DE10032268A1 - New supported catalyst containing oxygenated molybdenum or tungsten compounds, useful for preparation of tetrahydrofuran polymers and copolymers - Google Patents

Abstract

Catalyst (A) comprises active oxygen compounds of molybdenum and/or tungsten (I) on an oxide carrier and is prepared by: (i) applying precursors of (I) to the carrier (or its precursor); and (ii) calcining at 400-900 deg C. It is characterized by having transport pores of diameter over 25 nm and transport pore volume at least 50 mm<3>/g. Independent claims are also included for: (a) method for preparing (A); and (b) preparation of poly(tetrahydrofuran) or tetrahydrofuran (THF) copolymers (or their di- or mono-esters) by polymerization of THF in presence of at least one telogen and/or comonomer, and in presence of (A).

Description

The present invention relates to a catalyst based on an oxidic Support material a catalytically active amount of at least one oxygen-containing Contains molybdenum and / or tungsten compound, and after the application of Precursor compounds of the catalytically active compounds on the support material or a substrate precursor has been calcined at temperatures from 400 ° C to 900 ° C is. This catalyst is used in processes for the production of polytetrahydrofuran, Tetrahydrofuran copolymers and diesters or monoesters of these polymers are used.

Polytetrahydrofuran - hereinafter referred to as PTHF for short - also known as Polyoxybutylene glycol is known in the plastics and synthetic fiber industries Versatile intermediate product used and serves, among other things, for the production of Polyurethane, polyester and polyamide elastomers. Next to it, if necessary, in Form of its derivatives, a valuable auxiliary in diverse applications, such as. B. as Dispersing agent or when decolorizing ("deinking") waste paper.

PTHF is technically advantageous by polymerizing tetrahydrofuran suitable catalysts. Additional reagents are used, the addition of which controls the chain length of the polymer chains and thus the adjustment of the average molecular weight to the desired value. Such Chain termination reagents are also called "telogens". The control of the chain length is done by choosing the type and amount of the telogen. By choosing more suitable Telogens can also have functional groups at one end or at both ends of the Polymer chain are introduced. For example, by using Carboxylic acids or carboxylic anhydrides as telogens are the mono- or diesters of PTHF getting produced. Other telogens not only act as chain termination reagents, but are also built into the growing polymer chain of the PTHF and have  in addition to the function of a telogen, it is also equivalent to that of a comonomer. Examples of such comonomers are telogens with two hydroxyl groups, such as that Dialcohols. Examples of such dialcohols are ethylene glycol, propylene glycol, Butylene glycol, 1,4-butanediol, 2-butyne-1,4-diol, 1,6-hexanediol or low molecular weight PTHF. The use of such comonomers leads to the production of tetrahydrofuran Copolymers. In this way, the PTHF can also be chemically modified. On An example of this is the use of the telogen 2-butyne-1,4-diol, the addition of which to The presence of a proportion of C-C triple bonds in the polymer chains of the PTHF leads. Such modified PTHF can be due to the reactivity of these triple bonds these locations are further chemically refined, e.g. B. by hydrogenating the triple Double bonds, through subsequent polymerisation of other monomers ("grafting") to adjust the properties of the polymer, crosslinking to form polymers with a comparatively rigid structure or other common measures in polymer chemistry. The complete hydrogenation of the existing triple bonds is also possible generally leads to PTHF with a particularly low color number.

On an industrial scale, the production of PTHF is mainly based on two-stage processes performed in which tetrahydrofuran z. B. in the presence of fluorosulfonic acid PTHF esters polymerized and then hydrolyzed to PTHF. At a Another two-step process is tetrahydrofuran with acetic anhydride in the presence polymerized from acidic catalysts to PTHF diacetate and then with methanol transesterified to PTHF.

In addition to the fact that it has to work in two stages, it is particularly unfavorable that By-products such as hydrofluoric acid or methyl acetate are obtained.

Single-stage processes for producing PTHF are also known, in which the Polymerization of tetrahydrofuran with diols, water or low molecular weight PTHF is carried out as a telogen on acidic catalysts. The catalyst or that The catalyst system can be homogeneous, dissolved in the reaction system or it can heterogeneous, largely undissolved catalyst systems are used.

