JP2012172129A - Method for producing polyoxyalkylene monool or polyol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyoxyalkylene monool or polyol having a high rate of terminal primary hydroxyl groups with good production efficiency, capable of performing additive polymerization with less usage of a catalyst, securing a high yield with less byproducts, and reducing the amount of waste residues.SOLUTION: The method for producing a polyoxyalkylene monool or polyol includes: additively polymerizing an alkylene oxide (B) to an active hydrogen group-containing compound (A) in the presence of at least one compound (E) selected from titanium alkoxide, zirconium alkoxide and vanadium alkoxide, and a specific Lewis acid (C). The mole ratio of active hydrogen of the active hydrogen group-containing compound (A) to the compound (E) {(mole number of active hydrogen of A)/(mole number of E)} is 2,000-50,000, and the mole ratio of the compound (E) to the Lewis acid (C) {(mole number of E)/(mole number of C)} is 0.6-1.2.

Description

  The present invention relates to a method for producing a polyoxyalkylene monool or polyol.

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, freezers and the like. The polyether polyol used in the polyurethane foam is mainly a ring-opening polymer of propylene oxide in order to increase hydrophobicity.
The terminal hydroxyl group of an industrially general polypropylene oxide obtained using alkali as a catalyst has a secondary carbon atom bonded to the hydroxyl group, and this terminal hydroxyl group has extremely low reactivity with an isocyanate compound.
Therefore, polypropylene oxide having only a primary hydroxyl group with high reactivity at the terminal is advantageous for producing a polyurethane foam.

By the way, when ring-opening polymerization of propylene oxide using an anionic polymerization catalyst for alcohol, it is known that the ends of the obtained polyether monool and polyether polyol are almost secondary hydroxyl groups (for example, Non-Patent Document 1). .
On the other hand, when propylene oxide is subjected to ring-opening polymerization using a cationic polymerization catalyst, it is known that the ratio of primary and secondary hydroxyl groups to the polyether monool and polyether polyol all terminal hydroxyl groups is almost the same. (For example, nonpatent literature 2).
Recently, when the above propylene oxide ring-opening polymerization is carried out using a boron or aluminum compound substituted with a phenyl group or a tertiary alkyl group as a Lewis acid cation catalyst, the obtained polyether monool and polyether polyol It has been reported that the ratio of primary hydroxyl groups to all terminal hydroxyl groups is 70% or more (for example, Patent Document 1).

However, in the case of an anionic polymerization catalyst as described in Non-Patent Document 1, a dioxane derivative by dimerization of propylene oxide (hereinafter abbreviated as “PO”), propylene glycol and its PO addition polymer by a trace amount of water, and carbon- It is known that there are many by-products of the carbon double bond group-containing product, and as a result, the viscosity of the product increases.
In addition, in the case of a cationic polymerization catalyst such as Non-Patent Document 2 and Patent Document 1, there are many by-products such as propylene glycol, propionaldehyde, and acetal. It is known that there is a high cost problem.

In addition, in order to increase the content of the primary hydroxyl group at the end of the polyether monool and polyether polyol, after propylene oxide was ring-opening polymerized with polyhydric alcohol using an anionic polymerization catalyst, ethylene was then further used with an anionic catalyst. A so-called EO chip method for performing an addition reaction on oxide has been performed (for example, Patent Document 2).
However, when a polymer having a high content of polyethylene oxide chain is reacted with an isocyanate compound to form a polyurethane resin, the resin has high water absorption, so that physical properties such as strength and water resistance are lowered depending on its use.
Therefore, in order to increase the reactivity with the polyisocyanate compound without deteriorating the properties of the polyurethane resin, the terminal primary hydroxylation rate can be increased with a minimum amount of ethylene oxide addition and without using a special catalyst. A method of obtaining an enhanced polyether polyol is desired.

  On the other hand, by using trispentafluorophenylborane in which the pentafluoro group is substituted with titanium isopropoxide as a catalyst for the addition reaction of an alkylene oxide to an active hydrogen group-containing compound, by-products such as aldehydes and acetals It has been reported that alkylene oxide can be polymerized at a high reaction rate (for example, Non-Patent Document 3). However, under the conditions of Non-Patent Document 3, the terminal hydroxyl group primary ratio is low, and the reactivity as a polyurethane resin material is insufficient.

Japanese Patent Laid-Open No. 2002-187951 JP 2005-154783 A

Long.F.A. and J.G.Pritchard, J.Am.Chem.Soc., 78, 2663 (1956) Pricc.C.C. And M.Osgan, J.Am.Chem.Soc., 78, 4787 (1956) Inorganica Chimica Acta 357 (2004) 3911-3919

  The present invention enables addition polymerization even with a small amount of catalyst, yields a large amount of polyoxyalkylene polyol, reduces the amount of side-reacting aldehydes and acetals, and reduces the amount of waste residue generated after the reaction. An object of the present invention is to provide a method for efficiently producing a polyoxyalkylene monool or polyol having a high terminal primary hydroxyl group ratio.

