JP2805597B2 - Method for producing polymer polyol composition and polyurethane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer polyol composition for producing polyurethane and a method for producing polyurethane using the same.

[0002]

2. Description of the Related Art Heretofore, as a means for obtaining a polymer polyol having a high polymer content and good dispersion stability, a part of the polyol has been used as a coupling agent (silicon-containing compound, tetraxyalkoxyorthoformate, trialkoxyalkane). , Dialkoxyalkane, etc.) to polymerize a vinyl monomer in the presence of a modified polyol having a high molecular weight (for example, Japanese Patent Publication No. 6-62841), a method of polymerizing vinyl monomer in the presence of a macromer containing a urethane bond. Polymerization of monomer (for example, JP-A-61-115919)
Etc. are known.

[0003]

However, the above-mentioned method is obtained when a vinyl monomer having a high styrene content is polymerized in a polyol, particularly when the vinyl monomer is polymerized in a polyol having a molecular weight of less than 5000. There were problems such as poor dispersion stability and high viscosity of the polymer polyol, and it was difficult to obtain a polymer polyol having a high polymer content and good dispersion stability.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have developed a polymer polyol composition which has a low viscosity and a good dispersion stability even if the polymer content is high, and a foam having a high hardness and a good compression strain can be obtained. As a result of intensive studies, the present invention has been achieved. That is, the present invention provides a polymer polyol composition (A) obtained by polymerizing a vinyl monomer (c) in a polyol (a-1) in the presence of a reactive dispersant (b) below; The present invention relates to a method for producing a polyurethane, wherein A) is used as an essential polyol component. Reactive dispersant (b): at least a part of the hydroxyl group of polyol (a-2) is reacted with methylene dihalide and / or ethylene dihalide to have a high molecular weight, and the reaction product is further reacted with a vinyl group-containing compound. Vinyl group-containing modified polyol

The polyol (a) used in the present invention
-1) is at least two (preferably 2 to 8)
Compounds having an active hydrogen atom (polyhydric alcohol,
Compounds having a structure in which an alkylene oxide is polyadded to a polyhydric phenol, an amine, a polycarboxylic acid, phosphoric acid, and the like, and a mixture thereof.

Examples of the polyhydric alcohol include alkylene glycols (ethylene glycol, diethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.) and cyclic groups. Dihydric alcohols such as diols (for example, those described in JP-B-45-1474); trihydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, hexanetriol and triethanolamine; pentaerythritol, methylglycoside, diglycerin And tetrahydric alcohols such as; and alcohols having higher functional groups,
For example, pentitol (Adonitol, arabitol,
Xylitol, etc.), hexitol (sorbitol, mannitol, iditol, talitol, dulcitol, etc.), saccharides [sucrose, monosaccharides (glucose, mannose, fructose, sorbose, etc.), oligosaccharides (crehalose, lactose, raffinose, etc.)] and glycosides. [For example, glucoside of polyol (alkane polyol such as glycol, glycerin, trimethylolpropane, hexanetriol)]; polyalkane polyol [for example, polyglycerin such as triglycerin, tetraglycerin]; polypentaerythritol (dipentaerythritol, tripetaerythritol) And the like; cycloalkane polyols such as tetrakis (hydroxymethyl) cyclohexanol.

The polyhydric phenols include monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A and bisphenolsulfone; condensates of phenol and formaldehyde (Novolak); US Pat.
Polyphenol described in the specification of JP-A No. 41 is exemplified.

The amines include ammonia; alkanolamines such as mono-, di- and triethanolamine, isopropanolamine and aminoethylethanolamine; alkylamines having 1 to 20 carbon atoms;
C2-6 alkylenediamines such as ethylenediamine, propylenediamine, hexamethylenediamine, polyalkylenepolyamines such as aliphatic amines such as diethylenetriamine and triethylenetetramine; aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline; Aromatic amines such as diphenyletherdiamine; alicyclic amines such as isophoronediamine, cyclohexylenediamine and dicyclohexylmethanediamine; aminoethylpiperazine and other heterocyclic amines described in JP-B-55-21044. .