DE-A-44 33 606 describes a process for the preparation of PTHF, PTHF diesters of C ₂ to C ₂₀ monocarboxylic acids or PTHF monoesters of C ₁ to C ₁₀ monocarboxylic acids by the polymerization of tetrahydrofuran over a heterogeneous catalyst in the presence one of the telogens water, 1,4-butanediol, PTHF with a molecular weight of 200 to 700 daltons, a C ₁ to C ₁₀ monocarboxylic acid or a carboxylic anhydride from C ₂ to C ₂₀ monocarboxylic acids or mixtures of these telogens, the catalyst being a Supported catalyst which contains a catalytically active amount of an oxygen-containing tungsten or molybdenum compound or mixtures of these compounds on an oxidic support material and which after application of the precursor compounds of the oxygen-containing molybdenum and / or tungsten compounds to the support material precursor at temperatures of 500 ° C to 1000 ° C has been calcined.

DE-A-196 41 481 discloses a process for the preparation of polytetrahydrofuran, copolymers of tetrahydrofuran and 2-butyne-1,4-diol, diesters of these polymers with C ₂ to C ₂₀ monocarboxylic acids or monoesters of these polymers with C ₁ to C ₁₀ - monocarboxylic acids by the polymerization of tetrahydrofuran in the presence of one of the telogens water, 1,4-butanediol, 2-butyne-1,4-diol, polytetrahydrofuran with a molecular weight of 200 to 700 daltons, a C ₁ to C ₁₀ monocarboxylic acid or a carboxylic anhydride from C ₂ - to C ₂₀ -monocarboxylic acids or mixtures of these telogens on a heterogeneous supported catalyst. The supported catalyst contains a catalytically active amount of an oxygen-containing molybdenum and / or tungsten compound on an oxidic support material and was calcined after the application of the precursor compounds of the oxygen-containing molybdenum and / or tungsten compounds to the support material precursor at temperatures of 500 ° C. to 1000 ° C. and activated by treatment with a reducing agent before being used as a polymerization catalyst.

Starting from this prior art, the object of the present invention was based on providing a catalyst that has a higher activity than that known catalysts, the higher polymer yields and / or space-time To achieve yields.

This object is achieved by a catalyst which contains a catalytically active amount of at least one oxygen-containing molybdenum and / or tungsten compound on an oxidic support material and which after application of the precursor compounds, the catalytically active compounds to the support material or a support material precursor at temperatures of 400 ° C to 900 ° C has been calcined, the catalyst having a porosity with transport pores each having a diameter of <25 nm and a volume of these transport pores of at least 50 mm ³ / g.

The catalyst according to the invention comprises according to a preferred embodiment, a BET surface area of 25-200 m ² / g, preferably 40-150 m ² / g and more preferably 50 120 m ² / g.

Furthermore, the catalyst according to the invention can have an acidity at pKs <-3 of have at least 10 µmol / g. The pKs value was determined using the Hammett titration determined.

Suitable catalytically active compounds are those molybdenum or tungsten compounds which, without the addition of a carrier, are mainly in the form of MoO ₃ or WO ₃ after prolonged heating to 600 ° C. in moist air, or mixtures of these compounds. Examples of the compounds mentioned are all types of tungsten and molybdic acids, such as WO ₃ , WO ₃ .H ₂ O, WO ₃ .2H ₂ O, meta and paratungstic acid and the isopoly acids and the corresponding analog molybdenum compounds. In addition, the heteropolyacids, such as H ₃ PW ₁₂ O ₄₀ , H ₄ SIW ₁₂ O ₄₀ , H ₄ GeW ₁₂ O ₄₀ and correspondingly up to H ₆ P ₂ W ₁₈ O ₅₆ or the corresponding molybdenum compounds and the salts, should be mentioned in this connection the abovementioned acids, such as the ammonium ortho-, ammonium meta- and ammonium paratungstates, the corresponding molybdenum compounds and reduced tungsten and molybdenum compounds and organomolybdenum or tungsten compounds.

Preference is given to using oxygen-containing tungsten compounds or mixtures of oxygen-containing tungsten compounds with oxygen-containing molybdenum compounds, in which the proportion of tungsten compounds predominates. It is particularly preferred to use catalysts whose catalytically active compounds, apart from usual impurities, consist practically only of oxygen-containing tungsten compounds. WO ₃ , tungstic acid and ammonium paratungstate are particularly worth mentioning here.

