DE2534558A1 - Hydroxy-phenyl-isopropylbenzene prepn. - from substd. isopropylbenzens and phenols catalysed by sulphonated polystyrene crosslinked by divinylbenzene - Google Patents

Abstract

The prepn. of opt. substd. 4-hydroxy-phenyl-isopropylbenzenes comprises reacting opt. alpha-OH- or alpha-alkoxy-substd. isopropylbenzenes having formula (I) (where n is no. 1-3; R1 areopt. different when n = 2 or 3 and denote H, OH or 1-6C alkyl) with opt. substd. phenols. Acid catalysts are used and consists of light-coloured sulphonated polystyrene crosslinked with max. 10(2-4) wt. % divinylbenzene. Process is partic. suitable for condensing alpha,alpha'-dihydroxy-diisopropylbenzenes and their derivs. with phenols to give alpha,alpha'-bis-(4-hydroxyphenyl)-diisopropylbenzenes (II). (II) are starting materials for prodn. of polycarbonates, polyesters and polysulphones. Catalysts cause no corrosion and are easily sepd. High space-time yields are achieved. Yields reach 98% of theoretical. Prods. are highly pure. In an example, 300g/hr alpha,alpha'-dihydroxy-1,4-diisopropylbenzene and 3600 g/hr. phenol were pumped through catalyst bed of 400g ion exchanger having degree of crosslinking 2% and Lovibond colour values 0.5, 0 and 2.1 in red, blue and yellow ranges. alpha,alpha'-Bis-(4-hydroxyphenyl) p-diisopropylbenzene was obtd. in 94% yield. M. pt. 196-197 degrees C (from toluene).

Description

Process for the preparation of oX bis- (4-hydroxyphenyl) -dilsopropylbenzenes The invention relates to a process for the preparation of α, α'-bis (4-hydroxyphenyl) -diisopropylbenzenes by reaction of α, α'-dihydroxy-diisopropylbenzenes and / or their Derivatives with phenols in the presence of acidic ion exchangers.

α, α'-Bis- (4-hydroxyphenyl) -diisopropylbenzenes are known valuable starting products for the production of polycarbonates, polyesters and Polysulfones; however, very pure bisphenols are required to produce polycondensation products to obtain which have high molecular weights and thus good mechanical properties.

It is known to use α, α'-dihydroxy-diisopropylbenzenes Phenols in the presence of acidic catalysts to the corresponding α, α'-bis (hydroxyphenyl) -diisopropylbenzenes to implement. HCl, H2S04 and 3F3 are used as acidic catalysts (BE-PS 614,663 and BE-PS 604,516).

From US-PS 3,393,244 it is known that o (, «'- bis (4-hydroxy phenyl) 1,4- and 1,3-diisopropylbenzoi particularly simple and in good yield with dry Hydrogen chloride can be obtained as a catalyst.

However, the yields are generally not more than 90% of theory, i.e. by-products and isomers of the desired bisphenols are formed. The received The reaction product is therefore not without further purification and for polyconnections thus yield losses can be used. In addition, the necessary response times are relatively long and consistently take several hours acidic catalysts are removed from the reaction mixture after the reaction, in some cases, they also have a highly corrosive effect on the vessel material, in particular the preferred hydrogen chloride used.

In the Belgian patents, among others, acidic Catalysts such as concentrated hydrochloric acid, phosphoric acid, hydrofluoric acid, Hydrobromic acid, perchloric acid, benzene and toluene sulfonic acid, also acidic ion exchangers, especially sulfonated polystyrene mentioned, but their use is not described.

There was a process for the preparation of optionally substituted 4-hydroxyphenyl-isopropylbenzenes by reaction of compounds of the formula wherein n stands for a number from 1 to 3 and R1 can be identical or different for an n of 2 or 3 and stands for the hydroxyl group or a C1-C6-alkoxy radical, with optionally substituted phenols in the presence of acidic catalysts, characterized in that light-colored sulfonated polystyrenes crosslinked with a maximum of 10% by weight of divinylbenzene are used as acidic catalysts.