As a result of intensive studies to solve the above problems, the present inventor has reached the present invention.
That is, the method for producing the polyoxyalkylene monool or polyol of the present invention is represented by at least one compound (E) selected from the group consisting of titanium alkoxide, zirconium alkoxide and vanadium alkoxide, and the following general formula (1). A process for producing a polyoxyalkylene monool or polyol in which an alkylene oxide (B) is addition-polymerized to an active hydrogen group-containing compound (A) in the presence of a Lewis acid (C), the active hydrogen group-containing compound (A) The molar ratio of active hydrogen to compound (E) {(number of moles of active hydrogen of A) / (number of moles of E)} is 2,000 to 50,000, and compound (E) and Lewis acid (C The molar ratio {(number of moles of E) / (number of moles of C)} is 0.6 to 1.2.

[In General Formula (1), M represents a boron atom or an aluminum atom. R ¹ , R ² and R ³ are each independently a monovalent hydrocarbon group or hydrocarbon oxy group having 1 to 18 carbon atoms. The hydrogen atom of the hydrocarbon group or hydrocarbon oxy group may be substituted with a halogen atom. ]

  According to the production method of the present invention, the yield of the obtained polyoxyalkylene monool or polyol is large, the amount of side reaction aldehyde and acetal is small, the amount of waste residue generated after the reaction can be reduced, and the production efficiency is high. A polyoxyalkylene monool or polyol having a high terminal primary hydroxyl group ratio can be produced.

The present invention is described in detail below.
The addition polymerization of alkylene oxide (B) is a reaction for adding alkylene oxide (B) to active hydrogen-containing compound (A). Examples of the active hydrogen-containing compound (A) include compounds having a hydroxyl group, a carboxyl group, an amino group, a thiol group, and an acid amide group. Specific examples of the active hydrogen-containing compound (A) include the following (A1) to (A7). These may be one kind or a combination of two or more kinds.

(A1) Water (A2) Alcohol As the monohydric alcohol, an alcohol having 1 to 40 carbon atoms selected from the group consisting of linear, branched, saturated, unsaturated, alicyclic and aromatic, for example, methanol, Ethanol, n-propanol, 2-propanol, n-butanol, 2-ethylhexanol, n-octanol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, octadecyl alcohol, diethylene glycol monomethyl ether, benzyl alcohol And tripropylene glycol monomethyl ether.
The dihydric alcohol includes a dihydric alcohol having 2 to 40 carbon atoms selected from the group consisting of linear, branched, saturated, unsaturated, alicyclic and aromatic, and includes ethylene glycol, propylene glycol, 1, 3 -Propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol.
Examples of the trihydric alcohol include trivalent alcohols having 3 to 80 carbon atoms selected from the group consisting of linear, branched, saturated, unsaturated, alicyclic and aromatic, glycerin, trimethylolpropane, triethanolamine. And propylene oxide adduct of glycerin and propylene oxide adduct of trimethylolpropane.
Examples of the tetravalent to octavalent alcohols include tetravalent to octavalent alcohols having 5 to 80 carbon atoms selected from the group consisting of linear, branched, saturated, unsaturated, alicyclic and aromatic, pentaerythritol, sorbitol, Examples thereof include xylit, mannitol, dipentaerythritol, glucose, fructose, sucrose, a propylene oxide adduct of pentaerythritol, and a propylene oxide adduct of sucrose.

(A3) Phenol Monovalent phenol includes monohydric phenol having 6 to 40 carbon atoms, and examples thereof include phenol and cresol. The polyhydric phenol includes polyhydric phenol having 6 to 40 carbon atoms, and examples include pyrogallol, catechol, hydroquinone, and bisphenol A.

(A4) Carboxylic acid The monovalent carboxylic acid includes a monovalent carboxylic acid having 1 to 40 carbon atoms selected from the group consisting of linear, branched, saturated, unsaturated, alicyclic and aromatic, formic acid, Examples include acetic acid, propionic acid, butyric acid, octanoic acid, lauric acid, oleic acid, and linoleic acid. Examples of the divalent carboxylic acid include divalent carboxylic acids having 4 to 40 carbon atoms selected from the group consisting of linear, branched, saturated, unsaturated, alicyclic and aromatic, and include maleic acid, succinic acid, and adipine. Examples include acid and phthalic acid. Examples of the 3 to 8 carboxylic acid include 3 to 8 carboxylic acid having 4 to 40 carbon atoms selected from the group consisting of linear, branched, saturated, unsaturated, alicyclic, and aromatic. A 3-8 mer etc. are mentioned.