Oxidic supports are generally suitable as the support material, for example Zirconium dioxide, titanium dioxide, hafnium oxide, yttrium oxide, iron (III) oxide, aluminum oxide, Tin (IV) oxide or mixtures of these oxides. The use of is preferred Zirconium dioxide or titanium dioxide, titanium dioxide being particularly preferred and Titanium dioxide with a share of <65% in the anatase modification is particularly suitable  is. The carrier material can be used freshly precipitated, dried or calcined. The respective carrier material can be obtained by hydrolysis of the corresponding halides, Nitrates, sulfates or alkoxides, e.g. B. starting from titanium tetraisopropylate, titanyl chloride, Titanium nitrate, titanium tetrachloride or titanium sulfate can be obtained.

For the purposes of the present invention, the specification of the catalyst content of catalytically active compounds is based on the trioxides of tungsten and / or molybdenum. The catalysts generally contain 0.1 to 70% by weight, preferably 5 to 40% by weight and particularly preferably 10 to 35% by weight, of the catalytically active compounds, in each case calculated as MoO ₃ and / or WO ₃ and based on the total weight of the fully calcined and dry catalyst.

In addition, pore formers can be used, such as. B. tartaric acid, oxalic acid, Citric acid, ammonium nitrate, ammonium formate, ammonium oxalate, Guanidinium salts, urotropin, proteins, such as gelatin, polyvinyl alcohol, polyethylene oxide, Polymethylene oxide, carbohydrates such as glucose, sucrose (sugar) and soluble starch, PTHF, surfactants and sulfonic acids. Tartaric acid, citric acid and Oxalic acid, especially oxalic acid.

With regard to the proportion of the pore former with which it is contained in the catalyst, for the purposes of the present invention, the pore-forming agent content in% by weight, based on the fully calcined and dry catalyst. Therefore exceeds the sum of the weight percentages contained in the catalyst Connections 100%. According to the invention, the catalysts contain up to 200% by weight, preferably up to 100% by weight and particularly preferably up to 60% by weight of pore formers.

In addition, the catalyst can also contain a sulfur and / or phosphorus compound contain. Since it is believed that the sulfur in the invention Catalysts as sulfate and the phosphorus as phosphate is present, the proportion of these Compounds in the catalyst as sulfate or phosphate, based on the total weight of the fully calcined and dry catalyst. Then you can Catalysts up to 15% by weight, preferably up to 10% by weight and particularly preferably up to 8% by weight Contain sulfate and / or phosphate.  

Sources for the corresponding phosphorus and / or sulfur compounds are e.g. B. Sulfuric acid, soluble sulfates, such as ammonium sulfate or ammonium hydrogen sulfate or the corresponding sulfites or hydrosulfites, phosphoric acid, soluble phosphates, such as Ammonium phosphate or the ammonium hydrogen phosphates or the corresponding Phosphites.

As a further additive, the catalysts can also contain a binder, such as silica sol, clays, boric acid or AlPO ₄ .

The invention also relates to a process for the preparation of polytetrahydrofuran, tetrahydrofuran copolymers, diesters or monoesters of these polymers by polymerizing tetrahydrofuran in the presence of at least one telogen and / or comonomer using the aforementioned catalyst in one of its embodiments according to the invention. The production of polytetrahydrofuran and tetrahydrofuran copolymers is preferred. In the production of polytetrahydrofuran, the production from tetrahydrofuran and 1,4-butanediol or H ₂ O is particularly preferred as the telogen.

The invention will be explained in more detail below with the aid of examples.

1. Preparation of the catalyst 1a. Soak the support with the catalytically active compound

To produce the catalyst, the support is coated with the corresponding molybdenum and / or tungsten compound soaked in water. You can choose between this drinking solution a soluble pore former, as exemplified above, is also added become. In addition, a binder can optionally be in the form of a powder or in the form of a Suspension can be added.  

