JP2000038443A - Production of polyoxyalkylenepolyol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyoxyalkylenepolyol free from turbidity such as cloudiness and having excellent transparency. SOLUTION: This method for producing a polyoxyalkylenepolyol comprises adding an active hydrogen compound, a phosphazenium compound in an amount of 5×10-5 to 5×10-1 mole per mole of the active hydrogen compound, and a solvent in an amount of at least 20 wt.% based on that of the phosphazenium compound to a reaction system, subjecting the mixture to a degassing treatment under a reduced pressure of <=6.65 kPa at 40-150 deg.C to prepare a polymerization initiator, controlling the water content of the reaction system to <=0.1 wt.%, and subsequently adding an epoxide compound to the controlled reaction system to initiate the addition polymerization of the epoxide compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyoxyalkylene polyol. Specifically, the present invention relates to a method for producing a polyoxyalkylene polyol having no cloudiness such as cloudiness.

[0002]

2. Description of the Related Art Generally, a polyoxyalkylene polyol used as a raw material of polyurethane is prepared by reacting an active hydrogen compound with an alkali metal compound to produce an alkali metal salt of the active hydrogen compound (corresponding to a polymerization initiator). Then, it is produced by performing addition polymerization of an epoxide compound. 2. Description of the Related Art Conventionally, in producing a polyoxyalkylene polyol, various studies have been made for the purpose of improving productivity and improving quality.

[0003] The present applicant has previously proposed a novel active hydrogen compound as a method for producing polyalkylene oxide simply and efficiently using an initiator system which does not contain any metal components and does not leave odor. Phosphazenium salts and novel phosphazenium hydroxide compounds have been proposed to be effective (EP-A-0791600). Then, a method is described in which an ether solvent such as tetrahydrofuran or diethyl ether is added to the reaction system when preparing the phosphazenium salt of the active hydrogen compound and the phosphazenium hydroxide compound as the polymerization initiator. However, the influence of the amount of water in the polymerization initiator,
No mention is made of a method for reducing the water content in the polymerization initiator, and the like.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a polyoxyalkylene polyol which is free from turbidity such as white turbidity and has excellent transparency.

[0005]

Means for Solving the Problems As a result of extensive studies to solve the above problems, the present inventors have found that when preparing a polymerization initiator from an active hydrogen compound and a phosphazenium compound,
After adding a specific amount of solvent to the reaction system and performing decompression and degassing under specific conditions to control the water content in the reaction system to a specific value or less, start addition polymerization of the epoxide compound. Finds that the above problem can be solved,
The present invention has been reached.

That is, according to the present invention, there is provided a method for producing a polyoxyalkylene polyol in which a polymerization initiator is prepared from an active hydrogen compound and a phosphazenium compound, and an epoxide compound is addition-polymerized to the obtained polymerization initiator. A solvent of 5 × 10 ^{-5 to} 5 × 10 ^-1 mol and at least 20% by weight of the phosphazenium compound is added to the reaction system with respect to 1 mol of the active hydrogen compound, and the solvent is added at 40 to 150 ° C. and 6.65 kPa or less Wherein a polymerization initiator is prepared while performing decompression and degassing treatments, and after controlling the water content in the reaction system to 0.1% by weight or less, addition polymerization of the epoxide compound is started. A method for producing a polyoxyalkylene polyol is provided.

According to the present invention, when a polymerization initiator is prepared, since a specific amount of a solvent is present in the system, water can be easily removed from the system by decompression and degassing. . Therefore, it is easy to control the water content in the system to 0.1% by weight or less. The polyoxyalkylene polyol produced by the present invention has no turbidity such as white turbidity and is colorless and transparent. Therefore, in addition to polyurethane resins such as adhesives, paints, sealing materials, elastomers and flooring materials, or raw materials for rigid, flexible and semi-rigid polyurethane foams, surfactants, sanitary products, deinking agents, lubricating oils, It can be suitably used in a wide range of fields such as liquids.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The outline of the method for producing the polyoxyalkylene polyol according to the present invention is to prepare a polymerization initiator from an active hydrogen compound and a phosphazenium compound while degassing under a specific temperature and pressure conditions in the presence of a solvent, and This is a method of controlling the water content in the solution to a specific value or less, and then subjecting the obtained polymerization initiator to addition polymerization of an epoxide compound.

