CS238938B1 - Processing of terrobutyl arylalkylphenole - Google Patents

Abstract

Arylalkylphenol or a mixture of arylalkylphenols of formula C8H5C / RRVCgH4OH, wherein R and R 'are the same or different and may be H or CH, preferably benzylphenol or cumylphenol is tert -butyl isobutylene in molar ratio to arylalkylphenol or to the arylalkylphenol of 0.5 to 5 L at 20 to 250 ° C under catalytic conditions the effect of strong mineral acids or ansolvo acids, is also present solvent or solvent, that at least one starting compound of formula R "OC / CH 2, wherein R" is H or alkyl of C atoms 1 to 12 or cycloalkyl of C-atoms 6 to 8 decomposes at 60 DEG-240 DEG C. under catalytic conditions the effect of liquid or solid acid, wherein the water or alcohol formed is separated with an efficiency of 50 to 100% and recovered isobutylene, optionally also recirculated is led to tert-butylation. The method can be used to produce disinfectants components, antioxidants and oil-soluble bitumen.

Description

The invention relates to a process for the preparation of tert-butylated arylalkylphenol or a mixture of arylalkylphenols, in particular tert-butylated benzylphenol, respectively. tert-butylated benzylphenols, tert-butylated benzylmethylphenol as well as tert-butylated cumylphenol, or cumylphenols, which utilize a wide range of petrochemical tert-butylating agents, respectively. isobutylene donors.

It is known that alkylation of phenol with benzyl chloride produces benzylphenol, respectively. 4-benzylphenol and 2-benzylphenol, to a small extent dibenzylphenols ^ Abdurashuleva, Aohmedov: Uzb. cftim. žur.

15, no. 2, 54 (1972): Cs. pat. 152 190} Murohashi Susumi: Chem. Abstr, 80, 132 946 z and 82,

868 µl and the alkylation of alpha-methylstyrene with cumylphenol, respectively. 4-cumylphenol and 2-cumylphenol / Polish pat. 100 643} Chem. Abstr. 90, 151,732.

Similarly, alkylation of phenol with styrene gives 1-phenyl-1- (4-hydroxyphenol) ethane, 1-phenyl-1- (2-hydroxyphenyl) ethane and optionally 1-phenoxy-1-phenylethane. In addition, cumylphenol, in particular p-cumylphenol, respectively. 4-Cumylphenol can be isolated from distillation residues from phenol production by decomposition of cumene hydroperoxide / British Pat. 1,235,415 /.

It is also known to alkylate p-cumylphenol with isobutene (2-methylpropene) to 2,6-di-tert-butyl-4-cumylphenol. pat. 150 822} Ersov, Nikiforov, Volodkln: Prostrastranstvenno zatrudnennyje phenoly Khimija Moscow / 1972 /} NSR Pat, 2 440 950} Kostova, Dimov: Chim.

Ind. / Sofia / 1 982, no. 2, 62} Khoa Hoa et al.: Jap Chi Hoc (Hanoi) 11 (4), 27 (1980)} Chem. Abstr. 95, 61 656 b (1981) J under the catalytic action of sulfuric acid or p-toluenesulfonic acid.

However, it requires pure 2-methylpropene as an alkylating agent, which is difficult to manufacture or obtain from a technical and economic point of view, but also exhausts the possibilities of alkylation by other alkylating agents.

