JPS6191211A - Polymer polyol composition and its use - Google Patents

Abstract

PURPOSE:The titled composition useful for the production of a polyurethane excellent in mold release, moldability and impact resistance, prepared by polymerizing a specified, ethylenically unsaturated group-containing polyorganosiloxane in a polyol. CONSTITUTION:The titled composition produced by polymerizing an ethylenically unsaturated monomer in a polyol and comprising said polyol and a polymer of said ethylenically unsaturated monomer, dispersed in said polyol. In the production of said composition, said monomer comprises at least partially a monomer containing one ethylenically unsaturated group-containing polyorgano siloxane in the molecule. For instance, said monomer comprises 1-100wt% mono(meth)acryloxypolyorganosiloxane and 0-99wt% (meth)acrylonitrile and 0-80wt% other ethylenically unsaturated monomers. This composition is useful for the production of, especially, nonexpanded or lowly expanded reaction injection-molded polyurethane elastomer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel polymer polyol composition and a method for using the same, and more particularly, to a method for polymerizing a polyorganosiloxane containing a specific ethylenically unsaturated group in a polyol. The present invention relates to a polymer polyol composition obtained by using the same and a method for using the same in polyurethane production.

[Conventional technology]

Polymeric polyols are colloidal dispersions of linear polymers (some of which are thought to be graft polymerized with polyols) suspended in polyols; Salel produced by radical polymerization of monomers (eg acrylonitrile or a combination of acrylonitrile and styrene). The literature also describes the use of siloxanes having two or more unsaturated groups in the molecule as such monomers, but because of the multiple unsaturated bonds, they tend to become three-dimensional (gelled) during the polymerization process. It is difficult to obtain flowable polymer polyols.

[Purpose of the invention]

One aspect of the invention is to provide a polymeric polyol having pendant polyorganosiloxane groups on the polymer portion.

[Structure of the Invention] The present invention consists of a polymer of a polyol and an ethylenically unsaturated monomer dispersed in the polyol, produced by polymerizing the ethylenically unsaturated monomer in the polyol. A polymer polyol composition characterized in that (8) a polyorganosiloxane having one ethylenically unsaturated group in the molecule is used as at least a part of the monomer. and a polyol containing this polymer polyol composition as an essential component, optionally in the presence of a blowing agent, a catalyst, and other additives, is reacted with a polyisocyanate to produce a foamed or non-foamed polyurethane. .

A method of using a polymer polyol composition.

The polyorganosiloxane having one ethylenically unsaturated group in the prisoner molecule that can be used for producing the polymer polyol of the present invention has the general formula (1) in which the ethylenically unsaturated group is present at the end of the molecule, ( Those having a chain or branched structure as shown in It) can be used.

(In the formula, A represents a monovalent organic group having one ethylenically unsaturated group, R represents an organic group having no ethylenically unsaturated group, and n is a positive number from 5 to 200.

a, b, and c are positive numbers of 1 or more satisfying 5≦a+b+c≦200. ) A is a monoethylenically unsaturated hydrocarbon group having 2 to 10 carbon atoms [vinyl group, (meth)allyl group (indicates allyl group and metaallyl group. The same expressions will be used hereinafter), butenyl group, pentenyl group, Octenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, etc.]
; Examples include a (meth)acryloxyalkyl group having 5 to 20 carbon atoms and a monoethylenic organic group thereof. Among these, a (meth)acryloxyalkyl group is preferred, and a methacryloxypropyl group is more preferred.

R is an alkyl group having 1 to 20 carbon atoms (ethyl group).

Ethyl group, propyl group, butyl group, octyl group.

dodecyl group, stearyl group, etc.); C6-15 aryl group (phenyl group, tolyl group, xylyl group, etc.);
Contains an aralkyl group having 7 to 20 carbon atoms (benzyl group, styryl group, α-methylstyryl group, etc.) and functional groups such as hydroxyl group, amino group, carboxyl group, epoxy group, mercapto group, amide group, polyoxyalkylene group, etc. Examples include saturated organic groups. Among these, alkyl groups,
A free group having a hydroxyl group is preferable, and a methyl group is most preferable. Further, the molecular weight of the compound of general formula (1) or (1) is usually 600 to 20,000, preferably 1,000 to
6,000 more preferably 1,500~a, o o o
These can be used alone or as a mixture. Preferred specific examples of the monoethylenically unsaturated polyorganosiloxane represented by the general formulas (1) and (1) include methacryloxypropyl-modified polydimethylsiloxane or polyrimythylsiloxane having a molecular weight of 1,500 to 8,000. Examples include methacryloxypropylpolydimethylsiloxane in which the methyl group in the moiety is substituted with a saturated barbed group containing a hydroxyl group.

