DE19851944C1 - Purification of 3-(4-hydroxyphenyl)-1,1,3-trimethylindan-5-ol (I), useful for the production of polycarbonate materials, comprises dissolution in a solvent and addition of a reducing agent. - Google Patents

Abstract

A process for the purification of 3-(4-hydroxyphenyl)-1,1,3-trimethylindan-5-ol (I) comprises dissolution of (I) in an organic solvent or aqueous medium followed by addition of a reducing agent, preferably a metal that forms nascent hydrogen in contact with an acidic medium or sodium dithionite and/or tin(II) chloride followed by isolation of (I).

Description

The invention relates to a process for the purification of 3- (4-hydroxyphenyl) -1,1,3- trimethylindan-5-ol by treatment with selected reducing agents.

For the production and purification of 3- (4-hydroxyphenyl) -1,1,3-trimethylindan-5- ol, hereinafter called bisphenol-indan, are various processes became known.

Thus US-A 2 754 285 and US-A 2 819 249 disclose a manufacturing route through that acid-catalyzed dimerization of α-methylstyrene to indanes, which then send sulfonated and then saponified with potassium hydroxide.

US-A 2 979 534 teaches that the mono obtained by cleavage of bisphenols mer isopropenylphenols in the presence of aromatic sulfonic acids or mineral acids can be dimerized at temperatures of 110 to 160 ° C to bisphenol indane can. Bisphenol cleavage and indane formation can also be done in one step be performed. A low purity product was obtained by this method ten, which has a melting point of even after recrystallization from benzene / cyclohexane only showed 165-166 ° C.

US-A 3 264 357 discloses the preparation of bisphenols by reaction of one Mixture of the two isomeric forms of the dimeric isopropenylphenol with Phenols in the presence of strong acids. It is reported that in absentia reactive phenols formed at a reaction temperature of 90 ° C bisphenol indane becomes. According to US Pat. No. 3,264,358, bisphenol-indan can be prepared by reacting a mixture of the two isomeric forms of dimeric isopropenylphenol with strongly acidic kata lysators are obtained, for example by tempering in conc for two hours hydrochloric acid at boiling point.  

US-A 3 288 864 discloses the production of bisphenol indan by self-condensation sation of monomeric isopropenylphenol in the presence of Friedel-Crafts-Kataly Isators at temperatures of 50 to 150 ° C, JP-A 60/35150 teaches the isomerization of isopropenylphenol or its oligomers in the presence of solid catalysts like aluminum oxide or terra alba.

According to US-A 4,334,106, bisphenol-indane can be reacted with isopropenyl phenol or its oligomers in halocarboxylic acids or formic acid Temperatures from 0 to 90 ° C can be produced.

According to JP-A 5/294879 bisphenol-indan can be broken down by thermal decomposition of Bisphenol-A can be obtained in the presence of activated clay, US-A 3,271,463 discloses the formation of bisphenol indan as a by-product in the treatment of bisphenol A with aqueous sulfuric acid at 90-150 ° C. With both methods larger amounts of spirobisindane bisphenol are formed, which by Um crystallization from aromatic hydrocarbons must be separated.

German patent application 197 28 377.2 discloses a process in which bisphenol-indane is prepared from isopropenylphenol in the presence of BF ₃ .Et ₂ O in chlorobenzene and is recrystallized from acetic acid / water. Bisphenol-indan of high purity is obtained in this way, although it still has unsatisfactory color numbers. A product of lower purity is obtained by recrystallization from methanol / water instead of acetic acid / water.

The cleaning methods of the prior art provide a product which The color obviously does not meet industrial requirements. It was now a improved process, by which bisphenol-indane in high color can produce quality.

The invention relates to a process, a process for the purification of 3- (4- Hydroxyphenyl) -1,1,3-trimethylindan-5-ol.  

Bisphenol-indan is initially in an organic solvent or in dissolved in an aqueous medium, preferably at a temperature of 0-250 ° C, be particularly preferably 20-110 ° C, and preferably a pressure of 0.5-10 bar, particularly preferably 1-2 bar.

