JPH0615038B2 - Alkoxylation catalyst - Google Patents

Description

TECHNICAL FIELD The present invention relates to an alkoxylation catalyst, and more particularly to an alkoxylation catalyst containing magnesium oxide as a main component.

[Prior Art] Alkylene oxide adducts of organic compounds having active hydrogen, such as alcohols and phenols, are valuable compounds having use as, for example, solvents, surfactants and intermediates of various chemical products. The alkoxylation reaction for obtaining such an alkylene oxide adduct has conventionally been carried out based on the following formula in the presence of a catalyst composed of an acid or an alkali.

Examples of the catalyst that has been conventionally used in the above reaction include soluble, strongly basic compounds of alkali metals such as lithium, sodium, calcium, rubidium and cesium, and metals such as boron, tin, zinc, antimony, iron, nickel and aluminum. Acid such as halide, sulfuric acid and phosphoric acid,
Phosphates of metals such as magnesium, zinc, calcium,
There are sulfates, perchlorates, oxalates, carboxylates and acetates.

[Problems to be Solved by the Invention] However, all of these catalysts have drawbacks. That is,
Acid catalysts such as Lewis acids and Friedel-Crafts catalysts
When the number of moles of alkylene oxide added increases, a side reaction occurs and a large amount of an undesired by-product such as dioxane, dioxolane or polyalkylene glycol is formed. Further, it has many disadvantageous properties as an industrial catalyst, such as strong corrosiveness to metals. Strongly basic catalysts such as caustic potash and caustic soda yield only a wide addition molar distribution. Soluble / basic compounds of alkaline earth metals described in U.S. Pat. Nos. 4,210,764, 4,223,164, 4,239,917, and 4,302,613. According to the catalyst consisting of, the addition mole distribution is narrower than that of the conventional strong alkaline catalyst, but it is still considerably wider than that of the acid catalyst.

Therefore, it is an object of the present invention to provide an alkoxylation catalyst which has an extremely narrow molar distribution of alkylene oxide addition and is capable of obtaining an unreacted and by-produced alkylene oxide adduct.

[Means for Solving the Problems] According to the present invention, Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl
Organic compound having active hydrogen and alkylene, which is composed of magnesium oxide to which one or more metal ions selected from the group consisting of ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , and Mn ²⁺ are added An alkoxylation catalyst for reacting with oxide is provided.

According to the alkoxylation catalyst of the present invention, the addition polymerization reaction of an organic compound having active hydrogen such as alcohol or phenol with an alkylene oxide is carried out with a small amount of unreacted and by-products, and the alkylene oxide addition mole An alkylene oxide adduct with a very narrow distribution is obtained.

The catalyst of the present invention is very useful as a catalyst for obtaining an alkylene oxide adduct by an addition polymerization reaction of an organic compound having active hydrogen with an alkylene oxide.

The organic compound having active hydrogen used in the present invention may be any one that can be alkoxylated, but alcohols, phenols, polyols, carboxylic acids, thiols, amines, and these A mixture of two or more kinds is preferably used.

The alkylene oxide used in the present invention may be any one as long as it can react with an organic compound having active hydrogen to form an adduct, but has 2 to 8 carbon atoms.
Of which adjacent carbons are epoxidized are preferred.
Particularly preferred alkylene oxide is ethylene oxide, propylene oxide, or a mixture of both.

In the catalyst of the present invention, Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc added to magnesium oxide.
The amount of ³⁺ , La ³⁺ , or Mn ²⁺ is 0.1 to 3 of the catalytic amount.
0 wt% is preferable, and 0.5 to 20 wt% is more preferable.

The method for producing the catalyst of the present invention is not particularly limited, but it can be produced by a known method as a method for preparing a multi-component complex oxide. For example, Al ³⁺ , Ga ³⁺ , In ³⁺ , T
An aqueous solution of nitrate or carbonate containing l ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , or Mn ²⁺ is impregnated with magnesium oxide having a purity of 99% or more, and then in a nitrogen stream or under vacuum. At 400 to 1000 ° C., preferably 500 to 80
A method of firing at 0 ° C. (impregnation method), or mixing magnesium nitrate and nitrates of the above-mentioned respective metals at a predetermined ratio to form an aqueous solution thereof, and then adding a hydrate of hydroxide or complex oxide After precipitation, filtration, washing and drying, a method of baking in the same manner as the impregnation method (coprecipitation method), and a general formula Mg _1-x A
1 _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O is used as a layered compound (hydrotalcite) or a metal ion Al ³⁺ in the general formula, Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co
It can be produced by a method of forming a composite oxide by firing a compound substituted with ³⁺ , Sc ³⁺ , or La ³⁺ under the same conditions as in the above-mentioned impregnation method.

