rd, 4,5,13,14 families, more preferably Ti, Zr, Hf, Nb, Al, Si salt are preferably Ti, Zr, Al, Nb salt especially.

Kind for salt is not particularly limited, preferably nitrate, acetate, vitriol, oxynitrate, muriate, oxychloride, more preferably oxynitrate, oxychloride, vitriol.

That is, as nitrate, acetate, vitriol, oxynitrate, muriate, the oxychloride of metal-salt preferred cycle table the 2～14 family's metals, more preferably Zircosol ZN, basic zirconium chloride, zirconium sulfate, titanium chloride, Tai-Ace S 150, niobium oxychloride.

These metal-salts both can be used alone, and also can share two or more.

(4) precipitation agent precursor

Precipitation agent precursor of the present invention is meant, causes that by processing such as heat in dipping solution hydrolysis or other chemical reactions are to generate the material of precipitation agent.Precipitation agent be meant with dipping solution in reacting metal salt generate the sedimentary material of metal hydroxides and/or metal oxide.In the precipitation agent precursor, to produce alkali (promptly as the material of precipitation agent, in dipping solution, produce alkali, the pH of solution risen, make metal-salt with the sedimentary material of the form of oxyhydroxide and/or oxide compound by hydrolysis or other chemical reaction) be called " alkali precursor ".

Be not particularly limited for the precipitation agent precursor that is used to carry out the homogeneous precipitator method, use the alkali precursor usually.

As the alkali precursor, amide compound that generally use urea, tricyanic acid, alkyl substituted ureas, thiocarbamide, alkyl substituting thioureido, constitutes by amine and carboxylic acid etc.Preferred urea, tricyanic acid, the alkyl substituted ureas of using is from being easy to obtain and the consideration of cost aspect preferred especially urea, tricyanic acid.These alkali precursors can be used alone, and also can share two or more.

(5) alkaline matter

In dipping solution, not only can add above-mentioned alkali precursor, and the alkaline matter that can be in advance adds predetermined amount in not generating sedimentary scope is to improve pH.By using alkaline matter, consumption, the minimizing that can reduce the alkali precursor generate the precipitation time necessary.

Be not particularly limited for alkaline matter, can enumerate oxyhydroxide, carbonate, supercarbonate, phosphoric acid salt, the acetate of basic metal, alkaline-earth metal and ammonium, ammonia, organic amine etc., preferred ammonia, organic amine, the carbonate of ammonium, supercarbonate, phosphoric acid salt, more preferably volatile salt, bicarbonate of ammonia.

These alkaline matters both can be used alone, and also can share two or more.

(6) dipping solution

Dipping solution prepares by above-mentioned metal-salt, precipitation agent precursor and the alkaline matter that uses as required are dissolved in the water usually.

Concentration to metal-salt in the dipping solution and precipitation agent precursor is not particularly limited, as long as can keep dissolved state and can realize the charge capacity that is fit to the aftermentioned carrier, usually metal salt concentrations is 0.01 weight %～50 weight %, be preferably 0.1 weight %～40 weight %, be preferably 0.5 weight %～30 weight % especially, for the precipitation agent precursor as described later, with respect to being enough to make the whole sedimentary theoretical amount of this metal-salt is 0.1～10 times, be preferably 0.2～8 times, be preferably 0.3～5 times especially.

Can suitably use alkaline matter to obtain required pH condition.That is, owing to generate the necessary pH condition of precipitation according to the kind of employed metal-salt and precipitation agent precursor or concentration and different, so can use the alkaline matter of necessary amount according to these conditions.

In addition, among the present invention, in order in carrier, to implement the homogeneous precipitator method, make before the precipitation agent precursor is converted to the processing of precipitation agent, needing at least a metal-salt and precipitation agent precursor is liquid phase in dipping solution, be dissolved state,, in dipping solution, exist and all can with random order for the material except this at least a metal-salt and precipitation agent precursor.

(7) the homogeneous precipitator method

＜dipping solution is to the infiltration method of carrier 〉

Be not particularly limited for the method that above-mentioned dipping solution is infiltrated up in the carrier, load to equably on the carrier, preferably implement with the hole completion method in order to make metal-salt.In this case, the volume that is infiltrated up to the dipping solution in the carrier is preferably 60%～120% of carrier pore volume, and more preferably 70%～110%, be preferably 80%～105% especially.If this hypovolia, then dipping solution can not enter in the carrier pore equably, and causes uneven homogenize.Conversely, if this hypervolia, then steeping fluid still can cause uneven homogenize attached to the carrier outside surface.

In addition, the charge capacity that loads on the metal-salt on the carrier by infiltration can be selected to measure arbitrarily, but be 0.01 weight %～50 weight % with respect to vehicle weight usually, be preferably 0.05 weight %～40 weight %, more preferably 0.1 weight %～30 weight %.Charge capacity for the precipitation agent precursor, if being enough to make the whole sedimentary theoretical amount of the metal-salt that is carried on the carrier is,, in 0.1～10 scope, use the precipitation agent precursor usually at 1 o'clock with molar ratio computing, be preferably 0.2～8 scope, more preferably 0.3～5 scope.

＜sedimentary generation and post-treating method 〉

In the 3rd aspect, dipping solution is infiltrated up in the carrier, the state that makes the metal-salt that is carried on the carrier and precipitation agent precursor in the carrier pore, keep solution thus, implement heating in this state and wait the processing that the precipitation agent precursor is converted to precipitation agent, utilize the precipitation agent that evenly produces in carrier inside that metal-salt is converted to corresponding metal hydroxides.

Usually use the alkali precursor as the precipitation agent precursor, in the processing that the alkali precursor is converted to alkali, utilize the hydrolysis of the alkali precursor that causes by heating.

As mentioned above, in the 3rd aspect, in order in the carrier pore, to implement the homogeneous precipitator method, need be before carrying out that the precipitation agent precursor is converted to the processing of precipitation agent, make at least a metal-salt and precipitation agent precursor be solution state, be liquid phase, all can and the material except this at least a metal-salt, precipitation agent precursor is any state.

In based on the hydrolysis reaction that adds thermal initiation, the alkali precursor is converted under the situation of alkali,, adopts 50 ℃～300 ℃ scope usually, preferably adopt 60 ℃～200 ℃ scope as Heating temperature.Heating temperature is changed in time.If Heating temperature is low excessively, the reaction of precipitation agent then might not take place to be generated by the precipitation agent precursor, or need expend the very long time; If Heating temperature is too high, then the necessary moisture of hydrolysis sometimes may all be removed before the reaction that is generated precipitation agent by the precipitation agent precursor finishes.In order to implement the good and stable homogeneous precipitator method, preferably when the sedimentary reaction of generation finished, the moisture entrapment in the dipping solution of infiltration in carrier is more than 5%, and was more preferably residual more than 10%.

As the fixed bed heating unit, can there be the carrier of dipping solution to heat to infiltration at the immobilising state of load carriers, but especially under the situation of a large amount of catalyzer of preparation, more preferably the thermopnore device of working load carrier flow, revolving heating unit etc.It is believed that, when heating, occur under the situation of moisture evaporation, make load carriers mobile method that the water evaporation quantity of every particle loading carrier is changed, thereby further increase uniformity.

In addition, if the moisture evaporation during heating is too fast, then moisture was all removed before the hydrolysis of alkali precursor finishes fully, sometimes can not fully carry out the supply of precipitation agent, therefore it is desirable to usually, by begin to be heated to through precipitation after formation reaction finishes, till removing moisture fully, with more than 1 hour, preferred more than 3 hours, further preferred time more than 6 hours carries out removing fully of moisture.

Thereafter, water, alkaline aqueous solution, aqueous acid, organic solvent etc. clean resulting catalyzer as required, after the drying, under inert gas atmospheres such as nitrogen, argon gas or oxidizing gas atmosphere such as air or dilution oxygen, fire, thus the solid acid catalyst that can obtain having desired performance.Heating firing temperature as this moment is generally 100 ℃～1200 ℃, is preferably 300 ℃～1100 ℃, more preferably 500 ℃～1000 ℃.Fire by carrying out such heating, the catalyst activity of resulting solid acid catalyst and stability are improved.

(8) solid acid catalyst

On the solid acid catalyst that obtains by above-mentioned operation the crystallite dimension of the metal oxide of load and/or metal hydroxides because of the kind of the kind of metallic element, charge capacity, carrier, to fire condition etc. different, use same metal-salt same charge capacity, identical carrier, same firing under the situation about being prepared under the condition, this crystallite dimension is below 90% of crystallite dimension during with prior art for preparing, be preferably below 80%, more preferably below 75%.In addition, this crystallite dimension utilizes the peak width at half height at XRD determining peak to calculate.

