JPH08333508A - Polymer polyol composition and production of polyurethane - Google Patents

Abstract

PURPOSE: To obtain a composition having a high content of a polymer, excellent in dispersion stability and useful as a raw material for producing a foamed polyurethane for an automobile interior trim, etc., by polymerizing a vinyl monomer in a polyol in the presence of a specific reactive dispersant. CONSTITUTION: This composition is obtained by polymerizing (C) a vinyl monomer (e.g. a vinyl monomer containing >=95wt.% of styrene) in (A) a polyol in the presence of (B) a reactive dispersant, a vinyl group-containing modified polyol, produced by reacting at least a part of OH of a polyol (B1 ) with methylene dihalide or ethylene dihalide to make it high molecular weight and subsequently reacting the reaction product with a vinyl group-containing compound [e.g. (meth)acrylic acid derivative]. Preferably, a weight-average molecular weight (MW) of the component A and that of B1 are each in 500-10,000, and MW of the composition B is 2-6 times that of B1 . The objective composition preferably contains 1-60wt.% of the component B.

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 Conventionally, as means for obtaining a polymer polyol having a high polymer content and good dispersion stability, a part of the polyol is a coupling agent (silicon-containing compound, tetraxyalkoxyorthoformate, trialkoxyalkane). , A 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), and a vinyl monomer in the presence of a macromer containing a urethane bond. A method of polymerizing a monomer (for example, JP-A-61-115919).
Etc. are known.

[0003]

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

[0004]

DISCLOSURE OF THE INVENTION The present inventors have found that a polymer polyol composition capable of obtaining a foam having a high viscosity, a low viscosity, a good dispersion stability, a high hardness and a good compression strain. As a result of repeated 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 the presence of the following reactive dispersant (b) in the polyol (a-1); The present invention relates to a method for producing a polyurethane, which comprises using A) as an essential polyol component. Reactive dispersant (b): At least a part of the hydroxyl groups of the 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. Modified vinyl group-containing polyol

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

The polyhydric alcohol has an alkylene glycol (ethylene glycol, diethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.) and a cyclic group. Dihydric alcohols such as diols (for example, those described in Japanese Patent Publication No. 45-1474); trihydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, hexanetriol, triethanolamine; pentaerythritol, methylglycoside, diglycerin. Tetrahydric alcohols such as; and alcohols having a higher number of functional groups,
For example, pentitol (Adonitol, arabitol,
Xylitol, etc.), hexitol (sorbitol, mannitol, iditol, taritol, dulcitol, etc.), sugars [sucrose, monosaccharides (glucose, mannose, fructose, sorbose, etc.), oligosaccharides (crehalose, lactose, raffinose, etc.)]; glycosides; [Glucosides of polyols (alkane polyols such as glycol, glycerin, trimethylolpropane and hexanetriol)]; polyalkane polyols [eg polyglycerin such as triglycerin and tetraglycerin]; polypentaerythritol (dipentaerythritol, tripentaerythritol) Etc.); cycloalkane polyols [tetrakis (hydroxymethyl) cyclohexanol, etc.] and the like.

The polyhydric phenols include monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A and bisphenol sulfone; condensates of phenol and formaldehyde (Novolak), US Pat. No. 32,656.
Examples thereof include polyphenols described in No. 41.

As the above amines, ammonia; alkanolamines such as mono-, di- and triethanolamine, isopropanolamine, aminoethylethanolamine; alkylamines having 1 to 20 carbon atoms;
Aliphatic amines having 2 to 6 carbon atoms such as ethylenediamine, propylenediamine, hexamethylenediamine, polyalkylenepolyamines such as diethylenetriamine and triethylenetetramine; aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline, Aromatic amines such as diphenyl ether diamine; alicyclic amines such as isophorone diamine, cyclohexylene diamine, dicyclohexyl methane diamine; aminoethyl piperazine and other heterocyclic amines described in JP-B-55-21044. .

Two or more kinds of these active hydrogen atom-containing compounds may be used in combination. Of these, polyhydric alcohols are particularly preferable.