As alcohols, linear or side chain primary or secondary alcohols having 2 to 30 carbon atoms are preferable, and primary alcohol having 6 to 24 carbon atoms is more preferable. These alcohols can be used not only alone but also as a mixture of two or more kinds. Typical alcohols include linear primary alcohols such as n-octanol, n-decanol, n-dodecanol, n-tetradecanol and n-octadecanol, 5-ethylnonanol-2,2,5. Side chain secondary alcohols such as, 8-trimethylnonanol-4,2-methyl-7-ethylundecanol-4 and 3,9-diethyltridecanol-6,
Side chain primary oxo alcohol having 8 to 22 carbon atoms, DOBA
DOL-23 (trade name, mixture of C12 / C13 = 45/55, linear ratio: about 80%, manufactured by Mitsubishi Petrochemical Co., Ltd.), DIALOL
-13 (trade name, C13, linear rate: about 50%, manufactured by Mitsubishi Kasei), NEODOL-23 (trade name, C12 / C13 = 45)
/ 55 mixture, linear ratio: about 80%, manufactured by Shell Co.) and the like.

[Operation] The alkoxylation reaction using the catalyst of the present invention can be easily carried out under usual operating procedures and reaction conditions.
The reaction temperature is preferably 80 to 230 ° C, more preferably 120 to 180 ° C, most preferably 120 to 160 ° C.
Is. If the reaction temperature is too low, the reaction rate will be slow, and if it is too high, the product will decompose. The pressure depends on the reaction temperature, but is preferably 0 to 20 atm, more preferably 2 to 8 atm.
atm.

The amount of the catalyst used varies depending on the molar ratio of the alkylene oxide to be used in the reaction and the alcohol or the like, but is usually preferably 0.1 to 20% by weight of the amount of the alcohol or the like,
0.5 to 6% by weight is more preferable.

The alkoxylation reaction using the catalyst of the present invention is, for example, charging an alcohol and a catalyst in an autoclave, introducing an alkylene oxide under a predetermined temperature and pressure conditions in a nitrogen atmosphere to cause a reaction, and then cooling. It can be carried out by filtering off the catalyst.

The products obtained with the catalysts according to the invention are essentially neutral, so it is not necessary to neutralize the products by addition of acids or alkalis as with the conventional catalysts.

[Effect] According to the alkoxylation catalyst of the present invention, the addition polymerization reaction of an organic compound having active hydrogen such as alcohol or phenol with an alkylene oxide is carried out with a small amount of unreacted and by-products, and An alkylene oxide adduct having a very narrow molar distribution of oxide addition is obtained.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention.

Example 1 20 g of magnesium oxide (MgO) powder (purity 99%) was added to 500 g of a 1% aluminum nitrate aqueous solution, and after sufficiently stirring, the mixture was evaporated to dryness. Then, after drying at 110 ° C overnight, pulverize and gradually raise the temperature in a nitrogen stream to 600 ° C.
It was heat-treated for 2 hours to obtain a catalyst. Al in this catalyst
The amount of ³⁺ was 3% by weight.

Next, 120 g of lauryl alcohol having a water content of 100 ppm and 2.5 g of the above-mentioned catalyst were charged into the autoclave, the inside of the autoclave was replaced with nitrogen, and then the temperature was raised with stirring. Next, the temperature is 160 ° C and the pressure is 3 atm.
While maintaining the above temperature, 84 g of ethylene oxide (EO) was introduced and reacted for about 2.0 hours. Next, it cooled at 70 degreeC and filtered off the catalyst.

The average number of moles of EO added of the ethoxylate thus obtained was 3.0. EO of this ethoxylate
When the addition mole distribution was determined by the liquid chromatography method, the result shown by the curve A in FIG. 1 was obtained. In FIG. 1, the vertical axis represents the weight% of each ethoxylate component relative to the weight of ethoxylate, and the horizontal axis represents the number of moles of EO added. The curve B shows the EO-added mole distribution of the ethoxylate obtained by using the conventional NaOH catalyst, as shown in the comparative example 2 described above.

As is clear from the comparison between curve A and curve B, the ethoxylates obtained with the catalyst of the invention show a much narrower EO-added mole distribution than the ethoxylates obtained with the conventional catalysts. Recognize.

The unreacted alcohol was 5.2% by weight, and the by-product polyethylene glycol was 0.1% by weight, which were very small.

Example 2 A reaction was carried out in the same manner as in Example 1 except that the amount of catalyst was 5 g and the reaction temperature was 180 ° C.