According to the invention, the process for the production of tert-butylated arylalkylphenols or a mixture of tert-butylated arylalkylphenols, preferably mono-tert-butylated, or mono-tert-butylated arylalkylphenols t-butylation arylalkylphenols or mixtures arylalkylphenols formula CgHgC / RR "/ CGH ₄ OH, the wherein R and R 'are the same or different and may be H or CH-i, preferably benzylphenol or cumylphenol, isobutylene in a molar ratio to arylalkylphenol or to arylalkylphenol of 0.5 to 5: 1, at a temperature of 20 to 250 ° C catalyzed by strong minerSlnych acid and / or ansolvokyselín, optionally also in the presence of solvent or solvents and the carrier gas is carried out by at least one starting compound of the formula ROC / CH _3/3, wherein R is H or an alkyl of carbon numbers 1 to 12 and / or cycloalkyl. having a carbon number of 6 to 8, decomposes at 60 to 240 ° C under the catalytic action of a liquid and / or solid strong acid, the water and / or alcohol formed being separated with an efficiency of 50 to 100% and the isobutylene obtained; The resulting tert-butylated arylalkylphenol or the mixture of tert-butylated arylalkylphenols is separated and the unconverted starting materials as well as any unconverted isobutylene are preferably recirculated.

An advantage of the process according to the invention is that it is possible to carry out the tert-butylation of arylalkylphenol or a mixture with a high selectivity of tert-butylation, e.g. to position 2, or at higher temperatures, also at multiple sites on the phenol nucleus, as well as other aryl groups.

Another advantage is the possibility of utilizing a wider range of isobutylene donors, whether tert-butyl alcohol, alkyl tert-butyl ethers or cycloalkyl tert-butyl ethers.

The tert-butylated substrate of the present invention is an arylalkylphenol or a mixture of arylalkylphenols of the general formula CgH ₅ C / RR '/ CgH ₄ OH, wherein R and R' are either the same or different and can be H or CH ₃ .

In particular, it is benzylphenol which may be a single isomer such as e.g.

ortho- or 2-benzylphenol, para- or 4-benzylphenol or mixtures thereof, optionally also dibenzylphenols, in particular 2,4-dibenzylphenol and 2,6-dibenzylphenol, optionally with admixtures of starting materials and benzylphenol derivatives such as phenol, methylated benzylphenol and the like .

Then, benzylmethylphenol or a mixture of isomers of benzylmethylphenols C 8 H 4 CH / CH 2 / C 4 H 4 OH, as well as cumylphenol, which also typically represents two isomers, namely 4-cumylphenol and 2-cumylphenol. Cumylphenol can be obtained either by alkylation of phenol with alpha-methylstyrene, arylalkylation of phenol with dimethylphenylcarbinol, arylalkylation of phenol with alpha-methylstyrene dimers or isolated from so-called phenol. phenolic pitch.

This group of arylalkylphenols includes the aforementioned phenol arylalkylation products with styrene, namely 1-phenyl-1- (2-hydroxyphenyl) ethane, 1-phenyl-1,4-hydroxyphenyl ethane, and optionally the O-alkylation product of 1-phenoxy-1- phenylethane.

Arylalkylphenols may also contain derivatives as components and optionally other alkylphenol or arylalkylphenols.

The tert-butylation according to the invention can be carried out in the liquid and / or vapor phase, and the tert-butylation on the trickled solid catalyst is also meant. If heterogeneous catalysts are used, the final product is more easily separated, and no waste water is contaminated. Homogenous catalysts tend to be more efficient.

Decomposition Catalysts ROC / CH _3/3, but the t-butyl acetate are used arylalkylf enol main types of aprotic and proton acids. These include aluminum chloride, boron trifluoride, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, alkylbenzene sulfo acids, trifluoromethanesulfonic acid and the like.

In particular, the solvolves are sulfonated polymers and copolymers, such as copolymerized sulfonated styrene-divinylbenzene and phenol-formaldehyde resins, i.e., H-form cation exchangers, sulfonated polypropylene, sulfonated polyethylene, and the like.

Other natural and synthetic zeolites; phosphorus pentoxide alone and especially on carriers, similar to phosphoric acid and polyphosphoric acids, e.g. the tetraphosphoric acid, and the acid carrier may also be an ansolic acid, as in the case of phosphorus oxides or polyphosphoric acids on aluminosilicates, optionally activated (bleaching clay).

A suitable tert-butylation catalyst is also aluminum phenolate and other active aluminum-containing alkylation catalysts (alumoxanes) as well as heteropolyacids.