[0009] Two or more of these active hydrogen atom-containing compounds may be used in combination. Among them, particularly preferred are polyhydric alcohols.

Examples of the alkylene oxide to be added to the active hydrogen atom-containing compound include ethylene oxide (EO), propylene oxide (PO), butylene oxide, styrene oxide and a combination of two or more of these (block and / or random addition). Is mentioned. Preferred among the polyether polyols are those having a polyoxypropylene chain and those having a polyoxypropylene chain and a polyoxyethylene chain (EO content is 25% by weight or less). Examples of the polyether polyol include those obtained by adding PO to the active hydrogen atom-containing compound; and those obtained by adding PO and another alkylene oxide (hereinafter abbreviated as AO) in the following manner. PO-AO added in order (tip) PO-AO-PO-AO added (balanced) AO-PO-AO added PO-AO-PO added Block adducts such as those (active secondary) and random adducts in which PO and AO are mixed and added, in the order described in JP-A-57-209920, and in the order described in JP-A-53-13700. Random / block adducts such as adducts These may be used in combination of two or more.

The polyol (a-1) in the present invention is preferably a polyether polyol, but other polyols can be used instead of or together with this. Examples of the other polyol include a polymer polyol (polyester polyol, polybutadiene polyol, acrylic polyol, etc.) and / or
Or a low molecular polyol is mentioned. Polyol (a
The hydroxyl value (average) of -1) is usually 200 or less, preferably 15 to 100, and particularly preferably 20 to 70. If the hydroxyl value exceeds 200, foaming becomes difficult. The weight average molecular weight of the polyol (a-1) is generally 500 to 10,000, preferably 1,000 to 8,000,
More preferably, it is 1000-5000. If the weight average molecular weight is less than 500, foaming becomes difficult and 10,000
If it exceeds, the viscosity of the resulting polymer polyol composition increases and handling becomes difficult.

As the polyol (a-2) constituting the reactive dispersant (b) in the present invention, those exemplified as the above (a-1) can be used. The (a-2) and (a-
1) may be the same or different.

The methylene dihalide used in the production of the reactive dispersant (b) includes dichloromethane, dibromomethane, etc., and is preferably dichloromethane. Examples of the ethylene dihalide include 1,2-dichloroethane and 1,2-bromoethane, and preferably 1,2-dibromoethane.

The vinyl group-containing compound (d) used in the production of the reactive dispersant (b) is a vinyl group-containing compound having a hydroxyl-reactive functional group, and may be (meth) acrylic acid or a derivative thereof [glycidyl ( Meth) acrylate, and (anhydride) maleic acid. Among them, particularly preferred is glycidyl (meth) acrylate.

The reactive dispersant (b) used for producing the polymer polyol composition (A) of the present invention includes, for example, the polyol (a-2), methylene dihalide and / or
Alternatively, it can be produced by reacting ethylene dihalide with the vinyl group-containing compound (d) by a conventional method. In this case, it is desirable that a part of the hydroxyl groups in (a-2) be converted to an alcoholate of an alkali metal (for example, potassium or sodium) and then reacted. Although the alkali metal halide by-produced by the reaction may be removed,
It is not necessary to remove it. The reaction temperature is usually 10 to 200 ° C,
The reaction pressure is preferably 50 to 150 ° C., and the reaction pressure is not particularly limited, but is usually 0 to 20 atm, preferably 0 to 10 atm in consideration of the boiling point of methylene dihalide or the like (particularly, in the case of dichloromethane). In the above reaction, a solvent may be used if necessary. When a solvent is used, a solvent that uniformly dissolves the reaction system (toluene, tetrahydrofuran, N, N dimethylformamide, etc.) is desirable. Examples of the reaction vessel include a reaction tank provided with a stirring device or various known mixers. Examples of known various mixers include an extruder, a Brabender, a kneader, and a Banbury mixer.

