JP2012072260A - Polyoxyalkylene polyol and polyurethane resin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyoxyalkylene polyol which can manufacture a urethane elastomer and a polyurethane foam which are excellent enough in machine physical properties and moisture resistance.SOLUTION: The polyoxyalkylene polyol comprises adding an alkylene oxide to an active hydrogen-containing compound which has three or more active hydrogens, wherein the added 3-14C alkylene oxide is at least 50 mol%, at least 5 mol% of a terminal structure to which the 3-14C alkylene oxide is added is a structure expressed by general formula (I), hydroxyl value x, total unsaturation degree y, and ethylene oxide content z fulfill the relation of mathematical expression (1): y≤28.3×x×(100-z)/100, and the content of two functional component is at most 10 wt.%. In the general formula (I), Rdenotes a 1-12C alkyl group, a cycloalkyl group or a phenyl group, and may be substituted by a halogen atom or an aryl group; and in the residue excluding the structure in the parenthesis of formula (I) from the polyoxyalkylene polyol, X is a residue by the side of the active hydrogen-containing compound, and Y is a residue by the side of the hydroxy group.

Description

  The present invention relates to a polyoxyalkylene polyol and a polyurethane resin using the same.

  Usually, polyether polyols are prepared using an alkali metal such as potassium hydroxide as an anionic polymerization catalyst, or phosphoric acid, Lewis acid and their organic ligand compounds, trifluoromethylsulfonate and tetrakispentafluorophenylborate. Are added to the active hydrogen-containing compound by addition polymerization of alkylene oxide (hereinafter abbreviated as AO) such as propylene oxide (hereinafter abbreviated as PO) or ethylene oxide (hereinafter abbreviated as EO). Can be obtained. In addition polymerization of PO using an anionic polymerization catalyst, a by-product low molecular weight monool is produced by transfer of PO to allyl alcohol. On the other hand, in cationic polymerization, a diol is generated starting from the transfer of PO to propionaldehyde. The by-product low molecular weight monool and diol component cause a decrease in the number of functional groups of the polyether polyol, and a urethane resin using such a polyol has a problem that mechanical properties are deteriorated. As a measure for reducing the amount of by-product low molecular weight monool produced, a method using cesium hydroxide or double metal cyanide as an anionic polymerization catalyst is known. (For example, see Patent Documents 1 and 2.)

  On the other hand, polyether polyols obtained by addition polymerization of AO having 3 or more carbon atoms in the presence of an anionic polymerization catalyst have a very low primary hydroxyl group conversion rate (for example, usually when potassium hydroxide is used). 2% or less), most terminal hydroxyl groups are secondary hydroxyl groups. For this reason, this polyol has insufficient reactivity as a polyol component of a thermosetting resin. For example, the reactivity with an isocyanate group of an isocyanate group-containing compound (tolylene diisocyanate or the like) is low, and the reactivity is insufficient as a polyol component of a urethane resin.

The polyether polyol obtained by addition polymerization of AO having 3 or more carbon atoms in the presence of a cationic polymerization catalyst is known to have the same proportion of primary hydroxyl groups and secondary hydroxyl groups in all terminal hydroxyl groups. The reactivity as a polyol component of a thermosetting resin improves, so that the ratio of a primary hydroxyl group increases.
In order to ensure sufficient reactivity with the isocyanate group, the terminal hydroxyl group must be a primary hydroxyl group. For this purpose, a polyether polyol obtained by addition polymerization of AO having 3 or more carbon atoms is further added. A method is known in which 50 to 100% of terminal hydroxyl groups are converted to primary hydroxyl groups by addition polymerization of EO. However, since the polyethylene oxide part is hydrophilic, this method reduces the hydrophobicity of the polyether polyol, and the use of such a polyol greatly changes the physical properties of the urethane resin due to humidity. There is.
In addition, a method is known in which the amount of primary hydroxyl group in the terminal hydroxyl group is increased to 70% or more by using a specific catalyst. (For example, refer to Patent Document 3.)

  Furthermore, by first performing AO addition polymerization with cesium hydroxide or a double metal cyanide catalyst, and then performing AO addition polymerization using a specific catalyst, while reducing the amount of by-product low molecular weight monool produced. It is known that a polyoxyalkylene polyol having improved reactivity with an isocyanate group can be obtained. (For example, see Patent Document 4)

JP 2007-131845 A JP 2007-131845 A Japanese Patent No. 3076032 Japanese Patent No. 3688667

However, it is difficult to say that the mechanical properties and moisture resistance of urethane elastomers and urethane foams using the above polyether polyols are sufficient.
The problem to be solved by the present invention is to provide a polyoxyalkylene polyol capable of producing a urethane elastomer and a urethane foam sufficiently excellent in mechanical properties and moisture resistance.

［一般式（Ｉ）中、Ｒ¹は、炭素数１〜１２のアルキル基、シクロアルキル基又はフェニル基を表し、ハロゲン原子又はアリール基で置換されていてもよい。；ポリオキシアルキレンポリオールから式（Ｉ）の括弧内の構造を除いた残基のうち、Ｘは活性水素含有化合物側の残基であり、Ｙは水酸基側の残基である。］
また、本発明のポリウレタン樹脂は、ポリオール成分（Ｐ）と有機ポリイソシアネート成分（Ｉ）とを反応させて得られる発泡又は非発泡ポリウレタン樹脂であって、ポリオール成分の少なくとも一部として、本発明のポリオキシアルキレンポリオールを用いる発泡又は非発泡ポリウレタン樹脂であることを要旨とする。 That is, the polyoxyalkylene polyol (S) of the present invention is a polyoxyalkylene polyol obtained by adding an alkylene oxide to an active hydrogen-containing compound (H) having 3 or more active hydrogens,
The added alkylene oxide having 3 to 14 carbon atoms is 50 mol% or more based on the number of moles of added alkylene oxide,
5 mol% or more of the terminal structure to which an alkylene oxide having 3 to 14 carbon atoms is added is a structure represented by the general formula (I),
The relationship between the hydroxyl value x, the total unsaturation y, and the ethylene oxide content z is represented by the formula (1).
The gist is that the content of the bifunctional component is 10% by weight or less based on the weight of the polyoxyalkylene polyol.
y ≦ 28.3 × x ⁻² × (100−z) / 100 (1)
[In Formula (1), x represents the hydroxyl value represented by the unit mgKOH / g, and y represents the total degree of unsaturation represented by the unit meq / g. z is the ethylene oxide content based on the weight of (S), and is 0 to 50% by weight. ]

[In General Formula (I), R ¹ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or a phenyl group, and may be substituted with a halogen atom or an aryl group. Among the residues obtained by removing the structure in parentheses of the formula (I) from the polyoxyalkylene polyol, X is a residue on the active hydrogen-containing compound side, and Y is a residue on the hydroxyl side. ]
The polyurethane resin of the present invention is a foamed or non-foamed polyurethane resin obtained by reacting the polyol component (P) and the organic polyisocyanate component (I), and is used as at least a part of the polyol component. The gist is that it is a foamed or non-foamed polyurethane resin using a polyoxyalkylene polyol.

The polyoxyalkylene polyol of the present invention has a reduced amount of by-produced monool and diol, and has sufficient reactivity as a raw material for producing polyurethane resin, and is a urethane resin having good mechanical properties and moisture resistance. Obtainable.
Moreover, the foamed or non-foamed polyurethane resin of the present invention has good mechanical properties and moisture resistance.

FIG. 3 is a diagram showing a process flow of Example 1. FIG. 6 is a diagram showing a process flow of Example 3. FIG. 10 is a diagram showing a process flow of Example 5. It is a figure which shows the process flow of Comparative Examples 1, 2, and 4.

