JPH04503517A - Method for producing 1,4-bis(4-phenoxybenzoyl)benzene using certain metal-containing catalysts - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] name of invention J-14-bis(4-phenoxybenzoyl) base using certain metal-containing catalysts How to make zene Background of the invention The present invention provides a method for treating 1 , relates to a method for producing 4-bis-(phenoxybenzoyl)-benzene. Ru.

1,4-bis-(fluoride) is an important intermediate in the production of polyetherketone resins. (enoxybenzoyl)-benzene (hereinafter sometimes referred to as BPBB) is currently a salt Chemical formula 1. Fouridel-Craft of 4-benzenedicarbonyl and diphenyl ether catalyst, usually at least 3 moles per mole of 1,4-benzenedicarbonyl chloride. produced industrially by reaction in the presence of aluminum chloride used in amounts of It is built. Polyetherketones are polyetherketones themselves, poly( ether ether ketones), poly(ether ketone ketones), and the former of commercial resins containing mixed copolymers having both type fractions and fractions of the latter type. This is a well-known general classification. Diphenyl ether minimizes formation of higher oligomers Usually used in significant excess to limit This reaction is usually carried out using solvent 1. Ta For example, it is carried out in 1,2-dichlorobenzene at a temperature of about 0°C.

After the reaction is complete, methanol is added to precipitate the product, from which the catalyst is extracted. Remove. The product was filtered off, washed repeatedly with methanol and washed with N.

Recrystallize from N-dimethylacetamide or 1,2-dichlorobenzene.

The use of aluminum chloride produces various disadvantages. The recovered aluminum chloride It cannot be reused, which creates problems with waste dumping and reduces the cost of work. Increase costs. Additionally, aluminum chloride exhibits high individual isomer selectivity. but with a significant proportion of the orthobara isomer, i.e. [1-(2-phenoxy) , which also has a tendency to produce 4-(4-phenoxy)]-dibenzoylbenzene. . For extensive purification, repeated filtration is required and long recovery times are required. Ru.

BPBB was also granted and currently patented on July 14, 1988. Co-pending application of Corbin et al., Serial No. 07/21894. 1,4-benzenedicarbonyl chloride and excess diphenyl ether as suggested in 1. Highly disjointly isomer-selective hydrogen-exchanged zeolite at 190-258 °C with It can also be produced by reaction in the presence of a light catalyst. patented The invention disclosed and claimed in the application addresses the current industrial methods described above. Although it represents a considerable advantage over the conventional method, it also has some disadvantages. this The method uses a very large excess of diphenyl ether and a significant amount of zeolite catalyst. I need. Diphenyl ether for 1,4-benzenedicarbonyl chloride The high ratio and large amount of catalyst make the operation extremely expensive.

Additionally, hydrogen-exchanged zeolites must be regenerated or disposed of; also increases manufacturing costs.

Therefore, BPBB can be used as an isomer-selective, solvent-free, diphenyl ether. It can be prepared in a simple operation with a small excess of ester and with significantly less catalyst. It is desirable that Furthermore, the catalyst can be reused without regeneration or According to the present invention, which is highly desirable to be able to be disposed of without cost, diphenyl ether at a temperature of about 220-258°C for about 60 minutes to about 360 minutes, about 5:1 to about 2 1,4-benzenedicarbonyl chloride and unsupported iron(II) chloride in a molar ratio of 5.1. (ferrous chloride), iron sulfate (IT) (ferrous sulfate), gallium sulfate (III) , and indium(III) sulfate: and iron(II) chloride on an inert support. ), iron(II) sulfate, gallium(III) sulfate, indium(III) sulfate , and a small amount selected from the group consisting of iron(III) chloride (ferric chloride). (In the presence of one type of catalyst, for a catalyst of 1,4-benzenedicarbonyl chloride) excess diphenyl ether. separating and recovering the product BPBB from both the fuel and the catalyst. A method of manufacturing a BB is provided herein.

detailed description of the invention The basic reaction involved in the method described in this invention is as follows: %Formula% Starting materials for this reaction are well known and readily available.

