JPS5949226B2 - Dihydroxysulfonate containing ether structure - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an ether structure-containing dihydroxysulfonate obtained by adding a bisulfite to a (poly)alkoxylated dihydroxyalkene.

It is known that alkali metal salts of bisulfites can be added to double bonds activated by electron-withdrawing groups such as nitrile or ester groups. ,E.

J.Schenck and J.Danishefsky, Journal of Organic Chemistry (J.Org, Chem.), Vol. (Ang, Chem,) Volume 61, 233
Page, '-1949]. It is also known that bisulfite can be added to aliphatic double bonds that are only slightly activated. The addition of bisulfite to allyl alcohol is thus described in the literature [M.S.
Paper by E. M. May and F. R. Moyo, Journal of Organic Chemistry (J, Org, Chem), Vol. 3, page 175, 1939. reference〕. However, this reaction produced only 5 to 30% yield of 3-hydroxypropanesulfonic acid in its salt form. Although the yield of this reaction of allyl alcohol and bisulfite was high (German patent no.
15693), it was probably not possible to suppress the formation of a secondary product, which is a compound having the following groove structure.

Moreover, the separation of the inorganic salts formed from the sulfonate salts during the reaction is not complete.

Salts of 3-hydroxy-2-hydroxymethylpropanesulfonic acid are also known.

Salts of this type can be obtained by reacting 2-methylene-1,3-propanediol with bisulfite (DE 2224304). However, 2-methylene-1,3-propanediol can only be obtained in small amounts at considerable expense, and as a result, the salt of 3-hydroxy-2-hydroxymethyl-1-propanesulfonic acid obtained from it is It cannot be used on a wide scale. Additionally, 3-
The salts of hydroxy-2-hydroxymethylpropanesulfonic acid are relatively difficult to isolate. This also applies to the production of salts of 1,4-dihydroxy-2-butanesulfonic acid, which can be used to produce stable baths for copper plating in the absence of electrical current (DE 2132003 issue). Therefore, there is a need for sulfonic acid group-containing diols that can be easily and inexpensively produced and that, due to their favorable properties, can be used in a variety of applications. Surprisingly, it has been found that bisulfite can be added to alkoxylated dihydroxyalkenes with high yield and high purity.

Therefore, the present invention includes an ether structure, and is represented by the following general formula (in this formula, A is a linear or branched alkylene group having 1 to 6 carbon atoms, and R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). group, Me represents NH4 or an alkali metal, n is 1
to 10, m being 1 or preferably 0).

The present invention also provides an unsaturated diol represented by the following general formula (in which A, R, Me, n, and m are as described above), in which Me represents NH4 or an alkali metal. in the presence of catalytically active oxygen in an aqueous medium at a temperature of up to 100° C. and with a valency of 3 to 9, preferably 5 to 8,
It relates to a process for the preparation of these compounds, characterized in that the reaction is carried out at a molar ratio of bisulfite to diol of 1:1 to 5:1.

These dihydroxysulfonic acid salts containing an ether structure can be obtained in highly pure form and in very good yields by the above-mentioned production method.

Separation of the inorganic salts formed during the reaction is surprisingly easy and can be carried out by extracting the sulfonate salts of the invention with acetone, a mixture of acetone and water, a chlorinated hydrocarbon, an alcohol or a mixture of alcohol and water. It will be done. After extraction, the sulfonate no longer contains salt (not even a trace can be detected)
. Besides the ease with which salt-free compounds can be separated quantitatively, another notable advantage is the wide range of applications of the compounds of the present invention.

They are excellently suitable for use as comonomers in the production of acid-modified polyesters and polyurethanes and, for example, after reaction with chloroacetic acid (or its esters), in the production of acid-modified polyamides. The more highly ethoxylated and/or propoxylated derivatives, optionally after reacting them with isocyanates to form e.g. Used as an additive in the production of acrylonitrile or polyamide films, sheets and filaments. The unsaturated diol used as a starting material has the following general formula (in this formula, A represents a linear or branched alkylene group having 1 to 6 carbon atoms, and m is 1 or preferably O). The dihydroxyalkenes represented can be obtained in known manner by (poly)alkoxylation, for example with ethylene oxide, propylene oxide or butylene oxide.