(A5) Amine Monovalent amines include monovalent amines having 2 to 40 carbon atoms selected from the group consisting of linear, branched, saturated, unsaturated, alicyclic and aromatic, and include diethylamine, diisopropylamine and And dioleylamine. Examples of the divalent amine include divalent amines having 1 to 40 carbon atoms selected from the group consisting of linear, branched, saturated, unsaturated, alicyclic and aromatic, methylamine, ethylamine, propylamine and n -Butylamine etc. are mentioned. Examples of the trivalent to pentavalent amine include ammonia and a trivalent to pentavalent amine having 2 to 40 carbon atoms selected from the group consisting of linear, branched, saturated, unsaturated, alicyclic and aromatic. -Methylaminoethylamine, ethylenediamine, propylenediamine, diethylenetriamine, dipropylenetriamine and the like.
In addition, the valence of an amine means the number of active hydrogen which an amine has.

(A6) Thiol Examples of the thiol include monovalent and polyvalent thiols having 1 to 80 carbon atoms selected from the group consisting of linear, branched, saturated, unsaturated, alicyclic and aromatic. 1-5 functional thiol obtained by the reaction of 1-5 pentahydric alcohol and thiourea, and 1-5 functional thiol obtained by the reaction of epichlorohydrin or 2-5 mer of epichlorohydrin and sodium hydrosulfide, etc. Can be mentioned.
(A7) Acid amide Examples of the acid amide include monovalent and polyhydric acid amides having 1 to 40 carbon atoms selected from the group consisting of linear, branched, saturated, unsaturated, alicyclic, and aromatic. Examples thereof include dimers and pentamers of acid amides and unsaturated monocarboxylic acid amides (monocarboxylic acid amides such as acrylamide and methacrylamide).

  Among the active hydrogen-containing compounds (A), from the viewpoint of easy availability, the compounds (A1) to (A7) are preferable, more preferably (A1) to (A3), and particularly preferably (A2). is there. The number of active hydrogens in (A) is preferably 1 to 8, more preferably 1 to 4, from the viewpoint that the viscosity of the resulting polyoxyalkylene monool or polyol does not become too high and is easy to handle.

Examples of the alkylene oxide (B) include ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, and glycidyl ether. Is mentioned. Of these, 1,2-alkylene oxide (1,2-propylene oxide, 1,2-butylene oxide, styrene oxide, epichlorohydrin is preferred from the viewpoint of easily achieving the effect of the present invention having a higher primary hydroxyl group ratio than conventional ones. And glycidyl ether) are preferred, and 1,2-propylene oxide is more preferred.
The alkylene oxide (B) may be used alone or in combination of two or more. The addition reaction may be random addition or block addition. From the viewpoint of easily achieving the effect of the present invention of having a higher primary hydroxyl group ratio than before, (B) preferably contains at least one 1,2-alkylene oxide.

  The production method of the present invention uses a Lewis acid (C) represented by the following general formula (1). The combined use of the compound (E) and Lewis acid (C) described later dramatically improves the prevention of by-products such as aldehydes and acetals.

In general formula (1), M represents a boron atom or an aluminum atom. When M is an atom other than these, the polymerization activity is not improved, which is not preferable. Further, since boron and aluminum are amphoteric elements, if they are the central element (M), the hydrolyzate becomes a neutral compound when (C) is hydrolyzed, so that polyoxyalkylene monool or polyol Even if it remains in, there is no adverse effect on quality.
In the general formula ^{(1), R 1, R} 2 and R ³ are each independently a monovalent hydrocarbon group or a hydrocarbon oxy group having 1 to 18 carbon atoms. The hydrogen atom of the hydrocarbon group or hydrocarbon oxy group may be substituted with a halogen atom.

  Specific examples of the Lewis acid (C) include the following (C1) to (C4). These may be one kind or a combination of two or more kinds.

(C1) aromatic and halogen-substituted aromatic borane triphenylborane, tris (4-fluorophenyl) borane, tris (2,6-difluorophenyl) borane, tris (2,4,6-trifluorophenyl) borane, Examples include tris (pentafluorophenyl) borane, tris (3-methyltetrafluorophenyl) borane, tris (pentafluorophenoxy) borane, and tris (2-pentafluorophenyltetrafluorophenyl) borane.
(C2) Alkylborane Examples include trimethylborane, triethylborane, triisobutylborane, tri-n-butylborane, trihexylborane, tricyclohexylborane, and trioctylborane.
(C3) aromatic and halogen-substituted aromatic aluminum triphenylaluminum, tris (4-fluorophenyl) aluminum, tris (2,6-difluorophenyl) aluminum, tris (2,4,6-trifluorophenyl) aluminum, Examples include tris (pentafluorophenyl) aluminum, tris (3-methyltetrafluorophenyl) aluminum, and tris (pentafluorophenoxy) aluminum.
(C4) Alkyl aluminum Examples include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, ethyldiisobutylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, and trioctylaluminum.