The weight average molecular weight of the reactive dispersant (b) is generally 2 to the weight average molecular weight of the polyol (a-2).
It is 6 times, preferably 2 to 4 times. If it is less than 2 times, the dispersion stability of the polymer polyol (A) becomes insufficient, and if it exceeds 6 times, the viscosity becomes high. As a result, the viscosity of (A) also becomes high and handling becomes difficult.

The viscosity of (b) is usually from 600 to 10,000 cps at 25 ° C., preferably from 800 to 8 cps.
000 cps, more preferably 1000-6000 c
ps. If the molecular weight is less than 600 cps, a sufficient dispersion stabilizing effect cannot be obtained. On the other hand 10
If it exceeds 000 cps, the viscosity of (A) becomes too high and handling becomes difficult.

The amount of (b) used in producing the polymer polyol composition (A) of the present invention is usually 1 to 60% by weight, preferably 2 to 40% by weight, based on the weight of (A).
More preferably, it is 2 to 20% by weight. If it is less than 1% by weight, good dispersion stability (A) cannot be obtained, and 60% by weight.
Exceeding the viscosity of (A) makes handling difficult.

The vinyl monomer (c) used for producing the polymer polyol (A) includes aromatic hydrocarbon monomers (c-2), unsaturated nitriles (c-3), (meth) Acrylic esters (c-4) and mixtures of two or more thereof are preferred. (C-2) includes styrene, α
-Methylstyrene, hydroxystyrene, chlorostyrene and the like. Examples of (c-3) include acrylonitrile and methacrylonitrile. (C
-4) include (meth) acrylic acid alkyl esters (alkyl group having 1 to 30 carbon atoms) [specifically, methyl (meth) acrylate, butyl (meth) acrylate, nonyl (meth) acrylate, decyl ( (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) Acrylate, docosyl (meth) acrylate, etc.], and hydroxypolyoxyalkylene ether mono (meth) acrylates.

If necessary, other monomers (c)
-5) can also be used. Examples of (c-5) include ethylenically unsaturated carboxylic acids and derivatives thereof (such as (meth) acrylic acid and (meth) acrylamide), aliphatic hydrocarbon monomers [such as ethylene and propylene], and fluorine-containing vinyl monomers. (Eg, perfluorooctylethyl methacrylate, perfluorooctylethyl acrylate), nitrogen-containing vinyl monomers (eg, diaminoethyl methacrylate, morpholinoethyl methacrylate), and vinyl-modified silicon.

(C-2), (c) in the vinyl monomer (c)
The weight ratio of (-3), (c-4) and, if necessary, (c-5) can be changed according to the required physical properties of the polyurethane and the like, and are not particularly limited. is there. (C-2): usually 5 to 100% by weight, preferably 20 to 100% by weight
100% by weight, more preferably 50 to 100% by weight. (C-3): usually 0 to 95% by weight, preferably 20 to 8%
0% by weight. (C-4): usually 0 to 50% by weight, preferably 0 to 20%
weight%. (C-5): Usually 0 to 10% by weight, preferably 0 to 5% by weight.

The weight ratio of (c-2) to (c-3) is usually (5:95) to (100: 0), and preferably (2:95).
0:80) to (100: 0), and more preferably (5
0:50) to (100: 0).

In the production of (A) of the present invention, by dispersing (A) by using a bifunctional or higher-functional polyfunctional vinyl monomer (c-1) as at least a part of vinyl monomer (c). Stability can be further improved. The (c-
1) divinylbenzene, ethylenedi (meth)
Examples include acrylate, polyalkylene oxide glycol, di (meth) acrylate, pentaerythritol triallyl ether, and trimethylolpropane tri (meth) acrylate.

The amount of (c-1) is usually 0.01% to 5%, preferably 0.05% to 1%, based on the total weight of (c).
%.

