JP2005179567A - Method of producing polyether polyol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide polyethers having a narrow molecular weight distribution and suitable as a raw material for a polyurethane resin or the like. <P>SOLUTION: The polyethers are produced by using as an initiator at least one kind selected from the group consisting of a polycarbonate monool and a polyol, and polyoxytetramethylene monool and polyol, and by subjecting an alkylene oxide to a ring-opening addition polymerization to the initiator in the presence of a composite metal cyanide complex having an organic ligand. Wherein between the number-average molecular weight (Mn<SB>1</SB>) and the weight-average molecular weight (Mw<SB>2</SB>) of the initiator and the number-average molecular weight (Mn<SB>2</SB>) and the weight-average molecular weight (Mw<SB>2</SB>) of the polyethers obtained by subjecting the alkylene oxide to a ring-opening addition polymerization to the initiator, there are provided relations of Mn<SB>1</SB>=300-20,000, Mw<SB>1</SB>/Mn<SB>1</SB>≥1.2, Mn<SB>2</SB>/Mn<SB>1</SB>≥1.5, and (Mw<SB>2</SB>/Mn<SB>2</SB>)/(Mw<SB>1</SB>/Mn<SB>1</SB>)<0.8. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention uses a double metal cyanide complex catalyst to open an alkylene oxide on at least one initiator selected from the group consisting of polycarbonate monool, polycarbonate polyol, polyoxytetramethylene monool and polyoxytetramethylene polyol. The present invention relates to a method for producing a polyether polyol obtained by addition polymerization and having a specific molecular weight distribution with respect to the molecular weight distribution of an initiator, and a polyether polyol produced by the production method.

  In general, polyether polyols used as raw materials for polyurethane products such as polyurethane elastomers, adhesives, and sealants and functional oils are obtained by subjecting an initiator having an active hydrogen atom to an addition polymerization of alkylene oxides such as ethylene oxide and propylene oxide. It is manufactured. It is necessary to control the hydrophilicity, hydrophobicity, heat resistance, weather resistance, mechanical properties, etc. of these polyether polyols or polyurethane products obtained by the reaction of polyether polyols and isocyanates to desired properties. Yes. As a method for controlling these characteristics, it is produced by subjecting alkylene oxide to ring-opening addition polymerization (hereinafter also simply referred to as ring-opening polymerization) using polyester polyol, polycarbonate polyol, or polyoxytetramethylene glycol as an initiator. It has been proposed to use a polyether polyol having an ester bond or a carbonate bond in the polyether chain of the main chain of the alkylene oxide addition polymer as a polyurethane product raw material.

  Polycarbonate polyols and polyoxytetramethylene polyols, which are the initiators, and polyols obtained by ring-opening polymerization of alkylene oxides with these initiators are used in the presence or absence of an initiator using a cationic or anionic polymerization catalyst. It is known that it can be produced by ring-opening polymerization of at least one monomer selected from alkylene oxide, cyclic carbonate, and cyclic ester. However, the polyols produced using this known method have a broad molecular weight distribution, so when the molecular weight is increased, the viscosity of the product becomes very high and handling is difficult, and the polyol and polyisocyanate It was difficult to control the heat resistance and mechanical properties of the reaction product with desired properties.

On the other hand, oxiranes (3-membered ring ether compounds) such as ethylene oxide and propylene oxide can be subjected to ring-opening polymerization using a polymerization catalyst other than an anion and a cation catalyst. Among them, a double metal cyanide complex (hereinafter also referred to as a DMC catalyst) is known as a representative highly active coordination polymerization catalyst. The DMC catalyst is a complex catalyst containing an organic ligand and a metal salt. For example, an organic ligand, water, and ZnCl ₂ are coordinated to zinc hexacyanocobaltate (Zn ₃ [Co (CN) ₆ ] ₂ ). These compounds are representative.

  The polyether polyol obtained by ring-opening polymerization of alkylene oxide in the presence of an initiator such as polyoxypropylene polyol using the above DMC catalyst performs the same polymerization reaction using a conventional general alkali catalyst. It has been reported that the molecular weight distribution is narrower than that of the obtained polyether polyol (see Non-Patent Document 1, for example).

  In addition, in the alkylene oxide polymerization reaction using the DMC catalyst, the ring-opening addition reaction of alkylene oxide to the polyether polyol terminal hydroxyl group occurs preferentially at the terminal hydroxyl group of the polyether polyol having a lower molecular weight. It is also known that the molecular weight distribution of polyether polyol does not widen with progress (see, for example, Patent Document 1). However, it is known only when polyoxypropylene polyol is used as an initiator that the molecular weight distribution of the polyether polyol does not widen with the progress of the ring-opening polymerization reaction of the alkylene oxide when the DMC catalyst is used. ing.

