JPS6029370B2 - Method for producing alkylene oxide adducts - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing alkylene oxide adducts, and more particularly to a process for producing alkylene oxide adducts in which the product has a significantly narrow distribution of degree of polymerization in the presence of a novel catalyst.

In recent years, alkylene oxide adducts, in which alkylene oxides such as ethylene oxide and propylene oxide are added to alcohols, have rapidly expanded as surfactants due to their excellent performance as surfactants, either as they are or when further sulfated. It has come to be widely used in pharmaceuticals, cosmetics, pharmaceuticals, etc.

In order to produce this alkylene oxide adduct, generally an alkali catalyst such as caustic soda, caustic potash, or sodium alkoxide is used as a catalyst, and boron trifluoride, boron trifluoride complex (etherate, phenolate, acetate, etc.), antimony pentachloride, Acidic catalysts such as tin tetrachloride are used.

However, each of these known catalysts has advantages and disadvantages.

In other words, when an alkali catalyst is used, it is possible to produce an alkylene oxide adduct with a desired average number of added moles for primary alcohols in one step, but even in that case, the amount of unreacted alcohol remaining remains. It is known that many have a relatively wide polymerization degree distribution. If unreacted alcohol remains, it may impart an unpleasant odor to the alkylene oxide adduct or its sulfate ester salt (
(Japanese Patent Publication No. 51-43483 (Specification of Japanese Patent Publication No. 51-43483)), it is desirable that the remaining amount of unreacted alcohol be as small as possible since this may cause unfavorable results in performance as a surfactant (Specification of US Pat. No. 3,682,84y). On the other hand, when the alcohol is a secondary or tertiary alcohol, these problems become even more pronounced, and not only a large amount of unreacted alcohol remains, but also the distribution of the number of moles of alkylene oxide added is significantly broadened. In practice, it is completely impractical to add alkylene oxides to secondary and tertiary alcohols with alkaline catalysts.

On the other hand, when acidic catalysts are used, even with secondary and tertiary alcohols, these drawbacks are considerably alleviated, but if one wants to obtain high molar adducts in one step, alkylene oxides must be used. Since a large amount of by-products are produced and the yield of alkylene oxide is reduced, a method of adding alkylene oxide in two steps must be used.

That is, in the first stage, low molar adducts (
The average number of moles added is 1 to 6 moles), then the remaining unreacted alcohol is removed by distillation or other operations, and then a predetermined high-molar adduct is produced using a re-alkali catalyst. It's unbearable. Therefore, even when an acidic catalyst is used, it is required that the remaining amount of unreacted alcohol be as small as possible. Several attempts have been made in recent years to meet these requirements, and the use of oxonium salts of boron trifluoride and antimony pentachloride has been proposed, but none of them are as effective as expected, and alkylene oxide At present, it has not been put to practical use as a catalyst for producing adducts.

As a result of intensive research and exploration to improve these drawbacks, the present inventors surprisingly discovered that indium halide has a unique and excellent catalytic effect not found in known catalysts.

That is, in the reaction of adding alkylene oxide to alcohol, the inventors discovered that when indium halide is used as a catalyst, an adduct with a significantly narrow polymerization degree distribution and a significantly high alcohol conversion rate can be obtained, and this led to the completion of the present invention. Ta. The present invention is a method for producing an alkylene oxide adduct, which is characterized by reacting an alkylene oxide and a compound having an alcoholic hydroxyl group in the presence of an indium halide.

In general, it is known that some Lewis acids, mainly metal halides, have an effective catalytic effect on the reaction between alkylene oxides and alcohols as acidic catalysts, and representative examples include boron trifluoride, Boron trichloride complex, tin tetrachloride, antimony pentachloride, and zinc chloride are well-known, but titanium tetrachloride and aluminum chloride, which are known as alkylene oxide polymerization catalysts, are of little use as catalysts for this addition reaction. It is known that (Industrial Chemistry Magazine No. 6 Group No. 11, page 94 (1)
963 King)).

When the present inventors investigated the above-mentioned acid catalysts, it was found that zinc chloride had extremely low catalytic ability, and when antimony pentachloride was used alone, it caused significant coloring and did not provide useful results as a catalyst.