The content of the polymer comprising (c) in (A) is usually 5 to 60% by weight, preferably 20 to 55% by weight, more preferably 35 to 50% by weight based on the weight of (A).
% By weight. If the content of the polymer is less than 5% by weight, sufficient foam compression hardness cannot be obtained, and if it exceeds 60% by weight, the viscosity of (A) becomes high and handling becomes difficult.

The production of the polymer polyol composition (A) of the present invention can be carried out in the presence of the reactive dispersant (b) in the same manner as in the usual method for producing a polymer polyol. Specific examples of the polymerization method include a polyol (a) containing (b)
-1), a method of polymerizing a vinyl monomer (c) in the presence of a polymerization initiator (for example, US Pat. No. 3,383,351, JP-B-39-24737, JP-B-47-47).
47999 and a method described in JP-A-50-15894. Examples of the polymerization initiator include those which generate free radicals to initiate polymerization, for example, 2,2′-azobisisobutyronitrile, 2,2′-
Azobis (2,4-dimethylvaleronitrile), 2,
2′-azobis (2-methylbutyronitrile), 1,
1′-azobis (cyclohexane-1-alkonitrile), 2,2′-azobis (2,4,4-trimethylpentane), dimethyl 2,2′-azobis (2-methylpropionate), 2,2 ′ Azo compounds such as -azobis [2- (hydroxymethyl) propionitrile] and 1,1'-azobis (1-acetoxy-1-phenylethane); dibenzoyl peroxide, dicumyl peroxide, bis (4-t -Butylcyclohexyl) peroxydicarbonate, benzoyl peroxide, lauroyl peroxide, organic peroxides such as persuccinic acid and peroxides other than those described in JP-A-61-76517; persulfates, perborates Inorganic peroxides such as acid salts can be used. These may be used in combination of two or more.

The amount of the polymerization initiator to be used is generally 0.05 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.2 to 5% by weight, based on the weight of the vinyl monomer (c).
2.5% by weight. If the amount of the polymerization initiator used is less than 0.1% by weight, the polymerization rate of (c) decreases, and a sufficient content of the polymer composed of (c) in the polymer polyol (A) cannot be obtained, so that 10% by weight is not obtained. If the ratio exceeds the above range, the molecular weight of the polymer (c) decreases, and a sufficient foam compression hardness cannot be obtained.

The above polymerization reaction can be carried out without a solvent, but can be carried out in the presence of an organic solvent if necessary (especially when the polymer concentration is high). Examples of the organic solvent include benzene, toluene, xylene, acetonitrile, ethyl acetate, hexane, heptane, octene, nonene, decene, dioxane, N, N-dimethylformamide, N,
N-dimethylacetamide, isopropyl alcohol,
n-butanol and the like. If necessary, a chain transfer agent [for example, alkyl mercaptans (dodecyl mercaptan, mercaptoethanol, etc.), alcohols (isopropyl alcohol, methanol, 2-butanol, allyl alcohol, etc.), halogenated hydrocarbons (carbon tetrachloride, tetrabromide) , Chloroform, etc.), enol ethers described in JP-A-55-31880, etc.].

The polymerization can be carried out either batchwise or continuously. The polymerization reaction is at or above the decomposition temperature of the polymerization initiator, usually 6
The reaction is carried out at a temperature of 0 to 180 ° C, preferably 90 to 160 ° C, particularly preferably 100 to 150 ° C, and can be carried out under normal pressure or under pressure, and further under reduced pressure. The polymer polyol composition (A) thus obtained may be directly used for the production of polyurethane without any post-treatment, but after the polymerization reaction is completed, an organic solvent, a decomposition product of a polymerization initiator, an unreacted product, It is desirable to remove impurities such as monomers by conventional means (eg, stripping). The hydroxyl value of the polymer polyol composition (A) is usually 5 to 10
0, preferably 7 to 80, more preferably 10 to 50.

