DE2064108A1 - Process for the preparation of 4,4 bis phenol A. - Google Patents

Description

2 U 6 4 \ Π 13 dr. 'W. Schalk · Di pl.- ι ng. P. W \ rth · Di pl.-i ng. G. Dam ν ε nberg DIi. V. SCMM I FD-KOWARZI K · DR. P. WE IN HOLD · DR. D. GUDEL

6 FUANKI URT AM MAIfJ

IF. F-SCIIFNtIEIMCK STRAiSC 30 - ',

Uli / i)

li /

Union Carbide Corporation

^ 70 Park Avenue

Now York, Ν.Y. lO'Jl? / UUA

Procedure "λιγ i

The vox'.I. Miserable invention relates to a process for the production of ^ -, ^ '- Bisphcnal-A. ίϊie rel!. ·, in particular; utf a procedure. for the emergent M'OTiJOilöunp: remaining by-products from known bisphenol- ¹ / experienced as iioh ^ atfcrial for the ^, Λ '-Bisphonol-A productionuri; - :.

1-h.in usual process for the production of 'f-jA ¹ -bisphenol-A of the general formula:

W. V- /

b - f5tf..ht ui π ': - r iM.setzun, "from Acj.-jtr.n r-iit rhanol in eincim MoI-V obtained L ^r ; ν ca 1: 2.

in eli ι or '. <: · Ν- 1 rt 'irre u Vi-Ti'.v.hr'-ri ', ■ rfu.-n otvi-a οί. · .. · _Λ ) ₍ , des Vürbrauciiten KoIimati-r i-'tlri in dar., "ewiin.schU;'ί -, ^ ΐ- ¹ -i'J.'. phoiioi-A UTi; <; fiv / Hndalt, Häbrend V / ,. <in air; lüifj .- '. r : t,; ir; 'J 7 Tt ^ i'; ibfudf: iit! v..ri.jrodukl ".ti, ν.'ΐ, π 2, ¹ P -lJit; pruTioL-A-ir.ot '] erf ;, TrJ.r; phf; i! ol ·.:, iiocüi rfiolf: l; nl.cirti Pc-l./ -h-Tioltj und- uirjri in - VorbJndun; ', en ut.i, "; (H ..- üi-flfiLt ι. "Rriifj. Vorhr-rrr ^ -iK.-nd im tot- γΓιμκρ.π r.-t.-rji-npiv-diiktffi ir; I. dan

10982 7/1985

BATH ORIGINAL

2,4'-bisphenol isomers from i'Ormel:

CH ₃

W 'w

which can be responsible for a loss of raw material up to 11? a. Heretofore, these by-products have been discarded as unusable impurities without any value as a raw material or a product. Hence was. a key goal in reducing the cost of known processes for the production of bisphenol the reuse of the. Byproducts.

The cleavage of dihydric more nuclear phenol to form the corresponding one monovalent alkenylphenol by heating the divalent polynuclear Phenol in contact with an alkaline catalyst is described in U.S. Patent 3,281,4-8. This "reaction can be caused by the the following equation can be represented:

More alkaline

K ata Iy s at or u " // ~~~ Y,

Rl ^ R2

10 9 8 2 7/1985

BAD OR (GfN _AL

in which R, R * and R ', which can be identical or different, stand for hydrogen or alkyl, and when they mean allyl, usually contain 1-4, preferably 1-2 carbon atoms, such as HeUq ^1- I, ethyl, n -Propyl _r isopropyl, η-butyl, etc .; and each hydroxyl group is in a position other than the m-position with respect to the group linking the aromatic groups.

However, the reference in the above patent that the products of cleavage are phenol and the corresponding monohydric alkenylphenol does not take into account what the product would be if the dihydric polynuclear phenol is an isomer such as 2,4'-bisphenol-A , is. Indeed, from the known data on substituted phenols, such as p-isopropenylphenol and. o-Isopropenylphenol, it is to be expected that the more stable o-monohydric alkenylphenol or a mixture of the o- and p-monohydric alkenylphenols is formed in the cleavage of a 2,4'-different polynuclear phenol.

Invention device has now been found that 2,4'-bisphenol-A in valuable, reusable cleavage prodxicts, namely phenol and p-isopropenylphenol, can be converted by adding 2,4'-bisphenol-A to a base catalyzed Subjects to split.

