JPH09124787A - Polyoxyalkylene compound excellent in heat resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyoxyalkylene compound excellent in heat resistance by using a hydroxylated polyoxyalkylene compound having a specified functionality, an ethylene oxide content and a hydroxyl number or a polyoxyalkylene compound comprising this compound having the terminal hydroxyl groups blocked. SOLUTION: This polyoxyalkylene compound comprises a hydroxylated polyoxyalkylene compound which has a functionality of 1 to 2, an ethylene oxide content of less than 65wt.% and a hydroxyl number VOH of at most 56.0(mg KOH/g) and of which the total degree of unsaturation VUS (meq/g) and the hydroxyl number VOH satisfy the relation of the formula, or a polyoxyalkylene compound obtained by blocking the terminal hydroxyl groups of a hydroxylated polyoxyalkylene compound having a functionality of 1 to 2, an ethylene oxide content of less than 65wt.% and a hydroxyl number VOH of at most 56.0(mg KOH/g).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyoxyalkylene compound having excellent heat resistance.

[0002]

2. Description of the Related Art Polyoxyalkylene compounds obtained by subjecting an initiator to a ring-opening polymerization reaction of alkylene oxide are widely used in fields such as surfactants, lubricants, hydraulic oils and raw materials for polyurethane.

Conventionally, a method of reacting an alkylene oxide in the presence of an alkali catalyst and an initiator has been widely used as a method for producing a polyoxyalkylene compound. Generally, potassium hydroxide (KO) is used as an alkali catalyst.
Alkali metal compounds such as H) and sodium hydroxide (NaOH) are used, but when KOH or NaOH is used, the following problems occur.

When propylene oxide (PO) is reacted as the alkylene oxide, the unsaturated monool produced by the isomerization of PO serves as an initiator, and the reaction of PO with this results in the unsaturated polyether monool. Is generated. The isomerization rate increases as the molecular weight of the target polyoxyalkylene compound increases.
On the other hand, the unsaturated polyether monool produced as a by-product may adversely affect the viscosity index, the thermal decomposition temperature, and the lubricity when the polyoxyalkylene compound is used for a surfactant, a lubricant, a hydraulic oil, or the like. is there.

[0005]

Conventionally, it has been known that the heat resistance of a polyoxyalkylene compound is better as the ethylene oxide (EO) content is higher and the PO content is lower. It is presumed that the reason is that the amount of unsaturated monool generated due to the isomerization of PO is small because the PO content is small, and the number of PO chains that easily cause the hydrogen abstraction reaction of the methyl group is small. On the contrary, the polyoxyalkylene compound having a high PO content does not have sufficient heat resistance as described above.

An object of the present invention is to provide a polyoxyalkylene compound having a high thermal decomposition temperature, that is, excellent heat resistance, despite its low EO content.

[0007]

As a result of diligent efforts to solve the above problems, the present inventors have reduced by-products (unsaturated polyether monools) even in polyoxyalkylene compounds having a low EO content. As a result, the thermal decomposition temperature was increased, and it was found that a polyoxyalkylene compound excellent in heat resistance was obtained, and the present invention was accomplished.

That is, the present invention is a polyoxyalkylene compound comprising the following (a) or (b) having excellent heat resistance. (A) Number of functional groups is 1-2, ethylene oxide content is 65
Less than wt%, hydroxyl value V _OH is 56.0 (mgKOH /
g) a polyoxyalkylene compound having the following range, the total unsaturation degree V _US (meq / g) and the hydroxyl value V
_A hydroxyl group-containing polyoxyalkylene compound whose relationship with _OH (mgKOH / g) satisfies the formula (1).

[0009]

[Equation 3] 0 <V _US ≦ 7 / V _OH −0.125 (1)

(B) The number of functional groups is 1-2, the ethylene oxide content is less than 65% by weight, and the hydroxyl value V _OH is 56.0 (m).
gKOH / g) A polyoxyalkylene compound obtained by sealing terminal hydroxyl groups of a hydroxyl group-containing polyoxyalkylene compound in the range of gKOH / g) or less.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Generally, a hydroxyl group-containing polyoxyalkylene compound is obtained by polymerizing an alkylene oxide in the presence of a catalyst using an active hydrogen compound having an active hydrogen containing group as an initiator.

The active hydrogen-containing compound used as the initiator is a compound having a functional group capable of reacting with an alkylene oxide such as a hydroxyl group, an amino group, a mercapto group and a carboxyl group, and has 1 to 2 active hydrogens. It is a compound.