1,4-Benzenedicarbonyl chloride is also known as terephthalyl chloride. terephthalic acid by suitable known reactions such as phosphorus pentachloride, phosphorus trichloride, or or thionyl chloride.

1,4-Benzenedicarbonyl chloride is also available from E.I. DuPont-Des. Nell1ours (E, I, DuPont de Nell1ours an d Company).

Diphenyl ether is available from Dow Chemical Company, among others. It is commercially available from Pany.

The above catalyst is manufactured by Morton Thiokol's Alfa Division. .

n of Morton Th1okol Co, ) and Aldrich Chemical Available from several sources including (^1drich Chemicals) Can be done. These catalysts are soluble in the reaction mixture at the reaction temperature to a sufficient degree of It can be used homogeneously and is free when deposited on an inert carrier material. It can also be used in a homogeneous system. Suitable carrier materials include, for example, silica, aluminum Contains carbon and carbon.

In the practical operation of the method according to the invention, the reactants and catalyst are charged to a reactor. , the temperature is raised to 220-258°C. Excess diphenyl ether required However, the model for 1,4-benzenedicarbonyl chloride of diphenyl ether is Preferably, the ratio is kept in the range of 6-10:1. 1,4-benzenedica chloride The preferred molar ratio of rubonyl to catalyst is 50 to 300. preferred anti The applicable temperature range is 240-258°C. Within this temperature range, the preferred reaction time is is 180 to 360 minutes. The most preferable temperature condition and time is 250℃ It takes about 5 hours. Diphenyl ether to 1,4-benzenedicarbonyl chloride The most preferred molar ratio for 1,4-benzenedicarbonyl chloride is about 8; The most preferred molar ratio to catalyst is about 200. Preferred unsupported catalysts are chloride It is the first railway.

Many metal compounds contain diphenyl ether and 1,4-benzenedicarbonyl chloride. The presence of catalysts listed in the Summary of the Invention has been found to catalyze the condensation of Only BPBB prepared below provides a thermally stable polyetherketone.

Generally, if the process temperature is too low, the starting material will contain primarily 1 mole of diphenyl ether. and 1 mole of 1,4-benzenedicarbonyl chloride to give the desired Conversion to the desired product, BPBB, will remain minimal. temperature too high (if the reaction is carried out under pressure), large amounts of by-products and 1,4-benzene chloride are produced. Due to the decomposition of the carbonyl dicarbonyl, the conversion rate will decrease here as well. Jife If the molar ratio of nyl ether to 1,4-benzenedicarbonyl chloride is too low, , the conversion to BPBB will be low, and if this is too high, high BPB in the reaction mixture will result. The benefits of having a B product concentration would not be realized. 1,4-benzene chloride If the molar ratio of dicarbonyl to catalyst is too high, the reaction will be too slow; If it is too long, separation of BPBB from the catalyst becomes more difficult.

If the catalyst is present in solution in a homogeneous system, the catalyst is discarded without being recovered; Supported catalysts used in one system can be recovered and reused without the need for regeneration. Ru. Additional benefits are realized if the catalyst can be reused. Supported catalysts can be filtered or can be easily separated from the hot liquid reaction mixture by other methods. . Unsupported catalysts that contaminate the solid BPBB product can be removed using a suitable solvent such as methanol. It can be easily removed by washing with water.

BPBB is released from the diphenyl ether solution upon cooling (e.g. to 30-50°C). crystallizes, but in any case wash with a solvent, e.g. methanol to remove the diphenyl ether and 1 mole of diphenyl ether, which may crystallize during cooling. and 1 mole of 1,4-benzenedicarbonyl chloride must be removed. Must be. Other solvents suitable for this purpose include, among others, tetrahydrofuran , isopropyl alcohol, and acetone. If desired, BPBB can be from a medium such as N,N-dimethylacetamide and 1,2-dichlorobenzene. It can be further purified by recrystallization. Washed with solvent or recrystallized B is an additional 1,4-benzenedicarbonyl chloride (or other dicarboxylic acid dichloride) by condensation using methods known in the art. It can be used in the final stage of the production of ketones.

Excess diphenyl ether recovered from the production of BPBB according to the method described in the invention A file can be reused several times without being generated. We believe that purification is recommended. If desired, purification is most conveniently carried out by distillation at reduced pressure.