  Of the Lewis acid (C), (C1) and (C3) are preferable from the viewpoint of polymerization activity, and (C1) is more preferable.

  The compound (E) is at least one compound selected from the group consisting of titanium alkoxide, zirconium alkoxide, and vanadium alkoxide.

The alkoxide group is a functional group having a structure in which a hydrogen atom of a hydroxyl group is removed from an alcohol, and the alcohol has 1 carbon atom selected from the group consisting of linear, branched, saturated, unsaturated, alicyclic and aromatic. To 18 alcohols, such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, s-butanol, isobutanol, t-butanol, 2-ethylhexanol, n-octanol, decyl alcohol, dodecyl alcohol , Tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, octadecyl alcohol and the like.
Among these, from the viewpoint of ease of use and availability, an alcohol having 1 to 12 carbon atoms is preferable, and an alcohol having 1 to 8 carbon atoms is more preferable.

  As the compound (E), the following (E1) to (E3) are included. (E) may be one type or a combination of two or more types.

(E1) Titanium alkoxide Titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetra-2-ethylhexoxide and the like can be mentioned.
(E2) Zirconium alkoxide Zirconium tetraisopropoxide, zirconium tetranormal propoxide, zirconium tetranormal butoxide, zirconium tetra-t-butoxide and the like can be mentioned.
(E3) Vanadium alkoxide Vanadium tetraisopropoxide, vanadium tetranormal butoxide, vanadium tetra-2-ethylhexoxide and the like can be mentioned.

  Among these (E), (E1) and (E2) are preferable from the viewpoint of ease of use and availability, and (E1) is more preferable.

  As a method of using the compound (E) and the Lewis acid (C), the compound (E) and the Lewis acid (C) may be used after being uniformly mixed in a container different from the reaction tank. Further, the mixture may be dissolved in hexane, purified by filtration and vacuum distillation, and then used.

  In the production method of the present invention, the molar ratio of the active hydrogen of the active hydrogen group-containing compound (A) to the compound (E) {(number of moles of active hydrogen of A) / (number of moles of E)} is the polymerization reaction rate. From the viewpoint of the reaction rate, it is 2,000 to 50,000, more preferably 3,000 to 30,000. If it is less than 2,000, the amount of the compound (E) is too much, so that there are a lot of catalyst residues after the polymerization reaction, and there is a problem of production efficiency and cost because it must be recovered and treated. Further, since the amount of the Lewis acid (C) added increases with the amount of (E), the amounts of by-products aldehyde and acetal also increase, and the polymerization reaction rate decreases. On the other hand, if it exceeds 50,000, the concentration of the catalyst is low, so the reaction rate is slow, the reaction rate is low, and the terminal primary hydroxyl group rate is low.

In the production method of the present invention, the molar ratio {(number of moles of E) / (number of moles of C)} of the compound (E) and the Lewis acid (C) is determined in terms of the rate of formation of terminal primary hydroxyl groups and the reaction rate. From 0.6 to 1.2, preferably from 0.65 to 1.0. Within this range, one R ¹ , R ² and R ³ (ie, a monovalent hydrocarbon group or hydrocarbon oxy group) in the molecule of Lewis acid (C) is substituted, and the Lewis acidity of the catalyst and The structure is optimized, and both a high rate of polymerization reaction and a high terminal primary hydroxyl group ratio can be achieved, and the catalytic activity is improved. On the other hand, if it is less than 0.6, the Lewis acidity of the catalyst becomes strong, the amount of by-products aldehyde and acetal increases, and the terminal primary hydroxyl group ratio and the polymerization reaction ratio decrease. On the other hand, if it exceeds 1.2, the activity of the catalyst is lowered, the terminal primary hydroxyl group ratio is low, and the reaction rate is slow.

  In the production method of the present invention, the molar ratio of the active hydrogen of the active hydrogen group-containing compound (A) to the Lewis acid (C) {(number of moles of active hydrogen of A) / (number of moles of C)} is Lewis acid. From a viewpoint of the density | concentration of (C), a reaction rate, or a primary hydroxyl group rate, 2,000-75,000 are preferable, More preferably, it is 1,800-45,000. Within the above range, since the amount of compound (C) is appropriate, propylene aldehyde is difficult to be oxidized, the amount of by-products aldehyde and acetal is reduced, the polymerization reaction rate is improved, and the terminal primary grade is improved. The hydroxyl group ratio increases.

  In the production method of the present invention, the catalyst is prepared by uniformly mixing the compound (E) and the Lewis acid (C) (if necessary, the mixture is dissolved in hexane, purified by operations such as filtration and vacuum distillation, and impurities are removed. (Removing) step (step 1), then active hydrogen group-containing compound (A) and alkylene oxide (B), and optionally adding an organic solvent to carry out addition polymerization (step 2), then polyoxyalkylene monool or polyol. Preferred is a method of producing a polyoxyalkylene monool or polyol through a step (step 3) of treating the mixture, removing catalyst residues, and / or removing solvents and low-boiling substances under thermal decomposition and reduced pressure. It can be illustrated.