In the present invention, the system for preparing the polymerization initiator and the system for addition polymerization of the epoxide compound are preferably systems substituted with an inert gas. Examples of the inert gas include argon, helium, and nitrogen. Industrially, nitrogen is preferably used. The purity of nitrogen is preferably at least 90 vol%. The active hydrogen compound may be any compound having an active hydrogen group in the molecule. For example, alcohols, phenol compounds, alkanolamines, polyamines, saccharides and the like can be mentioned.

Examples of the alcohol include monohydric alcohols such as butanol, octanol and allyl alcohol. Water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol,
Dihydric alcohols such as 1,3-propanediol, 1,4-cyclohexanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanediol are also included. . Polyhydric alcohols such as glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and polyglycerol are also included.

Examples of the phenol compound include phenol compounds such as bisphenol A, bisphenol F, bisphenol S, novolak, resole, resorcin, hydroquinone and Mannich compound. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine. As the polyamine, ethylenediamine, di (2-
Fatty acid amines such as aminoethyl) amine and hexamethylenediamine; and aromatic amines such as tolylenediamine and diphenylmethanediamine. Examples of the saccharide include saccharides such as glucose, sorbitol, dextrose, fructose, sucrose, methyl glucoside, and hydroxyethyl glucoxide, and derivatives thereof.

Further, a compound obtained by addition polymerization of 6 mol or less of an epoxide compound to 1 equivalent of an active hydrogen group to these active hydrogen compounds by a conventionally known method can also be used. These active hydrogen compounds can be used in combination of two or more. Next, the phosphazenium compound used in the present invention will be described. Examples of the phosphazenium compound include EP-A-079 filed earlier by the present applicant.
It is preferable to use the compounds described in JP-A-1600.

Specifically, the chemical formula (1)

[0014]

Embedded image [A, b, c and d in the chemical formula (1) are each 0
A, b, c and d are not all 0 at the same time. R is the same or different and has 1 to 1 carbon atoms;
It is 0 hydrocarbon groups, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. Q ^- represents a hydroxy anion, an alkoxy anion, an aryloxy anion or a carboxy anion].

A, b, c and d in the phosphazenium cation represented by the chemical formula (1) in the present invention are each a positive integer of 0 to 3. However, they are not all 0 at the same time. Preferably it is an integer of 0 to 2. More preferably, regardless of the order of a, b, c and d, (2,
(1,1,1), (1,1,1,1), (0,1,1,
1), (0, 0, 1, 1) or a number in a combination of (0, 0, 0, 1). More preferably, (1,
(1,1,1), (0,1,1,1), (0,0,1,
1) or a number in the combination of (0,0,0,1).

R in the phosphazenium cation of the salt represented by the chemical formula (1) in the present invention is the same or different and is a hydrocarbon group having 1 to 10 carbon atoms. Is, for example, methyl, ethyl, n-propyl,
Isopropyl, allyl, n-butyl, sec-butyl,
tert-butyl, 2-butenyl, 1-pentyl, 2-
Pentyl, 3-pentyl, 2-methyl-1-butyl, isopentyl, tert-pentyl, 3-methyl-2-butyl, neopentyl, n-hexyl, 4-methyl-2-
Pentyl, cyclopentyl, cyclohexyl, 1-heptyl, 3-heptyl, 1-octyl, 2-octyl, 2
-Ethyl-1-hexyl, 1,1-dimethyl-3,3-
It is selected from aliphatic or aromatic hydrocarbon groups such as dimethylbutyl (tert-octyl), nonyl, decyl, phenyl, 4-toluyl, benzyl, 1-phenylethyl or 2-phenylethyl. Of these, methyl,
An aliphatic hydrocarbon group having 1 to 10 carbon atoms such as ethyl, n-propyl, isopropyl, tert-butyl, tert-pentyl and tert-octyl is preferred, and a methyl group or an ethyl group is more preferred.

When two Rs on the same nitrogen atom in the phosphazenium cation combine to form a ring structure, the divalent hydrocarbon group on the nitrogen atom is 4 to 6 A divalent hydrocarbon group having a main chain composed of carbon atoms (the ring is a 5- to 7-membered ring containing a nitrogen atom), preferably, for example, tetramethylene, pentamethylene or hexamethylene; These are those whose main chains are substituted by an alkyl group such as methyl or ethyl. More preferably, it is a tetramethylene or pentamethylene group. Such a ring structure may be employed for all possible nitrogen atoms in the phosphazenium cation, or a part thereof may be employed.

