JPH08301949A - Production of polymer polyol composition, and composition produced thereby - Google Patents

Abstract

PURPOSE: To obtain a polymer polyol compsn. which has a low viscosity, a small dispersed-particle diameter, and a high polymer content by polymerizing a vinyl monomer (C) in a polyol (A) in the presence of a specific vinyl oligomer (B) to thereby form a dispersion. CONSTITUTION: Pref. the component A has an average hydroxyl value of 20-70 and is a polyether polyol. The component B having a wt. average mol.wt. of 1,000-30,000 is used usually in an amt. of 0.5-20wt.% of the objective compsn. Pref. examples of the component C are a styrenic compd., an unsatd. nitrile, and a (meth)acrylic ester. The compsn. is produced by a conventional process for producing a polymer polyol, except that the polymn. is conducted in the presence of the component B. For instance, the compsn. having a hydroxyl value of 5-100 is obtd. by polymerizing component C in the component A in the presence of a polymn. initiator at the decomposition temp. of the initiator or higher (usually at 60-180 deg.C) in a wt. ratio of A/B of (99:1)-(3:2).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polymer polyol composition and a polymer polyol composition which can be suitably used as an active hydrogen compound component for polyurethane production.

[0002]

2. Description of the Related Art Conventionally, when a urethane foam is produced by using an organic polyisocyanate and an active hydrogen atom-containing compound as a polyurethane production method, styrene and A method using a polymer polyol obtained by copolymerizing acrylonitrile is known. In order to increase the compressive strength of the urethane foam, it is necessary to increase the polymer content in the polymer polyol, but if the polymer content is increased, the dispersion stability becomes poor and the viscosity becomes high. To solve this problem, Japanese Patent Publication No. 63-27371 and Japanese Patent Laid-Open No. 172462/1994 propose a method of polymerizing a vinyl monomer in a polyol containing a preformed polymer polyol.

[0003]

However, the polymer concentration in the examples of JP-B-63-27371 is about 36% by weight, and if the polymer concentration is higher, sufficient effect cannot be obtained. In addition, JP-A-6-1724
Even when the method described in Japanese Patent Publication No. 62-62 is used, the polymer content is 31.
It is about wt% (Example 2). Furthermore, JP-A-6-17
When a polymer polyol for a slab foam is produced by using a preformed polymer polyol according to the method described in Japanese Patent No. 2462, there is a problem that a slab urethane foam using the polymer polyol causes scorch.

[0004]

Means for Solving the Problems The present inventor has conducted extensive studies as to a method for producing a polymer polyol having a low viscosity, good dispersion stability, and a high polymer content, and as a result, in the presence of a vinyl-based oligomer. The inventors have found a method for producing a polymer polyol composition and arrived at the present invention. That is, the present invention has a weight average molecular weight of 1,000 to 3 in the polyol (a).
A method for producing a polymer polyol, characterized by polymerizing and dispersing a vinyl monomer (c) in the presence of 50,000 vinyl oligomers (b); and a weight average molecular weight of 1,000 to 30, 000 vinyl oligomers (b)
A polymer which is formed by forming polymer dispersed particles of a vinyl monomer (c) in a polyol (a) in which is dissolved, and has an average particle size on a volume basis of 2 μm or less. The present invention relates to a polyol composition.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the vinyl monomer constituting the vinyl oligomer (b) is a polyol (a).
It can be selected from the same group as the vinyl monomer (c) used for the polymerization inside. As the vinyl monomer (c), styrenes (c-1), unsaturated nitriles (c-2) and (meth) acrylic acid esters (c-3) are preferable.
Examples of (c-1) include styrene, α-methylstyrene,
Examples thereof include hydroxystyrene, chlorostyrene, styrene sulfonic acid alkali metal salts and the like. Examples of (c-2) include acrylonitrile and methacrylonitrile. Examples of (c-3) include (meth) acrylic acid alkyl esters (wherein the alkyl group has 1 to 30 carbon atoms), such as methyl (meth) acrylate, butyl (meth) acrylate, nonyl (meth) acrylate, and the like. 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) Examples thereof include (meth) acrylate and docosyl (meth) acrylate.

