JP5364966B2 - Method for producing polyether polyol or polyether monool - Google Patents

Description

  The present invention is obtained by ring-opening polymerization of an alkylene oxide having 3 or more carbon atoms to an initiator using a cationic polymerization catalyst, has a relatively high proportion of terminal primary hydroxyl groups, and has a low content of multimeric by-products. The present invention relates to a method for producing polyether polyol or polyether monool (hereinafter collectively referred to as polyether poly (mono) ol), and a polyether poly (mono) ol obtained by the production method.

  Polyurethane resins produced by mainly reacting polyether polyols with active hydrogen and polyisocyanates, and in some cases chain extenders, among others, polyurethane foams (polyurethane foams) are widely used industrially. . The flexible polyurethane foam generally has excellent elasticity and is widely used for automobile seats, furniture, bedding and the like. Rigid polyurethane foam generally has excellent heat insulating performance, and is widely used as a heat insulating material for refrigerators, showcases, heat storage warehouses, and freezing warehouses.

  So far, polyether polyol, which is one of the raw materials of polyurethane resin, has been produced by polymerizing an alkylene oxide such as ethylene oxide and propylene oxide with an initiator having active hydrogen. Representative catalysts for alkylene oxide polymerization include anionic polymerization catalysts such as alkali metal compounds, alkaline earth metal compounds, phosphazene compounds, phosphoric acid, Lewis acid, and organic ligand compounds thereof, trifluoromethylsulfonic acid. Cationic polymerization catalysts such as salts and tetrakispentafluorophenylborate, and coordination polymerization catalysts such as water / organic zinc and double metal cyanide complexes are known.

Normally, when ring-opening polymerization of propylene oxide, which is an alkylene oxide having 3 or more carbon atoms, using an anionic polymerization catalyst in the presence of an active hydrogen-containing initiator, almost 100 of the terminal hydroxyl groups of the resulting polyether poly (mono) ol are obtained. % Is a secondary hydroxyl group. On the other hand, when ring-opening polymerization of propylene oxide in the presence of an initiator using a cationic polymerization catalyst, the ratio of primary hydroxyl groups and secondary hydroxyl groups in the total terminal hydroxyl groups of the polyether polyether (mono) ol obtained is approximately It is known to be the same. In addition, recently, when a propylene oxide ring-opening polymerization is performed using a boron or aluminum compound having a phenyl group or a tertiary alkyl group as a substituent as a Lewis acid cation catalyst, all ends of the resulting polyether polyol are obtained. It has been reported that the proportion of primary hydroxyl groups in the hydroxyl groups is 70% or more (see, for example, Patent Documents 1 to 3).
JP 2000-344881 A JP 2002-187951 A JP 2003-113219 A

  However, when a known method is used for ring-opening polymerization of an alkylene oxide having 3 or more carbon atoms until the proportion of primary hydroxyl groups in all terminal hydroxyl groups is 60% or more, the ring-opening polymerization of alkylene oxide to the initiator is performed. In addition, there is a problem that a side reaction occurs in which a large amount of multimer by-products corresponding to the molecular weight increased such as dimerization and trimerization of the obtained polymer occurs, and as a result, the viscosity of the product increases. I found out. In particular, this side reaction becomes more prominent as the amount of alkylene oxide added to the initiator is increased. And when a multimer by-product increased, there existed a problem that the viscosity of an alkylene oxide polymer became high.

  The present invention is obtained by ring-opening polymerization of an alkylene oxide having 3 or more carbon atoms to an initiator having one or more hydroxyl groups, and has a high proportion of primary hydroxyl groups in all terminal hydroxyl groups, more preferably the degree of unsaturation. An object of the present invention is to provide a method for producing a polyether poly (mono) ol having a low multimer by-product content and a polyether poly (mono) ol produced using the production method.

The method for producing the polyether poly (mono) ol of the present invention is as follows. That is, it has one or more hydroxyl groups per molecule in the presence of one or more cationic polymerization catalysts selected from the group consisting of aluminum or boron compounds having at least one fluorine-substituted phenyl group or fluorine-substituted phenoxy group. In addition, an initiator having a hydroxyl group equivalent of 1200 or more is subjected to ring-opening polymerization of an alkylene oxide having 3 or more carbon atoms, and has an average of 2 or more oxyalkylene units per hydroxyl group terminal of the initiator. The proportion of primary hydroxyl groups in all terminal hydroxyl groups is 45 to 85%, and the total area of all peaks obtained by measuring gel permeation chromatography is derived from the following multimer by-products. Method for producing polyether polyol or polyether monool having a peak area ratio of 30% or less There,
(A) the amount of water in the initiator when mixed with the cationic polymerization catalyst is 5 to 100 ppm,
(B) the amount of the cationic polymerization catalyst relative to the initiator is 10 to 120 ppm,
(C) The condition that the water content in the alkylene oxide having 3 or more carbon atoms is 3 to 100 ppm is used.
Multimer by-product: contained in a polymer obtained by subjecting an alkylene oxide to ring-opening polymerization reaction as an initiator, and corresponding to an integer multiple of 2 or more of the polymer molecular weight corresponding to the main peak in gel permeation chromatography An alkylene oxide polymer observed as a peak having a molecular weight.

