DE1618016A1 - Process for the production of bisphenols - Google Patents

Description

The present invention relates to a Terfanren for Production of bisphenols. It particularly relates to a process for the production of bisphenols by reaction a phenol with a ketone in a Reaktiunemisohung, the a mercaptan and a solid, insoluble ion exchange resin with pendant sulfonic acid groups.

In the past, bisphenols were produced by reacting a phenol with a ketone in a reaction medium; the one mineral acid, like; Hydrochloric acid, sulfuric acid etc /., ^ Thialt. However, this process of making bisphenol presented difficult problems and was inefficient. Since mineral acids are highly corrosive, they attack the device for carrying out the reaction and corrode it. Furthermore, since Minsralsäüren in phenols and ketones are soluble, "it is extremely difficult to Minetalsäuren tone the unreacted starting materials to be removed. Außerdem.verringert '

BAD OBiGlNAL 20981671463

itself, the catalytic effectiveness of the. Mineral acid !!, noticeable in the presence of the water formed during the reaction; at a concentration of about 1.2% by weight of water, based on the weight of the initial reactants (if the molar ratio of the reactants used is, for example, ΐ moles of ketone to TO moles of a phenol and the amount of minerals used is 1% by weight *) Mineral acids show little or no catalytic activity.

When trying to improve the catalytic! Effectiveness of Mineral acids have been suggested to include an accelerator such as a mercaptan such as ethyl mercaptan. This has turned out to be however, it has not been found to be particularly effective in creating a suitable catalyst system. The catalyst system remains always compared to the device for carrying out the reaction still corrosive; Furthermore, there are severe process problems with regard to the removal and recovery of mercaptan, unreacted phenol and unreacted ketone the mineral acids. - '

Also the use of ion exchange resins as catalysts in the preparation of bisphenols by reacting a phenol with a ketone has been proposed .. Ion exchange resins however, they are also sensitive to water and lose at water concentrations, in which mineral acids lose their catalytic effectiveness, also practically their entire catalytic effectiveness Effectiveness.

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The 'present invention creates a method': to produce ' you 13is henolen by. Reaction of a phenol with; elneiB, ketone In a, Heaktjonssystem, which contains ^ a Γ, ηβηοΙΙϋ s borrowed sMereapt and a solid, insoluble iOnenäus-baüscherJa.arz: with attached Sull'cns-whore groups .. '; . _v

By using a catalyst system consisting of an above-mentioned rear tan and a solid, insoluble ion exchanger with an additional sulfonic acid gradient, the reactivity between the phenol and the ketone is further increased, and higher conversions of the ketone are increased - up to JOO fo - is achieved, and the bisijhenol, which is divided into grains, is practically free of uneventful levy products, such as dianine compounds. Achieving this Yorteile is also possible in a inediuiii Beaktions-, enthult more than about \, 2 Gev /.-^ water ,; under Reaktidnabedlngeii, \; as they were described above with respect to the Ifineralsauren ji-JIuiiaxiaustauscherharze per se *

Inventions of suitable ketones have the general formula;

E-C-GH ^ ti ■. -2

in which & for a monovalent hydrocarbon radical, not necessarily with 12 carbon atoms, preferably with libcb-.tens 6 iichlexistoffato;: ieh ,. stands. . i

Suitable ketones of the above formula are, for example: saturated ali ^ hatiscne ketenes ^ such as Dinetlvlistohj Chlorate clay, Methylatixyllcetone, ■ Jet-jl-n-oro ^ yliietoii, Kethylisbutylcetone etc .; ketones such as aforaatly.che _f Hienylmetliylketon etc .; and unsaturated ketones,

like: Cesitylox / d etc.

■ - ^: '. ■ - -' - ■ -. ■ - BAQ

2098 16/1463

Other suitable ketones include "cyclohexanone, - methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, etc .; Polyketones, like acetony! ketone etc.