  In step 1, the method for mixing the compound (E) and the Lewis acid (C) is not particularly limited, and examples thereof include a method in which a solvent solution of the compound (E) is added to (C) and mixed. If necessary, the mixture is dissolved in hexane, purified by filtration and distillation under reduced pressure, and impurities are removed. The temperature at the time of distilling off the solvent is preferably 120 ° C. or less, more preferably 100 to 110 ° C., from the viewpoint of the thermal stability of the produced catalyst. Moreover, it carries out under reduced pressure of -0.005 MPa (gauge pressure).

  In step 2, the method for adding the alkylene oxide (B) is not particularly limited, and the whole amount may be added at once, or may be added in multiple portions. A block copolymer can be obtained by sequentially adding different types of alkylene oxide (B) and completing the polymerization reaction each time the alkylene oxide (B) is added.

  The conditions for the polymerization are not particularly limited, and are determined according to the active hydrogen group-containing compound (A) or alkylene oxide (B) to be used, the amount of Lewis acid (C) and compound (E) used, the target molecular weight, and the like. do it. The pressure at the time of superposition | polymerization can be performed on the conditions of the addition reaction of the conventional alkylene oxide. The temperature during the polymerization is preferably 0 to 100 ° C., more preferably 10 to 80 ° C. from the viewpoint of the thermal stability of the catalyst and the molecular weight of the polymer. The polymerization time is preferably 5 minutes to 24 hours depending on the reaction temperature and pressure.

  After the predetermined alkylene oxide (B) is addition-polymerized, the mixture containing the polyoxyalkylene monool or polyol is then treated in Step 3 to remove the catalyst residue and / or the solvent and the low-boiling point are reduced under reduced pressure. Remove with. As a treatment method for removing the catalyst residue, a known adsorbent {Kyoward 1000 (manufactured by Kyowa Chemical Co., Ltd.)} is used at 90 to 100 ° C. using 0.05 to 1% by weight based on the total weight of the obtained reaction mixture. Examples of the method include a method of removing by filtration after performing an adsorption treatment for 1 hour.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. Hereinafter, unless otherwise specified, parts means parts by weight.

  In addition, the analysis of the obtained polyoxyalkylene monool or polyol measured the terminal primary hydroxyl group rate and the hydroxyl value.

The terminal primary hydroxyl group ratio was calculated by measuring ¹ H-NMR after treating the hydroxyl group with trifluoroacetic anhydride. The purpose of pretreatment with trifluoroacetic anhydride is to shift only the hydrogen peak bonded to the carbon to which the terminal hydroxyl group is bonded to a low magnetic field and identify whether the carbon having the terminal hydroxyl group is methylene or methine. .
A signal derived from a methylene group to which a primary hydroxyl group is bonded is observed at around 4.3 ppm, and a signal derived from a methine group to which a secondary hydroxyl group is bonded is observed at around 5.2 ppm. Therefore, the terminal primary hydroxyl group ratio was calculated by the following formula.

Terminal primary hydroxyl group ratio (%) = [a / (a + 2 × b)] × 100
However, a is an integral value of a signal derived from a methylene group having a primary hydroxyl group bonded thereto around 4.3 ppm, and b is an integral value of a signal derived from a methine group having a secondary hydroxyl group bonded thereto around 5.2 ppm.

Specifically, it was measured and calculated by ¹ H-NMR as follows.
<Calculation method of terminal primary hydroxyl group ratio>
(1) About 30 mg of a measurement sample is weighed into a sample tube for ¹ H-NMR having a diameter of 5 mm, and about 0.5 ml of deuterated solvent is added and dissolved. Thereafter, about 0.1 ml of trifluoroacetic anhydride is added to obtain a sample for analysis.
Examples of the deuterated solvent include deuterated chloroform, deuterated acetone, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide, and the like, which can dissolve the sample. Is appropriately selected.
(2) ¹ H-NMR of the adjusted sample is measured under normal conditions and calculated from the above formula.