Although the above description relates to the batch process of the present invention, the method The important variables are the molar ratio of 1,4-benzenedicarbonyl chloride to catalyst, Molar ratio of phenyl ether to 1,4-benzenedicarbonyl chloride, temperature and It can also be applied to continuous operations with long and residence times. various daily tasks In both batch and continuous processes, the working efficiency: e.g. only by filtration. In both cases, time, energy consumption and The maximum efficiency of separation of solids from liquids is the most expedient from the standpoint of safety and equipment availability. can be improved to obtain a higher rate.

The invention will now be illustrated by representative examples of some preferred embodiments thereof. all In all examples, the conversion rate of 1,4-benzenedicarbonyl chloride to BPBB was calculated as follows: conversion rate (%) = Number of moles of BPBB in the product A partial consisting of one molecule of each reactant, which may have been formed as a by-product. Any reaction products were ignored. All catalysts should be used as received. Ta.

Example 1 Various metal compounds were used as catalysts for BPBB synthesis. diphenyl ether (13 4g, 0.787 mol) to 20g (0,099 mol) of 1,4-benzene chloride Dicarbonyl and 0.5 g of metal compound were mixed in the reactor. this mixture It was heated to 250° C. under a nitrogen purge and held at this temperature for 5 hours. 80 in this reactor C. diphenyl ether (187 g) was added to quench the reaction system to about 180.degree.

This solution was filtered at about 180°C and allowed to cool. The product was filtered at 50°C and diluted with methanol. Washed with water and fanned dry. The results of these experiments are summarized in Table 1 below. below Use column names: A=metal compound.

B = conversion rate to BPBB.

C = a/b melting peak by scanning differential calorimeter, °C, 20 °C/min under nitrogen atmosphere heating rate. where "a" and "b" are the initial heating and remelting temperatures, respectively. This is the melting peak during melting. Minus sign indicates shoulder and/or secondary peak means an extremely impure substance with Melting temperature and remelting temperature are only 2.3 degrees If the material is not far away, it is quite thermally stable and therefore usually Although it is pure, this is not the only criterion for purity.

D = Melt stability of polymer made from BPBB. Here, "+" = stable melting : “−” = melt unstable: “0” = measured due to lack of purity or low yield. not present.

Table 1 Aluminum chloride 57.6 212/208 0 Aluminum bromide (1g used ) 49.3 210/206 0 Aluminum sulfate octahydrate None Bis-(cyclopentadienyl)titanium dichloride vanadium(v) oxide 17.3 212/212 0 Chromium(III) chloride hexahydrate trace acid Chromium(III) chloride 13.8 '212/212-0 Manganese chloride tetrahydrate Japanese item none Iron metal powder (0,], g used>70.6 212/2011-0 Iron chloride (II ) Tetrahydrate 72.9 217/206 + Iron(III) chloride 77.0 21 4/205 - - Iron (II) sulfate heptahydrate 73.9 215/206 + sulfuric acid Iron (HI) 73.9 210/202--Iron (III) fluoride 78.8 211/203 - Iron (III) nitrate anhydride 72.3 211/204 - Iron (III) oxide (hematite) 70.5 212/213-0 Iron sulfide ( II) 75.3 213/204 0 Cobalt chloride hexahydrate 57.6 21 4/208- 0 Nickel (II) chloride Yamato water trace amount copper chloride (1) 20. 7 213/213 0 Zinc chloride 69.0 208/204- 0 Gallium chloride Mu(III) 83.7 213/207 - Gallium(III) sulfate 74. 6 211/204 + [Sil=1=um(IV) 34.6 213/20 8 0 Molyfden oxide (VI) 73.3 211/205 0 Ruthenium chloride Dihydrate 12.3 219/217 0 Rhodium chloride trihydrate None Palladium chloride (m none) No silver nitrate Cadmium nitrate tetrahydrate None Indium (III) sulfate hydrate 74.6 216/208 + tin sulfate (I I) None Cerium(III) nitrate 3.5 181/150-0 Europium chloride 19 ．． 6 206/203-0 Tantalum (V) fluoride 75.9 212/205 -Tungsten oxide (VI) 63.0 211/203 0 Rhenium chloride ( III) 76.6 216/108-0 Alumina supported platinum (1%) 2.0 217/214 0 Tantalum sulfate (1) None No lead(II) chloride Lead(II) titanate None Example 2 Silica-supported iron(III) chloride catalyst, Alpha 10677 from Morton Thiokol was tested in repeated experiments. The same catalyst was used in all trials without regeneration. I used it a lot. Between each run, the catalyst was stored in a vacuum oven at 110°C under a nitrogen purge. I stored it. In each trial, 1.5 g of this catalyst was combined with 267.5 g (1,572 mol ) of diphenyl ether and 40 g (0°197 mol) of 1,4-benze chloride mixed with dicarbonyl. This mixture was heated to 250°C under nitrogen and this temperature It was kept for 5 hours. Add 374.5 g of diphenyl ether at 80°C to the reactor. The reaction system was rapidly cooled to about 180°C. When the solution is filtered at about 180°C and allowed to cool, the BP BB crystals began to precipitate at about 140°C. The product was filtered at 50°C and diluted with methanol. Washed and dried. The conversion rate to BPBB is given below.

