JP4869276B2 - Method for producing polymer polyol and polyurethane - Google Patents

Description

  The present invention relates to a method for producing a polymer polyol and polyurethane. More specifically, the present invention relates to a polymer polyol that is suitable as a raw material for cushions for vehicle seats and the like, has excellent reactivity with isocyanate and imparts excellent mechanical properties to polyurethane, and a method for producing polyurethane using the same.

Conventionally, as a polymer polyol used for the production of polyurethane, for the purpose of improving the mechanical properties of polyurethane, ethylene in a polyol containing a plurality of polyols having a specific number of functional groups, a hydroxyl value, and a polyoxyethylene content at a terminal in a specific ratio is used. Polymer polyols obtained by polymerizing an unsaturated compound (for example, see Patent Document 1), polymer polyols obtained by polymerizing an ethylenically unsaturated compound in a polyol having a specific hydroxyl value (for example, see Patent Document 2), and the like are known. It has been.
Japanese Patent Laid-Open No. 3-81314 JP 2003-226734 A

  However, the above-mentioned conventional polymer polyol has a high viscosity, and there is a problem that, for example, moldability at the time of producing a polyurethane foam is lowered. Therefore, there is a need for a polymer polyol that provides a polyurethane having a low viscosity and excellent mechanical properties.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention relates to a polymer polyol in which polymer particles (JR) containing an ethylenically unsaturated compound (E) as a structural unit are contained in a polyol (PL), wherein 40 to 97% by weight of (E) is acrylonitrile. The ratio of the molecular terminal primary hydroxyl group based on the molecular terminal hydroxyl group of (PL) is 70 to 100 mol%, and the content of the oxyethylene unit of (PL) is 0 based on the weight of (PL). 1 to 20% by weight,
The content (% by weight) of (JR) in (A) is 30 to 55 based on the weight of (A),
(JR) content x (% by weight) of polymer polyol and viscosity y (mPa · s) measured at 25 ° C. using a No. 3 rotor, 12 rpm or 6 rpm using a Brookfield viscometer of polymer polyol A polymer polyol (A) characterized by satisfying the following formulas (2) and (3), and a method for producing a polyurethane by reacting a polyol component and an isocyanate component, wherein the polyol component converts the polymer polyol into a polyol component: It is a manufacturing method of the polyurethane characterized by containing 10 to 100 weight% on the basis of the weight of this.
y ≧ 250x−5000 (2)
y ≦ 400x-8400 (3)

The polymer polyol (A) of the present invention has the following effects.
(1) The polyurethane produced using the polymer polyol of the present invention is excellent in mechanical properties.
(2) The polymer polyol of the present invention has a low viscosity and, for example, is excellent in moldability when producing a polyurethane foam.

The polymer polyol in the present invention includes polymer particles (JR) obtained by polymerizing an ethylenically unsaturated compound (E) containing acrylonitrile (hereinafter abbreviated as ACN) as an essential component in the polyol (PL). It will be.
As (E), in addition to ACN, styrene (hereinafter abbreviated as St), other ethylenically unsaturated monomers (e), and the like can be used. As an ethylenically unsaturated compound (E), it is preferable to make St and ACN into an essential component.

  The proportion (% by weight) of ACN based on the weight of (E) constituting (JR) is 40 to 97, preferably 55 to 90, preferably from the viewpoint of reducing the content of coarse particles and coloring the polymer polyol. Preferably it is 60-80.

  The proportion (%) of St based on the weight of (E) constituting (JR) is preferably 40 or less, more preferably 6 to 37, and most preferably from the viewpoint of the color reduction of the polymer polyol and the content of coarse particles. Is 15-34.

  The weight ratio of ACN to St (ACN: St) is preferably 97: 0 to 40:40, more preferably 90: 6 to 55:37, most preferably from the viewpoint of the content of coarse particles and the reduction in coloration of the polymer polyol. Preferably it is 80: 15-60: 34.

  The other ethylenically unsaturated monomer (e) has 2 or more carbon atoms (hereinafter abbreviated as C) and a number average molecular weight [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method. If it is less than 1,000 and can be copolymerized with ACN, there is no particular limitation. Monofunctional ones shown below [unsaturated nitrile (e1), aromatic ring-containing monomer (e2), (meth) acrylate ( e3), (poly) oxyalkylene ethers of α-alkenyl group-containing compounds and alkylene oxide adducts (e4) of unsaturated esters having a hydroxyl group, other ethylenically unsaturated monomers (e5)] and polyfunctional (2 or The monomer (e6) and the like can be used. These may be used alone or in combination of two or more.

(E1) includes C4-10, such as methacrylonitrile.
Examples of (e2) include C8-14, such as α-methylstyrene, hydroxystyrene, and chlorostyrene.
As (e3), C4-27, for example, alkyl such as methyl, butyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, eicosyl and docosyl (meth) acrylate (alkyl group is C1-24) ) (Meth) acrylate; hydroxypolyoxyalkylene (alkylene group is C2-8) mono (meth) acrylate.
The (meth) acrylate means acrylate and / or methacrylate, and the same applies to (meth) acrylic acid, (meth) allyl and the like in the following, and the same notation is used hereinafter.

(E4) includes (poly) oxyalkylene ethers of α-alkenyl group-containing compounds and alkylene oxide adducts of unsaturated esters having a hydroxyl group. Examples of the (poly) oxyalkylene ether of the α-alkenyl group-containing compound include adducts of alkylene oxide (hereinafter abbreviated as AO) of C3-24 terminal unsaturated alcohol, and the terminal unsaturated alcohol includes allyl alcohol, 2-buten-1-ol, 3-buten-2-ol, 3-buten-1-ol, 1-hexen-3-ol and the like can be mentioned. Examples of the AO adduct of an unsaturated ester having a hydroxyl group include an AO adduct of an unsaturated ester having a C3-24 hydroxyl group. Examples of the unsaturated compound having a hydroxyl group include hydroxyalkyl (C2-12) (meth). Acrylate is included, and examples thereof include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
Of these, from the viewpoint of reactivity with the ethylenically unsaturated compound and the viscosity of the polymer polyol, an AO adduct of allyl alcohol and an AO adduct of hydroxyalkyl (C2-12) (meth) acrylate are preferred. From the viewpoint of the viscosity of the polymer polyol, the number of added moles of AO is preferably 1 to 9, particularly preferably 1 to 6, and most preferably 1 to 3.
Examples of the AO include C2-12 or more, such as ethylene oxide, 1,2-propylene oxide, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran and 3-methyl. -Tetrahydrofuran (hereinafter abbreviated as EO, PO, BO, THF and MTHF), 1,3-propylene oxide, isoBO, C5-12 alpha-olefin oxide, substituted AO (styrene oxide, epihalohydrin, etc.), and these Two or more types of combination (random addition and / or block addition) can be mentioned.
AO is preferably C2-8, more preferably C2-4, particularly preferably C2-3, and most preferably PO and / or EO, from the viewpoint of the viscosity of the polymer polyol and the physical properties of the polyurethane.
AO is preferably used alone or in combination of two or more AOs, more preferably PO or EO alone and PO and EO in combination, from the viewpoint of the physical properties of the polyurethane.
The Mn of (e4) is preferably 110 to 490, the lower limit is more preferably 120, next more preferably 160, particularly preferably 170, most preferably 180, and the upper limit is more preferably 480, More preferred is 450, particularly preferred is 420, and most preferred is 300. When the Mn is 110 or more, the polymer polyol has a low viscosity, which is preferable in terms of handleability, and the hardness of the polyurethane obtained therefrom is also good. When the Mn is 490 or less, the hardness of the polyurethane obtained using the polymer polyol is good. It is.

  The number of α-alkenyl groups or unsaturated ester groups in (e4) is preferably 1 or more on average, and preferably 1 to 10, more preferably 1 to 2 from the viewpoint of reducing the viscosity of the polymer polyol and the properties of the polyurethane described later. Especially preferably one.

Further, the solubility parameter (hereinafter abbreviated as SP value) of (e4) is preferably from 9.5 to 13, more preferably from 9.8 to 12.2, from the viewpoint of reducing the viscosity of the polymer polyol and the compression hardness of the polyurethane described later. 5, particularly preferably 10 to 12.2.
The SP value is represented by the square root of the ratio between the cohesive energy density and the molecular volume as shown below.