The phosphazenium compound is preferably used as an aqueous solution. In that case, the aqueous solution concentration is 1
To 99.9% by weight, preferably 1.5 to 80% by weight, and more preferably 1.9 to 70% by weight.

In preparing a polymerization initiator from the active hydrogen compound and the phosphazenium compound, the solvent to be added to the reaction system includes alcohols, ketones, aliphatic hydrocarbons, aromatic hydrocarbons, and halogens. Hydrocarbons. In the present invention, considering that the solvent is used to facilitate the removal of water in the reaction system to the outside of the reaction system, among these solvents, the solvent having a boiling point having a difference of at least 20 ° C. from that of the active hydrogen compound is considered. Is selected.

Alcohols include methanol, ethanol, propanol and the like; ketones such as acetone and methyl ethyl ketone; and aliphatic hydrocarbons such as n-hexane, n-pentane and 2,2,4-trimethylpentane. , Cyclohexane and the like, aromatic hydrocarbons such as toluene and xylene, and halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, monochlorobenzene and o-dichlorobenzene. Among these solvents, preferred are alcohols, ketones, and aliphatic hydrocarbons.

In the present invention, a solvent having a boiling point difference of at least 20 ° C. from the boiling point of the active hydrogen compound is selected from these solvents and used. Preferably the boiling point difference is at least 30
° C, more preferably a solvent having a boiling point difference of at least 40 ° C. Usually, those lower than the boiling point of the active hydrogen compound in the above range are preferable.

The amount of the solvent used is at least 20% by weight, preferably at least 30% by weight, more preferably at least 40% by weight, based on the phosphazenium compound. When the amount of the solvent used is less than 20% by weight,
The water content of the reaction system including the polymerization initiator is 0.1% by weight.
The time to reach is longer. The upper limit is preferably 80% by weight or less based on the phosphazenium compound in consideration of economy.

In the present invention, in the presence of the solvent,
A polymerization initiator is prepared from the active hydrogen compound and the phosphazenium compound. At that time, the inside of the reaction system is preferably replaced with an inert gas. After replacing the inside of the pressure-resistant reactor with an inert gas, a solvent, an active hydrogen compound and a phosphazenium compound are added, and then, at 40 to 150 ° C. and 6.65.
The polymerization initiator is prepared while degassing under kPa or less. The preparation temperature is from 50 to 50, depending on the properties of the solvent used.
140 ° C. is preferred. More preferably, it is 60 to 130 ° C. The pressure is preferably 3.99 kPa or less. More preferably, it is 2.66 kPa or less.

The preparation (reaction) time varies depending on the temperature, the molar ratio of the active hydrogen compound to the phosphazenium compound, the reaction scale and the like, but is usually about 3 to 15 hours.
During the preparation of the polymerization initiator, the depressurization and the deaeration are continued. A known method using a water jet pump, a vacuum pump, a roots-type exhaust blower, or the like can be applied to the method of decompression and degassing. Degassing rate depends on the capacity of the reactor, but usually,
It is preferably about 0.1 to 10 m ³ / m ³ · min.

The water content in the reaction system containing the polymerization initiator depends on the opacity of the resulting polyoxyalkylene polyol,
Turbidity, affecting transparency. If the water content is high, the appearance of the polyoxyalkylene polyol after the addition polymerization of the epoxide compound, particularly the ethylene oxide, becomes cloudy, and the transparency is reduced. From this point of view, in the present invention, it is important to control the water content in the reaction system containing the polymerization initiator to 0.1% by weight or less by performing depressurization and degassing by the above method. Preferably 0.0
It is at most 5% by weight, more preferably at most 0.02% by weight.

When performing the decompression treatment, the liquid phase (polymerization initiator)
Preferably, an inert gas is ventilated. By passing the inert gas into the liquid phase, the time required for the water content in the reaction system containing the polymerization initiator to reach 0.1% by weight or less can be shortened. The flow rate of the inert gas depends on the capacity of the reactor, but is preferably about 0.01 to ⁵ m ³ / m ³ · min. The solvent removed outside the system can be recovered and reused. If the solvent used has low water solubility, it is separated from water and recovered. Further, the solvent can be extracted from the recovered liquid by a conventionally known method such as distillation.

