CS250861B1 - Method of arylalkylation of phenol and/or alkylphenol - Google Patents

Description

(54) Method of arylalkylation of phenal and / or alkylphenol

2

Phenol (C 1 to C 6 alkylphenol) is arylalkylated in the liquid or vapor phase under the catalytic action of bronsted or lewisic acid, eventually the phenolate h of Unika, but mainly on a heterogeneously scrubbed catalyst (HsPOi supported, cation exchangers in H-form). zeolites) at 70 to 2-3 ° C (120 to 180 ^° C). The arylalkylating agent is at least one of: methylphenylcarbinol, dimethylphenyicarbinol, methylphenylcarboline with 2-95% styrene, dimer α-methylstyrene, dimer α-imethylsyrene with 2-95% α-methylstyrene, dimethylphenyicarbinol with 2-methylphenyicarbinol with 2-95% styrene . Mainly used are components from the distillation residues from the production of phenol and acetone by catalytic sludge to unhydrin peroxide (methylphenylcarbinol, dimethylphenylcarbinol). The reaction water is removed from the arylalkylation environment.

It is used in the chemical industry.

The invention relates to the arylalkylation of phenol and / or alkylphenol by non-traditional alkylating agents based on by-products from petrochemical production of certain oxygenated organic substances.

Arylalkylphenols are known antioxidants for fuels, oils and polymers, but also as intermediates for even more potent stabilizers, as well as intermediates in the production of epoxy resin accelerators, polyvinyl chloride stabilizers, herbicides, insecticides and fungicides. Recently, they are also appreciated. high disinfection, resp. bactericidal and antifungal action.

Some of them, such as the cumylphenols are isolated from tev. phenolic pitch by fractional distillation (US Pat. No. 2,769,844, Romanian Pat. No. 57169 and V. Brit. Pat. No. 1,235,415) or by crystallization with the interaction of n-pentane or n-heptane (Dutch Pat. 722 524, CA 68, P 95512 j, Czech author's certificate No. 195 234J.

Known is [Gajibalaev A. A.. and others: Izv. higher. textbooks. introduce, chim. 'Technol. no. 14 (3j, 472 (1971); Kaminsky A., et al., Neftechimija 10, 559 (1970); Kurashev, V., et al., Neftechimija 17, 507 (1977); Polish Patent No. 100,643 ] arylalkylation of phenol and alkylphenol with α-methylstyrene under the catalytic action of both trihydrogenphosphoric acid and zeolites, as well as arylalkylation of phenol with styrene under the catalytic action of both Lewis and Brnstedsted acids [U.S. Pat. No. 2,247,402; , 428 (1969); Pauškin, J. M. et al., Nephtechimija 9, 842 (1969); Lukasik et al., Przem. Chemicz., 56, 530 (1977)].

A disadvantage is the need for a technological degree of dehydrogenation of ethylbenzene, respectively. dehydration of methylphenylcarbinol to styrene or dimethylphenylcarbinol to α-methylstyrate, as well as thermal energy consumption for these endothermic reactions.

Also known is the alkylation of phenol as well as alkylphenols not only with olefins but also with aliphatic alcohols (U.S. Patent No. 203,60 · 7), such as alkenyl and allyl allyl alcohol (Niederl. B. et al., Am. Chem.). Soc., 53, 3,390 (1981), Shujkin NI and others: Izv AN AN USSR otd.chim · nauk 1961, 1 094, Isafuljanc VI and others: Zh.Chim 23, 1964 (1963) ), however, there is a lack of data on the arylalkylation of phenol and alkylphenols with aromatic alcohols.

According to the present invention, a process for arylakylating phenol and / or alkylphenol with a number of C-atoms in the alkyl of 1 to 8, in liquid and / or vapor phase at 70 to 260 ° C under the catalytic effect of at least one Brdsted and / or Lewis acid or the aluminum compound, in liquid and / or solid form, as a rule, with recirculation of the unconverted feedstock, such that the phenol and / or alkylphenol is at least arylalkylated at least 120 DEG C. and 240 DEG C. on the heterogeneous catalyst immediately and / or one of a group of reagents:

methylphenylcarbinol, dimethylphenylcarbinol, methylphenylllcarbinol with 2-95% styrene, α-methylstyrene dimer, α-methylstyrene dimer having 2-95% α-methylistyrene, dimethylphenyllcarbinol with 2-95% α-methylstyrene.