1b. Mix the carrier with the catalytically active compound

As an alternative to this impregnation process, the carrier can also be treated with the molybdenum and / or Tungsten compound and water are mixed. This can e.g. B. in a pan mill or kneader. In addition, a water soluble or insoluble Pore-forming agent and a binder in the form of a powder or a suspension are added become. This procedure is compared to watering, as in 1a. described, prefers.

2. Spray the mash obtained

An optional intermediate stage is the spraying of the mash thus obtained, the drying and precalcination of the spray material at about 80 to 600 ° C., preferably at 100 to 500 ° C., under oxidizing, inert or reducing, either still or flowing atmosphere oxidizing atmosphere can be air or the like, as inert atmosphere N ₂ , Ar, CO ₂ and as reducing atmosphere organic compounds in inert gas, CO or H ₂ can be used.

3. Rolling or kneading the material

The next step in the production process is to roll or knead the catalyst, whereby either a water-soluble or insoluble pore former and a Binder can be added.

4. Deforming the catalyst

Then the catalyst is z. B. by extrusion, extrusion or tableting formed into shaped bodies such as cylinders, balls, rings, spirals, strands or grit.  

5. Pre-calcine

Precalcination can now optionally be carried out at about 80 to 600 ° C., preferably at 100 to 500 ° C, under oxidizing, inert or reducing, in each case still or flowing Atmosphere.

6. Final calcination

The final calcination is then carried out at 400 to 900 ° C, preferably at 550 to 850 ° C and particularly preferably at 600 to 800 ° C, again under oxidizing, inert or reducing, still or flowing atmosphere and using a Gases such as B. given as an example under 2.. At a temperature of 600 to 800 ° C results in a catalyst with a particularly high space-time yield.

Also used catalysts that have been regenerated by the usual methods, e.g. B. by treatment with solvents, steam or calcining for 0.1 to 10 hours at 300 ° C to 600 ° C in air, CO ₂ or a reducing atmosphere, such as H ₂ or CO, can be used. Furthermore, catalyst powder, shaped bodies and / or catalyst chips can be reused by adding them to the production steps described above.

Optionally, this final calcination can be followed by a targeted reduction, such as this has been described in DE-A-196 41 481.

Basically, the catalyst is prepared analogously to that in DE-A-44 33 606 or the methods described in DE-A-196 49 803, to which express reference is hereby made is taken.  

II. Production of PTHF

In principle, any THF can be used as a monomer for producing PTHF be used. However, commercially available, by acid treatment, such as described for example in EP-A 003 112, or THF pre-purified by distillation used.

Suitable telogens in the one-step process are saturated or unsaturated, unbranched or branched alpha, omega-C ₂ to C ₁₂ diols, water, polytetrahydrofuran with a molecular weight of 200 to 700 daltons, cyclic ethers or mixtures thereof. Water, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polytetrahydrofuran with a molecular weight of 200 to 700 daltons, 1,6-hexanediol, 1,8-octanediol are preferred , 1,10-decanediol, 2-butyne-1,4-diol and neopentyl glycol or mixtures thereof, water, 1,4-butanediol and / or polytetrahydrofuran having a molecular weight of 200 to 700 daltons being particularly preferred.

As a telogen for the production of PTHF and THF copolymers according to the two-stage Process serve carboxylic anhydrides and / or carboxylic anhydride / protonic acid Mixtures. Preferred carboxylic anhydrides are those which are aliphatic or aromatic, poly- and / or monocarboxylic acids are derived, which 2 to 12, preferably 1 contain up to 8 carbon atoms. Acetic anhydride is particularly preferred. The Protonic acids are preferred organic and inorganic acids, which in Reaction system are soluble. Preferred carboxylic acids are aliphatic or aromatic Poly- and / or monocarboxylic acids containing 2 to 12, preferably 1 to 8 carbon atoms contain. Examples of aliphatic carboxylic acids are acetic acid, lactic acid, Propionic acid, valeric acid, caproic acid, caprylic acid and pelargonic acid. examples for aromatic carboxylic acids are phthalic acid and naphthalene carboxylic acid. Of these Carboxylic acids are preferably acetic acid.