The cationic polymerization catalyst is one or more compounds selected from the group of tris (pentafluorophenyl) borane, tris (pentafluorophenyl) aluminum, tris (pentafluorophenyloxy) borane, trispentafluorophenyloxy) aluminum. preferably there, it is particularly preferable to use tris (pentafluorophenyl) borane.

  Moreover, in the manufacturing method of the said polyether poly (mono) ol, it is preferable to carry out ring-opening polymerization of 2-12 said alkylene oxides per C1-hydroxyl group of the said initiator.

The alkylene oxide having 3 or more carbon atoms is preferably propylene oxide.
The initiator is preferably a polyoxyalkylene polyol or a polypolyoxyalkylene monool.
Moreover, it is preferable that 70% or more of the hydroxyl groups of the initiator are secondary hydroxyl groups.
The total unsaturation degree of the initiator is preferably 0.04 meq / g or less.

  In the present specification, “multimer by-product” is included in a polymer obtained by subjecting an alkylene oxide to ring-opening polymerization reaction as an initiator, and corresponds to a heavy peak corresponding to a main peak in gel permeation chromatography. An alkylene oxide polymer observed as a peak having a molecular weight corresponding to an integer multiple of 2 or more of the combined molecular weight.

  By using the above production method, the proportion of primary hydroxyl groups in the proportion of all terminal hydroxyl groups is relatively high despite having an oxyalkylene unit obtained by ring-opening polymerization of an alkylene oxide having 3 or more carbon atoms, and A polyether poly (mono) ol with a low content of multimeric by-products is obtained. This polyether poly (mono) ol is suitable for use as a polyurethane resin raw material.

  The present invention uses a poly (mono) ol initiator having a hydroxyl group equivalent of 1200 or more and the specific cationic polymerization catalyst of 10 to 120 ppm relative to the initiator, and the initiator is brought into contact with the cationic catalyst. The amount of primary hydroxyl groups in all terminal hydroxyl groups is high and the by-products of the multimer are kept low by keeping the moisture content of 5 to 100 ppm low, and further using the alkylene oxide having 3 to 100 ppm and a small moisture content of 3 or more carbon atoms. The present inventors have found that a polyether poly (mono) ol having a low content of and having a low viscosity can be produced.

  Each raw material used for production of the polyether poly (mono) ol of the present invention and a production method using the same will be described in detail below.

[Initiator]
The initiator used in the production method of the present invention is a compound having one or more hydroxyl groups per molecule and having a hydroxyl group equivalent of 1200 or more, that is, a polyol or monool. The hydroxyl equivalent of the initiator is preferably 1300 or more, and more preferably 1500 or more. The number of hydroxyl groups per molecule of the initiator is not limited, but is preferably 2 to 8, and more preferably 2 to 4. Although there is no upper limit of the hydroxyl equivalent of the initiator, it is preferably 10,000 or less, and more preferably 5000 or less. The hydroxyl equivalent means a value obtained by dividing the average molecular weight by the average number of hydroxyl groups per molecule.

  The initiator may be a compound having a hydroxyl group such as a polyol or monool having a hydroxyl group equivalent of 1200 or more. Examples of the initiator include dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, monoethanolamine, diethanolamine, triethanolamine, and bisphenol A, and polyoxypropylene poly having a hydroxyl equivalent weight of less than 1200. Ring-opening polymerization of an active hydrogen-containing compound such as (mono) ol with one or more alkylene oxides selected from, for example, ethylene oxide, propylene oxide, styrene oxide, and butylene oxide in the presence of a polymerization catalyst. And polyether poly (mono) ol having a hydroxyl equivalent weight of 1200 or more. As the alkylene oxide, propylene oxide is particularly preferable. The polymerization catalyst is preferably at least one selected from the group consisting of alkali metal compounds, alkaline earth metal compounds, phosphazene compounds, and double metal cyanide complexes.

Examples of the alkali metal compound catalyst include sodium hydroxide, potassium hydroxide, cesium hydroxide, and sodium alkoxide.
As the phosphazene compound catalyst, known compounds (for example, compounds described in JP-A-10-36499, JP-A-11-106500, or JP-A-11-302371) can be used.