Phenols, which according to the invention with the ketones for the formation of Bisphenols can be converted are'alle phenolic compounds unsubstituted with at least one other than the m-position Position. Such phenols have the formula:

in which each R ¹ , which can be the same or different, represents an alkyl radical, such as methyl, ethyl, n-propyl, n-hexyl, etc., preferably an alkyl radical with 1-4 carbon atoms, or a halogen atom, ie chlorine, bromine, Iodine or fluorine, or an alkoxy radical, such as methoxy, ÄtJaoxy, n-propoxy, n-amyloxy, etc., preferably an alkoxy radical with 1-4 carbon atoms, or an aryl radical, such as phenyl etc., or a cycloaliphatic radical, such as cyclohexyl etc. , stands, · η is a number with a value from 0 to 4, with the further restriction that at least one position other than the m-position is unsubstituted.

Suitable phenols include phenol, the cresols, m-ethylpheriol, m-n-propylphenol, m-isoproplyphenol, m-n-butyl ^ henol, m-sec-butylphenol, p-tert. -Butylphenol, o-Methoxyxjhenol, m-Ethoxyphenol, ρ-n-propoxyphenol, m-amyloxyphenol, m-chlorophenol, m-bromophenol, p-chlorophenol, 2,6-dimethylphenol, 2-methyl-6-methoxyphenol, a-methyl-chlorophenol, o-pheny! phenol, p-pheny! phenol, p-cyclohexylphenol, etc.

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- ■ " ¹ V." ■■ ^: - .; "- ^x - ..;" i 5 ^; ^: - ■; ···: ■ 7 -; IBfEOl6

Ion exchange resins suitable according to the invention are solid, insoluble resins of polymeric structures, with chemically bonded, pendant sulfonic acid groups. Bas. Exchanging the potential of the chemically bound suIf orLsäuregruppeirimd the AxLzaiü. this for the Korttakt with "." the. Eeaktianst & ilnehjEern available groups, shows the katalytisciie efficacy of a "besonderen- Ionenaustausciierharzes. ^ Although, therefore, the number of chemically the theoretical to the polymeric basic structure of, .Harzesgebundenen sulfonic acid groups" exchange capacity "determined same, a more accurate Eriterion is the katalytisqhen effectiveness of the The number of suIf; onsäiir groups that are actually available for contact with the respondents. This contact can take place on the inner as well as on the outer surfaces of the ion exchange resin. In general, therefore, a form of ion exchange resin that creates a maximum amount of surface area is particularly suitable, ζ.B. porous likrospheres or pearls. ;

The larger the "Austauscherlapazität ¹¹ of a lonenaustauciGherharzes, ie the greater the number of MilliäijuiTalenten acid per g dry resin is inHso better suited check the resin for the erfindungsgemäflen purposes. Preferred are resins having an" exchange capacity "acid over about 2 ffiilliaiiuiValente" per g dry resin ^{BesondersVgeeignete.} ion exchange resins are _t include: sulfonated S% rol / BiTdnylbenzol-HarzeV ^ Ifonierte, crosslinked styrene resins, j ^ enol / ibrmaldehyd / Sulfoiiaäure-Mar ze, benzene / formaldehyde / sulfonic acid resins, etc. These and other such Resins are commercially available under the following trade names

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available: "Amberlite XE-100" (Rohm and Haas Co.); "Dowex 50-X-4" (Dow Chemical Co. ) ', "Permutit QH" (.Permutit Co.-); and. "Chempro C-20" (Chemical Process Co.) ·

According to the invention, as stated, are particularly preferred those ion exchange resins which are practically anhydrous, i.e. ion exchange resins which are less than about 1% by weight Contain water. Ion exchange resins can be used according to the process U.S. Patent 3,211,061 rendered practically anhydrous will.

Mercaptans which can be used according to the invention are those compounds which are soluble in phenol and contain at least one -SH group. Such mercaptans have the following formula:

H ² SH

ρ
in which ü for a monovalent hydrocarbon radical,

generally having at most 12 carbon atoms, preferably with a maximum of 6 carbon atoms, or hydrogen,