Cyclic ethers which can be polymerized to open the ring as comonomers are preferably three-membered, four-membered and five-membered rings such as the THF derivatives, 2- Methyltetrahydrofuran or 3-methyltetrahydrofuran, cyclic ethers such as 1,3-dioxolane, Trioxane, oxetane, substituted oxetanes such as 3,3-dimethyloxetane, 1,2-alkylene oxides, for  Example ethylene oxide or propylene oxide, where 2-methyltetrahydrofuran or 3- Methyltetrahydrofuran are particularly preferred.

The telogen is expediently fed to the polymerization in solution in the THF, where a telogen content of 0.04 to 17 mol%, based on tetrahydrofuran, is preferred. Comonomers are also advantageously dissolved in THF from the polymerization supplied, the comonomer content up to 30 mol%, preferably 20 mol%, based on tetrahydrofuran. However, it is also possible that Polymerization reactor THF and the telogen and / or the comonomer separated supply. Since the telogen causes the termination of the polymerization, can be Telogen amount used the average molecular weight of the PTHF or THF Control copolymers. The more telogen is in the reaction mixture, the lower becomes the average molecular weight of the PTHF or the relevant THF copolymers. ever according to the telogen content of the polymerization mixture, PTHF and THF copolymers can be used average molecular weights from 650 to 5000 daltons, preferably from 650 to 3000 Dalton and particularly preferably from 1000 to 3000 Dalton.

The polymerization is generally carried out at from 0 to 80 ° C., preferably at 25 to 75 ° C, and particularly preferably at 40 to 70 ° C. The applied one Pressure is usually not critical to the result of the polymerization, which is why generally at atmospheric pressure or under the autogenous pressure of the Polymerization system is worked.

To avoid the formation of ether peroxides, the polymerization is advantageously carried out under an inert gas atmosphere. As inert gases such. B. nitrogen, carbon dioxide or the noble gases are used, nitrogen is preferably used.

The polymerization can be carried out in the presence of hydrogen at hydrogen pressures of 0.1 up to 10 bar.

The process according to the invention is preferably operated continuously. However, it is the polymerization stage and / or one, several or all of the To operate batch stages of the process according to the invention discontinuously,  however, preferably at least the polymerization is preferably carried out continuously becomes.

The implementation can preferably in conventional, for continuous processes suitable reactors or reactor arrangements in suspension or fixed bed mode, in suspension mode, for example in loop reactors or stirred reactors, or in the case of a fixed bed mode of operation in tubular reactors or fixed bed reactors. The Fixed bed style is preferred.

In the fixed bed mode of operation, the polymerization reactor can be operated in the bottom mode, i.e. H. the Reaction mixture is led from the bottom up, or in trickle mode, d. H. Reaction mixture is passed through the reactor from top to bottom, operated. The educt mixture (feed) of THF and telogen and / or comonomer is the Polymerization reactor fed continuously, the catalyst loading 0.05 to 0.8 kg THF / (l.h), preferably 0.1 to 0.6 kg THF / (l.h) and particularly preferably 0.15 to 0.5 kg THF / (l.h).

In addition, the polymerization reactor can be operated in a single pass, that is without Product return, or in circulation, that is, the one leaving the reactor Polymerization mixture is circulated, operated. In the Circulation mode is the ratio of circulation to inlet ≦ 100: 1, preferably <40: 1 and particularly preferably <30: 1.

III. Porosity measurement

The porosity of the catalysts was determined using the Hg intrusion method made according to DIN 66133.  

IV. Acidity measurement

The determination of the amount of acidic centers with pKs <-3 ("acidity") was carried out by Titration with pyrazine as the base in absolute toluene as the solvent Dicinnamalacetone (CAS 622-21-9) performed as an indicator. Implementation of the Titration was carried out as e.g. B. "H. Benesi and B. Winquist, Advances in Catalysis, Vol. 27, 1978, Academic Press, ISBN 0-12-007827-9 "and references contained therein specified.

V. Discontinuous THF polymerization

The batch polymerization experiments were carried out in 40 ml GC vials under an argon atmosphere. 5 g of catalyst strands which had been dried for 18 hours at 400 ° C. in a stream of O ₂ / N ₂ (“synthetic air”) before being used to remove adsorbed water were dissolved in 20.75 g of THF containing butanediol (butanediol concentration 2000 ppm) heated to 60 ° C with shaking under Ar for 6 hours. The reaction vessel was then cooled, the catalyst was filtered off and washed three times with 10 g of THF each. The filtrates were combined, concentrated at 70 ° C./20 mbar on a rotary evaporator and weighed.

