JPS60235816A - Polymer polyol composition and its use - Google Patents

Abstract

PURPOSE:The titled composition having a high polymer concentration, a low viscosity, good dispersion stability and suited for use in the production of polyurethane, prepared by polymerizing a plurality of specified monomers in a polyol. CONSTITUTION:A polymer polyol composition (of a hydroxyl value of about 3-225) prepared by polymerizing (A) an ethylenically unsaturated monomer of the formula (wherein R1 is H or methyl and R2 is a 1-4C alkyl), e.g., methyl methacrylate, with (B) (meth)acrylonitrile and, optionally, (C) other monomers (e.g., styrene) in a polyol (e.g., glycerin/propylene oxide adduct) and comprising 20-55wt% above polyol and 80-45wt% copolymer of monomers A, B, and C dispersed therein. This composition is used in the production of polyurethane by reaction with a polyisocyanate in the presence of, if necessary, a blowing agent, catalyst and other additives.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polymer polyol composition and a method for using the same, and more particularly, to a polymer polyol composition obtained by polymerizing a plurality of specific ethylenically unsaturated monomers (hereinafter referred to as monomers) in a polyol. The present invention relates to polymeric polyol compositions and methods of using the same in the production of polyurethanes.

Polymer polyols are usually produced by polymerizing monomers in polyols, but acrylonitrile alone has traditionally been considered to have high practical value in terms of dispersion stability, viscosity, and physical properties of polyurethane using it. Or multiple 7mers with a high proportion of acrylonitrile.
A polymer obtained by polymerizing a combination of (for example, acrylonitrile and styrene) is about 20% by weight of a polymer polyol.

However, even when acrylonitrile is used, when the polymer concentration becomes high (for example, 30 kg or more), the viscosity suddenly increases (when the amount of acrylonitrile is large) or the generation of particulates (when the amount of acrylonitrile is minimal, especially when using styrene as a comonomer). It has been difficult to obtain a highly concentrated polymer polyol with low viscosity and excellent dispersion stability.

As a result of repeated studies aimed at obtaining a polymer polyol that provides polyurethane with good dispersion stability and high physical properties (particularly high rigidity) even at high concentrations, the inventors of the present invention discovered that they polymerized multiple specific monomers in the polyol. By doing this, a polymer polyol with low viscosity, good dispersion stability, and a high concentration (for example, 70% by weight) not found in conventional methods can be obtained. The present invention was achieved by discovering that polyurethane can be produced.

That is, the present invention is composed of 20 to 55% by weight of a polyol and 45 to 80% by weight of a polymer of ethylenically unsaturated monomers dispersed in the polyol, and methyl group and bird are alkyl groups having 1 to 4 carbon atoms. Produced by polymerizing one or more ethylenically unsaturated monomers represented by (B) acrylonitrile and/or methacrylonitrile and optionally (q) other ethylenically unsaturated monomers in the polyol. and a method of using the polymer polyol composition to react with a polyisocyanate to produce a polyurethane.

Used in the production of the polymer polyol composition of the present invention (
Specific examples of the 7-mers include methyl (meth)acrylate (indicating methyl acrylate and methyl methacrylate; similar expressions will be used hereinafter), ethyl (meth)acrylate, isopropyl (meth)acrylate, Examples include butyl (meth)acrylate and tert-butyl (meth)acrylate.

In the present invention, it is essential to use the monomers mentioned above and monomers 4 and 4 (isolated acrylonitrile and/or meccrylonitrile), but if necessary, other monomers (q) can be used in combination as optional components. .

Used as necessary (as the monomer for q,
Examples thereof include other monomers described in Japanese Patent Application No. 8-166208 and Japanese Patent Application No. 58-280842 (excluding the monomer (A) above).

(As the monomer, methyl methacrylate, ethyl methacrylate, and butyl methacrylate are preferable, and methyl methacrylate is more preferable.

The monomer for FB) is preferably acrylonitrile, and the monomer for (C) is preferably styrene or α-methylstyrene, and more preferably styrene.