Have light-colored polystyrenes by the process of the invention for example in the Lovibond tintometer (G.J. Chamberlin: Visual Aids to the Teaching of Color and Colorimetry and Colorimetric Analysis, Salisbury 1965) color values of reflected light in the red and blue areas of less than 1.0 and in the Have a yellow area of less than 4.5. Preferred catalysts are in the red range a Lovibond color value of 0.8, in the blue range of 0.2 and in the yellow range of 3. Particularly preferred catalysts have Lovibond color values in the red range of 0.6, in the blue area of O and in the yellow area of 2.5.

The sulfonated polystyrenes according to the invention, which with a maximum of 10 % By weight divinylbenzene can be crosslinked in a known manner (USP 2,366,007) Sulphonation of the corresponding polystyrenes at temperatures from 0 to 50 0C with Chlorosulfonic acid are produced.

It is preferred to use ion exchangers that are produced after the process of DT-OS 1 570 565 crosslinked by sulfonation, suspended in swelling agents aromatic vinyl polymers with chlorosulfonic acid in the presence of phosphorus trichloride can be obtained.

The degree of crosslinking of the ion exchangers used according to the invention can be varied within certain limits. The amount of divinylbenzene used for crosslinking is expediently between 1 to 10% by weight, preferably 1.5 to 6% by weight, in particular but 2 to 4% by weight of the polystyrene.

A catalyst in particular is used for the process according to the invention preferred, which consists of sulfonated polystyrene with 2 wt. Divinylbennol is networked and Lovibond color values in the red range of 0.5, in the blue range of 0 and in the yellow area of 2.1.

The acidic ion exchangers are preferably as gel-like or macroporous bead polymers used, but they can also be broken or find ground form as a powder use. The simplest form of application the ion exchanger is made when carrying out the process according to the invention in that the reaction mixture is arranged in a fixed or fluidized bed Exchangers pumped through. The method according to the invention is therefore particularly suitable for a continuous way of working.

The ion exchangers are used in acid or acid form. There they still contain a lot of water from manufacture, water contents above about 8 % in the reaction mixture can reduce the reaction rate considerably, the ion exchangers are expediently dried before use.

This is done in a known manner by displacing the water with a water-miscible solvents such as isopropanol or phenol or by azeotropic Distillation with aliphatic, aromatic or halogenated hydrocarbons, Alcohols or the phenols to be converted.

I-Hydroxyisopropylbenzenes are used as starting compounds of the formula I and «-alkoxy-isopropylbenzenes in question.

Examples of -Hydroxy-isopropylbenzenes are: α-Hydroxy-isopropylbenzene, α, α'-dihydroxy-m-diisopropylbenzene, α, α'-dihydroxy-p-diisopropylbenzene and α, α ', α "- trihydroxysym-triisopropylbenzene.

Examples of A-alkoxy-isopropylbenzenes which may be mentioned are compounds in which the alkyl radical represents a straight-chain or branched C1-C6 hydrocarbon radical, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, Hexyl or the isohexyl radical. t-Alkoxyisopropylbenzenes are for example: α-Methoxy-isopropylbenzene, α, α'-dimethoxy-m-diisopropylbenzene, α, α'-dimethoxy-p-diisopropylbenzene, α, α ', α ", -trimethoxy-sym-triisopropylbenzene, α-ethoxyisopropylbenzene, α, α'-diethoxy-m-diisopropylbenzene, α, α'-diethoxy-p-diisopropylbenzene, α, α ', α "-triethoxy-sym-triisopropylbenzene.

Preferred starting compounds of the formula I are: α-hydroxyisopropylbenzene, α, α'-dihydroxy-m-diisopropylbenzene, α, α'-dihydroxy-p-diisopropylbenzene, α, α ', α "-trihydroxy-symtriisopropylbenzene, α-methoxy-isopropylbenzene, α, α'-dimethoxym-diisopropylbenzene, α, α'-dihydroxy-p-diisopropylbenzene, α, α ', α "-triethoxy-sym-triisopropylbenzene.