Moreover, the measuring method of a hydroxyl value is performed as follows.
Hydroxyl value (mgKOH / g): JISK1557-1 (phthalic anhydride / pyridine method)
The polymerization reaction rate was calculated by the following formula.
Polymerization reaction rate (%): {(molecular weight from the hydroxyl value of the polymer)-(active hydrogen group-containing compound molecular weight)} / {(number of moles of charged alkylene oxide) × molecular weight of alkylene oxide ÷ charged active hydrogen group Number of moles of active hydrogen in the compound contained)} × 100
In addition, the method of calculating | requiring the molecular weight from the hydroxyl value of a polymer is as follows.
Molecular weight = (56100 × active hydrogen number of active hydrogen group-containing compound) / hydroxyl value

<Synthesis Example 1>
In a 200 ml three-necked glass flask in an ice bath, 0.97 parts of titanium tetraisopropoxide (purity 98 wt%) and 3 wt% toluene of tris (pentafluorophenyl) borane (purity 90 wt%) under nitrogen flow The mixture was stirred for 3 hours while charging 63.5 parts of the solution. Furthermore, it stirred at 25 degreeC for 10 hours, and synthesize | combined the crude product of the catalyst.

<Synthesis Example 2>
Toluene was distilled off from the catalyst crude product synthesized in Synthesis Example 1 at 100 ° C. for 2 hours under a reduced pressure of −0.03 MPa (gauge pressure), and then 100 parts of hexane was added, dissolved by stirring, and then filtered. It was. From the filtrate, the solvent was distilled off under reduced pressure of −0.005 MPa (gauge pressure) at 110 ° C. for 2 hours to synthesize a purified catalyst product.

<Synthesis Example 3>
In Synthesis Example 1, the same procedure as in Synthesis Example 1 was performed, except that 63.5 parts of a 3 wt% toluene solution of tris (pentafluorophenyl) borane (90%) was changed to 95.1 parts. The crude product was synthesized.

<Synthesis Example 4>
In Synthesis Example 1, the same operation as in Synthesis Example 1 was performed except that 63.5 parts of a 3% by weight toluene solution of tris (pentafluorophenyl) borane (purity 90% by weight) was changed to 76.0 parts, A crude product of the catalyst was synthesized.

<Synthesis Example 5>
In Synthesis Example 1, tris (pentafluorophenyl) borane (purity 90 wt%) in 3 wt% toluene solution 63.5 parts tris (pentafluorophenoxy) aluminum (purity 90 wt%) 3 wt% toluene solution 71 A crude product of the catalyst was synthesized by the same operation as in Synthesis Example 1 except that 3 parts were used.

<Synthesis Example 6>
In Synthesis Example 1, instead of 63.5 parts of a 3 wt% toluene solution of tris (pentafluorophenyl) borane (purity 90 wt%), a tris (pentafluorophenyl) aluminum (purity 90 wt%) 3 wt% toluene solution 65 A crude product of the catalyst was synthesized by the same operation as in Synthesis Example 1 except that 3 parts were used.

<Synthesis Example 7>
In Synthesis Example 1, the same operation as in Synthesis Example 1 was performed except that 1.5 parts of zirconium tetranormal propoxide (purity 74% by weight) was used instead of 0.97 parts of titanium tetraisopropoxide (purity 98% by weight). The crude product of the catalyst was synthesized.

<Synthesis Example 8>
In Synthesis Example 1, the same operation as in Synthesis Example 1 was performed except that vanadium tetraisopropoxide (purity 80% by weight) 1.2 was used instead of 0.97 parts of titanium tetraisopropoxide (purity 98% by weight). The crude product of the catalyst was synthesized.

<Synthesis Example 9>
A crude product of the catalyst was synthesized in the same manner as in Synthesis Example 1 except that 0.97 part of titanium tetraisopropoxide (purity 98% by weight) was changed to 9.7 part in Synthesis Example 1.

<Synthesis Example 10>
A crude catalyst product was synthesized in the same manner as in Synthesis Example 1 except that 0.97 part of titanium tetraisopropoxide (purity 98% by weight) was changed to 0.05 part in Synthesis Example 1.

<Example 1>
The autoclave was charged with 200 parts of an 8.8 mol PO addition product of glycerin as an active hydrogen group-containing compound and 1.7 parts of a 3% by weight toluene solution of the crude product of the catalyst obtained in Synthesis Example 1, and after mixing, After 800 parts of 2-propylene oxide was continuously introduced over 2 hours, the mixture was aged at the same temperature for 2 hours. Thereafter, 30 parts of water was added, and volatile components were distilled off under reduced pressure of −0.03 MPa (gauge pressure) at 150 ° C. for 2 hours. Next, 5 parts of KYOWARD 1000 (manufactured by Kyowa Chemical Co., Ltd.) were charged and subjected to an adsorption treatment at 95 ° C. for 1 hour, followed by filtration to remove the remaining catalyst to obtain a polyoxyalkylene polyol. The obtained polyoxyalkylene polyol was odorless and colorless and transparent liquid. The terminal primary hydroxyl group ratio was 80%, the hydroxyl value was 57 mgKOH / g, and the polymerization reaction rate was 97%.