The advantage of the method according to the invention is the low energy consumption and the energy consumption. rational use of ary laymen of fasting heat. The method makes it possible to utilize mixtures of alkylating agents and other organic components and to utilize complexly for the production of arylalkylphenols of the components of the distillation residue from phenol and acetone production by catalytic decomposition of cumene hydroperoxide. Finally, the advantage is also the high selectivity of phenol arylalkylation, the low formation of arc-ethers and, last but not least, the fact that the process allows practically waste-free production of aryl alkylphenols.

As the arylalkylation catalysts, the alkylation catalysts known (cf. Aut. Certificate No. 202,607) may be used. However, sulfuric acid, hydrophosphoric acid, polyphosphoric acids, in particular heterogeneous catalysts, are among the most prominent. These include sulfonated macromolecular substances (especially cation exchangers in the II-form), phosphorus oxides, trihydroxyphosphoric acid and lyphosphoric acids on active clay supports, strong alkyl synthetic and natural zeolites. These can. dispersed in a phenolic arylalkylation environment, in a single bed.

The latter variant is more preferred because it provides an arylalkylate which does not need to be deprived of the catalyst. In addition to the latter variant, it is possible to work with the short-circuited catalyst, whereby the effect of the reaction water is also less

If it is necessary to produce arylalkylphenols by a higher proportion of arylalkylation of phenol in the 2-position, a suitable catalyst is also aluminum, respectively. a phenolate or aluminum alkylphenolate which is rapidly formed from a phenol such as α] alkylphenol and aluminum.

Suitable arylalkylating agents are methylphenylcarbinol, e.g. formed as a by-product in the production of methyloxirane by epoxidation of propylene with ethyrbenzene hydroperoxide -ap. Thereafter, the nonylphenylcarbinol with styrene, which can be derived as unconverted feed from phenol arylalkyllate, respectively. alkylphenol or as a by-product from the dehydration of methylphenylcarbinol to styrene and the like.

The α-methylistyrene dimers may be derived from the reaction product of propane epoxidation with cationic hydroperoxide similar to α-methylstyrene and dimethylphenylcarbinol, but mainly from the distillation residues of phenol and acetone production, the so-called. .cumen isposobom.

The manner of arylalkylation carried out

750561 o-ntinualia, semi-ontinuously, but also intermittently. However, care should be taken to remove the reaction or feed water from the arylalkylation environment as it retards the arylalkylation and may also poison the catalyst.

Unconverted arylalkylating reagents as well as phenol and -alkylphenols generally recirculate.

Further details of the process as well as other advantages are apparent from the examples.

Example 1

Fraction I is distilled off from fresh phenolic pitch at a boiling point of 27-16 ° C (2.67 kPa) and, taking into account the amount of α-methylstyrene present and dimethylenenyl carbinol, additional phenol is added to the phenol present. so that the raw material obtained has the following composition (in% by weight):

0,7 α-methylstyrene,

36.9 acetophene,

22,4 dicetylphenylcarbinol,

20.9 phenol a

2,6 cumylphenol.

This raw material is in addition to the continuously-working arylalkylation of phenol. After pre-heating, it is fed to a reactor containing 100 cm ^{3 of a} phosphate-catalysed catalyst for ortho-lithium in the form of spheres with a diameter of 5 mimes, containing 22.6 percent by weight of phosphorus and having a value of 298 mi. KOH / g. The reaction mixture starting from the arylalkylation reactor with the phosphate catalyst added is cooled, weighed and analyzed. Hmotncstný spraying a raw material for the f · osιf hours · ¹ · Hand AYOVI catalyst-is 0.3 g <om ³ h ^_ i. The results obtained for the composition of the crude arylalkylate, the conversion of the dimethylphenylaluminum and phenol as well as their selectivity to the methylphenols are shown in Table 1.