Table I1 1 72, 3 78.0 2 66.1 71.3 3 72, 5 78.2 4 73.1 78.9 This example shows that the supported iron(III) catalyst does not regenerate and its catalytic activity increases. This shows that it can be reused several times while retaining its properties.

Example 3 The diphenyl ether recovered from the first trial of Example 1 was collected one day after that trial. This recovered diphtherium was not purified (reused) except that it was refiltered at 30°C. phenyl ether (134 g, 0.787 mol) to 20 g (0,099 mol) of salt 1,4-benzenedicarbonyl and a new silica-supported iron(III) chloride catalyst (Morton Thiokol Alpha 10677) 0.75g mixed in a reactor. did. The mixture was heated to 250°C in a reactor under a nitrogen purge and heated to 250°C for 5 Saved time. 187 g of recovered diphenyl ether at 80°C was added to reduce the reaction system to about 1 It was rapidly cooled to 80°C. When the solution is filtered at about 180°C and allowed to cool, BPBB crystals are formed. Precipitation began at about 140°C. 5. Filter the product at 50°C and wash with methanol. Dry. The weighing result was 33.10 g, corresponding to a conversion rate of 71.4%. Miscellaneous Very small amounts of impurities were found by differential calorimetry.

This example shows that diphenyl ether can be reused without redistilling. are doing.

Example 4 This example describes four different BPBB purification methods.

Silica-supported iron(III) chloride catalyst, Alpha 1067 from Morton Thiokol. 7 was dried in a vacuum oven at 110° C. overnight under a nitrogen purge. 3g of this catalyst is 535 g (3,143 mol) of diphenyl ether and 80 g (0,394 mol) of 1,4-benzenedicarbonyl chloride in a reactor. 50% of this mixture °C and held at this temperature for 30 minutes under a strong nitrogen purge to remove any residual oxygen. Removed from system. The mixture was then heated to 250° C. under a low nitrogen purge, This temperature was maintained for 5 hours.

A total of 749 g (4,401 mol) of diphenyl ether at 80°C was added. The reaction system was rapidly cooled to about 180°C. When the solution is filtered at about 180°C and allowed to cool, the BP BB crystals began to precipitate at about 140°C. Diphenyl ether of the product at about 40°C. filtered from the bottle and divided into four parts, which were processed as follows: ■ Wash with 350 ml of methanol twice with agitation for 30 minutes each time, and then and filtered. After drying in a vacuum oven at 110°C overnight, the product weighed 35. It was 8g. The melting peak a/b (value measured in column C of Table ■) is 213/ It was 206.

Il, washed twice with 350 ml of tetrahydrofuran for 30 minutes each time with agitation. and then filtered. Although it was dried as above, the product weighed 32 ．． It was 0g. The melting peak a/b was 215/206.