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

The polyol (a-1) in the present invention is preferably a polyether polyol, but other polyols may be used instead of or together with the polyether polyol. Examples of other polyols include polymer polyols (polyester polyols, polybutadiene polyols, acrylic polyols, etc.) described below, and / or
Alternatively, a low molecular weight polyol may be used. Polyol (a
The hydroxyl value (average) of -1) is usually 200 or less, preferably 15 to 100, 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 usually 500 to 10000, preferably 1000 to 8000,
More preferably, it is 1000 to 5000. If the weight average molecular weight is less than 500, foaming becomes difficult and 10,000
If it exceeds, the viscosity of the polymer polyol composition obtained 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-
It may be the same as or different from 1).

Examples of the methylene dihalide used for producing the reactive dispersant (b) include dichloromethane, dibromomethane and the like, preferably dichloromethane. Examples of the ethylene dihalide include 1,2-dichloroethane, 1,2-bromoethane and the like, and 1,2-dibromoethane is preferable.

The vinyl group-containing compound (d) used for producing the reactive dispersant (b) is a vinyl group-containing compound having a hydroxyl group-reactive functional group, and is (meth) acrylic acid or its derivative [glycidyl ( (Meth) acrylate, etc.], (anhydrous) maleic acid and the like. Among these, glycidyl (meth) acrylate is particularly preferable.

The reactive dispersant (b) used for producing the polymer polyol composition (A) of the present invention includes, for example, the above-mentioned 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 group of (a-2) is converted to an alkali metal alcoholate (for example, potassium, sodium, etc.) and reacted. Although the alkali metal halide salt by-produced by the reaction may be removed,
It need not be removed. The reaction temperature is usually 10 to 200 ° C,
The reaction pressure is preferably 50 to 150 ° C., but the reaction pressure is not particularly limited, but is usually 0 to 20 atm, preferably 0 to 10 atm in consideration of the boiling points of methylene dihalide and the like (particularly in the case of dichloromethane). A solvent may be used if necessary in the above reaction. When a solvent is used, a solvent (toluene, tetrahydrofuran, N, N dimethylformamide, etc.) capable of uniformly dissolving the reaction system is desirable. Examples of the reaction container include a reaction tank equipped with a stirrer and various known mixers. Examples of various known mixers include an extruder, a Brabender, a kneader, and a Banbury mixer.

The weight average molecular weight of the reactive dispersant (b) is usually 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) will be insufficient, and if it exceeds 6 times, the viscosity will be high, and as a result, the viscosity of (A) will be high and handling will be difficult.

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

The amount of (b) used in the production of 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, (A) having good dispersion stability cannot be obtained, and 60% by weight
If it exceeds, the viscosity of (A) becomes high and handling becomes difficult.

The vinyl monomer (c) used for producing the polymer polyol (A) includes aromatic hydrocarbon monomers (c-2), unsaturated nitriles (c-3) and (meth). Acrylic acid esters (c-4) and a mixture of two or more thereof are preferable. Examples of (c-2) include styrene and α
-Methylstyrene, hydroxystyrene, chlorostyrene and the like. Examples of (c-3) include acrylonitrile and methacrylonitrile. (C
-4) includes (meth) acrylic acid alkyl esters (wherein the alkyl group has 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.

In addition to the above, other monomers (c
-5) can also be used. Examples of the (c-5) include ethylenically unsaturated carboxylic acid and its derivative [(meth) acrylic acid, (meth) acrylamide, etc.], aliphatic hydrocarbon monomer [ethylene, propylene, etc.], fluorine-containing vinyl monomer Body [perfluorooctylethylmethacrylate, perfluorooctylethylacrylate, etc.], nitrogen-containing vinyl monomer [diaminoethylmethacrylate, morpholinoethylmethacrylate, etc.], vinyl-modified silicone and the like.

(C-2) and (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 is not particularly limited, but an example is as follows. is there. (C-2): usually 5 to 100% by weight, preferably 20 to
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), preferably (2).
0:80) to (100: 0), more preferably (5
0:50) to (100: 0).