In addition, be 0.05 weight %～40 weight % with respect to the metal hydroxides of carrier and/or the charge capacity of metal acidulants in the solid acid catalyst that obtains with the method for the 3rd aspect, be preferably 0.1 weight %～30 weight % especially.

[manufacture method of polyethers]

The solid acid catalyst of making according to the method for the 3rd aspect can be well as the catalyst for polymerization in the manufacturing of polyethers (particularly utilizing the manufacturing of polyethers of the ring-opening polymerization of ring-type ethers).

Below to using solid acid catalyst of the present invention to describe as the manufacture method of the polyethers of catalyst for polymerization.

Make under the situation of polyethers with the ring-opening polymerization of ring-type ethers, as the cyclic ether as reaction raw materials, the formation carbonatoms that can enumerate ring is 3～10 cyclic ether, and, can use the cyclic ether that replaces with alkyl, halogen radical, acyl group etc.Specifically, can use tetrahydrofuran (THF), trimethylene oxide, oxepane, 1,4-dioxane, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran etc.And, can only use a kind of homopolymerization of ring-type ethers and use any polymerization in the copolymerization of two or more ring-type ethers.

Consider that from the aspect of control molecular weight the ring-opening polymerization of cyclic ether preferably carries out in the presence of carboxylic acid anhydride and/or carboxylic acid.As carboxylic acid anhydride and/or carboxylic acid, generally use aliphatics or aromatic carboxylic acid anhydride and/or carboxylic acid, preferred carboxylic acid anhydride and/or the carboxylic acid that use with 2～8 carbon atoms with 2～12 carbon atoms.These carboxylic acid anhydride and/or carboxylic acid both can be used alone, and also can share two or more.Carboxylic acid anhydride and/or carboxylic acid are comparatively suitable with respect to cyclic ether to be that 0.01～1.0 (mol ratio) added usually.

Can in reaction, use inert solvent during polyreaction.As this solvent, use the divided ring polyreaction to be in inert aliphatic hydrocarbon, the aromatic hydrocarbon etc. one or more usually.

Reaction formation uses the general form of using such as grooved, tower, can be any of batch mode, continuous mode.Following method etc. is for example arranged: cyclic ether, catalyzer, carboxylic acid anhydride and/or carboxylic acid are under agitation fed intake carry out polymeric method (batch mode); In containing the reactor of catalyzer, supply with cyclic ether, carboxylic acid anhydride and/or carboxylic acid and continuous method (continuous mode) of extracting reaction solution out etc. continuously.Consider preferred continuous mode from the aspect of productivity.

The consumption of solid acid catalyst depends on its kind, be not particularly limited, but for example in the batch-type reactor, if catalytic amount is very few, then polymerization velocity is slack-off, conversely if too much, then be difficult to remove heat of polymerization.And, because the slurry concentration of reaction system uprises, cause stirring difficulty, and be easy to go wrong in the separatory of catalyzer after polyreaction finishes and reaction solution.Therefore,, can consider under the condition of reaction form of batch reactions, circulation reaction, be generally 0.001～50 times of weight with respect to liquid phase, be preferably in the scope of 0.01～20 times of weight and select for catalyst consumption.Wherein, under the situation of circulation reaction, catalyst consumption is represented the amount with respect to the catalyzer of liquid phase feed rate of time per unit.

Temperature of reaction is generally 0 ℃～200 ℃, is preferably 10 ℃～80 ℃.

Reaction pressure is that reaction system can keep the pressure of liquid phase to get final product, usually from normal pressure～10MPa, preferably select from the pressure range of normal pressure～5MPa.

Reaction times is not particularly limited, consider itself and catalytic amount the two, consider yield, economy, the reaction times is 0.1 hour～20 hours scope, is preferably 0.5 hour～15 hours scope.The said herein reaction times is meant, in batch mode, plays the time till reaction finishes to begin to cool down when rising to temperature of reaction by temperature; In continuous mode, the residence time of liquid in reactor formed in reaction.

Use is carried out according to the solid acid catalyst of the 3rd aspect manufacturing under the situation of ring-opening polymerization of tetrahydrofuran (THF) (THF), and can obtain number-average molecular weight (Mn) is 200～80,000, particularly 200～40, the polyethers of low～middle molecular weight of about 000.And then the polyethers that can easily produce narrow molecular weight distribution also is one of feature.Promptly, the Mw/Mn of the polyethers that industrial requirement is bigger is 1.3～2.5, by utilizing solid acid catalyst of the present invention, can access Mw/Mn less than 3, for example Mw/Mn is 1.1～3.0 polytetramethylene ether diol (PTMG), particularly by selecting optimum condition of the present invention for use, can also obtain Mw/Mn and be about 1.5～1.8 the very narrow polyethers of molecular weight distribution.And according to the present invention, the yield that can make product is more than 25%, is preferably more than 30%, further is more than 35%.

[embodiment and comparative example]

Enumerate embodiment and comparative example below the 3rd aspect is further specifically described, but following embodiment not delimit the scope of the invention.

In addition, in the content below, the yield of polytetramethylene ether diol acetic ester (PTME), number-average molecular weight (Mn), molecular weight distribution (Mw/Mn) utilize following GPC (gel permeation chromatography) to obtain.

The GPC device: Tosoh society makes GPC 8220

Post: TSK-GEL H 30cm * 2

Detection method: RI

Column temperature: 40 ℃

Mobile phase: THF

Flow velocity: 1ml/min

Sample injection rate: 100 μ L

Sample concentration: the concentration that is adjusted to polyethers is about 0.1 weight %

Embodiment 2-1

The preparation of＜solid acid catalyst 〉

[dipping of dipping solution]

(new Japanese metallochemistry society makes ZrO at the 89.66g Zircosol ZN aqueous solution ₂Conversion concentration 18.12 weight %) add 18.72g de-salted water and uniform mixing in.To wherein adding 11.84g urea uniform mixing, the preparation dipping solution.In this solution, add 80g SiO ₂(Silysia of Fuji makes, CARiACT Q15, particle diameter 75 μ m～500 μ m, median size 200 μ m, pore volume 1.16ml/g, average fine pore 15nm), vibrate and mixed in about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).

[heat treated]

There is the carrier of above-mentioned dipping solution to pack in the 500ml pyriform flask infiltration, at flask top jointing be plugged with the bend pipe of glass wool, connects thermometer in measurement section.With anchor clamps flask be fixed on the turning axle of rotating dryer on thereafter.Speed rotation turning axle with 10rpm is set at 105 ℃ with the drying machine temperature, carries out 6 hours heating.At this moment, by the moisture entrapment 90% in the changes in weight affirmation dipping solution.Then, unload the bend pipe that is plugged with glass wool on top after, the drying machine temperature is set at 120 ℃, carry out 16 hours heating.

Then, unload the joint on top after, the drying machine temperature is set at 140 ℃, carry out 4 hours heating, moisture is almost completely removed.After 4 hours, stop heating, rotation, take out catalyzer.

Catalyzer is transferred in the beaker of 500ml and naturally cools to room temperature, add the de-salted water of about 300ml then, carry out about 10 minutes suspension cleaning.Behind the filtering catalyst, be transferred to once more in the beaker of 500ml, the suspension that amounts to 3 times is cleaned.Next, behind the air-dry catalyzer, under airiness, implement 2 hours fire in 900 ℃ then a dry night in 120 ℃ drying machine, obtain solid acid catalyst.Obtain the zirconic average crystallite footpath that is carried on this solid acid catalyst by XRD determining, the result is 22 And, be 16.9 weight % by calculating by the zirconic charge capacity of obtaining forming of steeping fluid with respect to the catalyzer total amount.

The manufacturing of＜polyethers 〉

In the four-hole boiling flask of 500ml, add 133.5g THF, 6.85g diacetyl oxide under the condition of nitrogen gas and mix.The solid acid catalyst that weighing 4.68g obtains in the preparation of above-mentioned solid acid catalyst under condition of nitrogen gas is after stirring is added to it in above-mentioned mixed solution down, in 40 ℃ of reactions 5 hours.With the gpc analysis reaction solution, number-average molecular weight (Mn), the molecular weight distribution (Mw/Mn) of transformation efficiency and the PTME of THF are measured, transformation efficiency is 56.3% as a result, and Mn is 2563, and Mw/Mn is 1.88.