Examples of the unsaturated nitrile (2) that can be used in combination include [meth)acrylonitrile, with acrylonitrile being particularly preferred.

Other ethylenically unsaturated monomers (C
) include, for example, monomers other than those described in Japanese Patent Application No. 58-166208 and Japanese Patent Application No. 58-210842. Among (C), the preferred one is (
Methyl acrylate, ethyl (meth)acrylate,
These include styrene, α-methylstyrene, and glycidyl (meth)acrylate, with methyl methacrylate, styrene, and glycidyl methacrylate being more preferred.

The proportion of (A) in all monomers is usually 1% (wt%,
The same applies hereinafter) It is preferably 2 to 95%, more preferably 8 to 90%, particularly preferably 5 to 80%.

The ratio of each monomer in a preferable monomer consisting of (A), ■, and (C) if necessary is that (A) is usually 1 to 1.
00% preferably 2 to 95, more preferably 3 to 90
% Particularly preferably 5 to 80%, (B) usually 0 to 99%
% preferably 5-98% more preferably 10-97%
Particularly preferably 20 to 95%, (C) is usually θ to 80%
% is preferably 0 to 60%, more preferably 0 to 40%.

Examples of polyols that can be used to produce the polymer polyol of the great invention include those described in Japanese Patent Application No. 58-166208 and Japanese Patent Application No. 58-230842 (
polyether polyols, polyester polyols, polymer polyols thereof, modified polyols thereof, etc.) and polysiloxane-polyoxyalkylene copolymers.

These polyols usually have 2 to 8 hydroxyl groups and 200 to
4,000 OH equivalents, preferably 2 to 4 water groups and 4
It has an OH equivalent of 00 to a, ooo.

Among these, starting materials (propylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.) are combined with alkylene oxides (ethylene oxide,
Polyether polyols to which propylene oxide, butylene oxide, etc. have been added are preferred. More sophisticated polyether polyols have 0 to 50% by weight of ethylene oxide chains arbitrarily distributed in the molecule, and 0 to 3% by weight of ethylene oxide chains.
0% by weight of ethylene oxide chains are tipped at the end of the molecule. Particularly preferred polyether polyols contain 5 to 40 M% of ethylene oxide chains arbitrarily distributed in the molecule and have 5 to 25% by weight of ethylene oxide chains tipped at the ends of the molecules. In addition, the primary hydroxyl group content of polyether polyol is usually θ~100%.
Preferably 30-100, most preferably 50-100
Most preferably it is 70-100%.

The amount of monomer used in producing the polymer polyol of the present invention is usually 5 to 400, preferably 10 to 250, more preferably 15 to 100 parts (by weight, same hereinafter) of the polyol.
~200 most preferably 25 to 150 parts by weight (provided that if the polyol is a polymer polyol, the polymer portion is calculated as the monomer).

A polymerization initiator is usually used to polymerize these monomers. The polymerization initiator is one that generates free radicals to initiate polymerization, such as 2,2'-azobisisobutyronitrile (AIBN).

2. Azo compounds such as 2'-azobis-(A,4-dimethylvaleronitrile); dibenzoyl peroxide, dicumyl peroxide and those described in Japanese Patent Application No. 166208/1982 and Japanese Patent Application No. 280842/1983 Peroxides other than those mentioned above, persulfates, perborates, persuccinic acid, etc. can be used, but for practical purposes, azo compounds, especially 2.2'-
Azobisisobutyronitrile is preferred.

The amount of polymerization initiator used is from 01 to 0.01 based on the total amount of monomers.
20, preferably 0.2 to 10% by weight.

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 monopolymer concentration is high. Examples of organic solvents include benzene, toluene, xylene, acetonitrile, ethyl acetate,
Hexane, heptane.