Typical examples of polyols used in the present invention include polyether polyols and polyester polyols, both of which are commonly used as raw materials for polyurethane, and can be used alone or as a mixture. is a product obtained by adding alkylene oxide to an active hydrogen-containing compound such as polyhydric alcohol, polyhydric phenol, amines, or phosphoric acid. Specific examples of active hydrogen-containing compounds include water, ethylene glycol, and propylene glycol.

1.3 butylene glycol, 1.4 butanediol.

Glycols such as hekinlene glycol and 1.6 hexanediol; glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, α-methylglucoside.

dipentaerythritol, sorbitol, xylitol,
mannitol, glucose, fructose.

Tri- to octahydric alcohols such as sucrose: birogallol, hydroquinone, bisphenol A.

Polyhydric phenols such as bisphenolsulfone and condensates of phenol and formaldehyde; ammonia; monoethanolamine, jetanolamine, triethanolamine, triisozolopanolamine, etc. and other alkanolamines; C1-C2o alkylamines, Ethylenediamine, diethylenetriamine, hexamethylenediamine and other aliphatic amines such as nianiline.

Phenyl diamine, diaminotoluene, quinolyl diamine, methylene dianiline, diphenyl ether diamine and other aromatic amines: isophorone diamine and other alicyclic amines; aminoethyl piperazine and others described in Japanese Patent Publication No. 55-21044 Examples include heterocyclic amines.

Ethylene oxide is an alkylene oxide.

Examples include propylene oxide, butylene oxide, epichlorohydrin, and styrene oxide. Preferred alkylene oxides are propylene oxide and combination systems of propylene oxide and ethylene oxide (random, block, and mixed systems). The addition reaction of alkylene oxides can be carried out by a conventional method, and can be carried out without a catalyst or with a catalyst (alkali). catalyst, amine catalyst, acidic catalyst)
It is carried out in one stage or in multiple stages under normal pressure or increased pressure in the presence of. Examples of polyester polyols include di- to trivalent alcohols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, I+4-butanediol, neopentyl glycol, 1,6-hexanediol, glycerin, and trimethylolpropane. and/or the aforementioned polyether polyols and adipic acid.

Those produced by condensation reactions with aliphatic or aromatic dicarboxylic acids such as sebacic acid, phthalic anhydride, and dimethyl terephthalate, acid anhydrides, and ester-forming carboxylic acid derivatives; and lactones (such as caprolactone). Examples include those produced by ring-opening polymerization and the like.

These polyols usually contain 2 to 8 hydroxyl I+ (and 20
It has an OH equivalent of θ˜4.000, preferably 2 to 4 hydroxyl groups and an OH equivalent of 400 to 3.000.

Among polyether polyols and polyester polyols, polyether polyols are preferred A.

A preferred polyether polyol has ethylene oxide chains arbitrarily distributed in the molecule at a weight of θ to 50, and has 0 to 30% by weight of ethylene oxide chains tipped at the end of the molecule. Particularly preferred polyether polyols contain 5 to 40% by weight of ethylene oxide chains arbitrarily distributed in the fraction, and have 5 to 25% by weight of ethylene oxide chains tipped at the molecular ends. The primary hydroxyl group content of the polyether polyol is usually 0 to 100%, preferably 30 to 100%, more preferably 50 to 100%, and most preferably 70 to 100%.

In the present invention, modified polyols such as urethane polyols produced from a large excess of polyol and polyisocyanate, polyols containing polymerizable unsaturated bonds in the molecule, etc. can also be used.

In the present invention, usually 8 parts by weight per 100 parts by weight of polyol.
5 to 400, preferably 100 to 250 parts by weight of monomer can be used.

In order to polymerize these monomers, polymerization initiators are usually used. 6 Polymerization initiators are those that generate free radicals to initiate polymerization, such as 2,2'-azobisisobutyronitrile ( AIBN).