<Example 2>
Example 1 is the same as Example 1 except that 0.05 parts of the purified product of the catalyst in Synthesis Example 2 is used instead of 1.7 parts of the 3 wt% toluene solution of the crude product of the catalyst obtained in Synthesis Example 1. Thus, a polyoxyalkylene polyol was obtained. The obtained polyoxyalkylene polyol was an odorless colorless and transparent liquid. The terminal primary hydroxyl group ratio was 90%, the hydroxyl value was 57 mgKOH / g, and the polymerization reaction rate was 97%.

<Example 3>
In Example 1, instead of 1.7 parts of the 3 wt% toluene solution of the crude catalyst product obtained in Synthesis Example 1, 0.9 part of the 3 wt% toluene solution of the crude catalyst product obtained in Synthesis Example 3 was used. Except for this, the same operation as in Example 1 was carried out to obtain a polyoxyalkylene polyol. The obtained polyoxyalkylene polyol was odorless and colorless and transparent liquid. The terminal primary hydroxyl group ratio was 75%, the hydroxyl value was 62 mgKOH / g, and the polymerization reaction rate was 87%.

<Example 4>
In Example 1, 9.3 parts of the 3 wt% toluene solution of the crude catalyst product obtained in Synthesis Example 4 was used in place of 1.7 parts of the 3 wt% toluene solution of the crude catalyst product obtained in Synthesis Example 1. Except for this, the same operation as in Example 1 was carried out to obtain a polyoxyalkylene polyol. The obtained polyoxyalkylene polyol was odorless and colorless and transparent liquid. The terminal primary hydroxyl group ratio was 70%, the hydroxyl value was 70 mgKOH / g, and the polymerization reaction rate was 74%.

<Example 5>
In Example 1, the same operation as Example 1 was carried out except that 50 parts of diethylene glycol was used instead of 200 parts of 8.8 mol PO adduct of glycerin, and 950 parts were used instead of 800 parts of 1,2-propylene oxide. And polyoxyalkylene polyol was obtained. The obtained polyoxyalkylene polyol was odorless and colorless and transparent liquid. The terminal primary hydroxyl group ratio was 70%, the hydroxyl value was 56 mgKOH / g, and the polymerization reaction rate was 94%.

<Example 6>
In Example 1, polyoxyalkylene polyol was obtained in the same manner as in Example 1 except that 200 parts of tripropylene glycol monomethyl ether was used instead of 200 parts of 8.8 mol PO adduct of glycerin. The obtained polyoxyalkylene monool was an odorless colorless and transparent liquid having a terminal primary hydroxyl group ratio of 68%, a hydroxyl value of 56 mgKOH / g, and a polymerization reaction rate of 96%.

<Example 7>
In Example 1, 1.7 parts of the 3% by weight toluene solution of the crude product of the catalyst obtained in Synthesis Example 5 were used in place of 1.7 parts of the 3% by weight toluene solution of the crude product of the catalyst obtained in Synthesis Example 1. Except for this, the same operation as in Example 1 was carried out to obtain a polyoxyalkylene polyol. The obtained polyoxyalkylene polyol was odorless and colorless and transparent liquid. The terminal primary hydroxyl group ratio was 69%, the hydroxyl value was 66 mgKOH / g, and the polymerization reaction rate was 80%.

<Example 8>
In Example 1, 1.7 parts of the 3 wt% toluene solution of the crude product of the catalyst obtained in Synthesis Example 6 was used instead of 1.7 parts of the 3 wt% toluene solution of the crude product of the catalyst obtained in Synthesis Example 1. Except for this, the same operation as in Example 1 was carried out to obtain a polyoxyalkylene polyol. The obtained polyoxyalkylene polyol was odorless and colorless and transparent liquid. The terminal primary hydroxyl group ratio was 68%, the hydroxyl value was 62 mgKOH / g, and the polymerization reaction rate was 87%.

<Example 9>
In Example 1, 1.7 parts of the 3% by weight toluene solution of the crude product of the catalyst obtained in Synthesis Example 7 was used instead of 1.7 parts of the 3% by weight toluene solution of the crude product of the catalyst obtained in Synthesis Example 1. Except for this, the same operation as in Example 1 was carried out to obtain a polyoxyalkylene polyol. The obtained polyoxyalkylene polyol was odorless and colorless and transparent liquid. The terminal primary hydroxyl group ratio was 72%, the hydroxyl value was 60 mgKOH / g, and the polymerization reaction rate was 91%.

<Example 10>
In Example 1, 1.7 parts of the 3% by weight toluene solution of the crude product of the catalyst obtained in Synthesis Example 8 was used instead of 1.7 parts of the 3% by weight toluene solution of the crude product of the catalyst obtained in Synthesis Example 1. Except for this, the same operation as in Example 1 was carried out to obtain a polyoxyalkylene polyol. The obtained polyoxyalkylene polyol was odorless and colorless and transparent liquid. The terminal primary hydroxyl group ratio was 73%, the hydroxyl value was 62 mgKOH / g, and the polymerization reaction rate was 87%.

