JP5697963B2 - Polymer polyol and method for producing polyurethane using the same - Google Patents

Description

  The present invention relates to a polymer polyol and a method for producing a polyurethane using the polymer polyol. More specifically, the present invention relates to a polymer polyol that is suitable as a polyurethane raw material such as polyurethane foam and polyurethane elastomer and imparts excellent mechanical properties to polyurethane.

Conventionally, as a polymer polyol obtained by polymerizing an ethylenically unsaturated compound containing acrylonitrile in a polyol, acrylonitrile in the ethylenically unsaturated compound is used for the purpose of improving the scorch resistance of a polyurethane foam using the polymer polyol as a raw material. It is required to reduce the ratio (67 mol% or less). As a polymer polyol in which the acrylonitrile ratio in the polymer is lowered to increase the styrene ratio, a polymer polyol having a prescribed particle size distribution (see, for example, Patent Document 1) is known. Further, there is known a polymer polyol (see, for example, Patent Document 2) obtained by a continuous polymerization production method in which the dissolved oxygen concentration is controlled to 5 to 120 ppm and having a coarse particle concentration of 100 μm or more in diameter of 5 to 120 ppm.
On the other hand, when producing a urethane foam with a specific polyol satisfying a specific relationship between the average number of moles of ethylene oxide added per active hydrogen and the primary OH conversion rate of the terminal hydroxyl group, vibration characteristics can be obtained. It is known that a flexible polyurethane foam having good quality can be produced (Patent Document 3). Patent Document 3 describes that a vinyl monomer can be produced by polymerizing the specific polyol in a usual manner.

Japanese Patent Laid-Open No. 11-236499 JP 2005-162791 A JP-A-2005-290202

However, in the production of the specific polyol, there is a problem that a by-product low molecular weight monool is generated and the total degree of unsaturation in the specific polyol is increased. And the polyurethane foam which used the polymer polyol manufactured using this specific polyol as a raw material has the problem that foam hardness, mechanical property, and moisture resistance are inadequate.
The object of the present invention is to provide a polymer polyol that solves these problems.

［一般式（１）中、Ｒ¹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。アルキル基、シクロアルキル基又はフェニル基は、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。］

［一般式（２）中、Ｒ²は、活性水素含有化合物（Ｈ）からｍ個の活性水素を除いたｍ価の基；Ｚは下記一般式（３）又は（４）で表される炭素数２〜１２のアルキレン基又はシクロアルキレン基である。アルキレン基又はシクロアルキレン基は、ハロゲン原子又はアリール基で置換されていてもよい。；Ａは下記一般式（５）又は（６）で表される炭素数３〜１２のアルキレン基又はシクロアルキレン基である。アルキレン基又はシクロアルキレン基は、ハロゲン原子又はアリール基で置換されていてもよい。；複数のＺ又はＡがある場合、それぞれは同一でも異なっていてもよい；ｍは２〜１００の整数；ｐは０以上２００以下の整数、ｑは１以上２００以下の整数；ｒは０以上２００以下の整数である。］

［一般式（３）及び（４）中、Ｒ³は水素原子、又は炭素数１〜１０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。アルキル基、シクロアルキル基又はフェニル基は、ハロゲン原子又はアリール基で置換されていてもよい。；一般式（５）及び（６）中、Ｒ⁴は炭素数１〜１０のアルキル基、シクロアルキル基又はフェニル基を表す。アルキル基、シクロアルキル基又はフェニル基は、ハロゲン原子又はアリール基で置換されていてもよい。］
ｙ≦２８．３×ｘ^-2×（１００−ｚ）／１００ （１）
［数式（１）中、ｘは単位ｍｇＫＯＨ／ｇで表される水酸基価、ｙは単位ｍｅｑ／ｇで表される総不飽和度を表す。ｚは、（ａ）の重量を基準とするエチレンオキサイド単位含有量であり、０〜５０重量％である。］
また、本発明のポリウレタンの製造方法は、ポリオール成分とイソシアネート成分とを反応させてポリウレタンを製造する方法において、ポリオール成分としてこのポリマーポリオール（Ａ）をポリオール成分の重量を基準として１０〜１００重量％含有するポリオール成分を用いることを要旨とする。
That is, the polymer polyol (A) of the present invention is a polymer polyol in which polymer fine particles (JR) having an ethylenically unsaturated compound (E) as a constituent unit are contained in the polyol (PL), wherein (PL) is The gist is to contain the following polyol (a).
Polyol (a): an alkylene oxide adduct of the active hydrogen-containing compound (H), wherein 40% or more of the hydroxyl groups located at the terminals are primary hydroxyl group-containing groups represented by the following general formula (1). Of the part of (AO) q in the general formula (2) represented by the general formula (2), 40% or more of the structure of A located at the terminal is the structure represented by the general formula (6). The polyoxyalkylene polyol in which the hydroxyl value x, the total degree of unsaturation y, and the ethylene oxide unit content z satisfy the relationship of formula (1).

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

[In general formula (2), R ² is an m-valent group obtained by removing m active hydrogens from the active hydrogen-containing compound (H); Z is a carbon represented by the following general formula (3) or (4) It is an alkylene group or a cycloalkylene group having a number of 2 to 12. The alkylene group or cycloalkylene group may be substituted with a halogen atom or an aryl group. ; A is a C3-C12 alkylene group or cycloalkylene group represented by the following general formula (5) or (6). The alkylene group or cycloalkylene group may be substituted with a halogen atom or an aryl group. When there are a plurality of Z or A, each may be the same or different; m is an integer of 2 to 100; p is an integer of 0 to 200, q is an integer of 1 to 200; r is 0 or more It is an integer of 200 or less. ]

[In General Formulas (3) and (4), R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, 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. In the general formulas (5) and (6), R ⁴ represents an alkyl group having 1 to 10 carbon atoms, 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. ]
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 unit content based on the weight of (a), and is 0 to 50% by weight. ]
The polyurethane production method of the present invention is a method for producing a polyurethane by reacting a polyol component and an isocyanate component. In this method, the polymer polyol (A) is used as a polyol component in an amount of 10 to 100% by weight based on the weight of the polyol component. The gist is to use the polyol component contained.

The polyurethane obtained by using the polymer polyols (A) and (A) of the present invention has the following effects.
(1) The polyurethane foam produced using the polymer polyol (A) improves the mechanical properties and moisture resistance of the polyurethane, such as good hardness.

6 is a diagram showing a process flow of Production Example 1. FIG.

The polymer polyol in the present invention is obtained by polymer fine particles (JR) obtained by polymerizing an ethylenically unsaturated compound (E) as a structural unit in the polyol (PL).
The polyol (PL) contains the polyol (a) as an essential component.
The polyol (a) is an alkylene oxide adduct of the active hydrogen-containing compound (H), and 40% or more of the hydroxyl groups located at the terminals are primary hydroxyl group-containing groups represented by the following general formula (1). The polyoxyalkylene polyol in which the hydroxyl value x, the total degree of unsaturation y, and the ethylene oxide unit content z satisfy the relationship of the following formula (1).

y ≦ 28.3 × x ⁻² × (100−z) / 100 (1)

  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. If x is 5 mgKOH / g or more, the viscosity of the polyoxyalkylene polyol is low and easy to handle, and if it is 280 mgKOH / g or less, the elongation property of the synthesized polyurethane is good. In addition, x is calculated | required by JISK-1557.

y is the total unsaturation degree (meq / g) of the polyoxyalkylene polyol, and is determined according to JISK-1557.
The range of y is preferably 0 to 0.04, more preferably 0 to 0.02, particularly preferably 0 to 0.01 from the viewpoint of mechanical properties of polyurethane. When y is in this range, it means that the degree of unsaturation is small. In particular, the polyol (a) used in the present invention means that the monool content is small.

  Z is the ethylene oxide unit content (% by weight) based on the weight of the polyol (a). The range of z is 0-50, preferably 0-25, particularly preferably 0-20. When z exceeds 50, the polyurethane moisture resistance is deteriorated.

In addition, Numerical formula (1) can also represent the hydroxyl value x also by the hydroxyl equivalent w, In that case, the hydroxyl equivalent w, total unsaturation degree y, and ethylene oxide unit content z satisfy | fill the relationship of Numerical formula (2). The hydroxyl group equivalent w is a value obtained by dividing the number average molecular weight of the polyol (a) by the number average hydroxyl number of (a).
y ≦ (9.0 × 10 ⁻⁹ ) w ² × (100−z) / 100 (2)

  The number average molecular weight (hereinafter abbreviated as Mn) of the polyol (a) is preferably from 500 to 20,000, more preferably from the viewpoint of the mechanical properties of the polyurethane, the low viscosity of the polymer polyol, and the handleability of the polymer polyol. Is 1,200 to 15,000, particularly preferably 2,000 to 9,000.

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

More preferably, (a) satisfies the relationship of Equation (3).
y ≦ 18.9 × x ⁻² × (100−z) / 100 (3)
In (a) satisfying the mathematical formula (3), the amount of unsaturated monool is reduced as compared with the case where the mathematical formula (1) is satisfied, and a polyurethane or polyurethane foam machine produced using such a polyoxyalkylene polyol is used. Physical properties are further improved.

The polyol (a) is an alkylene oxide adduct of the active hydrogen-containing compound (H).
Examples of the active hydrogen compound (H) include a compound having 2 to 8 or more polyvalent hydroxyl groups, an amino group-containing compound having polyvalent active hydrogen, a polyvalent carboxyl group-containing compound, a polyvalent thiol group-containing compound, And phosphoric acid compounds having active hydrogen; and compounds having two or more active hydrogen-containing functional groups in the molecule; and mixtures of two or more thereof.