2. Azo compounds such as 2'-azobis-(2,4-)methylvaleronitrile); dibenzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide,
Dicumyl peroxide, t-1-butyl-hydroperoxide, diisopropyl peroxide carbonate,
t-Butylperoxy-2-ethylhexanoate, t
-Butyl pervivalate, 2,5-dimethylhexane-
2,5-di-per-2-ethylhexoate, I-butyl percrotonate, t-butyl perisobutyrate,
Peroxides such as di-t-butyl perphthalate, persulfates, perborates, persuccinic acids, etc. can be used.
Practically speaking, azo compounds, especially 2,2'-azobisisobutyronitrile, are preferred, and the amount of polymerization initiator used is 0.1 to 20%, preferably 0.2 to 10% by weight, based on the total amount of monomers. A method of generating free radicals by a conventional method, that is, a method of generating free radicals by irradiation with ultraviolet rays or "TR-rays" can also be used.

Although the polymerization reaction in a polyol can be carried out without a solvent, it is preferably carried out in the presence of an organic solvent when the polymer concentration is high. Examples of organic solvents include benzene, toluene, xylene, acetonitrile, ethyl acetate,
Hexane, heptane.

Dioxane, N,N-dimethylformamide, N,N
-dimethylacetamide, inopropyl alcohol,
Examples include fi-butanol.

In addition, if necessary, known chain transfer agents other than alkyl mercaptans (carbon tetrachloride, carbon tetrabromide, RI00 * JL
Polymerization can be carried out in the presence of enol ethers described in JP-A-55-81880).

Polymerization can be carried out either batchwise or continuously.

The polymerization reaction is carried out at a temperature higher than the decomposition temperature of the polymerization initiator, usually 60 to 18
0°C, preferably 90-160°C, particularly preferably 100-160°C
It can be carried out at 150°C, and it can also be carried out under atmospheric pressure, increased pressure, or even reduced pressure.

After the polymerization reaction is completed, the resulting polymer polyol can be used as a polyurethane raw material or a raw material for other resin modification without any post-treatment. It is desirable to remove impurities such as reactive monomers by conventional means.

The polymer polyol composition thus obtained is (A180
~70% by weight, preferably 85-65% by weight; (13)8
0-70% by weight, preferably 85-65% by weight; (C)
The monomer composition is 0 to 80% by weight, preferably 0 to 20% by weight. (A) , (B) , (C1
If the ratio exceeds the above range, the resulting polymer polyol composition will have a high viscosity and will tend to generate particulate matter.

The polymer polyol composition of the present invention is generally a translucent to opaque white or tan dispersion in which 45 to 80% by weight, preferably 50 to 70% by weight of total polymerized monomer, i.e. polymer, is stably dispersed in the polyol. When the content of the 0 polymer exceeds 80%, the viscosity becomes high and fluidity deteriorates, and when it is less than 45%, the rigidity of the polyurethane decreases.

The hydroxyl value of the polymer polyol composition of the present invention is usually 3 to 3.
225, preferably 4 to 112, more preferably 5 to 45.

The present invention also includes a polyol of 20 to 55 weights and the +1
? A type of ethylenically unsaturated monomer consisting of 45 to 80% by weight of a polymer of ethylenically unsaturated monomers dispersed in lyol, represented by 1 methyl group (for birds, an alkyl group having 1 to 4 carbon atoms) A polymer polyol composition prepared by polymerizing υ and (13+ acrylonitrile and/or methacrylonitrile and optionally (C) other ethylenically unsaturated monomers in the polyol, optionally with a blowing agent) , in the presence of catalysts and other additives, with polyisocyanates to produce foamed or non-foamed polyurethanes.

The present invention relates to methods of using polymer polyol compositions.