Preferred initiators are hydroxyl group-containing compounds or amino group-containing compounds. As the hydroxyl group-containing compound, methanol, ethanol, propanol, butanol, 2-ethylhexanol, higher aliphatic monoalcohol, other monohydric alcohol, phenol, alkyl substituted phenol such as nonylphenol, other monohydric phenol, ethylene glycol, diethylene glycol,
Propylene glycol, dipropylene glycol, water,
Examples include neopentyl glycol, 3-methyl-1,5-pentanediol, 1,4-butanediol, 1,6-hexanediol, other dihydric alcohols, and dihydric phenols such as bisphenol A. Examples of the amino group-containing compound include piperazine and aniline.
A relatively low molecular weight compound obtained by reacting these compounds with an alkylene oxide can also be used. These initiators may be used in combination.

Examples of the catalyst include alkali catalysts, amine catalysts, diethylzinc, iron chloride, metalloporphyrin complexes and complex metal cyanide complex catalysts.

As the complex metal cyanide complex, cobalt zinc cyanide-glyme (ethylene glycol dimethyl ether) is particularly preferable. An aluminum porphyrin complex catalyst is particularly preferable as the metal porphyrin complex. Examples of the alkali catalyst include alkali metals and hydroxides thereof, carbonates and the like, and specifically, metal sodium, metal potassium, metal cesium, sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium methoxide, sodium. Ethoxide, sodium propoxide, potassium methoxide, potassium ethoxide, potassium propoxide, cesium methoxide, cesium ethoxide, cesium propoxide, sodium carbonate, potassium carbonate, cesium carbonate and the like can be mentioned. Particularly, cesium metal and cesium hydroxide are preferable. Examples of amine-based catalysts include tertiary amines such as trimethylamine, triethylamine and triethylenediamine.

As the alkylene oxide, EO, P
Examples thereof include O, 1,2-butylene oxide, 2,3-butylene oxide, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether.

Two or more of these alkylene oxides can be used in combination, and in that case, they can be mixed and reacted, or can be reacted sequentially. Preferred is PO alone or a combination of PO and EO. The EO content in the polyoxyalkylene compound used in the present invention is 65% by weight.
Must be less than.

The hydroxyl group-containing polyoxyalkylene compounds for use in the present invention is the hydroxyl value V _OH is 56.0 (mg KOH
/ G) It is indispensable to be in the following range.

(A) In the polyoxyalkylene compound, the total unsaturation degree V _US (meq / g) and the hydroxyl value V _OH (m
In order to obtain a polyoxyalkylene compound whose relationship with gKOH / g) satisfies the formula (1), the selection of the catalyst and the alkylene oxide addition temperature are particularly important.

As the catalyst, of the above-exemplified catalysts,
It is particularly preferable to use an alkali catalyst mainly containing cesium, a complex metal cyanide complex catalyst, or a metal porphyrin complex. From the viewpoint of heat resistance, an alkali catalyst mainly containing cesium is particularly preferable.

The reaction temperature of the alkylene oxide is preferably 70 to 160 ° C., particularly preferably 80 to 130 ° C., although it depends on the combination with the catalyst.

As the polyoxyalkylene compound having excellent heat resistance obtained by sealing the terminal hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (b), a hydrocarbon group is bonded through a bond such as an ether bond or an ester bond. The compound which did is mentioned. A compound in which the end of the hydroxyl group-containing polyoxyalkylene compound is sealed with a hydrocarbon group through an ether bond is particularly preferable. It is preferable that (b) is a polyoxyalkylene compound having substantially no hydroxyl group.

Specifically, there is a method in which the terminal OH of the polyoxyalkylene compound is made OM (M is an alkali metal) and then reacted with an alkyl monohalide for oxyalkylation.

Examples of the alkyl monohalide include methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, propyl chloride, propyl bromide, propyl iodide and the like. These alkyl chain moieties may be linear, branched or cyclic, and the halogen substitution site may be a terminal carbon or an internal carbon.

The polyoxyalkylene compound (b) is preferably a polyoxyalkylene compound obtained by sealing the terminal of the hydroxyl group-containing polyoxyalkylene compound (a).

The polyoxyalkylene compound in the present invention has excellent heat resistance. In particular, the heating rate is 10 ° C
/ Min, 10% weight loss temperature T (° C.) by differential thermal analysis under a nitrogen atmosphere preferably satisfies the expression (2).