As the experiments show, the use of catalysts leads to a high Proportion of transport pores <25 nm in the process according to the invention increases in all cases an increase in activity. When using the method according to the invention, the Capacity of existing plants for the production of PTHF without retrofitting is therefore clear can be increased or future plants can be smaller and therefore with correspondingly reduced investment volume.

VII. Examples Comparative Example 1

130 kg TiO ₂ .aq (= 100 kg TiO ₂ ), 26.7 kg tungsten acid (= 25 kg WO ₃ ) with 1.52 kg H ₃ PO ₄ (85%) and 46.7 kg H ₂ O compresses the resulting paste extruded and shaped into strands of 4 mm in diameter. These were dried at 170 ° C and then calcined at 690 ° C for 2 hours.

example 1

119 kg of TiO ₂ .aq (= 95.6 kg of TiO ₂ ), 25.6 kg of tungstic acid (= 23.9 kg of WO ₃ ) with 1.46 kg of H ₃ PO ₄ (85%) and 48 kg H ₂ O is compressed, the resulting paste is extruded and shaped into strands with a diameter of 4 mm. These were dried at 170 ° C and then calcined at 690 ° C for 2 hours.

Example 2

150.2 g of TiO ₂ .aq (= 115.7 g of TiO ₂ ), 40.46 g of tungstic acid (= 37.63 g of WO ₃ ) with 94 g of stearic acid, 9.4 of tartaric acid and 2.2 g were mixed in a laboratory kneader H ₃ PO ₄ (85%) and 92 g H ₂ O kneaded and the resulting paste is deformed into strands of 4 mm in diameter. These were dried in a stream of N ₂ at 400 ° C. for 4 hours and then calcined in air at 650 ° C. for 3 hours.

Example 3

200 g TiO ₂ .aq (= 160 g TiO ₂ ), 43 g tungstic acid (= 40 g WO ₃ ) with 48.6 g stearic acid, 12.2 tartaric acid, 38.6 g aqueous silica sol (15.8 % SiO ₂ ) and 40 g of H ₂ O and kneaded the resulting paste into strands of 4 mm in diameter. These were then air dried at 350 ° C for 2 hours and air calcined at 700 ° C for 3 hours.

Example 4

128.7 TiO ₂ .aq (= 99 g TiO ₂ ), 35.4 g tungstic acid (= 33 g WO ₃ ), 65.9 g oxalic acid, 6.9 g methyl cellulose and 70 g H ₂ O were kneaded in a laboratory kneader and the resulting paste is shaped into strands of 4 mm in diameter. These were then calcined in air at 650 ° C. for 2 hours.

Example 4a

100 g of TiO ₂ .aq (= 80 g of TiO ₂ ), 31.3 g of ammonium paratungstate (= 28.2 g of WO ₃ ), 91.9 g of oxalic acid, 4 g of polyvinyl alcohol, 4 g of polyethylene oxide and 80 g of H were mixed in a laboratory kneader ₂ O kneaded and the resulting paste formed into strands of 4 mm in diameter. These were then calcined in air at 650 ° C for 1.5 hours.

Example 5

143.2 g of TiO ₂ .aq (= 110 g of TiO ₂ ), 29.6 g of tungstic acid (= 27.5 g of WO ₃ ), 68.7 g of stearic acid, 6.9 of tartaric acid and 60.8 g were mixed in a laboratory kneader Guanidinium carbonate, 1.6 g H ₃ PO ₄ (85%) and 80 g H ₂ O kneaded and the resulting paste is deformed into strands of 4 mm in diameter. These were dried in a stream of N ₂ at 400 ° C. for 4 hours and then calcined in air at 650 ° C. for 3 hours.

Example 6

217.5 g of TiO ₂ .aq (= 167.6 g of TiO ₂ ), 44.9 g of tungstic acid (= 41.8 g of WO ₃ ), 104.4 g of ammonium citrate, 10.4 g of tartaric acid, 2 , 5 g of H ₃ PO ₄ (85%) and 41.5 g of 25% NH ₃ solution, kneaded and the resulting paste was deformed into strands of 4 mm in diameter. These were calcined in air at 650 ° C for 3 hours.