  By the way, the known polycarbonate polyol and polyoxytetramethylene glycol originally have a broad molecular weight distribution. It has not been reported what molecular weight distribution the obtained polyethers exhibit when ring-opening polymerization of alkylene oxide in the presence of a DMC catalyst using polycarbonate polyol or polytetramethylene glycol as an initiator. Furthermore, it has not been reported that the properties of polyurethane products and functional oils can be made favorable by using the polyethers thus obtained as raw materials.

JP-A-6-16806 J.L.SHUCHAR and S.D.HARPER, “Preparation of High Molecular Weight Polyols Using Double Metal Cyanide Catalysts”, 32ND ANNUAL POLYURETHANE TECHNICAL / MARKETING CONFERENCE, OCTOBER1-4, 1989, pp.360.

  As described above, polycarbonate polyol and polytetramethylene glycol have a high viscosity due to a wide molecular weight distribution and a large cohesive force between molecules derived from the molecular structure. Therefore, although polycarbonate polyol and polytetramethylene glycol have various excellent characteristics, it may be difficult to use them as a raw material depending on applications.

  Therefore, the present invention is preferable as a raw material used for producing a polyurethane product and a functional oil agent having a narrow molecular weight distribution and having excellent characteristics while utilizing the excellent characteristics of polycarbonate polyol and polytetramethylene glycol. It is intended to provide polyethers, as well as a process for their production.

The method for producing the polyethers of the present invention includes a composite metal cyanide having an organic ligand using at least one selected from the group consisting of polycarbonate monool and polyol, and polyoxytetramethylene monool and polyol as an initiator. A method for producing a polyether comprising ring-opening addition polymerization of an alkylene oxide to an initiator in the presence of a complex catalyst, the number average molecular weight (Mn ₁ ) and the weight average molecular weight (Mw ₁ ) of the initiator And the following relationship between the number average molecular weight (Mn ₂ ) and the weight average molecular weight (Mw ₂ ) of the polyether polyol obtained by ring-opening addition polymerization of alkylene oxide to the initiator:
Mn ₁ = 300-20000;
Mw ₁ / Mn ₁ ≧ 1.2;
Mn ₂ / Mn ₁ ≧ 1.5; and (Mw ₂ / Mn ₂ ) / (Mw ₁ / Mn ₁ ) <0.8
It is characterized by having.

  In the production method of the polyethers of the present invention, the composite metal cyanide complex catalyst is tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, N, N. -It is preferable to have as an organic ligand one or more selected from dimethylacetamide, ethylene glycol mono-tert-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, iso-propyl alcohol, and dioxane. .

  Using the production method of the present invention, a polycarbonate monool and a polyol (hereinafter also referred to as a hydroxyl group-containing polycarbonate) and a polyoxytetramethylene monool and a polyol (in the presence of a double metal cyanide complex catalyst having an organic ligand) In the following, it is also referred to as a hydroxyl group-containing polyoxytetramethylene.) By carrying out ring-opening addition polymerization of alkylene oxide using at least one selected from the group consisting of as initiators, a molecular weight distribution narrower than the molecular weight distribution of the initiator is obtained. It is possible to produce polyethers having the same. Further, the organic ligand is tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, N, N-dimethylacetamide, ethylene glycol mono-tert-butyl ether, ethylene When it is one or more selected from glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, iso-propyl alcohol, and dioxane, the alkylene oxide polymerization activity of the double metal cyanide complex catalyst can be increased, Narrower molecular weight distribution of polyethers obtained by ring-opening addition polymerization of alkylene oxide to hydroxyl group-containing polycarbonate and / or hydroxyl group-containing PTMG. Can.

  Polyethers produced using the production method of the present invention have a low viscosity and a low melting point even when the number average molecular weight (Mn) is the same when compared with a hydroxyl group-containing polycarbonate and a hydroxyl group-containing polyoxytetramethylene. And there are few components whose molecular terminal is an unsaturated group. Therefore, the viscosity of the isocyanate-terminated or hydroxyl-terminated prepolymer obtained by reacting this polyether with polyisocyanate is the prepolymer obtained by reacting the hydroxyl group-containing polycarbonate or hydroxyl group-containing polyoxytetramethylene with the polyisocyanate. It has the characteristic that it is easier to handle because of its lower viscosity. In addition, the polyurethane resin obtained using the above polyethers and polyisocyanate as raw materials has higher tensile strength than the polyurethane resin obtained using a polyoxyalkylene polymer containing no polycarbonate bond or polyoxytetramethylene bond as a raw material. It has the characteristics. Polyethers produced using the production method of the present invention are preferred as raw materials for polyurethane products such as polyurethane elastomers, adhesives and sealants, and functional oils.