On the other hand, in the reaction between a random secondary alcohol having 11 to 19 carbon atoms and ethylene oxide, we investigated using boron trifluoride etherate and tin tetrachloride catalysts.
The distribution constant (C) calculated on the assumption that the degree of polymerization distribution follows the distribution law of Weibul 1 is as shown in Comparative Example 1 (described later) using a boron trifluoride etherate catalyst and a C=4.1 tin tetrachloride catalyst (described later). As in Comparative Example 2, a value of C=1.82 was obtained, indicating that the degree of polymerization distribution was relatively wide. On the other hand, in the case of caustic soda, which is an alkali catalyst, as in Comparative Example 5 described below, the degree of polymerization distribution was extremely wide, with C=36.1. However, surprisingly, when an indium halide catalyst was used, a value of C = 1.0 to 1.2 was obtained.
It was found that the degree of polymerization distribution was extremely close to the distribution of the degree of polymerization.
Furthermore, when ethylene oxide was added to 1-dodecanol and 2-octanol using indium halide as a catalyst as in Examples 3 and 4 described later, the distribution constants were extremely narrow with C=0.27 and C=0.63, respectively. An adduct with a degree of polymerization distribution was obtained. Weib
A sail distribution constant of 1 or less than 1 means that the reaction rate at which alkylene oxide is added to alcohol is equal to the rate at which alkylene oxide is added to what has already been added, or the former is faster.
This shows that indium halide has a much narrower polymerization degree distribution than boron trifluoride enalate or tin tetrachloride, and gives an adduct with an extremely small amount of unreacted alcohol remaining. In particular, in the reaction between nododecanol, which is a primary alcohol, and ethylene oxide, when a common catalyst such as caustic soda or boron trifluoride etherate catalyst is used, the average number of moles added ( n) The amount of unreacted alcohol remaining at 2.0 mol is 22. Although the neck weight% is 11.2% by weight, as is clear from Example 3 of the present invention, when an indium halide catalyst is used, the residual amount of unreacted alcohol is 1% by weight or less. That's surprising. The alkylene oxide used in the present invention may be any epoxide-containing substance in terms of its properties, but ethylene oxide, propylene oxide, and butylene oxide are particularly important industrially.

The compounds having an alcoholic hydroxyl group used in the present invention are monohydric and polyhydric alcohols of aliphatic, alicyclic, and alkyl aromatic alcohols having 1 to 24 carbon atoms.

These alcohols may be saturated or unsaturated, linear or branched, may contain heteroatoms in their alkyl groups or rings, or may be substituted with heteroatoms. . Moreover, these alcoholic hydroxyl groups can be primary, secondary and tertiary alcoholic hydroxyl groups. Specifically, examples of aliphatic alcohols include methanol, ethanol, n-propanol, i-propanol, 1-butanol, 2-phtanol, tertiary butanol, 1-hequinol, 1-octanol, 2-octanol, 2-ethylhexanol, and 1-propanol. -decanol, 1-dodecanol, 1-tetradecanol, oleyl alcohol, linoleyl alcohol, stearyl alcohol, 4-chlorptanol-1,
These include 3-oxyethyl methyl ether, 8-oxyethyl ethyl ether, 8-oxyethyl butyl ether, oxo alcohol using olefin as a raw material, Ziegler alcohol using ethylene as a raw material, and secondary alcohols produced by paraffin oxidation.

Examples of the alicyclic alcohol include tetrahydrofurfuryl alcohol, cyclohexanol, cyclododecanol, cyclononadecanol, and alkylcyclohexanol having an alkyl group having 1 to 12 carbon atoms.

Examples of the alkyl aromatic alcohol include penzyl alcohol and cinnamyl alcohol.

Examples of polyhydric alcohols include glycerin, sorbitol, hexanetriol, bentaerythritol,
These include trimethylolethane, trimethylolpro/gum, sorbitol, mannitol, monoethylene glycol, diethylene glycol, triethylene glycol, and the like.

The indium halides used as catalysts in the present invention are indium trivalent halides of fluorine, chlorine, bromine, and iodine, and may be anhydrous halides or hydrated (for example, trivalent, trivalent, and pentavalent halides). (Japanese) may also be used. Preferably, it is advantageous to use an anhydride because the amount of undesirable by-products can be reduced. The amount of indium halide added as a catalyst varies depending on the desired number of moles of ethylene oxide added and the alcohol used.
A range of 0.01 to 1% by weight based on the alcohol is practically preferred.