Conversion and α-methylstyrene are not envisaged in the calculation for practical reasons, since in the crude arylalkylate its concentration is higher than in the raw material. This is understandable because probably - at least a substantial portion of the dimethylphenylcarbinol arylalkylates the phenol via the intermediate formation of α-methylstyrene.

Oumyleenol [a mixture of 1-cumylphenol, respectively, was isolated from the arylalkylate in 95% yield. 4- (α, α-dimethylbenzyl) phenol -s-2-methylphenol, respectively. 2- (α, α-idimethylbenzyl) phenol as such or in the form of sodium cumyllenolate by treatment with an aqueous solution of 10% by weight aqueous hydroxide, filtering, washing and drying sodium cumyl phenolate.

Table 1

Temperature Analysis of crude arylalkylate (% w / w) Conversion {%] Selectivity to cumylphenols arylalky- (%) tert-matyl-acetophenone drmethylphenylphenol cumylphenols dimethylphenylphenol dimethylphenylphenol (° C) styrene i-arbinol carbinol carbinol carbinol lo o ”o” I drill co O ¹

T-1

CD СО СП CD co co co co co co oo

VF CD 00 co

CD co t t <co CD CD CD CD CD rH CM ~ Vt ^ ID VtT r-T r-Γ vF

O t \ Ln O OJ CD CM г t — I CM

Example 2

From the phenolic pitch obtained as a distillation residue from the production of the pool and acetone by the catalytic decomposition of quinine hydroperoxide, the first fraction is distilled off in the boiling range 30 to 160 ° C / 2.67 kPa and has the following composition (in wt.

α-imethylstyrene = 1, acetophenone = 35, dimethylphenylcarbolol = 23, phenol-19, α-methylstyrene dimers = 8, β-methylphenols = 2.

This fraction I is further hydrogenated in the liquid phase at a hydrogen pressure of 10 to 13 MPa and temperatures of 100, 110 and 150 ° C for 4 h using 10% by weight (calculated on the whole batch of the 1st fraction) of copper-chromium-barium a catalyst (Adkins catalyst). The results obtained are summarized in Table 2.

The hydrogenate obtained by hydrogenation at an average temperature of 100 ° C is then fed to the phosphate catalyst specified in Example 1, wherein the temperature of the arylalkylation phosphate catalyst reactor is 16Ό + 5 ° C. The hydrogenate is fed to the catalyst in a nitrogen stream of 13 cm ³ . . cm ^-3 . ^h1 with hydrogenated feed in an amount of 0.3 g. om ³ . h ¹ . After cooling the crude product coming out of the arylalkylarium reactor, this was analyzed. It Includes:

7.0% by weight of α-methylstyrene,

0.2% by weight of dimethylphenylcarbinol,

0,1% by weight, methylphenylcarbinol,

0.5% by weight of acetophenone,

17.9 wt. cumylphenol (a mixture of 4-cumylphenol with 2- (cumylphenol), 23.0% by weight, a mixture of 1-phenoxy-1-phenylethane with .2-phenoxy-2-phenylprapanoim; and

22.1% by weight of a mixture of 1-phenyl-1- (4-hydroxyphemyl) ethane with 1-phenyl-1- (2-hydroxyphenyl) ethane.

The individual products are isolated by distillation under reduced pressure and extra crystalline crystallization at 0 ° C.

Table 2

Temperature Hydrotrogenic composition

hydrogenation (° C) α-methyls maltreated acetophenone dimetylfenyllkarfenyl'karblinol methylphenylcarbinol phenol to-mylfenol version of acetphenone (%) vita to methyl-Ifenylcarbimol 100 0.5 0.3 20.6 25.2 '25, 6 1.5 99.4 72.3 110 0.4 i0, l 19.9 33.6 14.2 3.7 99.7 96.3 150 0.4 0.4 22.9 27.2 16.5 2.3 98.9 78.6 '

Example 3

The phenol pitch was distilled off at a boiling point of 29.5-100 ° C / 2.67 kPa in an amount of 28.5% by weight, to the weight of the phenolic pitch used for distillation under reduced pressure. The fraction I obtained contains the most important constituents (in% by weight): α-methylstyrene ~ 0.5, acetophenone = 36.8, dimethylphenylcarbimoil = 21.5, phenol = 16.7, α-methylstyrene dimers = 6, 8, cumylphenol = 2.4.