SP value = (ΔE / V) ^1/2

Here, ΔE represents the cohesive energy density, V represents the molecular volume, and its value is Robert F. Fedors et al., For example, described in Polymer Engineering and Science Vol. 14, pages 147-154.

  Other ethylenically unsaturated monomers (e5) include C2-24, unsaturated carboxylic acids such as (meth) acrylic acid; aliphatic hydrocarbon monomers such as ethylene and propylene; perfluorooctylethyl methacrylate, perfluorooctyl Fluorine-containing (meth) acrylates such as ethyl acrylate; nitrogen-containing monomers other than unsaturated nitriles such as diaminoethyl methacrylate and morpholinoethyl methacrylate; vinyl-modified silicones.

  As the polyfunctional monomer (e6), C10-40, for example, bifunctional [divinylbenzene, ethylene di (meth) acrylate, polyalkylene oxide glycol di (meth) acrylate, etc.], trifunctional [pentaerythritol triallyl ether, trimethylol] Propane tri (meth) acrylate etc.] and tetrafunctional [pentaerythritol tetra (meth) acrylate etc.] monomers; cyclic olefins such as norbornene, cyclopentadiene, norbornadiene or diene compounds.

  Of (e1) to (e6), (e3), (e4) and (e6) are preferred from the viewpoint of the viscosity of the polymer polyol and the physical properties of the polyurethane, more preferred is (e4), and particularly preferred is terminal unsaturation. Alcohol PO and / or EO adducts, bifunctional monomers, most preferred are allyl alcohol PO adducts.

  In particular, the use amount (% by weight) of the polyoxyalkylene ether of the α-alkenyl group-containing compound and the AO adduct (e4) of the unsaturated ester having a hydroxyl group is 0.1 to 20 based on the weight of (E). More preferably, it is 4-15, Most preferably, it is 5-10. Within this range, the polymer polyol has a low viscosity and the polymer polyol of the present invention is easily obtained.

  The shape of the polymer 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 volume average particle diameter (μm) of (JR) is preferably from 0.05 to 1.0, more preferably from 0.1 to 0.9, and particularly preferably from the viewpoint of the viscosity of the polymer polyol and the physical properties of the polyurethane. ~ 0.7. The volume average particle diameter is measured by the method described later.

In the polyol (PL) in the present invention, the proportion of the molecular terminal primary hydroxyl group based on the molecular terminal hydroxyl group in (PL) is 70 to 100 mol%, and the content of the oxyethylene unit in (PL) is (PL). The proportion of the molecular terminal primary hydroxyl group based on the molecular terminal hydroxyl group in (PL) is preferably 72 to 95 mol%, more preferably 75, based on the weight of ~ 92 mol%, then more preferably 80-90 mol%. When the proportion of the primary hydroxyl group at the molecular end is less than 70 mol%, the reactivity of (PL) and the mechanical properties of the resulting polyurethane are deteriorated. Here, the ratio of the molecular terminal primary hydroxyl group is obtained by ¹ H-NMR analysis method after esterifying (PL) in advance.

The polyol (PL) in the present invention includes a polyol (PL1) having a primary hydroxyl group-containing molecular terminal represented by the following general formula (1) and other polyols (PL2).
(PL1) is an AO adduct of an active hydrogen-containing compound, which is obtained by adding C3 or more 1,2-alkylene oxide (hereinafter abbreviated as 1,2-AO) to terminal active hydrogen, It is a polyol having a primary hydroxyl group-containing molecular end represented by (1).

In the formula, R represents a C1-10 hydrocarbon group which may be substituted with a halogen atom.
Specific examples of R in formula (1) include linear alkyl groups (such as methyl, ethyl and propyl groups), branched alkyl groups (such as isopropyl and 2-ethylhexyl groups), (alkyl-substituted) phenyl groups (phenyl and p -Methylphenyl group etc.), halogen atom substituted alkyl groups (chloromethyl, bromomethyl, chloroethyl and bromoethyl groups etc.), halogen atom substituted phenyl groups (p-chloro- and p-bromophenyl groups etc.), and two or more of these Can be used in combination.

The active hydrogen-containing compound is the same as the active hydrogen-containing compound described later.
C3- or higher 1,2-AO includes C3-12 or higher 1,2-AO among the aforementioned AOs. Specifically, PO, 1,2-butylene oxide, C5-12 α-olefin oxide, substituted AO (styrene oxide, epihalohydrin, etc.) and the like can be mentioned. Of these, PO, 1,2-butylene oxide, C5-12 α-olefin oxide, styrene oxide, and epichlorohydrin are preferable from the viewpoint of the viscosity of the polymer polyol and the mechanical properties of the polyurethane, and more preferably PO, , 2-butylene oxide, C5-12 α-olefin oxide, particularly preferably PO, 1,2-butylene oxide, most preferably PO.

  The preferred range of hydroxyl equivalent and Mn of (PL1) is the same as (PL) described later.

(PL1) can be produced by adding AO to an active hydrogen-containing compound in the presence of a specific catalyst (α).
Examples of (α) include those described in Japanese Patent Application Laid-Open No. 2000-344881, and specifically, boron or aluminum compounds to which fluorine atoms, (substituted) phenyl groups and / or tertiary alkyl groups are bonded. For example, for boron compounds, triphenylborane, diphenyl-t-butylborane, tri (t-butyl) borane, tris (pentafluorophenyl) borane, bis (pentafluorophenyl) -t-butylborane, Examples include phenylaluminum, diphenyl-t-butylaluminum, tri (t-butyl) aluminum, tris (pentafluorophenyl) aluminum, and bis (pentafluorophenyl) -t-butylaluminum.
Of these, triphenylborane, tris (pentafluorophenyl) borane, triphenylaluminum, and tris (pentafluorophenyl) aluminum are preferable, and tris (pentafluorophenyl) aluminum is more preferable, from the viewpoints of generation of primary hydroxyl group-containing molecular ends and AO addition reaction rate. (Pentafluorophenyl) -borane and -aluminum.
The conditions for addition of AO may be the same as those described in the above publication, for example, usually 0.0001 to 10% of the weight of the ring-opening polymer to be produced, and the reaction rate of AO addition and polyurethane are produced. Preferably, 0.001 to 1% of the above catalyst is used from the viewpoint of reactivity at the time, and the reaction is usually performed at 0 to 250 ° C., preferably from 20 to 180 ° C. from the viewpoint of the reaction rate of AO addition and the mechanical properties of polyurethane. It can be carried out.

As the polyol (PL2), other than (PL1), known polyols used for the production of polymer polyols (for example, JP 2005-162791 A, JP 2004-018543 A, JP 2006-016611 A, etc.) Can be used.
Specific examples of (PL2) include, for example, an AO adduct of at least two (preferably 2 to 8) active hydrogen-containing compounds (polyhydric alcohol, polyhydric phenol, amine, polycarboxylic acid, phosphoric acid, etc.). And mixtures thereof. Of these, AO adducts of polyhydric alcohols are preferred from the viewpoint of mechanical properties of polyurethane.

  The AO includes those described above. Among these AOs, C2-8 are preferable from the viewpoint of mechanical properties of polyurethane, and more preferably EO, PO, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran, styrene oxide, and 2 of them. Combination of more than two species (block addition and / or random addition), particularly preferably, PO or a combination of PO and EO [EO content is 20% or less, preferably 15% or less, more preferably, based on the weight of (PL) Is 5 to 10%].

Specific examples of the AO adduct include a PO adduct of a known active hydrogen-containing compound (Japanese Patent Application Laid-Open No. 2005-162791, etc.) and PO and other AO (preferably EO) added in the following manner, And esterified products of these adducts with polycarboxylic acid or phosphoric acid.
(1) Block added in the order of (PO block)-(Other AO block) (2) [(PO block)-(Other AO block)] Block added in the order of ₂ (3) (Other Block added in the order of (AO block)-(PO block)-(other AO block) (4) block added in order of (PO block)-(other AO block)-(PO block) ( 5) Random addition of PO and other AOs (6) Random and block additions in the order described in US Pat. No. 4,226,756.

  The preferred range of the hydroxyl equivalent and Mn of (PL2) is the same as (PL) described later.

  The hydroxyl equivalent of (PL) (measurement conforms to JIS K-1557-1970) is preferably 200 to 4,000, more preferably 400 to 3,000, from the viewpoint of the viscosity of the polymer polyol and the mechanical properties of the polyurethane. .