Example 7

143 g of TiO ₂ .aq (= 110 g of TiO ₂ ), 29.6 g of tungstic acid (= 27.5 g of WO ₃ ), 68.7 g of guanidinium carbonate, 35 g of formic acid, 6.9 g of tartaric acid, 1 , 6 g of H ₃ PO ₄ (85%) and 15 g of 1120 are kneaded and the resulting paste is shaped into strands of 4 mm in diameter. These were calcined in air at 650 ° C for 3 hours.

Example 8

150 g of TiO ₂ .aq (= 115.7 g of TiO ₂ ), 40.46 g of tungstic acid (= 37.63 g of WO ₃ ) with 94 g of gelatin, 9.4 g of tartaric acid, 2.2 g of H were mixed in a laboratory kneader ₃ PO ₄ (85%) and 117 g H ₂ O kneaded and the resulting paste is deformed into strands of 4 mm in diameter. These were then calcined in air at 700 ° C for 3 hours.

Example 9

150.2 g of TiO ₂ .aq (= 115.7 g of TiO ₂ ), 40.46 g of tungstic acid (= 37.63 g of WO ₃ ) with 94 g of pure, soluble starch, 9.4 g of tartaric acid were mixed in a laboratory kneader. 2.2 g of H ₃ PO ₄ (85%) and 140 g of H ₂ O kneaded and the resulting paste was shaped into strands of 4 mm in diameter. These were then calcined in air at 700 ° C for 3 hours.

Example 10

150.2 g of TiO ₂ .aq (= 115.7 g of TiO ₂ ), 40.46 g of tungstic acid (= 37.63 g of WO ₃ ) with 93.9 g of cold-ground paraffin, 9.4 g of tartaric acid were mixed in a laboratory kneader , 2.2 g H ₃ PO ₄ (85%) and 100 g H ₂ O kneaded and the resulting paste is deformed into strands of 4 mm in diameter. These were then dried in a stream of N ₂ at 400 ° C. for 4 hours and calcined in air at 700 ° C. for 3 hours.

Example 11

160 g of TiO ₂ .aq (= 128 g of TiO ₂ ), 34.4 g of tungstic acid (= 32 g of WO ₃ ) with 77.8 g of carbon black (Printex 75, from Degussa), 9.8 g of tartaric acid were mixed in a laboratory kneader , 2.3 g of H ₃ PO ₄ (85%), 20.4 g of alkali-free lutensol and 120 g of H ₂ O kneaded and the resulting paste deformed into strands of 4 mm in diameter. These were then dried in a stream of N ₂ at 400 ° C. for 4 hours and calcined in air at 600 ° C. for 8 hours.

Example 12

200 g TiO ₂ .aq (= 160 g TiO ₂ ), 41.4 g H ₃ PW ₁₂ O ₄₀ .aq (= 33.2 g WO ₃ ) were stirred in a beaker with 520 g H ₂ O and at 60 ° C evaporated in vacuo. The material was then heated to 500 ° C. in a stream of N ₂ and calcined in air at this temperature for 2 hours. The product was finely ground in an analytical mill, kneaded in a laboratory kneader with 120.8 m H ₂ O and the resulting paste was shaped into strands with a diameter of 4 mm. These were then calcined in air at 700 ° C for 3 hours.

Example 13

In a beaker, 375 g TiOz.aq (= 300 g TiO ₂ ), 103.4 g H ₃ PW ₁₂ O ₄₀ .aq (= 82.9 g WO ₃ ) were stirred with 1040 g H ₂ O and at 60 ° C evaporated in vacuo.

The material was then heated to 500 ° C. in a stream of N ₂ and calcined in air at this temperature for 2 hours. The product was ground in a spiral jet mill at 8 bar into particles of an average size of 0.8 μm, kneaded in a laboratory kneader with 120.8 m H ₂ O and the resulting paste was shaped into strands with a diameter of 4 mm. These were then calcined in air at 650 ° C. for 1 hour.