IIl, washed twice with 350 ml of methanol with agitation for 30 minutes each time; This was followed by filtration. It was recrystallized from 457 g of 1,2-dichlorobenzene. disturbance Wash twice with 350 ml of methanol for 30 minutes each time, followed by filtration. Ta. After drying as described above, the product weighed 36.7 g. melt The melting peak a/b was 214/206.

IV, wash twice with 350 ml of tetrahydrofuran for 30 minutes each time with agitation. and then filtered. Recrystallized from 457 g of 1,2-dichlorobenzene . Wash with 350 ml of tetrahydrofuran twice for 30 minutes each time with agitation. , followed by filtration. The dry product weighed 26.8 gT. melting peak A/B was 214/206.

Therefore, the total amount of purified BPBH was 131.3g, and the conversion rate was 70.8%. It was.

The usefulness of BPBB produced in the presence of various catalysts was determined as follows: Using 1,3-benzenedicarbonyl chloride and 1,4-benzenedicarbonyl chloride with a screening agent, excess aluminum chloride as a catalyst, and 1, as a solvent. BPBB to aromatic poly(etherketoneketone) in the presence of 2-dichlorobenzene ) to extend the chain. After synthesis, the polymer was filtered from the solvent and dissolved in methanol. Decoordinate from aluminum chloride and wash with methanol to remove residual aluminum. was extracted and dried. Melt stability was tested in an extrusion plastometer. polymerization fruit The following procedure was used for the experiment.

BPBB 23.53g (0,050mol), aluminum chloride 29.32g (0.22 mol) and 313 g of 1,2-dichlorobenzene in 11 magnetic stirring units. The mixture was placed in a Luhlenmeyer flask, which was then sealed tightly.

Separately, 3.54 g (0,017 mol) of 1,4-benzenedicarbonyl chloride, salt 5.87 g (0,029 mol) of 1,3-benzenedicarbonyl chloride, benzene chloride carbonyl 0.34g (0,0024 mol), aluminum chloride 13.78 g (0,103 mol) and 313 g of 1,2-dichlorobenzene in 500 ml The mixture was placed in a magnetically stirred Erlenmeyer flask, which was then capped tightly. Each mixture The mixture was stirred at room temperature for 20 minutes, then cooled to 0° C. in a water/acetone solution. 0℃ The contents of the 500 ml flask were transferred to 11 flasks. 500m1 flask was washed with 39 g of 1,2-dichlorobenzene, and the washings were transferred to 11 flasks. Then, it was sealed tightly. The mixture was collected and kept at 0°C for 30 minutes, then 11 jacketed lintel heating vessels equipped with stirrers and nitrogen purging equipment. Moved.

This heating container is heated with saturated steam, and the temperature of the reactor reaches 100℃ in about 10 minutes. I let it happen. At about 50° C., solids began to precipitate, indicating that polymer had formed. 1 After the apparatus was kept at 00°C for 1 hour, the heating container was cooled to 25°C with running water. Filter the slurry The produced polymer/aluminum chloride chains were recovered. 500 polymers Place the polymer in a beaker with methanol at 15°C and add alkaline chloride. Decoordinated from minium. After stirring for 30 minutes, the polymer was filtered out and stirred. Washed three times for 30 minutes each with 500 ml of methanol in a 11 beaker.

The polymer was then washed with 800 ml of boiling water for 45 minutes, filtered and placed in a vacuum oven for 45 minutes. It was dried at 10°C for 16 hours.

Evaluate the melt stability of a polymer by measuring the melt flow rate and also provide an index of its molecular weight. Obtained. Flow rate is according to ASTM D 1238-85 with a load of 8.2 kg Measured using an extrusion blast meter. A flow rate of 10 g/10 minutes or less is The high molecular weight (and high viscosity) makes it difficult to process the polymer in the melt. I see, it shows that it is too hard. The flow rate of 10 g/10 minutes is approximately 12,000 number average minutes. Represents molecular weight. A flow rate of about 200 g/10 minutes or more is due to its elastic modulus and tensile strength. The low strength means that the molecular weight is too low for most applications. 20 At a flow rate of 0 g/10 min, the number average molecular weight is approximately 5000. Normally , the most useful number average molecular weight for this type of polymer is about 7,000 to 9°0. It is 00.