In the present invention, after the water content in the reaction system containing the polymerization initiator is controlled to 0.1% by weight or less by the above method, the addition polymerization of the epoxide compound to the obtained polymerization initiator is started. . Examples of the epoxide compound include propylene oxide, ethylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether, and triglyceride. And fluoropropylene oxide. These may be used in combination of two or more. Of these, propylene oxide, 1,2-butylene oxide and ethylene oxide are preferred.

As the polymerization method of the epoxide compound,
In the case of propylene oxide and ethylene oxide as an example, after polymerization of propylene oxide, an ethylene oxide cap reaction for copolymerizing ethylene oxide in blocks, a reaction method for randomly copolymerizing propylene oxide and ethylene oxide, and copolymerizing ethylene oxide. Is mentioned.

The method for producing a polyoxyalkylene polyol of the present invention is preferably performed under the following conditions. That is, the chemical formula (1) based on 1 mole of the active hydrogen compound
The phosphazenium compound represented by is 5 × 10 ^{−5 to} 5 ×
10 ^-1 mol, preferably 1 x 10 ^-4 to 1 x 10 ^-1 mol,
More preferably, it is in the range of 1 × 10 ⁻³ to 1 × 10 ⁻² mol. The addition polymerization reaction temperature of the epoxide compound is 15 to 1
The range is 70 ° C, preferably 40 to 150 ° C, and more preferably 50 to 120 ° C.

The maximum pressure during the reaction of the epoxide compound is preferably 882 kPa. Usually, the reaction of the epoxide compound is performed by a pressure-resistant reactor. The reaction of the epoxide compound may be started from a reduced pressure state or an atmospheric pressure state. When starting the reaction from an atmospheric pressure state, it is desirable to carry out the reaction in the presence of an inert gas such as nitrogen or helium. Maximum reaction pressure of epoxide compound is 8
If it exceeds 82 kPa, the amount of by-product monol increases. The maximum reaction pressure is preferably 686 kPa, more preferably 490 kPa. As an epoxide compound,
When using propylene oxide, the maximum reaction pressure is preferably 490 kPa.

The crude polyoxyalkylene polyol obtained by addition polymerization of an epoxide compound to a polymerization initiator is subjected to an acid neutralization method using phosphoric acid, sulfuric acid, hydrochloric acid, maleic acid, oxalic acid, etc., synthetic magnesium silicate, Purification is carried out by a treatment method using an adsorbent such as magnesium / aluminum silicate, activated carbon, or a method using both acid neutralization and an adsorbent. It is preferable to add an antioxidant during the purification treatment.

[0032]

EXAMPLES Examples of the present invention will be shown below to clarify the present invention, but the present invention is not limited to these examples. In addition, each characteristic value shown in the Example was measured by the following method. (1) The hydroxyl value (m) of the polyoxyalkylene polyol
gKOH / g) It was determined by the method described in JIS K-1557. (2) Appearance of polyoxyalkylene polyol The polyoxyalkylene polyol was collected in a 100 ml test tube, and the appearance was visually evaluated. The evaluation was based on three criteria: colorless, transparent, slightly turbid, and turbid. (3) Water content (% by weight) of polymerization initiator preparation system Karl Fischer moisture meter [manufactured by Kyoto Electronics Co., Ltd., type: M
KC-210] was used. Acetic acid for non-aqueous titration (manufactured by Wako Pure Chemical Industries, Ltd.) was added to dehydrated solvent MS (manufactured by Mitsubishi Chemical Corporation), and a weighed sample was injected into the mixed solution to remove water in the polymerization initiator preparation system. It was measured. The measurement frequency is 3 before stopping the reaction.
The interval was 0 to 10 minutes. <Synthesis of phosphazenium compound (hereinafter referred to as P5NMe2OH)> In the synthesis of the polyoxyalkylene polyol of the example, the following phosphazenium compound was used as a catalyst for the epoxide compound. In a 3000 ml three-necked flask equipped with a thermometer and a dropping funnel, 60.20 g of phosphorus pentachloride (manufactured by Junsei Chemical Co., Ltd.) was weighed.
525 ml of orthodichlorobenzene [hereinafter ODCB
Manufactured by Mitsui Chemicals, Inc.]. This was heated to 30 ° C., and 900 ml of ODCB was added to Reinhard Schwezinger et al.
International Edition English "
32, pp. 1361-1363, tris (dimethylamino) phosphazene} (Me ₂
N) ₃ P = solution 1 obtained by dissolving NH} 439.27g
It was dropped over time. After stirring at the same temperature for 30 minutes, the temperature was raised to 160 ° C. over about 30 minutes, and the mixture was further stirred for 20 hours.

