DE1197469B - Process for the production of polynuclear polyphenols - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY Int. Cl .:

C07c

GERMAN

PATENT OFFICE

EDITORIAL

German class: 12q-16

Number:
File number:
Registration date:
Display day:

1197469
F37839IVb / 12q
September 19, 1962
July 29, 1965

It is known that 4,4'-dihydroxydiphenylalkanes when heated in the presence of acidic or alkaline catalysts in the corresponding Can split p-vinylphenols and phenols. However, this split is reversible because it is on the other hand also known that under the same conditions from p-vinylphenols and phenols di- or polyhydroxydiarylalkanes develop.

Both implementations can be used technically if certain conditions are met, in the first one Case for the production of p-vinylphenols, in the second case for the production of di- or polyhydroxydiarylalkanes or polynuclear polyphenols. This is because 4,4'-dihydroxydiphenylalkanes are heated in the presence of the catalysts mentioned under reduced pressure, the cleavage products succeed immediately to be removed from the reaction mixture after their formation. The distillate is then slightly in Separate phenol and p-vinylphenol. On the other hand, by heating p-vinylphenols with Phenols in the presence of the catalysts mentioned give the corresponding di- or polyhydroxydiphenylalkanes or polynuclear polyphenols, especially if you use the phenols in excess applies.

It has now been found that the reversible cleavage of 4,4'-DihydroxydiphenylaIkanen in the presence of acidic or alkaline catalysts can advantageously also be used to prepare polynuclear polyphenols directly from these alkane derivatives, namely by converting the 4,4'-Dihydroxydiphenylalkane in Presence of acidic or alkaline catalysts to temperatures between about 100 and 250 ⁰ C under reduced pressure, preferably between about 5 and 50 Torr, heated with exclusion of oxygen and the resulting vapors fractionated in such a way that the phenol escapes, the p-vinylphenol on the other hand in the reaction vessel runs back. The amount of p-vinylphenol equivalent to the phenol split off and distilled off is combined with the 4,4'-dihydroxydiphenylane still present in the reaction mixture to form a trinuclear triphenol of the general formula Process for the preparation of polynuclear
Polyphenols

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Heinrich Krimm, Krefeld-Bockum;

Dr. Hermann Schnell, Krefeld-Uerdingen

in which Ri and R _{2 represent} a hydrogen atom or an alkyl radical to.

Since the immediately resulting reaction mixture, however, is usually a resin from which one by recrystallization or fractional distillation of this trinuclear triphenol only in more. or less large amounts - depending on whether you previously split off a relatively large or small amount of phenol and has distilled off ■ - can separate, but the remainder of the reaction mixture from higher There are boiling or no longer distillable products that have not yet been obtained in crystallized form could be assumed that the reaction released p-vinylphenol with the reaction mixture Phenols present in some cases go further with the formation of mixtures approximately as follows polynuclear polyphenols:

HO

509 628/389

and possibly even higher polyphenols. In the formulas, Ri and Ra have the above meanings.

The trinuclear triphenol of the formula I, but optionally also the resinous mixtures of different polynuclear polyphenols have z. B. as stabilizers, anti-aging agents and intermediates for the production of plastics technical value.

4.4'-DihydroxydiphenyIalkane, which are suitable for the present process, are, for. B. 1.1- (4,4'-Dihydroxydiphenyl) ethane, 1,1 - (4,4'-dihydroxydiphenyl) propane. 2.2- (4,4'-dihydroxydiphenyl) propane. 1,1 - (4,4'-dihydroxydiphenyl) butane, 2,2- (4,4'-dihydroxydiphenyl) butane, 2,2- (4,4'-dihydroxydiphenyl) -3-methyl-butane, 1,1- (4,4'-dihydroxydiphenyl) -2-methyl-propane, 2,2- (4,4'-dihydroxydiphenyl) pentane, 3,3- (4,4'-dihydroxydiphenyl) pentane, 2.2- (4,4'-dihydroxydiphenyl) -4-methylpentane . 4.4- (4.4'-dihydroxy-diphenyl) -heptane. 1,1.1- (4,4'-dihydroxytriphenyl) ethane and 2,2- (4,4'-dihydroxy-3,3'-dimethyl-diphenyl) propane and mixtures of these alkanes.

As acidic catalysts, for. B. benzenesulfonic acids. p-toluenesulfonic acids, the so-called Lewis acids, such as magnesium chloride, zinc chloride. Boron fluoride, boron fluoride etherate, boron fluoride acetic acid. Aluminum chloride, Ferric chloride and tin tetrachloride are used. Cation exchange resins are also used Suitable catalysts of the sulfonated polystyrene type.

As alkaline catalysts, for. B. Alkalibzw. Alkaline earth metals, oxides, hydroxides. -alcoholates, phenates, alkyl carboxylates, carbonates, amides and hydrides are used.

