JP2784622B2 - Method for producing polyether compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerization method for producing a polyether having a narrow molecular weight distribution when a nonionic surfactant or the like is produced by addition-polymerizing an alkylene oxide to a compound containing active hydrogen. .

[0002]

2. Description of the Related Art Polyether compounds obtained by addition-polymerizing an alkylene oxide to a compound containing active hydrogen, such as alcohols, phenols, amines, and organic carboxylic acids, are used in various surfactants, solvents, and chemical intermediates. body,
It is a compound useful as a polyurethane resin raw material and the like. The polyether compound is conventionally, for example, a halide of a metal such as boron, tin, nickel zinc, or aluminum, an acidic catalyst such as sulfuric acid and phosphoric acid, or a hydroxide, a carbonate or an alkali metal such as lithium, sodium, potassium, and cesium. It was manufactured using a basic catalyst such as an amine compound.

[0003]

However, each of these catalysts has disadvantages. For example, in the case of an acidic catalyst, a dioxane derivative or the like is by-produced by a side reaction when the number of added moles of the alkylene oxide is increased, and the acidic catalyst is often corrosive to metals, and is used for industrial production of polyether compounds It is disadvantageous as a catalyst. On the other hand, when a basic catalyst is used, there is a problem that only a polyether compound having a wide addition molar distribution can be obtained. In order to solve these problems, a method using a calcined magnesium oxide-containing compound as a catalyst (Japanese Patent Laid-Open No. 1-14433).
7), a method using calcined hydrotalcite as a catalyst (Japanese Patent Laid-Open No. 2-71841) has been proposed,
These catalysts are used to provide a catalytic activity of 400 to 60.
It requires firing at a high temperature of 0 ° C. for 2 to 8 hours, and there is a problem that the process is complicated and requires unnecessary energy.
It is not economical because it cannot be easily reused repeatedly.

[0004]

Means for Solving the Problems The present inventors have made intensive studies on a method for solving the above-mentioned problems, and as a result, have reached the present invention. That is, in the present invention, a mixed system of a hydrotalcite (A) and an initiator (B) containing active hydrogen in a molecule is pretreated under reduced pressure at 100 to 300 ° C., and then an alkylene oxide (C) Which is a process for producing a polyether compound.

The hydrotalcites (A) used in the present invention include compounds represented by the following general formula (1). [Mg _1-x Al _x (OH) ₂ ] ^{x +} [CO _{3x / 2} · mH ₂ O] ^x− (1) [where x and m are 0 <x ≦ 0.33, 0 <m ≦ 1. 0 is satisfied. As specific examples of (A), the following formulas (2) and (3)
The following are mentioned. _{Mg 6 Al 2 (OH) 16} CO 3 · 4H 2 O (2) Mg 4.5 Al 2 (OH) 13 CO 3 · 3.5H 2 O (3) mineral These are naturally occurring or obtained by synthesis, And published in West German Patent Publication No. 1592126.
And known substances described in European Patent Publication No. 0207811, and the like. The Mg ²⁺ / Al ³⁺ ratio of these natural and synthetic hydrotalcites is variable and is about 1-8, and the OH ⁻ / CO ₃ ^2- ratio is also variable and is about 10-20.

The amount of (A) used in the present invention is usually 0.1 to 15, preferably 1 to 10% by weight based on the final finished amount of the polyol compound to be produced.

The initiator (B) containing an active hydrogen atom in the molecule used in the present invention includes, for example, monohydric alcohols (eg, methanol, butanol, lauryl alcohol, stearyl alcohol and allyl alcohol); polyhydric alcohols (2 Octahydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane,
Castor oil, pentaerythritol, sorbitol and sucrose); amine compounds (for example, mono- or dialkyl (C1-30) amine, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, toluenediamine and isophoronediamine); alkanols Amines (eg, monoethanolamine, monoisopropanolamine, diethanolamine and triethanolamine); phenols (eg, alkylphenols and bisphenols); organic carboxylic acids (eg, propionic acid, acrylic acid, phthalic acid, adipic acid, stearic acid and trimellitate). Acid); compounds obtained by addition-polymerizing an alkylene oxide to these compounds having active hydrogen; Include mixtures of more.