  Mn of (PL) is preferably from 500 to 20,000, more preferably from 1,200 to 15,000, particularly preferably from 2,000 to 9,000, from the viewpoints of mechanical properties of polyurethane, viscosity of polymer polyol, and handling properties. 000.

  The content (% by weight) of the oxyethylene unit in (PL) is 0.1 to 20, preferably 0.1 to 15, more preferably 1.2 to 14, based on the weight of (PL). More preferably, it is 2-13, Most preferably, it is 5-10. When the proportion of (PL1) is less than 0.1% by weight, the reactivity of (PL) and the mechanical properties of the resulting polyurethane are deteriorated, and when it exceeds 20% by weight, the moldability of the polyurethane is deteriorated.

  The content (% by weight) of the polymer particles (JR) in the polymer polyol (A) is preferably 20 to 60 based on the weight of (A), from the viewpoint of mechanical properties of polyurethane and prevention of aggregation of (JR). More preferably, it is 25-58, Most preferably, it is 30-55. In addition, content of (JR) in (A) is measured by the method mentioned later.

  The content (% by weight) of the polyol (PL) in (A) is preferably 40 to 80, more preferably 42 to 75, and most preferably 45, from the viewpoint of preventing aggregation of (JR) and mechanical properties of polyurethane. ~ 70.

  The viscosity (mPa · s) of (A) is preferably 1,250 to 12,000, more preferably 1,500 to 10,000, and most preferably 2,500 to 8,000, from the viewpoint of moldability. is there.

In the polymer polyol (A) of the present invention, from the viewpoint of moldability, the content x (% by weight) of the polymer particles (JR) in the polymer polyol and the viscosity y (mPa · s) of the polymer polyol are represented by the following formula (2 ) And (3) are preferably satisfied, more preferably the expressions (2) and (4) are satisfied, and most preferably the expressions (2) and (5) are satisfied. In addition, these relational expressions are the preferable range calculated | required by experiment from the relationship of content and viscosity of (JR) of (A), and the mechanical physical property of urethane obtained using (A).
y ≧ 250x−5000 (2)
y ≦ 400x-8400 (3)
y ≦ 400x−9000 (4)
y ≦ 400x-9300 (5)
The viscosity of the polymer polyol is measured at 25 ° C. using a Brookfield viscometer.

The manufacturing method (A) includes the following manufacturing methods (1) and (2).
(1) A method for producing an ethylenically unsaturated compound (E) by polymerization in (PL).
(2) A method of producing (JR) by polymerizing the ethylenically unsaturated compound (E) and then dispersing (JR) in (PL).

The production method (1) is a method of polymerizing the ethylenically unsaturated compound (E) in a dispersion medium composed of polyol (PL).
Examples of the polymerization method include radical polymerization, coordination anion polymerization, metathesis polymerization, Diels-Alder polymerization, and the like. From an industrial viewpoint, radical polymerization is preferable.

  As the radical polymerization method, various methods, for example, a method of polymerizing (E) in the presence of the radical polymerization initiator (K) in (PL) containing the dispersant (D) (for example, US Pat. No. 3,383,351) Can be used.

As the dispersant (D), various dispersants having Mn of 1,000 or more (preferably 1,100 to 10,000 from the viewpoint of dispersibility), for example, known dispersants used in the production of polymer polyols (for example, (As described in JP-A-2005-162791, etc.) can be used, and (D) includes a reactive dispersant having an ethylenically unsaturated group that can be copolymerized with ACN, and ACN. Non-reactive dispersants that do not polymerize are included.
In the present invention, the reactive dispersant having an ethylenically unsaturated group is Mn 1,000 or more, and is distinguished from the other ethylenically unsaturated monomers (e) having Mn of less than 1,000.

As a specific example of (D),
[1] Macromer-type reactive dispersant obtained by reacting polyol (PL) with an ethylenically unsaturated compound Modified polyether polyol having an ethylenically unsaturated group (for example, those described in JP-A-08-333508), etc. ;
[2] Graft type non-reactive dispersant (PL) in which a polyol and an oligomer are combined. The difference in solubility parameter is 1.0 or less, and (PL) two or more affinity segments are side chains, (E) A graft type polymer (for example, described in JP-A-05-059134) having a polymer particle (JR) affinity segment having a solubility parameter difference of 2.0 or less as a main chain;
[3] Modification in which high molecular weight polyol type non-reactive dispersant (PL) is converted to high molecular weight (average molecular weight 1000 to 60,000) by reacting at least part of hydroxyl groups with methylene dihalide and / or ethylene dihalide Polyols (for example, those described in JP-A-07-196749) and the like;
[4] Oligomer type reactive dispersant 1,000 to 30,000 weight average molecular weight (hereinafter abbreviated as Mw) [measurement is by gel permeation chromatography (GPC) method. And at least a part of the vinyl oligomer that is soluble in (PL), and a dispersant comprising a combination of the oligomer and a vinyl group-containing modified polyol obtained by reacting the modified polyol having a high molecular weight described in [3]. (For example, those described in JP 09-77968 A) and the like;
[5] A nitrogen-containing bond-containing unsaturated polyol obtained by bonding (PL) and a monovalent active hydrogen-containing compound having at least one ethylenically unsaturated group via a polyisocyanate (for example, JP 2002-308920 A). Reactive dispersants such as those described in Japanese Patent Publication No.

  As (D), it is preferable to use a vinyl oligomer dispersant (D1) and / or a reactive dispersant (D2) described below.

(D1) is a vinyl-based oligomer obtained by polymerizing an ethylenically unsaturated compound. As the ethylenically unsaturated compound constituting (D1), the same ethylenically unsaturated compound (E) as described above can be used.
Among these, from the viewpoint of the particle diameter of (JR), at least a part of the ethylenically unsaturated compound constituting (D1) is the same as the ethylenically unsaturated compound (E) constituting (JR). More preferably, 30% by weight or more of the ethylenically unsaturated compound constituting (D1) is the same as (E), then more preferably 70% by weight, particularly preferably 80% by weight. That's it.

  The weight average molecular weight (hereinafter abbreviated as Mw) of (D1) is preferably 500,000 to 800,000 on the basis of polystyrene by gel permeation chromatography (GPC) measurement from the viewpoint of the particle diameter of (JR), More preferably, it is 600,000-750,000. In addition, (D1) is soluble in polyol (PL) from the viewpoint of the particle diameter of (JR) [5% by weight (D1) is uniformly mixed in (PL) based on the total weight of (D1) and (PL). It is desirable that the transmittance of the laser beam of the obtained mixture is 10% or more.

  The production of (D1) can be carried out by a usual polymerization method of ethylenically unsaturated compounds, except that the degree of polymerization is adjusted so that the weight average molecular weight is 500,000 to 800,000. For example, it is a method of polymerizing the ethylenically unsaturated compound (E) in the presence of a polymerization initiator described later, if necessary, in a solvent. Further, (D1) may be obtained by polymerizing (E) in polyol (PL). In this case, the polymerization concentration is preferably 1 to 40%, more preferably 5 to 20%. You may use for the production of a polymer polyol as it is, without refine | purifying what was obtained by superposition | polymerization. The polymerization initiator is used in a relatively large amount, for example, preferably 2 to 30%, more preferably 5 to 20% based on the mass of the total ethylenically unsaturated compound.

Solvents used as necessary for the polymerization reaction include benzene, toluene, xylene, acetonitrile, ethyl acetate, hexane, heptane, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, isopropyl alcohol, n-butanol and the like. Can be mentioned.
Among these solvents, toluene, xylene, isopropyl alcohol, and n-butanol are preferable from the viewpoint of viscosity and urethane mechanical strength.

  If necessary, chain transfer agents such as alkyl mercaptans (dodecyl mercaptan, mercaptoethanol, etc.), alcohols (isopropyl alcohol, methanol, 2-butanol, etc.), halogenated hydrocarbons (carbon tetrachloride, carbon tetrabromide, chloroform, etc.) ), Polymerization can be carried out in the presence of enol ether described in JP-A-55-31880. The polymerization can be carried out either batchwise or continuously. The polymerization reaction can be performed at a temperature higher than the decomposition temperature of the polymerization initiator (usually 50 to 250 ° C., preferably 80 to 200 ° C., particularly preferably 100 to 180 ° C.), and can be performed under atmospheric pressure or under pressure. it can.