It has also been found that 4,4'-bisphenol-A is derived from 2,4'-bisphenol-A, Obtain bisphenol tar containing trisphenol and polyphenol compounds can by putting these compounds in the tar in the presence of a basic Catalyst for the formation of p-isopropenylphenol and phenol cleaves, the cleaved products p-isopropenylphenol and phenol are distilled and the cleaved products again in the presence of a stoichiometric Excess phenol and an acidic catalyst combined.

109827/1985

BATH ORIGINAL

The line of the 2, V-bisphenol-A-isoraeren in p-isopropeny! Phenol and Phenol can be represented by the following reaction equation:

Ü, 3 ? ~~ \ alkaline o— *, “2

-C - / Sv-. Catalyst ν Hü- / ⁷ WG

- '. CH

^J OH

The cleavage of polyphenols, in particular 2,4'-bisphenol-A and trisphenol, takes place at sufficient temperature and pressure to allow the alkenyl phenol to distill over. Usually the 2,4'-bisphenol-A is applied at a pressure of about 5-100 mm Hg, preferably about 5-30 mm Hg ₈ to a temperature of about 100-300 ° C., preferably about 150-25O ⁰ G., heated.

As mentioned, the polyphenol is broken down by contact with one basic catalyst. Any basic catalyst that can theoretically react with bisphenols to form a phenoxide ion is suitable »

Such suitable basic catalysts are compounds that are in admixture give with water / water an aqueous medium with a pH above 7, e.g. Compounds of alkali metals such as lithium, sodium-potassium, rubidium and cesium, and compounds of the alkaline earth metals such as calcium, strontium and barium ·. Notable compounds are the alkali metal oxides, such as Lithium oxide, sodium oxide, potassium oxide, etc., the alkali metal hydroxides, such as Lithium hydroxide, sodium hydroxide, potassium hydroxide, etc .; the alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carboat, etc .; Alkali Potash around ph en at, metal phenoxides, such as lithium phenate, sodium phsnate, / as well as the alkali metal salts dihydric, more pithy phenols; the alkaline earth metal oxides, such as Calcium oxide, strontium oxide, barium oxide, etc .; the Erdälkaliracta-Hhyd.roxydc,

BAD ORIGINAL 109 8 27/198 5

such as calcium hydroxide, stroritrium hydroxide, barium hydroxide, etc .; the ardalkali metal carbonates, such as calcium carbonate, strontrium carbonate, barium carbonate etc.; the alkaline earth metal phenoxides, such as calcium phenate, stront triumphenate, Barium minate etc .; as well as the alkaline earth metal salts of divalent, polynuclear phenols,

The basic catalysts are more catalytic! Quantities used, i.e.

in amounts sufficient to accelerate the splitting of the polyphenols.

Usually an amount of about 0.5-10, preferably about 0.5-2 wt. / J,

based on the polyphenols. If necessary, the extraction %

of p-isopropenylphenol and phenol from the treated bisphenol tar can also advantageously be carried out by fractional distillation and recovery of the p-isopropenylphenol and phenol fractions.

Then the fraction is at room temperature, ie about 23 ° C. cooled to deliver the crystalline products. The cleavage products of p-isopropenylphenol and phenol can also under reduced pressure from the tar at 50-30O ⁰ C, preferably 50-200 C, is distilled off. This process is expediently used if subsequently from the cleavage products ^, k ¹ -Bisphenol-

A is to be produced. ■ "

The reaction of the cleavage products to form the desired 4, ^ ¹ -bisphenol-A proceeds as follows:

OH OH .

l | ⁺ C Β ^H s ^ÜH - f \ - c -ξ% - ° ¹¹

ClL,

10 9827/1985

. BATH ORIGINAL

This reaction takes place in a medium with a pH value below about 2, preferably less than 1.5 x Any acid or mixture thereof ending in "in the Reaction mixture causing a pH below about 2 can interact with the reactants be mixed. The mineral acids such as hydrochloric acid, phosphoric acid, sulfuric acid, etc. are particularly preferred for this purpose. Other suitable acids include hydrobromic acid, p-toluenesulfonic acid etc.

An excess amount of phenol should preferably be present in reaction system I. Thus, more phenol is usually added to the distillate cleavage products in order to achieve a molar ratio of about 2: 1 to about 20: 1, preferably about 5 ^; lf phenol to give p-isopropenylphenol.

The temperature for. Carrying out the new combination is usually about 25-? 5 ° Go, preferably about * K) ~ 60 ^o C.

p-Isopropenylphenol is a major source of the off-color components «in Bisphenol A products. In the presence of air it becomes p-isopropenylphenol easily oxidized to a peroxide, which in turn forms colored polymeric compounds continue to react. The formation of these color bodies can be caused by a nitrogen blanket over the sensitive areas in the process be reduced.