In the process for producing a polyurethane of the present invention, which comprises reacting a polyol with an organic polyisocyanate,
The polymer polyol composition (A) can be used in combination with another known active hydrogen atom-containing compound, if necessary. As the other active hydrogen atom-containing compound, other high molecular polyols (B) and / or low molecular weight active hydrogen atom-containing compounds (C) commonly used for producing polyurethane can be used.

As the other high molecular polyol (B), polyether polyol, polyester polyol, modified polyol and a mixture thereof can be used. Examples of the polyether polyol include those similar to the polyether polyol exemplified in the section of the raw material polyol (a-1) in the above (A). Examples of the polyester polyol include the above-mentioned polyhydric alcohols (eg, dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol; And glycerin, trimethylolpropane and other trivalent or higher alcohols) and polycarboxylic acids or their anhydrides, and ester-forming derivatives such as lower esters (eg, adipic acid, sebacic acid, maleic anhydride, phthalic anhydride) Acid, dimethyl terephthalate, etc.); alkylene oxide (EO, PO, etc.) addition reactants; and products obtained by ring-opening polymerization of lactones (ε-caprolactone, etc.). As modified polyols, polyols obtained by polymerizing these polyols (such as polyether polyols and / or polyester polyols) and ethylenically unsaturated monomers (JP-A-54-1018)
No. 99, JP-A-54-122396, etc.). In addition, polydiene polyols (such as polybutadiene polyol) and hydroxyl-containing vinyl polymers (acrylic polyols) (for example,
-57413 and JP-A-58-57414) and natural oil-based polyols such as castor oil.
The modified polyol can also be used. These other high molecular polyols (B) are usually 2 to 8, preferably 3
It has up to 8 hydroxyl groups and an OH equivalent of usually 200-4000, preferably 400-3000. Particularly preferred as (B) is a polyether polyol.

As the low molecular weight active hydrogen atom-containing compound (C) to be used if necessary, at least two (preferably two to three, particularly preferably two) active hydrogen atoms (hydroxyl group, amino group, mercapto group) Etc., preferably having a molecular weight of 500 or less (preferably 60 to 4) having a hydroxyl group.
00), for example, low molecular polyols and amino alcohols. Low molecular polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4
-Dihydric alcohols such as butanediol, neopentyl glycol and hexanediol; glycerin, trimethylolpropane, pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylitol, mannitol, dipentaerythritol, glucose, fructose, sucrose Trihydric or higher polyhydric alcohols; low molecular weight (for example, molecular weight 200 to 400) polyhydric alcohol alkylene oxide adducts (polyethylene glycol, polypropylene glycol, etc.); low molecular weight diols having a cyclic group [for example, 14
No. 74 (propylene oxide adduct of bisphenol A, etc.)]; tertiary or quaternary nitrogen atom-containing low molecular polyol [for example, JP-A-54-1306]
No. 99 (N-alkyldialkanolamines such as N-methyldiethanolamine, N-butyldiethanolamine and the like and quaternary compounds thereof); trialkanolamines (triethanolamine, tripropanolamine, etc.)]; thiodiethylene glycol And the like. Amino alcohols include mono- or di-alkanolamines such as monoethanolamine, diethanolamine, monopropanolamine, and the like. Of these, low molecular polyols (particularly diols) are preferred, and specific examples thereof include ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, and a mixture of two or more of these. It is.

The amount of (A) in the active hydrogen atom-containing compound [(A) and, if necessary, (B) and / or (C)] in the process for producing the polyurethane of the present invention is usually at least 5% by weight, preferably at least 5% by weight. It is at least 10% by weight, more preferably at least 20% by weight. When the amount of (A) is less than 5% by weight, the compression hardness of the urethane foam becomes insufficient. The amount of (B) is usually 0 to 95.
%, Preferably from 0 to 80% by weight. (B) is 9
If it exceeds 5% by weight, the foam hardness is not high. further,
The amount of (C) is usually 0 to 30% by weight, preferably 0 to 10% by weight.
% By weight. When the amount of (C) exceeds 30% by weight,
The exothermic temperature during the reaction increases, causing scorch.