In addition to the above, other monomers (c
-4) can also be used. Examples of (c-4) include: ethylenically unsaturated carboxylic acid and its derivative [(meth) acrylic acid, (meth) acrylic acid alkali metal salt,
(Meth) acrylic acid alkaline earth metal salts, (meth) acrylamide, etc.]-Aliphatic hydrocarbon monomers [ethylene, propylene, etc.]-Fluorine-containing vinyl monomers [perfluorooctylethyl methacrylate, perfluorooctyl] Ethyl acrylate, etc.], nitrogen-containing vinyl monomers [diaminoethyl methacrylate, morpholinoethyl methacrylate, etc.], and vinyl-modified silicone at both ends.

Among these, at least a part (usually 30% by weight) of the vinyl monomer (c) used in the production of (b).
It is desirable that the above is the same as at least a part (usually 30% by weight or more) of the vinyl monomer (c) used for the polymerization in the polyol (a). It is further preferred that the vinyl monomer (c) used for the production of (b) and the vinyl monomer (c) used for the polymerization in the polyol (a) are the same.

Aromatic hydrocarbon monomers (c-1), unsaturated nitriles (c-2), and (meth) when the vinyl monomer (c) is used for producing the vinyl oligomer (b). Acrylic esters (c-3), other monomers (c-
The type and ratio of 4) can be changed according to (c) used for the polymerization in the polyol (a), and are matched with the type and ratio of (c) used for the polymerization in the polyol (a) described later. Is desirable. When the monomer (c) is used in the vinyl-based oligomer (b), the types and ratios are as follows: The content of (c-1) is preferably 0 to 100% by weight,
It is particularly preferably 20 to 100% by weight. (C-2)
The content of is preferably 0 to 100% by weight, particularly preferably 40 to 80% by weight. The content of (c-3) is preferably 0 to 50% by weight, particularly preferably 0 to 20% by weight. The content of (c-4) is preferably 0 to 10% by weight, particularly preferably 0 to 5% by weight. (C-1) and (c-
The weight ratio of 2) is preferably (0: 100) to (10).
0: 0), particularly preferably (0: 100) to (80: 2)
0).

The molecular weight of the vinyl-based oligomer (b) is usually 1,000 to 1,000 in terms of weight average based on polystyrene measured by gel permeation chromatography (GPC).
30,000, preferably 2,000 to 20,000,
More preferably, it is 3,000 to 15,000, and is soluble in the polyol (a) [the content of (b) is 5% based on the total weight of (b) and (a). Is 10% or more]. If the molecular weight exceeds 30,000 or is less than 1,000, a sufficient dispersing effect cannot be obtained and the dispersed particle size becomes large. If (b) is not soluble in (a), a sufficient dispersion effect after the polymerization cannot be obtained.

The vinyl oligomer (b) can be produced by a usual vinyl monomer polymerization method except that the degree of polymerization is adjusted so that the weight average molecular weight is 1,000 to 30,000. it can. For example, it is a method of polymerizing the vinyl monomer (c) in a solvent in the presence of a polymerization initiator (such as a radical generator described later). Further, (b) may be obtained by polymerizing (c) in polyol (a) (substantially free of a polymer having a weight average molecular weight of more than 30,000), and the concentration of (b) in this case is It is usually 1 to 40% by weight, preferably 5 to 20% by weight, and it can be used for producing a polymer polyol without purification treatment. The polymerization initiator is used in a relatively large amount, for example, usually 2 to 3 based on the weight of all vinyl monomers.
It is 0% by weight, preferably 5 to 20% by weight.

Examples of the solvent used in the above polymerization reaction include benzene, toluene, xylene, acetonitrile, ethyl acetate, hexane, heptane, dioxane,
Examples thereof include 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, The polymerization can be carried out in the presence of enol ethers described in JP-A-55-31880 and the like. The polymerization can be carried out either batchwise or continuously. The polymerization reaction is
Above the decomposition temperature of the polymerization initiator (usually 50 to 250 ° C, preferably 80 to 200 ° C, particularly preferably 100 to 180).
C.) and also under atmospheric pressure or under pressure.

The amount of the vinyl oligomer (b) used in the method of the present invention is usually 0.5 to 20% by weight, preferably 0.5 to 10% by weight, based on the total weight of the obtained polymer polyol composition. , And more preferably 1 to 5% by weight. If the amount of (b) exceeds 20% by weight, the strength of the polyurethane will decrease when used in the production of polyurethane,
If it is less than 0.5% by weight, a sufficient dispersing effect cannot be obtained.