The resulting insolubles were filtered, ion-exchanged water was added to the filtrate, and the mixture was washed three times with water. To 1091.2 g of the water-insoluble layer (hereinafter, abbreviated as an organic layer) after the water washing treatment, 619.26 g of ion-exchanged water and 2N of 1N hydrochloric acid were added.
89.5 ml was added, the aqueous layer was separated, and tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride {[(Me ₂ N) ₃ P = N] ₄ P ⁺ Cl ⁻ }.
I got Further, ion-exchanged water was added to prepare a 2.5% by weight aqueous solution.

Next, tetrakis tris was added to a polycarbonate cylindrical column filled with ion exchange resin Levatit MP-500 (manufactured by Bayer) whose exchange group was changed to a hydroxyl group with a 1 × 10 ⁻³ mol / l aqueous sodium hydroxide solution. (Dimethylamino) phosphoranylideneamino] 2.5 wt% aqueous solution of phosphonium chloride at 23 ° C.
SV (Space Velocity) 0.5 (1 /
In h), the solution was passed through the column from the bottom in an ascending flow, and ion exchange was performed with tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide. Furthermore,
Ion exchange water was passed through the column filled with the ion exchange resin, and the phosphazenium compound remaining in the column was recovered. Thereafter, an aqueous solution of tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide is subjected to a dehydration treatment under reduced pressure at 80 ° C. and a reduced pressure of 7980 Pa for 2 hours, and further at 80 ° C. and 133 Pa for 7 hours. To give powdered tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide {[(Me ₂ N) ₃ P = N] ₄ P ⁺ OH
^- ｝ (P5NMe2OH) was obtained.

After drying, the yield of the compound determined by weight measurement was 98%. ¹ H-N with tetramethylsilane in deuterated dimethylformamide solution as internal standard
The chemical shift of MR (400 MHz NMR, manufactured by JEOL) was 2.6 ppm (d, J = 9.9 Hz, 72H). Elemental analysis: C: 38.28, H: 9.82, N;
29.43, P: 19.94 (theoretical value, C: 38.0)
9, H: 9.72, N: 29.61, P: 20.46)
Met. In the chemical formula (1), the phosphazenium compound is represented by R in the order of a, b, c, and d (1,1,1,1).
There is a methyl group, Q ^- is a hydroxy anion ^- is OH.

The synthesis of the polyoxyalkylene polyol will be described. An apparatus for synthesizing and refining a polyoxyalkylene polyol is a pressure-resistant autoclave (Nitto Kogaku Co., Ltd.) having a 2.5 L internal volume equipped with a stirrer, a thermometer, a pressure gauge, a nitrogen inlet, and an epoxide compound inlet as a monomer. )It was used. During the synthesis and purification of the polyoxyalkylene polyol, the rotation speed is 100 to 3
50r. p. m. The stirring was performed under the following conditions.

Example 1 Polyoxyalkylene polyol A 50% by weight of P5NMe2OH using ion-exchanged water
An aqueous solution was prepared (hereinafter, referred to as a 50% by weight aqueous solution of PZN). Under a nitrogen atmosphere, in a 1 L four-necked flask equipped with a stirrer, a capillary tube through which nitrogen is passed through the liquid phase, and a thermometer, with respect to 1 mol of glycerin, 0.03 mol of P5NMe2OH was added. A 50% by weight aqueous solution of PZN was added. Then, for P5NMe2OH,
80% by weight of toluene was added. Toluene (manufactured by Wako Pure Chemical Industries, special grade reagent) was used after nitrogen bubbling overnight. Thereafter, heating, decompression, and deaeration were performed at 105 ° C. and 1.33 kPa or less until the water content of the polymerization initiator became 0.009% by weight.