The present invention is a polyoxyalkylene polyol obtained by adding an alkylene oxide to an active hydrogen-containing compound (H) having 3 or more active hydrogens,
The added alkylene oxide having 3 to 14 carbon atoms is 50 mol% or more based on the number of moles of added alkylene oxide,
5 mol% or more of the terminal structure to which an alkylene oxide having 3 to 14 carbon atoms is added is a structure represented by the general formula (I),
The relationship between the hydroxyl value x, the total unsaturation y, and the ethylene oxide content z is represented by the formula (1).
The polyoxyalkylene polyol (S) has a bifunctional component content of 10% by weight or less based on the weight of the polyoxyalkylene polyol.

y ≦ 28.3 × x ⁻² × (100−z) / 100 (1)
[In Formula (1), x represents the hydroxyl value represented by the unit mgKOH / g, and y represents the total degree of unsaturation represented by the unit meq / g. z is the ethylene oxide content based on the weight of (S), and is 0 to 50% by weight. ]

［一般式（Ｉ）中、Ｒ¹は、炭素数１〜１２のアルキル基、シクロアルキル基又はフェニル基を表し、ハロゲン原子又はアリール基で置換されていてもよい。；ポリオキシアルキレンポリオールから式（Ｉ）の括弧内の構造を除いた残基のうち、Ｘは活性水素含有化合物側の残基であり、Ｙは水酸基側の残基である。］

[In General Formula (I), R ¹ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or a phenyl group, and may be substituted with a halogen atom or an aryl group. Among the residues obtained by removing the structure in parentheses of the formula (I) from the polyoxyalkylene polyol, X is a residue on the active hydrogen-containing compound side, and Y is a residue on the hydroxyl side. ]

  In the above formula (1), the range of x is preferably 5 to 280 mgKOH / g, more preferably 10 to 115 mgKOH / g, and particularly preferably 25 to 75 mgKOH / g. When x is 5 mgKOH / g or more, the viscosity of the polyoxyalkylene polyol is low, so that the handling is easy, and when it is 280 mgKOH / g or less, the elongation property of the synthesized urethane resin is good. In addition, x is calculated | required by JISK-1557-1.

  y is the total unsaturation degree (meq / g) of the polyoxyalkylene polyol, and is determined according to JISK-1557-3. y is preferably 0 to 0.04, more preferably 0 to 0.03, and particularly preferably 0 to 0.02. When y is in this range, the physical properties of the urethane resin are improved.

  Z is the ethylene oxide content (% by weight) based on the weight of the polyoxyalkylene polyol. The range of z is 0-50, preferably 0-25, particularly preferably 0-20. If z exceeds 50, the resulting polyurethane resin has poor moisture resistance.

As described above, the relationship among the hydroxyl value x, the total degree of unsaturation y, and the ethylene oxide content z of the polyoxyalkylene polyol (S) of the present invention satisfies the relationship of the formula (1).
y ≦ 28.3 × x ⁻² × (100−z) / 100 (1)
The polyoxyalkylene polyol (S) of the present invention is characterized by having sufficient reactivity with an isocyanate and hydrophobicity. The urethane resin obtained using this (S) has high reactivity at the time of production, and the mechanical properties (hardness, elongation at break, tensile strength, tear strength) and moisture resistance of the resin are good.

(S) of the present invention more preferably satisfies the relationship of the mathematical formula (2).
y ≦ 18.9 × x ⁻² × (100−z) / 100 (2)
The polyoxyalkylene polyol (S) satisfying the formula (2) has a reduced amount of unsaturated monool as compared with the case where the formula (1) is satisfied, and the polyurethane resin produced using such a polyoxyalkylene polyol Alternatively, the mechanical properties of urethane foam are further improved.

The right side is a value calculated from the hydroxyl value x and the ethylene oxide content z. The right side decreases as the hydroxyl value x increases, that is, decreases as the molecular weight per hydroxyl group of (S) decreases. Further, the right side becomes smaller as the ethylene oxide content z becomes larger.
The left side of the above formula (1) is the total degree of unsaturation y.
By the way, the unsaturated group of the polyoxyalkylene polyol is produced by a transfer reaction of alkylene oxide (especially propylene oxide) other than ethylene oxide in this production process. Therefore, the smaller the ethylene oxide content in the polyoxyalkylene polyol, the less the unsaturated group. The degree of saturation y tends to increase, and the degree of unsaturation y tends to increase as the molecular weight increases. Therefore, a polyoxyalkylene polyol having a small ethylene oxide content or a large molecular weight tends to be difficult to satisfy the formula (1).
That is, Formula (1) shows the area | region where the total unsaturation degree y is small compared with the hydroxyl value x and ethylene oxide content z. In addition, the said Formula (1) represents the range in which the effect of this invention found experimentally is acquired.

The polyoxyalkylene polyol (S) of the present invention is a compound obtained by adding alkylene oxide to an active hydrogen-containing compound (H) having 3 or more active hydrogens.
Examples of the active hydrogen compound (H) include a hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, a thiol group-containing compound, a phosphoric acid compound; and a mixture of two or more thereof.

Examples of the hydroxyl group-containing compound include 3 to 8 valent polyhydric alcohols and polyhydric phenols. Specifically, trihydric alcohols such as glycerin and trimethylolpropane; 4- to 8-valent alcohols such as pentaerythritol, sorbitol and sucrose; polyhydric phenols such as pyrogallol; polybutadiene Polyols; castor oil-based polyols; (co) polymers of hydroxyalkyl (meth) acrylates and polyfunctional (eg, having 3 to 100 functional groups) polyols such as polyvinyl alcohol.
(Meth) acrylate means methacrylate and / or acrylate, and the same applies hereinafter.

  Examples of the amino group-containing compound include amines, polyamines, amino alcohols and the like. Specifically, ammonia; aliphatic polyamines such as ethylenediamine, hexamethylenediamine and diethylenetriamine; heterocyclic polyamines such as N-aminoethylpiperazine; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; phenylenediamine, tolylene Aromatic polyamines such as amines and diphenylmethanediamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; polyamide polyamines obtained by condensation of dicarboxylic acids with excess polyamines; polyether polyamines; hydrazines (hydrazines and hydrazines) Monoalkyl hydrazine etc.), dihydrazide (eg succinic acid dihydrazide and terephthalic acid dihydrazide), guanidine (butyl guanidine and the like) - cyanoguanidine, etc.); dicyandiamide; and mixtures of two or more thereof.

Examples of the carboxyl group-containing compound include aromatic polycarboxylic acids such as trimellitic acid; polycarboxylic acid polymers (functional group number: 3 to 100) such as (co) polymers of acrylic acid, and the like.
The thiol group-containing compound includes a polythiol compound, and examples thereof include 3 to 8 valent polyvalent thiols. Specific examples include pentaerythritol poly (thioglycolate) and pentaerythritol poly (3-mercaptopropionate).
Examples of the phosphoric acid compound include phosphoric acid and phosphonic acid.

  Among these active hydrogen-containing compounds (H), from the viewpoint of reactivity, a hydroxyl group-containing compound and an amino group-containing compound are preferable, and alcohols and amines are particularly preferable.

  From the viewpoint of the physical properties of the urethane resin obtained using the polyoxyalkylene polyol (S), the number of active hydrogens possessed by (H) is preferably 3-8, and more preferably 3-6.

  The alkylene oxide (hereinafter abbreviated as AO) added to the active hydrogen-containing compound (H) is AO having 2 to 14 carbon atoms, preferably AO having 2 to 6 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO). ), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propyloxide, 1,2-butylene oxide, 1,4-butylene oxide, etc., some of which are halogenated Or the like can be used. Of these, PO, EO, and 1,2-butylene oxide are preferable from the viewpoints of properties and reactivity. When two or more types of AO are used (for example, PO and EO), block addition or random addition may be used, or a combination thereof may be used.

  In the present invention, the added alkylene oxide having 3 to 14 carbon atoms is 50 mol% or more based on the number of moles of the added alkylene oxide, and the moisture resistance of the urethane resin obtained using the polyoxyalkylene polyol (S) From a thermal viewpoint, 70-100 mol% is preferable. When the added alkylene oxide having 3 to 14 carbon atoms is less than 50 mol%, the heat and humidity resistance of the urethane resin is deteriorated.

  The number of moles of AO added to the active hydrogen-containing compound (H) is preferably 1 to 200 moles, more preferably 1 from the viewpoint of mechanical properties of the urethane resin per active hydrogen of the active hydrogen-containing compound (H). ~ 100 moles.

In the structure of the polyoxyalkylene polyol (S), 5 mol% or more of the terminal structure to which AO having 3 to 14 carbon atoms is added is a structure represented by the general formula (I). From the viewpoint of easily satisfying the relationship, it is more preferably 60 mol% or more, and further preferably 65 mol% or more. If it is less than 5 mol%, the mechanical strength of the resulting urethane resin will deteriorate.
In addition, in the above, the terminal structure to which AO having 3 to 14 carbon atoms is added refers to each active hydrogen in the structure in which AO having 3 to 14 carbon atoms is added to the active hydrogen of the active hydrogen-containing compound (H). Means the structure closest to the terminal hydroxyl group.