Instead of the starting compounds mentioned in formula I, it is also possible to use compounds which are formed from compounds of the formula I by splitting off water or alcohol. Examples are compounds of the formula where n has the abovementioned meaning, m stands for a number from 1 to 3 and R2 stands for hydrogen or a C1 to C6 alkyl radical. For example, the following individual compounds may be mentioned: α-Hydroxy-isopropyl-m-isopropenylbenzene, α-Hydroxyieopropyl-p-isopropenylbenzene, m-diisopropenylbenzene, p-diisopropenylbenzene, 5-propoxy-m-isopropenylbenzene and Xylbenz-isopropenylbenzene.

Optionally substituted phenols which can be used as starting compounds in the process according to the invention are those which have a free p-position. They generally correspond to the formula in which R3 and R4 are identical or different and represent hydrogen, the hydroxyl group, a C1 to C12 alkyl or a C12 cycloalkyl radical, halogen, a C6 to 012 aryl, a C1 to C6 alkoxy or a C6 to C12 Aroxy group, or together with adjacent ring carbon atoms can form a carbocyclic 5- or 6-ring.

Halogen which may be mentioned is fluorine, chlorine, bromine, iodine, preferably chlorine. The alkyl radicals are straight-chain or branched alkyl radicals with up to 12 O atoms in question, preferably with up to 6 carbon atoms.

Examples include: methyl, ethyl, propyl, isopropyl, butyl, Isobutyl, tert. Butyl.

Cyclopentyl and cyclohexyl radicals are particularly suitable as cycloalkyl radicals in carrier, which may optionally be substituted by lower alkyl radicals.

Particularly the phenyl and naphthyl radicals are used as aryl radicals Question, which can optionally be substituted by lower alkyl radicals.

As phenols which are used for the process according to the invention can be mentioned, for example: phenol, o-cresol, 2.6-xylenol, 2.6-diethylphenol, o-cyclohexylphenol, o-tert. -Butylphenol, 5,6,7,8-tetrahydronaphthol-1, o-phenylphenol, o-chlorophenol, o-methoxyphenol, o-phenoxyphenol, 3 <-naphthol and 1 -hydroxy-2-methoxynaphthalene, Resorcinol.

The reaction in which ion exchangers are used according to the process according to the invention is illustrated using the example of α, α'-dihydroxydiisopropylbenzene and phenol by the equation below.

In general, the phenol is used in excess based on the dihydroxydiisopropylbeneol or the corresponding derivative is used. The molar ratio is expediently the reaction partner 1: 5, preferably 1: 6 to 1:20; also a larger excess of phenol is possible.

In general, in the temperature range between 0 ° to 1200 ° C., is preferred between 20 to 100 ° C and in particular in the temperature range of 45 to 95 ° C worked.

Generally, the reaction will be carried out in the absence of a solvent carried out in the used excess of the phenol used. However, it is also possible to work in the presence of a solvent. As such solvent come aliphatic, cycloaliphatic, aromatic and halogenated hydrocarbons and ether in question; Examples include: isooctane, cyclohexane, benzene, Toluene, xylene, methylene chloride, chloroform, chlorobenzene, tetralin, dibutyl ether, Anisole, tetrahydrofuran, dioxane and phenetole.

It may even be particularly beneficial or necessary in the presence of a solvent to work, especially if it is used Phenol has a higher melting point than the selected reaction temperature or a particularly poor dissolving power for the dihydroxydiisopropylbenzene used or the corresponding derivative, In general, the inventive Procedure performed as follows.

The reaction components are with the catalyst and optionally mixed with the solvent and reacted at the chosen reaction temperature. In a preferred embodiment of the method according to the invention, the mixture is the reaction components at the selected temperature by the in a solid or Catalyst arranged in a fluidized bed is pumped through it.

The water formed during the reaction or that in the case of use an alkoxy- or dialkoxy-diisopropylbenzene resulting alcohol with the The reaction mixture is separated off from the exchanger and removed during work-up.

This does not reduce the catalytic effectiveness of the exchanger impaired.

The reaction mixture obtained can be worked up in a customary manner Manner according to known methods, e.g. by distillation or crystallization. The apparatus configuration of the method according to the invention can also be carried out in the usual way In accordance with the state of the art (Ullmann, Encyklopadie der technical Chemie, 1972, Vol. 2, pp. 491-545; Pp. 672-689; BE PS 614 663).