Of course, it is clear from the following examples that there is no upper limit to the amount added. Usage forms include powder, sand, granules, and liquid dissolved in organic solvents such as ether, among which the appropriate form should be selected based on ease of handling, price, etc. Especially for reaction systems. It is desirable to have a material that can be finely dispersed in the liquid and easily dissolved.

The catalyst will be added by mixing it with the alcohol or by providing an independent addition port, but in either case, the catalyst can be added in its entirety from the beginning, or it can be added in a fixed amount continuously or intermittently during the reaction. There is. Either method is possible. Practically speaking, it may be selected appropriately taking into consideration the reaction format, operating method, etc. The reaction formula in the present invention can be a batch type, a semi-batch type, or a continuous type. The reaction temperature is 10 to 20,000, especially 50 to 150
qo is preferred from the viewpoint of reaction rate; temperatures below 1,000 cause the reaction to be extremely slow, and temperatures above 20,000 impart undesirable coloration to the reaction product and should therefore be avoided. In addition, there is no particular restriction on the reaction pressure, and it is possible to use either normal pressure or elevated pressure, but if the pressure is low, the reaction rate may decrease due to a decrease in the solubility of the alkylene oxide, and the alkylene oxide may escape. is produced, so pressurization with an inert gas such as nitrogen is preferred industrially. In the present invention, after the reaction of alkylene oxide and a compound having an alcoholic hydroxyl group in the presence of indium halide, the catalyst may remain in the product, or if this is inconvenient, water, Alternatively, the solid produced by adding an alkaline aqueous solution may be removed by filtration or by dissolving it in an acid, or may be removed using an ion exchange resin or the like.

The advantage of the present invention is that indium halide has a unique and excellent effect that conventionally known catalysts do not have, that is, in the reaction between alcohol and alkylene oxide, the product has a narrow degree of polymerization distribution, and the amount of unreacted alcohol remaining is extremely small. The point is that it gives

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited only to the examples. In addition, the polymerization degree distribution constant C of the ethylene oxide adduct based on Weib's distribution law in the Examples and Comparative Examples is in accordance with the following definition. u=c lno female-(c-1)(1-
where u: Average number of moles of ethylene oxide added per mole of alcohol no: Number of moles of alcohol no: Number of moles of unreacted alcohol in the reaction product C: Distribution constant Example 1 Gas exhaust pipe and glass 3 with gas blowing pipe with filter
00' glass cylindrical reactor with capacity scale, carbon number 11
~19% random secondary alcohol (Hydroxyl number H
V=279) for 100 nights and 2 nights for indium trichloride (
After adding the anhydride), the temperature was raised to 100°C.

Next, nitrogen gas was passed through the ethylene oxide cooled to 8 to 10 q0 at a rate of 80 min, and the entrained ethylene oxide was introduced into the reactor. Reaction temperature 100℃
Ethylene oxide was continued to be introduced while maintaining the temperature until the weight increase reached 46 days. After the ethylene oxide injection was completed, the mixture was aged at 10,000°C for 3 minutes, and then 20 minutes of water was added to hydrolyze the catalyst, followed by mixing at 90°C for 30 minutes. After solid precipitation, the treated solution was subjected to a furnace, and water-butanol extraction method (Industrial Chemistry Magazine No. 64, No. 4, pp. 635-638, 19
After removing the by-product polyethylene glycol (1961), the treated solution was dehydrated under reduced pressure. The analytical value of the obtained ethylene oxide adduct was HV=194 (corresponding to the average number of added moles of ethylene oxide n=2.0 moles), and the amount of reaction alcohol was 11.2% by weight. The distribution constant (C) calculated on the assumption that this adduct complies with the Weib Mountain 1 distribution law was 1.18. Example 2 The same method as in Example 1 was used except that 10 tons of indium trichloride (tetrahydrate) was added and the weight increase was 48 mm, but n = 2.
．． 0 mol of adduct was obtained.

The amount of unreacted alcohol in the adduct was 10.5% by weight, and C=1.11. Example 3 In the same manner as in Example 1, n=2.
0 mol of adduct was obtained.