The average number of moles of EO added to the ethoxylate thus obtained, the amount of unreacted alcohol, and the amount of polyethylene glycol, which is a by-product, were measured in the same manner as in Example 1, and each was 5.7. , 0.1% by weight, and 1% by weight. Further, as shown in FIG. 2, the EO-added molar distribution of the ethoxylate is very narrow in the ethoxylate obtained by using the catalyst of the present invention as compared with the ethoxylate obtained by using the conventional catalyst. Recognize. In FIG. 2, the curve C is the EO of the ethoxylate obtained in this example.
The addition mole distribution is shown, and the curve D shows the EO addition mole distribution of the ethoxylate obtained by using the conventional NaOH catalyst as shown in Comparative Example 3 described later.

Example 3 0.9% instead of 500 g of 1% aluminum nitrate aqueous solution
% In the same manner as in Example 1 except using gallium nitrate aqueous solution 500 g, to obtain a MgO catalyst Ga ³⁺ was added. The amount of Ga ^{3+ in} this catalyst was 6% by weight.

Using 5 g of this catalyst, an EO amount of 93 g and a reaction time of 1.
The reaction was performed in the same manner as in Example 1 except that the time was 5 hours.

The average number of moles of EO added and the amount of unreacted alcohol of the ethoxylate thus obtained were measured in the same manner as in Example 1, and were 3.3 and 3.8% by weight, respectively. The EO addition molar distribution of ethoxylate is
As shown by the curve E in FIG. 3, it can be seen that it is very narrow.

Example 4 0.5 instead of 500 g of 1% aluminum nitrate aqueous solution
% Mn ²⁺ aqueous solution was used in the same manner as in Example 1 to obtain a MgO catalyst to which Mn ²⁺ was added. The amount of Mn ^{2+ in} this catalyst was 3% by weight.

A reaction was performed in the same manner as in Example 1 except that 5 g of this catalyst was used, the EO amount was 67 g, and the reaction time was 6 hours.

The average number of moles of EO added and the amount of unreacted alcohol of the ethoxylate thus obtained were measured in the same manner as in Example 1, and were 2.4 and 11.3% by weight, respectively. Further, the EO-added mole distribution of ethoxylate was narrow as shown by the curve F in FIG.

Comparative Example 1 Only 20 g of MgO powder (purity 99%) was heat-treated in a nitrogen stream in the same manner as in Example 1 as a catalyst, and the reaction was carried out in the same manner as in Example 1 to obtain a catalyst. Showed no activity at all.

Comparative Example 2 After 376 g of lauryl alcohol and 0.2 g of caustic soda (0.05% by weight / lauryl alcohol) were charged into the autoclave and the inside of the autoclave was replaced with nitrogen,
After stirring and depressurizing to 130 ° C to dehydrate,
Furthermore, while raising the temperature to 180 ° C. and maintaining the pressure at 3 atm, 260 g of EO was introduced and the reaction was carried out for about 2.0 hours.

The thus obtained ethoxylate has an EO average addition mole number of 2.9, unreacted alcohol is 14% by weight,
Polyethylene glycol was 1% by weight. When the EO-added molar distribution of this ethoxylate was determined, the result shown by the curve B in FIG. 1 was obtained.

As is clear from the comparison between the curve A and the curve B, the ethoxylate obtained using the conventional catalyst exhibits a much broader EO-added mole number distribution than the ethoxylate obtained using the catalyst of the present invention. I understand.

Comparative Example 3 The reaction was carried out in the same manner as Comparative Example 2 except that the amount of EO was 440 g and the reaction time was 1.5 hours.

When the average number of moles of EO added and the amount of unreacted alcohol of the obtained ethoxylate were measured in the same manner as in Example 1, they were 5.0 and 6% by weight, respectively. Further, it can be seen that the EO-added mole distribution of the ethoxylate is much wider than that of the ethoxylate obtained using the catalyst of the present invention (curve C), as shown by the curve D in FIG.

Example 5 140 g of methyl 9-hydroxymethylstearate and 5.5 g of the catalyst obtained in Example 1 were charged into an autoclave, the inside of the autoclave was replaced with nitrogen, the pressure was reduced to 1 mmHg or less with stirring, and the temperature was raised to 80 ° C. It was heated and dehydrated for 1 hour. While maintaining the temperature at 120 ° C. and the pressure at 3 to 5 atm, 95 g of EO was introduced and the reaction was performed for about 6 hours. The thus obtained ethoxylate had an average added mole number of EO of 5.0.

Example 6 Magnesium nitrate (hexahydrate) 31 was added to 1250 g of pure water.
8g and aluminum nitrate (9-hydrate) 21.5g were added,
250m of 28% aqueous ammonia was added to the mixed aqueous solution.
l was added for coprecipitation. The precipitate was then filtered, washed with water, dried at 110 ° C. and sieved to a particle size of 20-50 mesh. The powder thus obtained was gradually heated in a nitrogen stream and heat-treated at 600 ° C. for 2 hours to obtain a catalyst.