  In the general formula (I), among the residues obtained by removing the structure in parentheses of the formula (I) from the polyoxyalkylene polyol, X is a residue on the active hydrogen-containing compound side, and Y is a residue on the hydroxyl side. is there.

  In the polyoxyalkylene polyol (S), the ratio of the primary hydroxyl group-containing group represented by the general formula (II) to the total hydroxyl groups at the ends (this ratio is defined as the primary hydroxyl group ratio in this specification). The same applies hereinafter) is preferably 5 mol% or more, more preferably 60 mol% or more from the viewpoint of the reactivity of (S), based on the amount of all terminal hydroxyl groups of the polyoxyalkylene polyol (S). Next, it is more preferably 65 mol% or more.

  In addition, as the structure of the hydroxyl group located at the terminal of (S), there are two types, a primary hydroxyl group-containing group represented by the general formula (II) and a secondary hydroxyl group-containing group represented by the following general formula (III) Can be considered. For example, 5 mol% of the hydroxyl group located at the above-mentioned end means that the primary hydroxyl group-containing group represented by the following general formula (II) is 5 mol% with respect to the total number of moles of hydroxyl groups located at the end. It means that there is. .

［一般式（ＩＩ）中、Ｒ²は、水素原子、又は炭素数１〜１２のアルキル基、シクロアルキル基若しくはフェニル基を表す。］

［一般式（ＩＩＩ）中、Ｒ²は、水素原子又は、ハロゲン原子若しくはアリール基で置換されていてもよい炭素数１〜１２のアルキル基、シクロアルキル基若しくはフェニル基を表す。］

[In General Formula (II), R ² represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or a phenyl group. ]

[In General Formula (III), R ² represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group or a phenyl group which may be substituted with a halogen atom or an aryl group. ]

R < ² > in said general formula (II) or (III) represents a hydrogen atom or a C1-C12 alkyl group, a cycloalkyl group, or a phenyl group. The alkyl group, cycloalkyl group or phenyl group may be substituted with a halogen atom or an aryl group.
Specific examples of R ² include a hydrogen atom; a linear alkyl group such as a methyl group, an ethyl group, and a propyl group; a branched alkyl group such as an isopropyl group; a substituted phenyl group such as a phenyl group and a p-methylphenyl group; A substituted alkyl group such as a methyl group, a bromomethyl group, a chloroethyl group and a bromoethyl group; a substituted phenyl group such as a p-chlorophenyl group and a p-bromophenyl group; a cyclic alkyl group such as a cyclohexyl group; and a combination of two or more of these Is mentioned.

In the present invention, the primary hydroxyl group ratio is measured and calculated by a ¹ H-NMR method after pre-treatment of the sample in advance.

The method for measuring the primary hydroxyl group ratio will be specifically described below.
<Sample preparation method>
About 30 mg of a measurement sample is weighed into an NMR sample tube 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 toluene, deuterated dimethyl sulfoxide, and deuterated dimethylformamide, and a solvent that can dissolve the sample is appropriately selected.
<NMR measurement>
¹ H-NMR measurement is performed under normal conditions.

<Calculation method of primary hydroxyl group ratio>
By the pretreatment method described above, the terminal hydroxyl group of the polyoxyalkylene polyol reacts with the added trifluoroacetic anhydride to become a trifluoroacetic acid ester. As a result, a signal derived from a methylene group bonded with a primary hydroxyl group was observed at around 4.3 ppm, and a signal derived from a methine group bonded to a secondary hydroxyl group was observed at around 5.2 ppm (deuterated chloroform was used as a solvent). Used as). The primary hydroxyl group ratio is calculated by the following calculation formula.
Primary hydroxyl group ratio (%) = [a / (a + 2 × b)] × 100
In the formula, a is an integral value of a signal derived from a methylene group to which a primary hydroxyl group is bonded in the vicinity of 4.3 ppm; b is an integrated value of a signal derived from a methine group to which a secondary hydroxyl group is bonded in the vicinity of 5.2 ppm. .

  The content of the bifunctional component contained in the polyoxyalkylene polyol (S) of the present invention is 10% by weight or less based on the weight of (S). From the viewpoint of mechanical properties of the polyurethane resin obtained by using (S), the content is preferably 5% by weight or less, and more preferably 3% by weight or less. When the content of the bifunctional component exceeds 10% by weight, the mechanical properties as a polyurethane resin are insufficient.

The method for measuring the content of the bifunctional component will be specifically described below.
<Sample preparation method>
Polyoxyalkylene polyol (S) is diluted in methanol. The dilution concentration is diluted so that the polyoxyalkylene polyol (S) becomes 100 ppm based on the weight of the diluted solution. In addition, in order to perform calibration of the bifunctional component, the bifunctional polyol as a standard sample was diluted to 1,5,10,20 ppm in methanol so as to be 1,5,10,20 wt% of the sample of (S). Use things. As the bifunctional polyol, those having the same molecular weight per functional group as the target polyol (S) to be measured are desirable.
<LC-TOFmass measurement>
The LC-TOF mass of each sample is measured under normal conditions.
<Diol component amount calculation>
-Calibration curve The LC total area of the bifunctional polyol standard sample is added together, and the horizontal axis is the content (% by weight) and the vertical axis is the area.
-Calculation of amount of bifunctional component in sample From the LC-TOF mass measurement result of the sample, a component having a precise mass derived from the bifunctional component is extracted, and the LC area in each component is added up. Calculate the percentage of the total amount of ingredients.

  The number average molecular weight of the polyoxyalkylene polyol (S) of the present invention is appropriately selected according to the use of (S), for example, required physical properties of a thermosetting resin such as a polyurethane resin to be produced, and is not particularly limited. From the viewpoint of physical properties, 400 to 100,000 is preferable, and 400 to 20,000 is preferable.

  Specific examples of the polyoxyalkylene polyol (S) include glycerin PO adduct, pentaerythritol PO adduct, sucrose PO adduct, glycerin EO / PO copolymer adduct, pentaerythritol EO / PO co-adduct. Polymerization adduct, PO / butylene oxide copolymerization adduct of pentaerythritol, EO / PO copolymerization adduct of sucrose, PO / butylene oxide copolymerization adduct of sucrose, EO / PO / butylene oxide copolymerization of glycerin Examples include adducts, copolymerized adducts of pentaerythritol with EO / PO / butylene oxide, and copolymerized adducts of sucrose with EO / PO / butylene oxide.

  The polyoxyalkylene polyol (S) of the present invention can be obtained by subjecting an active hydrogen-containing compound (H) to ring-opening addition polymerization of an alkylene oxide having 2 to 14 carbon atoms in the presence of a Lewis acid catalyst (B). . Moreover, you may carry out 0-50 weight% ring-opening addition polymerization after that as needed. The method for carrying out the ring-opening addition weight of EO may be a condition known in the art, and the catalyst is not particularly limited.

  The Lewis acid catalyst (B) is preferably a compound represented by the following general formula (IV-1), (IV-2) or (IV-3). By using this for ring-opening addition polymerization of an alkylene oxide having 2 to 14 carbon atoms, a ring-opening polymer is obtained with good yield, and a polyoxyalkylene polyol having a high primary hydroxyl group ratio of terminal hydroxyl groups is obtained. preferable.

  In the general formula (IV-1), (IV-2) or (IV-3), X represents a boron atom or an aluminum atom, respectively. From the viewpoint of reactivity, a boron atom is preferable.

R ³ in the general formula (IV-1), (IV-2) or (IV-3) is represented by the (substituted) phenyl group represented by the following general formula (V) or the following general formula (VI). When there are a plurality of R ³ groups, the plurality of R ³ groups may be the same or different.

Z in the general formula (V) represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group, or a cyano group, which may be the same or different. Of these, a hydrogen atom, a halogen atom and a cyano group are preferable, and a halogen atom and a cyano group are more preferable.
Moreover, k represents the number of 0-5.
Specific examples of the phenyl group or substituted phenyl group represented by the general formula (V) include a phenyl group, a pentafluorophenyl group, a p-methylphenyl group, a p-cyanophenyl group, and a p-nitrophenyl group. A phenyl group, a pentafluorophenyl group and a p-cyanophenyl group are preferable, and a phenyl group and a pentafluorophenyl group are more preferable.