It is surprising that the process according to the invention can be carried out is and brings considerable technical progress. When using aryl sulfonic acids such as p-toluenesilfonic acid, sulfonated polymers, which are usually instead of the catalyst according to the invention are used, the condensation of N, '- Dihydroxy-diisopropylbenzenes and their derivatives with phenols in principle catalyzed, the yields and the quality of the reaction products are however so bad that their practical use is out of the question.

In contrast, the use of the ion exchangers to be used according to the invention brings about a number of advantages. Once it is possible to use the corrosive mineral acids such as hydrogen chloride, without sacrificing the yield and quality of the reaction product to have to accept. Continue to let yourself be unlike the mineral acids easy separate without impurities in the reaction product stay. Furthermore, when the ion exchanger is used, it is several times faster Implementation than is known in the prior art, from which a far higher one The space-time yield results.

The most important progress, however, can be seen in the fact that the yields up to 98% of theory and the reaction products with a according to the state purity not known to the art can be obtained.

The 4, d '-Bis- (4-hydroxyphenyl) -diisopropylbenzenes, which according to the invention Process can be obtained are valuable starting materials for manufacture of polycarbonates (USP 3,466,260), polyesters (USP 3,536,665) and polysulfones (DOS 2 025 467, 2 038 516, R.J. Cornell ACS Polymer Reprints Jl (No. 1) p. 607 - 6t0 (1972)); their further implementation can be carried out by customary processes.

EXAMPLE 1 (COMPARATIVE EXAMPLE) 900 g (9.6 Mol) Phenol saturated by passing in hydrogen chloride with HCl and at 55 ° C 100 g of α, α'-dihydroxy-1,4-diisopropylbenzene within one hour added with stirring. Hydrogen chloride, water and phenol are released after a reaction time distilled off under vacuum for 2 1/2 hours. The distillation residue is in 400 ml of hot toluene were taken up and crystallized. 156 g of end product are obtained (corresponding to 88% of theory) with a melting point of 190 to 19200.

Example 2 (comparative example) A mixture of 97 g (0.5 mol) of α, α'-dihydroxy-p-diisopropylbenzene, 940 g (10 mol) of phenol and 10 g of p-toluenesulfonic acid are stirred for 5 hours Maintained 70 to 800C. The toluenesulfonic acid is then treated with 45% sodium hydroxide solution neutralized, water and phenol distilled off in vacuo and the residue from 800 ml of toluene recrystallized. 109 g (64% of theory) of α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene are obtained with a melting point of 171 to 1830C.

No further crystals could be isolated from the mother liquor.

Example 3 (comparative example) 900 g of phenol are placed in a flask with 100 g ion exchanger with a degree of crosslinking of 2% and Lovibond color values of 2.0 in the red, 7.7 in the yellow and 1.2 in the blue area.

100 g of α, α'-dihydroxy-1,4-diisopropylbenzene are added within one hour added at 55 ° C. with stirring. After a reaction time of 3 hours with stirring at 550 water and phenol are distilled off, the residue is boiling in 250 ml Toluene dissolved and crystallized. 86 g (48% of theory) of crude α, α'-bis (4-hydroxyphenyl) -p-diisopropylbentol are obtained with a melting point of 190 to 19200.

Example 4 (comparative example) 1200 g of phenol are placed in a flask with 100 g ion exchanger with a degree of crosslinking of 18% and Lovibond color values of 1.6 in the red, 4.5 in the yellow and 1.0 in the blue area.

100 g of α, α-dihydroxy-1,4-diisopropylbenzene are added within half an hour added at 550C with stirring. After a reaction time of 3 hours with stirring water and phenol are distilled off, the residue is dissolved in 300 ml of boiling toluene dissolved and crystallized. 132 g (corresponding to 74% of theory) of raw material are obtained α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene with a melting point from 190 to 19200.

Example 5 400 g of ion exchanger are used in a tubular reactor a degree of crosslinking of 2% and with the Lovibond color values 0.5 in red, 2.1 in Yellow and 0 in the blue area are used. Through the catalyst bed every hour 300 g of i, d'-dihydroxy-1,4-diisopropylbenzene and 3600 g of phenol are pumped.