The isobutyrene (2-methylpropene) donors are ethers of the formula R @ 1 OC (CH3 _{) 3} in which R is hydrogen or alkyls having a carbon number of 1 to 12 or cycloalkyl of a carbon number of 6 to 8, wherein tert-butyl alcohol, the ethers can also be prepared relatively easily by reacting water or alcohols ROH with isobutylene (2-methylpropene), preferably with a mixture of hydrocarbons containing 2-methylpropene (pyrolysis C-fraction).

Particularly suitable are the readily available methyl tert-butyl ether and isobutyl tert-butyl ether, which can even give up to 2 moles of isobutylene (2-methylpropene) from 1 mole even at higher decomposition temperatures.

The water introduced into the reaction medium as well as the water and alcohol formed must be removed before the 2-methylpropene enters the tert-butylation, since they retard the tert-butylation. The by-products are usually isolated after the end of the tert-butylation. The crude alkylate, especially when homogeneous catalysts are used, contains at least residues thereof which are suitable to be removed from the crude product.

The crude product is at least partially disposed of by-products as well as unconverted raw materials that can be recirculated. Further refining can be accomplished by vacuum, especially molecular distillation, extraction, recrystallization, as well as refining with adsorbents, e.g. active clays.

The method of the invention may be carried out continuously, semi-continuously or continuously. Further details as well as advantages of the present invention are apparent from the examples.

Example 1

Per h) of a 500 mm long-glass reactor with an inner diameter of 30 mm containing 50 cm ^{3 of a} phosphate catalyst having a grain size of 2 to 4 mm and a content of 22.5% by weight. phosphorus with an acid number of 298 mg KOH / g, over which there is a layer of 50 cm ^{3 of} Rashig rings,

Methyl tert-butyl ether of 99% wt. in an amount of 4.2 gh ³ for 10 h.

The reactor is tempered by means of a jacket with resistance electric heating to a temperature of 140-1 ° C. The reaction product leaving the reactor is cooled with a water condenser and the condensed fractions are collected in a trap. Weskondenzované steam is fed to the bottom three neck flask a 250 ^cm3 equipped with a stirrer and a thermometer, which is 50 g kumylfenolu purity 98 * / of which 98% p-cumylphenyl phenol and 2% mesh wash ha phenol / o at point 74, 5 to 7.5 [deg.] C. 100 g of 1,2-dichloroethane as solvent and 1.5 g of 96% by weight sulfuric acid.

The contents of the flask were heated to 55 ° C and 2 ° C with stirring. After the tert-butylation is complete, the contents of the flask are cooled, weighed and analyzed. 165 g of crude product are obtained, which, after deduction of the solvent, contains 89 wt. 2-tert-butyl-4-cumylphenol, 8% 2,6-di-tert-butyl-4-cumylphenol and 1.5% 4-cumylphenol.

25 g of a liquid product of the composition (% w / w): 12.5% of isobutylene are collected in the trap; 10.1 methyl tert-butyl ether; 2.5 diisobutenes and 74.9 methanol. From the crude naalkylated product, pure 2-tert-butyl-4-cumylphenol is isolated by crystallization under reduced temperature to give 56 g of 98% by weight of 2-tert-butyl-4-cumylphenol.

Example 2

The procedure is similar to that of Example 1, except that the temperature of the methyl tert-butyl ether decomposition reactor is raised to 150-2 ° C and 5 g of water are introduced into the separator downstream of the reactor. 167 g of crude product are obtained, containing 91% by weight. 2-tert-butyl-4-cumylphenol, 6% 2,6-di-tert-butyl-4-cumylphenol and 1.0% 4-cumylphenol after deduction of solvent. The isobutylene content of the product separates to 2.5% by weight. and a methyl tert-butyl ether content of 6.5 wt.