Dioxane, N,N-dimethylformamide, N,
N-dimethylacetamide, isopropyl alcohol,
Examples include n-butanol.

Furthermore, if necessary, polymerization can be carried out in the presence of a known chain transfer agent other than alkyl mercaptans (carbon tetrachloride, carbon tetrabromide, chloroform, enol ethers described in JP-A-55-31880, etc.). .

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°C
It can be carried out at a temperature of -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 raw material for polyurethane without any post-treatment. It is desirable to remove it by practical means.

The pendant polyorganosiloxane group-containing polymer polyol thus obtained is usually 3 to 80%, preferably 5%.
~70% more preferably 10-65% most preferably 2
It is a translucent to opaque white to tan dispersion of 0 to 60% of total polymerized monomer or polymer dispersed in a polyol. When the polymer content exceeds 80%, the viscosity becomes high and fluidity deteriorates, and when the content is less than 3%, the improvement in the physical properties of the polyurethane is small.

The hydroxyl value of the polymer polyol composition of the present invention is usually 3 to 3.
250, preferably 4 to 125, more preferably 5 to 50.

In a method of using the polymer polyol composition of the present invention for producing polyurethane (second invention).

The polymer polyol composition of the present invention can be used in combination with other polyols if necessary.

As such a polyol, a polymer polyol having at least two hydroxyl groups and an OH equivalent of 200 to 4,000 can be used. Polyether polyols, polyester polyols, modified polyols and polymer polyols can be mentioned. Polybutadiene polyols can also be used, as well as polyols obtained from natural oils such as castor oil. Among these, starting materials include ethylene oxide, propylene oxide, butylene oxide, and any mixture thereof, particularly propylene oxide alone or propylene oxide and ethylene oxide added, having 2 to 8 hydroxyl groups and 200 to 4,000 OH equivalents, particularly. Polyether polyols and their polymer polyols having 2 to 4 hydroxyl groups and 400 to a, ooo Of(equivalents) [In the polyether polyols, the monomer (b) (especially acrylonitrile) and optionally (
C) (in particular, those obtained by polymerizing styrene and methyl methacrylate) are suitable.

These polymer polyols are used in an amount of usually 0 to 500 parts by weight, preferably 0 to 800 parts by weight, and particularly preferably 0 to 200 parts by weight, per 100 parts by weight of the polymer polyol composition of the present invention.

In the present invention, in addition to the polymer polyol composition and polymer polyol of the present invention described so far for the purpose of reacting with polyisocyanate, if necessary, a polymeric active hydrogen-containing compound [for example, two or more active hydrogen and 200~
4,000 equivalent weight) and/or e.g. Japanese Patent Application No. 58-166208,
Low-molecular active hydrogen-containing compounds described in Japanese Patent Application No. 58-280842 [for example.

Ethylene glycol, 1,4-butanediol, triethanolamine, diethyltoluenediamine.

methylene dianiline, alkylene oxide adducts of aniline with an equivalent weight of less than 200, etc.) can be used. These low-molecular active hydrogen-containing compounds are usually used in an amount of 0 to 10 parts by weight per 100 parts by weight of the above polyol (the polymer polyol composition of the present invention and, if necessary, other polymer polyols).
0 parts by weight, preferably 0 to 50 parts by weight, particularly preferably 0 to 50 parts by weight
An amount of 80 parts by weight is used. The proportion of the polymeric polyol composition of the invention in the total active hydrogen-containing component is usually 20 to 100% by weight.

The content of polymer in the total active hydrogen-containing components is usually 5-80%
Preferably it is 10-70%.

Polyisocyanates used in polyurethane production include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group) (e.g. tolylene diisocyanate, diphenylmethane diisocyanate, etc.), aliphatic polyisocyanates having 2 to 18 carbon atoms. (for example, hexamethylene diisocyanate, etc.), alicyclic polyisocyanate having 4 to 15 carbon atoms (for example, isophorone diisocyanate, etc.).

Aroaliphatic polyisocyanates having 8 to 15 carbon atoms (for example, xylylene diisocyanate) and modified products of these polyisocyanates (urethane groups).