Examples of the polyhydric hydroxyl group-containing compound include water, divalent to octavalent polyhydric alcohols and polyhydric phenols. Specifically, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane and 1,4-bis (hydroxyethyl) Dihydric alcohols such as benzene; Trihydric alcohols such as glycerin and trimethylolpropane; 4- to 8-valent alcohols such as pentaerythritol, sorbitol, and sucrose; pyrogallol, catechol, and hydroquinone Polyphenols; bisphenols such as bisphenol A, bisphenol F and bisphenol S; polybutadiene polyols; castor oil-based polyols; (co) polymers of hydroxyalkyl (meth) acrylates and polyfunctionals such as polyvinyl alcohol ( For example, sensuality The number 2-100) polyols, and the like.
(Meth) acrylate means methacrylate and / or acrylate, and the same applies hereinafter.

  Examples of the amino group-containing compound having a polyvalent active hydrogen include amines, polyamines and amino alcohols. Specifically, ammonia; monoamines such as C1-C20 alkylamine (butylamine and the like) and aniline; aliphatic polyamines such as ethylenediamine, hexamethylenediamine and diethylenetriamine; heterocyclics such as piperazine and N-aminoethylpiperazine Polyamines; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; aromatic polyamines such as phenylenediamine, tolylenediamine and diphenylmethanediamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and dicarboxylic acids Polyamide polyamine obtained by condensation with excess polyamine; polyether polyamine; hydrazine (such as hydrazine and monoalkylhydrazine), dihydrazide ( Etc. Haq acid dihydrazide and dihydrazide terephthalate), guanidine (butyl guanidine and 1-cyanoguanidine, etc.); dicyandiamide; and mixtures of two or more thereof.

  Polyvalent carboxyl group-containing compounds include: aliphatic polycarboxylic acids such as succinic acid and adipic acid; aromatic polycarboxylic acids such as phthalic acid and trimellitic acid; polycarboxylic acid heavy compounds such as (co) polymers of acrylic acid Combined (functional group number 2-100) etc. are mentioned.

Examples of the polyvalent thiol group-containing compound include polythiol compounds, and examples include divalent to octavalent polyvalent thiols. Specific examples include ethylenedithiol and 1,6-hexanedithiol.
Examples of the phosphoric acid compound having polyvalent active hydrogen include phosphoric acid, phosphorous acid, and phosphonic acid.

Of these active hydrogen-containing compounds (H), from the viewpoint of the mechanical properties of polyurethane, polyhydric hydroxyl group-containing compounds and amino group-containing compounds having polyvalent active hydrogen are preferred, and water, polyhydric alcohols and amines are particularly preferred. It is.
The active hydrogen equivalent of the active hydrogen-containing compound is preferably 20 to 300 from the viewpoint of mechanical properties of the resulting polyurethane.

  Examples of the alkylene oxide (hereinafter abbreviated as AO) to be added to the active hydrogen-containing compound (H) include AO having 2 to 6 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter referred to as AO). , Abbreviated as PO), 1,3-propyloxide, 1,4-butylene oxide, and the like. Among these, PO and EO are preferable from the viewpoint of mechanical properties of polyurethane. 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.

  AO is preferably composed only of C3 or more 1,2-AO and EO, but in addition to these, AO other than these is contained in a small proportion (for example, 5% by weight or less based on the weight of the total AO). You may go out. In the AO to be used, the content of 1,2-AO of C3 or more is preferably 50% by weight or more, more preferably 70% by weight or more based on the weight of all AOs, from the viewpoint of the moisture resistance of the resulting polyurethane. .

  The AO adduct of the active hydrogen-containing compound (H) includes a polyoxyalkylene polyol represented by the following general formula (2).

In the general formula (2), R ² is an m-valent group obtained by removing m active hydrogens from the active hydrogen-containing compound (H). m is the number of active hydrogens which (H) has, and is a number of 2-100.
m is preferably 50 or less, more preferably 10 or less, from the viewpoint of the viscosity of the polyol and the mechanical properties of the polyurethane.

  In said general formula (2), Z represents a C2-C12 alkylene group or cycloalkylene group represented by the following general formula (3) or (4). The alkylene group or cycloalkylene group may be substituted with a halogen atom or an aryl group.

In the general formulas (3) and (4), R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, 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 Z include ethylene group, propylene group, butylene group, chloropropylene group, phenylethylene group, 1,2-cyclohexylene group and the like, and combinations of two or more thereof. From the viewpoint of productivity of the polyol (a), a propylene group, a butylene group, and an ethylene group are preferable. When taking into consideration ensuring the hydrophobicity of the resulting polyol (a), a propylene group, a butylene group or the like may be used, or an ethylene group and another alkylene group may be used in combination.

  In the general formula (2), A is a C 3-12 alkylene group or cycloalkylene group represented by the following general formula (5) or (6). The alkylene group or cycloalkylene group may be substituted with a halogen atom or an aryl group.

In general formulas (5) and (6), R ⁴ represents an alkyl group having 1 to 10 carbon atoms, 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 A include a propylene group, a butylene group, a chloropropylene group, a phenylethylene group, a 1,2-cyclohexylene group, and a combination of two or more thereof. Among these, a propylene group and a butylene group are preferable from the viewpoint of productivity of the polyol (a).

  When there are a plurality of Z or A, each may be the same or different.

In general formula (2), p and r are 0 or an integer of 1 or more and 200 or less. q is an integer of 1 or more and 200 or less.
From the viewpoint of the viscosity of the polyol (a), p + q + r is preferably an integer of 1 or more and 400 or less, more preferably 200 or less.

  Among those represented by the general formula (2), those in which r is 0 represent that EO is not added to the terminal portion of the polyol (a).

Among those represented by the general formula (2), 40% or more of the structure of A located at the terminal in the portion of (AO) _{q in} the general formula (2) is represented by the general formula (6). The structure is preferably 50% or more, more preferably 65% or more. Within this range, it is easy to satisfy the relationship of Equation (1).

The polyol (a) is a primary hydroxyl group-containing group in which 40% or more of the hydroxyl groups located at the terminals are represented by the general formula (1).
For example, when (a) is represented by the above general formula (2), the hydroxyl group-containing group located at the terminal includes a primary hydroxyl group-containing group represented by the above general formula (1) and r = 0. Two types of secondary hydroxyl group-containing groups represented by the following general formula (7) can be considered, but (a) is a hydroxyl group located at the terminal regardless of the value of r in the general formula (2). 40% or more is the primary hydroxyl group-containing group represented by the general formula (1).
In (a), the ratio of the primary hydroxyl group-containing group represented by the general formula (1) to the total hydroxyl groups at the ends (this is the primary hydroxyl group ratio in the present specification. The same applies hereinafter. Is 40% or more based on the amount of all terminal hydroxyl groups in (a), and is preferably 60% or more, more preferably 65% or more, from the viewpoint of the reactivity of (a). When the primary hydroxyl group ratio is less than 40%, the reactivity as a polyol component is insufficient.

R ¹ in the above general formula (1) represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group or a phenyl group, and the alkyl group, cycloalkyl group or phenyl group is a halogen atom or an aryl group. May be substituted. R ⁵ in the general formula (7) represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or a phenyl group, and the alkyl group, the cycloalkyl group, or the phenyl group may be substituted with a halogen atom or an aryl group. Good.
Specific examples of R ¹ 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. Specific examples of R ⁵ include those obtained by removing a hydrogen atom from R ¹ .

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 hydroxyl group at the end of the 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 number average molecular weight of the polyol (a) is appropriately selected depending on the use of (a), for example, the required physical properties of a thermosetting resin such as polyurethane to be produced, and is not particularly limited. , 000 is preferred, preferably 400-20,000.

  Specific examples of the polyol (a) include water EO adduct, water PO adduct, glycerin EO adduct, glycerin PO adduct, water EO / PO copolymer adduct, water PO / butylene oxide. Examples thereof include a copolymerization adduct, an EO / PO copolymerization adduct of glycerin, a copolymerization adduct of EO / PO / butylene oxide with water, and a copolymerization adduct of EO / PO / butylene oxide with glycerin.

The active hydrogen-containing compound (J) represented by the following general formula (8) can be produced by a generally known method. For example, an active hydrogen-containing compound (H) is opened with AO having 2 to 12 carbon atoms. It can manufacture by cycloaddition polymerization and the catalyst of this polymerization is not specifically limited.
The polyol (a) is obtained by ring-opening addition polymerization of AO having 3 to 12 carbon atoms to (J) in the presence of the catalyst (C) to obtain an active hydrogen compound (K) represented by the following general formula (9). Can be obtained at Moreover, you may carry out 0-50 weight% ring-opening addition polymerization of EO at the terminal of (K) as needed. The method for the ring-opening addition weight of EO to (K) may be the conditions known in the art, and the catalyst is not particularly limited. When EO is not addition-polymerized at the end of (K), (K) is (a), and the hydroxyl value x and total unsaturation y of (a) obtained satisfy the relationship of formula (1). Just do it.

In the general formula (8), R ² , Z, p, and m are the same as those in the general formula (2), and the above can be exemplified in the same manner.
In General Formula (9), R ² , Z, A, p, q, and m are the same as those in General Formula (2), and the above-described products can be exemplified in the same manner.

  Specific examples of the active hydrogen-containing compound (J) include those similar to those described above as the active hydrogen-containing compound (H) when p is 0.

When p is 1 or more, examples thereof include compounds obtained by adding AO having 2 to 12 carbon atoms to the above-mentioned p having 0, that is, (H). The catalyst used in the addition reaction is not limited.
For example, specific examples of (J) include adducts such as EO, PO, and butylene oxide to (H), and more specifically, an EO adduct of water, a PO adduct of water, and glycerin. EO adduct, glycerin PO adduct, water EO / PO copolymer adduct, water PO / butylene oxide copolymer adduct, glycerin EO / PO copolymer adduct, glycerin EO / butylene oxide copolymer Examples include adducts, PO / butylene oxide copolymerization adducts of glycerin, EO / PO / butylene oxide copolymerization adducts of water, and EO / PO / butylene oxide copolymerization adducts of glycerin.