The alkylene oxide (C) used in the present invention includes ethylene oxide, propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide, tetrahydrofuran, etc., preferably ethylene oxide and propylene oxide. Oxide, particularly preferably ethylene oxide.

In the present invention, as a specific example of a pretreatment method for imparting catalytic activity to (B), for example, (B) and (A) are mixed in a reaction vessel in advance, and the mixture is subjected to normal pressure, preferably reduced pressure. (0 to 50 mmHg), a method of performing dehydration usually at 100 to 300 ° C, preferably 140 to 200 ° C for 1 to 4 hours.

As a method for addition polymerization of the alkylene oxide (C), for example, after pretreating a mixture of (A) and (B) by the above-mentioned method, the temperature in the reaction system is raised to 80 to 200.
° C and the pressure in the reaction system is -0.5 to 6 kgf / cm ²
For example, a method in which (C) is introduced so as to reach G, and after completion of the addition of a predetermined amount of (C), aging is performed at 80 to 200 ° C. until the pressure in the reaction system reaches equilibrium.

After completion of the polymerization by the method of the present invention, the desired polyether compound can be obtained by separating the polymer and (B) by a usual filtration operation. At this time, if necessary, a diatomaceous earth-based filter aid (for example, radiolite manufactured by Showa Chemical Industry Co., Ltd.) can be used as a filter aid to shorten the time required for the filtration operation.

After the reaction, the polymer (B) separated from the polymer is mixed with fresh (A) and subjected to the above-mentioned pretreatment (dehydration) to give the catalyst activity again. This reuse can be repeated.

[0013]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Parts in Examples and Comparative Examples are parts by weight.

EXAMPLE 1 270 parts (1 mol) of stearyl alcohol were placed in a stainless steel autoclave having stirring and temperature control functions.
And “Kyoword 500” [Kyowa Chemical Industry Co., Ltd.
24.2 parts (0.04 mol) of Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O], and put the mixture under reduced pressure (1 to 5 mmH).
g) and pretreated at 160 ° C. for 3 hours. Then, 176 parts (4 mol) of ethylene oxide (hereinafter abbreviated as EO) were introduced at 180 ° C. so that the gauge pressure became 1 to 3 kgf / cm ² . The time required for the addition polymerization reaction of EO is 6
It was time. A polymer obtained by filtering off the catalyst from the reaction product was sampled, and the product obtained by silylating the hydroxyl group with a silylating agent was subjected to gas chromatography to obtain each E.
FIG. 1 shows the results of measuring the content (area ratio of gas chromatography chart) for each number of moles of O added (degree of ethoxylation).
Shown in

Example 2 186 parts (1 mol) of lauryl alcohol and "Kyoward 1000" (Kyowa Chemical Industry Co., Ltd.) were placed in a stainless steel autoclave having stirring and temperature control functions.
_{Ltd.: Mg 4.5 Al 2 (OH)} 13 CO 3 · 3.5H 2 O ] 2
0.3 parts (0.04 mol) were charged and the mixture was placed under reduced pressure (1 to 5
mHg) at 160 ° C. for 3 hours. Next, 176 parts (4 mol) of EO were introduced at 180 ° C. so that the gauge pressure became 1 to 3 kgf / cm ² . The time required for the EO addition polymerization reaction was 6.5 hours. FIG. 1 shows the results obtained by measuring the content of each polymer added by filtration in the same manner as in Example 1 for the filtered polymer.

Example 3 270 parts (1 mol) of stearyl alcohol were placed in a stainless steel autoclave having stirring and temperature control functions.
And 24.2 parts (0.04 mol) of "Kyoward 500" were charged and pretreated at 180 ° C for 2 hours under reduced pressure (1 to 5 mmHg). Then, 61 parts (1.05 mol) of propylene oxide (hereinafter abbreviated as PO) were introduced at 150 ° C. so that the gauge pressure became 1 to 3 kgf / cm ² . The time required for the addition polymerization reaction of PO was 8 hours. Next, 132 parts (3 moles) of EO were introduced at 180 ° C. so that the gauge pressure became 1 to 3 kgf / cm ² .
The time required for the EO addition polymerization reaction was 8 hours. With respect to the polymer separated by filtration, each P was obtained in the same manner as in Example 1.
FIG. 2 shows the result of measuring the content for each number of added O and EO moles (degree of alkoxylation).