The double metal cyanide complex catalyst is typically represented by the following formula (1).
M ¹ _a [M ² _b (CN) _c ] _de (M ¹ _f X _g ) h (H ₂ O) i (R) (1)
(In the formula, M ¹ and M ² are metals, X is a halogen atom, R is an organic ligand, a, b, c, d, e, f, g, h, and i are metal valences and organic coordinates. Indicates the number that can change depending on the coordination number of the 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. In the above formula, M ² is Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), Ni A metal selected from (II), V (IV), and V (V) is preferred, and Co (III) or Fe (III) is particularly preferred. II, III, IV and V in the parentheses indicate valences.

  As the double metal cyanide complex catalyst, a zinc hexacyanocobaltate complex having an organic ligand as a ligand is preferable. Examples of the organic ligand include t-butyl alcohol, n-butyl alcohol, isobutyl alcohol, t-pentyl alcohol, isopentyl alcohol, N, N-dimethylacetamide, glyme (ethylene glycol dimethyl ether), and diglyme (diethylene glycol dimethyl ether). , One or more compounds selected from the group consisting of triglyme (triethylene glycol dimethyl ether), ethylene glycol mono-t-butyl ether, isopropyl alcohol, and dioxane. Examples of dioxane include 1,4-dioxane and 1,3-dioxane, but it is preferable to use 1,4-dioxane.

In the presence of a polymerization catalyst, polyoxyalkylene poly (mono) ol that can be used as an initiator of the present invention can be produced by ring-opening polymerization of an alkylene oxide to an active hydrogen-containing compound. Only one type of alkylene oxide can be used, or two or more types can be used in combination.
When two or more types of alkylene oxide are used in combination, any polymerization method of block polymerization and random polymerization may be used. Furthermore, one type of polyoxyalkylene poly (mono) ol is obtained by combining both block polymerization and random polymerization. Can also be polymerized. Furthermore, ring-opening polymerization of cyclic esters such as ε-caprolactone can be performed together with alkylene oxide. In that case, alkylene oxide and cyclic ester can be randomly polymerized or block polymerized.

  The initiator used in the production method of the present invention is preferably a polyoxyalkylene poly (mono) ol having a hydroxyl group equivalent of 1200 or more. Particularly preferred are polyoxyalkylene diols or triols having a hydroxyl group equivalent × average number of hydroxyl groups per molecule of 2400 to 10,000, especially polyoxypropylene diols or triols. Furthermore, a compound selected from the group consisting of polycarbonate polyol, polyester polyol, and polytetramethylene glycol can also be used as an initiator.

  As polyoxyalkylene poly (mono) ol used as an initiator, polyoxypropylene polyoxyethylenediol or triol which is a copolymer of propylene oxide and ethylene oxide may be used in addition to polyoxypropylene poly (mono) ol. . In the present invention, it is preferable to use an initiator whose secondary hydroxyl group is 70% or more, particularly 90% or more of the terminal hydroxyl group. According to the present invention, a polyether (mono) ol having a high proportion of primary hydroxyl groups can be produced from such a polyether (mono) ol having a high proportion of secondary hydroxyl groups.

Furthermore, the total unsaturation degree (value measured in accordance with JIS K 1557) of polyoxypropylene poly (mono) ol used as an initiator is 0.04 meq / g or less, preferably 0.02 meq / g, more preferably Is 0.01 meq / g or less, particularly preferably 0.007 meq / g or less. In order to produce polyoxypropylene poly (mono) ol having a low total unsaturation, it is preferable to use a double metal cyanide complex, cesium hydroxide, or a phosphazene compound as a polymerization catalyst. It is particularly preferable to use it.
In the present invention, when a compound having a low total unsaturation is used as the initiator, the total unsaturation of the finally obtained polyether poly (mono) ol can be reduced. A polyurethane resin produced using a polyoxyalkylene polyol having a low total unsaturation can provide an effect of excellent mechanical strength.

  Furthermore, when a double metal cyanide complex catalyst is used as the polymerization catalyst, the amount of catalyst used in the polymerization reaction can be reduced because the catalyst is particularly high in the ring-opening polymerization activity of the alkylene oxide. In this case, it is possible to carry out ring-opening polymerization of an alkylene oxide having 3 or more carbon atoms without adding a cationic polymerization catalyst. The amount of catalyst remaining in polyoxyalkylene poly (mono) ol produced by ring-opening polymerization of alkylene oxide in the presence of an active hydrogen-containing compound is 100 ppm or less, preferably 50 ppm or less, particularly preferably 30 ppm or less. It is preferable to use a double metal cyanide complex catalyst. By setting the amount of the double metal cyanide complex remaining in the polyoxyalkylene poly (mono) ol to 100 ppm or less, it is possible to prevent the subsequently added cationic polymerization catalyst from being deactivated. In contrast, when polyoxyalkylene poly (mono) ol is produced using an alkali metal compound such as cesium hydroxide, an alkaline earth metal compound, or a phosphazene compound as a polymerization catalyst, it prevents deactivation of the cationic polymerization catalyst. Therefore, operations such as purification and removal of the catalyst are necessary. Purification can be performed using general neutralization, adsorption, dehydration, and separation processes.