Example 15

8.38 kg TiO ₂ .aq (= 6.44 kg TiO ₂ ) and 2.00 kg H ₃ PW ₁₂ O ₄₀ .aq (= 1.61 kg WO ₃ ) were mixed with 138 kg H ₂ O and mixed in one Spray tower sprayed at 120 ° C to a powder with an average particle size of 2.7 microns, which was then calcined at 500 ° C for 2 hours. 200 g of this spray powder were kneaded with 10 g of methyl cellulose and 120 g of H ₂ O in a laboratory kneader and the resulting paste was shaped into strands of 4 mm in diameter. These were then calcined in air at 700 ° C for 3 hours.

Example 16

7.86 kg TiO ₂ .aq (= 6.04 kg TiO ₂ ) and 2.50 kg H ₃ PW ₁₂ O ₄₀ .aq (= 2.01 kg WO ₃ ) were mixed with 138 kg H ₂ O and mixed in one Spray tower sprayed at 120 ° C to a powder with an average particle size of 2.6 microns, which was then calcined at 500 ° C for 2 hours. 200 g of this spray powder were kneaded with 10 g of methyl cellulose and 120 g of H ₂ O in a laboratory kneader and the resulting paste was shaped into strands of 4 mm in diameter. These were then calcined in air at 650 ° C. for 3 hours.

Example 17

7.86 kg TiO ₂ .aq (= 6.04 kg TiO ₂ ) and 2.50 kg H ₃ PW ₁₂ O ₄₀ .aq (= 2.01 kg WO ₃ ) were mixed with 138 kg H ₂ O and mixed in one Spray tower sprayed at 120 ° C to a powder with an average particle size of 2.6 microns, which was then calcined at 500 ° C for 2 hours. 200 g of this spray powder were kneaded with 6 g of polyethylene oxide and 116 g of H ₂ O in a laboratory kneader and the resulting paste was shaped into strands of 4 mm in diameter. These were then calcined in air at 650 ° C. for 2 hours.

Claims (11)

1. Catalyst which contains a catalytically active amount of at least one oxygen-containing molybdenum and / or tungsten compound on an oxidic support material and which after application of the precursor compounds of the catalytically active compounds to the support material or a support material precursor at temperatures of 400 ° C to 900 ° C has been calcined, characterized by a porosity of the catalyst
Transport pores each with a diameter of <25 nm, and
a volume of these transport pores of at least 50 mm ³ / g. 2. Catalyst according to claim 1, characterized by a BET surface area of 25 to 200 m ² / g, preferably 40 to 150 m ² / g and particularly preferably 50 to 120 m ² / g. 3. Catalyst according to claim 1 or 2, characterized by an acidity at pKs <-3 of at least 10 µmol / g. 4. Catalyst according to one of claims 1 to 3, characterized in that the Catalyst a catalytically active amount of at least one oxygen-containing Contains tungsten compound. 5. Catalyst according to one of claims 1 to 4, characterized in that the oxidic carrier material is zirconium dioxide or titanium dioxide, preferably titanium dioxide. 6. Catalyst according to one of claims 1 to 5, characterized in that the catalyst 0.1 to 70 wt .-%, preferably 5 to 40 wt .-%, particularly preferably 10 to 35 wt .-% of the catalytically active compound ( en) contains, calculated as MoO ₃ and / or WO ₃ and based on the total weight of the catalyst. 7. Catalyst according to one of claims 1 to 6, characterized by a content of Pore formers of up to 200 wt .-%, preferably up to 100 wt .-%, particularly preferably up to 60% by weight, based in each case on the proportion of the catalytically active Connection together with the carrier material.   8. Catalyst according to one of claims 1 to 7, characterized in that the Catalyst up to 15% by weight, preferably up to 10% by weight, particularly preferably up to 8% by weight Contains sulfate and / or phosphate. 9. Process for the preparation of polytetrahydrofuran, tetrahydrofuran copolymers, Diesters or monoesters of these polymers by polymerizing tetrahydrofuran in the presence of at least one telogen and / or comonomer using of a catalyst according to one of claims 1 to 8. 10. The method according to claim 9 for the production of polytetrahydrofuran. 11. The method according to claim 10 for the production of polytetrahydrofuran from tetrahydrofuran and 1,4-butanediol or H ₂ O as telogen.