Examples of the active hydrogen-containing compound (K) include compounds obtained by addition polymerization of AO having 3 to 12 carbon atoms to the active hydrogen-containing compound (J). Since the polyol (a) can be easily obtained, the catalyst used in this addition polymerization is preferably the catalyst (C).
For example, (K) includes adducts such as PO and butylene oxide to (J).

  The catalyst (C) is a compound represented by the following general formula (10-1), (10-2) or (10-3). Using this, ring-opening addition polymerization of AO having 3 to 12 carbon atoms yields a ring-opening polymer with good yield, and a polyol (a) having a high primary hydroxyl group ratio of terminal hydroxyl groups is obtained. .

  In the general formulas (10-1), (10-2), and (10-3), X represents a boron atom or an aluminum atom, respectively. From the viewpoint of reactivity, a boron atom is preferable.

R ⁶ in the general formula (10-1), (10-2) or (10-3) is a (substituted) phenyl group represented by the following general formula (11) and / or the following general formula (12). When the tertiary alkyl group represented and there are a plurality of R ⁶ groups, the plurality of R ⁶ groups may be the same or different.

Y in the general formula (11) 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 (11) 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 ⁷ , R ⁸ or R ^{9 in the} general formula (12) each independently represents an alkyl group having 1 to 4 carbon atoms and 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 (12) include a t-butyl group and a t-pentyl group.

  Specific examples of the catalyst (C) include triphenylborane, diphenyl-t-butylborane, tri (t-butyl) borane, triphenylaluminum, and tris (pentafluorophenyl) borane.

  In the presence of the catalyst (C), AO is added to the active hydrogen-containing compound (J) to obtain the active hydrogen compound (K), and the number of moles of AO to be added is the active hydrogen-containing compound (J). The amount is preferably 1 to 200 mol, more preferably 1 to 100 mol, based on the molecular weight of the ring-opening polymer to be produced and its use.

  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%.

  When AO is added to the active hydrogen-containing compound (J) in the presence of the catalyst (C) to obtain the active hydrogen compound (K) represented by the general formula (9), the pressure is 0.1 MPa. It is preferable to continuously or intermittently remove the by-product low-boiling compound (t) having a boiling point of 150 ° C. or lower, because a polyol (a) satisfying the above-described formula (1) is easily obtained. The removal method may be carried out by any of the commonly known methods. For example, a method of removing (t) from the reaction mixture by heating and / or decompressing, a method of removing the gas phase in the reaction vessel from the reaction vessel using a gas-phase circulation pump, and removing the (t) with an adsorbent, a reaction A method in which the gas phase in the tank is extracted from the reaction tank using a gas-phase circulation pump (t) is reacted with a catalyst to separate it as a high-boiling compound, and the gas phase in the reaction tank is extracted using a gas-phase circulation pump. For example, there is a method of extracting (t) from the reaction tank and separating it by distillation.

  Specific examples 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 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 polyol (a) when adding AO.

  When AO is added to the active hydrogen-containing compound (J), the active hydrogen-containing compound (J), AO, and the catalyst (C) may be charged together and reacted, or the active hydrogen-containing compound ( A) may be dropped to react with the mixture of J) and catalyst (C), or AO and the catalyst (C) may be dropped to react with the active hydrogen-containing compound (J). From the viewpoint of controlling the reaction temperature, AO is dropped into a mixture of the active hydrogen-containing compound (J) and the catalyst (C), or AO and the catalyst (C) are dropped into the active hydrogen-containing compound (J). Is preferred.

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

  The polyol (a) obtained when the EO is not added and polymerized to the produced active hydrogen-containing compound (K) contains the catalyst (C). Depending on the application, decomposition of the catalyst (C) and Execute removal process.

  As a decomposition method, there is a method of adding water and / or an alcohol compound and, if necessary, a basic substance such as an alkali compound or an amine compound. As the alcohol compound, the aforementioned polyhydric alcohol and / or polyhydric phenol can be used. Moreover, as alcohol compounds, monovalent alcohols such as methanol, ethanol, butanol and octanol, and phenols such as phenol and cresol 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. As the amine compound, one or more selected from the aforementioned amino group-containing compounds having polyvalent active hydrogen can be used. 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. The water or alcohol compound 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 or amine 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 removing method, any known method 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.)} 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.

  Two or more of the polyols (a) used in the present invention may be used in combination. The average number of functional groups per molecule of (a) is preferably 2 to 6, more preferably 2.5 to 4.5, from the viewpoint of the physical properties of polyurethane (compression set, elongation, etc.).

The polyol (PL) contains the polyol (a) as an essential component, but may contain other polyols (a2). (A2) is a polyol that does not correspond to the polyol (a), and is a known polyol used in the production of polymer polyols (Japanese Patent Laid-Open Nos. 2005-162791, 2004-018543, and 2004-002800). Publications (corresponding to US Patent Application: US2005 / 245724 A1) etc. can be used.
Specific examples of the polyol (a2) include compounds having a structure in which AO is added to the aforementioned active hydrogen-containing compound (H) and mixtures thereof. Among these, AO adducts of polyhydric alcohols are preferred from the viewpoint of mechanical properties of polyurethane.

  Examples of the AO include those described above. Of these AOs, C2-8 are preferred from the viewpoint of the mechanical properties of the resulting polyurethane, more preferably EO, PO, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran, styrene. Oxides and combinations of two or more of these (block addition and / or random addition), particularly preferably, PO or a combination of PO and EO [EO content is 25% by weight or less based on the weight of (PL), preferably 1 to 20% by weight].

  Specific examples of the AO adduct include PO adducts and POs of known active hydrogen-containing compounds {JP 2005-162791 A, JP 2004-002800 A (corresponding US patent application: US 2005/245724 A1)}. And other AO (EO is preferred).

  Two or more of the polyols (a2) used in the present invention may be used in combination. The average number of functional groups per molecule, hydroxyl equivalent, hydroxyl value, and Mn in (a2) are the same as those in the polyol (a) described above, and the preferred ranges are also the same.

  The content (% by weight) of the polyol (a) in the polyol (PL) is preferably 20 to 100, more preferably 30 to 100, based on the weight of (PL), from the viewpoint of the mechanical properties of the resulting polyurethane. Next, it is more preferably 40-100.

  The average number of functional groups per molecule, hydroxyl equivalent, hydroxyl value, and Mn of the polyol (PL) are the same as those of the polyol (a) described above, and the preferred ranges are also the same.

  The polymer polyol (A) of the present invention is obtained by polymerizing the ethylenically unsaturated compound (E) in the polyol (PL) to produce polymer fine particles (JR).

  As the ethylenically unsaturated compound (E), styrene (hereinafter abbreviated as St), acrylonitrile (hereinafter abbreviated as ACN), other ethylenically unsaturated monomers (e), and the like can be used. (E) preferably includes St and / or ACN as essential components.

  The St content (% by weight) is preferably from 49 to 100, more preferably from 51 to 91, and still more preferably from the viewpoint of the discoloration of polyurethane and the content of coarse particles, based on the total weight of (E). 57-82, most preferably 66-78.

  The content (% by weight) of ACN is preferably 0 to 51, more preferably 9 to 49, and still more preferably 18 to 43, most preferably, based on the total weight of (E), from the same viewpoint as above. Is 22-34.

  The weight ratio of St to ACN (St: ACN) is preferably 100: 0 to 49:51, more preferably 57:43 to 82:18, and most preferably 78:22 to 66 from the same viewpoint as described above. : 34.

  As other ethylenically unsaturated monomers (e), C2 or more and Mn {Mn are measured by gel permeation chromatography (GPC). } There is no particular limitation as long as it is less than 1,000 and can be copolymerized with St and / or ACN, and the following monofunctional ones {unsaturated nitrile (e1), aromatic ring-containing monomer (e2) , (Meth) acrylic acid ester (e3), polyoxyalkylene ether of α-alkenyl group-containing compound and AO adduct (e4) of unsaturated ester having a hydroxyl group and other ethylenically unsaturated monomers (e5)} and many A functional monomer (e6) etc. can be used. These may be used alone or in combination of two or more.

Examples of (e1) include methacrylonitrile.
Examples of (e2) include α-methylstyrene, hydroxystyrene, and chlorostyrene.
(E3) includes (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, butyl (meth) acrylate and docosyl (meth) acrylate (alkyl group is C1-24); hydroxypolyoxyalkylene (alkylene group is C2 -8) Mono (meth) acrylate and the like.
In addition, (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester. The same notation is used for (meth) acrylic acid and (meth) allyl in the following.

Examples of the (poly) oxyalkylene ether of the (e4) α-alkenyl group-containing compound include AO adducts of C3-24 unsaturated alcohols, and terminal unsaturated alcohols are preferably used as the unsaturated alcohols. Examples of the terminal unsaturated alcohol include allyl alcohol, 2-buten-1-ol, 3-buten-2-ol, 3-buten-1-ol, and 1-hexen-3-ol.
Examples of AO adducts of unsaturated esters having hydroxyl groups include AO adducts of unsaturated esters having C3-24 hydroxyl groups. Examples of unsaturated compound esters having hydroxyl groups include hydroxyethyl (meth) acrylate and hydroxypropyl. Examples include (meth) acrylate.

Examples of the AO include C2-12, and examples thereof include EO, PO, BO, tetrahydrofuran (hereinafter abbreviated as THF), and combinations of two or more thereof (random addition and / or block addition). AO is preferably PO and / or EO from the viewpoint of dispersion stability and viscosity.
The number of moles of AO added is preferably 1 to 9, more preferably 1 to 6, and still more preferably 1 to 3, from the viewpoints of dispersion stability and viscosity.

  Other ethylenically unsaturated monomers (e5) are preferably C2-24 ethylenically unsaturated monomers, vinyl group-containing carboxylic acids such as (meth) acrylic acid; aliphatic hydrocarbon monomers such as ethylene and propylene; Fluorine-containing vinyl monomers such as fluorooctylethyl methacrylate and perfluorooctylethyl acrylate; nitrogen-containing vinyl monomers such as diaminoethyl methacrylate and morpholinoethyl methacrylate; vinyl-modified silicones; cyclic olefins and cyclic dienes such as norbornene, cyclopentadiene and norbornadiene; etc. Is mentioned.