R ⁴ , R ⁵ or R ^{6 in the} general formula (VI) each independently represents an alkyl group having 1 to 4 carbon atoms, which may be the same or different. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Specific examples of the tertiary alkyl group represented by the general formula (VI) include a t-butyl group and a t-pentyl group.

  Specific examples of the Lewis acid catalyst (B) include triphenylborane, diphenyl-t-butylborane, tri (t-butyl) borane, triphenylaluminum, tris (pentafluorophenyl) borane and tris (pentafluorophenyl) aluminum. Is mentioned.

  Although the usage-amount of a Lewis' acid catalyst (B) is not specifically limited, 0.0001-10 weight% is preferable with respect to the ring-opening polymer to manufacture, More preferably, it is 0.0005-1 weight%.

  When the alkylene oxide is added to the active hydrogen-containing compound (H) in the presence of the Lewis acid catalyst (B), the by-product low-boiling compound (t) having a boiling point of 150 ° C. or lower at a pressure of 0.1 MPa is continuously or It is preferable to remove intermittently because (S) of the present invention satisfying the above-described formula (1) is easily obtained.

  The removal of (t) may be carried out by any generally known method. For example, (t) and alkylene oxide are extracted from the reaction mixture with a vacuum pump from the reaction mixture, and alkylene oxide and (t) are distilled. Although there is a method of separation, the catalyst (C) containing the transition metal of the fifth or sixth period of the periodic table is brought into contact with (t), and (t) is decomposed and removed to lower boiling point (u). It is preferable because it is easier to satisfy the formula (1) and the amount of diol in (S) is easily reduced. The decomposed low boiling point substance (u) derived from (t) does not affect the physical properties of (S) and may or may not be removed from the reaction system. The method for removing (u) from the reaction system may be carried out by any of the commonly known methods. For example, there are a method of removing (u) from the reaction mixture by heating and / or depressurization, a method of extracting the gas phase in the reaction vessel from the reaction vessel using a vacuum pump, and a method of separating (u) by distillation.

  The decomposition of (t) by the catalyst (C) is performed simultaneously with the addition reaction of alkylene oxide to the active hydrogen compound (H) in the presence of the catalyst (B), that is, in the presence of (B) and (C) ( Even when AO is added to H), the product obtained by adding AO to (H) in the presence of (B) is treated in the presence of (C) (for example, the addition reaction and A decomposition reaction may be performed). In order to reduce the content of the bifunctional component of the resulting polyoxyalkylene polyol (S), it is more desirable to add AO to (H) in the presence of (B) and (C).

The catalyst (C) is a metal complex catalyst composed of a transition metal in the 5th or 6th period of the periodic table and a ligand. The central metal is molybdenum, ruthenium, rhodium, palladium, silver, indium, antimony. Tungsten, iridium, platinum and the like can be used, but ruthenium, rhodium, palladium, platinum and iridium are particularly preferable from the viewpoint of the reactivity of the catalyst (C).
The ligands that coordinate to these transition metals to form the catalyst (C) include phosphorus-containing compounds such as phosphines and phosphites, alcohols, double bond-containing compounds, and nitrogen-containing compounds such as amines and amides. From the viewpoint of the reactivity of (C), phosphine is preferable, and trimethylphosphine, diphenylphosphinopropane and diphenylphosphinobutane are more preferable.

  Although the usage-amount of a catalyst (C) is not specifically limited, 0.0001-10 weight% is preferable with respect to the ring-opening polymer to manufacture, More preferably, it is 0.0005-1 weight%.

  Specific examples of the by-product low-boiling compound (t) having a boiling point of 150 ° C. or less at a pressure of 0.1 MPa include formaldehyde (boiling point−19 ° C.), acetaldehyde (boiling point 20 ° C.), propionaldehyde (boiling point 48 ° C.), and allyl alcohol. And compounds having 0 to 2 mol of AO added thereto. (T) is often generated in an amount of 0.0001 to 10% by weight based on the weight of the polyoxyalkylene polyol (S) when AO is added.

  Specific examples of the low boiling point compound (u) which is a decomposition product of the by-product low boiling point compound (t) having a boiling point of 150 ° C. or less at a pressure of 0.1 MPa include carbon monoxide (boiling point −192 ° C.), methane (boiling point − 162 ° C), ethane (boiling point -89 ° C), butane (boiling point -0.5 ° C).

  When AO is added to the active hydrogen-containing compound (H), the active hydrogen-containing compound (H), AO, and the catalyst (B) may be charged together and reacted, or the active hydrogen-containing compound (H H), catalyst (B) and catalyst (C) may be reacted dropwise with AO, or AO and catalyst (B) may be dropped into active hydrogen-containing compound (H) or active hydrogen. You may react by dripping (C) and AO to the mixture of a compound (H) and (B). Further, the contact of the by-product low boiling point compound (t) having a boiling point of 150 ° C. or less at a pressure of 0.1 MPa and (C) may be continuous or intermittent. From the viewpoint of controlling the reaction temperature, AO is added dropwise to the mixture of active hydrogen-containing compound (H) and catalysts (B) and (C), or AO is added to the mixture of active hydrogen-containing compound (H) and catalyst (C). And a method in which the catalyst (B) is dropped.

  The reaction temperature for adding AO to the active hydrogen-containing compound (H) is preferably 0 ° C to 250 ° C, more preferably 20 ° C to 180 ° C.

  The temperature when the by-product low-boiling compound (t) having a boiling point of 150 MPa or less at a pressure of 0.1 MPa is decomposed with the catalyst (C) is preferably 20 to 300 ° C., and the addition reaction to the active hydrogen compound (H) and From the viewpoint of the stability of the polyoxyalkylene polyol, 20 to 180 ° C. is more preferable.

  In the case where the produced polyoxyalkylene polyol (S) contains the catalyst (B) and / or the catalyst (C), the decomposition and / or removal treatment of the catalyst (B) as necessary depending on the use, The catalyst (C) is removed.

  As a decomposition method of the catalyst (B), there is a method of adding a basic substance such as water and / or an alcohol compound and, if necessary, an alkali compound. As the alcohol compound, the aforementioned alcohol and / or phenol can be used. Examples of the alkali compound include alkali metal hydroxides (potassium hydroxide, sodium hydroxide, cesium hydroxide, etc.), alkali metal alcoholates (potassium methylate, sodium methylate, etc.) and mixtures of two or more of these. Of these, alkali metal hydroxides are preferred from the viewpoint of productivity. In the decomposition, the decomposition temperature is preferably 10 to 180 ° C, more preferably 80 to 150 ° C. The decomposition may be performed in a sealed state, may be performed while exhausting by connecting to a vacuum source, or may be performed while continuously adding water or an alcohol compound. Water or alcohol to be added may be added in a liquid state, or may be added in a vapor or solid state. The amount of water and / or alcohol compound used is preferably 0.1 to 100% by weight, more preferably 1 to 20% by weight, based on the weight of the addition product. The amount of the alkali compound used is preferably 0.1 to 10% by weight, more preferably 0.3 to 2% by weight, based on the weight of the addition product.

  As a method for removing the catalysts (B) and (C), any method known in the art may be used. For example, hydrotalcite-based adsorbents {KYOWARD 500, KYOWARD 1000, KYOWARD 2000 etc. (all manufactured by Kyowa Chemical Industry Co., Ltd.)} and filter aids such as diatomaceous earth {Radiolite 600, Radiolite 800 and Radiolite 900 (Both manufactured by Showa Chemical Co., Ltd.)}, synthetic zeolite {Molecular Sieves 4A, 3A}, silica gel, and the like can be used. The filtration may be either pressure filtration or vacuum filtration, but pressure filtration is preferred because it is easy to prevent oxygen contamination. The material of the filter is not particularly limited. For example, paper, polypropylene, polytetrafluoroethylene, polyester, polyphenylene sulfide, acrylic, and meta-aramid are exemplified, and paper is preferable. The retained particle diameter of the filter is preferably 0.1 to 10 μm. Furthermore, the thing of 1-5 micrometers is preferable.