A large number of organic solvents can be used in the process according to the invention be set. These include aliphatic carboxylic acids, e.g. B. ants acid, acetic acid, propanoic acid, butyric acid, oxalic acid, hexanedioic acid, malonic acid or succinic acid, halogenated carboxylic acids such as chloroacetic acid, trichloroacetic acid acid, trifluoroacetic acid, aromatic carboxylic acids such as phthalic acid, benzoic acid, Terephthalic acid, aliphatic anhydrides such as acetic anhydride, halogenated ali phatic anhydrides, aromatic hydrocarbons, e.g. B. benzene, toluene, Mesitylene, xylenes, partially halogenated aromatic hydrocarbons such as chlorine benzene, halogenated aliphatic hydrocarbons, e.g. B. methylene chloride, dichloro ethane, carbon tetrachloride, carbon tetrachloride, chloroform, aliphatic ethers, e.g. B. THF, cycloaliphatic ethers such as dioxane, aromatic ethers such as anisole, aliphatic Ketones such as acetone, methyl isobutyl ketone, butanone, acetylacetone, cycloaliphatic Ketones such as cyclohexanone, aliphatic esters such as ethyl acetate, methyl acetate, butyl acetate, propyl acetate, dimethyl carbonate, propylene carbonate, cyclic esters, e.g. B. δ- Valerolactone, aromatic esters such as methyl benzoate, aliphatic alcohols such as Methanol, ethanol, propanol, butanol, ethanediol, propanediol, glycerin, cyclo aliphatic alcohols such as cyclohexanol, other solvents such as DMF, DMSO, NMP, pyridine and the solvents mentioned in GB-A 2088857, the Mi and their mixtures with water. Preferred solvents are Carboxylic acids, especially acetic acid.

In a further embodiment of the invention, the crude bisphenol indane in dissolved in an aqueous solution of a base. Suitable bases are, for example Alkali hydroxides, especially sodium hydroxide.  

According to the invention, the solution of the bisphenol indane is reduced medium offset. Metals in a acidic medium have been found as reducing agents form nascent hydrogen (e.g. zinc), sodium dithionite and tin (II) chloride proven. Other reducing agents, e.g. B. hydrazine, have been fictional for the Proven unsuitable methods, In a preferred embodiment of the Invention, the crude bisphenol indane is dissolved in acetic acid and then with Reductant or a mixture of reducing agents added.

The reducing agent or mixture of reducing agents is used in an amount of 0.0001 to 100 wt .-%, preferably 0.1 to 5 wt .-%, based on the amount of bis phenol indane. The reaction mixture is then left at tem temperatures between 0 ° C and the boiling point of the solvent used rea yaw. The required reaction time depends on the temperature of the reak tion mixture. Generally it will range from a few seconds up to a few hours. To keep the response time as short as possible, preferably work near the boiling point of the solvent used. For example, the required reaction time in boiling acetic acid Solution only about 5 to 10 minutes.

The product purified in this way can then be crystallized. The crystallization can be carried out according to methods known to those skilled in the art, e.g. B. by Multiple crystallization, gradual crystallization, zone crystallization or precipitation solution crystallization.

The crystalline product is, in a manner familiar to the person skilled in the art, from the mother liquor severed. Afterwards, it can be washed to remove adhering impurities remove tendencies, e.g. B. residues of the reducing agent or its reaction pro products. As a rule, distilled water is used for the last washing step put. It may be advantageous to use the product several times in distilled water slurry. The product is then produced in a manner known to the person skilled in the art dried.  

Because of its high purity and low color number, this is after inventing Processed bisphenol-indane according to the invention in an outstanding manner is suitable as a raw material for the production of high-quality plastics, e.g. B. Polycarbonates. The bisphenol-indane obtained according to the invention can be used Polycarbonate with low birefringence and good mechanical properties produce that is particularly suitable for optical applications. Because of his Flow behavior, it is particularly suitable for the production of optical data storage, especially compact discs.