Example 4 270 parts (1 mol) of stearyl alcohol were placed in a stainless steel autoclave having stirring and temperature control functions.
And "Kyoward 5" which was separated from the polymer by filtration in Example 1.
00 "under reduced pressure (1-5 mmH
g) and pretreated at 160 ° C. for 3 hours. Then EO17
6 parts (4 moles) at 180 ° C, gauge pressure 1-3 kg
f / cm ² was introduced. The time required for the EO addition polymerization reaction was 6.5 hours. The content of each polymer was measured in the same manner as in Example 1 for each number of moles of EO added.

Example 5 136 parts (1 mol) of pentaerythritol were placed in a stainless steel autoclave having stirring and temperature control functions.
And 18.2 parts (0.03 mol) of "Kyoward 500" were charged, and the mixture was pretreated at 160 ° C for 3 hours under reduced pressure (1 to 5 mmHg). Next, 176 parts (4 mol) of EO were introduced at 180 ° C. so that the gauge pressure became 1 to 3 kgf / cm ² . The time required for the addition polymerization reaction of EO is 3
It was time. The unreacted pentaerythritol content of the polymer measured in the same manner as in Example 1 was 0.1%.
% Or less.

EXAMPLE 6 228 parts (1 mol) of bisphenol A and 24.2 parts (0.04 mol) of "Kyoward 500" were placed in a stainless steel autoclave equipped with stirring and temperature control functions.
At 160 ° C. under reduced pressure (1 to 5 mmHg).
Time pretreated. Next, 110 parts (2.5 mol) of EO were introduced at 180 ° C. so that the gauge pressure became 1 to 3 kgf / cm ² . The time required for the EO addition polymerization reaction was 3.5 hours. The unreacted bisphenol A content of the polymer measured in the same manner as in Example 1 was 0.1%.
3%.

Comparative Example 1 270 parts (1 mol) of stearyl alcohol were placed in a stainless steel autoclave having stirring and temperature control functions.
And 0.27 part of sodium methylate (0.005
Mol) and put under reduced pressure (0.1 to 10 mmHg)
Demethanol was performed at 0 ° C. for 1 hour. Then EO1
76 parts (4 mol) at 180 ° C, gauge pressure 1-3k
gf / cm ² was introduced. The time required for the EO addition polymerization reaction was 3 hours. Adsorbent (acid clay)
After removing the catalyst using a filter aid and the obtained polymer, the results of measurement of the content of the obtained polymer by gas chromatography for each number of moles of added EO in the same manner as in Example 1 are shown in FIG.

Comparative Example 2 270 parts (1 mol) of stearyl alcohol were placed in a stainless steel autoclave having stirring and temperature control functions.
And 0.27 part of sodium methylate (0.005
Mol), and under reduced pressure (0.1 to 10 mmHg), 1
Demethanol was performed at 30 ° C. for 1 hour. Then PO
87 parts (1.5 mol) at 110 ° C. and a gauge pressure of 1
It was introduced so as to be 3 kgf / cm ² . The time required for the PO addition polymerization reaction was 3.5 hours. Then EO
132 parts (3 moles) at 180 ° C., gauge pressure 1-3
kgf / cm ² was introduced. The time required for the addition polymerization reaction of EO was 2.5 hours. After removing the catalyst by the same operation as in Comparative Example 1, the polymer was treated as in Example 3
FIG. 2 shows the results of the measurement of the content of each PO and EO added moles in the same manner as described above.

Comparative Example 3 270 parts (1 mol) of stearyl alcohol were placed in a stainless steel autoclave having stirring and temperature control functions.
And 24.2 parts (0.04 mol) of "Kyoward 500". Then 4.4 g of EO without pretreatment
(0.1 mol) was introduced at 180 ° C., but the decrease in internal pressure was about 0.1 kgf / cm ² in 6 hours, and there was substantially no reaction.