Polyisocyanates used for polyurethane production include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group), aliphatic polyisocyanates having 2 to 18 carbon atoms, and alicyclic polyisocyanates having 4 to 15 carbon atoms. Polyisocyanates, araliphatic polyisocyanates having 8 to 15 carbon atoms, and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanates, urea groups, biuret groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone groups) modified substances, etc.) can be used. Examples of such polyisocyanates include 1,3- and 1,4-phenylene diisocyanate, 2,4- and/or 2,6-1-lylene diisocyanate (TDI), diphenylmethane-2,4'- and/ or 4,4'-diisocyanate (MDI), naphthylene-1,5-diisocyanate triphenylmethane-4,4',4"-triisocyanate, polyphenylene polyisocyanate jPAPI obtained by aniline-formaldehyde condensation followed by phoskenization)
, m- and p-ino/anatophenylsulfonyl isocyanate, aromatic polyiso/anates; ethylene diisocyanate, tetramethylene diiso/anate,
Hexamethylene diisocyanate, dodecamethylene diinocyanate, 1.6.11-undecane triisocyanate, 2,2.4-1-limethylhexane diisocyanate, lysine cyinone anate, 2.6-diiso/anate methyl capro ate, bis(2-iso/anetoethyl) fumarate, bis(2-inocyanatoethyl)carbonate, 2-isonoanatoethyl-2
,5-diisocyanate! - Aliphatic polyisocyanate of hexanoate, isophoronodiisocyanate, dicyclohexylmecundiiso/-.'-ate, noclohexyl/diynonate, methylcyclohexylene diinocyanate.

Bis(2-isocyanatoethyl) 4- to chloro
Alicyclic polyisocyanates such as xene-1,2-dicarboxylate; xylylene diisocyanate.

Examples include aromatic aliphatic polyisocyanates such as diethylbenzene diisocyanate; modified polyisocyanates such as urethane-modified MDI, carbodiimide-modified MDI, and urethane-modified TDI, and mixtures of two or more thereof. Among these, commercially readily available polyisocyanates such as 2,4- and 2,6-TDI
and mixtures of these isomers, crude TDI, 4.4
'- and 2,4'-MDI and mixtures of these isomers, PAPI, also called crude MDI, and urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, isocyanurates derived from these polyisocyanates. Modified polyisocyanates containing groups are preferred.

In the production of polyurethane, in addition to the polymer polyol composition according to the present invention, low-molecular and high-molecular active hydrogen-containing compounds can also be used if necessary.

The low-molecular active hydrogen-containing compound is usually called a crosslinking agent or chain extender, and has at least 2 active hydrogen atoms, preferably 2 to 5 active hydrogen atoms, and an equivalent of 30 to less than 200 (molecular weight per active hydrogen-containing group). ) can be used. Specific examples include ethylene glycol, propylene glycol, 1,3-butylene glycol, 114-
Butanediol.

1. Di- to trihydric alcohols such as 6-hexanediol, glycerin, trimethylolpropane; jetanolamine, triethanolamine, triinopropaturamine, diaminotoluene, diethyltoluenediamine, methylene dianiline.

Amines of methylene bis-orthochloroaniline; and the above di- to tri-hydric alcohols, tetra- to octa-hydric alcohols (pentaerythritol, methyl glucoside, sorbitol, saccharose, etc.), polyhydric phenols (bisphenol A, hydroquinone, etc.) , the above amines,
These fi, 2
Mention may be made of polyhydroxy compounds of less than 00. These low-molecular active hydrogen-containing compounds are generally used in an amount of 0 to 100 parts by weight, preferably 0 to 50 parts by weight, particularly preferably 0 to 30 parts by weight, per 100 parts by weight of the polymer polyol composition.

The polymeric active hydrogen-containing compound is a compound having at least two active hydrogen atoms and an equivalent weight of 200 to 4,000, such as a polyether polyol, a polyester polyol, or a polyether polyol produced by reacting ammonia under high pressure. Examples include polyether polyamines in which most of the molecular terminals are amino groups, and lerfoliol obtained from natural oils such as castor oil. As the polyether polyol and polyester polyol, the same polyols as those for producing the polymer polyols mentioned above can be used.

Among these, ethylene oxide is the starting material.

Propylene oxide, butylene oxide and any mixture thereof, especially propylene oxide alone or propylene oxide and ethylene oxide added 2-8
hydroxyl groups and 200 to 4,000 OH equivalents, especially 2 to 4
Polyether polyols having 400 to 3,000 hydroxyl groups and an O11 equivalent weight of 400 to 3,000 are preferred.