  As the polyfunctional monomer (e6), C8-40 polyfunctional monomers are preferable, and divinylbenzene, ethylene di (meth) acrylate, polyalkylene oxide glycol di (meth) acrylate, pentaerythritol triallyl ether and trimethylolpropane tri (meth). ) Acrylate and the like.

  Of (e1) to (e6), from the viewpoint of the viscosity of the polymer polyol and the physical properties of the polyurethane, (e3), (e4) and (e6) are preferable, more preferably (e4) and (e6), particularly preferably. PO and / or EO adducts of terminal unsaturated alcohols and bifunctional monomers, most preferably PO adducts of allyl alcohol and divinylbenzene.

The polymer polyol (A) of the present invention is a polymer polyol in which polymer fine particles (JR) having an ethylenically unsaturated compound (E) as a constituent unit are contained in the polyol (PL). The volume average particle diameter (R) of the polymer fine particles (JR) is preferably from 0.1 to 1.5 μm, more preferably from 0.25 to 1.2 μm, from the viewpoint of the viscosity of the polymer polyol and the physical properties of the polyurethane. More preferably, it is 0.3-1.1 micrometers, Most preferably, it is 0.4-0.9 micrometers.
The volume average particle diameter is measured by the method described later.

  The shape of the polymer fine particles (JR) is not particularly limited, and may be any shape such as a spherical shape, a spheroid shape, and a flat plate shape, but a spherical shape is preferable from the viewpoint of mechanical properties of polyurethane.

  The polymer fine particle (JR) content (% by weight) in the polymer polyol (A) is preferably 30 to 75, more preferably 32, from the viewpoint of mechanical properties of polyurethane and prevention of aggregation of (JR) in the polymer polyol. -60, particularly preferably 35-57, most preferably 38-55. The (JR) content is measured by the following method.

<Content of polymer particles (JR)>
About 5 g of polymer polyol is precisely weighed in a 50 ml centrifuge tube for centrifugal separation made of SUS, and the weight is set to the weight of polymer polyol (W1). Dilute with 15 g of methanol. Using a cooling centrifuge [model number: GRX-220, manufactured by Tommy Seiko Co., Ltd.], centrifuge at 18,000 rpm for 60 minutes at 20 ° C. The supernatant is removed using a glass pipette. The operation of adding 15 g of methanol to the residual sediment, diluting, and centrifuging in the same manner as above to remove the supernatant is repeated three more times. The residual sediment in the centrifuge tube is dried under reduced pressure at 2,666-3,999 Pa (20-30 torr) at 60 ° C. for 60 minutes, the dried sediment is weighed, and the weight is defined as (W2). The value calculated by the following formula is the polymer particle content (% by weight).

Polymer particle content (% by weight) = (W2) × 100 / (W1)

  The content (% by weight) of the polyol (PL) in the polymer polyol (A) is preferably from 25 to 70, more preferably from the viewpoint of preventing aggregation of the polymer fine particles (JR) and mechanical properties of the resulting polyurethane. To 68, particularly preferably 43 to 65, and most preferably 45 to 62.

The viscosity (mPa · s) of the polymer polyol (A) is preferably 1,250 to 12,000, more preferably 1,500 to 10,000, and most preferably 2,500 to 8,8, from the viewpoint of moldability. 000.
The viscosity of the polymer polyol is measured by a method described in JIS K1557-5: 2007 at 25 ° C. using a Brookfield viscometer.

  The polymer polyol (A) of the present invention is obtained by a method of polymerizing the ethylenically unsaturated compound (E) in the polyol (PL) to produce polymer fine particles (JR).

  Examples of the polymerization method include radical polymerization, coordination anion polymerization, metathesis polymerization, Diels-Alder polymerization, and the like. Radical polymerization is preferable from an industrial viewpoint.

  In the radical polymerization, for example, a method of polymerizing the ethylenically unsaturated compound (E) in the presence of the radical polymerization initiator (K) in the polyol (PL) containing the dispersant (B) (described in US Pat. No. 3,383,351). Can be used.

  Examples of the radical polymerization initiator (K) include azo compounds and peroxides {things described in JP 2005-162791 A, JP 2004-002800 A (corresponding US patent application: US 2005/245724 A1)}. Can be used. Further, the 10-hour half-life temperature of (K) is preferably 30 to 150 ° C., more preferably 40 to 140 ° C., particularly preferably from the viewpoint of the polymerization rate and polymerization time of (E) and the productivity of the polymer polyol. 50-130 ° C.

  The amount (% by weight) of (K) used is preferably 0.05 to 20, more preferably 0 based on the total weight of (E) from the viewpoint of the degree of polymerization of (E) and the mechanical properties of the resulting polyurethane. .1 to 5, particularly preferably 0.2 to 2.

As the dispersant (B), a dispersant having a Mn of 1,000 or more (preferably 1,000 to 10,000), for example, a known dispersant used in the production of polymer polyol {Japanese Patent Laid-Open No. 2005-162791 , JP 2004-002800 (corresponding to US Patent Application: US2005 / 245724 A1), etc. can be used, and (B) includes an ethylenically unsaturated copolymerizable with St or ACN. And reactive dispersants having groups and non-reactive dispersants that do not copolymerize with St or ACN.
In the present invention, the reactive dispersant containing an ethylenically unsaturated group has a Mn of 1,000 or more, and is distinguished from an ethylenically unsaturated compound (E) having a Mn of less than 1,000.

Specific examples of the dispersant (B) include the following.
[1] A modified polyol obtained by reacting at least a part of the hydroxyl groups of the polyol (PL) with an alkylene dihalide such as methylene dihalide (described in JP-A-07-196749);
[2] Ethylenically unsaturated group-containing modified polyol obtained by further reacting the modified polyol of [1] with an ethylenically unsaturated group-containing compound {JP 08-333508 A, JP 2004-002800 A (corresponding) US Patent Application: US2005 / 245724 A1)};
[3] A difference in solubility parameter with a polymer of an ethylenically unsaturated compound having two or more (PL) affinity segments having a solubility parameter difference with a polyol (PL) of 1 or less is a side chain. Graft type polymer having a polymer fine particle (JR) affinity segment as the main chain (as described in JP-A-05-059134;
[4] Weight average molecular weight (hereinafter abbreviated as Mw), at least a part of which is soluble in polyol (PL) [measurement is by gel permeation chromatography (GPC) method. ] Of 1,000 to 30,000 vinyl-based oligomers and dispersants using ethylenically unsaturated group-containing modified polyols obtained by reacting these oligomers and modified polyols of [1] (Japanese Patent Laid-Open No. 09-77968) As described);
[5] A dispersant comprising a nitrogen-containing bond-containing unsaturated polyol in which a polyol (PL) and a monofunctional active hydrogen-containing compound having at least one ethylenically unsaturated group are bonded via a polyisocyanate 2002-308920 (as described in corresponding US Pat. No. 6,756,414);
Among these, [2], [4] and [5] are preferable from the viewpoint of the particle diameter of the polymer fine particles (JR), and [5] is particularly preferable.

  From the viewpoint of the particle diameter of the polymer fine particles (JR) and the viscosity of the polymer polyol, the amount of use (% by weight) of the dispersant (B) is preferably 2 to 20, more preferably, based on the weight of the polyol (PL). Is 5-15.

In the radical polymerization, a diluting solvent (c) may be used if necessary. (C) includes C6-10 aromatic hydrocarbons (toluene, xylene, etc.); C5-15 saturated aliphatic hydrocarbons (hexane, heptane, normal decane, etc.); C5-30 unsaturated aliphatic hydrocarbons (Octene, nonene, decene, etc.); and other known solvents (for example, those described in JP-A-2005-162791). Among (c), an aromatic hydrocarbon is preferable from the viewpoint of the viscosity of the polymer polyol.
The use amount (% by weight) of (c) is preferably from 0.1 to 50, more preferably from the viewpoint of the viscosity of the polymer polyol and the mechanical properties of the polyurethane, based on the total weight of the ethylenically unsaturated compound (E). Is 1-40. (C) may remain in the polymer polyol after the completion of the polymerization reaction, but it is desirable to remove by a vacuum stripping after the polymerization reaction from the viewpoint of the mechanical properties of the polyurethane.

In the radical polymerization, a chain transfer agent (g) may be used as necessary. (G) is a chain transfer agent such as C1-20 aliphatic thiol (n-dodecanethiol, mercaptoethanol, etc.) {JP 2005-162791 A, JP 2004-002800 A (corresponding US patent application: US 2005). / 245724 A1)}.
The amount (% by weight) used of (g) is preferably 0.01 to 2, based on the total weight of the ethylenically unsaturated compound (E), from the viewpoint of the viscosity of the polymer polyol and the mechanical properties of the resulting polyurethane. More preferably, it is 0.1-1.

  The polymerization temperature is 100 to 200 ° C., more preferably 110 to 180 ° C., and particularly preferably 120 to 160 ° C. from the viewpoint of productivity and prevention of polyol decomposition.

As a production method for obtaining the polymer polyol of the present invention, a batch polymerization method and a continuous polymerization method are preferable, and a multistage continuous polymerization method described below is more preferable.
The batch polymerization method and the continuous polymerization method are known for producing polymer polyols (Japanese Patent Laid-Open No. 2005-162791, Japanese Patent Laid-Open No. 8-333508, Japanese Patent Laid-Open No. 2004-002800 (corresponding US Patent Application: US2005)). / 245724 A1)} method can be used.