The following examples illustrate the present invention without to limit themο

BATH ORIGINAL

1098 27/1 985

Example 1

Fission and Fractional Dest- '. Tion

A melt of 4000 g bottled mother liquor with a content of 4,4'-bisphenol-A of 529 g (2.32 $>) was NaI) H mixed and heated at 55 mm Hg to 220 ⁰ g ₀ g 2.0 , whereby at the same time first phenol at 50-60 ° C. / 5 mm Hg and then a mixture of phenol and (dimeric) p-isopropylene phenol at 110 ° G. / 5 ecm Hg distilled over a small fractionation column. 3882 g of a yellowish distillate contained 252 g (1.88 hol) p-isopropenylphenol, 48.50 g (0.18 mol) dimeric p-isopropenylphenol, 42.60 g (0.126 mol) unreacted 4,4 bisphenol A and some impurities. The total phenol yield was 3550 g (112 f *), the p-isopropenylphenol yield 300.5 g (2.24 mol or 105: «) and 88 g tar residue. ■. '

Example 2

Another combination

A 2,000 cc three-necked flask with a thermometer, water-cooled A condenser and stirrer was provided which was driven by a variable speed motor. The flask was placed in a water bath of

55 C. - then 1000 g of a phenol solution containing 7j5 # p-isopropenylphenol from the base-catalyzed cleavage reaction of Example 1 were added. Than the solution 55 ° C. 100 grams of "Dowex" ion exchange resin catalyst was added. The stirring was interrupted at certain intervals and a sample was taken from the reaction mixture for VPC analysis. The first sample taken after 20 minutes showed the complete disappearance of monomeric! p-isopropenylphenol.

109827/198 5.

BATH

206A108

After a reaction time of 2 hours, the reaction mixture was filtered to separate off the catalyst and the phenol was distilled to determine the total amount of higher molecular weight material. The yield was 130 g (125 g of 4,4-bisphenol-A), which is about a Unnvandlung of 98 ^ ^1, based on p-Isopropenj ^ lphenol corresponded. At 55 ° G. almost no 2, ^ + '- bisphenol-A was formed <■

BATH ORIGINAL

109827/198 5

Claims (1)

Claims / 1 · / Process for the preparation of phenol and p-isopropenylphenol from Z, k ^l - bisphenol-A, characterized in that the 2,4'-bisphenol-A is treated with a catalytic amount of a basic catalyst at a temperature between lüO- 300 C, and a pressure of 5-100 mm Hg. 2o- method according to claim 1, characterized in that da / 3 is more basic Catalyst uses a basic compound of alkali or alkaline earth metals will. · 3.- The method according to claim 2, characterized in that as ÄLkalischer j Sodium hydroxide catalyst is used. 4. - Process according to claim 1 to 3i, characterized in that 2, ^ t- ^1- bisphenol-A with the alkaline catalyst at a temperature of 150-25) ° G. and a pressure of 5-30 mm Hg. 5.- A process for the preparation of ¹ I-, 4 '-bisphenol-A from tars containing 2, Ψ-bisphenol-A, trisphenols and Rüyphenols, characterized in that the bisphenol and polyphenol compounds in the presence of a catalytic one Amount of a basic catalyst to obtain cleaved p-isoproponylphenol and phenol products cleaves, the cleaved λ products are distilled and the cleaved products are combined again in the presence of a stoichiometric excess of phenol and an acid catalyst. 6.- The method according to claim 5, characterized in that daJ3 is more basic Catalyst a basic compound of alkali or alkaline earth metals, preferably sodium hydroxide is used. 10982 7/1985 BAD ORiGINAL 7. Method according to Claims 5 and 6, characterized in that the polyphenonic compounds in p-isopropenylphenol and phenol at temperatures from 100-r300 ° C. and a pressure of about 5-100 mm Hg. 8. Process according to claim 7, characterized in that the polyphenol compounds are split into p-isopropenylphenol and phenol at a temperature of 150-250 ° C. and a pressure of 5-30 mm Hg. 9 · - Method according to claim 5 to 8, characterized in that the cleaved products at a temperature of 50-210 G. under reduced B pressure to be distilled. 10.- The method according to claim 5 to 9, characterized in that as Acid catalyst a mineral acid is used. • 11.- The method according to claim 5 to 10, characterized in that the recombine at a temperature of ^ 0-60 ° C. is carried out. The patent attorney: BAD ORiGiNAL 109827/1985