Embodiment 2-2

42.46g basic zirconium chloride 8 hydrates are dissolved in the 59.48g de-salted water, and to wherein adding 11.84g urea and uniform mixing, the preparation dipping solution similarly carries out Preparation of catalysts with embodiment 2-1 in addition, utilizes this catalyzer to carry out the manufacturing of polyethers.The zirconic average crystallite that draws by XRD determining directly is detection lower limit (10 ) below, be 16.9 weight % with respect to the zirconic charge capacity of catalyzer total amount.Transformation efficiency is 55.1%, and Mn is 2520, and Mw/Mn is 1.87.

Embodiment 2-3

(Japanese light metal society makes, ZrO with the 46.95g zirconium sulfate aqueous solution ₂Conversion concentration is 15.1 weight %) be dissolved in the 56.95g de-salted water, to wherein adding 23.78g urea and uniform mixing, the preparation dipping solution similarly carries out Preparation of catalysts with embodiment 2-1 in addition, utilizes this catalyzer to carry out the manufacturing of polyethers.The zirconic average crystallite that draws by XRD determining directly is 22 Zirconic charge capacity with respect to the catalyzer total amount is 16.9 weight %.Transformation efficiency is 51.2%, and Mn is 2252, and Mw/Mn is 1.87.

Embodiment 2-4

(new Japanese metallochemistry society makes ZrO to the 86.80g Zircosol ZN aqueous solution ₂Conversion concentration is 18.72 weight %) middle 17.84g de-salted water and the uniform mixing of adding, to wherein little by little adding 10.84g Ammonium Bicarbonate, Food Grade and uniform mixing, to wherein adding 7.92g urea and uniform mixing, the preparation dipping solution.In this solution, add 80g SiO ₂(Silysia of Fuji make, CARiACT Q15), vibration mixed about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).

It is added in the 500ml pyriform flask, to change 1.5 hours into by 6 hours in the heat-up time in temperature is 105 ℃ drying machine, similarly operate with embodiment 2-1 in addition, carry out a series of heating, clean, fire processing, obtain solid acid catalyst.The zirconic average crystallite that obtains by XRD determining directly is 22

, be 16.9 weight % with respect to the zirconic charge capacity of catalyzer total amount.

Use this solid acid catalyst, similarly carry out the manufacturing of polyethers with embodiment 2-1.Transformation efficiency is 55.4%, and Mn is 2626, and Mw/Mn is 1.87.

Comparative example 2-1

(new Japanese metallochemistry society makes ZrO to the 89.66g Zircosol ZN aqueous solution ₂Conversion concentration 18.12 weight %) add 18.72g de-salted water and uniform mixing in.To wherein adding 11.84g urea and uniform mixing, the preparation dipping solution.In this solution, add 80g SiO ₂(Silysia of Fuji make, CARiACT Q15), vibration mixed about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).Remove the moisture of steeping fluid more than 97% by it being carried out drying under reduced pressure, obtain the metal-salt of drying and precipitation agent precursor load carriers thus with the solid state shape load.

It is added in the 500ml pyriform flask, similarly operate, carry out a series of heating, clean, fire processing, obtain solid acid catalyst with embodiment 2-1.The zirconic average crystallite that obtains by XRD determining directly is 47 , be 16.9 weight % with respect to the zirconic charge capacity of catalyzer total amount.

Use this solid acid catalyst, similarly carry out the manufacturing of polyethers with embodiment 2-1.Transformation efficiency is 29.8%, and Mn is 3019, and Mw/Mn is 2.01.

Comparative example 2-2

(new Japanese metallochemistry society makes ZrO to the 89.66g Zircosol ZN aqueous solution ₂Conversion concentration 18.12 weight %) add 27.72g de-salted water and uniform mixing in.In this solution, add 80gSiO ₂(Silysia of Fuji make, CARiACT Q15), vibration mixed about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).

In its 500ml pyriform flask of packing into,, connect thermometer in measurement section at flask top jointing and the bend pipe that is plugged with glass wool.With anchor clamps flask be fixed on the turning axle of rotating dryer on thereafter.Speed rotation turning axle with 10rpm is set at 105 ℃ with the drying machine temperature, carries out 6 hours heating.Then, unload the bend pipe that is plugged with glass wool on top after, the drying machine temperature is set at 120 ℃, carry out 16 hours heating.

Then, unload the joint on top after, the drying machine temperature is set at 140 ℃, carry out 4 hours heating.After 4 hours, stop heating, rotation, take out catalyzer.

Catalyzer is transferred to naturally cool to room temperature in the beaker of 500ml after, be added on the solution that dissolving 35g Ammonium Bicarbonate, Food Grade obtains in the 350ml de-salted water, stir about 10 minutes.Behind the filtering catalyst, add the de-salted water of about 300ml, carry out about 10 minutes suspension and clean.Behind the filtering catalyst, be transferred to once more in the beaker of 500ml, the suspension that amounts to 3 times is cleaned.Next, behind the air-dry catalyzer, under airiness, implement 2 hours fire in 900 ℃ then a dry night in 120 ℃ drying machine, obtain solid acid catalyst.Obtaining zirconic average crystallite by XRD determining directly is 30

, be 16.9 weight % with respect to the zirconic charge capacity of catalyzer total amount.

Use this solid acid catalyst, similarly carry out the manufacturing of polyethers with embodiment 2-1.Transformation efficiency is 45.7%, and Mn is 2947, and Mw/Mn is 2.03.

Embodiment 2-5

(new Japanese metallochemistry society makes ZrO to the 89.66g Zircosol ZN aqueous solution ₂Conversion concentration is 18.12 weight %) middle 20.65g de-salted water and the uniform mixing of adding.To wherein little by little adding 6.74g volatile salt and uniform mixing.To wherein adding 11.84g urea and uniform mixing, the preparation dipping solution.In this solution, add 80g SiO ₂(Silysia of Fuji makes, CARiACT Q30, particle diameter 75 μ m～500 μ m, median size 200 μ m, pore volume 1.21ml/g, average fine pore 30nm), vibration mixed about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).

It is added in the 500ml pyriform flask, similarly operate, carry out a series of heating, clean, fire processing, obtain solid acid catalyst with embodiment 2-2.The zirconic average crystallite that obtains by XRD determining directly is 28

, be 16.9 weight % with respect to the zirconic charge capacity of catalyzer total amount.

Use this solid acid catalyst, similarly carry out the manufacturing of polyethers with embodiment 2-1.Transformation efficiency is 52.7%, and Mn is 2875, and Mw/Mn is 1.85.

Embodiment 2-6

(new Japanese metallochemistry society makes ZrO to the 88.01g Zircosol ZN aqueous solution ₂Conversion concentration is 18.46 weight %) middle 26.83g de-salted water and the uniform mixing of adding.To wherein adding 11.84g urea and uniform mixing, the preparation dipping solution.In this solution, add 80g SiO ₂(Silysia of Fuji make, CARiACT Q30), vibration mixed about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).

It is added in the 500ml pyriform flask, will change 2 hours into by 6 hours, similarly operate with embodiment 2-1 in addition, carry out a series of heating, clean, fire processing, obtain solid acid catalyst in the heat-up time in temperature is 105 ℃ drying machine.The zirconic average crystallite that obtains by XRD determining directly is 28 , be 16.9 weight % with respect to the zirconic charge capacity of catalyzer total amount.

Use this solid acid catalyst, similarly carry out the manufacturing of polyethers with embodiment 2-1.Transformation efficiency is 41.9%, and Mn is 2436, and Mw/Mn is 1.73.

Comparative example 2-3

(new Japanese metallochemistry society makes ZrO to the 89.66g Zircosol ZN aqueous solution ₂Conversion concentration 18.12 weight %) add 22.72g de-salted water and uniform mixing in.To wherein adding 11.84g urea and uniform mixing, the preparation dipping solution.In this solution, add 80g SiO ₂(Silysia of Fuji make, CARiACT Q30), vibration mixed about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).Remove the moisture of steeping fluid more than 97% by it being carried out drying under reduced pressure, the load that obtains drying thus has the load carriers of the metal-salt and the precipitation agent precursor of solid state shape.

It is added in the 500ml pyriform flask, similarly operate, carry out a series of heating, clean, fire processing, obtain solid acid catalyst with embodiment 2-1.The zirconic average crystallite that obtains by XRD determining directly is 71 , be 16.9 weight % with respect to the zirconic charge capacity of catalyzer total amount.

Use this solid acid catalyst, similarly carry out the manufacturing of polyethers with embodiment 2-1.Transformation efficiency is 13.0%, and Mn is 3167, and Mw/Mn is 2.13.