The molecular weight is determined by mixing 0.025g of polymer with phenol and 1.2.4-trichlorobenze. The mixture was heated at 175°C overnight to reduce the weight. The coalesce is dissolved and the solution is filtered at 115°C and a polystyrene of known molecular weight is added. Operating at 115 °C, corrected using a solution of ren in the same solvent mixture. It was measured by injecting it into a gas chromatograph.

Melt stability is evaluated based on the physical appearance of the extrudate from the plastometer did. A smooth surface without bubbles means the polymer is melt stable: rough , and/or extrudates with air bubbles mean that the polymer is not thermally stable. Ru.

Example 5 In Example 1, the catalyst was catalyzed with iron(II) chloride tetrahydrate and iron(II) sulfate heptahydrate. In each case, 32g of BPBB was It was dissolved in 457 g of 1,2-dichlorobenzene at ℃, filtered while hot, and the filtrate was BPBB was recrystallized by cooling to 0.degree. C. and filtration. Next, 350 BPBB Washed with methanol for 30 minutes, dried in a vacuum oven at 110°C, and polished in a mixer. Shattered. This BPBB was chain extended as described above. I get the following result Ta.

Table III Catalyst polymer flow rate (g/10 min) Iron(II) chloride tetrahydrate 27 Iron(II) sulfate heptahydrate 29 Extrudates of both polymers are smooth and bubble-free, an indicator of melt stability. It is. BP catalyzed with iron(II) chloride tetrahydrate and iron(II) sulfate heptahydrate The polymer extrudates from BB were light brown and dark brown, respectively.

Comparative example 1 Tightly stopper a mixture of 53.5 g of diphenyl ether and 1.4 g of anhydrous #2 chloride. This was stirred overnight and then filtered. centre The ferric chloride remaining in the filter was dried and weighed. Based on weight loss, 0. 0,005 moles (0,078 g) of ferric chloride were dissolved. diphenyl ether One half of the ferric chloride filtrate was mixed with another 107.3 g of diphenyl ether and ferric chloride. 1. Mix 20 g (0,099 mol) of 4-benzenedicarbonyl in a reactor. Ta. The mixture was heated to 250°C under nitrogen purge. The reaction takes place at this temperature for 6 hours. As it progressed, the color changed from black to red and finally to dark brown.

Add 187 g of diphenyl ether at 80°C to the reactor to bring the reaction system to about 180°C. It was rapidly cooled. The solution was filtered hot and allowed to cool. The product was filtered at 30°C and diluted with methanol. Washed and dried. The weighing result was 35.70g, which corresponds to a conversion rate of 77°0%. I guess. A small amount of ortho-para isomer was detected by proton nuclear magnetic resonance.

Comparative example 2 Chain extension was the same as in Example 5, except that the starting BPBB was from Comparative Example 1. It was like that. The flow rate in the extrusion blast meter was 104 g/10 min. . The extrudate was black and had bubbles. Extrusion with this high flow rate and bubbles Molded articles are those in which the starting BPBB does not have sufficient purity and the polymer is not stable in the molten state. It shows that From this comparative example, unsupported ferric chloride enhances the formation of BPBB. Catalyzes high conversion rates but is a pure product suitable for chain extension to poly(etherketoneketone). It is concluded that no pure substance is produced.

Comparative example 3 32 g of BPBB was dissolved in 375 g of N,N-dimethylacetamide at 160 °C. filter while hot, then cool the filtrate to 30°C and recover BPBB from the filtration system. The BPBB of Example 1 catalyzed with gallium (III) chloride was recrystallized in the method . The recrystallized material was washed twice with 350 ml of methanol for 30 minutes each and placed in a vacuum oven. , dried at 110° C. and ground in a mixer. 0.34g of this purified BPBB (0,0024 mol) of benzenedicarbonyl chloride. 0 mol) was replaced with 3°5-dichlorobenzenedicarbonyl chloride. The chain was then extended as described above. Extrusion production from an extrusion plastometer The shaped product was black, had bubbles, and was extremely brittle. The flow rate was I1g/10min. . This comparative example shows that gallium(III) chloride is suitable for polymerization for the production of high quality BPBB. This shows that it is not a catalyst.