  The ring-opening polymerization of the alkylene oxide is performed by supplying the alkylene oxide into a reaction vessel containing an active hydrogen-containing compound selected from monoalcohol, polyalcohol, aminoalcohol, phenol and the like and a polymerization catalyst. It is preferable to carry out while maintaining the internal temperature of the reaction vessel at a desired temperature by adjusting the supply rate of the alkylene oxide into the reaction vessel together with the cooling of the reaction vessel. An active hydrogen-containing compound and / or a polymerization catalyst can be continuously supplied together with alkylene oxide in the reaction vessel. The polymerization temperature is usually 60 to 180 ° C., preferably 80 to 140 ° C., and the polymerization time is usually 1 to 24 hours, preferably 6 to 12 hours.

The initiator used in the method for producing the polyether poly (mono) ol of the present invention is preferably as the moisture content is lower. The amount of water in the initiator when mixing the initiator with the cationic polymerization catalyst is particularly important. Specifically, the water content in the initiator is preferably 5 to 100 ppm, more preferably 5 to 70 ppm, and particularly preferably 5 to 70 ppm. 30 ppm is preferred. Multimers contained in the polyether poly (mono) ol obtained by ring-opening polymerization of an alkylene oxide having 3 or more carbon atoms after setting the water content of the initiator when mixed with the cationic polymerization catalyst to 100 ppm or less The amount of by-products can be reduced.
Therefore, in the present invention, it is preferable to sufficiently perform dehydration before mixing the initiator (for example, the polyoxyalkylene poly (mono) ol described above) with the cationic polymerization catalyst. The initiator is usually preferably dehydrated at 80 to 130 ° C. for 30 minutes to several hours under reduced pressure.

[Aluminum or boron compound having at least one fluorine-substituted phenyl group or fluorine-substituted phenoxy group]
A cationic polymerization catalyst for ring-opening polymerization of an alkylene oxide having 3 or more carbon atoms to an initiator having one or more hydroxyl groups is selected from the group consisting of aluminum or boron compounds having at least one fluorine-substituted phenyl group or fluorine-substituted phenoxy group. One or more selected compounds are used. Examples of the aluminum or boron compound having at least one fluorine-substituted phenyl group or fluorine-substituted phenoxy group include compounds described in Patent Document 1 or International Publication No. 03/000750. Preferable examples include tris (pentafluorophenyl) borane, tris (pentafluorophenyl) aluminum, tris (pentafluorophenyloxy) borane, and tris (pentafluorophenyloxy) aluminum. Of these, tris (pentafluorophenyl) borane has a large catalytic activity for ring-opening polymerization of alkylene oxides having 3 or more carbon atoms, and is a particularly preferred catalyst.

[Alkylene oxide having 3 or more carbon atoms]
Examples of the alkylene oxide having 3 or more carbon atoms used in the present invention include propylene oxide, butylene oxide, isobutylene oxide, hexene oxide, glycidol, and styrene oxide. Propylene oxide is particularly preferable. These alkylene oxides can be used alone or as a mixture, and two or more alkylene oxides can be block-polymerized.
The alkylene oxide having 3 or more carbon atoms used in the present invention preferably has a water content of 3 to 100 ppm, more preferably 3 to 60 ppm, and particularly preferably 3 to 40 ppm. By using an alkylene oxide having a water content of 100 ppm or less and having 3 or more carbon atoms, the amount of multimeric by-products can be reduced. When the amount of water in the alkylene oxide is large, the cationic polymerization catalyst is easily deactivated when heated in the presence of water, and the amount of the cationic catalyst used may have to be increased.

[Method for producing polyether poly (mono) ol]
The method for producing the polyether poly (mono) ol of the present invention is specifically performed as follows. The pressure-resistant reactor equipped with a stirrer and a cooling jacket is charged with the above-mentioned initiator having a hydroxyl equivalent weight of 1200 or more, and further comprises an aluminum or boron compound having at least one fluorine-substituted phenyl group or fluorine-substituted phenoxy group. One or more cationic polymerization catalysts selected from the group are added. Here, as described above, the amount of water in the initiator when the cationic polymerization catalyst is added is 5 to 100 ppm, preferably 5 to 70 ppm, more preferably 5 to 30 ppm. The amount of multimeric by-products in the ether poly (mono) ol can be kept low.
The cationic polymerization catalyst used for the reaction is preferably used in an amount of 10 to 120 ppm, particularly 20 to 100 ppm, based on the initiator. The smaller the amount of catalyst used, the better from the viewpoint of purification and cost of the resulting polyether poly (mono) ol, but by setting the amount of cationic catalyst used to 10 ppm or more, a reasonably fast alkylene oxide polymerization rate can be obtained.