  In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the initiator and the polyethers are molecular weights called so-called polystyrene equivalent molecular weights. Specifically, gel permeation chromatography (GPC) of several types of monodisperse polystyrene polymers with different degrees of polymerization that are commercially available as standard samples for molecular weight measurement are measured using a commercially available GPC measurement device, A calibration curve is created based on the relationship between the molecular weight of polystyrene and the retention time (retention time). Using the calibration curve, the GPC spectrum of the sample compound is computer-analyzed to determine the number average molecular weight and the weight average molecular weight of the compound. Such measurement methods are known.

In the present specification, the number average molecular weight of the initiator is represented by Mn ₁ , the weight average molecular weight is represented by Mw ₁ , and the number average molecular weight of polyethers obtained by ring-opening addition polymerization of alkylene oxide to the initiator is represented by Mn _2. represents the weight average molecular weight Mw _2.

  As described above, the method for producing the polyether of the present invention is a double metal cyanide complex having an organic ligand using at least one selected from the group consisting of a hydroxyl group-containing polycarbonate and a hydroxyl group-containing polyoxytetramethylene as an initiator. In the presence of a catalyst, an alkylene oxide is subjected to ring-opening addition polymerization with respect to the initiator to obtain a polyether.

  Examples of the hydroxyl group-containing polycarbonate include those obtained by ring-opening polymerization of alkylene carbonate, and those obtained by transesterification of a diol compound with phosgene, chloroformate, dialkyl carbonate, or diallyl carbonate. Examples of the diol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentane. Diol, 2-methylpentanediol, 3-methylpentanediol, 2,2,4-trimethyl-1,6-hexanediol, 3,3,5-trimethyl-1,6-hexanediol, 2,3,5- Trimethylpentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, dimer diol, and the like can be used. Particularly preferred diol compounds used in the present invention are 1,6-hexanediol, 1,3-butanediol, 1,4-butanediol, and neopentyl glycol. In addition, a compound having three or more hydroxyl groups per molecule, for example, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol and the like can be used in a small amount in combination with the diol compound. Examples of the alkylene carbonate include ethylene carbonate and propylene carbonate. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate. Examples of the diallyl carbonate include diphenyl carbonate. In addition, what is marketed, such as a polyethylene carbonate polyol, a polytetramethylene carbonate polyol, a polyhexamethylene carbonate polyol, can also be used as an initiator of this invention.

  Examples of the hydroxyl group-containing polyoxytetramethylene used as an initiator in the present invention include zeolite, metalloaluminosilicate, super strong acid such as fluorosulfonic acid, a mixture of acid and acetic anhydride, perfluorosulfonic acid resin, bleaching earth, and crystal water. Examples thereof include polyoxytetramethylene polyols obtained by ring-opening polymerization of tetrahydrofuran (THF) using a catalyst selected from the group consisting of heteropoly acids whose contents are controlled within a specific range. Copolymer polyoxytetramethylene obtained by random copolymerization of at least one compound selected from the group consisting of alkanediols having 2 to 10 carbon atoms, alkylene oxide, oxetane, cyclic acetal, 2-methyltetrahydrofuran and the like with THF. Polyols can also be used as initiators in the present invention.

The hydroxyl group-containing polycarbonate and the hydroxyl group-containing polyoxytetramethylene used as the initiator in the present invention are generally difficult to produce those having a narrow molecular weight, and therefore are started from the viewpoint of ease of production or availability. The molecular weight distribution (Mw ₁ / Mn ₁ ) of the agent is preferably 1.2 or more, and more preferably 1.5 or more. In order to produce an initiator having a molecular weight distribution (Mw ₁ / Mn ₁ ) of less than 1.2, a special catalyst and / or process may be required, resulting in an increase in cost.

  The average number of hydroxyl groups possessed by the hydroxyl group-containing polycarbonate or hydroxyl group-containing polyoxytetramethylene used as the initiator is preferably 1 to 6 and more preferably 1 to 4 per molecule. If the average number of hydroxyl groups per molecule of the initiator is 7 or more, it may be difficult to narrow the molecular weight distribution of the polyether polyol obtained by ring-opening addition polymerization of alkylene oxide with the initiator.

As the initiator, it is preferable to use a hydroxyl group-containing polycarbonate and / or a hydroxyl group-containing polyoxytetramethylene having a number average molecular weight (Mn ₁ ) of 300 to 20000, and more preferably 600 to 5000. By setting the number average molecular weight (Mn ₁ ) of the initiator to 300 or more, it is possible to shorten the time until the alkylene oxide ring-opening polymerization reaction using the double metal cyanide complex catalyst having an organic ligand is started. it can. Further, by setting the number average molecular weight (Mn ₁ ) of the initiator to 20000 or less, the viscosity of the initiator can be prevented from becoming too high, and an alkylene oxide polymerization reaction with high uniformity to the initiator can be advanced.