After the reaction, 1300 g of reaction solution become water and phenol distilled off, the residue is taken up hot in 450 ml of toluene and crystallized. 167 g of end product are obtained.

The yield is 94% of theory of crude X, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene with a melting point of 196 to 197 ° C.

Examples 6 to 20 In Table I below are each the Number of the example, type and amount of used, X, f-dihydroxydiisopropylbenzene, Type and amount of catalyst used, Reaction time and temperature, and the yield of reaction product in% of theory, the isomer content of the Reaction product and its melting point indicated. The comparative examples 1 * to 4 * and example 5 are also listed for a better overview. In addition to the specified conditions, Examples 6 to 14 were carried out by the method described in Example 4 described was carried out.

Table 1 Biscar phenol catalyst reaction product binol * Lovibond Color value 1 * p 100 phenol 1200 12 g HCl 150 55 88 12 190 - 192 2 * p 97 phenol 940 10 g p-toluenesulfonic acid 300 55 64 - 171 - 183 3 * p 100 phenol 1200 100 g 2 2.0 7.7 1.2 180 55 48 10 190 - 192 4 * p 100 phenol 1200 100 g 18 1.6 4.5 1.0 40 55 74 9 191 - 192 5 p 300 phenol (g / h) 3600 g / h comt. 2 0.5 2.1 0 14 55 94 0.5 196 - 197 6 p 100 phenol 1200 100 g 2 0.5 2.1 0 10 55 94 0.5 196 - 197 7 p 100 phenol 1200 100 g 4 0.5 2.0 0 10 55 95 0.5 196 - 197 8 p 100 phenol 1200 100 g 2 0.5 2.1 0 20 55 94 0.6 196 - 197 9 m 100 phenol 1200 100 g 2 0.5 2.1 0 20 55 94 0.8 134 - 136 10 p 100 o-cresol 1400 100 g 2 0.5 2.1 0 20 55 92 0.6 159 - 161 11 p 2,6-dimethyl-1400 100 g 2 0.5 2.1 0 30 55 93 - 154 - 155 phenol 12 p 40 phenol 1200 100 g 2 0.5 2.1 0 20 55 92 0.8 m 60 13 p 100 phenol 2000 100 g 4 0.5 2.0 0 15 55 98 0.4 196 - 197 14 p 100 phenol 1200 100 g 4 0.5 2.0 0 15 70 93 0.6 196 - 197 * Notes p = α, α'-dihydroxy-p-diisopropylbenzene m = α, α'-dihydroxy-m-diisopropylbenzene isomer content = sum of α- (2-hydroxyphenyl) -α '- (4-hydroxyphenyl) -diisopropylbenzene and α , α'-bis (2-hydroxyphenyl) diisopropylbenzene

Claims (5)

Claims: 1. Process for the preparation of optionally substituted 4-hydroxy-phenrl-isopropylbenzenes by reacting compounds of the formula where n stands for a number from 1 to 3 and R1 can be identical or different for an n of 2 or 3 and stands for hydrogen, the hydroxyl group or a C 1 -C 6 -alkyl radical, with optionally substituted phenols in the presence of acidic catalysts, thereby characterized in that the acidic catalysts used are sulfonated polystyrenes which are light-colored and crosslinked with a maximum of 10% by weight divinylbenzene. 2. The method according to claim 1, characterized in that one light-colored Polystyrenes used, the color values of the reflected light in the Lovibond Tintometer in the red and blue areas of less than 1.0 each and in the yellow area of less than have 4.5. 3. The method according to claim 1 and 2, characterized in that one ion exchangers used as acidic catalysts, which are crosslinked by sulfonation, aromatic vinyl polymers suspended in swelling agents with chlorosulfonic acid have been obtained in the presence of phosphorus trichloride. 4. The method according to claim 1 to 3, characterized in that one sulfonated polystyrenes crosslinked with 2 to 4% divinylbenzene are used. 5. The method according to claim 1 to 4, characterized in that one a catalyst is used, which consists of sulfonated polystyrene, which with 2 Divinylbenzene by weight is crosslinked and Lovibond color values in the red range of 0.5, in the blue area of 0 and in the yellow area of 2.1.