These polymeric active hydrogen-containing compounds are generally used in an amount of 0 to 500 parts by weight, preferably 0 to 300 parts by weight, particularly preferably 0 to 200 parts by weight, per 100 parts by weight of the polymer polyol composition.

The proportion of the polymer polyol composition of the present invention in the total active hydrogen-containing components is usually from 20 to 100% by weight, preferably from 60 to 100% by weight. The content of polymer in the total active hydrogen-containing component is usually from 5 to 80, preferably from 25 to 80.

The following known substances can be used as blowing agents, catalysts and other additives that may be used as necessary in the production of polyurethane.

(1) Examples of blowing agents include methylene chloride.

Chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane.

Halogenated hydrocarbons such as chlorodifluoromethane and dichlorofluoromecne; low-boiling hydrocarbons such as butane, hexane, and heptane; acetone.

Use of 0 blowing agents which may include halogen-free volatile organic solvents such as ethyl acetate and diethyl ethernatate; reactive blowing agents such as water which reacts with iso/anate to generate carbon dioxide, and combination systems thereof. The support is based on the desired density of the polyurethane (e.g. 0.01-1.497
c) can be changed.

(2) Examples of catalysts include triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N,N',N'-tetramethylethylenediamine, and pentamethyldiethylenetriamine.

Triethylenediamine, N-methyl-N'-dimethylaminoethylpiperazine, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, N
, N, N', N'-tetramethyl-1,3-butanediamine, 1,2-dimethylimidazole and other tertiary amines; secondary amines such as dimethylamine;
N-Methyl-jetanolamine, N-ethyl-jetanolamine, N,N-dimethyl-J-ethanolamine, and other j'lukanolamines, tetramethylammonium hydroxide, benzyltrimethylammonium hydroxide, and other tetramethylammonium hydroxides. ]・Alkali metal phenolates such as alkyl ammonium hydroxides and sodium phenolate; alkali metal hydroxides such as potassium hydroxide; alkali metal alkoxides such as sodium methoxide; potassium acetate, sodium acetate, 2-ethylhexanoic acid Alkali metal salts of carboxylic acids such as potassium; phosphinic acids such as triethylphosphine; metal compounds such as potassium salicylaldehyde; stannath acetate, stannath octoate-1 (stannath 2-ethylhexony 1-) and other organotin (I) compounds, dibutyltin oxide/de, dibutyltinodichloride,
Dibutyltin diacetate-1-.

dibutyltin dilaure], dibutyltin maleate, dioctyltin diacetate and other organotins (
Intermediate compounds; Other organometallic compounds such as dialkyl titanates can be mentioned.

Tris(dimethylaminomethyl)-phenol.

Isocyanuration promoting catalysts such as N,N',N''-tris(dimethylaminopropyl)hexahydro-5-triazine may also be used. Used in small quantities.

(3) Other additives that can be used include surfactants as emulsifiers and foam stabilizers, especially polysiloxane-
Polyoxyalkylene copolymers are important.

Additives that can be used in the thin ice invention include flame retardant, reaction retardant, coloring agent, and internal mold release agent.

Known additives include anti-aging agents, antioxidants, plasticizers, bactericides and carbon black, titanium oxide, diatomaceous earth, cut glass, milled glass, glass flakes, talc, mica and other fillers.

When using the polymer polyol composition of the present invention for producing polyurethane, the isocyanate index is usually 80 to 12.
0 (preferably 100 to 110), but the isocyanate index is higher than the above range (e.g. 300 to 100).
0) It is also possible to produce polyiso/amelate.

The production of polyurethane using the polymer polyol composition of the present invention can be carried out by known methods such as the one-shot method, semi-prepolymer method, and prepolymer method. Polyurethane production can be carried out. Polyurethane is usually produced by mixing and reacting raw materials using low or high pressure mechanical equipment. RJ in hand
Non-foaming or low foaming R by M (reaction injection molding) method
IM molded polyurethane elastomers (density osmotic or semi-rigid polyurethane foams are conveniently produced).