Comparative example 2-4

(new Japanese metallochemistry society makes ZrO to the 89.66g Zircosol ZN aqueous solution ₂Conversion concentration 18.12 weight %) add 31.72g de-salted water and uniform mixing in.In this solution, add 80gSiO ₂(Silysia of Fuji make, CARiACT Q30), vibration mixed about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).In its 500ml pyriform flask of packing into, 2-2 similarly heats with comparative example, similarly handle and carry out with Ammonium Bicarbonate, Food Grade catalyzer filtration, cleaning, drying, fire, obtain solid acid catalyst.Obtaining zirconic average crystallite by XRD determining directly is 53

, be 16.9 weight % with respect to the zirconic charge capacity of catalyzer total amount.

Use this solid acid catalyst, similarly carry out the manufacturing of polyethers with embodiment 2-1.Transformation efficiency is 35.9%, and Mn is 3943, and Mw/Mn is 1.97.

The result of the foregoing description 2-1～2-6 and comparative example 2-1～2-4 gathers among the 2-1 in table and provides.

[table 2-1]

2-1 is known as below content by table.

By the contrast of embodiment 2-1～2-3 and comparative example 2-1 as can be known, do not utilize the homogeneous precipitator method in the carrier pore, but after making solid state shape with impregnating metal salt and precipitation agent precursor, dry impregnated carrier begins heat treated again, the poor-performing of the catalyzer that obtains thus.

In addition, by the contrast of embodiment 2-1～2-3 and comparative example 2-2 as can be known, do not utilize the homogeneous precipitator method in the carrier pore, supply with alkali but have the carrier of metal-salt to put in the alkaline solution infiltration by the outside, the performance of the catalyzer that obtains thus is also relatively poor.

In addition, by the contrast of embodiment 2-5～2-6 and comparative example 2-3～2-4 as can be known, also identical result can be obtained under the situation of use different carriers,, just high performance solid acid catalyst can be made so long as implement method based on the homogeneous precipitator method in the carrier pore of the 3rd aspect.

[explanation of the 4th aspect]

The inventor finds, by in the presence of catalyzer, the cyclic ether ring-opening polymerization being made in the method for polyethers, use to contain as catalyzer and be selected from by periodictable the 1st, 2,4,6,8,9,12,13,14,15,16, one or more elements in the group of 17 group compositions and can be with itself solid acid catalyst with the cyclic ether ring-opening polymerization, when carrying out the manufacturing of polyethers, can be simply and effectively the molecular-weight average of resulting polyethers be controlled at desired value and can produce detrimentally affect to other performances, thereby finish the invention of the 4th aspect.

Promptly, the main points of the 4th aspect are a kind of manufacture method of polyethers, it is by the cyclic ether ring-opening polymerization being made the method for polyethers in the presence of catalyzer, it is characterized in that, use the following catalyzer that obtains as catalyzer: be selected from by periodictable the 1st containing, 2,4,6,8,9,12,13,14,15,16, at least a element in the group of 17 group compositions and can make it contain being selected from of not comprising in this solid acid catalyst with in itself solid acid catalyst with the cyclic ether ring-opening polymerization by periodictable the 3rd, 5,10, at least a metallic element in the group of 11 group compositions.

In the 4th aspect, as can be with itself solid acid catalyst with the cyclic ether ring-opening polymerization, preferred one or more the solid acid catalyst that is selected from the group of forming by catalyzer, O composite metallic oxide catalyst, clay catalyst and the zeolite catalyst of metal oxide by load that uses.

As being selected from of not comprising in the described solid acid catalyst, preferably use copper and/or nickel by the metallic element in the group of periodictable the 3rd, 5,10,11 group compositions.

As can be with the solid acid catalyst of cyclic ether ring-opening polymerization, preferred one or more the solid acid catalyst that is selected from the group of forming by clay catalyst, silica-alumina, silica-titania and silicon-dioxide-zirconium white that uses.

Described catalyzer is preferably by utilizing the homogeneous precipitator method in the carrier pore to make at the pore internal burden metal hydroxides and/or the metal oxide of carrier.

Manufacture method according to the polyethers of the 4th aspect need not change reaction conditions, only changes the composition and the composition thereof of employed catalyzer, just can change the molecular-weight average of resulting polyethers, and can not produce detrimentally affect to the performance beyond the molecular-weight average.

Therefore, according to the 4th aspect, can produce the polyethers with desired molecular-weight average of the purposes that meets polyethers simply and effectively.

Embodiment to the 4th aspect is elaborated below, but the explanation of the constitutive requirements of following record only is an example (typical example) of the embodiment of the 4th aspect, and only otherwise exceed its main points, the 4th aspect is not subjected to the restriction of these contents.

[catalyzer]

At first the catalyzer that uses in the 4th aspect is described.The catalyzer that uses among the present invention is the catalyzer that contains the metallic element of specific (periodictable the 3rd, 5,10,11 families) in solid acid catalyst.

＜solid acid catalyst 〉

Among the present invention,, can enumerate the zeolites of crystalline structure such as for example having MFI, X, Y as solid acid catalyst; Metal oxide-type such as silicon-dioxide, aluminum oxide, titanium dioxide, zirconium white; The complex metal oxides class that two or more oxide-metal combinations such as silica-titania, silica-alumina, silicon-dioxide-zirconium white, aluminum oxide-titanium dioxide form; With metal oxide, clay, zeolite is that carrier and load have the metal oxide that is different from this carrier or have the loading type acid catalyst class of the compound of acid matter; Clay classes such as atlapulgite; Or the like.

Wherein, preferred complex metal oxides class, loading type acid catalyst class, clay class, preferred especially silicon-dioxide-zirconium white, silica-alumina, silica-titania, clay class.

The manufacture method of＜solid acid catalyst 〉

As the manufacture method of solid acid catalyst, can use technique known and be not particularly limited, specifically, can adopt the manufacture method of record in above-mentioned patent documentation 1, the patent documentation 2 etc.

As the catalyzer that the 4th aspect is used, preferably utilize the interior homogeneous precipitator method of carrier pore at the pore internal burden metal hydroxides of carrier and/or the catalyzer of metal oxide.

＜make the method that contains specific metallic element in the solid acid catalyst 〉

Contain being selected from of not comprised in this solid acid catalyst method in the solid acid catalyst as making, can adopt any method in following (1), (2), (3) by at least a metallic element in the group of periodictable the 3rd, 5,10,11 group compositions (hereinafter being sometimes referred to as " adding metallic element (additive element) "):

When (1) preparing solid acid catalyst, make employed carrier contain the method for this interpolation metallic element in advance;

Make it contain the method for this interpolation metallic element when (2) preparing solid acid catalyst simultaneously;

(3) prepare the method for adding this interpolation metallic element after the solid acid catalyst; But the method for preferred (2) makes it contain the method for this interpolation metallic element simultaneously when promptly preparing solid acid catalyst.

＜utilize the homogeneous precipitator method to carry out the manufacturing of catalyzer 〉

Below the method for making the employed catalyzer in the 4th aspect is described, in the preparation solid acid catalyst, make it contain the interpolation metallic element when homogeneous precipitator method in this method in utilizing the carrier pore are made catalyzer.

Under the situation of the catalyzer that uses in the 4th aspect as the loading type acid catalyst, with respect to whole content of metal of its carrier, as the content of metal of solid acid catalyst, add the metallic element charge capacity and be preferably the amount that converts and obtain by metal-salt described later or metal oxide supported amount.

The following enforcement of the homogeneous precipitator method, for example, infiltrate metal-salt and the precipitation agent precursor that in solution, produces precipitation agent simultaneously in carrier by chemical reactions such as hydrolysis after, this impregnated carrier is carried out heat treated etc. is generated precipitation agent by the precipitation agent precursor processing.Owing to be the homogeneous precipitator method, therefore importantly metal-salt and precipitation agent precursor form the liquid phase ie in solution.That is, the dipping solution that will contain metal-salt and precipitation agent precursor is infiltrated up in the carrier, then, carries out being generated by the precipitation agent precursor processing of precipitation agent.

As the metal-salt that is dissolved in this immersion solvent, will be used to generate the metal-salt (hereinafter being sometimes referred to as " acid generates metal-salt ") of solid acid catalyst and be used to generate the metal-salt (hereinafter being sometimes referred to as " salt that adds metallic element ") that adds metallic element and share.

(1) carrier

Carrier for catalyzer is not particularly limited, preferable alloy is oxide-based, complex metal oxides class, zeolites, clay class, more preferably silicon-dioxide, aluminum oxide, zirconium white, titanium dioxide, silica-alumina, silicon-dioxide-zirconium white, silica-titania, clay class, preferred especially silicon-dioxide, aluminum oxide, zirconium white, clay class.

These carriers both can be used alone, and also can share two or more.