Further, the production method of the present invention includes a number average molecular weight (Mn ₂ ) and a weight average molecular weight (Mw ₂ ) of a polyether polyol obtained by ring-opening addition polymerization of an alkylene oxide to an initiator, and a number average molecular weight of the initiator. The following relationship between (Mn ₁ ) and weight average molecular weight (Mw ₁ ):
Mn ₂ / Mn ₁ ≧ 1.5 and (Mw ₂ / Mn ₂ ) / (Mw ₁ / Mn ₁ ) <0.8
It is characterized by having. The above relationship is that the production method of the present invention polymerizes alkylene oxide to the initiator until the number average molecular weight of the initiator is 1.5 times or more, and the ring-opening addition of alkylene oxide to the initiator. It shows that the value of the molecular weight distribution of the polyether polyol obtained by polymerization is smaller than 0.8 times the value of the molecular weight distribution of the initiator. In the present invention, Mn ₂ / Mn ₁ ≧ 1.5, more preferably 5.0 ≧ Mn ₂ / Mn ₁ ≧ 1.5, and particularly preferably 3.0 ≧ Mn ₂ / Mn ₁ ≧ 1.5. . In the present invention, (Mw ₂ / Mn ₂ ) / (Mw ₁ / Mn ₁ ) <0.8 and (Mw ₂ / Mn ₂ ) / (Mw ₁ / Mn ₁ ) <0.7. It is particularly preferred.

  By optimally controlling the number average molecular weight of the initiator, the molecular weight distribution of the initiator, the type and amount of the catalyst used for the polymerization reaction, the amount of alkylene oxide to be subjected to ring-opening addition polymerization to the initiator, and the polymerization reaction conditions, etc. The relationship between the above parameters can be realized. The polymerization reaction conditions include the polymerization reaction temperature, the stirring strength, the supply rate of alkylene oxide to the reaction vessel, and the like. In the following, preferred embodiments of the polymerization reaction will be described in carrying out the present invention. Those skilled in the art can easily carry out the present invention by appropriately determining preferable polymerization conditions based on the following description.

  Below, the double metal cyanide complex catalyst which has an organic ligand used for the manufacturing method of this invention, and the polymerization conditions using the same are demonstrated.

[Double metal cyanide complex catalyst with organic ligand]
The double metal cyanide complex catalyst (hereinafter also simply referred to as DMC catalyst) used in the present invention is typically represented by the following formula (1).
M ¹ _a [M ² _b (CN) _c ] _d e (M ¹ _f X _g ) h (H ₂ O) i (R) (1)
(M ¹ and M ² represent a metal atom, X represents a halogen atom, R represents an organic ligand, a, b, c, d, e, f, g, h, i are atoms of the metal atom. It represents a number that can vary depending on the valence and the coordination number of the organic ligand.)

In the above formula (1), M ¹ is Zn (II), Fe (II), Fe (III), Co (II), Ni (II), Mo (IV), Mo (VI), Al (III) , V (V), Sr (II), W (IV), W (VI), Mn (II), Cr (III), Cu (II), Sn (II), and Pb (II) Are preferred, and Zn (II) or Fe (II) is particularly preferred. The Roman numeral in parentheses after the metal atomic symbol represents the valence, and so on.

Furthermore, in the above formula (1), M ² is Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn ( III), Ni (II), V (IV) and V (V) are preferred, with Co (III) or Fe (III) being particularly preferred.

  Furthermore, in said formula (1), R is an organic ligand. The organic ligand is preferably water-soluble, and specific examples include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, N, N-dimethylacetamide. 1 selected from ethylene glycol dimethyl ether (also referred to as glyme), diethylene glycol dimethyl ether (also referred to as diglyme), triethylene glycol dimethyl ether (also referred to as triglyme), ethylene glycol mono-tert-butyl ether, iso-propyl alcohol, and dioxane. Species or two or more compounds. The dioxane may be 1,4-dioxane or 1,3-dioxane, but 1,4-dioxane is preferred.

  Particularly preferred organic ligands in the present invention are one or more compounds selected from tert-butyl alcohol, tert-pentyl alcohol, and ethylene glycol mono-tert-butyl ether, and tert-butyl alcohol or tert-butyl alcohol A combination of -butyl alcohol and ethylene glycol mono-tert-butyl ether is most preferred because high polymerization catalyst activity can be obtained.