The polymer polyol composition of the present invention is characterized by low viscosity and excellent dispersion stability even in areas where the concentration of the polymer is high. While conventional polymer polyols lose their practicality in terms of dispersion stability and fluidity when the polymer concentration is 80%, especially 40% by weight or more, the polymer polyol composition of the present invention has a polymer concentration of 60% by weight or even 70% by weight.
It not only does not lose fluidity even at a polymer concentration of , but also has good dispersion stability, and its practical value is high.

The polymer polyol compositions of the present invention also provide polyurethanes with superior stiffness compared to conventional polymer polyols.

Accordingly, the polymer polyol compositions of the present invention are useful in a variety of polyurethanes, such as flexible, semi-rigid, and rigid polyurethane foams or polyurethane elastomers.
In particular, RIM molded polyurethane elastomer (hereinafter referred to as RIM)
(called urethane).

The advantage of using the polymer polyol composition of the present invention is that extremely high rigidity polyurethane can be easily and inexpensively produced.
It is also possible to obtain old M-urethane, which is comparable to the stiffness of M-urethane (abbreviated as M-urethane), without the addition of glass fibers. R4
While IM urethane has problems that can be called condensation, such as damage to equipment due to glass abrasion, adverse effects on paintability and aesthetics due to the glass on the surface of the molded product, and directionality inherent in the molded product, this book RI from the polymer polyol composition of the invention
M urethane has almost no such problems, so it can be used on car bumpers and fenders.

It is promising as an exterior material for door panels, etc., or as a coating material for electrical equipment.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited only to these Examples.

The composition of the raw materials used in the Examples and Comparative Examples is as follows. Hereinafter, "parts" and "%" will represent "parts by weight" and "% by weight," respectively.

(1) Polyol A: An octafunctional polyol with a hydroxyl value of 56, which is made by adding 3.000 parts of propylene oxide (hereinafter abbreviated as PO) to 92 parts of glycerin.

(2) Polyol B: 92 parts of glycerin with PO5.0
00 parts then ethylene oxide (hereinafter abbreviated as EO -j) 8
A trifunctional polyol with a hydroxyl value of 33 to which 00 parts have been added.

(3) Polyol C: P in 76 parts of propylene glycol
2,000 parts of O, 500 parts of EO, 2,000 parts of po,
A bifunctional polyol with a hydroxyl value of 28 to which 700 parts of EO was sequentially added.

(4) Polyol D: PO5,10 in 92 parts of glycerin
After adding a mixture of 0 parts and EOsoo parts, further EO
T,oo.

trifunctional polyol with a hydroxyl value of 28.

(5) Coronate 1055: Carbodiimide-modified liquid Ml)I (NC028, 8th), manufactured by Nippon Polyurethane Kogyo Co., Ltd.

(6) Catalyst: DBTDL... Dibutyltin dilaurate 1) A
BCOBB LV...88% of triethylenediamine
Dipropylene glycol solution.

(7) Black toner: 50% carbon black mixed into polyoxypropylene diol (molecular weight 2.000).

(8) Crushed glass fiber Nifuji fiberglass ■Cut glass FESS-0418 Example 1 450 parts of polyol D, 310 parts of methyl methacrylate,
A mixture of 210 parts of acrylonitrile and 4 parts of AIBN was continuously fed by a pump to a pressure-resistant reaction vessel equipped with a stirring and temperature control device. It took 2 hours to feed the raw materials, during which time the reaction temperature was controlled at 115-120°C while stirring. After further stirring at the same temperature for 80 minutes, polyol D
1 part of ATT3N dispersed in 50 parts was supplied with a pump,
Stirring was continued for an additional 30 minutes. Finally, low volatile matter was removed and collected using a vacuum pump, and a pale yellow polymer polyol composition with a polymer concentration of 508% and good dispersion stability was obtained.
Viscosity (25”C) 11.800 cps, hydroxyl value 1
3.9rvKOI-I/g.

Comparative Example 1 The method of Example I was repeated, replacing 600 parts of Polyol D with 700 parts and replacing the 700 parts with 315 parts of acrylonitrile.