In the method of the present invention, the aromatic hydrocarbon monomers (c-
The types and ratios of 1), unsaturated nitriles (c-2), (meth) acrylic acid esters (c-3), and other monomers (c-4) depend on the required physical properties of polyurethane and the like. It can be changed accordingly. The type and ratio of each monomer in (c) used in the polymerization are preferably as follows:
The content of (c-1) is preferably 0 to 100% by weight, particularly preferably 20 to 100% by weight. The content of (c-2) is preferably 0 to 100% by weight, particularly preferably 4
It is 0 to 85% by weight. The content of (c-3) is preferably 0 to 50% by weight, particularly preferably 0 to 20% by weight. The content of (c-4) is preferably 0 to 10% by weight, particularly preferably 0 to 5% by weight. When (c-4) exceeds 10% by weight, the dispersed particle size becomes large, which is not preferable.

The content of the polymer dispersed particles formed from (c) in the polymer polyol composition is preferably 10 to 60% by weight, particularly preferably 20 to 50% by weight, based on the total weight of the composition. Is. The content of polymer dispersed particles is 60
When it exceeds the weight%, the viscosity of the polymer polyol increases. On the other hand, if it is less than 10% by weight, the strength of the polyurethane decreases when it is used in the production of polyurethane.

The volume-based average particle diameter of the polymer dispersed particles obtained by polymerizing (c) in the present invention is usually 2 μm or less, preferably 1 μm or less, more preferably 0.7 μm.
m or less. When the particle size of the polymer dispersed particles exceeds 2 μm, the foam continuity decreases when used in the production of cold cure mold high elasticity polyurethane foam.

As the polyol (a) used for producing the polymer polyol composition of the present invention, polyether polyol can be used. As a polyether polyol,
Compounds having a structure in which an alkylene oxide is added to a compound having at least two (preferably 2 to 8) active hydrogen atoms (polyhydric alcohol, polyhydric phenol, amines, polycarboxylic acid, phosphoric acid, etc.) and their compounds A mixture may be mentioned. Examples of the polyhydric alcohol include: ethylene glycol, diethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, alkylene glycol such as neopentyl glycol, and diol having a cyclic group ( For example, dihydric alcohols such as those described in Japanese Patent Publication No. 45-1474); trihydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, hexanetriol, triethanolamine; pentaerythritol methyl glycoside, diether. Tetrahydric alcohols such as glycerin; and sugar sugars having higher functional groups such as pentitols such as adonitol, arabitol, xylitol, sorbitol, mannitol, iditol, talito. Hexitols such as le, dulcitol; saccharides; monosaccharides such as glucose, mannose, fructose, sorbose, sucrose, crehalose,
Oligosaccharides such as lactose and raffinose; glycosides such as polyols (eg glycols such as ethylene glycol and propylene glycol;
Glucosides of alkane polyols such as glycerin, trimethylolpropane, hexanetriol; polyalkane polyols, eg triglycerin,
And polyglycerin such as tetraglycerin, polypentaerythritol such as dipentaerythritol, tripentaerythritol; and cycloalkane polyols such as tetrakis (hydroxymethyl) cyclohexanol.
Examples of the polyphenols include monocyclic polyhydric phenols such as pyrogallol, hydroquinone, and phloroglucin; bisphenols such as bisphenol A and bisphenol sulfone; condensates of phenol and formaldehyde (novolak), for example, US Pat. No. 3,265,641. Examples include polyphenols described in the book.

The amines include: Ammonia; Alkanolamines such as mono-, di- and triethanolamine, isopropanolamine, aminoethylethanolamine; Alkyl (C1-20) amines; Alkylene Aliphatic amines such as diamines having 2 to 6 carbon atoms (ethylenediamine, propylenediamine, hexamethylenediamine, etc.), polyalkylenepolyamines (diethylenetriamine, triethylenetetramine, etc.); aniline, phenylenediamine, diaminotoluene,
Aromatic amines such as xylylenediamine, methylenedianiline, diphenyletherdiamine; alicyclic amines such as isophoronediamine, cyclohexylenediamine, dicyclohexylmethanediamine; aminoethylpiperazine and JP-B-55-2104
The heterocyclic amines described in JP-A No. 4 are listed. Two or more of these active hydrogen atom-containing compounds may be used in combination. Among these, polyhydric alcohols are preferable.