In the production of (A) of the present invention, by using a bifunctional or more polyfunctional vinyl monomer (c-1) as at least a part of the vinyl monomer (c), the dispersion of (A) The stability can be further improved. The (c-
1) includes divinylbenzene and ethylenedi (meth)
Examples thereof 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 consisting of (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. When the content of the polymer is less than 5% by weight, sufficient foam compression hardness cannot be obtained, and when it exceeds 60% by weight, the viscosity of (A) becomes high and handling becomes difficult.

The polymer polyol composition (A) of the present invention can be produced in the presence of the reactive dispersant (b) in the same manner as a usual method for producing a polymer polyol. Specific examples of the polymerization method include a polyol (a) containing (b).
-1), a method of polymerizing the vinyl monomer (c) in the presence of a polymerization initiator (for example, U.S. Pat. No. 3,383,351, JP-B-39-24737, JP-B-47-).
No. 47799 and Japanese Patent Laid-Open No. 50-15894). The above-mentioned polymerization initiator is of a type that generates 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-arbonitrile), 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, persuccinic acid and other organic peroxides and peroxides other than those described above 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 above-mentioned polymerization initiator used is usually 0.05 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.2 to 10% by weight based on the weight of the vinyl monomer (c).
It is 2.5% by weight. When the amount of the polymerization initiator used is less than 0.1% by weight, the polymerization rate of (c) is lowered, and a sufficient amount of the polymer composed of (c) in the polymer polyol (A) cannot be obtained. If it exceeds, the molecular weight of the polymer composed of (c) decreases, and 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 (particularly 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,
Examples include n-butanol and the like. If necessary, a chain transfer agent [eg, alkyl mercaptans (dodecyl mercaptan, mercaptoethanol, etc.), alcohols (isopropyl alcohol, methanol, 2-butanol, allyl alcohol, etc.), halogenated hydrocarbons (carbon tetrachloride, tetrabromide, etc.) Carbon, chloroform, etc.), enol ethers described in JP-A-55-31880, and the like].

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

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

As the other polymer polyol (B), polyether polyol, polyester polyol, modified polyol and mixtures thereof can be used. Examples of the polyether polyol include the same as the polyether polyols exemplified in the section of the raw material polyol (a-1) in (A) above. As the polyester polyol, the polyhydric alcohol (dihydric alcohol such as ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, or the like And a mixture of triglyceride or trihydric alcohol such as glycerin or trimethylolpropane) and polycarboxylic acid or its anhydride, or an ester-forming derivative such as a lower ester (eg, adipic acid, sebacic acid, maleic anhydride, phthalic anhydride). Acid, dimethyl terephthalate, etc.); its alkyleonoxide (EO, PO, etc.) addition reaction product; and those obtained by ring-opening polymerization of a lactone (ε-caprolactone etc.). As the modified polyol, a polyol obtained by polymerizing these polyols (polyether polyol and / or polyester polyol, etc.) and an ethylenically unsaturated monomer (JP-A-54-1018).
99, JP-A No. 54-122396, etc.). Further, polydiene polyols (polybutadiene polyols, etc.), hydroxyl group-containing vinyl polymers (acrylic polyols) (for example, JP-A-58)
-57413 and JP-A-58-57414) and castor oil and other natural oil-based polyols,
The modified polyol etc. can also be used. These other polymer polyols (B) are usually 2 to 8, preferably 3
~ 8 hydroxyl groups and OH equivalent of usually 200 to 4000, preferably 400 to 3000. Particularly preferred as the (B) is a polyether polyol.

The low molecular weight active hydrogen atom-containing compound (C) optionally used is at least 2 (preferably 2 to 3, particularly preferably 2) active hydrogen atoms (hydroxyl group, amino group, mercapto group). Etc., preferably having a hydroxyl group, having a molecular weight of 500 or less (preferably 60 to 4)
00), such as low molecular weight polyols and amino alcohols. As the low molecular weight polyol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4
-Butanediol, neopentyl glycol, hexanediol and other dihydric alcohols; glycerin, trimethylolpropane, pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose, sucrose. Trihydric or higher polyhydric alcohol; low molecular weight (for example, 200 to 400) polyhydric alcohol alkylene oxide adducts (polyethylene glycol, polypropylene glycol, etc.); low molecular diols having a cyclic group [for example, Japanese Patent Publication No. 14
No. 74 (Propylene oxide adduct of bisphenol A, etc.)]; Tertiary or quaternary nitrogen atom-containing low molecular weight polyol [for example, JP-A-54-1306].
Those described in Japanese Patent Publication No. 99 (N-alkyldialkanolamines such as N-methyldiethanolamine, N-butyldiethanolamine and the like and their quaternary compounds); trialkanolamines (triethanolamine, tripropanolamine and the like)]; thiodiethylene glycol Etc. Amino alcohols include mono- or di-alkanolamines such as monoethanolamine, diethanolamine, monopropanolamine, etc.). Of these, preferred are low molecular weight polyols (particularly diols), specifically ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol and mixtures of two or more thereof. Is.