As the organic polyisocyanate used in the method for producing a polyurethane of the present invention, known organic polyisocyanates conventionally used for producing polyurethane can be used. Such polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group) (for example, 2,4- and / or 2,6-
Tolylene diisocyanate (TDI), crude TDI,
2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [condensation product of crude diaminophenylmethane} formaldehyde with an aromatic amine (aniline) or a mixture thereof: diaminodiphenylmethane and a small amount ( A phosgenated product of a mixture with a trifunctional or higher polyamine (for example, 5 to 20% by weight): polyallyl polyisocyanate (PAPI), etc.]; aliphatic polyisocyanate having 2 to 18 carbon atoms (for example, hexamethylene diisocyanate, lysine diisocyanate, etc.) Alicyclic polyisocyanate having 4 to 15 carbon atoms (eg, isophorone diisocyanate, dicyclohexylmethane diisocyanate);
5 aromatic aliphatic polyisocyanates (eg, xylylene diisocyanate); and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, buret group, uretdione group, uretonimine group, isocyanurate group, Oxazolidone group-containing modified products); and JP-A-61-7
No. 6517, other polyisocyanates described above;
And mixtures of two or more of these. Preferred among these are the commercially available polyisocyanates such as 2,4- and 2,6-T
DI, a mixture of these isomers, crude TDI, 4,4 ′
-And 2,4'-MDI, mixtures of these isomers,
PAPI, also referred to as crude MDI; and modified polyisocyanates containing urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, and isocyanurate groups derived from these polyisocyanates. In the present invention, the isocyanate index [NCO / equivalent ratio of active hydrogen atom-containing group × 100] in the production of polyurethane is usually 80 to 140, preferably 85 to 120, and particularly preferably 95 to 115. It is also possible to introduce polyisocyanurate groups into the polyurethane with an isocyanate index significantly higher than the above range (for example 300 to 1000 or more).

In the production of polyurethane, in order to accelerate the reaction, catalysts usually used for polyurethane reaction [for example, amine catalysts (tertiary amines such as triethyleneamine and N-ethylmorpholine), tin catalysts (octylic acid) Stannous, dibutyltin dilaurate, and other metal catalysts (such as lead octylate)]. The amount of catalyst is usually from 0.001 to 5% by weight, based on the weight of the reaction mixture. In the present invention, a foaming agent (for example, methylene chloride, monofluorotrichloromethane, water, etc.) can be used as needed in the production of polyurethane. The amount of the foaming agent can be arbitrarily changed depending on the desired density of the polyurethane. In the present invention, a foam stabilizer can be used if necessary. Examples of the foam stabilizer include a silicone surfactant (polysiloxane-polyoxyalkylene copolymer). In the present invention, a flame retardant can be used if necessary. Flame retardants include melamines, phosphate esters, halogenated phosphate esters, phosphazene derivatives and the like. Other additives that can be used in the present invention include known additives such as a reaction retarder, a colorant, an internal release agent, an antioxidant, an antioxidant, a plasticizer, a bactericide, carbon black and other fillers. No.

The production of the polyurethane can be carried out by a usual method, and can be carried out by a known method such as a one-shot method, a semi-prepolymer method or a prepolymer method. For the production of polyurethane, a commonly used production apparatus can be used. When no solvent is used, for example, a device such as a kneader or an extruder can be used. The production of various non-foamed or foamed polyurethanes can be carried out in closed or open molds. Polyurethane is usually produced by mixing and reacting raw materials using a low-pressure or high-pressure mechanical device. Further, polyurethane can be produced by removing a gas such as dissolved air in the raw material or air mixed during mixing before and after the raw material is mixed (particularly before the raw material is mixed) by a vacuum method. The method of the present invention is particularly useful for making flexible molded and slab foams. Also RI
It can also be applied to molding by the M (reaction injection molding) method.