[0027]

[Formula 4] T ≧ −0.6V _OH +330 (2)

Further, the polyoxyalkylene compound in the present invention has heat resistance as compared with the conventional one, and
It has excellent friction coefficient and load resistance. Therefore,
Suitable for lubricating oil applications. For compressors, vacuum pumps,
Lubricating oils for gears and water resistant gears can be mentioned.
The intended use is not limited to these.

[0029]

EXAMPLES The present invention will be described below with reference to Examples (Examples 1 to 5) and Comparative Examples (Examples 6 to 8), but the present invention is not limited thereto.

(Example 1) 1880 g of a polyoxyalkylene compound having a hydroxyl value of 112 (mgKOH / g) obtained by adding PO to n-butanol and 72 g of 50% cesium hydroxide aqueous solution were charged into a 5 L reactor, 120
The water inside the reactor was reduced to 400 ppm or less by dehydrating at 10 ° C. and a reduced pressure of 10 mmHg for 2 hours. Then, set the internal temperature to 95
The temperature was raised to 26 ° C., and 2620 g of PO was added and reacted. Further, the aging reaction was performed until the internal pressure did not decrease.
After completion of the reaction, the catalyst was removed to obtain polyoxyalkylene compound A.

(Example 2) 5225 g of polyoxyalkylene compound A and 72 g of 50% cesium hydroxide aqueous solution were added.
It was charged in a L reactor and dehydrated at 120 ° C. under a reduced pressure of 10 mmHg for 2 hours to reduce the water content in the reactor to 400 ppm or less. After that, the internal temperature was raised to 95 ° C. and the PO of 1270
g was added and reacted. Further, the aging reaction was performed until the internal pressure did not decrease. After completion of the reaction, the catalyst was removed to obtain polyoxyalkylene compound B.

Example 3 1450 g of a polyoxyalkylene compound having a hydroxyl value of 27.0 (mgKOH / g) obtained by adding PO to n-butanol using cobalt zinc cyanide-glyme as a catalyst and cyanation 0.9 g of cobalt zinc-glyme was charged to a 5 L reactor. Then, the internal temperature was adjusted to 120 ° C., and 3050 g of PO was added. Further, the aging reaction was performed until the internal pressure did not decrease. After completion of the reaction, the catalyst was removed to obtain a polyoxyalkylene compound C.

(Example 4) PO / E in propylene glycol
540 g of polyoxyalkylene compound a having a hydroxyl value of 56.0 (mgKOH / g) obtained by random addition of O (weight ratio 50/50) and 72 g of 50% cesium hydroxide aqueous solution were charged into a 5 L reactor, 120 ° C, 10m
It was dehydrated under reduced pressure of mHg for 2 hours to remove water in the reactor to 4
It was made less than 00 ppm. After that, the internal temperature is set to 80 ° C. and P
3960 g of O / EO (weight ratio 50/50) was added and the reaction was carried out randomly. Further, the aging reaction was performed until the internal pressure did not decrease. After the reaction, remove the catalyst,
A polyoxyalkylene compound D was obtained.

(Example 5) 4000 g of polyoxyalkylene compound A and 98% potassium hydroxide were added in an amount 1.3 times equivalent to the number of terminal hydroxyl groups of polyoxyalkylene compound A,
It was charged into a 5 L reactor and dehydrated at 120 ° C. under a reduced pressure of 10 mmHg for 2 hours, and the water content inside the reactor was 400 ppm.
I did it below. After that, methyl chloride was fed at 90 ° C. for 1.3 hours, which is 1.3 times equivalent to the number of terminal hydroxyl groups of the polyoxyalkylene compound A, and reacted. Further, the aging reaction was performed until the internal pressure did not decrease. After completion of the reaction, excess potassium hydroxide and by-produced potassium chloride and the like were removed to obtain a polyoxyalkylene compound E.

(Example 6) 1175 g of polyoxyalkylene compound b having a hydroxyl value of 140 (mgKOH / g) obtained by adding PO to n-butanol and 13.8 g of 98% potassium hydroxide were placed in a 5 L reactor. Preparation, 120
The water inside the reactor was reduced to 400 ppm or less by dehydrating at 10 ° C. and a reduced pressure of 10 mmHg for 2 hours. Then, set the internal temperature to 12
The temperature was raised to 0 ° C., and 2620 g of PO was added and reacted. Further, the aging reaction was performed until the internal pressure did not decrease. After completion of the reaction, the catalyst was removed to obtain a polyoxyalkylene compound F.