  The double metal cyanide complex catalyst having an organic ligand in the present invention can be produced using a known production method. As a known catalyst production method, for example, (i) an organic ligand is coordinated to a reaction product obtained by reacting a metal halide salt and an alkali metal cyanometalate in an aqueous solution, A method of washing the separated solid component with an aqueous organic ligand solution, or (ii) reacting a halogenated metal salt with an alkali metal cyanometalate in an aqueous organic ligand solution to obtain a reaction product Examples include a method of separating a product (solid component) and washing the separated solid component with an organic ligand aqueous solution.

The metal constituting the cyanometalate of the alkali metal cyanometalate used in the production of the DMC catalyst in the present invention is Fe (II), Fe (III), Co (II), Co (III), Cr (II) , Cr (III), Mn (II), Mn (III), Ni (II), V (IV), and V (V) are preferred, and Co (III) or Fe ( Particular preference is given to III). Preferred specific examples of alkali metal cyanometalates are H ₃ [Co (CN) ₆ ], Na ₃ [Co (CN)] ₆ , and K ₃ [Co (CN)] ₆ , and Na ₃ [Co (CN )] ₆ and K ₃ [Co (CN)] ₆ are most preferred.

  A DMC catalyst can be prepared by washing a reaction product obtained by using the above-described known production method of a composite metal cyanide complex catalyst and drying a cake (solid component) obtained by filtration and separation. . In addition, a reaction product of a metal halide salt and an alkali metal cyanometalate is washed with water and / or an organic ligand, and further dispersed in an aqueous solution of an organic ligand is dispersed in a polyol compound. A slurry-like DMC catalyst in which a DMC catalyst having an organic ligand is dispersed in a polyol compound can be prepared by distilling off an excessive amount of water and the organic ligand from the resulting dispersion. .

  A polyether polyol is mentioned as a polyol compound used in order to prepare the said slurry-like DMC catalyst. As a polyether polyol for this purpose, an average number of hydroxyl groups per molecule produced by ring-opening addition polymerization of alkylene oxide to an initiator selected from monoalcohol and polyhydric alcohol using an alkali catalyst or a cation catalyst is 1 A polyether monool or polyether polyol having a number average molecular weight of 300 to 5,000 is preferable.

  Examples of the alkylene oxide used in the production method of the present invention include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin, oxetane, styrene oxide, and tetrahydrofuran. 1 type or 2 types or more chosen from these can be used. In the present invention, it is preferable to use one or both selected from ethylene oxide and propylene oxide, and it is most preferable to use propylene oxide. The polymerization reaction can also be carried out using a small amount of a cyclic ester such as epichlorohydrin, oxetane, tetrahydrofuran, and lactone together with ethylene oxide and / or propylene oxide.

[Alkylene oxide polymerization method]
In the present invention, a polyether polyol can be produced by ring-opening addition polymerization of alkylene oxide as an initiator in the presence of a DMC catalyst in a reaction vessel. In the presence of an initiator and a DMC catalyst, the polymerization reaction can be carried out by adding one or a mixture of two or more of the above alkylene oxides into the reaction vessel. In the present invention, one kind of alkylene oxide can be homopolymerized using an initiator, or two or more kinds of alkylene oxide can be block polymerized and / or randomly polymerized.

  The amount of the DMC catalyst used in the polymerization reaction may be any amount as long as it is necessary for the ring-opening polymerization of the alkylene oxide, but is preferably as small as possible. The smaller the amount of DMC catalyst used in the polymerization reaction, the smaller the amount of DMC catalyst contained in the product polyethers. Thereby, the influence of the DMC catalyst on the reactivity of the polyethers obtained by the polymerization reaction with the polyisocyanate and the physical properties of polyurethane products and functional oils produced using the polyethers as raw materials can be reduced. Usually, after the ring-opening addition polymerization reaction of the alkylene oxide to the initiator, an operation of removing the DMC catalyst from the obtained polyethers is performed. As described above, the amount of the DMC catalyst remaining in the polyethers is reduced. When the amount is small and does not adversely affect thereafter, it is possible to proceed to the next step using the polyethers without performing the step of removing the DMC catalyst, so that the production efficiency of the polyethers can be increased. The solid catalyst component of the DMC catalyst (the component excluding the polyol compound and excess ligand) is subjected to an alkylene oxide polymerization reaction to the initiator using an amount of DMC catalyst of 10 to 80 ppm in the polymer immediately after polymerization. Preferably it is done. Sufficient polymerization catalyst activity can be obtained by setting the solid catalyst component of the DMC catalyst contained in the polymer to 10 ppm or more, and further sufficient polymerization activity can be obtained at 80 ppm or less. Is also not economical. However, there is no problem even if a catalyst containing 80 ppm or more of the solid catalyst component is used with respect to the obtained polymer.