  When (D1) is used, the amount (% by weight) of (D1) is preferably 0.01 to 100 based on the weight of (E) from the viewpoint of the particle diameter of (JR) and the mechanical strength of urethane. More preferably, it is 0.1-80, Most preferably, it is 1-60.

  The reactive dispersant (D2) contains a monofunctional active hydrogen compound (c) having at least one polymerizable unsaturated group bonded to a saturated polyol (b) via a polyisocyanate (f). It is a dispersant comprising a nitrogen bond-containing unsaturated polyol.

As (b) constituting the reactive dispersant (D2), the same ones exemplified as the aforementioned (PL) can be used. (B) and (PL) may be the same or different.
The number of hydroxyl groups in one molecule of (b) is at least 2, preferably 2-8, and more preferably 3-4.

(C) used to obtain (D2) is a compound having one active hydrogen-containing group and at least one polymerizable unsaturated group. Examples of the active hydrogen-containing group include a hydroxyl group, an amino group, an imino group, a carboxyl group, and an SH group, and a hydroxyl group is particularly preferable.
The polymerizable unsaturated group (c) is preferably a polymerizable double bond, and the number of polymerizable unsaturated groups in one molecule is preferably 1 to 3, particularly preferably 1. That is, an unsaturated monohydroxy compound having one polymerizable double bond is preferable as (c).
Examples of the unsaturated monohydroxy compound include monohydroxy substituted unsaturated hydrocarbon, monoester of unsaturated monocarboxylic acid and dihydric alcohol, monoester of unsaturated dihydric alcohol and monocarboxylic acid, alkenyl side chain Examples thereof include phenol having a group and unsaturated polyether monool.

Monohydroxy substituted unsaturated hydrocarbons include C3-6 alkenols such as (meth) allyl alcohol, 2-buten-1-ol, 3-buten-2-ol, 3-buten-1-ol; alkynol such as Propagyl alcohol is mentioned.
As monoesters of unsaturated monocarboxylic acid and dihydric alcohol, for example, C3-8 unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid and the dihydric alcohol (ethylene glycol, Monoesters with 2 to 12 carbon dihydric alcohols such as propylene glycol and butylene glycol), and specific examples thereof include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2 -Hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate and the like.

Examples of monoesters of unsaturated dihydric alcohol and monocarboxylic acid include monoesters of C3-8 unsaturated dihydric alcohol and C2-12 monocarboxylic acid, such as acetic acid monoester of butenediol.
Examples of the phenol having an alkenyl side chain group include phenols having an alkenyl side chain group in which C of the alkenyl group is 2 to 8, such as hydroxystyrene and hydroxy α-methylstyrene.
As the unsaturated polyether monool, an alkylene oxide (C2-8) 1 to 50 mol adduct of the above monohydroxy-substituted unsaturated hydrocarbon or phenol having the alkenyl side group [for example, polyoxyethylene (C2-10) Monoallyl ether] and the like.

Examples of (c) other than the unsaturated monohydroxy compound include the following.
Examples of (c) having an amino group or an imino group include mono- and di- (meth) allylamine, aminoalkyl (C2-4) (meth) acrylate [aminoethyl (meth) acrylate, etc.], monoalkyl (C1-12). ) Aminoalkyl (C2-4) (meth) acrylate [monomethylaminoethyl-methacrylate and the like]; (c) having a carboxyl group is the unsaturated monocarboxylic acid; and (c) having an SH group is And compounds corresponding to saturated monohydroxy compounds (OH is replaced by SH).
Examples of (c) having two or more polymerizable double bonds include poly (meth) allyl ethers of trihydric, tetrahydric, polyhydric or higher polyhydric alcohols or polyesters with unsaturated carboxylic acids. [For example, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, glycerin di (meth) acrylate, etc.].

Among these, preferred compounds are C3-6 alkenols, monoesters of C3-8 unsaturated monocarboxylic acids and C2-12 dihydric alcohols, and phenols having alkenyl side groups, more preferably (meta ) Monoesters of acrylic acid with ethylene glycol, propylene glycol or butylene glycol; allyl alcohol; and hydroxy α-methylstyrene, particularly preferably 2-hydroxyethyl (meth) acrylate.
The molecular weight of (c) is not particularly limited, but is preferably 1,000 or less, particularly 500 or less.

  The polyisocyanate (f) is a compound having at least two isocyanate groups, and includes aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products of these polyisocyanates (urethanes). Groups, carbodiimide groups, allophanate groups, urea groups, burette groups, isocyanurate groups or oxazolidone group-containing modified products), and mixtures of two or more of these.

Examples of the aromatic polyisocyanate include C (excluding carbon in the NCO group; the same as the following polyisocyanates) 6 to 16 aromatic diisocyanates, C6 to 20 aromatic triisocyanates, and crude products of these isocyanates. It is done. Specific examples include 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI), crude TDI, 2,4′- and 4,4 ′. -Diphenylmethane diisocyanate (hereinafter abbreviated as MDI), crude MDI [crude diaminodiphenylmethane {condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof: triamino or more of diaminodiphenylmethane and a small amount (for example, 5 to 20%)] Phosgenates of polyamines of polyamine}: polyallyl polyisocyanate (PAPI) and the like], naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate and the like.
Examples of the aliphatic polyisocyanate include C2-18 aliphatic diisocyanate. Specific examples include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and the like.

Examples of the alicyclic polyisocyanate include C4-16 alicyclic diisocyanate. Specific examples include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, and the like.
Examples of the araliphatic isocyanate include C8-15 araliphatic diisocyanate. Specific examples include xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.
Specific examples of the modified polyisocyanate include urethane-modified MDI, carbodiimide-modified MDI, sucrose-modified TDI, and castor oil-modified MDI.
Of these, aromatic diisocyanates are preferred, and 2,4- and 2,6-TDI are more preferred.

The nitrogen-containing bond of the reactive dispersant (D2) is generated by a reaction between an isocyanate group and an active hydrogen-containing group. When the active hydrogen-containing group is a hydroxyl group, a urethane bond is mainly generated, and an amino group In some cases, predominantly urea bonds are formed. In the case of a carboxyl group, an amide bond is formed, and in the case of an SH group, a thiourethane bond is formed. In addition to these groups, other bonds such as a burette bond and an allophanate bond may be formed.
This nitrogen-containing bond is generated by the reaction between the hydroxyl group of the saturated polyol (b) and the isocyanate group of the polyisocyanate (f), the active hydrogen-containing group of the unsaturated monofunctional active hydrogen compound (c) and the (f) Some are produced by reaction with isocyanate groups.

From the viewpoint of dispersion stability of the polymer polyol, the average value of the number of hydroxyl groups in one molecule of (D2) is usually 2 or more, preferably 2.5 to 10, and more preferably 3 to 7. The average value of the number of unsaturated groups in one molecule of (D2) is preferably from 0.8 to 2, more preferably from 0.9 to 1.2.
The viscosity of (D2) is preferably from 2,000 to 20,000 mPa · s / 25 ° C., more preferably from 3,000 to 9,000 mPa · s, from the viewpoint of the particle diameter of (JR) and the moldability of polyurethane. s / 25 ° C.

The method for producing the reactive dispersant (D2) is not particularly limited.
As a preferable method, a method in which polyisocyanate (f) is added to a mixture of unsaturated monofunctional active hydrogen compound (c) and saturated polyol (b) and the reaction is carried out in the presence of a catalyst, if necessary, (c) And (f), if necessary, in the presence of a catalyst to produce an unsaturated compound having an isocyanate group, and reacting this with (b). The latter method is the most preferable method because a nitrogen-containing bond-containing unsaturated polyol with less generation of by-products such as a compound having no hydroxyl group is obtained.
Alternatively, instead of (c) or (b), the precursor may be used to react with (f), and then the precursor portion may be modified to form (D2). [For example, after reacting with an isocyanate, an unsaturated monocarboxylic acid or an ester-forming derivative thereof is reacted to introduce an unsaturated group, and after reacting with an isocyanate, jumping with an alkylene dihalide, dicarboxylic acid or the like (D2) Form〕

Examples of the catalyst at the time of the reaction include a commonly used urethanization catalyst, a tin catalyst (dibutyltin dilaurate, stannous octoate, etc.), other metal catalysts (tetrabutyl titanate, etc.), amine catalysts ( Triethylenediamine or the like). Of these, tetrabutyl titanate is preferred.
The amount of the catalyst is preferably 0.0001 to 5%, more preferably 0.001 to 3%, based on the mass of the reaction mixture.