Examples Manufacture of bisphenol indan

In a 6 l three-necked flask with KPG stirrer, reflux condenser and thermometer 400 g of dimeric p-isopropenylphenol are placed in 2 l of chlorobenzene. The col Ben content is heated to 80 ° C, the p-isopropenylphenol completely solves. 150 g of bentonite or montmorillonite are added, the mixture is heated to the boil and left react the mixture at boiling heat for 60 minutes. Then that will The reaction mixture is filtered hot, the temperature not falling below 80 ° C. and distills about half of the solvent from the filtrate. The concentrated filtrate is then stirred at 0 to 10 ° C for 1 h to crystallize the product. That he Raw bisphenol-indane is separated from 1.2 kg of 70% acetic acid crystallized, washed neutral with distilled water and at 24 ° C for 24 h Water jet vacuum dried. Bisphenol-indan is obtained with a purity <99%.

example 1 Reduction with zinc / acetic acid

100 g of bisphenol indan were boiling in a nitrogen atmosphere in 250 g Acetic acid dissolved. After the bisphenol indane was completely dissolved, 1 g (1 wt .-%, based on bisphenol-indan) added zinc dust, ten more Stirred under reflux for minutes and then filtered hot. The filtrate was cooled with stirring, the precipitate formed was suction filtered and once washed with 50 ml of acetic acid. The precipitate (75 g) then became five times in 500 ml dist. Slurried water and vacuum dried at 80 ° C cupboard dried. A purity of 99.0% by weight was determined by gas chromatography. determined before treatment and 99.4% by weight after treatment. The color appraisal Division was carried out by measuring the YI (according to ASTM E-313) in 5% by weight  Solution in acetone. The yellowness index fell due to the cleaning procedure of 5.5 to 1.9.

Example 2 Reduction with zinc / acetic acid

500 g of bisphenol indane boiled in a nitrogen atmosphere in 1250 g Acetic acid dissolved. After the bisphenol indane was completely dissolved, 5 g (1 wt .-% based on bisphenol-indan) added zinc dust, then was stirred under reflux for a further ten minutes and then filtered hot. The filtrate was cooled with stirring, the precipitate formed was suction filtered and twice with 100 ml acetic acid and three times with 250 ml methylene chloride washed. The precipitate was in 2000 ml of 10 wt .-% hydrochloric acid then six times in 3000 ml dist. Slurried water. After drying 345 g of bisphenol indane were mixed with a gas at 80 ° C. in a vacuum drying cabinet purity of 99.4% by weight determined by chromatography.

Example 3 Reduction with sodium dithionite / acetic acid

100 g of bisphenol indan were boiling in a nitrogen atmosphere in 250 g Acetic acid dissolved. After the bisphenol indane was completely dissolved, 2 g (2 wt .-%, based on bisphenol-indan) sodium dithionite added. The Lö The solution was then stirred under reflux for a further ten minutes and then filtered hot. The filtrate was cooled with stirring, the resulting low beat (70 g) and suctioned off once with 50 ml of acetic acid, then with 250 ml of methy washed lenchlorid and finally five times in 500 ml dist. Water raised slurries and dried at 80 ° C in a vacuum drying cabinet. Gas chromatograph a purity of 99.0% by weight before the treatment and 99.4% by weight became determined after treatment. The color was assessed by measuring the  Y.I. (according to ASTM E-313) in 5% by weight solution in acetone. The Yellowness Index decreased from 5.5 to 1.1 due to the cleaning procedure.