  A polyether poly (mono) ol is produced by introducing and reacting the above-described alkylene oxide having 3 or more carbon atoms to a mixture of an initiator and a cationic polymerization catalyst. In the present invention, an alkylene oxide having 3 or more carbon atoms having a water content of 3 to 100 ppm, more preferably 3 to 60 ppm, and particularly preferably 3 to 40 ppm is used. By using an alkylene oxide having a water content of 100 ppm or less, the amount of multimer by-products generated can be reduced.

  Further, in the above reaction, the average of 2 to 12, more preferably 2.4 to 8.0, particularly 2.8 to 6.0, alkylene oxide having 3 or more carbon atoms per hydroxyl group of the initiator in the above reaction. Is preferably ring-opening polymerized. By making 2 or more alkylene oxides having 3 or more carbon atoms added per hydroxyl group of the initiator, the proportion of primary hydroxyl groups in all the terminal hydroxyl groups of the polyether polyether (mono) ol obtained is from 45%. Furthermore, it is easy to make it higher, and the amount of multimeric by-products can be reduced. Further, the proportion of the primary hydroxyl group in the terminal hydroxyl group increases as the amount of the alkylene oxide added to the initiator increases, but the upper limit is about 85%. Moreover, all the peaks obtained by measuring the gel permeation chromatography of the polyether poly (mono) ol obtained by reducing the number of alkylene oxides added per hydroxyl group of the initiator to 8.0 or less. It is easy to make the ratio of the peak area derived from multimer by-products out of the total area of 30% lower than 30%.

  In the above production method of the present invention, the internal temperature of the reaction vessel is maintained at a desired temperature by adjusting the supply rate of the alkylene oxide having 3 or more carbon atoms into the reaction vessel together with cooling the reaction vessel. However, it is preferable to carry out. The internal temperature of the reaction vessel is usually -15 to 140 ° C, preferably 0 to 120 ° C, particularly preferably 20 to 90 ° C. The polymerization time is usually 0.5 to 24 hours, preferably 1 to 12 hours.

  By using each of the above conditions, the proportion of primary hydroxyl groups in all the terminal hydroxyl groups of the obtained polyether poly (mono) ol can be 45 to 85%, and the gel permeation of polyether poly (mono) ol can be achieved. The ratio of the peak area derived from multimer by-products out of the total area of all peaks obtained by measuring the chromatography can be 30% or less.

[Properties of the polyether poly (mono) ol of the present invention]
The hydroxyl group equivalent of the polyether poly (mono) ol produced by the production method of the present invention exceeds 1200, preferably 1300 or more, more preferably 1400 or more, and particularly preferably 1600 or more. Although there is no upper limit in particular, 12000 or less is preferable and 7000 or less is especially preferable. The hydroxyl equivalent can be set to a desired value by adjusting the amount of alkylene oxide to be ring-opening polymerized by the initiator.
Furthermore, when the product is a polyether polyol, the average number of functional groups is usually 2 to 8, preferably 2 to 4.
Furthermore, the proportion of primary hydroxyl groups in the total terminal hydroxyl groups of the polyether poly (mono) ol obtained is 45 to 85% as described above, more preferably 55 to 75%, and particularly preferably 55 to 70%. In order to obtain a polyurethane resin raw material having an appropriate reaction rate with the isocyanate compound, it is preferable to adjust the amount of alkylene oxide having 3 or more carbon atoms added to the initiator.

  The total degree of unsaturation of the polyether poly (mono) ol obtained in the present invention is preferably less than 0.04 meq / g, more preferably 0.02 meq / g or less, and 0.01 meq / g or less. It is particularly preferred that it is 0.007 meq / g or less. This can be achieved by using a polyoxyalkylene poly (mono) ol having a total unsaturation of less than 0.04 meq / g as an initiator.

  The polyether poly (mono) ol according to the present invention uses the above-mentioned production conditions to determine the ratio of the area of the multimer by-product-derived peak to the total area of all peaks when measured using gel permeation chromatography. 30% or less. The total peak area of the multimer by-product-derived peak is more preferably 20% or less, and particularly preferably 10% or less. By reducing the amount of multimer by-products, the viscosity of a urethane prepolymer produced by reacting with an isocyanate compound can be kept low, and a prepolymer excellent in workability can be obtained.