[0037]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
In the following, parts,% and ratio indicate parts by weight,% by weight and ratio by weight, respectively.

The compositions, symbols, etc. of the raw materials used in the examples and comparative examples are as follows. (1) Polyol: Polyol a1: a polyol having a weight average molecular weight of 3000 and a hydroxyl value of 55 obtained by adding PO to glycerin. Polyol a2: PO is added to glycerin and then EO
Weight average molecular weight of 300
0, polyol having a hydroxyl value of 55 (EO content: 5%). Polyol a3: a polyol having a weight average molecular weight of 5,000 and a hydroxyl value of 34 obtained by adding PO to glycerin. Polyol a4: PO is added to glycerin and then E
O-added weight average molecular weight 7000, hydroxyl value 24
(EO content 14%). Polyol a5: PO is added to glycerin and then E
O-added weight average molecular weight 3500, hydroxyl value 46
(EO content 14%).

(2) Modified polyol: Modified polyol b1: A polymer having a weight average molecular weight of 16,800 and a viscosity of 23,600 cps (25 ° C.) synthesized from polyol a5 and tetraethoxysilane according to Example 2 described in JP-B-6-62841. Modified polyol. Modified polyol b2: a viscosity of 25,000 cp synthesized from a polyol having 2 functional groups and a weight average molecular weight of 5000, TDI and 2-hydroxyethyl methacrylate according to Reference Example 2 described in JP-A-61-115919.
s modified polyol.

(3) Vinyl monomer, etc .: ACN: acrylonitrile St: styrene GMA: glycidyl methacrylate EO: ethylene oxide PO: propylene oxide MDC: methylene dichloride

(4) Polymerization initiator: AVN: 2,2'-azobis (2,4-dimethylvaleronitrile) (5) Polyisocyanate: TDI-80 (manufactured by Nippon Polyurethane Industry Co., Ltd.) (6) Catalyst: Catalyst A: DABCO (diaminobicyclooctane) [manufactured by Nippon Emulsifier Co., Ltd.] Catalyst B: Neostan U-28 (tin catalyst) [manufactured by Nitto Kasei Co., Ltd.] MeONa: sodium methoxide (7) Foam stabilizer: F- 242T; polyether siloxane polymer [Shin-Etsu Silicone Co., Ltd.]

Production Examples 1 to 10 [Production of Reactive Dispersant (b) (Modified Polyol)] 1 L capacity equipped with a temperature controller, a vacuum stirring blade, a dropping funnel, a decompression device, a Dimroth, a nitrogen inflow and an outflow outlet In a four-necked flask, add 50 parts of polyol a1 under a nitrogen stream.
Then, 0 g was added and the mixture was dehydrated under reduced pressure at 120 ° C. and 1 Torr for 2 hours.
Subsequently, the mixture was cooled to 50 ° C., and 16 g of MeONa was added.
The methanol was removed at 0 ° C. and 1 Torr for 6 hours. Thereafter, the temperature is cooled to 120 ° C. and methylene dichloride (MDC)
20 g was added dropwise and the mixture was stirred for 3 to 6 hours. After cooling at 60 ° C., 8 g of glycidyl methacrylate was added and stirred for 1 hour. After cooling, the by-produced salt was removed by filtration to produce a reactive dispersant b3. According to the formulation shown in Table 1, reactive dispersants b4 to b12 were produced in the same manner. Table 1 shows the composition and properties of these raw materials.