The amount of (A) in the whole active hydrogen atom-containing compound [(A) and optionally (B) and / or (C)] in the method for producing the polyurethane of the present invention is usually 5% by weight or more, preferably It is 10% by weight or more, more preferably 20% by weight or more. If the amount of (A) is less than 5% by weight, the compression hardness of the foam will be insufficient when it is made into a urethane foam. The amount of (B) is usually 0 to 95.
% By weight, preferably 0-80% by weight. (B) is 9
If it exceeds 5% by weight, the foam hardness is not good. further,
The amount of (C) is usually 0 to 30% by weight, preferably 0 to 10%.
% By weight. If the amount of (C) exceeds 30% by weight,
The exothermic temperature during the reaction becomes high and scorch is generated.

As the organic polyisocyanate used in the method for producing polyurethane of the present invention, known ones which have been conventionally used for producing polyurethane can be used. Examples of such polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbons 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 [crude diaminophenylmethane {condensation product of formaldehyde with aromatic amine (aniline) or a mixture thereof: diaminodiphenylmethane and a small amount ( For example, 5 to 20% by weight of a mixture with a trifunctional or higher polyamine} phosgene: polyallyl polyisocyanate (PAPI) and the like]; aliphatic polyisocyanate having 2 to 18 carbon atoms (eg hexamethylene diisocyanate, lysine diisocyanate, etc.) ); C4-C15 alicyclic polyisocyanate (for example, isophorone diisocyanate, dicyclohexylmethane diisocyanate); C8-C1
5 araliphatic polyisocyanates (such as 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, etc.) and JP-A-61-7
Polyisocyanates other than the above described in Japanese Patent No. 6517;
And mixtures of two or more thereof. Preferred of these are the commercially readily available polyisocyanates such as 2,4- and 2,6-T.
DI, mixtures of these isomers, crude TDI, 4,4 '
-And 2,4'-MDI, mixtures of these isomers,
PAPI, which is also called 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 / active hydrogen atom-containing group equivalent ratio × 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 (eg 300 to 1000 or more).

In the production of polyurethane, in order to accelerate the reaction, catalysts usually used in polyurethane reactions [for example, amine catalysts (tertiary amines such as triethyleneamine and N-ethylmorpholine), tin catalysts (octyl acid) are used. Stannous, dibutyltin dilaurate, etc.), other metal catalysts (lead octylate, etc.)] can be used. The amount of catalyst is usually 0.001 to 5% by weight, based on the weight of the reaction mixture. Further, in the present invention, a foaming agent (for example, methylene chloride, monofluorotrichloromethane, water, etc.) can be optionally used in the production of polyurethane. The amount of the blowing agent used can be arbitrarily changed according to the desired density of polyurethane. In the present invention, a foam stabilizer may 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. Examples of flame retardants include melamines, phosphoric acid esters, halogenated phosphoric acid esters, and phosphazene derivatives. Other additives that can be used in the present invention include known additives such as a reaction retarder, a colorant, an internal mold release agent, an antioxidant, an antioxidant, a plasticizer, a bactericide, carbon black and other fillers. Can be mentioned.

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

[0037]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In the following, parts,% and ratios indicate parts by weight,% by weight and ratios by weight, respectively.