[Ratio of primary hydroxyl group occupied in all terminal hydroxyl groups of polyether poly (mono) ol]
The proportion of ^primary hydroxyl groups in all terminal hydroxyl groups of the polyether poly (mono) ol obtained by the production method of the present invention is measured by ¹ H-NMR method. First, trifluoroacetic anhydride is added to a CDCl ₃ solution of polyether poly (mono) ol to convert the terminal hydroxyl group to trifluoroacetic acid ester. The proportion of methine hydrogen atoms and methylene hydrogen atoms in the hydrogen atoms bonded to all carbon atoms to which the trifluoroacetate group is bonded is determined by NMR spectrum, and based on these, the hydrogen atoms are bonded. By calculating the proportion of carbon atoms present, it can be determined whether the hydroxyl group is a secondary hydroxyl group or a primary hydroxyl group occupied in the original terminal hydroxyl group. For example, when propylene oxide is used as an alkylene oxide having 3 or more carbon atoms, a methine hydrogen atom on the carbon atom to which the terminal hydroxyl group formed by beta-cleavage of propylene oxide is bonded (hydrogen bonded to the carbon atom of the secondary hydroxyl group). Multiple peak (corresponding to 5.20-5.30 ppm tetramethylsilane) intensity of methylene hydrogen atom (carbon atom of primary hydroxyl group) on the carbon atom to which the terminal hydroxyl group formed by alpha-cleavage of propylene oxide is bonded The ratio of the two types of double-line peaks (corresponding to hydrogen atoms attached to) at half the intensity of the 4.25 ppm and 4.30 ppm corresponds to the ratio of secondary hydroxyl groups to primary hydroxyl groups. The proportion of primary hydroxyl groups occupied in all terminal hydroxyl groups can be determined.
The final polyether poly (mono) ol obtained by polymerizing propylene oxide by cationic polymerization contains an end primary hydroxyl group derived from this oxyethylene unit. When remaining, the intensity of multiple peaks (4.48 to 4.50 ppm) of methylene hydrogen atoms of oxyethylene units is added to the multiple peak intensity (4.25 ppm and 4.30 ppm) due to propylene oxide alpha cleavage. Using the primary hydroxyl group peak intensity, the ratio of the primary hydroxyl group is calculated in relation to the peak intensity based on the methine hydrogen atom.

[Measurement of gel permeation chromatography (GPC) of polyether poly (mono) ol]
The amount of multimeric by-products contained in the polyether poly (mono) ol described above is the total peak area obtained by measuring gel permeation chromatography, the peak area derived from multimeric by-products. Determine by measuring. This measurement is performed using a detector based on the refractive index change. Chromatographic measurement was performed using TSKEL G4000 HXL manufactured by Tosoh Corporation as a column at a column temperature of 40 ° C. and tetrahydrofuran as a solvent at room temperature. In the GPC spectrum, the polyether poly (mono) ol of the present invention shows a main peak and a sub peak appearing at a position of a number average molecular weight corresponding to an integer multiple of the number average molecular weight of the main peak as shown in FIG. However, sub-peaks do not always appear.) By calculating the ratio (%) of the area of the sub-peak to the total area of these main peaks and sub-peaks, the ratio of the peak area derived from the multimer by-product can be determined. it can.

[Use of the polyether poly (mono) ol of the present invention]
The polyether poly (mono) ol obtained by the method of the present invention has a high proportion of primary hydroxyl groups in the terminal hydroxyl groups even when ring-opening polymerization of alkylene oxides having 3 or more carbon atoms without polymerizing ethylene oxide. In addition, since the content of the multimer by-product is small, the viscosity is low, and the ratio of primary hydroxyl groups to all the terminal hydroxyl groups is large although the hydrophilicity is low. The polyether (mono) ol of the present invention is particularly suitable as a raw material for producing polyurethane foam, polyurethane elastomer and the like.

〔Example〕
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. Reference Example 1 is a production example of a double metal cyanide complex catalyst.
The total degree of unsaturation was measured by a method of reacting an unsaturated group with a mercury acetate solution and titrating acetic acid with a KOH solution (based on JIS K 1557). The hydroxyl value was measured by esterifying a hydroxyl group with a pyridine solution of phthalic anhydride and titrating with a NaOH solution (based on JIS K 1557). Further, the number of moles of hydroxyl group contained in a 1 g sample can be calculated from the hydroxyl value, and the hydroxyl group equivalent was determined as the reciprocal of this value.
Moreover, the water | moisture content of alkylene oxide and an initiator is the value measured using the Karl Fischer moisture meter, and this method is well-known to those skilled in the art.

  In the following examples, Polyol P is a poly (polysiloxane) having a hydroxyl value of 168, which is produced by ring-opening polymerization of propylene oxide (hereinafter referred to as PO) to glycerin using a KOH catalyst and further purified by a known method. Oxypropylene triol. In addition, as a polymerization catalyst used for producing an initiator, a zinc hexacyanocobaltate complex catalyst coordinated with t-butyl alcohol is dispersed in a polyoxypropylene triol having a hydroxyl value of 168 (mgKOH / g). A slurry catalyst (hereinafter referred to as DMC catalyst) was used. The concentration of the solid catalyst component in the slurry was 3.8% by mass.