[0043]

[Table 1]

Comparative Examples 1 to 3 and Examples 1 to 9 According to the compositions shown in Tables 2 and 3, 1 L equipped with a temperature controller, a vacuum stirring blade, a dropping pump, a decompression device, a Dimroth, a nitrogen inlet and an outlet were provided. In a four-necked flask having a capacity of 25%, the equivalent of 25% of polyol a1 was added and stirred at 125 ° C.
Then, the raw material liquid (the remaining raw material blended liquid) is continuously dropped by a dropping pump over 4 hours to synthesize comparative polymer polyols A1 to A3 and polymer polyols A4 to A12 of the present invention. did. Unless otherwise indicated, unreacted monomers were stripped under reduced pressure. The properties and the like are shown in Tables 2 and 3.

[0045]

[Table 2]

[0046]

[Table 3]

Comparative Examples 4 and 5 and Examples 10 to 13 Comparative polymer polyols obtained according to the formulations shown in Tables 2 and 3 and some of the polymer polyols of the present invention were used and described in Table 4. A foamed polyurethane was produced according to the foaming recipe of Table 4 shows the evaluation results of these foam properties.

[0048]

[Table 4]

The evaluation method of the physical properties of the foam in Table 4 is as follows. Density (kg / m ³ ): JIS K6301 25% ILD (kg / 314 cm ² ): JIS K63
82 Tensile strength (kg / cm ² ): JIS K6301 Tear strength (kg / cm): JIS K6301 Cutting elongation (%): JIS K6301 Rebound resilience (%): JIS K 6382 Breathability (ft ³ / min): Dow Type flow meter method (specimen 5 × 5 × 2.5) Compression set (%): JIS K 6382

[0050]

Industrial Applicability The polymer polyol composition of the present invention has a higher polymer content and extremely excellent dispersion stability as compared with those of the prior art. Further, according to the method for producing a polyurethane of the present invention using the polymer polyol composition as an essential polyol component, a polyurethane foam having high hardness and good compression set, which does not generate scorch, as compared with the conventional method. Can be produced, and other foam properties such as elongation at break can be improved. Due to the above effects, the polyurethane foam obtained according to the present invention exhibits remarkable utility in applications such as interior preparation of interior parts and furniture of automobiles.

Continuation of the front page (58) Fields surveyed (Int. Cl. ⁶ , DB name) C08L 71/02 C08F 2/44 C08F 283/06 C08G 18/63 C08G 65/32

Claims (9)

(57) [Claims] 1. A polymer polyol composition (A) obtained by polymerizing a vinyl monomer (c) in a polyol (a-1) in the presence of a reactive dispersant (b) shown below. Reactive dispersant (b): at least a part of the hydroxyl group of polyol (a-2) is reacted with methylene dihalide and / or ethylene dihalide to have a high molecular weight, and the reaction product is further added to a vinyl group-containing compound (d ) Reacted vinyl group-containing modified polyol 2. The polymer polyol composition (A) according to claim 1, wherein at least 95% by weight of the vinyl monomer (c) is a styrene monomer. 3. The polymer polyol composition according to claim 1, wherein at least a part of the vinyl monomer (c) is a polyfunctional vinyl monomer (c-1) having two or more vinyl groups. Object (A). 4. The polymer polyol composition (A) according to claim 1, wherein the weight average molecular weight of (a-1) and (a-2) is from 500 to 10,000. 5. The weight average molecular weight of (b) is (a-2)
The polymer polyol composition (A) according to any one of claims 1 to 4, wherein the weight average molecular weight of the polymer polyol composition is 2 to 6 times. 6. The polymer polyol composition (A) according to claim 1, wherein the content of (b) is 1 to 60% by weight based on the weight of (A). 7. The polymer polyol composition (A) according to claim 1, wherein (d) is a (meth) acrylic acid derivative. 8. The content of the polymer (e) from (c) is:
The amount is from 5 to 60% based on the weight of (A).
The polymer polyol composition (A) according to any one of the above. 9. A method for producing a polyurethane by reacting a polyl with an organic polyisocyanate, wherein the polymer polyol composition (A) according to claim 1 is used as at least a part of a polyol. The method of producing polyurethane.