Suitable radicals represented by H are, for example, alkyl radicals,

like methyl, ethyl, n-propyl, η-butyl, n-hexyl, 2-ethyl-n-hexyl, n-octyl, n-dodecyl, etc .; Cycloalkyl radicals, such as Cyclone. ^ 1 uj ".; Alkenyl and cycloallcenyl radicals, such as allja, olyclopentenyl, etc .; alkoxy- and aryloxy-substituted alkyl and cycloalkyl radicals, such as methoxymethyl, ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl ^. 3-ethoxy-2-ethyl-n-hexyl, 2-methoxycyclohexyl, phenoxymethyl, 2-phenoxyethy1, 3-phenoxy-n-propyl, 2-phenoxycyclohexyl etc.; Aralkyl radicals such as benzyl, 2-phenylethyl, 3-phenylethyl, 3-pnenyl-n-propyl, 2-phenyl-n-butyl, 2-phenyl-n-hexyl, etc .;

BATH ORIGINAL 209816/1463

TB18016

Aryl radicals, such as phenyl, Ifeudithyl. etc.; halogenated aryl radicals, such as gGhlor ^ haiiyl, p-bromophenyl, p-fluorophenyl, -p-iodophenyl,. , 2-ChIOi ¹ IIaPiItIIyI, 2-Broniaaplitxiyl, etc .; alkoxy- and aryloxy-substituted aryl radicals, such as p-methoxyphenyl, p-ethoxyphenyl, p-Pro .oxy ^ nenyl, ρ-phenoxy phenyl, etc /; Aikaryl radicals, such as oilethylpheiiyl, p-ltlijrlphexiyl , pn-propylphenyl, δ-n-propylphenyl, ο-n-butylpheny 1, pn-DqdecyI _x heny 1, p- (2 -atlioxy-n-hexy 1) -phenyl, etc. .

Other suitable mercaptans are thioglycolic acid and dithioethane etc.

The realctin, deu phenol and ketone can be achieved over a wide temperature range. Usually \ ith the reaction at temperatures τοη about 50-150 ⁰ C *, preferably between about 50 durchgefSart-HO ⁰ C,.

Theoretically, j mole of ketone reacts with 2 moles of a phenol. In the In practice, however, the mole ratios of those used will vary Reactants from about 3: 1 to about 20: 1 phenol to ketone. Preferably, the reactants are in a molar ratio n; _s from about 4: 1 to about 12: 1 phenol to ketone is used.

The ion exchange resin is used in sufficient quantities for catalysis of the reaction, i.e. usually in an amount of about 0.1-1 equivalent (based on the sulfonic acid groups per mole Acetone is used. Optionally, more than about 1 equivalent can be used can be used, but this is uneconomical.

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The amount of mercaptan used is between about 0.1-5 wt. preferably about 0.01-1 wt% based on the combined Weight of the respondents.

The bisphenol reaction product is conveniently made from the reacted Mixture-by recrystallizing the product with phenol and subsequent mechanical recovery of the bisphenol obtained; the bisphenol can also be used in Example 1 and 2 of the present invention Registration described methods can be obtained.

The reaction according to the invention can be carried out at atmospheric or or under atmospheric pressure.

The following examples illustrate the present invention without restricting it.
example 1

Production of 2> 2-bis- (p-hydroxyphenylj; rpropane (usually referred to as bisphenol A)

125 g of "Dowex 50-X-4" and then a mixture of 470 g (5 mol) of distilled water were placed in a 1-1 flask equipped with a stirrer, thermometer, reflux condenser and Lieiz jacket. Phenol, 29 g (0.5 i,: ol) acetone and 0.5 g. Ethyl mercaptan given. The reactionary mix. was heated to 65 ^° C. and kept at this temperature for 5 hours with stirring. After these 5 hours, the reaction mixture was filtered through a sintered glass funnel, and the ion exchange resin obtained was mixed with 100 g of distilled water for 3 years. Phenol washed. The Mitrat and the washing water became., Combined and concentrated at reduced pressure (5 mm Hg) up to a blow e.nperatur ent of 200 ⁰ C. distilled. The raw product

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is. in 'melted' state-light straw-colored. The yield to Eohproduict corresponded to a conversion of 73.8% on the original acetone and calculated as bisphenol.

Recrystallization aes Hohproduirtes from about three times its weight of toluene gave fine, snow white ürito b, .1Ie, which were free of mercaptan odor, pie crystalline yield from the toluene was about 95 F °> which corresponds to a 75-f "igenumwandlung of the acetone in the 4,4-bisphenol-A-Isümere corresponded to ^ 2,2-bis- (p-hydroxyl) propane /.