Example 6 The BPBB used was gallium (III) sulfate or indium (III) sulfate water. Similar to Example 5, except that of Example 1, which was catalyzed by Ru. The results were as follows: Table IV Catalyst polymer flow rate (g/10 min) Gallium (III) sulfate 21 Indium (III) sulfate hydrate 20 Both polymer extrusion products are completely flat. It was smooth, had no bubbles, and showed sufficient melt stability. The color is brown in both cases. there were.

Example 7 Each of the four BPBB moieties of Example 4 was chain extended as described above. Ta. The flow rate and appearance of individual polymers are given below in two tables. BPBB flow rate Extrusion of sample (g/10 minutes) from extrusion blast meter Physical appearance of molded product 1 35 Dark brown, rough surface, with bubbles II 44 Dark brown, slightly rough surface, no bubbles, III 19 Brown, smooth H’30 Light brown, smooth This example shows that recrystallization of BPBB produced using supported ferric chloride further A substance of sufficient purity to be condensed into poly(etherketoneketone) This shows that it is possible to obtain

Comparative example 4 Diphenyl ether and 1,4-benzenedicarbonyl chloride are combined with 1,2-dichloro from that in benzene, in the presence of excess aluminum chloride, as disclosed in the art. BPBB was synthesized by a known method. This was washed several times with methanol and dried. all The amount is 1.8 kg of BPBB and 17 kg of N.

Dissolved in N-dimethylacetamide at 160°C, filtered while hot, cooled to 30°C, BPBB was recovered by filtration and recrystallized. This substance with methanol Washed, dried in a vacuum oven and ground in a mixer. This BPBB is the scanning differential calorific value (initial melting and remelting had a peak at 215°C), UV/visible spectroscopy It was found to be 99.9% pure as measured by photometer and proton nuclear magnetic resonance method. It was issued. This BPBB was polymerized by the above method and extruded at 26 g/10 minutes. A melt-stable material with a blastometer flow rate was obtained. The color of the extrusion is It was hazel in color. This comparative example shows that BPBB produced in the presence of the catalyst according to the invention Although the BPBB polymer prepared from Poly(etherketoneketone) made from higher purity BPBB and Provides poly(etherketoneketone) with approximately equivalent molecular weight and melt stability It is shown that.

international search report international search report LIS 9000421 S^　35387

Claims (10)

[Claims] 1. diphenyl ether at a temperature of about 220-258°C for about 60 to about 360 minutes. time, from about 5:1 to about 25:1 mole of 1,4-benzenedicarbonyl chloride. In ratio, unsupported iron(II) chloride (ferrous chloride), iron(II) sulfate (ferrous sulfate), Gallium (III) sulfate, and indium (III) sulfate: and an inert support. Iron(II) chloride, iron(II) sulfate, gallium(III) sulfate, indium sulfate on the body from the group consisting of um(III), and iron(III) chloride (ferric chloride) 1,4-benzenedicarbonyl chloride in the presence of at least one selected catalyst to the catalyst in a molar ratio of about 10:1 to 1000:1, with excess diphenylene Special feature is to separate and recover the product BPBB from both the nyl ether and the catalyst. A method for producing 1,4-bis-(4-phenoxybenzoyl)-benzene, characterized by . 2. Claim 1 characterized in that said reaction temperature is about 240-258°C. Method described. 3. The molar ratio of diphenyl ether to 1,4-benzenedicarbonyl chloride is The method according to claim 2, characterized in that the ratio is 6-10:1. 4. Claim 2, characterized in that the reaction time is 180-360 minutes. How to put it on. 5. Claim 4 characterized in that the above reaction is carried out at about 250° C. for about 5 hours. Method described. 6. Claim 1, wherein the catalyst is an unsupported iron(II) compound. Method described. 7. Claim 6, wherein the iron(II) compound is ferrous chloride. Method described. 8. Compounds of iron, gallium or indium supported by the above catalysts on an inert support. The method according to claim 1, wherein the method is a product. 9. A claim characterized in that the above catalyst is ferric chloride supported on an inert carrier. The method according to claim 8. 10. The method according to claim 9, wherein the inert carrier is silica. Law.