[Example 1]
(1) (Production of an initiator having one or more hydroxyl groups per molecule and a hydroxyl group equivalent of 1200 or more by a DMC catalyst)
In a 5 L reaction vessel equipped with a stirrer, 500 g of polyol P and 2.37 g of DMC catalyst (containing 0.090 g of solid catalyst component) were charged. After substituting the inside of the reaction vessel with nitrogen, the internal temperature was raised to 120 ° C., and 75 g of PO having a water content of 29 ppm was added for reaction. After the pressure in the reaction vessel that increased with the addition of PO dropped, PO was supplied into the 1310 g reaction vessel at a rate of 20 g / min, and then 630 g of PO was supplied at a rate of 10 g / min. While supplying PO into the reaction vessel, the polymerization reaction was carried out by stirring at a rotational speed of 220 rpm while maintaining the internal temperature of the reaction vessel at about 120 ° C. After the completion of the reaction, the mixture was further heated and stirred at 120 ° C. for 60 minutes to react unreacted PO as much as possible, and then degassed under reduced pressure at 130 Pa or less for 60 minutes while maintaining the internal temperature at 100 ° C. The amount of water was 160 ppm. Furthermore, while blowing a small amount of dry nitrogen gas at 120 ° C. for 3 hours, vacuum degassing was performed at 20 Pa or less to obtain a polyoxypropylene triol having a water content of 15 ppm and a hydroxyl value of 33.5 mgKOH / g, and was stored under nitrogen. This polyoxypropylene triol was used as an initiator of the present invention. The hydroxyl equivalent of this initiator is 1670.

(2) (ring-opening polymerization reaction of PO to an initiator using a cationic polymerization catalyst)
Next, B (C ₆ F ₅ ) ₃ (100 mg) in an amount of 40 ppm with respect to the initiator was added to the reactor containing polyoxypropylene triol (2510 g), which was the initiator synthesized in (1) above. did. While maintaining the internal temperature of the reactor at 70 ° C. and the rotation speed at 220 rpm, an amount (251 g) of PO corresponding to 2.88 to one hydroxyl group of the initiator was added to the reactor over 4 hours. After completion of the polymerization reaction, stirring was further continued at 70 ° C. for 60 minutes. Thereafter, 25 g of 0.3% by weight aqueous KOH solution was added as a neutralizing agent and stirred for 60 minutes. An amount of synthetic magnesium silicate corresponding to 1% by weight of the obtained polyoxypropylene triol (trade name: KW600S, Kyowa) Chemical Industry Co., Ltd.) was charged into the reactor, stirred at 100 ° C. for 60 minutes, vacuum degassed at 120 ° C. for 120 minutes, and filtered to obtain purified polyoxypropylene triol.
The purified polyoxypropylene triol obtained has a hydroxyl value (mgKOH / g), a total unsaturation degree (mmol / g), and a ratio (%) of primary hydroxyl groups to all terminal hydroxyl groups of the polyoxypropylene triol, multimers. The area (%) of the byproduct peak in GPC is shown in Table 1.

[Example 2]
Polyoxypropylene triol was added in the same manner as in Example 1 except that PO in an amount (376 g) corresponding to 4.31 hydroxyl groups per hydroxyl group of the initiator (2505 g) was added to the reactor over 6 hours. Manufactured. Table 1 shows the analysis results of the polyoxypropylene triol obtained by purification.

Example 3
The same procedure as in Example 1 was conducted, except that an amount (628 g) of PO corresponding to 7.20 per hydroxyl group of the initiator (2510 g) was added to the reactor over 8 hours.

Example 4
The above initiator (2510 g) was used which was degassed under reduced pressure of 60 Pa or less at 120 ° C. for 1 hour to bring the water content to 50 ppm, and B (C ₆ F ₅ ) ₃ catalyst (238 mg) corresponding to 95 ppm was used. The procedure was the same as in Example 1 except that there was.

Example 5
The same procedure as in Example 1 was performed except that PO having a water content of 8 ppm was used.

Example 6
The same procedure as in Example 1 was conducted, except that an amount (872 g) of PO corresponding to 10.0 hydroxyl groups per hydroxyl group of the initiator (2510 g) was added to the reactor over 8 hours.

[Comparative Example 1]
The amount of water contained in using the above initiator (2510G) is 160 ppm, and except for using the corresponding _{B (C 6} F _{5) 3} catalyst (238 mg) in 95 ppm, in the same manner as in Example 1 A ring-opening polymerization reaction of PO was performed. In this case, after introducing an amount of PO corresponding to 1.45 (126 g) per hydroxyl group of the initiator (2510 g) into the reactor, the catalyst was deactivated and the polymerization reaction was stopped.