After charging the polymerization initiator into an autoclave and performing nitrogen substitution, the reaction temperature was changed from the atmospheric pressure to a reaction temperature of 80 ° C.
Under the condition that the maximum pressure during the reaction is 392 kPa, OHV 29
The addition polymerization of propylene oxide was performed until the concentration reached mg KOH / g. Successively, with nitrogen, 219 kPa
At a reaction temperature of 90 ° C. and a maximum pressure of 39 during the reaction.
Under the conditions of 2 kPa, addition polymerization of ethylene oxide was performed until the OHV became 24 mgKOH / g. Then 1
Decompression treatment was performed at 05 ° C. and 665 Pa for 30 minutes to obtain a crude polyoxyalkylene polyol.

Crude polyoxyalkylene polyol 10
5 parts by weight of ion-exchanged water is added to 0 parts by weight, and then 3 moles of phosphoric acid (7 moles) is added to 1 mole of the phosphazenium compound in the crude polyoxyalkylene polyol.
5.1% by weight) at 80 ° C. under a nitrogen atmosphere.
For 2 hours. Antioxidant (trade name: irga
nox1010, manufactured by Ciba-Geigy Co., Ltd .;
pm, and dehydrated under reduced pressure.
In the state of Pa, the adsorbent (trade name: Tomita AD-600,
The same applies hereinafter) to the crude polyoxyalkylene polyol in an amount of 0.3% by weight. Subsequently, the same operation was finally performed for 4 hours under the condition of 105 ° C. and 1.33 kPa or less while performing the pressure reduction operation. Thereafter, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd., and polyoxyalkylene polyol was recovered. OH of polyoxyalkylene polyol
V was 24.2 mgKOH / g, and the appearance was colorless and transparent.

Example 2 Polyoxyalkylene polyol B Toluene was added in an amount of 100% by weight based on P5NMe2OH, and under the conditions of temperature and pressure described in Example 1, the water content of the polymerization initiator was reduced to 0.008% by weight. Heating, reduced pressure, and deaeration were performed until the temperature was reduced. The synthesis and purification of the polyoxyalkylene polyol were performed by the method described in Example 1.
OHV of the resulting polyoxyalkylene polyol is
It was 24.1 mgKOH / g, and the appearance was colorless and transparent.

Example 3 Polyoxyalkylene polyol C Under a nitrogen atmosphere, a 1 L four-necked flask equipped with a stirrer, a capillary tube through which nitrogen was passed through a liquid phase, and a thermometer was charged with respect to 1 mol of glycerin. 0.02 mol of P5
A 50% by weight aqueous solution of PZN was added so as to become NMe2OH. Next, 70% by weight of o-dichlorobenzene [manufactured by Mitsui Chemicals, Inc .; hereinafter, referred to as o-DCB] was added to P5NMe2OH. The o-DCB used was subjected to nitrogen bubbling overnight. afterwards,
Under the conditions of 105 ° C. and 1.33 kPa or less, heating, reduced pressure, and deaeration were performed until the water content of the polymerization initiator became 0.019% by weight.

After charging the polymerization initiator in an autoclave and performing nitrogen substitution, the reaction temperature was changed from the atmospheric pressure to 80 ° C.
Under the condition that the maximum pressure during the reaction is 392 kPa, OHV32
The addition polymerization of propylene oxide was performed until the concentration reached mg KOH / g. Successively, with nitrogen, 219 kPa
To a reaction temperature of 120 ° C and a maximum pressure of 4
Under the conditions of 92 kPa, addition polymerization of ethylene oxide was carried out until the OHV became 28 mgKOH / g. afterwards,
Under reduced pressure treatment at 120 ° C. and 665 Pa for 30 minutes, a crude polyoxyalkylene polyol was obtained.