(2) be dissolved in metal-salt in the dipping solution

(2-1) acid generates metal-salt

As being carried on the carrier and showing the metallic element of the metal-salt of solid acid, more than one in can life cycle table the 1,2,4,6,8,9,12,13,14,15,16,17 family's metallic elements.The metallic element of preferred life cycle table the 4 families, the 13rd family, the 14th family more preferably uses Ti, Zr, Hf, Al, Si metallic element, especially preferably uses Ti, Zr, Al.

Kind for salt is not particularly limited, preferably nitrate, acetate, vitriol, oxynitrate, muriate, oxychloride, more preferably oxynitrate, oxychloride, vitriol.

Promptly, generate metal-salt as acid, nitrate, acetate, vitriol, oxynitrate, muriate, the oxychloride of preferred cycle table the 1,2,4,6,8,9,12,13,14,15,16,17 families, more preferably Zircosol ZN, basic zirconium chloride, zirconium sulfate, titanium chloride, Tai-Ace S 150.

These acid generate metal-salt and both can be used alone, and also can share two or more.

(2-2) salt of interpolation metallic element

On the other hand, for being selected from of not containing in this solid acid catalyst that will in solid acid catalyst, add by at least a metallic element in the group of periodictable the 3rd, 5,10,11 group compositions (interpolation metallic element), the metallic element of life cycle table the 3 families, the 5th family, the 10th family, the 11st family, the metallic element of preferred Ni, Cu, Ce, preferred especially Ni, Cu.

Be not particularly limited preferably nitrate, acetate, vitriol, oxynitrate, muriate, oxychloride, more preferably oxynitrate, oxychloride, vitriol for these salt that add metallic element.

That is, as the salt that adds metallic element, preferred cycle table the 3 families, the 5th family, the 10th family, the nitrate of the 11st family's metal, acetate, vitriol, oxynitrate, muriate, oxychloride, more preferably nickelous nitrate, nickelous chloride, cupric nitrate, cupric chloride.

These salt that add metallic element both can be used alone, and also can share two or more.

(3) precipitation agent precursor

The precipitation agent precursor is meant, causes that by processing such as heat in dipping solution hydrolysis or other chemical reactions are to generate the material of precipitation agent.Precipitation agent be meant with dipping solution in reacting metal salt generate the material of precipitate metal hydroxides.In the precipitation agent precursor, to produce (promptly as the material of the alkali of precipitation agent, in dipping solution, produce alkali, the pH of solution risen, make metal-salt with the sedimentary material of the form of oxyhydroxide or oxide compound by hydrolysis or other chemical reaction) be called " alkali precursor ".

Be not particularly limited for the precipitation agent precursor that is used to carry out the homogeneous precipitator method, use the alkali precursor usually.

As the alkali precursor, amide compound that generally use urea, tricyanic acid, alkyl substituted ureas, thiocarbamide, alkyl substituting thioureido, constitutes by amine and carboxylic acid etc.Preferred urea, tricyanic acid, the alkyl substituted ureas of using is from being easy to obtain and the consideration of cost aspect preferred especially urea, tricyanic acid.These alkali precursors can be used alone, and also can share two or more.

(4) alkaline matter

In dipping solution, not only can add above-mentioned alkali precursor, and the alkaline matter that can be in advance adds predetermined amount in not generating sedimentary scope is to improve pH.By using alkaline matter, consumption, the minimizing that can reduce the alkali precursor generate the precipitation time necessary.

Be not particularly limited for alkaline matter, can enumerate oxyhydroxide, carbonate, supercarbonate, phosphoric acid salt, the acetate of basic metal, alkaline-earth metal and ammonium, ammonia, organic amine etc., preferred ammonia, organic amine, the carbonate of ammonium, supercarbonate, phosphoric acid salt, more preferably volatile salt, bicarbonate of ammonia.

These alkaline matters both can be used alone, and also can share two or more.

(5) dipping solution

Dipping solution usually by the salt that above-mentioned acid generated metal-salt and add metallic element and precipitation agent precursor and as required the alkaline matter of use be dissolved in the water and prepare.

Concentration to metal-salt in the dipping solution and precipitation agent precursor is not particularly limited, as long as can keep dissolved state and can realize the charge capacity that is fit to the aftermentioned carrier, usually metal salt concentrations is expressed as 0.01 weight %～50 weight % with the total concentration that acid generates the salt of metal-salt and interpolation metallic element, be preferably 0.1 weight %～40 weight %, be preferably 0.5 weight %～30 weight % especially, for the precipitation agent precursor as described later, with respect to being enough to make the whole sedimentary theoretical amount of this metal-salt is 0.1～10 times, be preferably 0.2～8 times, be preferably 0.3～5 times especially.

Can suitably use alkaline matter to obtain required pH condition.That is, owing to generate the necessary pH condition of precipitation according to the kind of employed metal-salt and precipitation agent precursor or concentration and different, so can use the alkaline matter of necessary amount according to these conditions.

In order in carrier, to implement the homogeneous precipitator method, before carrying out that the precipitation agent precursor is converted to the processing of precipitation agent, the at least two kinds of metal-salts and the precipitation agent precursor that need acid to generate metal-salt and add the salt of metallic element are liquid phase in dipping solution, be dissolved state, for the material beyond these at least two kinds of metal-salts and the precipitation agent precursor, in dipping solution, exist and all can with random order.

(6) the homogeneous precipitator method

(6-1) dipping solution is to the infiltration method of carrier

Be not particularly limited for the method that above-mentioned dipping solution is infiltrated up in the carrier,, preferably implement with the hole completion method for the salt that acid is generated metal-salt and interpolation metallic element loads on the carrier equably.In this case, the volume that is infiltrated up to the dipping solution in the carrier is preferably 60%～120% of carrier pore volume, and more preferably 70%～110%, be preferably 80%～105% especially.If this hypovolia, then dipping solution can not enter in the carrier pore equably, and causes uneven homogenize.Conversely, if this hypervolia, then steeping fluid still can cause uneven homogenize attached to the carrier outside surface.

In addition, the charge capacity that loads on the metal-salt on the carrier by infiltration can be selected to measure arbitrarily, but with respect to vehicle weight, be generally 0.01 weight %～50 weight % when representing with the total of acid generation metal-salt and interpolation metal-salt, be preferably 0.05 weight %～40 weight %, more preferably 0.1 weight %～30 weight %.Charge capacity for the precipitation agent precursor, if being enough to make the whole sedimentary theoretical amount of the metal-salt that is carried on the carrier is,, in 0.1～10 scope, use the precipitation agent precursor usually at 1 o'clock with molar ratio computing, be preferably 0.2～8 scope, more preferably 0.3～5 scope.

(6-2) sedimentary generation and post-treating method

Dipping solution is infiltrated up in the carrier, the state that makes the metal-salt that is carried on the carrier and precipitation agent precursor in the carrier pore, keep solution thus, implement heating in this state and wait the processing that the precipitation agent precursor is converted to precipitation agent, utilize the precipitation agent that evenly produces in carrier inside that metal-salt is converted to corresponding metal hydroxides.

Usually use the alkali precursor as the precipitation agent precursor, in the processing that the alkali precursor is converted to alkali, utilize hydrolysis based on the alkali precursor of heating.

As mentioned above, in order in the carrier pore, to implement the homogeneous precipitator method, need be before carrying out that the precipitation agent precursor is converted to the processing of precipitation agent, make at least two kinds of metal-salts and precipitation agent precursor be solution state, be liquid phase, all can and the material except these at least two kinds of metal-salts, precipitation agent precursor is any state.

In based on the hydrolysis reaction that adds thermal initiation, the alkali precursor is converted under the situation of alkali,, adopts 50 ℃～300 ℃ scope usually, preferably adopt 60 ℃～200 ℃ scope as Heating temperature.Heating temperature is changed in time.If Heating temperature is low excessively, then might not take place to generate the reaction of precipitation agent or need expend the very long time by the precipitation agent precursor; If Heating temperature is too high, then the necessary moisture of hydrolysis sometimes may all be removed before the reaction that is generated precipitation agent by the precipitation agent precursor finishes.In order to implement the good and stable homogeneous precipitator method, preferably when the precipitation formation reaction finished, the moisture entrapment in the dipping solution of infiltration in carrier is more than 5%, and was more preferably residual more than 10%.

As the fixed bed heating unit, can there be the carrier of dipping solution to heat to infiltration at the immobilising state of load carriers, but especially under the situation of a large amount of catalyzer of preparation, more preferably the thermopnore device of working load carrier flow, revolving heating unit etc.It is believed that, when heating, occur under the situation of moisture evaporation, make load carriers mobile method that the water evaporation quantity of every particle loading carrier is changed, thereby further increase uniformity.