The amount of terminally reacted alcohol in the adduct is 0. mother weight%,
C=0.27. Example 4 An adduct of 2.0 mol of Ni was obtained in the same manner as in Example 1, except that 100 mol of 2-octanol and 5 mol of indium trichloride (anhydride) were added as a catalyst to the raw material, and the weight increase was 70 mol. .

The amount of reaction alcohol in the adduct was 4.3% by weight,
C=0.63. Example 5 Indium trichloride (anhydrous) was used for 2 hours, and the weight increase was 3.
n = 1.0 using the same method as Example 4 except that 5 days were used.
A molar reaction solution was obtained.

When the addition mole distribution of this adduct was measured by gas chromatography, the peak area ratio was as shown in Table (1).
The distribution of the number of moles added was clearly narrower than that of the boron trifluoride etherate and tin tetrachloride catalysts described in Comparative Examples 6 and 7.
Example 6 In the same manner as in Example 1, except that 5 t of indium tribromide (anhydrous) was added instead of indium trichloride (anhydrous) and the weight increase was 35 mol, n = 1.5 mol was prepared. An adduct was obtained.

The amount of unreacted alcohol in the adduct was 16.3% by weight, and C=1.0. Example 7 An adduct with n: 1.5 mol was obtained in the same manner as in Example 6 except that 10 t of indium tribromide (anhydrous) was added instead of indium tribromide (anhydrous).

The amount of unreacted alcohol in the adduct is 18. % by weight, and C=1.16. Example 8 In the same manner as in Example 3, except that 10 tons of indium trichloride (anhydride) was added and the weight increase was 170 tons, n=
7.0 moles of adduct were obtained.

No amount of unreacted alcohol was detected in the adduct, there was no off-odor, and extremely good surface activity was exhibited. Comparative Example 1 The same method as in Example 1 was used except that 0.5 t of boron trifluoride etherate was used instead of indium trichloride (anhydride), the reaction temperature was 50 0, and the weight increase was 48 t. n = 2. .0 mol of adduct was obtained.

The amount of unreacted alcohol in the adduct was 27''% by weight, and C=4.15. Comparative Example 2 Comparative Example 1 except that tin tetrachloride (anhydrous) was used instead of boron trifluoride etherate and the weight increase was 46 mm.
An adduct with n=2.0 mol was obtained in the same manner as above.

The amount of unreacted alcohol in the adduct was 16.4% by weight, and C=1.82. Comparative Example 3 An adduct of n=2.0 mol was obtained in the same manner as in Comparative Example 1, except that 1 dodecanol was used as the raw material and the weight increase was 50 molar.

The amount of unreacted alcohol in the adduct was 11.2% by weight, and C=1.20. Comparative Example 4 Using 100 qo of 1-dodecanol as a raw material, 0.5 qo of caustic soda was added as a catalyst, and the sodium alcoholate of 1-dodecanol was made by heating and dehydrating under reduced pressure.
The reaction was carried out to obtain an adduct of n=2.0 mol.

The amount of unreacted alcohol in the adduct is 22. Box weight %, C=3.13. Comparative Example 5 An adduct of n=2.0 mol was obtained in the same manner as in Comparative Example 4, except that a random secondary alcohol was used as the raw material and the weight increase was 44 days.

The amount of unreacted alcohol in the adduct was 50.2% by weight, and C=36.1. Comparative example 6 Tri-boron etherate was added for 0.5 hours, weight increase was 36
An adduct of n=1.0 mol was obtained in the same manner as in Example 5 except that the reaction temperature was changed to 5 psi.

When the addition mole distribution of this adduct was measured by gas chromatography, the peak area ratio was as shown in Table (1).
The distribution was clearly wider than the results of Example 5. Comparative Example 7 n=1.
0 mol of adduct was obtained.

When this added mole number distribution was measured by gas chromatography,
The peak area ratio was obtained as shown in Table (1), and Example 5
The distribution was clearly wider than the results of . Table 1

Claims (1)

[Claims] 1. A method for producing an alkylene oxide adduct, which comprises reacting an alkylene oxide and a compound having an alcoholic hydroxyl group in the presence of an indium halide.