  The multistage continuous polymerization method is a continuous polymerization method in which a monomer-containing mixed solution (M1) containing a polyol (PL), an ethylenically unsaturated compound (E), a radical polymerization initiator (K), and a dispersant (B) is used. Obtained in the first step obtained by polymerizing in step 1, followed by polyol (PL), ethylenically unsaturated compound (E), radical polymerization initiator (K), dispersant (B) and the first step. This is a method for producing a polymer polyol comprising a second step of polymerizing a monomer-containing mixed liquid (M2) containing a polymer polyol by a continuous polymerization method.

  In the multistage continuous polymerization method, the continuous polymerization method is a method in which a monomer-containing mixed solution is continuously supplied to a reaction vessel to continuously obtain a polymer polyol, and the polymerization may be performed by a semi-batch polymerization method. Alternatively, it may be performed in continuous flow piping.

  If necessary, the polymer polyol obtained by polymerization may be subjected to monomer removal / solvent removal treatment. As the demonomer / desolvent treatment, a known method (Japanese Patent Application Laid-Open No. 2004-002800) can be applied. From the viewpoint of polyurethane whiteness, the residual ethylenically unsaturated compound and / or diluting solvent (c ) Or a method in which water is distilled under reduced pressure while continuously adding water (Japanese Patent Publication No. 62-36052).

If necessary, a solvent and a flame retardant may be added to the polymer polyol (A) of the present invention. As the solvent, the same solvent as the diluting solvent (c) described above can be used, and unsaturated aliphatic hydrocarbons and aromatic hydrocarbons are preferable from the viewpoint of the viscosity of the polymer polyol.
As the flame retardant, various flame retardants (such as those described in JP-A No. 2005-162791, or phosphoric esters, halogenated phosphoric esters, melamine, phosphazene, etc.) can be used. From the viewpoint of the viscosity of the polymer polyol, a flame retardant having a low viscosity (100 mPa · s or less / 25 ° C.) is preferable. Among halogenated phosphates, tris (chloroethyl) phosphate and tris (chloropropyl) phosphate are more preferable. is there.
The content (% by weight) of the solvent and the flame retardant in the polymer polyol (A) is determined from the viewpoint of the viscosity of the polymer polyol, the flame retardancy of the polyurethane, and the mechanical properties of the resulting polyurethane. Based on the total weight of (PL), each is preferably 10 or less, more preferably 0.01 to 5, particularly preferably 0.05 to 3.

  The polymer polyol (A) of the present invention can be used as a polyol used for producing polyurethanes such as polyurethane elastomers and polyurethane foams. That is, the polyol component (Po) containing (A) or (A) and the isocyanate component (Is) containing polyisocyanate [hereinafter, a composition comprising (Po) and (Is) is referred to as a polyurethane-forming composition. is there. ] Can be reacted by a known method {method described in JP 2004-263192 A (corresponding US patent application: US 2003/4217 A1)} or the like.

As the polyol component (Po) used for producing the polyurethane, in addition to the polymer polyol (A) of the present invention, as a raw material for producing the polyurethane, a polyol and ( A known polymer polyol other than A) may be used.
As the polyol, the above-described polyol (PL) or the like can be used, and as the known polymer polyol, JP 2005-162791 A, JP 2004-263192 A (corresponding US patent application: US 2003/4217 A1) and the like are described. These polymer polyols can be used.

  The use amount (% by weight) of the polymer polyol (A) in the polyol component (Po) is preferably 10 to 100, more preferably 15 to 90, particularly from the viewpoint of the mechanical properties of the resulting polyurethane and the viscosity of the polyol component. Preferably it is 20-80, Most preferably, it is 25-70.

As the isocyanate component (Is), known polyisocyanates conventionally used in the production of polyurethane {JP 2005-162791 A, JP 2004-263192 A (corresponding US patent application: US 2003/4217 A1)]. Can be used.
Among these, from the viewpoint of mechanical properties of polyurethane, 2,4- and 2,6-tolylene diisocyanate (TDI), crude TDI (residue when TDI is purified); 4,4′- and 2,4 '-Diphenylmethane diisocyanate (MDI), crude MDI (residue when MDI is purified) is preferred.

  The NCO index [equivalent ratio of NCO group and active hydrogen atom (NCO group / active hydrogen atom) × 100] in the production of polyurethane can be appropriately adjusted from the viewpoint of the mechanical properties of polyurethane, but is preferably 80 to 140. More preferably, it is 85-120, Most preferably, it is 95-115.

  Various catalysts used in the urethanization reaction (described in JP-A-2005-162791 and JP-A-2004-263192 (corresponding US patent application: US2003 / 4217 A1) in order to accelerate the reaction in the production of polyurethane) Can be used. The amount (% by weight) of the catalyst used is preferably 10 or less, more preferably 0.001 to 5, based on the total weight of the polyurethane-forming composition.

A foaming agent can be used in the production of the polyurethane foam. For example, water, HFC (hydrofluorocarbon), HCFC (hydrochlorofluorocarbon), methylene chloride, and those described in JP-A-2006-152188 and JP-A-2004-263192 (corresponding US patent application: US2003 / 4217 A1) Is mentioned.
The amount (% by weight) of the foaming agent can be changed depending on the desired density of the polyurethane foam, and is not particularly limited, but is preferably 20 or less based on the total weight of the polyurethane-forming composition.
A foam stabilizer can be used in the production of the polyurethane foam. Examples of the foam stabilizer include those described in JP-A No. 2005-162791, JP-A No. 2004-263192 (corresponding US patent application: US 2003/4217 A1), and the like. From the viewpoint, a silicone surfactant (for example, a polysiloxane-polyoxyalkylene copolymer) is preferable.
The amount of foam stabilizer used (% by weight) is preferably 5 or less, more preferably 0.01 to 2, based on the total weight of the polyurethane-forming composition.

In the production of polyurethane, a flame retardant can be used if necessary. Examples thereof include melamine, phosphate ester, halogenated phosphate ester, phosphazene, and those described in JP-A-2005-162791, JP-A-2004-263192 (corresponding US patent application: US2003 / 4217 A1). .
The amount (% by weight) of the flame retardant used is preferably 30 or less, more preferably 0.01 to 10, based on the total weight of the polyurethane-forming composition.

  In the production of polyurethane, if necessary, at least one selected from the group consisting of reaction retarders, colorants, internal mold release agents, anti-aging agents, antioxidants, plasticizers, bactericides, and fillers (including carbon black). Can be used.

Polyurethane can be produced, for example, by the method described in JP-A-2005-162791, JP-A-2004-263192 (corresponding US patent application: US2003 / 4217 A1). One-shot method, semi-prepolymer Method and prepolymer method.
For the production of polyurethane, a conventionally used production apparatus (such as a low-pressure or high-pressure machine) can be used. In the case of the absence of a solvent, an apparatus such as a kneader or an extruder can be used, and when a non-foamed or foamed polyurethane is produced, a closed mold or an open mold can be used.
When the polymer polyol (A) of the present invention is used, clogging of a small opening of a production apparatus used for producing polyurethane is reduced, maintenance is facilitated, and productivity can be improved. Particularly in a polyurethane foam foaming machine, clogging of the discharge head is extremely reduced, and the improvement in productivity is remarkable.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. In the following, “%”, “part” and “ratio” represent “% by weight”, “part by weight” and “weight ratio”, respectively, unless otherwise specified.

The composition and symbols of the raw materials used in Examples and Comparative Examples are as follows.
(1) Polyol Polyol (PL1-1): A polyol having a hydroxyl value of 56 and an internal EO unit content of 9%, which is block-added to glycerin in the order of PO-EO-PO. Terminal primary ratio = 2 mol%. [Product name "Sanniks (registered trademark) GP-3030", manufactured by Sanyo Chemical Industries, Ltd.]
Polyol (PL1-2): A polyol having a hydroxyl value of 32 and a terminal EO unit content of 14%, which is obtained by block addition of pentaerythritol in the order of PO-EO. Terminal primary conversion rate = 74 mol%. [Product name "Polyol 50", manufactured by Sanyo Chemical Industries, Ltd.]
Polyol (PL1-3): A polyol having a hydroxyl value of 37 and a terminal EO unit content of 17.5%, which is obtained by block addition of pentaerythritol in the order of PO-EO. Terminal primary ratio = 80 mol%.
Polyol (PL1-4): Polyol obtained by adding PO to bisphenol A and having a hydroxyl value of 216 and a terminal PO unit content of 56%. Terminal primary ratio = 1 mol%.
Polyol (PL1-5): A polyol having a hydroxyl value of 56 and a terminal EO unit content of 20%, which is block-added to glycerin in the order of PO-EO. Terminal primary conversion rate = 74 mol%. [Product name "Sanniks (registered trademark) GL-3000", manufactured by Sanyo Chemical Industries, Ltd.]
(2) Radical polymerization initiator K-1: 1,1′-azobis (2-methylbutyronitrile) [trade name “V-59”, manufactured by Wako Pure Chemical Industries, Ltd.]
(3) Dispersant B-1: hydroxyl value obtained by jointing 0.14 mol of polyol (PL1-2) and 0.07 mol of 2-hydroxymethacrylate with 0.16 mol of TDI, number of unsaturated groups / nitrogen-containing Reactive dispersant having a base number of 0.22 (see JP 2002-308920 A)
B-2: ACN: St = 70: 30 by weight ratio of ACN: St Mw = 600,000 ACN-St copolymer oligomer type non-reactive dispersant {content of this oligomer type dispersant is 10 % And mixed with polyol (PL1-2) to be used. Hydroxyl value of this mixture = 29.0}
(4) Polyisocyanate TDI-80: trade name “Coronate T-80” [manufactured by Nippon Polyurethane Industry Co., Ltd.]
CE-729: Trade name “CE-729” (manufactured by Nippon Polyurethane Industry Co., Ltd.)
(5) Catalyst Catalyst A: Trade name “Neostan U-28” (stannous octylate) [manufactured by Nitto Kasei Co., Ltd.]
Catalyst B: Trade name “TEDA-L33” (triethylenediamine / dipropylene glycol = 33/67 wt% solution) [manufactured by Tosoh Corporation]
Catalyst C: Trade name “TOYOCAT ET” {Bis-2-dimethylaminoethyl ether / dipropylene glycol = 70/30 (weight ratio) solution} [manufactured by Tosoh Corporation]
(6) Foam stabilizer Product name “SRX-280A” (polyether siloxane polymer) [manufactured by Toray Dow Corning Silicone Co., Ltd.]
Product name “SZ-1311” (polyether siloxane polymer) [manufactured by Nippon Unicar Co., Ltd.]
Product name "L-5309" (polyether siloxane polymer) [manufactured by Nippon Unicar Co., Ltd.]