Comparative Example 4 270 parts (1 mol) of stearyl alcohol were placed in a stainless steel autoclave having stirring and temperature control functions.
Then, 24.2 parts (0.04 mol) of “Kyoward 500” heat-treated at 200 ° C. for 3 hours using an electric furnace was charged. Then, 4.4 g (0.1 mol) of EO was added to 180
℃, but the internal pressure decreased by about 0.1 kg in 6 hours
f / cm ² , and did not substantially react.

COMPARATIVE EXAMPLE 5 270 parts (1 mol) of stearyl alcohol were placed in a stainless steel autoclave having stirring and temperature control functions.
And 24.2 parts (0.04 mol) of "Kyoward 500" calcined at 500 ° C. for 8 hours using an electric furnace. Next, 176 parts (4 mol) of EO were introduced at 180 ° C. so that the gauge pressure became 1 to 3 kgf / cm ² .
The time required for the EO addition polymerization reaction was 5.5 hours. The filtration residue separated from the polymer was filtered using an electric furnace at 500
When re-firing was attempted at ℃, a large amount of black smoke was generated, and the firing was stopped.

Comparative Example 6 136 parts (1 mol) of pentaerythritol were placed in a stainless steel autoclave having stirring and temperature control functions.
And 0.27 part of sodium methylate (0.005
Mol), and under reduced pressure (0.1 to 10 mmHg), 1
Demethanol was performed at 30 ° C. for 1 hour. Then EO
176 parts (4 moles) at 180 ° C. and a gauge pressure of 1 to 3
kgf / cm ² was introduced. The time required for the addition polymerization reaction of EO was 1.5 hours. The content of unreacted pentaerythritol measured in the same manner as in Example 1 was 5.7%.

[0026]

The method of the present invention has the following effects and is extremely useful industrially. (1) The polyether compound obtained by the method of the present invention has a sharper molecular weight distribution than that obtained using a conventional alkali catalyst, and has a very low content of unreacted initiator and high-molar adduct. . (2) Since the catalyst can be activated simply by dehydration under normal pressure or reduced pressure in the presence of an initiator, a complicated process such as calcination is not required, and the process is simple and economical. (3) The catalyst can be reused repeatedly and easily. (4) The catalyst can be easily removed from the reaction product.

[0027]

[Brief description of the drawings]

FIG. 1 is a graph showing the ethoxylation degree (the number of moles of EO added) and the respective contents in Examples 1, 2 and Comparative Example 1.

[0028]

FIG. 2 is a graph showing the degree of alkoxylation (the number of moles of PO and EO added) and the respective contents in Example 3 and Comparative Example 2.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 65/00-65/48 B01J 38/00-38/74 C07C 41/00-41/60 C07C 43 / 00-43/32

Claims (6)

(57) [Claims] 1. A mixed system of a hydrotalcite (A) and an initiator containing an active hydrogen in a molecule (B) is reduced under reduced pressure.
A method for producing a polyether compound, comprising pretreating at 100 to 300 ° C. and then introducing an alkylene oxide (C). 2. The method according to claim 1, wherein (A) is a compound represented by the following general formula (1). [Mg _1-x Al _x (OH) ₂ ] ^{x +} [CO _{3x / 2} · mH ₂ O] ^x− (1) [where x and m are 0 <x ≦ 0.33, 0 <n ≦ 1. 0 is satisfied. ] 3. The amount of (A) is from 0.1 to 15% by weight based on the final finished amount of the polyether compound.
Or the production method according to 2. (B) a monohydric alcohol, a polyhydric alcohol, an alkylphenol, a bisphenol, an amine compound, an alkanolamine, an organic carboxylic acid,
The production method according to any one of claims 1 to 3, wherein the production method is at least one selected from the group consisting of hydroxy fatty acids, fatty acid amides, and low molar addition products of alkylene oxides of these compounds. 5. The method according to claim 1, wherein (C) is ethylene oxide and / or
5. The production method according to claim 1, wherein the production method is propylene oxide. 6. The method according to claim 1, wherein (C) is introduced at a temperature in the reaction system of 80 to 200 ° C. and a pressure in the reaction system of −0.5 to 6 kgf / cm ² G. Manufacturing method.