The alkylene oxide to be added to the active hydrogen atom-containing compound is ethylene oxide (EO), propylene oxide (PO), butylene oxide, styrene oxide, etc., and a combination of two or more of these (block and / or random). Addition). 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. PO-AO added in order (chipped); PO-AO-PO-AO added in order (balanced); AO-PO-AO added in order; PO-AO-PO order Block addition products such as those added in step (active secondary); random addition products in which PO and AO are mixed and added; those added in the order described in JP-A-57-209920; JP-A-53-13700. Random / block addition products such as those added in the order described in Japanese Patent Publication; these may be used in combination.

As the polyol (a), a polyether polyol is preferable, but other polyols can be used instead of or together with the polyether polyol. Examples of other polyols include polymer polyols (polyester polyols, polybutadiene polyols, acrylic polyols, etc.) and / or low molecular weight polyols as described below. The hydroxyl value (average) of the polyol (a) is usually 200 or less, preferably 15 to 10.
0, particularly preferably 20 to 70. If it exceeds 200, foaming is difficult. The molecular weight of the polyol (a) is usually 2,000 to 30,000, preferably 2,
It is 500 to 10,000. When the molecular weight is less than 2,000, foaming is difficult, and when it exceeds 30,000, the viscosity of the obtained polymer polyol composition increases.

The production of the polymer polyol composition is carried out except that the polymerization is carried out in the presence of the vinyl-based oligomer (b).
It can be carried out by a usual method for producing a polymer polyol composition. For example, a method of polymerizing a vinyl monomer (c) in a polyol (a) in the presence of a polymerization initiator (radical generator, etc.) (US Pat. No. 3,383,351).
Japanese Patent Publication No. 39-24737, Japanese Patent Publication No. 47-47999
And Japanese Laid-Open Patent Publication No. 50-15894). The vinyl-based oligomer (b) may be present in the polymerization system in advance, and may be added to the polymerization system as a mixed solution with (a), a mixed solution with (c) or a mixed solution with (a) and (c). You may supply continuously. The weight ratio of the polyol (a) and the vinyl oligomer (b) is usually (99: 1) to (3:
2), preferably (80: 1) to (3: 1).
The weight ratio of (c) and [(a) + (b)] is usually (1: 2).
0) to (7: 3), preferably (1: 4) to (3: 2).
Is.

The above-mentioned polymerization initiator is of a type that produces free radicals to initiate polymerization, for example: 2,2'-azobisisobutyronitrile (AIB)
N), 2,2'-azobis- (2,4-dimethylvaleronitrile) (AVN), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-arbo) Nitrile), 2,2'-azobis (2,4,4-trimethylpentane), dimethyl 2,
2'-azobis (2-methylpropionate), 2,
2'-azobis [2- (hydroxymethyl) propionitrile], 1,1'-azobis (1-acetoxy-1-
Azo compounds such as phenylethane); peroxides such as dibenzoyl peroxide, dicumyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, benzoyl peroxide, lauroyl peroxide, and JP-A-61 -7
Peroxides other than the above described in Japanese Patent No. 6517, or persulfate, perborate, persuccinic acid and the like can be used.
The amount of the polymerization initiator used is usually 0.1 to 10% by weight, preferably 0.2 to 10% by weight based on the weight of the vinyl monomer (c).
It is 5% by weight.

The above polymerization reaction can be carried out without a solvent, but it can also be carried out in the presence of an organic solvent (particularly when the polymer concentration is high). Examples of the organic solvent include (b)
The same ones used in the production of can be used.

The polymerization can be carried out batchwise or continuously. The polymerization reaction can be carried out at a temperature not lower than the decomposition temperature of the polymerization initiator (usually 60 to 180 ° C., preferably 70 to 160 ° C., particularly preferably 90 to 150 ° C.), and also at atmospheric pressure or under pressure. it can. After the completion of the polymerization reaction, the obtained polymer polyol composition can be used as it is for the production of polyurethane without any post-treatment, but after the completion of the reaction, an organic solvent, decomposition products of the polymerization initiator, unreacted monomers, etc. It is desirable to remove impurities by conventional means. The hydroxyl value of the polymer polyol composition is usually 5
-100, preferably 7-80, more preferably 10
60.