(Example 7) 432 g of the polyoxyalkylene compound b and 9.2 g of 98% potassium hydroxide were charged into a 5 L reactor and dehydrated at 120 ° C. under a reduced pressure of 10 mmHg for 2 hours, and the water content in the reactor was 400 ppm or less. I chose Then, the internal temperature was adjusted to 120 ° C., and 4068 g of PO was added and reacted. Further, the aging reaction was performed until the internal pressure did not decrease. After the reaction, remove the catalyst,
A polyoxyalkylene compound G was obtained.

(Example 8) 540 g of polyoxyalkylene compound a and 28 g of 48% potassium hydroxide aqueous solution were added to 5 L.
Was charged into the reactor of No. 2 and dehydrated at 120 ° C. under a reduced pressure of 10 mmHg for 2 hours to reduce the water content in the reactor to 400 ppm or less. Then, the internal temperature was set to 120 ° C., 3960 g of PO / EO (weight ratio 50/50) was added, and the reaction was carried out randomly. Further, the aging reaction was performed until the internal pressure did not decrease. After completion of the reaction, the catalyst was removed to obtain a polyoxyalkylene compound H.

Kinematic viscosity ν (unit: cSt) of polyoxyalkylene A to H at 100 ° C., total unsaturation degree V _US (unit: meq / g) and hydroxyl value V _OH (unit: mg KO)
The measurement results of (H / g) are shown in Table 1. Hydroxyl value and total unsaturation are in accordance with JIS K1557, and kinematic viscosity is in JIS K1557.
2283. Note that the x value indicates the value of x calculated by the following formula (3).

[0039]

[Formula 5] x = 7 / V _OH −0.125 (3)

[0040]

[Table 1]

The results of measuring the items shown in Table 2 with respect to the polyoxyalkylene compounds A to H are shown in Tables 3 to 4.
The z value indicates the z value calculated by the following formula (4).

[0042]

## EQU6 ## z = -0.6V _OH +330 (4)

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

Comparing Example 1 and Example 6, which are polyoxypropylene monools having almost the same molecular weight, it can be seen that Example 1 has excellent heat resistance and friction coefficient, and has the same load resistance. Further, when Example 2 and Example 7 having a high molecular weight are compared, it can be seen that Example 2 is excellent in heat resistance, friction coefficient, and weight resistance. Comparing Example 4 and Example 8, which are polyoxypropylene oxyethylene glycols having almost the same molecular weight, it can be seen that Example 4 is excellent in heat resistance, friction coefficient, and weight resistance. Thus, as compared with the conventional polyoxyalkylene compound having a similar structure, the polyoxyalkylene compound of the present invention is excellent in heat resistance, and is also excellent or equivalent in friction coefficient and load resistance. . Example 5
Shows that the heat resistance is further excellent as compared with Example 1.

[0047]

The polyoxyalkylene compound according to the present invention is excellent in heat resistance and friction coefficient.

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Claims (3)

[Claims] 1. A polyoxyalkylene compound comprising the following (a) or (b) having excellent heat resistance. (A) Number of functional groups is 1-2, ethylene oxide content is 65
Less than wt%, hydroxyl value V _OH is 56.0 (mgKOH /
g) a polyoxyalkylene compound having the following range, the total unsaturation degree V _US (meq / g) and the hydroxyl value V
_A hydroxyl group-containing polyoxyalkylene compound whose relationship with _OH (mgKOH / g) satisfies the formula (1). ## EQU1 ## 0 <V _US ≤7 / V _OH -0.125 (1) (b) The number of functional groups is 1-2, and the ethylene oxide content is 65.
Less than wt%, hydroxyl value V _OH is 56.0 (mgKOH /
g) A polyoxyalkylene compound obtained by sealing the terminal hydroxyl groups of a hydroxyl group-containing polyoxyalkylene compound within the following range. 2. A 10% weight loss temperature T (° C.) determined by a differential thermal analysis in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min is expressed by the formula (2).
The polyoxyalkylene compound according to claim 1, which satisfies: [Formula 2] T ≧ −0.6V _OH +330 (2) 3. The polyoxyalkylene compound according to claim 1, which is used as a lubricating oil.