Then, II. Fraction at heat 160 to 215 ° C / 2.67 k ^! Pa in an amount of 46% by weight, calculated on the phenolic pitch feed. This fraction contains the following most important components (in% by weight):

α-methylstyrene = 0.2, acetophenone = 0.9, idimotylphenylcarbinol = 0.3, phenol = 0.2, α-methylstyrene dimers = 28.0 and cumylphenols - 33.2.

Next, 8.6 percent by weight of phenol was added to fraction I, and then the phosphorus catalyst specified in Example 1 was fed. The fraction of the fraction was 0.3 g. cm ~ ³ . h ^-1 in a nitrogen stream of 13 cm ³ . .cm · ' ³ . h ^_1 . The arylalkylation is carried out at a temperature of 158 + 5 ° C. The crude arylalkylate obtained has the following composition (in% by weight):

α-imethylstyrene = 2.9, acetophenone = 30.0, dimethylphenylcarbinol = 0.1, phenol ~ 10.0, α-methylstyrene dimers = 2.1 and cumylphenol = 15.6.

The crude arylalkylate is further rectified under reduced pressure (2.67 kPa). A fraction having a boiling point of 35 to 155 ° C / 2.67 kPa is collected with the following composition (in% by weight):

0 8 6 1

5.7 α-methylstyrene,

54,4 acetophenone,

0,1 dimethylphenylcarbinol,

19.0 phenol, α-methylstyrene dimer and cumylphenol.

From fraction o t. in. 155 to 215 ° C / 2.67 kPa, the cumylphenols or. with aqueous sodium hydroxide solution at conc. 12% by weight yielded sodium kiirnyllenolate, which was filtered off, washed on the filter with cold primary gasoline and dried.

A boiling point of 35 to 155 ° C / 2.67 kPa after addition of 9% by weight of phenol is passed in a stream of hydrogen (1: 5 molar ratio of acetophenone to hydrogen) to a copper-sized, cylindrical, hydrotreated catalyst of dimensions :

mm X 4 mm (copper oxide on silica gel with a bulk density of 1 080 kg. dm ^-3 , CuO content - 64,5% by weight, • diatomaceous earth = 34,5% by weight, R2O3 0,4% by weight, at 180 ° C weather for 6 h.

The fraction of the fraction (scrubbing the catalyst) is 0.3 g. cm ³ . h_1 and hydrogenation temperature 120 ° C. The hydrogenate obtained has the following composition (in% by weight):

α-methylstyrene = 0.2, acetophenone = 9.6, dimethylphenylcarbinol = 0.1, phenol = 39.4, α-methylstyrene dimers <0.1, cumylphenol <0.1 and methylphenylcarbinol = 33.3.

Acetophenone conversion reached 78.1% and selectivity to methylphenylcarbine 95.5%.

The hydrogenate obtained is further passed to the arylalkylation carried out on the phosphate catalyst specified in Example 1. The feed of the hydrogenate on the arylalkylation catalyst is 0.3 g. cm-3. h ¹ and arylalkylation temperature 155 + 5 ° C. The crude obtained, excluding water, contains:

0.2 wt. a-methylstyrene,

10.3% by weight, acetophenone, methylphenylcarbilbinol <0.05% by weight, phenol 22.5% by weight, and a mixture of 1'-phenol-4-yl-L- (4-hydroxyphenyl) ethane and Isodium- % (2-hydroxyphenyl) ethane is 25.8 wt.

The 1-phenyl-1- (hydroxyphenyl) ethane mixture is isolated from the arylalkylate by vacuum distillation or rectification.

Example 4

The phenolic pitch distilled II. a fraction having a boiling point of 160 to 215 ° 0 / 2.67 kPa in an amount of 46% by weight, calculated on the phenolic pitch feedstock, characterized in [Example 3], is used for the isolation of cumylphenol either by rectification, extractive crystallization or via intermediate formation of sodium kurnyl phenolates, the remainder (possibly also after separation of the extractant or water) after addition of phenol in an amount of 43% by weight, calculated on the remainder, is carried out on the arylalkylate.

