DE2241157B2 - PROCESS FOR THE PRODUCTION OF OXALKYLATED ALPHA-ACETYLENE ALCOHOLS - Google Patents

Description

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Simply oxyethylated acetylene alcohols are important industrial chemicals, which by manifold Implementations can be converted into important aids, the z. B. in the textile and paper industry are of interest. A particularly important type of use for these compounds is in the Electroplating, where these connections are used as brightening additives, especially in high-gloss nickel plating, Find use.

The previous production of alkoxylated acetylene alcohols took place in an alkaline medium; H., the reaction was base catalyzed. U.S. Patents 3,366,557 and 3,292,191 teach e.g. B. the production of simply oxyethylated butynediols by reacting butynediol with ethylene oxide and alkali or alkaline earth hydroxides or organic amines as catalysts.

The connections required for the above areas of application, but especially in electroplating, must meet high requirements in terms of their purity and chemical uniformity meet conditions that the manufacturing methods mentioned do not yet fully meet could become. The basic catalysts according to the above references tended in particular to bring about a higher oxalkylation stage and, above all, also catalyze the reverse reaction, d. H., the end product often contained unreacted acetylene alcohol or higher oxyalkylated products. However, unreacted acetylene alcohol often leads to explosions under the reaction conditions. Also the use of the amines mentioned as basic catalysts, which are gentler Hoped for a response, did not lead to the hoped-for success, as one now had higher temperatures needed so that these catalysts could develop their full effectiveness. Increasing the Temperatures, however, again led to the formation of by-products and increased readiness the triple bond for explosive decomposition. ', 5

DT-OS 20 36 278 teaches the latest development with regard to the base-catalyzed reaction. Here, basic ion exchange resins are proposed as basic agents, although with regard to the selectivity of the reaction bring progress, but the other disadvantages, such as reverse reaction and Risk of decomposition, cannot yet be completely ruled out.

It became: now a process for the preparation of oxalkylated u-acetylene alcohols by reaction found from 1 mole of acetylene alcohol with 1 to 3 moles of alkylene oxide per hydroxyl group, which is characterized is that the reaction in the presence of 0.1 to 10%, based on the weight of the Acetylene alcohol, organic derivatives of phosphine.

Organic derivatives of phosphine for the purposes of the invention are compounds of the formula I

PR ₃ (I)

in which R by alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, n- and iso-propyl, n- and iso-butyl and amyl groups, or by aryl groups, how optionally substituted phenyl groups are represented. Preferred in the sense of Invention is tributylphosphine and especially triphenylphosphine. Although it is known, e.g. B. as DT-OS 15 43 884 that acidic hydrogen atoms, for example of carboxyl and phenyl-OH groups, in The presence of triphenylphosphine can oxäthylieren, but not the much more inert alcoholic Hydroxyl groups of the u-acetylene alcohols.

The organic derivatives of phosphine - hereinafter referred to as "phosphines" for short - make it possible Surprisingly, a safe selective simple Oxalkyiierung, without reverse reactions or other side reactions occur, and also result in very light-colored products of great purity.

Starting products for the compounds to be prepared according to the invention are -acetylene alcohols Formula II

A-C = C-B (H)

in which A stands for a hydrogen atom or the radical B and B for the radical

- CHOH

R ²

stands in which R ^{2 stands} for a hydrogen atom or a lower alkyl group with usually 1 to 4 carbon atoms.

For the purposes of the invention, preferred compounds of the formula II are, for example, butyne-2-diol-1,4, Propargyl alcohol, butyn-1-ol-3, hexyn-1-ol-3 or Hexyne-3-diol-2,5. Butyn-2-diol-1,4 and propargyl alcohol are preferred.

The alkylene oxides required as further starting materials correspond to the formula III

R ³ -C

CH ₂

(Hl)

in which R ^{3 represents} a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group.

Ethylene oxide is particularly preferred from a technical point of view.

It is advisable to purify the acetylene alcohols before the reaction, for example by the distillation of which can easily be carried out under reduced pressure.

The implementation is simple and takes place, for example, in such a way that the «-acetylene alcohol in a pressure vessel, for example an autoclave, and the phosphine, expediently in concentrations of, based on the weight of the acetylene alcohol, 0.1 to 10%, preferably

0.5 to 3%, adds. Then, based on one equivalent of hydroxyl groups, 1 to 3, preferably 1 to 1.1, mol of alkylene oxide are injected and allowed to react for about 10 to 16 hours at 50 to 150 ° C., the internal pressure rising ^{to 1 to 20 atmospheres.}

In principle, the reaction can also be carried out in solvents which are inert under the reaction conditions will. Aromatic hydrocarbons such as benzene, which can optionally be substituted, but also customary paraffin hydrocarbons of the gasoline fraction into consideration.

The products produced according to the invention are very pure and can be used for all purposes will. Their importance in electroplating, where they mainly find use as a strength enhancer in nickel baths.

The parts given in the following examples are parts by weight.

example 1

860 parts of butynediol (10 molar equivalents) and 8.6 parts of triphenylphosphine are placed in a 3-1 autoclave stainless steel filled. After closing the autoclave, it is flushed several times with nitrogen and at 55 to 58 ° C 902 parts of ethylene oxide (20.5 molar equivalents) added in about 12 hours, the

Internal pressure rises to 3 to 4 atmospheres. The reaction is allowed to continue until the pressure no longer drops. To the relaxation is 1748 parts of the bis-hydroxyethyl ether of butynediol with the iodine color number <10 and the refractive index nf 1.4852. The salary of free butynediol is below 0.1%.

Example 2

560 parts of propargyl alcohol (10 molar equivalents) and 5.6 parts of triphenylphosphine are reacted with 451 parts of ethylene oxide (10.25 molar equivalents) at 80 to 85.degree. C. in a 2-1 autoclave made of stainless steel according to the procedure described in Example 1. 1002 parts of the crude ethylene glycol monopropargyl ether are obtained. 944 parts of the pure compound with a boiling point of _M 78 ° C and nl ° 1.4502 can be obtained therefrom by distillation.

Example 3

560 parts of propargyl alcohol (10 molar equivalents) and 5, ö parts of triphenylphosphine are at 95 to 100 ° C according to the procedure described in Example 1 with 609 parts of propylene oxide (10.5 mol

equivalent) implemented. This gives the roll Fropylenglykolmonopropargyläthers 1161 parts and 1098 parts by distillation of the pure ether, bp. _I5 74 ⁰ C and the refractive index nf 1.4449.

Claims (1)

Claim: Process for the preparation of alkoxylated (i-acetylene alcohols by reacting 1 mol Acetylene alcohol with 1 to 3 moles of alkylene oxide per hydroxyl group, characterized in that that the reaction is carried out in the presence of 0.1 to 10%, based on the weight of the acetylene alcohol, of organic derivatives of phosphine.