Crude polyoxyalkylene polyol 10
5 parts by weight of ion-exchanged water is added to 0 parts by weight, and then 3 moles of phosphoric acid (7 moles) is added to 1 mole of the phosphazenium compound in the crude polyoxyalkylene polyol.
5.1% by weight) at 80 ° C. under a nitrogen atmosphere.
For 2 hours. An antioxidant was added to the crude polyoxyalkylene polyol at 500 ppm, dehydration was performed under reduced pressure, and further, at a pressure of 67 kPa,
The adsorbent was added at 0.2% by weight based on the crude polyoxyalkylene polyol. Subsequently, the same operation was finally performed for 4 hours under the condition of 105 ° C. and 1.33 kPa or less while performing the pressure reduction operation. Thereafter, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd., and polyoxyalkylene polyol was recovered. OHV of polyoxyalkylene polyol
Was 28.4 mgKOH / g, and the appearance was colorless and transparent.

Example 4 Polyoxyalkylene polyol D 80% by weight of P5NMe2OH using ion-exchanged water
An aqueous solution was prepared (hereinafter, referred to as an 80 wt% PZN aqueous solution). Under a nitrogen atmosphere, in a 1 L four-necked flask equipped with a stirrer, a capillary tube through which nitrogen is passed through the liquid phase, and a thermometer, with respect to 1 mol of glycerin, 0.02 mol of P5NMe2OH was added. An 80% by weight aqueous solution of PZN was added. Then, for P5NMe2OH,
40% by weight of o-DCB was added. After that, 105 ° C,
Under the conditions of 2.66 kPa or less, heating, reduced pressure, and deaeration were performed until the water content of the polymerization initiator became 0.023% by weight.

After the polymerization initiator was charged into an autoclave and the atmosphere was replaced with nitrogen, the reaction temperature was changed from atmospheric pressure to 80 ° C.
Under the condition that the maximum pressure during the reaction is 392 kPa, OHV 25
The addition polymerization of propylene oxide was performed until the concentration reached mg KOH / g. Successively, with nitrogen, 219 kPa
To a reaction temperature of 120 ° C and a maximum pressure of 4
Under the conditions of 92 kPa, addition polymerization of ethylene oxide was carried out until the OHV became 18 mgKOH / g. afterwards,
Under reduced pressure treatment at 120 ° C. and 665 Pa for 30 minutes, a crude polyoxyalkylene polyol was obtained.

Crude polyoxyalkylene polyol 10
5 parts by weight of ion-exchanged water is added to 0 parts by weight, and then 3 moles of phosphoric acid (7 moles) is added to 1 mole of the phosphazenium compound in the crude polyoxyalkylene polyol.
5.1% by weight) at 80 ° C. under a nitrogen atmosphere.
For 2 hours. An antioxidant was added to the crude polyoxyalkylene polyol at 500 ppm, dehydration was performed under reduced pressure, and further, at a pressure of 67 kPa,
The adsorbent was added at 0.2% by weight based on the crude polyoxyalkylene polyol. Subsequently, the same operation was finally performed for 4 hours under the condition of 105 ° C. and 1.33 kPa or less while performing the pressure reduction operation. Thereafter, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd., and polyoxyalkylene polyol was recovered. OHV of polyoxyalkylene polyol
Was 18.1 mgKOH / g, and the appearance was colorless and transparent.

Example 5 As a solvent for polyoxyalkylene polyol E, n-hexane (manufactured by Wako Pure Chemical Industries, Ltd .; hereinafter, referred to as hexane) was used. Hexane addition amount is P5NMe2O
Heating, decompression and deaeration were carried out under the conditions of temperature and pressure described in Example 4 until the water content of the polymerization initiator became 0.042% by weight with respect to H and 25% by weight. The synthesis and purification of the polyoxyalkylene polyol were performed by the method described in Example 4. The OHV of the obtained polyoxyalkylene polyol was 18.1 mgKOH / g, and the appearance was colorless and transparent.

Comparative Example 1 A polymerization initiator was prepared according to the operation method described in Example 1 without using toluene with respect to polyoxyalkylene polyol FP5NMe2OH. Heating, reduced pressure, and deaeration were performed until the water content in the polymerization initiator reached 0.352% by weight. The synthesis and purification of the polyoxyalkylene polyol were performed by the method described in Example 1. O of the resulting polyoxyalkylene polyol
HV was 24.2 mgKOH / g, and the appearance was cloudy.

Comparative Example 2 Polyoxyalkylene polyol G The amount of toluene described in Example 1 was 10% by weight based on P5NMe2OH, and the water content of the polymerization initiator was 0.21%.
Heating, reduced pressure, and deaeration were performed until the content reached 6% by weight. The synthesis and purification of the polyoxyalkylene polyol were performed by the method described in Example 1. The OHV of the obtained polyoxyalkylene polyol was 24.2 mgKOH / g, and the appearance was cloudy.