  The ring-opening polymerization temperature of the alkylene oxide in the present invention is preferably 30 to 180 ° C, preferably 70 to 160 ° C, particularly preferably 90 to 140 ° C. When the polymerization temperature is 30 ° C. or lower, the ring-opening polymerization of alkylene oxide may not start, and when it is 180 ° C. or higher, the polymerization activity of the DMC catalyst may decrease.

  Further, the polymerization reaction of the alkylene oxide of the present invention is preferably performed under good stirring conditions. When using a general stirring method using a stirring blade, it is preferable to make the rotation speed of the stirring blade as high as possible within a range in which a large amount of gas in the gas phase is taken into the reaction solution and stirring efficiency does not decrease. . In this polymerization reaction, since the molecular weight distribution of the resulting polymer can be narrowed, the supply rate of alkylene oxide into the reaction vessel is preferably as slow as possible, but in that case the production efficiency is reduced, It is preferable to determine the supply rate of the alkylene oxide by comparing these.

  The alkylene oxide polymerization reaction of the present invention can also be carried out using a reaction solvent. Preferred reaction solvents include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogen solvents such as chloroform and dichloromethane. The amount of solvent used is not particularly limited, and a desired amount of solvent can be used.

In the production method of the present invention, the ratio Mn between the number average molecular weight (Mn ₁ ) of an initiator and the number average molecular weight (Mn ₂ ) of a polyether produced by polymerizing an alkylene oxide with respect to the initiator. _The alkylene oxide is polymerized with respect to the initiator so that ₂ / Mn ₁ is 1.5 or more, preferably 1.5 to 5.0, more preferably 1.5 to 3.0. By adjusting the polymerization amount of the alkylene oxide with respect to the initiator, Mn ₂ / Mn ₁ can be set to the above-mentioned preferable value. Generally, the greater the amount of alkylene oxide added to the initiator, the greater the Mn ₂ / Mn ₁ . When Mn ₂ / Mn ₁ is less than 1.5, it is difficult to produce a polyether having a narrow molecular weight distribution. In addition, since the alkylene oxide chain length in the polyether is short, the polyether is used. In some cases, flexibility such as polyurethane resin, adhesive, and sealant to be manufactured, adhesion to a base material, and the like are lowered.

  When the DMC catalyst contained in the obtained polyethers is removed after the completion of the polymerization reaction of the alkylene oxide, examples of the method include synthetic silicates (magnesium silicate, aluminum silicate, etc.), ion exchange resins, and activated clay. The catalyst is adsorbed using an adsorbent selected from, and the adsorbent is removed by filtration, and the catalyst is adsorbed using a neutralizing agent selected from amines, alkali metal hydroxides, organic acids, and mineral acids. Examples of the method include neutralization and further removal by filtration.

  Antioxidants and anticorrosives can be added to the polyethers produced using the production method of the present invention to prevent the polyethers from deteriorating during long-term storage.

[Use of polyethers]
The polyethers of the present invention are preferred as raw materials for producing polyurethane resins, elastomers, adhesives, sealants and the like by reacting with polyisocyanate compounds. The polyethers of the present invention can also be used for applications such as surfactants and functional oils, and can also be used as a raw material for polymer-dispersed polyether polyols containing polymer fine particles.

  When the polyethers produced using the method of the present invention are used for various applications as described above, the number average molecular weight of the polyethers is preferably 450 to 50000, more preferably 900 to 20000, and particularly preferably 1000 to 10,000. preferable.

  The polyurethane product obtained by reacting the raw material containing the polyethers of the present invention with a polyisocyanate compound is more hydrophilic and hydrophobic than conventional polyethers consisting essentially of polyoxyethylene and polyoxypropylene. Excellent heat resistance, weather resistance, and mechanical properties. Examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and polymethylene polyphenyl isocyanate; fats such as hexamethylene diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, lysine diisocyanate and tetramethylxylylene diisocyanate. Polyisocyanates; alicyclic polyisocyanates such as isophorone diisocyanate; and modified products of these polyisocyanate compounds.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these.
Polyol X in this example is a polyol having a number average molecular weight (Mn ₁ ) of 1000, obtained by addition polymerization of propylene oxide to dipropylene glycol.