The measurement and evaluation methods in the examples are as follows.
<Volume average particle diameter>
30 ml of methanol is put into a 50 ml glass beaker, 2 mg of polymer polyol is added, and the mixture is stirred and mixed with a magnetic stirrer at 400 rpm × 3 minutes using a stirrer piece having a major axis of 2 cm and a minor axis of 0.5 cm to obtain a uniform solution. After mixing, the sample is put into a measurement cell within 5 minutes, and the volume average particle size based on the volume is measured using a laser diffraction / scattering particle size distribution measuring device [model number: LA-750, manufactured by Horiba, Ltd.].

<Coarse particle content>
About 300 g of the polymer polyol is precisely weighed in a 1 L beaker to obtain the polymer polyol weight (W5). To this was added 300 g of methanol that had been filtered through an industrial woven wire mesh (JIS G3556, hereinafter the same) having an aperture of 0.10 mm in advance to obtain a uniform solution. The uniform liquid is filtered through an industrial woven wire mesh having an opening of 0.10 mm, and coarse particles remaining on the wire mesh are washed with 300 g of methanol from which foreign matters have been removed in advance. The washed coarse particles are dried in a circulating dryer at 70 ° C. for 30 minutes, and then the weight of the dried coarse particles is measured, and this is defined as the coarse particle weight (W6) (weighed with an accuracy of 4 digits after the decimal point). Unit g). The value calculated by the following formula is the coarse particle content in the polymer polyol (content of polymer fine particles having a particle diameter of 0.10 mm or more).
Coarse particle content (% by weight) = (W6) × 100 / (W5)

<Filterability>
Heat 300 g of polymer polyol to 70 ° C. An industrial woven wire mesh (JIS G3556) having an opening of 0.045 mm cut to the size of the filtration surface is fixed to a Buchner funnel having a filtration surface diameter of 96 mm with an aluminum adhesive tape. Fix the Buchner funnel to the top of the filter bell and connect directly to the vacuum pump. Open the temperature-controlled polymer polyol on the wire mesh surface of the Buchner funnel within 30 seconds, open the polymer polyol on the wire mesh, and operate the vacuum pump [model TSW-300, manufactured by Sato Vacuum Co., Ltd.] within 60 seconds. Let Time is started from the time when the vacuum pump is operated, and the time until a part of the wire mesh surface is seen is defined as the filtration time. The weight of the polymer polyol after filtration is measured, and this is defined as (W9). The value calculated by the following formula is defined as filterability.
Filterability (g / s · cm ² )
= (W9) (g) ÷ [Filtration time (seconds) x Filtration area [72.4 cm ² ]]

Production Example 1 [Production of polyol (a-1)]
As in the embodiment shown in FIG. 1, a stainless steel autoclave {reaction vessel (1)} equipped with a stirrer having a capacity of 2500 ml, a temperature controller and a raw material supply line (5), magnesium oxide (granule, diameter 2 to 0. 1 mm) of reaction tower (2) (stainless steel cylindrical tube, inner diameter 5.5 cm, two lengths of 30 cm are used) and distillation tower (3) (theoretical plate number 30, stainless steel cylindrical tube, inner diameter 5) 0.5 cm, 2 m in length) were connected by circulation lines (6), (7) and (8).
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 reaction tank (1), the reaction tower (2) and the circulation line ( 6), (7) and (8) were depressurized to 0.005 MPa. While controlling PO so that the reaction temperature is maintained at 50 to 60 ° 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. At a flow rate of min, circulate in the order of reaction tank (1) → circulation line (6) → reaction tower (2) → circulation line (7) → distillation tower (3) → circulation line (8) → reaction tank (1). It was. While controlling the reaction tower (2) at 75 ° C. and 0.08 to 0.15 MPa, the by-product low-boiling compound is continuously brought into contact with magnesium oxide to form a high-boiling compound. In the distillation tower (3) It was separated from PO and removed out of the system. The separated high boiling point compound was extracted from the bottom line (4) of the distillation column (3). When the amount of liquid in the autoclave reached 1920 ml, the PO was stopped, the gas phase circulation was terminated, the mixture was 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. Thereafter, water was distilled off at atmospheric 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 to 50 torr while introducing steam at 130 to 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, it was filtered using 1 micron filter paper and then dehydrated under reduced pressure to obtain a liquid glycerin POEO adduct (a-1).
The glycerin PO adduct used as a raw material was synthesized by a known method. After adding a predetermined amount of propylene oxide to glycerin using potassium hydroxide as a catalyst, water and synthetic silicate were used for catalyst removal. (KYOWARD 600 manufactured by Kyowa Chemical Co., Ltd.) was added and subjected to heat treatment, followed by filtration and dehydration under reduced pressure.

Production Example 2 [Production of polyol (a-2)]
As in the embodiment shown in FIG. 1, a stainless steel autoclave {reaction vessel (1)} equipped with a stirrer having a capacity of 2500 ml, a temperature controller and a raw material supply line (5), magnesium oxide (granule, diameter 2 to 0. 1 mm) of reaction tower (2) (stainless steel cylindrical tube, inner diameter 5.5 cm, two lengths of 30 cm are used) and distillation tower (3) (theoretical plate number 30, stainless steel cylindrical tube, inner diameter 5) 0.5 cm, 2 m in length) were connected by circulation lines (6), (7) and (8).
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 reaction tank (1), the reaction tower (2) and the circulation line ( 6), (7) and (8) were depressurized to 0.005 MPa. While controlling PO so that the reaction temperature is maintained at 50 to 60 ° 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. At a flow rate of min, circulate in the order of reaction tank (1) → circulation line (6) → reaction tower (2) → circulation line (7) → distillation tower (3) → circulation line (8) → reaction tank (1). It was. While controlling the reaction tower (2) at 75 ° C. and 0.08 to 0.15 MPa, the by-product low-boiling compound is continuously brought into contact with magnesium oxide to form a high-boiling compound. In the distillation tower (3) It was separated from PO and removed out of the system. The separated high boiling point compound was extracted from the bottom line (4) of the distillation column (3). When the amount of liquid in the autoclave reached 2000 ml, the PO was stopped, the gas phase circulation was terminated, 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. Thereafter, 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, and a liquid glycerin PO adduct ( a-2) was obtained.

Production Example 3 [Production of polyol (a-3)]
Instead of using 400 g of glycerin PO adduct (hydroxyl value 280), 240 g of glycerin PO adduct (hydroxyl value 280) is used, instead of “stopping PO addition when the amount of liquid in the autoclave reaches 1920 ml” In addition, the liquid glycerin POEO was synthesized in the same manner as in Production Example 1 except that the PO addition was stopped when the amount of liquid in the autoclave reached 1800 ml and that 200 g of EO was used instead of 80 g of EO. An adduct (a-3) was obtained.

Production Example 4 [Production of polyol (a-4)]
Instead of using 400 g of the glycerin PO adduct (hydroxyl value 280), 267 g of the pentaerythritol PO adduct (hydroxyl value 280) is used. “When the amount of liquid in the autoclave reaches 1920 ml, the PO addition is stopped”. Instead, it was synthesized in the same manner as in Production Example 1 except that PO charging was stopped when the amount of liquid in the autoclave reached 1840 ml, and 160 g of EO was used instead of 80 g of EO. Erythritol POEO adduct (a-4) was obtained.
The pentaerythritol PO adduct (hydroxyl value 280) was synthesized by a known method. After adding a predetermined amount of propylene oxide to pentaerythritol using potassium hydroxide as a catalyst, it was synthesized with water to remove the catalyst. A silicate (KYOWARD 600 manufactured by Kyowa Chemical Co., Ltd.) is added and subjected to heat treatment, followed by filtration and dehydration under reduced pressure.

Production Example 5 [Production of polyol (a-5)]
A liquid pentaerythritol POEO was synthesized in the same manner as in Production Example 4 except that 200 g of pentaerythritol PO adduct (hydroxyl value 280) was used instead of 267 g of pentaerythritol PO adduct (hydroxyl value 280). An adduct (a-5) was obtained.

Production Example 6 [Production of polyol (a-6)]
A liquid glycerin POEO adduct was synthesized in the same manner as in Production Example 5 except that 328 g of glycerin PO adduct (hydroxyl value 280) was used instead of 200 g of pentaerythritol PO adduct (hydroxyl value 280). (A-6) was obtained.

Production Example 7 [Production of polyol (a-7)]
A liquid pentaerythritol POEO addition was synthesized in the same manner as in Production Example 6 except that 328 g of pentaerythritol PO adduct (hydroxyl value 280) was used instead of 328 g of glycerin PO adduct (hydroxyl value 280). A product (a-7) was obtained.

Production Example 8 [Production of polyol (a-8)]
A liquid glycerin POEO adduct was synthesized in the same manner as in Production Example 5, except that 264 g of glycerin PO adduct (hydroxyl value 280) was used instead of 200 g of pentaerythritol PO adduct (hydroxyl value 280). (A-8) was obtained.

Production Example 9 [Production of polyol (a-9)]
A liquid pentaerythritol POEO addition was synthesized in the same manner as in Production Example 8 except that 264 g of pentaerythritol PO adduct (hydroxyl value 280) was used instead of 264 g of glycerin PO adduct (hydroxyl value 280). A product (a-9) was obtained.