This reaction is preferably carried out neat or in a solvent such as dioxane or dimethylformamide (DMF) in the presence of a small amount of a basic catalyst, preferably 0.2-2% by weight, such as NaOHlKOHl sodium or potassium methylate. The reaction is carried out at a temperature in the range of 50 to 180°C, preferably in the range of 100 to 160°C, optionally under pressure in a pressure cooker. Highly viscous or waxy substances are formed which can be characterized with respect to their degree of alkoxylation by OH value measurements or by nuclear magnetic resonance (NMR) spectroscopy. Sulfonation may be carried out using commercial grade bisulfite solutions or freshly prepared bisulfite solutions by introducing SO2 into the corresponding ammonium hydroxide or alkali metal hydroxide solutions. Can be done.

The addition reaction is preferably carried out at room temperature;
At temperatures up to 0° C., the unsaturated diol or its aqueous solution can be introduced into the bisulfite solution or added slowly dropwise.

The molar ratio of bisulfite to diol is 1:1 to 5:1
The ratio should be within the range of 1.1:1 to 2:1, preferably 1.1:1 to 2:1. Suitable catalysts for this reaction include air, oxygen or oxygen generating compounds such as H2O2, the oxygen having to be present in the reaction mixture as finely dispersed as possible, which can be achieved using a suitable stirrer. You can do it easily. High yields of sulfonate salts depend on the pH number of the reaction solution, which should be in the range 3-9, preferably in the range 5-8, about 7
A pH value of is particularly preferred. The required value is adjusted by adding the required amount of ammonia or lye to, for example, a bisulfite solution. During the reaction...the value changes towards the alkaline range. However, to adjust the pH value, do you add dilute acid at the same time?
Or it is kept at the required value by introducing more sulfur dioxide. The reaction... ends when there are no more fluctuations in value. Heating effects occurring during the reaction may optionally be offset by cooling. When relatively highly alkoxylated unsaturated diols are reacted, it is preferred to first introduce the unsaturated diol and then to heat the bisulfite solution in excess and add it dropwise under the above reaction conditions. .

Separation of most inorganic salts is best accomplished by concentrating the solution to about half its volume and eliminating precipitated crystals.

The desired reaction products can be separated from residual inorganic salts by extraction with acetone, mixtures of acetone and water, chlorinated hydrocarbons, alcohols and mixtures of alcohol and water. The sulfonate salts are obtained in analytically pure form with yields of up to 90%. The ether structure-containing sulfonic acid salts prepared according to the invention are eminently suitable for use as comonomers in the production of acid-modified polyesters and polyurethanes, for example when reacted with chloroacetic acid (ester). Later, it is also excellently suitable for producing acid-modified polyamides. Even more highly toxylated and/or propoxylated derivatives, optionally after reacting with isocyanate to form diurethanes, are excellent antistatic agents and can be used to prepare polyacrylonitrile with antistatic properties. or as an additive in the production of polyamide sheets, films and filaments. The preparation of copolyesters for polyester fibers dyeable with basic dyes is as described below. Terephthalic acid dimethyl ester 194.0 parts by weight? Ethylene glycol 186
．． A mixture of 0 parts by weight and 12.4 parts by weight of a dihydroxysulfonate represented by the following formula with 0.5 parts by weight of zinc acetate and 0.6 parts by weight of antimony trioxide was mixed with an anchor-shaped stirrer and a gas introduction pipe. , a dephlegmator, a condenser, a vacuum adapter and a receiver.