The reaction ratio of these three components is based on the total amount used in the reaction, and the equivalent ratio of the active hydrogen-containing group (c) and (b) to the isocyanate group (f) is (1.2 to 4): 1. Is more preferable, and (1.5-3): 1 is more preferable.
Further, the amount of (c) used for the reaction with respect to 100 parts of (b) is preferably less than 2 parts, more preferably 0.5 to 1.8 parts. Above and below, parts refer to parts by weight.
In addition, a large excess of (b) that reacts with (f) is used to form a mixture of (D2) and (b), and unreacted (b) is left as it is without separation of polyol (A). The method used as a part of can also be taken.

The reactive dispersant (D2) obtained by the above method may be a single compound, but in many cases, it is a mixture of various compounds such as a compound represented by the following general formula (6).

[In the formula, Z is an h-valent residue of (f) (where h is an integer of 2 or more); T is a residue of (c) (provided that it has a polymerizable unsaturated group); A ₁ is q residues of _monovalent polyol [(b), or (b) and (f) OH prepolymer from], a ₂ is from q ₂ dihydric polyol [(b), or (b) and (f) OH prepolymer] residue (where q ₁ and q ₂ are integers of 2 or more); X is a single bond, O, S, or
T ′ is H or an alkyl group having 1 to 12 carbon atoms; c is an integer of 1 or more; j is an integer of 1 or more; However, q ₁ −g ≧ 0 and h−j−1 ≧ 0. The total number of OH groups is 2 or more. ]

That is, one (b) and one (c) are combined through one (f), and a plurality of (c) is one (b) through one (f). ) And a combination of 3 or more (b) and (c) via a plurality of (f). Further, as by-products other than these, (b) comrades bonded via (f) (nitrogen-containing bond-containing polyol having no unsaturated group), (c) comrades bonded via (f) (A nitrogen-containing bond-containing unsaturated compound having no hydroxyl group) may be formed, and unreacted (b) or (c) may be included.
Although this mixture can be used as a dispersant as it is, those containing a nitrogen-containing bond-containing polyol having no unsaturated group or a nitrogen-containing bond-containing unsaturated compound having no hydroxyl group are preferred, and these impurities which can be further removed. It can also be applied after removing.
Moreover, since the unsaturated group in (D2) is located at or near the terminal of the molecular chain of the polyol, it is easy to copolymerize with the monomer.

(D2) is calculated by the following formula (7), and the average value of the ratio of the number of unsaturated groups to the nitrogen-containing bond derived from the NCO group of (f) in one molecule: K is 0.1 to 0.4 (B), (c) and (f) are reacted at such a ratio.
H = [number of moles of (c) × number of unsaturated groups of (c)] / [number of moles of (f) × number of NCO groups of (f)] (7)
The value of H is more preferably 0.1 to 0.3, and particularly preferably 0.2 to 0.3. When the value of H is within the above range, the dispersion stability of the polymer polyol is particularly good.

  When (D2) is used, the amount (% by weight) of (D2) is preferably 2 to 20%, more preferably 4 based on the weight of (E), from the viewpoint of dispersibility and the viscosity of the polymer polyol. -15%, particularly preferably 6-10%.

  As (K), compounds that generate free radicals and initiate polymerization, such as azo compounds and peroxides (for example, those described in JP-A No. 2005-162791, etc.) can be used. The 10-hour half-life temperature of (K) is preferably 30 to 150 ° C., more preferably 40 to 140 ° C., and particularly preferably 50 to 130 ° C. from the viewpoint of the polymerization rate and productivity of (E).

  The amount (% by weight) used of (K) is preferably 0.05 to 20, more preferably 0.1 to 0.1, based on the weight of (E) from the viewpoint of the polymerization rate of (E) and the mechanical properties of polyurethane. 5, particularly preferably 0.2-2.

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

In radical polymerization, a chain transfer agent (G) may be used if necessary. As (G), various chain transfer agents (for example, those described in JP-A-2005-162791, etc.) such as aliphatic thiols (C1-20, such as n-dodecanethiol, mercaptoethanol) can be used.
The use amount (% by weight) of (G) is preferably 0.01 to 2, more preferably 0.1 to 1, from the viewpoint of the viscosity of (A) and the mechanical properties of polyurethane based on the weight of (E). It is.

The production method of the polymer polyol includes various production methods such as a batch polymerization method and a continuous polymerization method (for example, those described in JP-A Nos. 2005-162791 and 8-333508). Batch polymerization methods include batch polymerization methods, drop polymerization methods, multistage batch polymerization methods and the like; continuous polymerization methods include multistage continuous polymerization methods and the like.
The production method for obtaining the polymer polyol (A) of the present invention can be carried out either batchwise or continuously.

  The radical polymerization initiator (K) may be used as it is, or a solution dissolved (or dispersed) in the diluent solvent (C), the dispersant (D) and / or the polyol (PL) is used.

Among the production methods (1) and (2) of the polymer polyol (A), the production method (2) comprises producing polymer particles (JR), and then dispersing (JR) in the polyol (PL). This is a method for obtaining a polymer polyol, and examples thereof include the following methods.
First, a dispersion is produced by emulsion polymerization or suspension polymerization of an ethylenically unsaturated compound by various methods (for example, methods described in JP-A-5-148328 and JP-A-8-100006). To do. If necessary, the obtained (JR) dispersion is classified using a wet classifier (precipitation tank system, mechanical classifier system, centrifugal classifier system, etc.). The polymer polyol (A) of the present invention can be obtained by dispersing (JR) thus obtained in (PL).
In dispersing, the (JR) dispersion obtained by polymerization or subsequent wet classification and classification may be used as it is, or after the dispersion medium is distilled off from the (JR) dispersion. When the (JR) dispersion is used as it is, the polymer polyol of the present invention is obtained by mixing the (JR) dispersion and the polyol (PL) and then distilling off the dispersion medium.
Also, when used after distilling off the dispersion medium from the (JR) dispersion, when (JR) is dispersed in (PL), if it is dispersed by applying high shear, aggregation of (JR) can be easily prevented. it can. As an apparatus used for the dispersion, a dispersion apparatus capable of applying a high share such as a homomixer is preferable.

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 dilution 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 (for example, those described in JP-A No. 2005-162791) can be used. From the viewpoint of the viscosity of the polymer polyol, a low viscosity (100 mPa · s or less / 25 ° C.) is preferable. Flame retardants, more preferred are tris (chloroethyl) phosphate and tris (chloropropyl) phosphate.
The amount (% by weight) of the solvent and flame retardant used in (A) is usually 10 or less, based on the total weight of (JR) and (PL), respectively, the viscosity of the polymer polyol, the flame retardancy of the polyurethane, and the polyurethane From the viewpoint of the mechanical properties, it is preferably 0.01 to 5, more preferably 0.05 to 3, respectively.

  The polymer polyol (A) of the present invention can be used as a polyol used for the production of polyurethane (polyurethane elastomer, polyurethane foam, etc.). That is, (A) or a polyol component (Po) containing (A) and an isocyanate component (Is) composed of a polyisocyanate [hereinafter, a composition composed of (Po) and (Is) is referred to as a polyurethane-forming composition. is there. ] Can be reacted by a known method (for example, the method described in JP-A No. 2004-263192) or the like to obtain a polyurethane.

As the polyol component (Po), in addition to (A) of the present invention, a polyol and a known polymer polyol other than (A) are used as a raw material when producing polyurethane as long as the effects of the present invention are not impaired. May be.
As the polyol, the above-described polyol (PL) or the like can be used, and as the known polymer polyol, for example, a polymer polyol described in JP-A-2005-162791 can be used.
Although the usage-amount (weight%) of a polyol can be suitably adjusted from a viewpoint of the mechanical physical property of a polyurethane based on the weight of (A), Preferably it is 1-1000.
The use amount (% by weight) of a known polymer polyol other than (A) is preferably based on the weight of (A) from the viewpoint of reducing the mechanical properties of polyurethane and clogging of strainers and discharge ports of polyurethane production equipment. 1-100.