When a polyurethane is produced by using the polymer polyol composition of the present invention [designated as (A)] obtained by the method of the present invention, the composition (A) of the present invention may optionally contain other active hydrogen. It can be used in combination with an atom-containing compound.
As the other active hydrogen atom-containing compound used as necessary, known high molecular weight 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 and modified polyol can be used. Examples of the polyether polyol include the same as the polyether polyol described in the section of the polyol (a) as a raw material of the composition (A) of the present invention. Examples of the polyester polyol include: -the above-mentioned polyhydric alcohols (dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and the like; or 3 such as glycerin and trimethylolpropane
A mixture with a polyhydric or higher alcohol), a polycarboxylic acid or an anhydride thereof, an ester-forming derivative such as a lower ester (eg, adipic acid, sebacic acid,
Reacting (condensing) maleic anhydride, phthalic anhydride, dimethyl terephthalate, etc., or its anhydride and alkyleonoxide (EO, PO, etc.), or ・ ring-opening polymerization of lactone (ε-caprolactone, etc.) The thing obtained by this is mentioned. Examples of modified polyols include: -polyols obtained by polymerizing these polyols, polyether polyols and / or polyester polyols) with an ethylenically unsaturated monomer (for example, JP-A Nos. 54-101899 and 54-54). -12
2396 gazette). Also, polybutadiene polyols, hydroxyl group-containing vinyl polymers (acrylic polyols) such as JP-A-58-574.
Nos. 13 and 57414, natural oil-based polyols such as castor oil, and modified polyols can also be used. These polymeric polyols (B) are
Usually 2 to 8, preferably 3 to 8 hydroxyl groups and usually 2
0 to 4,000, preferably 400 to 3,000 O
It has H equivalent weight.

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. Examples of the low molecular weight polyol include: dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, neopentyl glycol and hexanediol; glycerin, trimethylolpropane, pentaerythritol, diglycerin. , Trihydric or higher polyhydric alcohol such as α-methylglucoside, sorbitol, xylitol, mannitol, dipentaerythritol, glucose, fructose, sucrose; addition of low molecular weight (for example, 200 to 400) polyhydric alcohol alkylene oxide (Polyethylene glycol, polypropylene glycol, etc.); Low molecular weight diols having a cyclic group [eg, Japanese Patent Publication No. 45
Those described in JP-A-1474 (such as propylene oxide adducts of bisphenol A)];-Lower molecular polyols containing tertiary or quaternary nitrogen atoms [for example, those described in JP-A-54-130699 (N-methyl N-alkyl dialkanol amines such as diethanol amine and N-butyl diethanol amine and their quaternary compounds);-trialkanol amines (triethanol amine, tripropanol amine, etc.)];-Thiodiethylene glycol and the like. Examples of amino alcohols include mono- or di-alkanolamines such as monoethanolamine, diethanolamine and monopropanolamine. 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. Preferred among these other active hydrogen atom-containing compounds are polyether polyols. The amount of the composition (A) of the present invention in the whole active hydrogen atom-containing compound [(A) and optionally (B) and / or (C)] is
It is usually 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more. If (A) is less than 5% by weight, the foam hardness is not good. The amount of the other polymer polyol (B) is usually 0 to 95% by weight, preferably 0 to 8%.
0% by weight. When the content of (B) exceeds 95% by weight, the foam hardness is not good. The amount of the low molecular weight active hydrogen-containing compound (C) is usually 0 to 30% by weight, preferably 0 to 10% by weight. When the content of (C) exceeds 30% by weight, the exothermic temperature during the reaction becomes high and scorch is generated.

The composition of the present invention can be preferably used as an active hydrogen compound component for polyurethane production, but as the organic polyisocyanate used in polyurethane production, there are known publicly known organic polyisocyanates conventionally used in polyurethane production. Things 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 T
DI, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane {condensation product of formaldehyde with aromatic amine (aniline) or mixtures thereof: diaminodiphenylmethane Small amount (for example 5 to 2
(0% by weight) mixture with trifunctional or higher polyamine} phosgene compound: polyallyl polyisocyanate (PAP
I) etc.];-C2-C18 aliphatic polyisocyanate (for example, hexamethylene diisocyanate, lysine diisocyanate, etc.);-C4-C15 alicyclic polyisocyanate (for example, isophorone diisocyanate, dicyclohexylmethane diisocyanate); carbon Aroaliphatic polyisocyanates of the number 8 to 15 (for example, xylylene diisocyanate); and modified products of these polyisocyanates (urethane groups,
Carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretonimine group, isocyanurate group, oxazolidone group-containing modified product, etc.);
And-polyisocyanates other than the above described in JP-A-61-76517; and-a mixture of two or more of these. Preferred of these are the commercially readily available polyisocyanates such as 2,4- and 2,6-TD.
I, a mixture of these isomers, crude TDI, 4,4'-
And 2,4′-MDI, a mixture of these isomers, PAPI also called crude MDI, and urethane group, carbodiimide group, allophanate group, urea group, buret group, isocyanurate group derived from these polyisocyanates. It is a modified polyisocyanate containing. The isocyanate index [Equivalent ratio of NCO / active hydrogen atom-containing group × 100] in the production of polyurethane using the composition of the present invention is usually 80 to 140, preferably 85 to 120, and particularly preferably 95 to 115.
Is. It is also possible to introduce polyisocyanurate groups into the polyurethane by making the isocyanate index much higher than the above range (for example, 300 to 1,000).