In addition, if the moisture evaporation during heating is too fast, then moisture was all removed before the hydrolysis of alkali precursor finishes fully, sometimes can not fully carry out the supply of precipitation agent, therefore it is desirable to usually, by beginning to be heated to through precipitation after formation reaction finishes till removing moisture fully, with more than 1 hour, preferred more than 3 hours, further preferred time more than 6 hours carries out removing fully of moisture.

Thereafter, water, alkaline aqueous solution, aqueous acid, organic solvent etc. clean resulting catalyzer as required, after the drying, under inert gas atmospheres such as nitrogen, argon gas or oxidizing gas atmosphere such as air or dilution oxygen, fire, thus the catalyzer that can obtain having desired performance.Heating firing temperature as this moment is generally 100 ℃～1200 ℃, is preferably 300 ℃～1100 ℃, more preferably 500 ℃～1000 ℃.Fire by carrying out such heating, can make resulting catalyzer, promptly be added with the catalyst activity and the improved stability of the solid acid catalyst of specific metallic element.

Wherein, above-mentioned operation not all is essential operation, this solid acid catalyst do not contain is selected from catalyzer by at least a metallic element in the group of periodictable the 3rd, 5,10,11 group compositions as long as can obtain being added with in solid acid catalyst, to the restriction especially of its manufacturing process.

＜content of metal 〉

The catalyzer that obtains with aforesaid method normally in solid acid catalyst the form with oxide compound be added with the catalyzer that adds metallic element.

The catalyzer that uses among the present invention is under the situation of the metal oxide supported catalyzer that adds interpolation metallic elements such as Ni, Cu, Ce in the formed solid acid catalyst and obtain on carriers such as silicon-dioxide such as zirconium white, with respect to carrier, the content of metal of solid acid catalyst is preferably 0.1 mole of %～15 mole %, is preferably 0.5 mole of %～10 mole % especially.If charge capacity is more than this scope, then metal is difficult to the state load with even and high dispersing, if charge capacity is less than this scope, then can not generate enough acid amounts.And, with respect to carrier, the charge capacity of special metal element is preferably 0.01 mole of %～10 mole %, is preferably 0.05 mole of %～5 mole % especially, adding metallic element/solid acid catalyst metal molar ratio is preferably 0.01～5, is preferably 0.05～3 especially.

If add the metallic element charge capacity more than this scope, then may produce detrimentally affect to the catalyst performance beyond the molecular-weight average, if be less than this scope, then can't fully obtain the change effect of molecular-weight average.

In addition, the catalyzer that uses among the present invention is add to add metallic element and under the situation of the catalyzer that forms in as the clay catalyst of solid acid catalyst, with respect to clay catalyst, the addition that adds metallic element is preferably 0.01 weight %～20 weight %, is preferably 0.05 weight %～15 weight % especially.If the charge capacity of adding metallic element more than this scope, then may produce detrimentally affect to the catalyst performance beyond the molecular-weight average,, then can not fully obtain the change effect of molecular-weight average if be less than this scope.

[manufacture method of polyethers]

Below to using solid acid catalyst that containing of as above making add metallic element to describe as the manufacture method of the polyethers of the present invention of catalyst for polymerization.

The manufacture method of this polyethers by the ring-opening polymerization of ring-type ethers, promptly be that reaction raw materials carries out ring-opening polymerization to it and carries out with the ring-type ethers.

Make under the situation of polyethers with the ring-opening polymerization of ring-type ethers, as the cyclic ether as reaction raw materials, the formation carbonatoms that can enumerate ring is 3～10 cyclic ether, and, can use the cyclic ether that replaces with alkyl, halogen radical, acyl group etc.Specifically, can use tetrahydrofuran (THF), trimethylene oxide, oxepane, 1,4-dioxane, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran etc.And, can only use a kind of homopolymerization of ring-type ethers and use any polymerization in the copolymerization of two or more ring-type ethers.

Use one or more that as above contain the solid acid catalyst that adds metallic element as catalyzer.

Consider that from the aspect of control molecular weight the ring-opening polymerization of cyclic ether preferably carries out in the presence of carboxylic acid anhydride and/or carboxylic acid.As carboxylic acid anhydride and/or carboxylic acid, generally use aliphatics or aromatic carboxylic acid anhydride and/or carboxylic acid, preferred carboxylic acid anhydride and/or the carboxylic acid that use with 2～8 carbon atoms with 2～12 carbon atoms.These carboxylic acid anhydride and/or carboxylic acid both can be used alone, and also can share two or more.It is comparatively suitable that carboxylic acid anhydride and/or carboxylic acid add in the scope that with respect to cyclic ether is 0.01～1.0 (mol ratio) usually.

Can in reaction, use inert solvent during polyreaction.As this solvent, use the divided ring polyreaction to be in inert aliphatic hydrocarbon, the aromatic hydrocarbon etc. one or more usually.

Reaction formation uses the general form of using such as grooved, tower, can be any of batch mode, continuous mode.Following method etc. is for example arranged: cyclic ether, catalyzer, carboxylic acid anhydride and/or carboxylic acid are under agitation fed intake carry out polymeric method (batch mode); In containing the reactor of catalyzer, supply with cyclic ether, carboxylic acid anhydride and/or carboxylic acid and continuous method (continuous mode) of extracting reaction solution out etc. continuously.Consider preferred continuous mode from the aspect of productivity.

Catalyst consumption depends on its kind, be not particularly limited, but for example in the batch-type reactor, if catalytic amount is very few, then polymerization velocity is slack-off, conversely if too much, then be difficult to remove heat of polymerization.And, because the slurry concentration of reaction system uprises, cause stirring difficulty, and be easy to go wrong in the separatory of catalyzer after polyreaction finishes and reaction solution.Therefore, for catalyst consumption, can be generally 0.001～50 times of weight with respect to liquid phase under the condition of the reaction form of considering batch reactions, circulation reaction, be preferably in the scope of 0.01～20 times of weight and select.Wherein, under the situation of circulation reaction, catalyst consumption is represented the amount with respect to the catalyzer of the feed rate of liquid phase of time per unit.

Temperature of reaction is generally 0 ℃～200 ℃, is preferably 10 ℃～80 ℃.

Reaction pressure is that reaction system can keep the pressure of liquid phase to get final product, usually from normal pressure～10MPa, preferably select from the pressure range of normal pressure～5MPa.

Reaction times is not particularly limited, consider itself and catalytic amount the two, consider yield, economy, the reaction times is 0.1 hour～20 hours scope, is preferably 0.5 hour～15 hours scope.The said herein reaction times is meant, in batch mode, plays the time till reaction finishes to begin to cool down when rising to temperature of reaction by temperature; In continuous mode, the residence time of liquid in reactor formed in reaction.

The molecular weight distribution of the polyethers that generates depends on the kind of starting compound, carry out under the situation of ring-opening polymerization of tetrahydrofuran (THF) (THF), can obtain number-average molecular weight (Mn) is 200～80,000, particularly 200～40, the polyethers of low～middle molecular weight of about 000.And then the polyethers that can easily produce narrow molecular weight distribution also is one of feature.Promptly, the Mw/Mn of the polyethers that industrial requirement is bigger is 1.3～2.5, by utilizing solid acid catalyst of the present invention, can access Mw/Mn less than 3, for example Mw/Mn is 1.1～3.0 polyethers, particularly by selecting optimum condition of the present invention for use, can also obtain Mw/Mn and be about 1.3～2.0 the very narrow polyethers of molecular weight distribution.

In addition, cannot treat different things as the same with respect to the relation between the molecular-weight average of the addition of solid acid catalyst and gained polyethers for adding metallic element in the catalyst system therefor, according to the different polyethers that obtain various molecular-weight average of the kind of adding metallic element, but in general, same interpolation metallic element is added under the situation of same solid acid catalyst into, the addition that adds metallic element is many more, trends towards obtaining the big polyethers of molecular-weight average more.

Polyethers constructed in accordance can be used for purposes such as spandex fiber, thermoplastic polyester elastomer, Polyurethane Thermoplastic Elastomer, coating material.

[embodiment and comparative example]

Enumerate embodiment and comparative example below the 4th aspect is further specifically described, but following embodiment does not limit the scope of the 4th aspect.

In addition, in the content below, the number-average molecular weight (Mn) of the transformation efficiency of tetrahydrofuran (THF) (THF), polytetramethylene ether diol acetic ester (PTME), molecular weight distribution (Mw/Mn) utilize following GPC (gel permeation chromatography) to obtain.