Example 3

The procedure is similar to that of Example 1 except that the temperature of the tert-butylation is increased to 60-2 ° C. 170 g of crude product are obtained after deduction of the solvent in% by weight: 2-tert-butyl-4-cumylphenol 87,5} 2,6-di-tert-butyl-4-cumylphenol 10.0; Of 4-cumylphenol 0.5. Isolation gave 58 g of 2-tert-butyl-4-cumylphenol with a purity of 98.5% by weight.

attaches

The procedure is similar to that of Example 1, except that methyl tert-butyl ether is decomposed with isobutyl tert-butyl ether at a temperature of 178-2 ° C on activated natural zeolite (activated clinoptilolite by quadruple hydrochloric acid extraction), isobutyl tert-butyl ether is fed. in an amount of 3 gh, this amount generates a similar amount of isobutylene to 4.2 gh ^{1 of} methyl tert-butyl ether. The next procedure is similar to Example 1, except that the extracts differ with accuracy of 7 and rel.

Example 5

The procedure is similar to that of Example 1 except that 4-t-butyl alcohol in the amount of 4 g.h is fed instead of methyl tert-butyl ether. Water is separated from the decomposition product and the dry isobutylene is subjected to tert-butylation of a mixture of the o- and p-isomers of benzylphenol, which is carried out on a scrubbed thick-acid cation-exchanged H-form (sulfonated styrene-divinylbenzene resin) at 75-3 ° C. .

Mol. the ratio of benzylphenol to isobutylene is 1 2, with conversion of benzylphenol reaching 97%, isobutylene 61%, selectivity of formation of mono-tert-butylbenzylphenol is 95%. Unconverted isobutylene is recirculated.

Example 6

Via a contact packed with 50 cm granulated bleaching clay, methyl tert-butyl ether vapors of 4.2 gh ^{3 are} fed at 140-3 ° C for 10 h, the resulting isobutylene together with methanol vapors, diisobutenes are passed through a capacitor, where methanol, diisobutenes and unconverted methyl tert-butyl ether are condensed, the isobutylene being continued into a flask equipped with a thermometer and a stirrer containing 50 g of a mixture of 1-phenyl-1- (4-hydroxyphenyl) ethane with 1-phenyl-l / 2-hydroxyphenyl / ethane, 10 g of active bleaching earth and 3 µg of cation exchange resin in the H form, the tert-butylation being carried out at a temperature of 68 ° C to 2 ° C.

After separation of the catalysts, 54 g of isomers of mono-tert-butylated benzylmethylphenols C _g H ₅ CH / CH ₃ / C _g H ₃ / t C ₄ H ₉ / OH are isolated.

Claims (1)

Preparation of tert-butylated arylaikylfenolu or a mixture of tert-butylated arylalkylf enol, preferably mono-tert-butylated, or mono-tert-butylated arylalkylphenols t-butylation arylalkylphenols or mixtures arylalkylphenols formula C _g H _g C / RR "/ C _g H ₄ OH in which R and R 'are the same or different and can be H or CH ₃ , preferably benzylphenol or cumylphenol, isobutylene in a molar ratio to arylalkyphenol or to arylalkylphenol of 0.5 to 5: 1, at a temperature of 20 to 250 ° C, catalyzed by a strong mineral acid and / or ansolvokyselín, optionally also in the presence of solvent or solvents and the carrier gas, characterized in that the at least one starting compound of the formula ROC / CH _3/3, wherein R is H, or an alkyl having a carbon number of 1 to 12 and / or a cycloalkyl having a carbon number of 6 to 8 decomposes at a temperature of 60 to 240 ° C under the catalytic effect of a liquid and / or solid and the resulting isobutylene, optionally also re-circulated, is converted to a tert-butylation of an arylalkylphenol or a mixture of arylalkylphenols, wherein the tert-butylated arylalkylphenol formed or a mixture of tert-butylated arylalkylphenols is formed. Preferably, the unconverted starting materials as well as any unconverted isobutylene are recirculated.