Comparative Example 3 Polyoxyalkylene polyol H The amount of o-DCB described in Example 4 was set to 18% by weight based on P5NMe2OH, and the water content of the polymerization initiator was 0.1%.
Heating, reduced pressure, and degassing operations were performed until the content reached 67% by weight.
The synthesis and purification of the polyoxyalkylene polyol were performed by the method described in Example 4. OHV of the obtained polyoxyalkylene polyol was 18.1 mgKOH / g, and the appearance was slightly turbid.

Comparative Example 4 Polyoxyalkylene polyol I The amount of hexane added in Example 5 was 10% by weight based on P5NMe2OH, and the water content in the polymerization initiator was 0.15%.
Heating, reduced pressure, and deaeration were performed until the content became 4% by weight. The synthesis and purification of the polyoxyalkylene polyol were performed by the method described in Example 5. The OHV of the obtained polyoxyalkylene polyol was 18.2 mgKOH / g, and the appearance was slightly turbid.

The results of analysis of the polyoxyalkylene polyols obtained in each of the Examples and Comparative Examples are shown in Tables 1 and 2.

<Explanation of Symbols in Table> The amount of the solvent used (unit:% by weight) with respect to the phosphazenium compound (referred to as PZN), and the water content of the reaction system for preparing the polymerization initiator (unit: % By weight). Polyol means a polyoxyalkylene polyol.

[0054]

[Table 1]

[0055]

[Table 2] <Consideration of Examples> From [Table 1], it can be seen that a specific concentration of a solvent (toluene, o-DCB,
Hexane) and further reduce the water content by 0.1% by weight.
The polyoxyalkylene polyol using the polymerization initiator controlled below is colorless and transparent, and it can be seen that it is excellent in design.

[0056]

According to the method of the present invention, when a polymerization initiator is prepared from an active hydrogen compound and a phosphazenium compound, a specific amount of a solvent is added to the reaction system, and decompression and deaeration are performed under specific conditions. To reduce the water content in the reaction system to 0.1
By starting the addition polymerization of the epoxide compound after controlling the amount to not more than% by weight, it is possible to produce a polyoxyalkylene polyol which is free from turbidity such as white turbidity in appearance, has high transparency and is excellent in design. Accordingly, the polyoxyalkylene polyol obtained by the method of the present invention can be used in addition to a polyurethane resin such as an adhesive, a paint, a sealing material, an elastomer, or a flooring material, or a raw material for a rigid, flexible, or semi-rigid polyurethane foam, and a surfactant. It can be suitably used in a wide range of fields such as chemicals, sanitary products, deinking agents, lubricating oils, and hydraulic fluids.

Continuation of the front page (72) Fumio Yama ▲ saki ▼ 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi Prefecture Inside Mitsui Chemicals Co., Ltd. (72) Inventor Saku Izugawa 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi Address F-term in Mitsui Chemicals, Inc. (reference) 4J005 AA11 BB00 BB02 BB04

Claims (3)

[Claims] 1. A method for producing a polyoxyalkylene polyol in which a polymerization initiator is prepared from an active hydrogen compound and a phosphazenium compound, and an epoxide compound is addition-polymerized to the obtained polymerization initiator. 5 x 1 phosphazenium compound per mole
0 ^{-5 to} 5 × 10 ^-1 mol and at least 20% by weight of a solvent of the phosphazenium compound are added to the reaction system.
After preparing a polymerization initiator while performing decompression and degassing at 0 to 150 ° C. and 6.65 kPa or less, and controlling the water content in the reaction system to 0.1% by weight or less, adding an epoxide compound A method for producing a polyoxyalkylene polyol, wherein polymerization is initiated. 2. The method according to claim 1, wherein the solvent comprises at least 20 active hydrogen compounds selected from alcohols, ketones, aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons.
The method for producing a polyoxyalkylene polyol according to claim 1, wherein the compound is at least one compound having a boiling point difference of ° C. 3. The water content in the reaction system is 0.05% by weight.
The method for producing a polyoxyalkylene polyol according to claim 1, wherein the control is performed as follows.