In order to accelerate the reaction in the production of polyurethane, 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 0.001-5%, based on the weight of the reaction mixture. Further, when producing a polyurethane using the composition of the present invention, a foaming agent (for example, methylene chloride, monofluorotrichloromethane, water, etc.) can be used if necessary. The amount of blowing agent used can vary depending on the desired density of the polyurethane. When producing a polyurethane using the composition of the present invention, a foam stabilizer may be used if necessary. Examples of the foam stabilizer include silicone surfactants (for example, polysiloxane-polyoxyalkylene copolymer). When manufacturing a polyurethane using the composition of the present invention, a flame retardant can be used if necessary. Melamines as flame retardants,
Examples thereof include phosphoric acid esters, halogenated phosphoric acid esters, phosphazene derivatives and the like. Other additives that can be used in the production of polyurethane using the composition of the present invention include, for example, a reaction retarder, a colorant, an internal mold release agent, an antioxidant, an antioxidant, a plasticizer, a bactericide, and carbon black. Also, known additives such as other fillers can be used.

The polyurethane can be produced by a usual method, and can be performed 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 polymer polyol composition (A) obtained by the method of the present invention is particularly useful for producing flexible mold foams and slab foams. Further, it can be suitably used for molding by RIM (reaction injection molding) method.

[0031]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The parts,% and ratios are parts by weight,% by weight and ratios by weight, respectively.

The chemical compositions of the raw materials used in the examples and comparative examples, and the method for testing the dispersion stability of the polymer polyol compositions are as follows. (1) Polyol Polyol a1: A polyol having a hydroxyl value of 34 in which PO is added to glycerin. Polyol a2: A polyol having a hydroxyl value of 56 in which PO is added to glycerin. Polyol a3: PO is added to glycerin, then E
O-added polyol with a hydroxyl value of 34 (EO content 1
4%).

(2) Monomer ACN: Acrylonitrile St: Styrene (3) Polymerization initiator AVN: Azobisisovaleronitrile (4) Chain transfer agent DM: Dodecyl mercaptan, (5) Polyisocyanate CE-729: TDI 80 weight % And crude MDI 20% by weight [manufactured by Nippon Polyurethane Industry Co., Ltd.] (6) Catalyst Catalyst A: DABCO 33LV (33% dipropylene glycol solution of triethylenediamine) Catalyst B: DABCO XDM (amine catalyst) [Sankyo Air Products Co., Ltd.] (7) Foam stabilizer: SRX-274C (polyether siloxane polymer) [Nippon Unicar Co., Ltd.] (8) Preformed polymer / polyol PPP: JP-B-63-27371 Example RR of Book 7 of Table Preformed Polymer / Polio Synthesized by RR Le.

[Dispersion Stability Test] The polymer polyol composition was centrifuged at a radiation centrifugal force (g) of about 18,000 rpm and about 38,000 for about 30 minutes, and then the centrifuge tube was turned upside down for 1 hour. Place. The amount of the residue in the centrifuge tube was defined as the dispersion stability index by weight% of the initial weight of the polymer polyol.
Commercially acceptable values are usually about 10% or less, preferably 5% or less, more preferably 3% or less.

Production Examples 1 to 6 [vinyl-based oligomer (b)]
Production of] According to the composition shown in Table 1, 25% of the polyol (a) was added to a 1 L four-necked flask equipped with a temperature controller, a vacuum stirring blade, a dropping pump, a decompression device, a Dimroth, a nitrogen inflow and an outflow port. Then, the mixture is heated to 140 ° C. under stirring, and then the raw material liquid (remaining raw material mixture liquid) is continuously added dropwise over 4 hours by a dropping pump to obtain vinyl oligomers (states dissolved in polyol) b2 to b6. Synthesized. Those not otherwise indicated were used for the preparation of the polymer polyol composition without post-treatment. In Production Example 1, xylene was used instead of the polyol (a), the polyol was added after the polymerization, and then the xylene was distilled off under reduced pressure.