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

As the isocyanate component (Is), known polyisocyanates (for example, those described in JP-A No. 2005-162791) and the like conventionally used in the production of polyurethane can be used.
Of these, 2,4- and 2,6-TDI, a mixture of these isomers, crude TDI (residue when TDI is purified); 4,4 ′ are preferable from the viewpoint of mechanical properties of polyurethane. -And 2,4'-MDI, mixtures of these isomers, crude MDI (residue when MDI is purified); and urethane groups, carbodiimide groups, allophanate groups, urea groups derived from these polyisocyanates , A modified polyisocyanate containing a burette group or an isocyanurate group.

  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.

  In order to promote the reaction in the production of polyurethane, various catalysts (for example, those described in JP-A-2005-162791) used in the urethanization reaction can be contained in the polyurethane-forming composition. The amount (% by weight) of the catalyst used is usually 10 or less, preferably 0.001 to 5, based on the total weight of the polyurethane-forming composition.

In the production of polyurethane, various foaming agents (for example, those described in JP-A-2006-152188) [water, HFC (hydrofluorocarbon), HCFC (hydrochlorofluorocarbon), methylene chloride, etc.] are added to a polyurethane-forming composition. It can be made to contain in a thing and can be set as a polyurethane foam. 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 usually 20 or less based on the total weight of the polyurethane-forming composition.
When producing a polyurethane foam, if necessary, a foam stabilizer can be further contained in the polyurethane-forming composition. As the foam stabilizer, various foam stabilizers (for example, those described in JP-A No. 2005-162791) can be used. From the viewpoint of uniformity of cell diameter in the polyurethane foam, a silicone surfactant (for example, polysiloxane) is preferable. Siloxane-polyoxyalkylene copolymer).
The amount (% by weight) of the foam stabilizer used is usually 5 or less, 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 further contained in the polyurethane-forming composition as necessary. Examples of the flame retardant include those described in JP-A-2005-162791, such as melamine, phosphate ester, halogenated phosphate ester, and phosphazene.
The amount (% by weight) of the flame retardant used is usually 30 or less, preferably 0.01 to 10, based on the total weight of the polyurethane-forming composition.

  In the production of polyurethane, a reaction retarder, a colorant, an internal mold release agent, an anti-aging agent, an anti-oxidant, a plasticizer, a disinfectant, and a filler (carbon black) as long as the effects of the present invention are not impaired. The polyurethane-forming composition may contain at least one other additive selected from the group consisting of:

The polyurethane can be produced by various methods (for example, the method described in JP-A-2005-162791), and examples thereof include a one-shot method, a semi-prepolymer method, and a 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 no solvent, an apparatus such as a kneader or an extruder can be used. Further, when producing non-foamed or foamed polyurethane, a closed mold or an open mold can be used.

  The polyurethane produced by using the polymer polyol (A) of the present invention is excellent in mechanical properties and can be applied to conventional uses of polyurethane (urethane foam, urethane elastomer, urethane coating agent, etc.). In particular, it can be suitably used as a cushion material for automobiles from the viewpoint of moldability and mechanical properties during polyurethane production.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.

The composition and symbols of the raw materials used in the following examples are as follows.
(1) Polyol Polyol (PL-1): 1 mol of glycerin was added by block addition of PO61.5 mol and 7.2 mol of EO using potassium hydroxide as a catalyst in this order [catalyst consumption 0.3% (reaction product weight (Standard), reaction temperature 95-105 ° C.], potassium hydroxide was removed by a conventional method, and then, in the same manner as in Example 1 of Japanese Patent Laid-Open No. 2000-344881, tris (pentafluorophenyl) borane was used as a catalyst for PO9. 0 mol was added [catalyst amount 50 ppm (based on reaction product weight), reaction temperature 75 ° C.], and then the catalyst component was removed. Hydroxyl value = 37.4, internal EO content = 7%, primary hydroxyl group ratio 72 Mol% polyol Polyol (PL-2): 1 mol of pentaerythritol, 81.7 mol of PO and 9.5 mol of EO in this order using potassium hydroxide as a catalyst After adding a lock [amount of catalyst used: 0.3% (based on reaction product weight), reaction temperature: 95 to 105 ° C.] and removing potassium hydroxide by a conventional method, Example 1 of JP-A-2000-344881 and Similarly, 12.0 mol of PO was added using tris (pentafluorophenyl) borane as a catalyst [amount of catalyst: 50 ppm (based on reaction product weight), reaction temperature: 75 ° C.], and then the catalyst component was removed. Hydroxyl value = 37 4.4, internal EO unit content = 7%, polyol having a primary hydroxyl group ratio of 72 mol% Polyol (PL-3): 1 mol of glycerin and 70.5 mol of PO and 7.2 mol of EO in this order using potassium hydroxide as a catalyst [The amount of catalyst used is 0.3% (based on the weight of the reaction product), the reaction temperature is 95 to 105 ° C.], and potassium hydroxide is removed by a conventional method. Hydroxyl value = 37 4, EO content = 7%, primary hydroxyl group ratio 85 mol% of a polyol

Polyol (PL-4): 9 mol of PO and 9.5 mol of EO were added in block order in this order to 1 mol of pentaerythritol using potassium hydroxide as a catalyst [amount of catalyst used: 0.3% (based on weight of reaction product), Reaction temperature 95-105 ° C.] Potassium hydroxide was removed by a conventional method, hydroxyl value = 37.4, EO unit content = 7%, primary hydroxyl group ratio 85 mol% polyol polyol (PL-5): glycerin 1 mol of potassium hydroxide as a catalyst was added in block order with 55.3 mol of PO and 8.1 mol of EO in this order [catalyst use amount 0.3% (based on reaction product weight), reaction temperature 95 to 105 ° C.] After removing potassium hydroxide by the method, in the same manner as in Example 1 of Japanese Patent Application Laid-Open No. 2000-344881, PO9 using tris (pentafluorophenyl) borane as a catalyst. 0.0 mol was added [catalyst amount 50 ppm (based on reaction product weight), reaction temperature 75 ° C.], and then the catalyst components were removed, and then 7.2 mol of EO was added using potassium hydroxide as a catalyst [catalyst use amount] 0.3% (reaction product weight basis), reaction temperature 95-105 ° C.], potassium hydroxide was removed by a conventional method, hydroxyl value = 37.4, internal EO content = 8%, terminal EO content = 7% Polyol (PL-6) having a ratio of primary hydroxyl groups of 85 mol%: Polyphenol (PL-6): 7 mol of PO and 10.9 mol of EO were added in block order in this order to 1 mol of pentaerythritol [catalyst consumption 0 0.3% (reaction product weight basis), reaction temperature 95-105 ° C.], after removing potassium hydroxide by a conventional method, the same as in Example 1 of JP-A-2000-344881 12.0 mol of PO was added using lith (pentafluorophenyl) borane as a catalyst [catalyst amount 50 ppm (based on reaction product weight), reaction temperature 75 ° C.], and after removing the catalyst components, potassium hydroxide was further used as a catalyst. 9.5 mol of EO was added [amount of catalyst used: 0.3% (based on reaction product weight), reaction temperature: 95 to 105 ° C.], potassium hydroxide was removed by a conventional method, hydroxyl value = 37.4, internal EO Polyol with a content = 8%, a terminal EO content = 7%, and a primary hydroxyl group ratio of 85 mol%

Polyol (PL-7): 7 mol of PO and 4.1 mol of EO were added in this order to 1 mol of glycerin using potassium hydroxide as a catalyst in this order [catalyst consumption 0.3% (based on reaction product weight), reaction Temperature 95-105 ° C.] Potassium hydroxide was removed by a conventional method. Polyol having a hydroxyl value of 37.4, a terminal EO content of 4%, and a primary hydroxyl group ratio of 30 mol%. Polyol (PL-8): Pentaerythritol 9 mol of PO and 5.5 mol of EO were blocked in this order using potassium hydroxide as a catalyst in 1 mol [catalyst consumption 0.3% (reaction product weight basis), reaction temperature 95 to 105 ° C.] Potassium hydroxide was removed by the method, hydroxyl value = 37.4, terminal EO unit content = 4%, primary hydroxyl group ratio 30 mol% polyol polyol (PL-9): glyce 6 mol of PO and 20.4 mol of EO in this order were block-added to 1 mol of potassium hydroxide as a catalyst (amount of catalyst used 0.3% (based on reaction product weight), reaction temperature 95 to 105 ° C.), A polyol having a hydroxyl value of 37.4, a terminal EO content of 20%, and a primary hydroxyl group ratio of 85 mol% after removing potassium hydroxide by a conventional method