Using this catalyst, an EO addition reaction was conducted in the same manner as in Example 1 except that the reaction temperature was 140 ° C., and the obtained ethoxylate had an average EO addition mole number of 3.0. . The unreacted alcohol content and the EO addition mole distribution were the same as in Example 1.

Example 7 The same procedure as in Example 1 was carried out except that 7.4 g of the catalyst obtained in Example 6 was used, the amount of lauryl alcohol was 369 g, the amount of EO was 1039 g, and the reaction time was about 3.5 hours. EO addition reaction was carried out. The average added mole number of EO of the obtained ethoxylate was 11.9.

Example 8 In an autoclave, 512 g of DOBANOL-23 (manufactured by Mitsubishi Petrochemical Co., Ltd.) and 10 g of the catalyst obtained in Example 6 were charged, EO349 g was introduced by the same method and conditions as in Example 6, and EO was added for about 2 hours. The reaction was carried out. The average added mole number of EO of the obtained ethoxylate was 3.0.

Example 9 496 g of DOBANOL-13 (manufactured by Mitsubishi Petrochemical Co., Ltd.) and 20 g of the catalyst obtained in Example 6 were charged into an autoclave, and EO1941 g was introduced under the same method and conditions as in Example 6 for about 5.5 hours. The EO addition reaction was performed. The average added mole number of EO in the obtained ethoxylate was 17.2.

Example 10 Magnesium nitrate (hexahydrate) 318 was added to 500 g of pure water.
g and aluminum nitrate (9-hydrate) 21.5 g were added and mixed to obtain an aqueous solution, and 500 ml of 28% aqueous ammonia was added for coprecipitation. The precipitate was then filtered, washed with water, dried at 110 ° C. and sieved to a particle size of 20-150 mesh. The powder thus obtained was gradually heated in a nitrogen stream and heat-treated at 600 ° C. for 2 hours to obtain a catalyst.

An EO addition reaction was conducted in the same manner as in Example 1 except that 1.5 g of this catalyst was used and the reaction temperature was 140 ° C., and the average number of moles of EO added of the obtained ethoxylate was 3.0. Met. Unreacted alcohol content, E
The distribution of added moles of O was the same as in Example 1.

Example 11 100 g of hydrotalcite having a chemical composition of Mg ₆ Al ₂ (OH) ₁₆ (CO ₃ ) .4H ₂ O was added to 0.1 Torr.
Under reduced pressure, the temperature was gradually raised to 600 ° C., and heat treatment was performed for 2 hours to obtain 55 g of catalyst powder.

An EO addition reaction was carried out in the same manner as in Example 1 except that 1.5 g of this catalyst was used and the reaction temperature was 180 ° C. The average number of moles of EO added of the ethoxylate in the obtained product was 3.0. The unreacted alcohol content and the EO addition mole distribution were the same as in Example 1.

Example 12 An aqueous solution of various metal salts shown in Table 1 below was mixed with 20 g of magnesium oxide (MgO), sufficiently stirred, and then evaporated to dryness. Then, after drying at 110 ° C. overnight, the powder was pulverized and heat-treated at 600 ° C. for 2 hours in a nitrogen stream to obtain a MgO catalyst to which various metal ions were added.

Using this catalyst, an EO addition reaction was carried out under the same conditions as in Example 2. The average number of moles of EO added, the amount of unreacted alcohol, and the amount of by-produced polyethylene glycol of each obtained ethoxylate are shown in Table 1 below.

Further, the respective EO-added mole distributions are as shown in FIG. 4 curves GI and FIG. 5 curves J-L, and it was found that all exhibit extremely narrow EO-added mole distributions.

[Brief description of drawings]

FIG. 1 shows the EO adduct molar distribution of ethoxylates obtained using a catalyst according to one embodiment of the present invention in comparison with the EO adduct molar distribution of ethoxylates obtained using a conventional catalyst. FIG. 2 and FIG. 2 compare the EO addition mole distribution of ethoxylates obtained using the catalyst according to another embodiment of the present invention with the EO addition mole distribution of ethoxylates obtained using the conventional catalyst. And FIG. 3 are diagrams showing the EO addition mole distribution of ethoxylates obtained using the catalyst according to still another embodiment of the present invention, and FIGS. 4 and 5 are the present invention. FIG. 6 is a graph showing the EO addition mole distribution of the ethoxylate obtained using the catalyst according to yet another example of FIG.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C07C 41/03 43/11 8619-4H 67/29 8018-4H 69/708 Z 9279-4H // C07B 61 / 00 300

Claims (1)

[Claims] 1. A ³⁺ , Ga ³⁺ , In ³⁺ , T ³⁺ , C
an organic compound having active hydrogen, which comprises magnesium oxide to which one or more metal ions selected from the group consisting of o ³⁺ , Sc ³⁺ , La ³⁺ , and Mn ²⁺ is added, and an alkylene oxide. An alkoxylation catalyst for reaction.