[Comparative Example 2]
The opening of PO was carried out in the same manner as in Example 1 except that B (C ₆ F ₅ ) ₃ catalyst was added to the reactor before degassing under reduced pressure at 120 ° C. for 3 hours at 120 ° C. A ring polymerization reaction was performed. After introducing an amount (75 g) of PO corresponding to 0.86 hydroxyl groups per hydroxyl group of the initiator (2505 g), the catalyst was deactivated and the polymerization reaction was stopped.

[Comparative Example 3]
The initiator was vacuum degassed at 100 Pa or less at 120 ° C. for 1 hour, so that the water content in the initiator was 110 ppm. Except then it corresponds to 95ppm with respect to the initiator _{(2510g) B (C 6 F} 5) 3 that the addition of catalyst (238 mg), were the same as in Example 3.

[Comparative Example 4]
The same procedure as in Example 1 was conducted, except that B (C ₆ F ₅ ) ₃ catalyst (238 mg) corresponding to 150 ppm was added to the initiator (2510 g) having a moisture content of 160 ppm.

[Comparative Example 5]
Example 3 was repeated except that PO having a water content of 120 ppm was used.

  From the results shown in Table 1, according to the production method of the present invention, the amount of water in the initiator before contacting with the cationic polymerization catalyst, the amount of water in the alkylene oxide having 3 or more carbon atoms, the amount of the cationic polymerization catalyst used By controlling, it is possible to prevent the cation catalyst from being deactivated during the polymerization reaction, the content of multimer by-products is small, the proportion of primary hydroxyl groups in the terminal hydroxyl groups is large, and in some cases the total unsaturated It can be seen that a polyether poly (mono) ol having a small degree can be obtained.

It is a figure which shows the GPC spectrum of the polyether triol manufactured using the manufacturing method of this invention. In the spectrum, S2 is a peak corresponding to the main component polyether triol, and S1 is a peak corresponding to a multimeric by-product in which the polyether triol of S2 is multimerized.

Claims (8)

Having at least one hydroxyl group per molecule in the presence of one or more cationic polymerization catalysts selected from the group consisting of aluminum or boron compounds having at least one fluorine-substituted phenyl group or fluorine-substituted phenoxy group An initiator having an equivalent weight of 1200 or more is subjected to ring-opening polymerization of an alkylene oxide having 3 or more carbon atoms, has an average of 2 or more oxyalkylene units per hydroxyl group terminal of the initiator, and has a hydroxyl group equivalent of more than 1200 The ratio of primary hydroxyl groups to all terminal hydroxyl groups is 45 to 85%, and the total area of all peaks obtained by measuring gel permeation chromatography is the peak area derived from the following multimer by-product Is a method for producing a polyether polyol or polyether monool having a ratio of 30% or less,
(A) the amount of water in the initiator when mixed with the cationic polymerization catalyst is 5 to 100 ppm,
(B) the amount of the cationic polymerization catalyst relative to the initiator is 10 to 120 ppm,
(C) The water content in the alkylene oxide having 3 or more carbon atoms is 3 to 100 ppm.
A method for producing a polyether polyol or polyether monool, characterized by using the following conditions.
Multimer by-product: contained in a polymer obtained by subjecting an alkylene oxide to ring-opening polymerization reaction as an initiator, and corresponding to an integer multiple of 2 or more of the polymer molecular weight corresponding to the main peak in gel permeation chromatography An alkylene oxide polymer observed as a peak having a molecular weight. The cationic polymerization catalyst is one or more compounds selected from the group of tris (pentafluorophenyl) borane, tris (pentafluorophenyl) aluminum, tris (pentafluorophenyloxy) borane, trispentafluorophenyloxy) aluminum. The manufacturing method according to claim 1 . The production method according to claim 2, wherein the cationic polymerization catalyst is tris (pentafluorophenyl) borane. The production method according to any one of claims 1 to 3, wherein 2 to 12 of the alkylene oxides having 3 or more carbon atoms are subjected to ring-opening polymerization per hydroxyl group terminal of the initiator. The production method according to any one of claims 1 to 4 , wherein the alkylene oxide having 3 or more carbon atoms is propylene oxide. The production method according to any one of claims 1 to 5, wherein the initiator is a polyoxyalkylene polyol or a polypolyoxyalkylene monool. The production method according to any one of claims 1 to 6, wherein 70% or more of the hydroxyl groups of the initiator are secondary hydroxyl groups. The manufacturing method of the polyether polyol or polyether monool as described in any one of Claims 1-7 whose total unsaturation degree of the said initiator is 0.04 meq / g or less .

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