Example 2_

By means of a tubular ion exchanger containing 800 g of practically anhydrous, e.g. "Dowex 50-X-4" filled reaction vessel was frozen at a rate of 1.3 lbs based on the weight of the Eealctiona participants. The outflow was distilled ^{to 200 °} C. at 5 mm Hg. The yield of crude bisphenol corresponded to a 100% conversion, based on the acetone and calculated as bisphenol. Recrystallization of the crude bisphenol according to Example 1 gave a fine, snow-white, crystalline bisphenol which is free from mercaptan odor. The crystalline yield from toluene was about $ 94, which corresponds to a 74-70 conversion of the acetone to the 4.4 ^! -Bisj ... henol-A-Iaomere corresponded. ■

Example 5

Example 1 was carried out using different mercaptan concentrations ations repeated. The reaction conditions and results are shown in the table below

BATHROOM ORiGINAL 209016/1463 "

Molar ratio of 76 wt. Ethyl phenol to acetone mercaptan reaction conditions wt .- ^ conversion.

Time, wt. -Fo purity, - wt .- # um-

in bisphenol, esp. based on bisauf acetone »; henol A

convertible in BisiEnol A

10: 1 10: '. 10: '10:' 10: ' 10: '

0.0 5 65 51.8 0.05 5 65 72.8 0.10 • 5 . 65 78.8 0.25 5 65 81, 8 0.50 5 65 ■ 86.0 1.0 5 65 88.6

87
95
© 5
96
96
97

45.1

69.2 74.9 78.5

O O

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This example, carried out according to Example 1, shows 6LIb T / asserers / ^ fin ^ liikeii; of an ion exchange resin at different concentrations of mercaptan.

The results are listed in the following table ".

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Molar ratio wt .- $ water wt .- $ > ethyl wt .-% TJmwändl. "In wt .-% purity, wt .-% conversion in phenol to acetone in the mercaptan bisphenol, based on rel . on bisphenol bisphenol A delivery. ■ Acetone - A

10: 1 Θ , 2 '■■■ 0.0 10: 1 ■■ '■ ο , 7, 0.0 10: 1, 1 , 2 0.0 10: 1 0 , 2 0.1 10: 1 0 , 7 2 0 98 10: 1 _i; 1 , 2 0.1

45.0 21.0 0.0 76.9 7.2.8 51.0

82.0
83.0
0.0
95.0
94.0
91.4

35.5

17.4 0.0 73.1 68.4 46.6

If in Example 1 Vis A instead. "The fol- lowing mercaptans are used VPIi Ätkylinereaptan * so vergleiclibare results erziielti werderj -... Λ ■" .. "'.- - ·

1 - MethylmerGEaptan ■ ".-;" ". -: \

2 - n-propyl mercaptan ■ "-.:.

3 - n-butyl mercaptan. ".- ..; ■;": ". -..." ■■ "■ ■ '·"

4 - n-dodecylraercaptan :: ■ ".—" "'■ ---": ■■ ■ .- !? ■ - Benzyl mercaptan -

6 - diethylethane

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Claims (7)

1 ..- A process for preparing a bisphenol, characterized gexBwa.- characterized in that a phenol with a ketone in Anv / esenheit phenolloslichen a mercaptan and reacting a solid, insoluble Ionenaustauscherahrzes with Anna constricting sulfonic acid groups. 2.- The method according to claim 1, characterized in that as ^ Ketone acetone is used. _ ' 3.- Procedure according to Claim 1 and 2, characterized in that dä £ phenol is used as phenol. 4 · - procedure according to. Claims 1 to 5, characterized in that at that time mercaptan atii / luercaptan is used. b.- The method according to claim 1 to 4, "characterized in that the mercaptan in .Mengen of about 0, -01-b wt .-%, based on the combined weight of phenol and ketone, use ^ will, 6.- Catalyst system, consisting of a solid, insoluble ion exchanger with attached sulfanic acid groups and a phenolic-soluble mercaptan. 7.- Catalyst system according to claim 6, characterized in that the mercaptan is Äthyliäercaptan «, ■ '. . _v The patent attorney BADORiGINAL 20981 6 / U63