<Comparative Example 1>
In Example 1, in place of 1.7 parts of the 3% by weight toluene solution of the crude catalyst product obtained in Synthesis Example 1, 0.7 part of the 3% by weight toluene solution of the crude catalyst product obtained in Synthesis Example 9 was used. Except for the above, the same operation as in Example 1 was performed to obtain a polyoxyalkylene polyol. The obtained polyoxyalkylene polyol was odorless and colorless and transparent liquid. The terminal primary hydroxyl group ratio was 30%, the hydroxyl value was 107 mgKOH / g, and the polymerization reaction rate was 40%.

<Comparative example 2>
In Example 1, 22.1 parts of the 3 wt% toluene solution of the crude catalyst product obtained in Synthesis Example 10 was used instead of 1.7 parts of the 3 wt% toluene solution of the crude catalyst product obtained in Synthesis Example 1. Except for this, the same operation as in Example 1 was carried out to obtain a polyoxyalkylene polyol. The obtained polyoxyalkylene polyol was odorless and colorless and transparent liquid. The terminal primary hydroxyl group ratio was 58%, the hydroxyl value was 82 mgKOH / g, and the polymerization reaction rate was 60%.

<Comparative Example 3>
In Example 1, the same procedure as in Example 1 was carried out except that 28.3 parts were used instead of 1.7 parts of the 3 wt% toluene solution of the crude catalyst product obtained in Synthesis Example 1, and polyoxy An alkylene polyol was obtained. The obtained polyoxyalkylene polyol was odorless and colorless and transparent liquid. The terminal primary hydroxyl group ratio was 45%, the hydroxyl value was 82 mgKOH / g, and the polymerization reaction rate was 60%.

  The results are shown in Table 1 for the polyoxyalkylene monools or polyols obtained in Examples 1 to 10 and Comparative Examples 1 to 3.

In addition, the symbol of the compound used in Table 1 is as follows.
(1) Alkylene oxide (B)
PO: 1,2-propylene oxide (2) Compound (E)
Ti (O ⁱ Pr) ₄ : Titanium tetraisopropoxide Zr (OPr) ₄ : Zirconium tetranormal propoxide V (O ⁱ Pr) ₄ : Vanadium tetraisopropoxide (3) Lewis acid (C)
_{B (C 6 F 5) 3} : tris (pentafluorophenyl) borane _{Al (O-C 6 F 5} ) 3: tris (pentafluoro-phenoxy) aluminum _{Al (C 6 F 5) 3} : tris (pentafluorophenyl) aluminum

  As is clear from Table 1, the polyoxyalkylene monool or polyol obtained in Examples 1 to 10 of the present invention has a high terminal primary hydroxyl group ratio and a polymerization reaction rate in comparison with Comparative Examples 1 to 3. It can be seen that a high molecular weight polyoxyalkylene monool or polyol can be produced.

  According to the production method of the present invention, the resulting polyoxyalkylene monool or polyol has a high terminal primary hydroxyl group ratio, a large yield of polymerized product, and a process of removing and collecting a large amount of residue (waste) after the reaction. There is no need to perform the operation, and the polyoxyalkylene monool or polyol can be produced with high production efficiency. Therefore, it is suitable for the production of polyoxyalkylene monools or polyols used for urethane raw materials, cosmetic raw materials, surfactants and the like.

Claims (3)

In the presence of at least one compound (E) selected from the group consisting of titanium alkoxide, zirconium alkoxide and vanadium alkoxide and Lewis acid (C) represented by the following general formula (1) (A) ) Is a method for producing a polyoxyalkylene monool or polyol by addition polymerization of alkylene oxide (B) to a molar ratio of active hydrogen of compound (A) containing active hydrogen group and compound (E) {(activity of A (Number of moles of hydrogen) / (number of moles of E)} is 2,000 to 50,000, and the molar ratio of compound (E) to Lewis acid (C) {(number of moles of E) / (mol of C) Number)} is a method for producing a polyoxyalkylene monool or polyol having a value of 0.6 to 1.2.

[In General Formula (1), M represents a boron atom or an aluminum atom. R ¹ , R ² and R ³ are each independently a monovalent hydrocarbon group or hydrocarbon oxy group having 1 to 18 carbon atoms. The hydrogen atom of the hydrocarbon group or hydrocarbon oxy group may be substituted with a halogen atom. ] The molar ratio of the active hydrogen and the Lewis acid (C) in the active hydrogen group-containing compound (A) {(number of moles of active hydrogen in A) / (number of moles of C)} is 2,000 to 75,000. Item 2. A process for producing a polyoxyalkylene monool or polyol according to Item 1. The method for producing a polyoxyalkylene monool or polyol according to claim 1 or 2, wherein the alkylene oxide (B) is 1,2-propylene oxide or a mixture of 1,2-propylene oxide and ethylene oxide.