Polyol (PL-10): 8 mol of PO and 27.2 mol of EO were added in block order in this order to 1 mol of pentaerythritol using potassium hydroxide as a catalyst [amount of catalyst used: 0.3% (based on weight of reaction product), Reaction temperature 95-105 ° C.] Potassium hydroxide was removed by a conventional method. Polyol polyol (PL-11) having a hydroxyl value of 37.4, a terminal EO unit content of 20%, and a primary hydroxyl group ratio of 85 mol%: In the same manner as in Example 1 of Japanese Patent Laid-Open No. 2000-344881, 60.4 mol of PO was added to 1 mol of glycerin using tris (pentafluorophenyl) borane as a catalyst [amount of catalyst: 50 ppm (based on the weight of the reaction product). After the catalyst component was removed, 20.5 mol of EO was further added using potassium hydroxide as a catalyst. % (Reaction product weight basis), reaction temperature 95-105 ° C.], potassium hydroxide was removed by a conventional method, hydroxyl value = 37.4, terminal EO content = 20%, primary hydroxyl group ratio 92 mol% Polyol Polyol (PL-12): 1 mol of pentaerythritol was added with 80.6 mol of PO using tris (pentafluorophenyl) borane as a catalyst in the same manner as in Example 1 of JP-A-2000-344881 [catalytic amount of 50 ppm. (Reaction product weight basis), reaction temperature 75 ° C.], and after removing the catalyst component, 27.3 mol of EO was further added using potassium hydroxide as a catalyst [catalyst consumption 0.3% (reaction product weight basis) ), Reaction temperature 95 to 105 ° C.], potassium hydroxide was removed by a conventional method, hydroxyl value = 37.4, terminal EO content = 20%, primary hydroxyl group ratio 92 mol % Polyol

Polyol (PL-13): 7 mol of PO was added to 1 mol of glycerin in the same manner as in Example 1 of JP-A-2000-344881 using tris (pentafluorophenyl) borane as a catalyst [catalyst amount 50 ppm (reaction Product weight basis), reaction temperature 75 ° C.], and after removing the catalyst component, 1.2 mol of EO was further added using potassium hydroxide as a catalyst [catalyst consumption 0.3% (reaction product weight basis), Reaction temperature 95-105 ° C.] Potassium hydroxide was removed by a conventional method, hydroxyl value = 37.4, terminal EO content = 1.2%, primary hydroxyl group ratio 74 mol% polyol polyol (PL-14) : 1 mol of pentaerythritol was treated in the same manner as in Example 1 of JP-A-2000-344881, using tris (pentafluorophenyl) borane as a catalyst. 100.1 mol of O was added [catalyst amount 50 ppm (based on reaction product weight), reaction temperature 75 ° C.], and after removing the catalyst components, 1.6 mol of EO was further added using potassium hydroxide as a catalyst [catalyst use Amount 0.3% (based on reaction product weight), reaction temperature 95 to 105 ° C.], potassium hydroxide was removed by a conventional method, hydroxyl value = 37.4, terminal EO content = 20%, ratio of primary hydroxyl group 74 mol% polyol Polyol (PL-15): 1 mol of glycerin and potassium hydroxide as a catalyst were added in the order of 68.0 mol of PO and 10.5 mol of EO in this order [catalyst consumption 0.3% (reaction product (Based on weight), reaction temperature 95 to 105 ° C.], potassium hydroxide removed by a conventional method, hydroxyl value = 37.4, EO content = 10.3%, primary hydroxyl group ratio 68 mol% Le

Polyol (PL-16): 9 mol of PO and 14.0 mol of EO were added in block order in this order to 1 mol of pentaerythritol using potassium hydroxide as a catalyst [amount of catalyst used: 0.3% (based on weight of reaction product), Reaction temperature 95-105 ° C.] Potassium hydroxide was removed by a conventional method, hydroxyl value = 37.4, EO unit content = 10.3%, primary hydroxyl group ratio 68 mol% polyol polyol (PL-17) : In the same manner as in Example 1 of JP-A No. 2000-344881, 16.0 mol of PO was added to 1 mol of glycerin using tris (pentafluorophenyl) borane as a catalyst [amount of catalyst: 50 ppm (based on weight of reaction product), Reaction temperature 75 ° C.], and then the catalyst component was removed. Polyol having a hydroxyl value of 37.4, an internal EO content of 0%, and a primary hydroxyl group ratio of 72 mol%. Polyol (PL-18): To 1 mol of pentaerythritol, 101.3 mol of PO was added in the same manner as in Example 1 of JP-A-2000-344881, using tris (pentafluorophenyl) borane as a catalyst [amount of catalyst: 50 ppm. (Reaction product weight basis), reaction temperature 75 ° C.], after which the catalyst component was removed, polyol with hydroxyl value = 37.4, internal EO unit content = 0%, primary hydroxyl group ratio 72 mol%

Polyol (PL-19): In the same manner as in Example 1 of JP-A No. 2000-344881, 16.6 mol of PO was added to 1 mol of glycerin using tris (pentafluorophenyl) borane as a catalyst [amount of catalyst 50 ppm (reaction Product weight basis), reaction temperature 75 ° C.], and after removing the catalyst component, 25.6 mol of EO was further added using potassium hydroxide as a catalyst [catalyst consumption 0.3% (reaction product weight basis) Reaction temperature 95-105 ° C.] Potassium hydroxide was removed by a conventional method, hydroxyl value = 37.4, terminal EO content = 25%, primary hydroxyl ratio 94 mol% polyol polyol (PL-20): pentane In 1 mol of erythritol, tris (pentafluorophenyl) borane was used as a catalyst in the same manner as in Example 1 of JP-A-2000-344881. 75.5 mol of O was added [catalyst amount 50 ppm (based on reaction product weight), reaction temperature 75 ° C.], and then the catalyst component was removed, and 34.1 mol of EO was further added using potassium hydroxide as a catalyst [catalyst use Amount 0.3% (reaction product weight basis), reaction temperature 95-105 ° C.], potassium hydroxide was removed by a conventional method, hydroxyl value = 37.4, terminal EO content = 25%, ratio of primary hydroxyl group 94 mol% polyol

Polyol (PL-21): 71.9 mol of PO and 17.1 mol of EO were added in this order to 1 mol of glycerin using potassium hydroxide as a catalyst in this order [catalyst consumption 0.3% (based on reaction product weight), reaction (Temperature 95-105 ° C), potassium hydroxide removed by a conventional method, hydroxyl value = 33.5, terminal EO content = 15%, primary hydroxyl group ratio 75 mol% polyol (PL-22): glycerin to PO And EO randomly added, hydroxyl value = 34.0, EO content = 70%, primary hydroxyl group ratio 72 mol% polyol (PL-23): glycerol added with EO, hydroxyl value = 830 0.0 polyol (PL-24): a polyol having a hydroxyl value of 1057 obtained by adding EO to sorbitol (2) a radical polymerization initiator K-1: 1,1′-azobis (2- Chill butyronitrile) [trade name "V-59", manufactured by Wako Pure Chemical Industries, Ltd.]
(3) Dispersant D-1: ACN: St = 70: 30 Aw ratio of ACN: St = 70: 30 Mw = 600,000 ACN-St copolymer oligomer type non-reactive dispersant {this oligomer type dispersant Was mixed with polyol (PL-15) so that the content was 10% by weight. Hydroxyl value of this mixture = 29.0}
D-2: Dispersant described in Production Example 1 of JP-A-2002-308920 {Hydroxyl value = 20, number of unsaturated groups obtained by jointing polyol (PL-12) and 2-hydroxyethyl methacrylate with TDI / Reactive dispersant with nitrogen-containing group bond number = 0.22 / 1}
(4) Polyisocyanate TDI / Polymeric MDI = 80/20: Trade name “CE-729” [manufactured by Nippon Polyurethane Industry Co., Ltd.]
(5) Catalyst Catalyst A: Trade name “TEDAL-33” (triethylenediamine / dipropylene glycol = 33/67% solution) [manufactured by Tosoh Corporation]
Catalyst B: Trade name “TOYOCAT ET” (bis-2-dimethylaminoethyl ether / dipropylene glycol = 33/67 (%) solution) [manufactured by Tosoh Corporation]
(6) Foam stabilizer SZ-1346 (polyethersiloxane polymer) [manufactured by Nippon Unicar Co., Ltd.]
SZ-1327 (polyether siloxane polymer) [Nippon Unicar Co., Ltd.]