Example 4 Reduction with tin (II) chloride / acetic acid

500 g of bisphenol indan would boil in a nitrogen atmosphere in 1250 g Acetic acid dissolved. After the bisphenol indane was completely dissolved 25 g (5 wt .-%, based on bisphenol-indane) of tin (II) chloride dihydrate , it was stirred under reflux for a further ten minutes and then filtered hot. The filtrate was cooled with stirring, the resulting low suction filtered and twice with 100 ml of acetic acid and three times with 250 ml Washed methylene chloride. The precipitate was 10 wt .-% in 2000 ml Hydrochloric acid and then six times in 3000 ml dist. Slurried water. After drying at 80 ° C in a vacuum drying cabinet, 354 g of product hold. The color evaluation was carried out by measuring the Y. L (according to ASTM E-313) in 5% by weight solution in acetone. The yellowness index fell as a result of cleaning procedure from 5.5 to 1.8.

Example 5 Reduction with sodium dithionite in an alkaline medium

8.8 g of sodium hydroxide in 353.4 g of dist. water submitted at room temperature and 13.4 g bisphenol indane and 0.18 g sodium dithionite added. The reaction mixture was stirred at room temperature until a clear solution had emerged. After a further 5 minutes the solution became Precipitation of the bisphenol indane with 10% by weight hydrochloric acid was added until a pH value was reached by <2. The precipitate formed was suction filtered and electrolyte-free washed. The bisphenol indane was then dissolved in acetone and by Filtration separated from undissolved parts. The solvent was removed and the cleaned product dried at 80 ° C in a vacuum drying cabinet. The colourbe  Judgment was made by measuring the yellowness index (according to ASTM E-313) in 5% by weight solution in acetone. The yellowness index fell as a result of cleaning procedure from 5.6 to 4.2.

Example 6 (comparison) Reduction with hydrazine hydrate

100 g of bisphenol indane were refluxed in a nitrogen atmosphere 2000 ml of toluene dissolved. The solution was heated to boiling and 2 g (2% by weight, based on bisphenol indane) hydrazine hydrate added. The Lö solution was stirred under reflux for a further ten minutes and then hot filtered off. The filtrate was cooled with stirring, the resulting precipitate suction filtered and slurried with 250 ml of methylene chloride and at 80 ° C in Vacuum drying cabinet dried. The color was assessed by measurement of Y. I. (according to ASTM E-313) in 5 wt .-% solution in acetone. The Yellowness The procedure raised the index from 5.5 to 13.2.

Example 7 Production of a polycarbonate from bisphenol indane and bisphenol M (70/30)

In a solution of 88 g of sodium hydroxide in 2755.6 g of distilled water 175.21 g bisphenol-indan from Example 2 and 103.94 g bisphenol M dissolved, then 2071.9 ml of methylene chloride were added and 197.8 g of phosgene at 15-25 ° C. initiated. The pH of the reaction mixture was adjusted by adding 45% by weight sodium hydroxide solution was kept in the range from 10 to 13. 5 minutes after At the end of the introduction of phosgene, 4.51 g of p-tert-butylphenol and after a further 5 Minutes 1.37 ml of N-ethylpiperidine were added. The reaction mixture was still Stirred at pH 11 for 45 minutes. Then the phases were separated, the orga The acidic phase is acidified with 10% by weight hydrochloric acid and washed free of electrolytes. After removal of the solvent, the polycarbonate obtained was used as a test  bodies splashed. The results of the physical test are in Table 1 summarized.

Example 8 (comparison)

Example 6 was repeated, but with crude bisphenol indane as the starting material.

The results of the physical test of the polycarbonate obtained are shown in Table 1 summarized.

Table 1

Claims (4)

1. Process for the purification of 3- (4-hydroxyphenyl) -1,1,3-trimethylindan-5-ol, in which 3- (4-hydroxyphenyl) -1,1,3-trimethylindan-5-ol in an orga nical solvent or an aqueous medium then dissolves the solution with a reducing agent, which is a metal in acidic medium forms nascent hydrogen and / or sodium dithionite and / or tin (II) - chloride, and then from the solution 3- (4-hydroxyphenyl) -1,1,3-tri methylindan-5-ol isolated. 2. The method according to claim 1, wherein the solvent used is acetic acid becomes. 3. The method according to claim 2, in which zinc dust is used as the reducing agent is set. 4. The method according to claim 2, in which as a reducing agent sodium dithionite is used.