Production Example 10 [Production of polyol (a-10)]
Instead of using 264 g of a pentaerythritol PO adduct (hydroxyl value 280), 264 g of a glycerin PO adduct (hydroxyl value 280) is used. “When PO in the autoclave reaches 1840 ml, the PO addition is stopped”. Instead, the liquid glycerin was synthesized in the same manner as in Production Example 9 except that the PO charging was stopped when the amount in the autoclave reached 1700 ml and that 300 g of EO was used instead of 160 g of EO. A POEO adduct (a-10) was obtained.

Production Example 11 [Production of polyol (a-11)]
Instead of using 264 g of glycerin PO adduct (hydroxyl value 280), 264 g of pentaerythritol PO adduct (hydroxyl value 280) is used. “When the amount of liquid in the autoclave reaches 1700 ml, the PO addition is stopped”. Instead, the liquid glycerin was synthesized in the same manner as in Production Example 10 except that the PO charging was stopped when the amount in the autoclave reached 1750 ml, and 250 g of EO was used instead of 300 g of EO. A POEO adduct (a-11) was obtained.

Production Example 12 [Production of polyol (a-12)]
Instead of using 264 g of the pentaerythritol PO adduct (hydroxyl value 280), 329 g of glycerin PO adduct (hydroxyl value 280) is used, and “the PO addition is stopped when the amount in the autoclave reaches 1750 ml”. Instead, the liquid glycerin was synthesized in the same manner as in Production Example 11 except that the PO charging was stopped when the amount in the autoclave reached 1840 ml, and 160 g of EO was used instead of 250 g of EO. A POEO adduct (a-12) was obtained.

Production Example 13 [Production of polyol (a-13)]
Instead of using 329 g of glycerin PO adduct (hydroxyl value 280), use 61 g of glycerin PO adduct (hydroxyl value 1829), instead of “stopping PO addition when the amount in the autoclave reaches 1840 ml” In the same manner as in Production Example 12 except that the PO addition is stopped when the amount in the autoclave reaches 1920 ml, and 80 g of EO is used instead of 160 g of EO. An adduct (a-13) was obtained.

Production Example 14 [Production of polyol (a-14)]
Instead of “stopping PO when the amount in the autoclave reaches 1920 ml”, “stop pouring when the amount in the autoclave reaches 2000 ml” and use EO instead of 80 g of EO A liquid glycerin PO adduct (a-14) was obtained by synthesizing in the same manner as in Production Example 13, except that it was not present.

Production Example 15 [Production of polyol (b-1)]
[Step 1] After 31 parts of glycerin and 2.1 parts of potassium hydroxide are added to a stainless steel autoclave equipped with a stirrer and a temperature controller, PO687 parts are added dropwise at a reaction temperature of 90 to 110 ° C. over 12 hours. Aged at 100 ° C. for 6 hours. After cooling to 60 ° C., 29 parts of synthetic silicate (Kyoward 600, manufactured by Kyowa Chemical) and 14 parts of water were added and treated at 60 ° C. for 3 hours. After cooling to 25 ° C. and taking out from the autoclave, the mixture was filtered through a 1 μm filter and then dehydrated under reduced pressure to obtain a polyol intermediate (S-1).
[Second step] In a stainless steel autoclave equipped with a stirrer and a temperature controller, 718 parts of (S-1), 0.10 parts of tris (pentafluorophenyl) borane and 232 parts of PO are charged, and the reaction temperature is kept at 65 to 75 ° C. While being controlled in this manner, the solution was dropped over 10 hours and then aged at 70 ° C. for 5 hours. Water was added and propionaldehyde as a by-product was distilled off together with water at 105 to 110 ° C. for 4 hours at normal pressure. Thereafter, while maintaining the temperature at 90 to 100 ° C. and the pressure at 30 to 50 torr, the by-product propionaldehyde was distilled off with water under reduced pressure for 5 hours while continuously introducing water vapor. After stopping the introduction of water vapor, 0.67 part of potassium hydroxide was added, and the temperature was further raised to 130 ° C. for 3 hours, and the pressure was kept at 50 torr or less for dehydration. Subsequently, 50 parts of EO was added dropwise over 3 hours while controlling the reaction temperature to be 125 to 135 ° C., and then aged at 130 ° C. for 2 hours. After cooling to 60 ° C., 40 parts of synthetic silicate (Kyoward 600, manufactured by Kyowa Chemical) and 20 parts of water were added and treated at 60 ° C. for 3 hours. After cooling to 25 ° C. and taking out from the autoclave, the mixture was filtered through a 1 μm filter and then dehydrated under reduced pressure to obtain a liquid polyol (b-1).

  Table 1 shows the properties of the polyols of the polyols obtained in Production Examples 1 to 15.

Example 1 [Production of polymer polyol (A-1)]
In a four-necked flask equipped with a temperature controller, a vacuum stirring blade, a dripping pump, a decompression device, a Dimroth condenser, a nitrogen inlet and an outlet, polyol (a-1) 59.0 parts, (PL1-1) 236 parts Then, 57.4 parts of Dispersant (B-1) and 124 parts of xylene were added, and after substitution with nitrogen, the temperature was raised to 130 ° C. with stirring in a nitrogen atmosphere (until the end of polymerization). Next, 28.4 parts of polyol (a-1), 114 parts of (PL1-1), 17.5 parts of dispersant (B-1), 105 parts of ACN, 245 parts of styrene, 0.35 parts of divinylbenzene, radical polymerization start A monomer-containing mixed solution (Z1) obtained by mixing 3.5 parts of the agent (K-1) and 10.5 parts of xylene was continuously added dropwise at a rate of 25 parts / minute using a dropping pump. Polymerization was carried out at 30 ° C. for 30 minutes. Furthermore, it cooled to 25 degreeC and obtained the polymer polyol (A-1). The volume average particle diameter and polymer fine particle content (% by weight) of (A-1) were measured and shown in Table 2.

Examples 2 to 6 [Production of polymer polyols (A-2) to (A-6)]
In Example 1, polymer polyols (A-2) to (A-6) were obtained in the same manner as in Example 1 except that the initial charge of the number of parts shown in Table 2 and the monomer-containing mixed liquid were used. The volume average particle diameter and polymer fine particle content (% by weight) of (A-2) to (A-6) were measured and shown in Table 2.

Example 7 [Production of polymer polyol (A-7)]
[First step] Prepare two tanks of continuous polymerization equipment (2L SUS pressure-resistant reaction vessel connected with liquid feed line and overflow line), and connect the overflow line of the first tank to the inlet of the polymerization tank of the second tank. Place in series. The first tank and the second tank are respectively charged with 2000 parts of the initial charge liquid previously mixed at a ratio of 186 parts of polyol (a-1), 744 parts of (PL1-1) and 70.0 parts of xylene. The temperature was raised to 130 ° C. (A-1) 70.8 parts, (PL1-1) 283 parts, (B-1) 35.8 parts, ACN 40.3 parts, styrene 93.9 parts, divinylbenzene 1.34 parts, radical polymerization initiator (K-1) A raw material mixture obtained by mixing 1.34 parts and 56.8 parts of xylene was line-blended using a static mixer, and then transferred to the first polymerization tank at a feed rate of 129.6 parts / minute. The polymer polyol obtained by the 1st process was obtained by making it liquid-feed continuously and overflowing from a polymerization tank. The polymer polyol obtained in the first step overflowed from the first polymerization tank was continuously fed to the second polymerization tank at a feeding rate of 129.6 parts / min.
[Second Step] From the first tank, the polymer polyol obtained in the first step overflowed at a rate of 129.6 parts / minute, (a-1) 7.29 parts, (PL1-1) 210.0 parts of a raw material mixture obtained by mixing 29.2 parts, 93.9 parts of ACN, 219 parts of styrene, 3.13 parts of (K-1) and 9.39 parts of xylene was line-blended using a static mixer. The polymer polyol containing unreacted monomer and xylene is continuously fed to the second polymerization tank at a liquid feeding speed of / min, and the reaction liquid overflowed from the polymerization tank is stocked in a SUS receiving tank. Obtained. While adding unreacted monomer and xylene-containing polymer vapor to pervapor (adding 4% by weight of the polymer polyol over the course of 2 hours as the amount of water contained in the steam), the unreacted monomer is added from another port. And xylene were distilled off at 2,666-3,999 Pa (20-30 torr) for 2 hours at 130-140 ° C. under reduced pressure to obtain a polymer polyol (A-7). (A-7) was evaluated by the measurement and evaluation methods described above. The results are shown in Table 4. In Table 4, the St ratio and the ACN ratio are ratios based on the total amount of the ethylenically unsaturated monomer, and the unit is wt%.

Examples 8 to 21 [Production of polymer polyol (A-8) to (A-21)]
In Example 7, the polymer polyols (A-8) to (A-) were used in the same manner as in Example 7 except that in the first step and the second step, the initial charge and raw material mixture of the number of parts shown in Table 3 were used. 21) was obtained. (A-8) to (A-21) were measured and evaluated in the same manner as in Example 7. The results are shown in Table 4.

Comparative Example 1 [Production of polymer polyol (R-1)]
In Example 12, a polymer polyol (R-1) was obtained in the same manner as in Example 12 except that the polyol (PL1-2) was used instead of the polyol (a-3). (R-1) was measured and evaluated in the same manner as in Example 7. The results are shown in Table 4.