[Reference Example: Production Example of Double Metal Cyanide Complex Catalyst Having Organic Ligands]
An aqueous solution consisting of 10.2 g of zinc chloride and 10 g of water was placed in a 500 ml flask, and this aqueous solution was kept at 40 ° C. while stirring at 300 rpm, and 4.2 g of potassium hexacyanocobaltate (K ₃ [Co (CN)] ₆ ) and an aqueous solution consisting of 75 g of water were added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred for 30 minutes, then 40 g of ethylene glycol mono-tert-butyl ether (hereinafter abbreviated as EGMTBE), 40 g of tert-butyl alcohol (hereinafter abbreviated as TBA), 80 g of water, and 0. A mixture of 6 g of polyol X was added to the mixture, and the mixture was stirred at 40 ° C. for 30 minutes and further at 60 ° C. for 60 minutes. The obtained reaction mixture was filtered for 50 minutes under pressure (0.25 MPa) using a circular filter plate having a diameter of 125 mm and a quantitative filter paper for fine particles (No. 5C manufactured by ADVANTEC Co.) to obtain a solid. separated.

Next, a mixture comprising 18 g of EGMTBE, 18 g of TBA, and 84 g of water was added to the cake containing the double metal cyanide complex and stirred for 30 minutes, followed by pressure filtration (filtration time: 15 minutes). It was. To the cake containing the double metal cyanide complex obtained by filtration, a mixture of 54 g EGMTBE, 54 g TBA, and 12 g water was added and stirred for 30 minutes, and the double metal cyanide having an organic ligand was stirred. A slurry of EGMTBE / TBA containing the complex was obtained.
About 5 g of this slurry was weighed into a flask, dried roughly with a nitrogen stream, and then dried under reduced pressure at 80 ° C. for 4 hours. As a result of weighing the obtained solid, it was found that the concentration of the double metal cyanide complex contained in the slurry was 4.70% by mass.

[Production of polyetherol using 5000 ml reactor]
A stainless steel 5000 ml pressure reactor equipped with a stirrer was used for the following alkylene oxide polymerization reaction.

(Example 1)
In the reactor, 1000 g of polyoxytetramethylene glycol (Mw ₁ / Mn ₁ = 1.95, Mn ₁ = 1413, manufactured by BASF, appearance: white solid, melting point: 36 ° C.) as an initiator, and the above reference example 1100 mg (50 mg as a solid catalyst component) of the slurry catalyst prepared in (1) was added. After the reactor was purged with nitrogen, the temperature was raised to 120 ° C., and 100 g of propylene oxide was supplied into the reactor for reaction. After the pressure in the reactor dropped, 1000 g of propylene oxide was fed into the reactor at a rate of about 160 g / 1 hour. The supply of propylene oxide was completed over 6 hours and 30 minutes, and stirring was continued for another hour. Meanwhile, the reaction was allowed to proceed while maintaining the internal temperature of the reactor at 120 ° C. and the stirring speed at 500 rpm. The polyether polyol obtained by this reaction had Mw ₂ / Mn ₂ of 1.07 and Mn ₂ of 3340. The appearance of the obtained polyether polyol was a transparent liquid at room temperature, and the viscosity at 25 ° C. was 700 mPa · s. For the viscosity, an E-type viscometer VISCONIC EHD type (manufactured by Tokimec) was used. This is a value measured using one rotor, and so on.

(Example 2)
In the reactor, 1000 g of polyoxytetramethylene glycol (Mw ₁ / Mn ₁ = 2.01, Mn ₁ = 2844, manufactured by Hodogaya Chemical Co., Ltd., appearance: white solid, melting point 36 ° C.) as an initiator and the above reference example 1100 mg (50 mg as a solid catalyst component) of the slurry catalyst prepared in (1) was added. After the atmosphere in the reactor was replaced with nitrogen, the temperature was raised to 120 ° C., and 100 g of propylene oxide was supplied into the reactor for reaction. After the pressure in the reactor dropped, 550 g of propylene oxide was fed into the reactor at a rate of about 160 g / 1 hour. The propylene oxide supply was completed in 3 hours and 30 minutes, and stirring was continued for another hour. Meanwhile, the reaction was allowed to proceed while maintaining the internal temperature of the reactor at 120 ° C. and the stirring speed at 500 rpm. The polyether polyol obtained by this reaction had Mw ₂ / Mn ₂ of 1.19 and Mn ₂ of 4928. The appearance of the obtained polyether polyol was a white liquid at ordinary temperature, and the viscosity at 25 ° C. was 1960 mPa · s.

(Example 3)
In the reactor, 1000 g of polyoxytetramethylene glycol (Mw ₁ / Mn ₁ = 2.01, Mn ₁ = 2844, manufactured by Hodogaya Chemical Co., Ltd., appearance: white solid, melting point 36 ° C.) as an initiator and the above reference example 1100 mg (50 mg as a solid catalyst component) of the slurry catalyst prepared in (1) was added. After the atmosphere in the reactor was replaced with nitrogen, the temperature was raised to 120 ° C., and 100 g of propylene oxide was supplied into the reactor for reaction. After the pressure in the reactor dropped, 900 g of a mixture of propylene oxide and ethylene oxide (propylene oxide: ethylene oxide = 2: 1 by weight) was fed into the reactor at a rate of about 160 g / 1 hour. The supply of alkylene oxide was completed over 5 hours and 40 minutes, and stirring was continued for another hour. Meanwhile, the reaction was allowed to proceed while maintaining the internal temperature of the reactor at 120 ° C. and the stirring speed at 500 rpm. The polyether polyol obtained by this reaction had an Mw ₂ / Mn ₂ of 1.08, an Mn ₂ of 6471, an appearance of white liquid at room temperature, and a viscosity of 1960 mPa · s at 25 ° C.