  In addition, even if the catalyst (B) and the catalyst (C) remain in the polyoxyalkylene polyol (S), compared with the conventional alkaline catalyst, the reactivity of the polyol and isocyanate in the subsequent urethanization reaction, for example, Does not have a significant adverse effect. However, it is preferable to decompose and / or remove the remaining catalyst from the viewpoint of preventing coloring.

The polyoxyalkylene polyol (S) of the present invention (particularly a polyoxyalkylene polyol having 3 to 8 or more valences) can be used for various applications, but is preferably used for producing a foamed or non-foamed polyurethane resin. It is done.
That is, when producing a foamed or non-foamed polyurethane resin by reacting the polyol component (P) and the organic polyisocyanate component (I) as necessary in the presence of an additive, a polyoxyoxy compound is used as at least a part of the polyol component. An alkylene polyol (S) is used.

  The use amount of the polyoxyalkylene polyol (S) of the present invention is preferably 20 to 100% by weight, more preferably 50 to 50% based on the weight of the polyol component (P) from the viewpoint of the mechanical strength of the resulting polyurethane foam. 100% by weight.

The use of (S) as at least a part of the polyol component includes the use of a polymer alcohol (W) obtained by polymerizing the vinyl monomer (g) in (S).
The polymer alcohol (W) is a polymer alcohol in which polymer particles (P) are dispersed in (S).
The polymer alcohol (W) can be produced by polymerizing the vinyl monomer (g) in (S) (preferably a polyoxyalkylene polyol) by a known method. For example, in (S), the vinyl monomer (g) is polymerized in the presence of a radical polymerization initiator, and the obtained polymer (g) is stably dispersed. Specific examples of the polymerization method include those described in US Pat. No. 3,383,351 and Japanese Examined Patent Publication No. 39-25737.
(G) is preferably styrene and / or acrylonitrile.

  As the organic polyisocyanate component (I), those conventionally used for polyurethane production can be used. Examples of such isocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products thereof (for example, urethane groups, carbodiimide groups, allophanate groups, urea groups, burettes). Group, an isocyanurate group, or an oxazolidone group-containing modified product) and a mixture of two or more thereof.

As aromatic polyisocyanate, C6-C16 aromatic diisocyanate, C6-C20 aromatic triisocyanate, and crude products of these isocyanates (excluding carbon in the NCO group; the following isocyanates are also the same), etc. Is mentioned. Specific examples include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and / or 4, 4'-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI), and the like.
Examples of the aliphatic polyisocyanate include aliphatic diisocyanates having 6 to 10 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate and lysine diisocyanate.

Examples of the alicyclic polyisocyanate include alicyclic diisocyanates having 6 to 16 carbon atoms. Specific examples include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, and the like.
Examples of the araliphatic polyisocyanate include araliphatic diisocyanates having 8 to 12 carbon atoms. Specific examples include xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.
Specific examples of the modified polyisocyanate include urethane-modified MDI and carbodiimide-modified MDI.

When producing the polyurethane resin of the present invention, the reaction may be carried out in the presence of the additives described below, if necessary.
When producing a polyurethane foam, a foaming agent is used.
As the foaming agent, known foaming agents can be used, and examples thereof include water, hydrogen atom-containing halogenated hydrocarbons, low boiling point hydrocarbons, and liquefied carbon dioxide gas, and two or more kinds may be used in combination.
Specific examples of the hydrogen atom-containing halogenated hydrocarbon include methylene chloride and HCFC (hydrochlorofluorocarbon) type (for example, HCFC-123 and HCFC-141b); HFC (hydrofluorocarbon) type (for example, HFC-245fa). And HFC-365mfc).
The low boiling point hydrocarbon is a hydrocarbon having a normal boiling point of −5 to 70 ° C., and specific examples thereof include butane, pentane, and cyclopentane.

When the foaming agent is water, the amount of the foaming agent used relative to 100 parts of the polyol component is preferably 0.1 to 30 parts, and more preferably 1 to 20 parts. The hydrogen atom-containing halogenated hydrocarbon is preferably 50 parts or less, more preferably 10 to 45 parts. The low boiling point hydrocarbon is preferably 40 parts or less, more preferably 10 to 30 parts. The amount of liquefied carbon dioxide is preferably 30 parts or less, and more preferably 1 to 25 parts.
In addition, in the above and the following, a part means a weight part.

  Further, for example, foam stabilizers (dimethylsiloxane, polyether-modified dimethylsiloxane, etc.), urethanization catalysts {tertiary amine catalysts (triethylenediamine, N-ethylmorpholine, diethylethanolamine, N, N, N ′, N '-Tetramethylhexamethylenediamine, tetramethylethylenediamine, diaminobicyclooctane, 1,2-dimethylimidazole, 1-methylimidazole and 1,8-diazabicyclo- [5,4,0] -undecene-7), and / or Or metal catalysts (stannic octylate, dibutylstannic dilaurate, lead octylate, etc.), colorants (dyes and pigments), plasticizers (phthalate esters, adipates, etc.), organic fillers (synthesis short) Fibers, hollow microspheres made of thermoplastic or thermosetting resin, etc.), flame retardants Esters and halogenated phosphoric acid esters, etc.), antioxidant (triazole and benzophenone), antioxidants (which can be reacted in the presence of a hindered phenol and hindered amine and the like) and the like known additives.

  With respect to the amount of these additives used relative to 100 parts of the polyol component, the foam stabilizer is preferably 10 parts or less, more preferably 0.5 to 5 parts. The urethanization catalyst is preferably 10 parts or less, more preferably 0.2 to 5 parts. The colorant is preferably 1 part or less. The plasticizer is preferably 10 parts or less, more preferably 5 parts or less. The organic filler is preferably 50 parts or less, more preferably 30 parts or less. The flame retardant is preferably 30 parts or less, more preferably 5 to 20 parts. The anti-aging agent is preferably 1 part or less, more preferably 0.01 to 0.5 part. The antioxidant is preferably 1 part or less, and more preferably 0.01 to 0.5 part. The total amount of additives used is preferably 50 parts or less, more preferably 0.2 to 30 parts.

  The isocyanate index (NCO INDEX) [(NCO group / active hydrogen atom-containing group) equivalent ratio × 100] in the production of the polyurethane resin of the present invention is preferably 80 to 150, more preferably 85 to 135, particularly preferably. Is 90-130.

Moreover, the conditions which make a polyol component and organic polyisocyanate component (I) react may be the well-known conditions normally used.
As an example, first, a predetermined amount of a polyol component and, if necessary, an additive are mixed. The mixture and polyisocyanate are then rapidly mixed using a polyurethane low pressure or high pressure injection foamer or stirrer. The obtained liquid mixture is poured into a closed mold or an open mold (made of metal or resin) to cause urethanization reaction, and after curing for a predetermined time, it is demolded to obtain a polyurethane resin.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this.

<Example 1>
As shown in FIG. 1, a stainless steel autoclave as a reaction tank (1) with a 2500 ml capacity stirring device, a temperature control device, a raw material supply line (5), and a heat exchanger as a condensing facility (2) Were connected by a line (3), and an exhaust pressure valve and an exhaust line (4) connected at 0.6 MPa were connected to the condensing facility (2).
After charging 400 g of glycerin PO adduct (hydroxyl value 280), 0.09 g of tris (pentafluorophenyl) borane, and 2.0 g of chlorodiphenylphosphinopropanerhodium into the reaction tank (1), autoclave {reaction tank (1)}, the condensation facility (2), and the inside of the line (3) were depressurized to 0.005 MPa. PO was continuously put into the liquid phase through the raw material supply line (5) while controlling the reaction temperature so as to maintain 70 to 80 ° C. A refrigerant at −30 ° C. was circulated in order to condense and recover PO in the condensing facility. By separating (u), which is a decomposition product of a low boiling point compound (t) having a boiling point of 150 ° C. or less at normal pressure, from the exhaust line (4) so that the pressure of the reaction system does not exceed 0.6 MPa, Removed. When the amount of the liquid in the autoclave {reaction tank (1)} reached 2000 ml, the PO was stopped, aged at 70 ° C. for 4 hours, 200 g of water was added, and the mixture was heated at 130 to 140 ° C. for 1 hour. After heating for 1 hour, the water was distilled off at atmospheric pressure over 2 hours, and then the remaining water was distilled off under reduced pressure over 3 hours while maintaining the pressure at 30 to 50 torr while passing steam. An adduct (S-1) was obtained.
The glycerin PO adduct used as a raw material was synthesized by a known method, that is, after adding a predetermined amount of propylene oxide to glycerin using tris (pentafluorophenyl) borane as a catalyst, After the heat treatment and dehydration under reduced pressure.