Comparative Example 2 [Production of polymer polyol (R-2)]
[First step] Prepare two tanks of continuous polymerization equipment (2L SUS pressure-resistant reaction vessel connected with liquid feed line and overflow line), and connect the overflow line of the first tank to the inlet of the polymerization tank of the second tank. Place in series. The first tank and the second tank are respectively charged with 2000 parts of the initial charge liquid previously mixed at a ratio of 186 parts of polyol (b-1), 744 parts of (PL1-1) and 70.0 parts of xylene. The temperature was raised to 130 ° C. (B-1) 70.8 parts, (PL1-1) 283 parts, (B-1) 35.8 parts, ACN 40.3 parts, styrene 93.9 parts, divinylbenzene 1.34 parts, radical polymerization initiator (K-1) A raw material mixture obtained by mixing 1.34 parts and 56.8 parts of xylene was line-blended using a static mixer, and then transferred to the first polymerization tank at a feed rate of 129.6 parts / minute. The polymer polyol obtained by the 1st process was obtained by making it liquid-feed continuously and overflowing from a polymerization tank. The polymer polyol obtained in the first step overflowed from the first polymerization tank was continuously fed to the second polymerization tank at a feeding rate of 129.6 parts / min.
[Second Step] From the first tank, the polymer polyol obtained in the first step overflowed at a rate of 129.6 parts / minute, (b-1) 7.29 parts, (PL1-1) 210.0 parts of a raw material mixture obtained by mixing 29.2 parts, 93.9 parts of ACN, 219 parts of styrene, 3.13 parts of (K-1) and 9.39 parts of xylene was line-blended using a static mixer. The polymer polyol containing unreacted monomer and xylene is continuously fed to the second polymerization tank at a liquid feeding speed of / min, and the reaction liquid overflowed from the polymerization tank is stocked in a SUS receiving tank. Obtained. While adding unreacted monomer and xylene-containing polymer vapor to pervapor (adding 4% by weight of the polymer polyol over the course of 2 hours as the amount of water contained in the steam), the unreacted monomer is added from another port. And xylene were distilled off under reduced pressure at 130 to 140 ° C. for 2 hours at 2,666 to 3,999 Pa (20 to 30 torr) to obtain a polymer polyol (R-2). (R-2) was evaluated by the measurement and evaluation methods described above. The results are shown in Table 4.

Examples 22 to 31 and Comparative Example 3 [Production of polyurethane foam]
Polymer polyols (A-7) to (A-11), (A-15), (A-18) and (A-19) obtained in Examples 7 to 11, 15, 18 and 19 and Comparative Example 2 Using the comparative polymer polyol (R-2) obtained in the above, a polyurethane foam was produced by the foaming formulation shown below at the blending ratio shown in Table 5. The physical properties of these foams were evaluated by the following methods. The results are shown in Table 5.
<Foaming prescription>
[1] The temperature of each of the polymer polyol, polyol, and polyisocyanate was adjusted to 25 ± 2 ° C.
[2] Charge the polymer polyol, polyol, foam stabilizer, water, and catalyst in the order of a 1L stainless steel beaker, stir and mix at 25 ° C ± 2 ° C, immediately add polyisocyanate, stirrer [Homodisper, special (Mixing Co., Ltd.)] (stirring conditions: 2,000 rpm × 8 seconds).
[3] After the stirring was stopped, the contents of the beaker mixed in a wooden box (25 ° C. ± 2 ° C.) of 25 × 25 × 10 cm were added and foamed to obtain a polyurethane foam.

<Method for evaluating foam physical properties in Table 5>
(1) Density (kg / m ³ )
(2) 25% ILD (hardness) (kgf / 314 cm ² )
(3) Tensile strength (kgf / cm ² )
(4) Tear strength (kgf / cm)
(5) Cutting elongation (%)
(6) Compression residual strain (%)
(7) Breathability (ml / cm ² / s)
(1) to (7) are based on JIS K6400-2004.

Examples 32-43 and Comparative Examples 4, 5 [Production of polyurethane foam]
Polymer polyols (R-12) to (A-15) and (A-17) to (A-19) obtained in Examples 12 to 15 and 17 to 19 and polymer polyol (R) obtained in Comparative Example 1 -1), each raw material was stirred and mixed at 25 ± 2 ° C. according to the foaming formulation described in Table 6, the mold temperature was 60 ± 5 ° C., and the mold size was 40 × 40 × 10 (H) cm. A polyurethane foam was produced with a curing time of 6 minutes. These foam physical properties and flame retardancy (burning rate) test results are shown in Table 6.

<Method for evaluating foam physical properties in Table 6>
(1) Density (kg / m ³ )
(2) 25% ILD (hardness) (kgf / 314 cm ² )
(3) Tensile strength (kgf / cm ² )
(4) Tear strength (kgf / cm)
(5) Cutting elongation (%)
(6) Compression residual strain (%)
(7) Rebound resilience (%)
(1) to (7) are based on JIS K6400-2004.
(8) Wet heat compression residual strain (%)
(8) was a temperature of 50 ° C. and humidity of 95% in the test of (6).
(9) Combustion rate (cm / min): Evaluated according to US automobile safety standard (MVSS-302). In the results, SE means self-digestion (the flame ignited on the test piece disappears without propagating).

  From the results of Table 5, the polyurethane foam produced using the polymer polyol of the present invention has 25% ILD, tensile strength, tear strength, elongation at break, even though the density is equivalent to that of the comparative example. Excellent results were obtained in all the items of compressive residual strain and air permeability. In particular, the results are very good in terms of 25% ILD, tensile strength, and cut elongation.

  Further, from the results of Table 6, also in the polyurethane foam produced using the mold, in the polyurethane foam produced using the polymer polyol of the present invention, Examples 32-36 were compared with Comparative Example 4 and Examples. Despite 37-43 being comparable in density to Comparative Example 5, 25% ILD, tensile strength, tear strength, elongation at break, compression residual strain, wet heat compression residual strain, rebound resilience and burning rate Excellent results were obtained in all items. In particular, 25% ILD, compression residual strain, wet heat compression residual strain and rebound resilience are very good results.

  In general, the physical properties of polyurethane foam are 25% ILD, tensile strength, tear strength, cut elongation, impact resilience, and air permeability. The larger the values, the compression set, the wet heat compression residual strain, and the burning rate are numerical values. The smaller the value, the better.

Since the polymer polyol (A) of the present invention improves the mechanical properties of polyurethane using (A), it is suitable for a wide range of polyurethanes such as foams (soft, rigid, semi-rigid foams), elastomers, RIM molded products, etc. Can be used. In particular, when used in the production of polyurethane foam, the physical properties of the polyurethane foam can be adjusted with good balance, which is preferable.
Polyurethanes formed from the polyurethane-forming composition of the present invention are used in a wide variety of applications. Particularly, they are suitably used as polyurethane foams for automobile interior parts, indoor furniture for furniture, and the like.

DESCRIPTION OF SYMBOLS 1 Reaction tank 2 Reaction tower 3 Distillation tower 4 Bottom line 5 Raw material supply line 6 Circulation line 7 Circulation line 8 Circulation line

Claims (6)

In the polymer polyol in which the polymer fine particles (JR) containing the ethylenically unsaturated compound (E) as a constituent unit are contained in the polyol (PL), the polymer polyol in which (PL) contains the following polyol (a) (A).
Polyol (a): an alkylene oxide adduct of the active hydrogen-containing compound (H), wherein 40% or more of the hydroxyl groups located at the terminals are primary hydroxyl group-containing groups represented by the following general formula (1). Of the part of (AO) q in the general formula (2) represented by the general formula (2), 40% or more of the structure of A located at the terminal is the structure represented by the general formula (6). The polyoxyalkylene polyol in which the hydroxyl value x, the total degree of unsaturation y, and the ethylene oxide unit content z satisfy the relationship of formula (1).

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

[In general formula (2), R ² is an m-valent group obtained by removing m active hydrogens from the active hydrogen-containing compound (H); Z is a carbon represented by the following general formula (3) or (4) It is an alkylene group or a cycloalkylene group having a number of 2 to 12. The alkylene group or cycloalkylene group may be substituted with a halogen atom or an aryl group. ; A is a C3-C12 alkylene group or cycloalkylene group represented by the following general formula (5) or (6). The alkylene group or cycloalkylene group may be substituted with a halogen atom or an aryl group. When there are a plurality of Z or A, each may be the same or different; m is an integer of 2 to 100; p is an integer of 0 to 200, q is an integer of 1 to 200; r is 0 or more It is an integer of 200 or less. ]

[In General Formulas (3) and (4), R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, 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. In the general formulas (5) and (6), R ⁴ represents an alkyl group having 1 to 10 carbon atoms, 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. ]
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 unit content based on the weight of (a), and is 0 to 50% by weight. ] The polymer polyol according to claim 1, wherein x is 10 to 115 mgKOH / g. The polymer polyol according to claim 1 or 2, wherein 60% or more of the hydroxyl group-containing groups located at the terminals are primary hydroxyl group-containing groups represented by the general formula (1). The polymer polyol according to any one of claims 1 to 3, wherein the content of the polyol (a) is 20 to 100% by weight based on the weight of the polyol (PL). The polyol (a) is an active hydrogen-containing compound (J) represented by the following general formula (8), and an alkylene oxide having 3 to 12 carbon atoms is represented by the following general formula (10-1), (10-2) or ( If necessary, ethylene oxide may be present at the terminal of the active hydrogen compound (K) represented by the following general formula (9) obtained by ring-opening addition polymerization in the presence of the catalyst (C) represented by 10-3). The polymer polyol according to any one of claims 1 to 4, which is obtained by ring-opening addition polymerization of 0 to 50% by weight.

[In General Formula (8), R ² , Z, p, and m are the same as in General Formula (2). ]

[In General Formula (9), R ² , Z, A, p, q, and m are the same as those in General Formula (2). ]

[In General Formula (10-1), (10-2), or (10-3), X represents a boron atom or an aluminum atom, respectively. R ⁶ represents a tertiary alkyl group represented by represented by the following general formula (11) (substituted) phenyl group or the following general formula (12), if R ⁶ is plural, R ⁶ is, Each may be the same or different. ]

[In General Formula (11), Y 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. k represents the number of 0-5. ]

[In General Formula (12), R ⁷ , R ⁸ or R ⁹ each independently represents an alkyl group having 1 to 4 carbon atoms. ] A process for producing a polyurethane by reacting a polyol component and an isocyanate component, wherein the process comprises producing a polyurethane using a polyol component containing 10 to 100% by weight of the polymer polyol (A) according to any one of claims 1 to 5.

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