The amount of the acidic or basic catalysts is preferably about 0.001 to about 20 percent by weight. When using small amounts of the catalyst it is sometimes necessary that After the phenol has been distilled off, the reaction mixture continues to reach reaction temperature for some time keep to the reaction of p-vinylphenol with unreacted 4,4'-dihydroxydiphenylalkane or to be completed with polyphenols that have already formed.

The following examples illustrate the process of the invention.

example 1

456 g (2 mol) of molten 2,2-bis- (4-hydroxyphenyl) -propane are mixed with 4 g of powdered sodium hydroxide and heated to 175 ° C / 20 Torr while passing nitrogen over it, while at the same time phenol at 85 ° via a small Vigreux-Koionne up to 90 ⁰ C distilled off. If 94 g (1 mol) of phenol have been distilled off, the heating of the reaction mixture is continued for a further ¹ hour at atmospheric pressure. The reaction product is dissolved in ethylene chloride and shaken out with 50 ecm 2 η-hydrochloric acid and then with water until the reaction is neutral. After distilling off the solvent and a small amount (7 g) of phenol, 345 g of a yellowish hard resin with a hydroxyl number of 460 (calculated 464) are obtained at temperatures up to 200 ° C./20 Torr.

A 100 g sample of the resin is dissolved in toluene. 28 g of 2,4-bis (4-hydroxycumyl) phenol gradually separate in hard crystals from a melting point of 191 to 192 ° C.

If another 100 g sample of this resin is heated in a high vacuum, it is obtained at 170 ° C./0.1 Torr first a first run of 28 g of unreacted 2,2-bis (4-hydroxyphenyl) propane. From then The following fraction passing over at 230 to 255 ° C./0.1 torr becomes 28 g after trituration with toluene 2,4-Bis- (4-hydroxycumyl) -phenol is obtained, the melting point of which after recrystallization from methanol-water 191 to 192 ° C. Another fraction passing over at 260 to 280 ° C./0.1 Torr (20 g) cannot be made to crystallize. The distillation residue consists of a hard resin.

Example 2

484 g (2 moles) of molten 2,2-bis (4-hydroxyphenyl) butane are mixed with 5.6 g of potassium hydroxide and heated under a stream of nitrogen at 165 ⁰ C / 20 torr while simultaneously over a small Vigreux-Koionne 94 g (1 mol) of phenol are distilled off. The reaction mixture is kept at this temperature for a further 2 hours at normal pressure, the reaction product is then dissolved in methylene chloride, shaken neutral with 2η hydrochloric acid and water and the solution is evaporated, finally at 200 ° C./20 Torr.

A pale hard resin with a hydroxyl number of 425 (calculated 430) is obtained.

Example 3

673 g of molten 2,2-bis- (4-hydroxyphenyl) -propane are mixed with 13.6 g of the sodium salt of 2,2-bis- (4-hydroxyphenyl) -propane (corresponding to a total of 3 moles of bisphenol) and the mixture obtained under a pressure of 16 Torr ^{heated to 175 0} C, while at the same time 188 g (2 mol) of phenol are distilled off via a column. ^{The reaction mixture is then kept at 160 °} C. for a further 2 hours, the reaction product is then dissolved in methylene chloride, neutralized with dilute hydrochloric acid and washed with water. After the solvent has been distilled off, at the end in vacuo at 200 ^° C., 485 g of a light-colored resin with a hydroxyl number of 445 (calculated 452) are obtained.

Example 4
65

In 456 g (2 mol) of molten 2,2-bis- (4-hydroxyphenyl) -propane become 1 ecm in the course of one hour ^{at 145 to 155 0 C and a pressure of 100 torr}

Boron trifluoride etherate was added dropwise, while at the same time 94 g (1 mol) of phenol were distilled off. The reaction product is kept still for 1 hour at 120 ° C and then at a pressure of 16 Torr% hour at 200 ⁰ C heated, distilling another 47 grams of phenol while from. 315 g of a yellowish resin with a hydroxyl number of 438 (calculated 444) are obtained.

Claims (1)

Claim: Process for the preparation of polynuclear polyphenols, characterized in that 4,4'-dihydroxydiphenylalkanes are used in the presence of acidic or alkaline catalysts at temperatures between about 100 and 250 ^° C. under reduced pressure, preferably between about 5 and 50 Torr, with the exclusion of oxygen heated and the resulting vapors fractionated in such a way that the phenol escapes while the p-vinylphenol runs back into the reaction vessel. Considered publications: German Patent No. 544 801;
German Auslegeschrift No. 1 094 759;
published documents of Belgian patent No. 611 184. 509 628/389 7.65 @ Bundesdruckerei Berlin