The measurement and evaluation methods in the examples are as follows.
<Content of polymer particles (JR): (PC)>
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 (8) is taken as the polymer particle content (% by weight).

Polymer particle content (% by weight) = (W2) × 100 / (W1) (8)

<Polymerization rate>
The polymerization rate was calculated from the residual monomer content of each monomer with respect to the charged monomer amount. The residual monomer content was calculated from the area ratio with respect to the internal standard substance by gas chromatography. A specific analysis method is shown below using styrene as an example.

Polymerization rate [wt%]
= 100-100 × [(residual styrene content [%] / (styrene charge in raw material [%]))

Residual styrene content [%] = L / M x (factor for internal standard)
L = (peak area of residual styrene) / (weight of polymer polyol [g])
M = (peak area of internal standard) / (weight of internal standard [g])

The factor for the internal standard substance is obtained by dividing the peak area of each monomer when the weight is the same as the internal standard substance by the peak area of the internal standard substance.

Gas chromatograph measurement conditions (for styrene)
Gas chromatograph: GC-14B [manufactured by Shimadzu Corporation]
Column: inner diameter 4 mmφ, length 1.6 m, glass Column filler: polyethylene glycol 20M [manufactured by Shinwa Kako Co., Ltd.]
Internal reference material: Bromobenzene (manufactured by Nacalai Tesque)
Diluent: Dipropylene glycol monomethyl ether grade 1 [Wako Pure Chemical Industries, Ltd.]
Injection temperature: 200 ° C
Column temperature: 110 ° C
Temperature increase rate: 5 ° C / min
Column final temperature: 200 ° C
Sample injection volume: 1 μl

<Primary hydroxyl group ratio>
(Measuring method)
About 30 mg of a sample is weighed into a sample tube for ¹ H-NMR having a diameter of 5 mm, and about 0.5 ml of deuterated solvent is added and dissolved. Thereafter, about 0.1 ml of trifluoroacetic anhydride is added, and the mixture is well shaken and allowed to stand at 25 ° C. for about 5 minutes to make the polyol a trifluoroacetic acid ester, which is used as a sample for analysis. This analytical sample is measured by ¹ H-NMR.
The deuterated solvent here is deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide, or the like, and a solvent capable of dissolving the sample is appropriately selected.
(Calculation method of primary hydroxyl group ratio)
A signal derived from a methylene group with a primary hydroxyl group is observed at around 4.3 ppm, and a signal derived from a methine group with a secondary hydroxyl group is observed at around 5.2 ppm. The rate is calculated by the following formula.
Primary hydroxyl group ratio (mol%) = [r / (r + 2s)] × 100
r: 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 s: 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 <viscosity>
The polymer polyol is measured using a BL type viscometer [manufactured by Tokyo Keiki Co., Ltd.] under the conditions of No. 3 rotor, 12 rpm or 6 rpm, and 25 ° C.

<Content of coarse particles (particle frequency volume% of 1 μm or more)>
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 mixture is put into a measurement cell within 5 minutes, and the particle size distribution on a volume basis is measured using a laser diffraction / scattering particle size distribution measuring apparatus [model number: LA-750, manufactured by Horiba, Ltd.]. From the measurement results, the particle frequency volume% of a particle diameter of 1 μm or more was calculated and used as the content of coarse particles.

<Examples 1 to 9 and Comparative Examples 1 to 6>
A 3 L semi-batch polymerization tank equipped with a temperature controller, a stirring blade, and a raw material supply pump is charged with the number of polyols listed in Table 1 or 2 and heated to 125 ° C. with stirring. Next, a raw material liquid in which an ethylenically unsaturated compound, a dispersing agent, and a polymerization initiator having the composition shown in Table 1 or Table 2 were mixed in advance was continuously injected at 70 ml / min by a raw material supply pump. Next, the overflowed polymer polyol intermediate was charged into a glass Kolben equipped with a temperature controller and a stirring blade, and stripped at 125 ° C. under a reduced pressure of 20 to 30 mmHg for 3 hours to remove the remaining ethylenically unsaturated compound. It distilled off and polymer polyol (F-1)-(F-9) and (R-1)-(R-6) were manufactured. The results are shown in Table 1 or Table 2.

Examples 10 to 18 and Comparative Examples 7 to 12 [Production of polyurethane foam]
The polymer polyols (F-1) to (F-9) obtained in Examples 1 to 9 and the comparative polymer polyols (R-1) to (R-6) obtained in Comparative Examples 1 to 6 were used. , Each raw material in the number of parts of the foaming formulation shown in Table 3 is stirred and mixed at 25 ± 2 ° C., mold temperature 60 ± 5 ° C., mold size 40 × 40 × 10 (H) cm, curing time 6 minutes A polyurethane foam was produced. The polyurethane foam was evaluated and the results are shown in Table 3.

<Method for evaluating physical properties of foam>
(1) Core density (kg / m ³ ): Conforms to JIS K6400-1997 [Item 5].
(2) Foam hardness (25% ILD) (kgf / 314 cm ² ): Conforms to JIS K6382-1995 [Item 5.3].
(3) Tensile strength (kgf / cm ² ): Conforms to JIS K6301-1995 [Item 3].
(4) Tear strength (kgf / cm): compliant with JIS K6301-1995 [Item 9] (5) Compressive residual strain (%): compliant with JIS K6382-1995 [Item 5.5].

  From the results of Tables 1 to 3, the polymer polyols of Examples 1 to 9 had lower viscosities than Comparative Examples 1, 3 and 6. Also,···. And it turns out that the polyurethane foam manufactured using the polymer polyol of Examples 1-9 is improving the foam physical property compared with the case of the polymer polyol of Comparative Examples 1-6. In particular, it can be seen that the value of foam hardness (25% ILD) is improved.

Since the polymer polyol of the present invention has a low viscosity and improves the mechanical properties of polyurethane, it can be widely used in a wide range of polyurethanes such as foams (soft, rigid, semi-rigid foams, etc.), elastomers, RIM molded articles and the like. 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.

Claims (5)

In a polymer polyol in which polymer particles (JR) having an ethylenically unsaturated compound (E) as a constituent unit are contained in a polyol (PL), 40 to 97% by weight of (E) is acrylonitrile, (PL ) Of the molecular terminal primary hydroxyl group based on the molecular terminal hydroxyl group is 70 to 100 mol%, and the content of the oxyethylene unit of (PL) is 0.1 to 20 weight based on the weight of (PL). %
The content (% by weight) of (JR) in (A) is 30 to 55 based on the weight of (A),
(JR) content x (% by weight) of polymer polyol and viscosity y (mPa · s) measured at 25 ° C. using a No. 3 rotor, 12 rpm or 6 rpm using a Brookfield viscometer of polymer polyol A polymer polyol (A) characterized by satisfying the following formulas (2) and (3).
y ≧ 250x−5000 (2)
y ≦ 400x-8400 (3) The polymer according to claim 1, wherein the polymer particles (JR) are formed by polymerizing the ethylenically unsaturated compound (E) in the presence of the following dispersant (D1) and / or dispersant (D2). Polyol.
Dispersant (D1): Vinyl oligomer having a weight average molecular weight of 500,000 to 800,000.
Dispersant (D2): Saturated polyol (b) and monofunctional active hydrogen compound (c) having at least one polymerizable unsaturated group are bonded via polyisocyanate (f). A nitrogen-containing bond-containing unsaturated polyol having an average value of the ratio of the number of unsaturated groups to the number of nitrogen-containing bonds derived from the NCO group therein in the range of 0.1 to 0.4. The 0.1 to 20% by weight of the ethylenically unsaturated compound (E) is a (poly) oxyalkylene ether of an α-alkenyl group-containing compound and an alkylene oxide adduct (e4) of an unsaturated ester having a hydroxyl group. 3. The polymer polyol according to 1 or 2. In the method for producing a polyurethane by reacting a polyol component and an isocyanate component, the polyol component contains 10 to 100% by weight of the polymer polyol according to any one of claims 1 to 3 based on the weight of the polyol component. A method for producing a polyurethane. The cushion material for vehicle seats which consists of a polyurethane of Claim 4.