The resistance of the stirrer increased from the end of raw material supply, which caused difficulties. A considerable amount of solid matter adhered to the walls of the reaction vessel, and the resulting polymer polyol composition was a hard clay-like material with no fluidity mixed with glassy material.

Examples 2-10. Reference Example 1 In Example 1, when the type of polyol was changed, when the polymer concentration was changed, when the ratio of monomer (N and (Bl) was changed, when styrene was used as monomer (q), and when L7 was used, the present invention The results are shown in Table 1, which shows an example of producing a polymer polyol composition.The composition of the present invention has excellent dispersion stability even at high polymer concentrations.

Examples 11 to 17, Comparative Example 2! 100 parts of combined volume composition, ethylene grinder
-Jl/15 parts, 0.025 parts of DBTI)L and =+o,i-t1o55 in an amount such that the equivalent ratio of ynoneanate group/hydroxyl group is 1.05, and mix vigorously for 10 seconds at 60~70''C. Preheated 250 x 200
Cast into an iron mold with a size of x 2.5 m/m (thickness), removed from the mold after 5 minutes, and heated to 120°C.
A polyurethane elastomer molded article was obtained by annealing for 1 hour. Table 2 shows its physical properties. It can be seen that the elastomer according to the present invention has excellent rigidity.

Examples 18, 19, Comparative Examples 3 to 6 R-RIM machine (Krauss-Maf (e1PU40/
40) to make the raw materials 1.000 x 1.000 x 2
．． Cast into a mold of 5 m/m (thickness) and R, I M
Urethane and R-RIM urethane were obtained. Table 8 shows the raw material formulation and molding conditions, and Table 4 shows the physical properties of the elastomer.

The method of the present invention is more expensive than the conventional method of increasing the modulus by increasing the amount of chain extenders or crosslinkers.
It is advantageous in terms of cost since the amount used is small. Furthermore, the method of the present invention is superior to the reinforcing method using crushed glass fibers in terms of reinforcing effect.

The method for measuring the physical properties of polyurethane is as follows.

0 Surface hardness: Using Shore D hardness tester 0 Bending strength Sample size 25 x 70 x 2.5 u
+ (thickness), span 40111, measured at 25°C.

Claims (1)

[Claims] Comprising 20-55% by weight of a polyol and 45-80% by weight of a polymer of ethylenically unsaturated monomers dispersed in the polyol) R,O II fA) General formula CH2 c-c-o-R? (几 is H or a methyl group, R2 is an alkyl group having 1 to 4 carbon atoms. Polymeric polyol composition produced by polymerizing unsaturated monomers in said polyol. Monomer percentage power (A130
~7oMj11%, (B) so ~70! J1%
, fQ O~80 M first term! j: The composition according to item 2 of lj. 4, +R1 is 7'g'l tIr ) z IL (
L filter #+ 7F"5t'ito4" *nj111 A composition of 4f, (as described in the first, second or third paragraph). 5. (A patent claim in which Q is styrene or α-methylstyrene 6. The composition according to any one of Claims 1 to 4 JJl. 6. Special FF wherein the amount of polymerized Kaneko Tsumar in the polymer polyol composition is 50 to 70 wt.
The composition according to any one of items 1 to 5. 7. The composition according to any one of claims 1 to 6, wherein the polyol is a polyether polyol. 8 polyol and 45 to 80% by weight of a polymer of ethylenically unsaturated monomers dispersed in the polyol, with a methyl group; the base is an argyl group having 1 to 4 carbon atoms). Produced by polymerizing one or more ethylenically unsaturated monomers shown in the polyol with (Bl acrylonitrile and/or l acrylonitrile and optionally (q) other ethylenically unsaturated monomers) in the polyol. A monopolymer polyol composition used to produce a foamed or non-foamed polyurethane by reacting the resulting polymer polyol composition with a polyisocyanate, optionally in the presence of a blowing agent, a catalyst, and other additives. Method of use: 9. The method according to claim 7, in which the composition is reacted with a polyisocyanate by a reaction injection molding method. 10. A patent in which the other additive is glass fiber and/or crushed glass fiber. The method according to claim 8 or 9.