<Example 2>
A glycerin PO adduct (S-2) was obtained in the same manner as in Example 1 except that 2.0 g of chlorodiphenylphosphinopropanerhodium was changed to 0.1 g.

<Example 3>
As in the embodiment shown in FIG. 2, a stainless steel autoclave as a reaction vessel (1) with a 2500 ml capacity stirring device, a temperature control device, a raw material supply line (5), and a distillation column (7) (50 theoretical plates) And a stainless steel cylindrical tube having an inner diameter of 5.5 cm and a length of 3 m) were connected by circulation lines (6) and (8).
After charging 400 g of glycerin PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane in the reaction tank (1), autoclave {reaction tank (1)} and circulation line (6), ( 8) The pressure was reduced to 0.005 MPa. While controlling PO so that the reaction temperature is maintained at 70 to 80 ° C. through the raw material supply line (5), the gas phase in the reaction tank (1) is reduced to 5 L / L using a diaphragm pump. It was made to circulate in order of reaction tank (1)-> circulation line (6)-> distillation tower (7)-> circulation line (8)-> reaction tank (1) with the flow rate of min. The by-product low boiling point compound was removed from the system by separating it from PO in the distillation column (7). The separated by-product low boiling point compound was extracted from the bottom line (9) of the distillation column (7). When the amount of liquid in the autoclave {reactor (1)} reaches 2000 ml, the PO is stopped, the gas phase circulation is terminated, the mixture is aged at 70 ° C. for 4 hours, 200 g of water is added, and 130 to 140 ° C. is added for 1 hour. Heated. After heating for 1 hour, the water was distilled off at atmospheric pressure over 2 hours, and then the remaining water was distilled off under reduced pressure over 3 hours while maintaining the pressure at 30 to 50 torr while passing steam. An adduct (S-3) was obtained.
The glycerin PO adduct used as a raw material was the same as in Example 1.

<Example 4>
In Example 1, instead of glycerin PO adduct (hydroxyl value 280), a predetermined amount of propylene oxide was added to glycerin using potassium hydroxide as a catalyst, and then water and synthetic silicate (Kyowa Chemical Co., Ltd.) were used for catalyst removal. Glycerin PO adduct (S) in the same manner as in Example 1 except that the glycerin PO adduct (hydroxyl value 280) obtained by filtration and dehydration under reduced pressure was added. -4) was obtained.

<Example 5>
As shown in FIG. 3, a stainless steel autoclave as a reaction vessel (1) with a 2500 ml capacity stirring device, a temperature control device, a raw material supply line (5), and a packed tower (11) (stainless steel cylindrical tube) And an inner diameter of 5.5 cm and a length of 50 cm) were connected by circulation lines (10) and (12).
After charging 400 g of glycerin PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane into the reaction tank (1), the pressure in the autoclave {reaction tank (1)} was reduced to 0.005 MPa. did. While controlling PO so as to maintain the reaction temperature at 70 to 80 ° C. through the raw material supply line (5), 80 g which is 1/20 of the total input amount of 1600 g was continuously added to the liquid phase. After the PO was charged, the reaction was carried out for 30 minutes at 75 ° C. for the purpose of reacting the entire amount of the charged PO, and then the reaction solution containing the by-product low boiling point compound (u) was supported by 5% by weight of chlorodiphenylphosphinopropane rhodium. The product was circulated in the circulation lines (10) and (12) using a gear pump to an 80 ° C. packed tower (11) packed with 1 kg of synthetic zeolite and decomposed into (t). After decomposing (u), the step of reacting PO again as a by-product with (u) and decomposing it again in the packed tower (11) was repeated 20 times in total. Thereafter, 200 g of water was added and heated at 130 to 140 ° C. for 1 hour. After heating for 1 hour, the water was distilled off at atmospheric pressure over 2 hours, and then the remaining water was distilled off under reduced pressure over 3 hours while maintaining the pressure at 30 to 50 torr while passing steam. An adduct (S-5) was obtained.
The glycerin PO adduct used as a raw material was the same as in Example 1.

<Example 6>
The PO addition reaction to the PO adduct of glycerin (hydroxyl value 280) was carried out in the same manner as in Example 1, and when the amount of liquid in the autoclave {reaction vessel (1)} reached 1920 ml, the PO addition was stopped, The mixture was aged at 70 ° C. for 4 hours, 200 g of water was added, and the mixture was heated at 130 to 140 ° C. for 1 hour. After heating for 1 hour, the water was distilled off at atmospheric pressure over 2 hours, and then 2 g of potassium hydroxide was added and the remaining water was distilled under reduced pressure while maintaining the pressure at 30-50 torr while passing steam at 130-140 ° C. Left. Subsequently, 80 g of EO was added through the raw material supply line (5) over 2 hours while controlling the reaction temperature to be maintained at 130 to 140 ° C., followed by aging for 2 hours. After cooling to 90 ° C., 12 g of Kyoward 600 (manufactured by Kyowa Chemical Co., Ltd .; synthetic silicate) and 40 g of water were added and treated for 1 hour. After taking out from the autoclave {reaction tank (1)}, it was filtered using 1 micron filter paper and then dehydrated under reduced pressure to obtain a liquid glycerin POEO adduct (S-6).
The glycerin PO adduct used as a raw material was the same as in Example 1.

<Example 7>
The PO addition reaction to the PO adduct of glycerin (hydroxyl value 280) was carried out in the same manner as in Example 2, and when the amount of liquid in the autoclave {reaction vessel (1)} reached 1920 ml, the PO addition was stopped, The mixture was aged at 70 ° C. for 4 hours, 200 g of water was added, and the mixture was heated at 130 to 140 ° C. for 1 hour. After heating for 1 hour, the water was distilled off at atmospheric pressure over 2 hours, and then 2 g of potassium hydroxide was added and the remaining water was distilled under reduced pressure while maintaining the pressure at 30-50 torr while passing steam at 130-140 ° C. Left. Subsequently, 80 g of EO was added through the raw material supply line (5) over 2 hours while controlling the reaction temperature to be maintained at 130 to 140 ° C., followed by aging for 2 hours. After cooling to 90 ° C., 12 g of Kyoward 600 (manufactured by Kyowa Chemical Co., Ltd .; synthetic silicate) and 40 g of water were added and treated for 1 hour. After taking out from the autoclave {reaction tank (1)}, it was filtered using 1 micron filter paper and then dehydrated under reduced pressure to obtain a liquid glycerin POEO adduct (S-7).
The glycerin PO adduct used as a raw material was the same as in Example 1.

<Comparative Example 1>
As in the embodiment shown in FIG. 4, 61 g of glycerin and 4.0 g of potassium hydroxide are charged into a stainless steel autoclave as a reaction tank (1) with a 2500 ml stirring device, a temperature control device, and a raw material supply line (5). Thereafter, PO was added through the raw material supply line (5) while controlling the reaction temperature so as to maintain 90 to 100 ° C. However, PO was continuously introduced over 6 hours. The autoclave {reaction tank (1)} was charged until the amount of the liquid in the autoclave {reaction tank (1)} reached 2000 ml, and then aged at 100 ° C. for 3 hours. Next, 30 g of synthetic silicate (KYOWARD 600, manufactured by Kyowa Chemical) and 40 g of water were added and treated at 90 ° C. for 1 hour. After taking out from the autoclave {reaction tank (1)}, it was filtered through a 1 micron filter and dehydrated for 2 hours to obtain a liquid glycerin PO adduct (n-1).