The contents of the reactor are heated to about 165° C. with nitrogen bubbling and then allowed to transesterify for 2 hours. The temperature is then increased to 280° C. over a period of 3 hours. After cutting off the nitrogen supply, the pressure is gradually reduced to 0.03 torr over 1 hour. The speed of the stirrer must then be reduced from about 150 revolutions per minute to about 20 revolutions per minute due to the steady increase in the viscosity of the melt. Polycondensation ends after another 4 hours? Ru. This colorless, homogeneous, highly viscous melt can be processed into shaped articles, especially filaments. The drawn filament can be dyed dark blue with basic dyes. The dyed finish is durable against washing. The polyester has a softening point in the range of 254-264°C and a relative solution viscosity (ηRel) of 2.02 (25°C
(measured on a solution of substance 19 in metacresol 100d at a temperature of ).

Next, the present invention will be explained in more detail with reference to Examples. Example 1 Ethoxylated 1,2-dihydroxy-3-butene 1,2-
Dihydroxy-3-butene 264f! (3 mol) and 2.6 g of sodium were added, and the resulting mixture was reacted with ethylene oxide 5289 (12 mol) in a pressure cooker at 100-110°C. I tried to keep it.

The reaction mixture was stirred until the excess pressure disappeared.
Determination of the 0H value produced gives a value of 13.560H%, which corresponds to a molecular weight of 250.8 and a total content of ethylene oxide 2n=3.7. Example 2 Propoxylated 1,2-dihydroxy-3-butene As in Example 1, 1,2 dihydroxy-3-butene 2649
(3 mol) was added with 1% sodium as a catalyst and the resulting mixture was reacted with propylene oxide 3489 (6 mol) in a pressure cooker at 140-150<0>C.

When measuring the OH number, we obtained a value of <Yl 6.52 OH%, which corresponds to a molecular weight of 206 and a total propylene oxide content of 2n=2.04.

Example 3 Ethoxylated butanediol sulfonate Ethoxylation 1 250.89 (1 mol) of 2-dihydroxy-3-butene (prepared according to Example 1) in 75 ml of water
0d, then diluted sodium hydroxide to pH 7.
A solution of bisulfite 2601 (1 mol) adjusted to 1 ml was added dropwise.

The reaction was initiated by blowing air through the glass frit, causing the temperature and pH to rise. ...The value was maintained within the range of 7.0 to 7.1 by adding dilute sulfuric acid dropwise.

The reaction will continue until the pH value becomes constant or the pH of the reaction mixture
It ends when the value becomes acidic by the dropwise addition of sulfuric acid.
The neutral aqueous solution was evaporated to dryness and the sulfonate was extracted with methanol. Yield: 298 g (theoretical yield: 84 g).

Example 4 Propoxylated butanediol sulfonate As in Example 3,
Propoxylated 1,2-dihydroxy-3-butene (Example 2
206y (l mol) (prepared according to the method) was introduced into 600 ml of water.

260 g (l mol) of sulfite 40% solution were then added dropwise in the presence of finely dispersed air. Dilute sulfuric acid was added dropwise to maintain the pH number of the reaction medium within the range of 7 to 7.1. The aqueous solution was then evaporated to dryness and the sulfonate was extracted with methylene chloride.

Yield: 2601 (theoretical yield: 84 cm). Example 5 Propoxylated butanediol sulfonate 366.41 (1 mol) of propoxylated 1,2-dihydroxy-3-butene with a total degree of propoxylation of 2n = 4.8 in 1000 g of water
d and then added dropwise with bisulfite solution 260y at pH 7-7.1 in the presence of finely dispersed air.

Once the addition was complete, the sululfonate was extracted with methylene chloride. Yield 4191 (89 g of theoretical yield) Example 6 Propoxylated butanediol sulfonate Propoxylated 1,2-dihydroxy-3-butene (propoxylated Bisulfite was added to an aqueous solution having a total concentration of 2n=9.5) and 640y while maintaining the value at 7.0 to 7.1.

Claims (1)

[Claims] 1 Contains an ether structure, and has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In this formula, A is a linear or branched alkyl having 1 to 6 carbon atoms. group, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, M
(e represents NH_4 or an alkali metal, m is 0 or 1, and n is a number from 1 to 10). 2. The ether structure-containing dihydroxysulfonic acid salt according to claim 1, wherein m in the above general formula is 0.