[0036]

[Table 1]

Examples 1 to 6 and Comparative Examples 1 and 2 The polyol (a) was placed in a 3 L semi-batch type polymerization tank equipped with a temperature controller, a stirring blade, and a raw material supply pump, and stirred under stirring.
The mixture was heated to 5 ° C., and then the raw material liquid having the composition shown in Table 2 was continuously injected by the raw material supply pump to synthesize the polymer polyol compositions R1 and R2 and A1 to A6. Unless otherwise indicated, unreacted monomers were stripped under reduced pressure.

[0038]

[Table 2] * 1: Aggregated particles with a particle size of 3 μm or more

Using some of the polymer polyol compositions prepared by the synthetic method shown in Table 2, polyurethane foams were produced by the foaming formulation shown in Table 3 and the foam physical properties were evaluated. Table 3 shows the results.

[0040]

[Table 3]

The foaming conditions in Table 3 are as follows. Raw material temperature: 23 to 27 ° C Mold temperature: 55 to 65 ° C Mold size: 40 x 40 x 10 (H) cm

The methods for evaluating the physical properties of foam in Table 3 are as follows. Density (kg / m ³ ): JIS K6301 25% ILD (kg / 314 cm ² ): JIS K63
82 65% ILD (kg / 314 cm ² ): JIS K63
82 65% ILD change rate (%): 65% ILD 1 minute after demolding
The decrease rate of 65% ILD after 2 minutes, the smaller the value, the better the connectivity in the initial stage of foaming and the better the formability of the foam. Tensile strength (kg / cm ² ): JIS K6301 Tear strength (kg / cm): JIS K6301 Cutting elongation (%): JIS K6301 Repulsion elastic modulus (%): JIS K6382 Breathability (ft ³ / min): By Dow type flow meter (Test piece 5 × 5 × 2.5) ) Wet heat compression set (%): JIS K6382

[0043]

【The invention's effect】

(1) By using the method for producing a polymer polyol composition of the present invention, a polymer polyol composition having a low viscosity, a fine dispersed particle size and a high polymer content can be obtained as compared with the conventional method. (2) Further, the polyurethane foam using the polymer polyol composition of the present invention obtained by the method of the present invention has good moldability as compared with the polyurethane foam using the polymer polyol composition of the conventional method. (65 of Comparative Example 3 shown in Table 3
% ILD change rate is 9.2, while Example 7-
The 65% ILD change rate of 9 is 3.5 or less). From the above effects, the polyurethane foam using the polymer polyol composition of the present invention obtained by the method of the present invention is extremely useful for applications such as automobile interior parts, interior furnishings such as furniture. Exert.

Front page continuation (72) Inventor Isao Ishikawa, 1-11, Hitotsubashi-honmachi, Higashiyama-ku, Kyoto, Sanyo Kasei Kogyo Co., Ltd.

Claims (8)

[Claims] 1. A vinyl-based oligomer (b) having a weight average molecular weight of 1,000 to 30,000 in the polyol (a).
A method for producing a polymer polyol composition, which comprises polymerizing and dispersing a vinyl monomer (c) in the presence of 2. The method according to claim 1, wherein (b) is an oligomer soluble in (a). 3. The method according to claim 1, wherein at least a part of the vinyl monomer constituting (b) is the same as at least a part of (c). 4. The method according to claim 1, wherein (b) is an oligomer obtained by polymerizing a vinyl monomer in (a). 5. The amount of (b) is from 0.5 to 10% by weight, based on the total weight of the polymer polyol composition.
4. The method according to any one of 4 above. 6. The average particle size on a volume basis of polymer dispersed particles obtained by polymerizing (c) is 2 μm or less.
The method according to any one of 5 above. 7. A weight average molecular weight of 1,000 to 30,000.
In the polyol (a) in which the vinyl oligomer (b) of 0 is dissolved, polymer dispersed particles of the vinyl monomer (c) are formed, and the average particle diameter on a volume basis is 2 μm.
A polymer polyol composition characterized by the following: 8. The content of the polymer dispersed particles (c) is 10 to 10.
The polymer polyol composition according to claim 7, which is 60% by weight.