<Comparative example 2>
As shown in FIG. 4, 80 g of glycerin and 4.0 g of potassium hydroxide are charged into a stainless steel autoclave as a reaction tank (1) with a 2500 ml stirring device, a temperature control device, and a raw material supply line (5). Thereafter, PO was added through the raw material supply line (5) while controlling the reaction temperature so as to maintain 90 to 100 ° C. However, PO was continuously introduced over 6 hours. The autoclave {reaction tank (1)} was charged until the amount of the liquid in the autoclave {reaction tank (1)} reached 2000 ml, and then aged at 100 ° C. for 3 hours. Next, 30 g of synthetic silicate (KYOWARD 600, manufactured by Kyowa Chemical) and 40 g of water were added and treated at 90 ° C. for 1 hour. After taking out from the autoclave {reaction tank (1)}, it was filtered through a 1 micron filter and dehydrated for 2 hours to obtain a liquid glycerin PO adduct. After charging 1530 g of the resulting glycerin PO adduct and 0.09 g of tris (pentafluorophenyl) borane into the autoclave {reaction vessel (1)} again, PO is reacted at a reaction temperature of 70 to 80 ° C. through the raw material supply line (5). It was added over 3 hours while controlling to maintain the above. The autoclave {reaction vessel (1)} was charged until the amount of the liquid in the autoclave {reactor (1)} reached 2000 ml, and aged at 70 ° C. for 3 hours. Subsequently, 200 g of water was added and heated at 130 to 140 ° C. for 1 hour. After heating for 1 hour, the water was distilled off at atmospheric pressure over 2 hours, and then the remaining water was distilled off under reduced pressure over 3 hours while maintaining the pressure at 30 to 50 torr while passing steam. An adduct (n-2) was obtained.

<Comparative Example 3>
A liquid glycerin PO adduct (n-3) was obtained in the same manner as in Comparative Example 2 except that 4.0 g of cesium hydroxide was used instead of 4.0 g of potassium hydroxide.

<Comparative example 4>
As shown in FIG. 4, 84 g of glycerin and 4.0 g of cesium hydroxide were charged in a stainless steel autoclave as a reaction tank (1) with a 2500 ml stirring device, a temperature control device, and a raw material supply line (5). Thereafter, PO was added through the raw material supply line (5) while controlling the reaction temperature so as to maintain 90 to 100 ° C. However, PO was continuously introduced over 6 hours. The autoclave {reaction tank (1)} was charged until the amount of the liquid in the autoclave {reaction tank (1)} reached 2000 ml, and then aged at 100 ° C. for 3 hours. Next, 30 g of synthetic silicate (KYOWARD 600, manufactured by Kyowa Chemical) and 40 g of water were added and treated at 90 ° C. for 1 hour. After taking out from the autoclave {reaction tank (1)}, it was filtered through a 1 micron filter and dehydrated for 2 hours to obtain a liquid glycerin PO adduct. After 1460 g of the obtained glycerin PO adduct and 0.09 g of tris (pentafluorophenyl) borane were charged again into the autoclave {reaction tank (1)}, PO was reacted at a reaction temperature of 70 to 80 ° C. through the raw material supply line (5). It was added over 3 hours while controlling to maintain the above. When the amount of the liquid in the autoclave {reaction vessel (1)} reached 1920 ml, the PO was stopped, aged at 70 ° C. for 4 hours, 170 g of water was added, and the mixture was heated at 130 to 140 ° C. for 1 hour. After the water was distilled off at normal pressure over 2 hours, 2 g of potassium hydroxide was added, and the remaining water was distilled off under reduced pressure while maintaining the pressure at 30-50 torr while introducing steam at 130-140 ° C. Subsequently, 80 g of EO was added through the raw material supply line (5) over 2 hours while controlling the reaction temperature to be maintained at 130 to 140 ° C., followed by aging for 2 hours. After cooling to 90 ° C., 12 g of Kyoward 600 (manufactured by Kyowa Chemical Co., Ltd .; synthetic silicate) and 40 g of water were added and treated for 1 hour. After taking out from the autoclave {reaction tank (1)}, it was filtered using 1 micron filter paper and then dehydrated under reduced pressure to obtain a liquid glycerin POEO adduct (n-5).

The analysis results of the polyoxyalkylene polyols of Examples 1 to 7 and Comparative Examples 1 to 4 are shown in Table 1.
The verification result about Formula 1 (following, Formula (3)) of patent document 4 (patent 3688667 gazette) which the polyoxyalkylene polyol which is a prior art is satisfied was also described.

y ≦ (1.9 × 10 ⁻⁸ ) × w ² (3)
Equation (3) is an equation representing the relationship between the hydroxyl equivalent weight w and the degree of unsaturation y, and is a form corresponding to the equations (1) and (2) in the present invention, that is, the hydroxyl value x and the degree of unsaturation in (S). When transformed into the relational expression of y, the mathematical expression (3 ′) is obtained.
y ≦ 60 × x ⁻² (3 ′)

A method for measuring the hydroxyl value and the degree of unsaturation of the produced polyoxyalkylene polyol and these units are shown below.
Hydroxyl value: Based on JIS K1557-1, unit is mgKOH / g
Unsaturation degree: Conforms to JIS K1557-3, unit is meq / g

<Example 8>
In a four-necked flask equipped with a 2500 ml stirrer and a temperature controller, 162 g of 4,4′-diphenylmethane diisocyanate (trade name: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.), polyoxyalkylene polyol obtained in Example 1 (S-1) 412 g (molecular weight 3000), 26 g of ethylene glycol, and 1390 g of dimethylformamide were charged and reacted at 70 ° C. until the reaction rate (consumption rate) of isocyanate reached 100%. After extending the obtained polyurethane resin solution on a glass plate, urethane resin was obtained by heating at -0.1 MPa and 60 degreeC for 6 hours. The reaction rate of isocyanate groups during the reaction was 60% after 2 hours, 89% after 6 hours, and 100% after 8 hours.

<Example 9>
A urethane resin was synthesized in the same manner as in Example 8 except that the polyoxyalkylene polyol (S-2) was used instead of the polyoxyalkylene polyol (S-1). The reaction rate of isocyanate groups during the reaction was 59% after 2 hours, 90% after 6 hours, and 100% after 8 hours.

<Example 10>
A urethane resin was synthesized in the same manner as in Example 8 except that the polyoxyalkylene polyol (S-3) was used instead of the polyoxyalkylene polyol (S-1). The reaction rate of isocyanate groups during the reaction was 60% after 2 hours, 90% after 6 hours, and 100% after 8 hours.

<Example 11>
A urethane resin was synthesized in the same manner as in Example 8 except that the polyoxyalkylene polyol (S-4) was used instead of the polyoxyalkylene polyol (S-1). The reaction rate of isocyanate groups during the reaction was 58% after 2 hours, 90% after 6 hours, and 100% after 8 hours.

<Example 12>
A urethane resin was synthesized in the same manner as in Example 8 except that the polyoxyalkylene polyol (S-5) was used instead of the polyoxyalkylene polyol (S-1). The reaction rate of isocyanate groups during the reaction was 60% after 2 hours, 91% after 6 hours, and 100% after 8 hours.

<Example 13>
A urethane resin was synthesized in the same manner as in Example 8 except that the polyoxyalkylene polyol (S-6) was used instead of the polyoxyalkylene polyol (S-1). The reaction rate of isocyanate groups during the reaction was 65% after 2 hours, 94% after 6 hours, and 100% after 8 hours.

<Example 14>
A urethane resin was synthesized in the same manner as in Example 8 except that the polyoxyalkylene polyol (S-7) was used instead of the polyoxyalkylene polyol (S-1). The reaction rate of isocyanate groups during the reaction was 66% after 2 hours, 95% after 6 hours, and 100% after 8 hours.

<Comparative Example 5>
A urethane resin was synthesized in the same manner as in Example 8 except that the polyoxyalkylene polyol (n-1) was used instead of the polyoxyalkylene polyol (S-1). The reaction rate of isocyanate groups during the reaction was 30% after 2 hours, 60% after 4 hours, 86% after 8 hours, 96% after 16 hours, and 100% after 24 hours.

<Comparative Example 6>
A urethane resin was synthesized in the same manner as in Example 8 except that the polyoxyalkylene polyol (n-2) was used instead of the polyoxyalkylene polyol (S-1). The reaction rate of isocyanate groups during the reaction was 60% after 2 hours, 88% after 4 hours, and 100% after 8 hours.

<Comparative Example 7>
A urethane resin was synthesized in the same manner as in Example 8 except that the polyoxyalkylene polyol (n-3) was used instead of the polyoxyalkylene polyol (S-1). The reaction rate of isocyanate groups during the reaction was 61% after 2 hours, 87% after 4 hours, and 100% after 8 hours.