In the case of arylalkylation on a phosphate catalyst specified in Example 1, at a temperature of 165 + 5 ° C and a feed rate of 0.3 g · cm 3 · 3.h1, a crude alkylate of this is obtained. composition (in% by weight):

α-methylstyrene - 0.2, acetophenone = 0.4, dimethylphenylcarbinol <0.05, phenol = 15.0, α-methylstyrene dimers = 2.8, cumylphenols = 35.2 and a mixture of 2,4-dl (a, α-dimethylbenzylphenol with 2,6-di (α, α-dimethylbenzylphenol) and

2,4,6-R '(α, α-dimethylibenzyl) phenol = 3.6 additional amounts of cumylphenols are isolated as described above.

In another variation, the arylalkylation of the phenol (with residues and phenol added) is carried out by heating at 140-2 ° C in the presence of 2 wt. sulfuric acid was added with 2 h. The acid is then neutralized with sodium hydroxide and the arylalkylate distilled under vacuum. 53.5% (w / w), fractions with a boiling point of 160 to 210 ° C (2.67 kPa) of the following composition (% by weight) are obtained:

α-methylstyrene = 0.2, acetophenone = 0.7, dimethylphenylcarbinol = 0.1, phenol = 10.2, α-methylstyrene dimers = 9.0 and cumylphenols = 69.1.

Such a fraction can be utilized without further separation or prior to administration, or the cumylphenol can be isolated as described above.

Example 5

The phenol pitch I fraction boiling at 27 to 160 ° C / 2.67 kPa, characterized in Example 1, containing the added phenol, is taken. However, unlike Example 1, arylalkylation of this fraction is carried out on an inactivated synthetic zeolite:

(bulk density = 0.71 kg. ^_ dm 3, v = .port .0,56 cm @ 3. g_1, specific surface area = 310 m2.g1, SiO 2 = 87.66% .hmot., Al2O3 = 10.60 '% %, N20 = 0.90%, oxides of other metals = 0.84%)

at 190 ° C. The conversion of dimethylphenyl250861 carbinol reached 99.8%; phenol 61% and dimethylphenylcarbinol selectivity to cumylphenophils is 73%.

Example 6

Three-necked flask, 500 cm ⁵ opairenej imiešadlom, teiplomerom and water condenser was weighed 23 g of 4-etylfe.nolu, which is heated to 165 + 5 ° c .pridajú 2 g of aluminum powder. CoStoro forms aluminum ethylphenolate. Subsequently, 200 g of the I. fraction obtained from the phenolic pitch mentioned in Example 3 (containing 16.7% by weight of phenol) were fed to the bottom of the flask progressively.

21.5 wt. dimethyl phenyl).

Under these conditions, the arylalkylation of phenol and 4-ethylpheinol takes place and the reaction water along with other low boiling components is removed. After 2 h, the reaction mixture is cooled to 70-80 ° C, the aluminum phenolates are neutralized with hydrochloric acid and the arylalkylate obtained is separated from aluminum chloride and distilled under vacuum. A mixture of:

2-methylphenol, 4-cumylphemol and 2-cyclinyl-4-ethylphenol in a total yield of 61%.

Example 7

Mix 95 masses, fractions of the dimer fraction:

α-methylstyrene u [dimers: α-methylstyrene - 80.3%, o-ketyl-H-1-ol = 80.3%, α-methylstyrene · = 0.1%, p -cumylphenol (= 0.1%) with 5 wt. parts of crude α-meiylsyrene:

(α-methylstyrene = 95.0%, acetophenone = 0.4%, α-methylstyrene dimers - 2.3%, o-kuirnylphenol - 0.6%, = 1.2%) and with 100 wt. phenol.

The solution was continuously at 0.05 m ³ .m ~ ³ .h 'fed in a stream of nitrogen • ⁽³ · 84 m. ^M-3. H) arylalikylačný the heterogeneous catalyst consisting of phosphorus pentoxide on silica gel (3830 CHEROX ) operating at 150 + 3 ° C. Arylalkylate of the following composition is obtained (in% by weight):

o-kurnylphenol = 7.8, p-cumylphenol-49.2, α-methylstyrene dimers = 12.0, phenol-30.9 and α-methylstyrene = 20.05.

