DE1768068C3 - Process for the reductive removal of acidic organic derivatives of sulfuric acid from reaction mixtures with unsaturated terpene compounds - Google Patents

Description

The subject of the main patent 1 643 829 is a process for the reductive removal of sulfuric acid from reaction mixtures that also contain unsaturated terpene compounds such as turpentine oil and natural resin acids or contain their esters, natural rubber or polyisoprene, at an elevated temperature, the is characterized in that the reaction mixture heated to a temperature at which the reducti 3 decomposition of the sulfuric acid by exposure to water the unsaturated terpene compounds on the sulfuric acid and the reduction products the sulfuric acid are expelled. This separation can take place in the presence or absence of others Reactants and / or solvents are made in a simple manner, with the reduction products the sulfuric acid, such as sulfur dioxide or hydrogen sulfide, escapes in gaseous form. In this way, light-colored products can be produced while avoiding a neutralization and / or washout process can be obtained.

It has now been found that, instead of sulfuric acid, acidic organic derivatives of sulfuric acid whose SO ₃ grouping can be decomposed at elevated temperatures, generally above 120.degree. C., can be removed reductively with at least as good or even better results. Such derivatives are primarily the sulfonic acids formed from sulfuric acid and aromatic compounds, such as hydrocarbons, unsubstituted or substituted phenols and / or carboxylic acids, as well as soicfae sulfonic acids and sulfuric acid esters, which are formed from sulfuric acid and non-aromatic compounds, especially those of an unsaturated nature.

The acidic reacting " ^r e? N" * c ^ha " ^T > ° riv <j'e · *» * sulfuric acid can Linem Real ■ hn

pure Fcrm, e.g. B as KataKsator,; / i were or from sulfuric acid and aecuiru.-Naη 1 see connections in a vorpeschn ^! t · ·, beitsgani ;, possibly in the form of a Stan m ■ .. -v ■ call

be. Ais gcvigner: Verb'tidiiiiL ".- !; - So.vrcid-

acid derivatives react, come; , B -khe

in question, in the reactions, μ 'en'n;il!> - n 6 _a

are, or other verb r: _{l;! V} H ι 1 ^ i

phenols, nitrophenols. «... | f ₍ . ·>;. ·, · .-. _{;; ss} , -.

substances, e.g. B. aromatic Nu

You can also, for example, let rosin first react with sulfuric acid (see Example 3) and then by adding phenol and / or other reactants, such as substituted phenols known implementation with these carry out Berni When heated to higher temperatures, these sulfuric acid reaction products are also split and the sulphurous ones are reductively entterm.

Specifically, the acidic derivatives of sulfuric acid that can be decomposed are: o- and p-penenol sulfonic acid, the various phenolsulfonic acids or alkylphenolsulfonic acids, such as o- or p-cresol mono- or disulfonic acid, inι the SO ^ K groups adjacent to the OH-Gn-ppe suid, butylphenolsulfonic acids, Octyl- and uodecyipnenolsuifousaurer ^., Uifonic acids aryl-substituted phenols, such as phenylphenols, Sulphonic acids of multiple phenols, such as des Recorsins, sulfonic acids from rnenoi-Aiaenya condensates, such as dihydroxydiphenylmethane or the further condensates thereof known as novolaks, o- or p-halopheno-sulfonic acids or -disulfonic acids, 2,4-dichlorophenoisulfonic acid, p-toluenesulfonic acid, the various sulfonic acids of xylenes, mesitylene, diphenyl and naphthane Halosulfonic acids, such as chloric or bromosulfonic acid, sulfuric acid esters, such as those obtained by the addition of Sulfuric acid to olefins are formed, e.g. B. cyclic or acyclic terpenes, or sulfonic acids of these Terpenes.

An essential application of the invention The procedure results from those processes in which phenol and / or substituted phenols ah Reaction component and / or solvent are present.

The operation of the invention is generally in the temperature range of 50 to 320 C, preferably carried out between 17O ⁰ C and 280 ⁰ C. However, this temperature specification is to be understood that the decomposition, depending on the reactants present, even at very low temperatures, e.g. B. 50 ° C, can begin. For practically complete removal of the SCy grouping and / or to obtain practically uncolored products, however, temperatures of at least 170 ° C are necessary.

The present process thus represents a transfer of the possibilities described in the main patent on those derivatives of sulfuric acid that bind them, but are relatively easy to split off Form included. Thus, while avoiding a neutralization: .- and / or leaching process bright Final products are obtained. The procedure is on aiie in the main paieni angciüin icu Rcakiiunspi ureasewie Terpenepheni formation, cyclization of natural rubber or polyisoprene can be used.

The following examples, in which parts are parts by weight, illustrate known reactions. in which acidic derivatives of sulfuric acid are used as catalysts or as Sulphonation products arise, their removal according to the invention.