The compositions and symbols of the raw materials used in the examples and comparative examples are as follows. (1) Polyol: Polyol a1: A polyol obtained by adding PO to glycerin and having a weight average molecular weight of 3000 and a hydroxyl value of 55. Polyol a2: PO is added to glycerin and then EO
Weight average molecular weight of 300 with addition of PO and PO
0, a polyol having a hydroxyl value of 55 (EO content 5%). Polyol a3: A polyol having a weight average molecular weight of 5000 and a hydroxyl value of 34, which is obtained by adding PO to glycerin. Polyol a4: PO is added to glycerin and then E
O-added weight average molecular weight 7,000, hydroxyl value 24
Polyol (EO content 14%). Polyol a5: PO is added to glycerin and then E
O-added weight average molecular weight 3500, hydroxyl value 46
Polyol (EO content 14%).

(2) Modified polyol: Modified polyol b1: a weight average molecular weight of 16800 and a viscosity of 23600 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 a number of functional groups of 2 and a weight average molecular weight of 5000, TDI, and 2-hydroxyethyl methacrylate according to Reference Example 2 described in JP-A-61-115919.
Modified polyol of s.

(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)] A 1 L capacity equipped with a temperature controller, a vacuum stirring blade, a dropping funnel, a decompressor, a Dimroth, a nitrogen inflow and an outflow port. In a four-necked flask, 50 parts of the polyol a1 was added under a nitrogen stream.
0 g was added and dehydration was performed under reduced pressure at 120 ° C. and 1 Torr for 2 hours.
Then cool to 50 ° C and add 16g MeONa,
Methanol was removed at 0 ° C. and 1 torr for 6 hours. Then cool to 120 ° C and methylene dichloride (MDC)
20 g was added dropwise and 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 salt produced as a by-product was removed by filtration to produce a reactive dispersant b3. Reactive dispersants b4 to b12 were produced in the same manner according to the formulation shown in Table 1. 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 pressure reducing device, a Dimroth, a nitrogen inlet and an outlet. Into a four-necked flask with a capacity of 25% of polyol a1, was added and stirred at 125 ° C.
Then, the raw material liquid (remaining raw material mixture liquid) is continuously dropped by a dropping pump over 4 hours to synthesize comparative polymer polyols A1 to A3 and the polymer polyols A4 to A12 of the present invention. did. Unless otherwise indicated, unreacted monomer was stripped under reduced pressure. The properties thereof are shown in Tables 2 and 3.

[0045]

[Table 2]

[0046]

[Table 3]

Comparative Examples 4, 5 and Examples 10-13 Comparative polymer polyols obtained by the formulations in Tables 2 and 3 and some of the polymer polyols of the invention were used and are listed in Table 4. A foamed polyurethane was produced according to the foaming recipe. Table 4 shows the results of evaluation of physical properties of these foams.

[0048]

[Table 4]

The evaluation methods of the physical properties of foam in Table 4 are 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 Repulsion elastic modulus (%): JIS K6382 Air permeability (ft ³ / min): Dow Type flow meter method (test piece 5 × 5 × 2.5) compression set (%): JIS K6382

[0050]

EFFECT OF THE INVENTION The polymer polyol composition of the present invention has a high polymer content and extremely good dispersion stability as compared with those of the prior art. According to the method for producing a polyurethane of the present invention using the polymer polyol composition as an essential polyol component, scorch-free polyurethane foam having higher hardness and better compression set than those obtained by conventional methods. Can be manufactured, and other physical properties of the foam such as cutting elongation can be improved. Because of the above effects, the polyurethane foam obtained according to the present invention exhibits remarkable utility in applications such as interior furnishings for automobiles and interior furnishings for furniture.

Claims (9)

[Claims] 1. A polymer polyol composition (A) obtained by polymerizing a vinyl monomer (c) in the presence of the following reactive dispersant (b) in the polyol (a-1). Reactive dispersant (b): At least a part of the hydroxyl groups of the polyol (a-2) is reacted with methylene dihalide and / or ethylene dihalide to have a high molecular weight, and the reaction product further contains a vinyl group-containing compound (d). ) Modified vinyl group-containing 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 weights of (a-1) and (a-2) are 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, which has a weight average molecular weight of 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 polymer (e) from (c) is
It is 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 polyol with an organic polyisocyanate, wherein the polymer polyol composition (A) according to any one of claims 1 to 8 is used as at least a part of the polyol. The method of making polyurethane.