The phenol conversion thus contains 37.8%; the conversion of α-methylstyrene dimers = 71.0% and the yield of β-cumylphenol calculated to α-imethylstyrene and α-methyl-styrene dimers is 66.1%, with virtually complete α-methylstyrene kenversion.

Example 1. and d 8

Crude α-methylstyrene specified in Example 7 in an amount of 100% by weight, blended in portions with 100 himot, parts of pure phenol (purity > 99.4%), while the solution so obtained was in addition to arylalkylation under similar conditions to Example 7. realization mixture has the following composition (in% by weight):

p-cumylphenol-48.4, o-cumylphenol = 5.1, α-methylstyrene dimers = 19.7, phenol = 26.6 and α-methylstyrene.n <0.05.

Phenol conversion - 46.8% and p-cumylphenol yield calculated on converted α-methylstyrene 54 54.3%, slightly lower yield of alcohol is obtained in. of Example 7 from dimers ον and -methy fs thyrene.

The also formed α-methylstyrene dimers consist essentially of 1,1,3-trimethylphenyl-3-phenylindane. Moreover, the isomers of α-methyistyrene dimers are present in amounts below 0.1%.

Example 9

Technical methylphenylcarbinol, obtained by hydrogenation of acetophenone (methylphenylcarbinol = 95,0%; acetophenone 4,8 4,8 θ / o) in an amount of 98% by mass, parts are mixed with 2% by weight of styrene and 100% by weight of pure phenol.

The solution thus obtained is subjected to agitation in the presence of 2 parts by weight of active (bleaching earth) with vigorous stirring at 130 + 3 ° C for 2 hours. The crude arylalkylate obtained has the following composition (in% by weight):

Mixture of phthalenyl (4-hydroxyphenyl) ethane with:

β-phenyl-4- (2-hydroxyphenyl) ethane-44.2; 1-phenoxy-1-phenylethane ~ 20.1, phenol = 18.9, acetophenone = 2.4, water-6.5, styrene < 0.05 and methylphenylcarbinol &lt; 0.05.

Phenol conversion = 62.2%;

the conversion of carbohydrate and styrene is virtually complete. The selectivity of the conversion of methylphenylcarbinol and styrene to 1: β - (2-hydroxyroxyphenyl) ethane with Tphenyl (4-hydroxyphenyl) 250861 ethane 57% and to 1-phenoxy-1-phenylethan 26 per cent. -digomers of styrene.

Example 1-0

The technical n-phenylphenylcarbinol, as specified in Example 9, is added in an amount of 10 parts by weight to 90 parts by weight, parts of styrene having a purity of 99.8% and 100 parts by weight of parts of pure phenol. The arylalkylation is carried out under similar conditions to Example 9, with a catalytic effect of 2% by weight of active clay. The arylalkylate after separation of the catalyst has the following composition [in% by weight]:

a mixture of 1-phenyl-1- (4-hydroxyphenyl) ethane with:

1-phenyl-1- [2-hydroxyphenyl) ethane = 50.1,1-phenyxy-1-phenylethylamine = 2'0.4, imethylphenylcaribolinol <0.05, styrene <0.05, acetophenone 0.2, phenol = 16.5 and water = 0.6.

Phenol conversion = 67%.

The selectivity of the conversion of methylphenylcarbinol and styrene to 1-phenoxy-1-phenylethane = 22% and to 1-phenyl-1- (hydroxyphenyl) ethane = 54%.

Example 1 a -d 11

Mix 100 parts by weight of parts of α-methyl [styrene dimethyl dimethyl phenyl carbinol (20.1% by weight, dimethyl phenylcaribinol, 78.1% by weight α-methylstyrene and 1.8% dimers of ar-methylstyrene) with 100% by weight parts pure phenol. Aralkylation is carried out similarly to Example 7 to the f-osforečnanovom of the catalyst at 150 ^G + 3 C. The arylalkyl IMA following composition (in wt.%):

p-cumylphenol = 46.9, o-cumylphenol = 4.8, α-methyistyrene <0.05, dimethylphenylcarbinol <0.05, phenol = 27.0, α-methylstyrene dimers = 20.5, water = 1, 0th