Example! i

300 parts of phenol are mixed with 3 parts of o-chloropbenene sulfonic acid as a catalyst. Then iäßt at 50 ° C in the course of 3 hours, 600 parts ^x erpentinöl dropwise so that - caused by

the exothermic reaction - the temperature continuously increases and holds 280 parts of phenol heated to 60 ° C

rises up to 100 ° C. During three more the mixture for 2 hours at 120 ° C. When further

The temperature is increased slowly for hours until heating takes place at 170 to 190 ° C

190 ⁰ C and leaves the mixture so long with this evolution of sulfur dioxide instead of 220 to

Temperature, until the reaction mixture is light and practically 5 240 ° C a lightening of the reaction mixture

table is free of sulfur dioxide. Then you heat the mixture. After a treatment in the Va-

the mixture to 220 ° C and distilled excess kuum 700 parts of a yellow terpene-phenol resin

sige phenol. In the course of a further two hours with a melting point of 125 ° C, which was free of

den is heated up to 270 ° C, whereby resinous Be is sulfonation products

pass over components. There remain 700 parts of a _lo .

yellow terpene phenol resin at ⁷⁰ C (after B e ι s ρ ι e 1 4

Capillary method) melts. One solution in one 600 parts rosin and 320 parts one out

Mixture of equal parts by volume of toluene and metha- ί mol of phenol and 0.8 mol of formaldehyde in the usual

nol is practically neutral against methyl orange, novolaks manufactured in a manner that are produced at 120 ° C with

so it is free from o-chlorophenol sulfonic acid. 15 10 parts of chlorosulfonic acid were added as a catalyst

ο - ■ · i ₇ The temperature rises due to an exothermic reaction

s ρ 1 e 1 _ 130 ° C, the reaction mixture being dark and

300 parts of 300 parts of phenol become viscous at 175 ° C. In the temperature range between 180

crushed polyisoprene and 5 parts of a mixture and 200 ⁰ C takes place a strong sulfur dioxide

of o- "and p-phenolsulfonic acid as a catalyst. The resin becomes lighter. After a

ben and the mixture for 8 hours at this temperature treatment in vacuo gives 800 parts of a

held. The polyisoprene gradually turns into amber-colored resin with a melting point of 130 ° C,

Solution, whereby sulfur dioxide develops. Which is free from chlorosulfonic acid.

initially brown-black colored mass becomes lighter. .

considerably on. Then the excess 25 Example D

Phenol is distilled off at a temperature of up to 260 ° C. z- ~ Cig phenol, 12 g of concentrated p-Phe-

The product precipitates in a yield of 330 parts of nolsulfmwäiir- given as a catalyst. Then lets

and indicates the known key figures and Eigen- 112 g of diisobutylene to be added dropwise, which is exo-

properties c: s cyclo-rubber. React a solution in a thermal reaction with a dark color,

A mixture of equal parts by volume of toluene and 30 g of rosin is found

Ethanol reacts neutrally to methyl orange. a violent SCy development already takes place at 120 ^{c C,}

If, instead of synthetic polyisoprene, natural polyisoprene is sealed at 180 ° C. One receives after

rubber used nd / or the cyclization instead of working up in vacuo at 260 ° C 18Cg one

in the presence of Pnewol in the presence of an amber-colored product with a melting point

their solvent, such as an aliphatic, aro- 35 of 64 ° C, which is free of phenol sulfonic acid.

natural or halogenated hydrocarbons, _n . . . ,

is also obtained from Phenolsulfon- Example 0

acid free products. 94 g of phenol? " with 6 g of p-phenolsulfonic acid c

. added as a catalyst. Then 280 g of Rici

B s 1 s ρ ι el 5 _{4o nenfettsäure} j _m f _{Lau ea} j _ner hour at 50 ° C zutrop-

To 600 parts of rosin are fen at 100 ° C. The separation of the catalyst ar / reduktiyem 12 parts of concentrated sulfuric acid are slowly counteracted by adding 50 g of rosin b; n. Initially, a sulfonation product is formed. After working up in vacuo during The temperature rises with a dark coloration by exo 5 hours at 260 ° C., 380 g of a dark thermal is obtained Reaction up to 135 ° C, with the yellow, highly viscous product, which is free of phenolic action mixture becomes more viscous. Then there is sulfonic acid.

Claims (1)

Claim Further training of the process for the reductive removal of sulfuric acid from reac- «Mixtures of oils, sulfuric acid and unsaturation Terpenverbmdungen contain, at elevated temperature, whereby the reaction mixture heated to a temperature at which the reductive decomposition of sulfuric acid by action the unsaturated terpene compound takes place and expelled the reduction products of sulfuric acid are according to patent 1643 829, thereby marked that one of emem reaction mixture goes out, which in place contains organic derivatives of sulfuric acid which react acidic from sulfuric acid.