The GPC device: Tosoh society makes GPC 8220

Post: TSK-GEL H (30cm) * 2

Detection method: RI

Column temperature: 40 ℃

Mobile phase: THF

Flow velocity: 1ml/min

Sample injection rate: 500 μ L

Sample concentration: the concentration that is adjusted to polyethers is about 0.1 weight %

[comparative example 3-1]

The preparation of＜solid acid catalyst 〉

With 2.84g ZrO (NO ₃) ₂2H ₂O and 0.957g urea are dissolved in the homogeneous solution of making 12.1ml in the de-salted water.(Silysia of Fuji makes, CARiACT Q30, particle diameter 75 μ m～500 μ m to add the 10.0g silica supports under the room temperature in this steeping fluid, median size 200 μ m, pore volume 1.21ml/g, average fine pore 30nm), under vibration mixes every now and then, placed 1 hour, make its infiltration.Impregnated carrier is packed in the 100ml Erlenmeyer flask, and cover lid carries out 6 hours processing to it in 110 ℃ drying machine.Open the lid of flask after 6 hours, keep this state in 110 ℃ drying machine dry 16 hours.With it in 140 ℃ of further naturally cooling after dry 4 hours.Under the room temperature product that so obtains added and in the 72ml de-salted water, be dissolved with in the 7.2g bicarbonate of ammonia solution of (containing ammonia 20 weight %) in ammonia, stir 1 hour after-filtration, and then with after the 84ml de-salted water suspension cleaning 3 times, in 120 ℃ of dryings, under airiness, fire in 900 ℃ then, obtain catalyzer.

＜polyreaction 〉

Under nitrogen atmosphere, in the 500ml four-hole boiling flask, add 133.5g THF and 6.85g diacetyl oxide and mix.The above-mentioned catalyzer of weighing 4.68g under nitrogen atmosphere, and after under agitation adding in the described mixed solution, in 40 ℃ of reactions 5 hours.With GPC reaction solution is analyzed, measured transformation efficiency, the molecular-weight average (Mn) of PTME, the molecular weight distribution (Mw/Mn) of THF, transformation efficiency is 32% as a result, and Mn is 3002, and Mw/Mn is 1.84.

[embodiment 3-1]

With 2.86g ZrO (NO ₃) ₂2H ₂O, 0.464g Ce (NO ₃) ₃6H ₂O and 1.108g urea are dissolved in the de-salted water, form the homogeneous solution of 12.1ml, thereby prepare steeping fluid, in addition, contain the solid acid catalyst that adds metallic element with the method preparation identical, use this catalyzer similarly to implement polyreaction with comparative example 3-1.

Its result, transformation efficiency is 28%, and Mn is 2664, and Mw/Mn is 1.84.

[embodiment 3-2]

With 2.86g ZrO (NO ₃) ₂2H ₂O, 0.432g Fe (NO ₃) ₃9H ₂O and 1.108g urea are dissolved in the de-salted water, form the homogeneous solution of 12.1ml, thereby prepare steeping fluid, in addition, contain the solid acid catalyst that adds metallic element with the method preparation identical, use this catalyzer similarly to implement polyreaction with comparative example 3-1.

Its result, transformation efficiency is 36%, and Mn is 3241, and Mw/Mn is 1.82.

[embodiment 3-3]

With 2.86g ZrO (NO ₃) ₂2H ₂O, 0.311g Ni (NO ₃) ₂6H ₂O and 1.06g urea are dissolved in the de-salted water, make the homogeneous solution of 12.1ml, thereby prepare steeping fluid, in addition, contain the solid acid catalyst that adds metallic element with the method preparation identical, use this catalyzer similarly to implement polyreaction with comparative example 3-1.

Its result, transformation efficiency is 34%, and Mn is 4137, and Mw/Mn is 1.83.

[embodiment 3-4]

With 2.86g ZrO (NO ₃) ₂2H ₂O, 0.258g Cu (NO ₃) ₂3H ₂O and 1.059g urea are dissolved in the de-salted water, make the homogeneous solution of 12.1ml, thereby prepare steeping fluid, in addition, contain the solid acid catalyst that adds metallic element with the method preparation identical, use this catalyzer similarly to implement polyreaction with comparative example 3-1.

Its result, transformation efficiency is 30%, and Mn is 4059, and Mw/Mn is 1.76.

[comparative example 3-2]

The preparation of＜solid acid catalyst 〉

The zirconyl nitrate solution of making in the new Japanese metallochemistry of 88.01g society is (with ZrO ₂Meter is 18.46 weight %) middle 22.35g de-salted water, the uniform mixing of adding.To wherein adding 11.89g urea, uniform mixing is made dipping solution.(Silysia of Fuji makes to add the 80g silica supports in this solution, CARiACT Q15, particle diameter 75 μ m～500 μ m, median size 200 μ m, pore volume 1.16ml/g, average fine pore 15nm), vibrates and mixed in about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).

In its 500ml pyriform flask of packing into, at flask top jointing and the bend pipe that is plugged with glass wool.With anchor clamps flask be fixed on the turning axle of rotating dryer on thereafter.Speed rotation turning axle with 10rpm is set at 105 ℃ with the drying machine temperature, carries out 2 hours heating.Then, unload the bend pipe that is plugged with glass wool on top after, the drying machine temperature is set at 120 ℃, carry out 16 hours heating.Then, unload the joint on top after, the drying machine temperature is set at 140 ℃, carry out 4 hours heating.After 4 hours, stop heating, rotation, take out catalyzer.Catalyzer is transferred to naturally cool to room temperature in the beaker of 500ml after, add the de-salted water of about 300ml, after the cleaning that suspends was carried out 3 times in about 10 minutes, air-dry catalyzer, a dry night in 120 ℃ drying machine, under airiness, fire in 900 ℃ then, obtain catalyzer.

＜polyreaction 〉

Use the above-mentioned solid acid catalyst that obtains similarly to implement polyreaction as catalyzer and comparative example 3-1, transformation efficiency is 43% as a result, and Mn is 2116, and Mw/Mn is 1.75.

[embodiment 3-5]

The zirconyl nitrate solution of making in the new Japanese metallochemistry of 77.52g society is (with ZrO ₂Meter is 18.46 weight %) middle 23.22g de-salted water and the uniform mixing of adding.To wherein adding 1.03gCa (NO ₃) ₂4H ₂O and uniform mixing.And then add 10.92g urea and uniform mixing, thereby the preparation dipping solution uses the method preparation identical with comparative example 3-2 to contain the solid acid catalyst that adds metallic element in addition, uses this catalyzer similarly to implement polyreaction.

Its result, transformation efficiency is 46%, and Mn is 2279, and Mw/Mn is 1.75.

[embodiment 3-6]

The zirconyl nitrate solution of making in the new Japanese metallochemistry of 77.69g society is (with ZrO ₂Meter is 18.46 weight %) middle 20.31g de-salted water and the uniform mixing of adding.To wherein adding 2.12gNi (NO ₃) ₂6H ₂O and uniform mixing.And then add 11.81g urea and uniform mixing, thereby the preparation dipping solution uses the method preparation identical with comparative example 3-2 to contain the solid acid catalyst that adds metallic element in addition, uses this catalyzer similarly to implement polyreaction.

Its result, transformation efficiency is 47%, and Mn is 2687, and Mw/Mn is 1.76.

[embodiment 3-7]

The zirconyl nitrate solution of making in the new Japanese metallochemistry of 77.52g society is (with ZrO ₂Meter is 18.46 weight %) middle 23.22g de-salted water and the uniform mixing of adding.To wherein adding 1.05gCu (NO ₃) ₂3H ₂O and uniform mixing.And then add 10.92g urea and uniform mixing, thereby the preparation dipping solution uses the method preparation identical with comparative example 3-2 to contain the solid acid catalyst that adds metallic element in addition, uses this catalyzer similarly to implement polyreaction.

Its result, transformation efficiency is 47%, and Mn is 2983, and Mw/Mn is 1.74.

[embodiment 3-8]

The zirconyl nitrate solution of making in the new Japanese metallochemistry of 77.56g society is (with ZrO ₂Meter is 18.46 weight %) middle 20.95g de-salted water and the uniform mixing of adding.To wherein adding 0.35g Cu (NO ₃) ₂3H ₂O and 1.70g Ni (NO ₃) ₂6H ₂O and uniform mixing.And then add 11.13g urea and uniform mixing, thereby the preparation dipping solution uses the method preparation identical with comparative example 3-2 to contain the solid acid catalyst that adds metallic element in addition, uses this catalyzer similarly to implement polyreaction.

Its result, transformation efficiency is 46%, and Mn is 2667, and Mw/Mn is 1.74.

[comparative example 3-3]

Under airiness, 20g was fired 1 hour as the Tonsil OptimumFF of the SuedChemie society of clay (atlapulgite) catalyzer in 400 ℃, the product that use obtains is as catalyzer, in addition, 3-1 similarly operates with comparative example, implements polyreaction.