The phenol conversion is 46% and the dimethylphenylcarbonil is practically complete with α-methylstyrene. The selectivity of ipremeny dimethylphenycarbinol and α-methylstyrene to p-cumylphenol is

Claims (4)

2308G1 by 57% and by 1-phenoxy-i-phenylethane 26pereent. The methylphenylcarbinol or styrene moiety is reacted to styrene oligomers. Example 10 The technical methylphenylcarbinol, specified in Example 9, is added to 90 wt. parts of styrene having purity of 99.8% and 100% by weight; parts of purehofenol. Arylalkylation is carried out under similar conditions as in Example 9, with a catalytic effect of 2% by weight. active (bleaching) clay. The arylalkylate after separation of the catalyst has this composition (in% by weight): a mixture of 1-phenyl-1- (4-hydroxyphenyl) ethane with: 1-phenyl-1- (2-hydroxyphenyl) ethane = 50.1, 1-phenexyl-1 -femam tetam = 20.4, methylphenyl ketbinol <0.05, styrene <0.05, acetophenone = 0.2, phenol = 16.5 and water = 0.6. Phenol conversion = 67 ° / o. The selectivity of the conversion of methylphenylcarbinol and 14 of styrene to 1-phenoxy-1-phenylethane = 22% and 1-phenyl-1-hydroxyphenyl jetane - 54%. parts of [alpha] -methylstyrene pitch of dimethylphenylcarbinol (20.1% by weight of dimethyl phenyl phenylcarbinol, 78.1% by weight of [alpha] -methylstyrene and 1.8% of dimers of [alpha] -methylstyrene) with 100 wt. Particularly pure phenol. Arylalkylation is carried out in analogy to Example 7 on phosphate catalyst at 150 ± 3 ° C. The aryl alkylate obtained has the following composition (in% by weight): p-cumylphenol = 46.9, o-cumylphenol = 4.8, α-methylstyrene <0.05, dimethylphenylcarbinal <0.05, phenol = 27.0, dimers, α-methylstyrene = 20.5, water = 1.0. The phenol conversion is 46% and the dimethylphemyl-canonil is practically complete with α-methylstyrene. The selectivity of the conversion of dimethylphenylcarboline and α-methylstyrene to p-cumylphenol is 53.7%. OBJECT 1. Srposoib arylalkylation of phenol and / or alkylphenol having a C-atom number of 1 to 8, in a liquid and / or vapor phase at a temperature of 70 to 260 ° C, with a catalytic effect of at least one bronsted and / or or leuco-acid or aluminum compound, in bulk and / or in solid form, by recirculation of the converted raw materials, characterized in that the phenol and / or alkylphenol is safely / or after the arylalkylation agent is cleaved on a heterogeneous catalyst at a temperature of 120 to 240 ° C, arylalkylate at least one of a group of reagents including methylphenylcarbinol, dimethylphenylcarbinol, methylenenylcarbinol with 2 to 95% styrene, α-methyl-styrene dimer with 2 to 95% α-methylistyrene , and dimethyistyrene, and dimethylphenylcarbimol with 2-95% α-methylstyrene. 2. The method of arylalkylation of phenol and / or alkylphenol according to claim 1, characterized in that the arylalkylating agent is a fraction of the distillation residue from the production of phenol and acetone by catalyzed decomposition of hydroperoxide, preferably after separation at least substantially. acetophenone and ketylphenol containing mainly dimethylphenylcarbinol, α-methylstyrene, α-methylstyrene dimer and phenol. 3. The method of arylalkylation of phenol and / or of alkylphenol according to claim 1, wherein 2 and 3, respectively, wherein the arylalkylating agent and / or the aryl alkylating agent is cleaved by in situ aryl alkylation. the catalyst, preferably on a catalyst catalyst, at a temperature of 80 to 220 CIC, preferably 120 to 180 ° C. 4. The method of arylalkylation of phenol and / or alkylphenol according to items 1 to 4, characterized in that the water produced and / or recovered in the aryl-alkylation medium is removed at least in part by arylalkylation in the liquid phase with the raw materials. Severografia, n. P. Plant 7, Most Price 2,40 Kcs