<Comparative Example 8>
A urethane resin was synthesized in the same manner as in Example 8 except that the polyoxyalkylene polyol (n-4) was used instead of the polyoxyalkylene polyol (S-1). The reaction rate of the isocyanate groups during the reaction was 65% after 2 hours, 93% after 4 hours, and 100% after 8 hours.

  Table 2 shows physical property values of the polyurethane elastomers obtained in Examples 8 to 14 and Comparative Examples 5 to 8.

From the results in Table 2, it can be seen that the urethane elastomers of Examples 8 to 14 have improved mechanical strength (particularly, elongation at break and tensile strength at break) as compared with the urethane elastomers of Comparative Examples 5 to 8 obtained by the prior art. .
In particular, even when compared with a urethane elastomer (Comparative Example 7) obtained by using a polyoxyalkylene polyol which is a conventional technique that satisfies Formula 1 described in Japanese Patent No. 368867, the mechanical strength of the urethane elastomer obtained by the present invention is It has improved.

The measuring method and unit of the properties of the polyurethane elastomer are shown below.
Tensile strength at break: Conforms to JIS K6251, unit is kgf / cm ²
Breaking elongation: Conforms to JIS K6251, unit is%

<Examples 15 to 21, Comparative Examples 9 to 12>
According to the foaming formulation shown in Tables 3 and 4, polyurethane slab foam was foamed under the following foaming conditions, and after standing for a whole day and night, various physical properties of the polyurethane slab foam were measured. The measured values of physical properties are also shown in Tables 3 and 4, respectively.

(Foaming conditions)
BOX SIZE: 30cm x 30cm x 30cm Empty box Material: Wood Mixing method: Hand mixing

The raw materials of the polyurethane slab foam in the examples and comparative examples are as follows.
1. Urethane catalyst (c)
(1) Urethane catalyst (c-1): “Neostan U-28” (Stanus octoate) manufactured by Nitto Kasei Co., Ltd.
(2) Urethane catalyst (c-2): “TOYOCAT ET” manufactured by Tosoh Corporation (70% by weight dipropylene glycol solution of bis (dimethylaminoethyl) ether)
(3) Urethane catalyst (c-3): “DABCO-33LV” (33% by weight dipropylene glycol solution of triethylenediamine) manufactured by Air Products Japan Co., Ltd.

2. Foaming agent (d)
(1) Foaming agent (d-1): Water (2) Foaming agent (d-2): Methylene chloride

3. Foam stabilizer (e)
(1) Foam stabilizer (e-1): “L-540” manufactured by Toray Dow Corning Co., Ltd.

4). Isocyanate TDI: “Coronate T-80” (tolylene diisocyanate) manufactured by Nippon Polyurethane Industry Co., Ltd.

-The measurement method and unit of foam physical properties are shown below.
Core density: Conforms to JIS K6400, unit is kg / m ³
Breathability (cc / cm / sec): Conforms to JIS L1004 Hardness (25% -ILD): Conforms to JIS K6400, unit is N / 314 cm ²
Tensile strength: Conforms to JIS K6400, unit is kgf / cm ²
Tear strength: Conforms to JIS K6400, unit is kgf / cm
Elongation: Conforms to JIS K6400, unit is%
Compression residual strain ratio: Conforms to JIS K6400, unit is%
Humid heat compression residual strain ratio: Conforms to JIS K6400, unit is%

In Table 3, the urethane foams of Examples 15 to 19 of the present invention have improved foam physical properties, particularly foam hardness and wet heat compression residual strain ratio, as compared with the urethane foams of Comparative Examples 9 to 11 obtained by the prior art.
In particular, even when compared with a urethane foam obtained by using a polyoxyalkylene polyol (Comparative Example 11) which is a conventional technique that satisfies Formula 1 described in Japanese Patent No. 368867, the foam physical properties of the urethane foam obtained by the present invention are as follows. It has improved.

  Also in Table 4, the urethane foams of Examples 20 and 21 of the present invention are urethane foams obtained by using conventional techniques, in particular, polyoxyalkylene polyols which are conventional techniques satisfying Formula 1 described in Japanese Patent No. 368867 (Comparison). As compared with the urethane foam obtained in Example 12), the foam physical properties, particularly the foam hardness and the wet heat compression residual strain ratio are improved.

The polyurethane resin obtained by using the polyoxyalkylene polyol of the present invention can be used in various applications such as foams, elastomers and coating materials. Examples of foams include automotive cushioning materials, sound-absorbing and sound-insulating materials, and steering wheels. Examples of elastomers include cast potting materials. Examples of coating materials include adhesives and paints. The polyoxyalkylene polyol of the present invention is also useful as a raw material for a surfactant composition such as an oil agent, a cleaning agent, and an antifoaming agent for fiber treatment.
The polyurethane elastomers and polyurethane foams using the polyoxyalkylene polyols of the present invention are generally resin properties (tensile strength, hardness, curability, moisture resistance, durability) compared to the case of using polyoxyalkylene polyols obtained by conventional techniques. Excellent.
Therefore, the polyurethane resin of the present invention can be widely used as an adhesive, a sealing material, a coating material, a heat insulating material, a synthetic wood and the like.
Among the polyurethane foam resins of the present invention, the flexible polyurethane foam is excellent in hardness, foam strength, and durability as compared with conventional ones. Therefore, the foamed polyurethane resin of the present invention, particularly the flexible polyurethane foam, can be widely used for cushion materials, shock absorbers, cushioning materials, sound insulation materials, and the like.

1: Reaction tank 2: Condensing equipment 3: Line 4: Exhaust line 5: Raw material supply line 6: Circulation line 7: Distillation tower 8: Circulation line 9: Under-bottle line 10: Circulation line 11: Packing tower 12: Circulation line

Claims (7)

A polyoxyalkylene polyol obtained by adding an alkylene oxide to an active hydrogen-containing compound (H) having 3 or more active hydrogens,
The added alkylene oxide having 3 to 14 carbon atoms is 50 mol% or more based on the number of moles of added alkylene oxide,
5 mol% or more of the terminal structure to which an alkylene oxide having 3 to 14 carbon atoms is added is a structure represented by the general formula (I),
The relationship between the hydroxyl value x, the total unsaturation y, and the ethylene oxide content z is represented by the formula (1).
A polyoxyalkylene polyol (S) having a bifunctional component content of 10% by weight or less based on the weight of the polyoxyalkylene polyol.
y ≦ 28.3 × x ⁻² × (100−z) / 100 (1)
[In Formula (1), x represents the hydroxyl value represented by the unit mgKOH / g, and y represents the total degree of unsaturation represented by the unit meq / g. z is the ethylene oxide content based on the weight of (S), and is 0 to 50% by weight. ]

[In General Formula (I), R ¹ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or a phenyl group, and may be substituted with a halogen atom or an aryl group. Among the residues obtained by removing the structure in parentheses of the formula (I) from the polyoxyalkylene polyol, X is a residue on the active hydrogen-containing compound side, and Y is a residue on the hydroxyl side. ] The polyoxyalkylene polyol according to claim 1, wherein an alkylene oxide is added to the active hydrogen-containing compound (H) in the presence of the Lewis acid catalyst (B). The alkylene oxide is added to the active hydrogen-containing compound (H) in the presence of the Lewis acid catalyst (B) and the catalyst (C) containing a transition metal in the fifth or sixth period of the periodic table. 2. The polyoxyalkylene polyol according to 2. A polyoxyalkylene polyol obtained by adding an alkylene oxide to an active hydrogen-containing compound (H) in the presence of a Lewis acid catalyst (B) is converted into a catalyst containing a transition metal in the fifth or sixth period of the periodic table (C The polyoxyalkylene polyol according to claim 1, which is obtained by treatment with The polyoxyalkylene polyol according to any one of claims 1 to 4, wherein the active hydrogen-containing compound (H) contains 3 to 8 active hydrogens. The polyoxyalkylene polyol according to any one of claims 1 to 5, wherein the number of added moles of alkylene oxide per active hydrogen of the active hydrogen-containing compound (H) is 1 to 200. A foamed or non-foamed polyurethane resin obtained by reacting a polyol component (P) and an organic polyisocyanate component (I), wherein at least a part of the polyol component is a poly. A foamed or non-foamed polyurethane resin using an oxyalkylene polyol.

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