Example 4
Polycarbonate diol having a residue of 1,6-hexanediol as an initiator (Mw ₁ / Mn ₁ = 2.92, Mn ₁ = 2494, trade name: NIPPOLAN 980N, manufactured by Nippon Polyurethane Co., Ltd., appearance: white solid, melting point 54 g) and 1100 mg of the slurry catalyst prepared in Reference Example 1 (50 mg as a solid catalyst component) were charged into the reactor. After replacing the inside of the reactor with nitrogen gas, the temperature was raised to 120 ° C., and 100 g of propylene oxide was further supplied into the reactor for reaction. After the pressure in the reactor dropped, 550 g of propylene oxide was further fed into the reactor at a rate of about 160 g / hour. The supply of propylene oxide was stopped at 3 hours 30 minutes, and stirring was continued at a stirring speed of 500 rpm at about 120 ° C. for 1 hour to proceed the polymerization reaction. The polyol obtained by the polymerization reaction had Mw ₂ / Mn ₂ = 1.95 and Mn ₂ = 5311, the appearance was a white solid, and the melting point was 49 ° C.

(Comparative Example 1)
A polyether polyol was prepared using a method similar to that described in Example 1. However, instead of the slurry catalyst prepared in Reference Example, 6.3 g of NaOH was used as a polymerization catalyst. The polyether polyol obtained by this reaction had Mw ₂ / Mn ₂ of 1.84 and Mn ₂ of 2412. The appearance of this polyether was a transparent liquid, and its viscosity was 840 mPa · s at 25 ° C.

(Comparative Example 2)
A polyether polyol was prepared using a method similar to that described in Example 2. However, polypropylene glycol (Mw ₁ / Mn ₁ = 1.18, Mn ₁ = 315) was used in place of the polyoxytetramethylene glycol used as the initiator in Example 2. The polyether polyol obtained by this reaction had Mw ₂ / Mn ₂ of 1.19 and Mn ₂ of 481. The appearance of the polyether polyol was a transparent liquid, and the viscosity was 85 mPa · s at 25 ° C.

(Comparative Example 3)
A polyether polyol was prepared using a method similar to that described in Example 4. However, instead of the slurry catalyst prepared in Reference Example, 6.3 g of NaOH was used as a polymerization catalyst. In this case, the ring-opening addition polymerization of propylene oxide did not proceed smoothly, and after supplying 300 g of propylene oxide into the reactor, the pressure in the reactor reached 0.8 MPa. The propylene oxide remaining in the vessel was distilled off under reduced pressure. The polyether polyol obtained by this polymerization reaction had Mw ₂ / Mn ₂ of 2.88, Mn ₂ of 2163, and the appearance was a white solid.

As is clear from the above Examples and Comparative Examples, by using the method of the present invention, the molecular weight distribution (Mw ₂ / Mn ₂ ) is small, the viscosity is low, the melting point is low, and the content of unsaturated components is small. Ethers can be produced.

Claims (2)

Using at least one selected from the group consisting of polycarbonate monool and polyol, and polyoxytetramethylene monool and polyol as an initiator, in the presence of a double metal cyanide complex catalyst having an organic ligand, A method for producing a polyether by ring-opening addition polymerization of an alkylene oxide on the basis of the number average molecular weight (Mn ₁ ) and the weight average molecular weight (Mw ₁ ) of the initiator, and the ring opening of the alkylene oxide to the initiator The following relationship between the number average molecular weight (Mn ₂ ) and the weight average molecular weight (Mw ₂ ) of the polyethers obtained by addition polymerization:
Mn ₁ = 300-20000;
Mw ₁ / Mn ₁ ≧ 1.2;
Mn ₂ / Mn ₁ ≧ 1.5; and (Mw ₂ / Mn ₂ ) / (Mw ₁ / Mn ₁ ) <0.8
A process for producing a polyether polyol, characterized in that The composite metal cyanide complex catalyst is tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, N, N-dimethylacetamide, ethylene glycol mono-tert-butyl ether, ethylene 2. The polyether according to claim 1, comprising one or more selected from glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, iso-propyl alcohol, and dioxane as an organic ligand. Manufacturing method.