Its result, transformation efficiency is 42%, and Mn is 3497, and Mw/Mn is 2.01.

[embodiment 3-9]

With 0.35g Cu (NO ₃) ₂3H ₂O is dissolved in the 10g de-salted water and uniform mixing.It is infiltrated up among the Tonsil OptimumFF of 20g as the Sued Chemie society manufacturing of clay catalyst, placed 1 hour.Then, similarly under airiness, carry out 1 hour fire in 400 ℃, prepare and contain the solid acid catalyst that adds metallic element, use this catalyzer, similarly implement polyreaction with comparative example 3-3.

Its result, transformation efficiency is 42%, and Mn is 4002, and Mw/Mn is 2.00.

[embodiment 3-10]

With 0.78g Ni (NO ₃) ₂6H ₂O is dissolved in the 10g de-salted water and uniform mixing.It is infiltrated up among the Tonsil OptimumFF of 20g as the Sued Chemie society manufacturing of clay catalyst, placed 1 hour.Then, similarly under airiness, carry out 1 hour fire in 400 ℃, prepare and contain the solid acid catalyst that adds metallic element, use this catalyzer, similarly implement polyreaction with comparative example 3-3.

Its result, transformation efficiency is 39%, and Mn is 4380, and Mw/Mn is 2.01.

3-1～3-3 is shown in the results are summarized in of above embodiment and comparative example.

[table 3-1]

[table 3-2]

[table 3-3]

By comparative example 3-1 and embodiment 3-1～3-4 as can be known, owing to make the interpolation metallic element that contains periodictable 3,5,8,10,11 families in the solid acid catalyst, thereby can under same reaction conditions, only change molecular-weight average and can not produce detrimentally affect other performances.

And by comparative example 3-2 and embodiment 3-5～3-8 as can be known, the situation that changes the situation of creating conditions of solid acid catalyst and add two or more metallic elements also is same.

And then by comparative example 3-3 and embodiment 3-9,3-10 as can be known, the situation of adding metallic element afterwards again in solid acid catalyst also is same.

Use specific mode that the present invention is had been described in detail, but only it will be apparent to one skilled in the art that otherwise break away from the intent of the present invention and scope, can carry out various changes.

In addition, Japanese patent application that the application proposed based on September 6th, 2005 (the special 2005-258055 of hope) and the Japanese patent application (the special 2005-258056 of hope) that proposed on September 6th, 2005, and quote its full content by reference.

Claims (24)

1. a polyethers manufacturing solid acid catalyst is characterized in that, the surface hydroxyl amount of this catalyzer is 0.1 μ mol/m ²～2.5 μ mol/m ², the following acid amount of pKa-5.6 is more than the 20 μ mol/g.

2. the manufacture method of a polyethers, it is to make starting compound carry out the method that polyethers is made in polyreaction or condensation reaction in the presence of solid acid catalyst, the method is characterized in that as described solid acid catalyst, using the surface hydroxyl amount is 0.1 μ mol/m ²～2.5 μ mol/m ², the following acid amount of pKa-5.6 is the above solid acid catalysts of 20 μ mol/g.

3. the manufacture method of a polyethers, it is to make starting compound carry out the method that polyethers is made in polyreaction or condensation reaction in the presence of solid acid catalyst, the method is characterized in that, the solid acid catalyst that will have a surface hydroxyl with can with this surface hydroxyl reaction or interactional except that described polyethers organic compound and/or after mineral compound contacts, use it for described polyreaction or condensation reaction again.

4. the manufacture method of polyethers as claimed in claim 1 is characterized in that, described solid acid catalyst is at least a catalyzer that is selected from the group of being made up of the catalyzer and the clay catalyst of metal oxide O composite metallic oxide catalyst, load.

5. the manufacture method of polyethers as claimed in claim 3 is characterized in that, described solid acid catalyst is at least a catalyzer that is selected from the group of being made up of the catalyzer and the clay catalyst of metal oxide O composite metallic oxide catalyst, load.

6. the manufacture method of polyethers as claimed in claim 2, it is characterized in that described solid acid catalyst contains at least a metallic element that is selected from by in the group of periodictable the 2nd family, the 3rd family, the 4th family, the 5th family, the 8th family, the 10th family, the 11st family, the 13rd family and the 14th group composition.

7. the manufacture method of polyethers as claimed in claim 3, it is characterized in that described solid acid catalyst contains at least a metallic element that is selected from by in the group of periodictable the 2nd family, the 3rd family, the 4th family, the 5th family, the 8th family, the 10th family, the 11st family, the 13rd family and the 14th group composition.

8. the manufacture method of polyethers as claimed in claim 3 is characterized in that, described organic compound is at least a compound that is selected from the group of being made up of alcohols, silanizing agent and carbonates.

9. the manufacture method of polyethers as claimed in claim 2 is characterized in that, this method is by making cyclic ether carry out the method that ring-opening polymerization is made polyethers.

10. the manufacture method of polyethers as claimed in claim 3 is characterized in that, this method is by making cyclic ether carry out the method that ring-opening polymerization is made polyethers.

11. the manufacture method of polyethers as claimed in claim 9 is characterized in that, this method is by making cyclic ether carry out the method that ring-opening polymerization is made polyethers in the presence of carboxylic acid anhydride and/or carboxylic acid.

12. the manufacture method of polyethers as claimed in claim 10 is characterized in that, this method is by making cyclic ether carry out the method that ring-opening polymerization is made polyethers in the presence of carboxylic acid anhydride and/or carboxylic acid.

13. the manufacture method of polyethers as claimed in claim 2 is characterized in that, described solid acid catalyst is made by carry out the homogeneous precipitator method in the carrier pore.

14. the manufacture method of polyethers as claimed in claim 3 is characterized in that, described solid acid catalyst is made by carry out the homogeneous precipitator method in the carrier pore.

15. the manufacture method of a solid acid catalyst, it is the manufacture method with metal hydroxides and/or the metal oxide supported solid acid catalyst that forms on carrier, it is characterized in that this method comprises that the homogeneous precipitator method of utilizing in the carrier pore are in the pore internal burden metal hydroxides of carrier and/or the operation of metal oxide.

16. the manufacture method of solid acid catalyst as claimed in claim 15 is characterized in that, the described homogeneous precipitator method are homogeneous precipitator method of having utilized the precipitation agent precursor.

17. the manufacture method of solid acid catalyst as claimed in claim 15 is characterized in that, described precipitation agent precursor is the alkali precursor.

18. the manufacture method of solid acid catalyst as claimed in claim 15, it is characterized in that described metal hydroxides and/or metal oxide are oxyhydroxide and/or the oxide compounds that is selected from by at least a metallic element in the group of periodictable the 3rd family, the 4th family, the 5th family, the 13rd family and the 14th group composition.

19. the manufacture method of solid acid catalyst as claimed in claim 17 is characterized in that, described alkali precursor is a urea.

20. the manufacture method of a polyethers, it is by the cyclic ether ring-opening polymerization being made the method for polyethers in the presence of catalyzer, it is characterized in that, use the following catalyzer that obtains as described catalyzer: be selected from by periodictable the 1st for containing, 2,4,6,8,9,12,13,14,15, at least a element in the group of 16 and 17 group compositions and can make it contain being selected from of not comprising in this solid acid catalyst with itself solid acid catalyst with the cyclic ether ring-opening polymerization by periodictable the 3rd, 5, at least a metallic element in the group of 10 and 11 group compositions.

21. the manufacture method of polyethers as claimed in claim 20, it is characterized in that, as described can be with itself solid acid catalyst with the cyclic ether ring-opening polymerization, use one or more the solid acid catalyst that is selected from the group of forming by catalyzer, O composite metallic oxide catalyst, clay catalyst and the zeolite catalyst of metal oxide by load.

22. the manufacture method of polyethers as claimed in claim 20 is characterized in that, as being selected from by the metallic element in the group of periodictable the 3rd, 5,10 and 11 group compositions of not comprising in the described solid acid catalyst, uses copper and/or nickel.

23. the manufacture method of polyethers as claimed in claim 20, it is characterized in that, the solid acid catalyst of cyclic ether ring-opening polymerization can be used at least a above solid acid catalyst that is selected from the group of being made up of clay catalyst, silica-alumina, silica-titania and silicon-dioxide-zirconium white as described.

24. the manufacture method of polyethers as claimed in claim 20 is characterized in that, described catalyzer is by utilizing the homogeneous precipitator method in the carrier pore to make at the pore internal burden metal hydroxides and/or the metal oxide of carrier.