Carbodiimide group, allophanate group, urea group.

modified products containing biuret group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group, etc.)
and, for example, Japanese Patent Application No. 58-166208.

Polyisocyanates other than those described in Japanese Patent Application No. 58-280842 can be used. Of these.

Examples of commercially readily available polyisocyanates, such as 2,4- and 2,6-TDI () lylene diisocyanate) and mixtures of these isomers, crude TDI.

C4- and H2,4'-MDI (diphenylmethane diisocyanate) and mixtures of these isomers, crude MD
PAPI, also referred to as I, and modified polyisocyanates containing urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, and isocyanurate groups derived from these polyisocyanates are preferred.

In the present invention, when producing polyurethane, for example, Japanese Patent Application No. 58-166208 1 Japanese Patent Application No. 58-28
Known blowing agents described in No. 0842 (for example, methylene chloride, monofluorotrichloromethane, water, etc.)
, known catalysts (for example, tertiary amines such as triethylene diamine; metal catalysts such as tin octylate, dibutyltin dilaurate, lead octylate, etc.) can be used. The amount of blowing agent used can vary depending on the desired density of the polyurethane (e.g. 0.01 to 1.4 g/cm3) and the amount of catalyst used can vary, e.g.
It is used in small amounts of 1 to about 5%.

Other additives that can be used in the present invention include surfactants as emulsifiers and foam stabilizers;
Particularly important are polysiloxane-polyoxyalkylene copolymers, which also include flame retardants, reaction retarders, colorants, internal mold release agents, anti-aging agents, antioxidants, plasticizers, fungicides and carbon black.

Known additives such as zinc oxide, calcium oxide, calcium carbonate, titanium oxide, diatomaceous earth, glass fiber and its crushed products (cut glass, milled glass, glass fiber, etc.), talc, mica, and other fillers can be used. .

When the polymer composition of the present invention is used for producing polyurethane, the isocyanate index is usually 80 to 120 (preferably 100 to 11O). Furthermore, polyisocyanurate is introduced into the polyurethane by making the isocyanate index significantly higher than the above range (isocyanate index 300~
1,000).

The polymer polyol composition of the present invention has pendant polyorganosiloxane groups derived from monomer (A). Due to the surfactant effect of the pendant polyorganosiloxane groups, the polyurethane obtained using the polymer polyol composition of the present invention has an excellent self-stretching ratio. Therefore, there is no need to add molding agent to the mold every time the mold is demolded. Further, by using the polymer polyol composition of the present invention, it is possible to obtain a polyurethane molded article with a beautiful appearance (few pin-6-holes and air voids).

Polyurethane using the polymer polyol assembly of the present invention can be produced by known methods such as the one-shot method, semi-prepolymer method, and prepolymer method. Various types of unfoamed or foamed polyurethanes can be produced in closed or open molds.

The production of polyurethane is usually carried out by mixing and reacting raw materials using low-pressure or per-pressure mechanical equipment.

The polymer polyol composition of the present invention can be produced in particular in semi-rigid polyurethane foam (density 0) by the RIM (reaction injection molding) process.
．． 1 to 0.7 g/cm3) It is particularly useful for producing non-foamed or low-foamed (density 0.8 to 1.4 g/cm3) RIM-molded polyurethane elastomer (hereinafter referred to as RIM urethane). Molding by the RIM method can be carried out under the same conditions as conventional methods. For example, 100 to 200 kg/cm of raw materials (components A to 4) whose temperature is usually controlled at 25 to 90°C
After impact-mixing at a pressure of 2G and casting into a mold whose temperature has been previously controlled at 30 to 200°C (preferably 60 to 90°C).

C can be easily performed by doing one exercise in 0.1 to 5 minutes. After molding, the resulting molded product can be used as is or annealed (e.g. 70-180°C x 0.3-10°C).
time) and then the product.

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 Examples and Comparative Examples is as follows. Hereinafter, "parts" and "%" will represent "parts by weight" and "% by weight," respectively.

(1) Polyol A: 76 parts of propylene glycol, 2,000 parts of nipropylene oxide (hereinafter abbreviated as PO), 500 parts of ethylene oxide (hereinafter abbreviated as EO), P
A bifunctional polyol with a hydroxyl value of 28 to which 2,000 parts of O and 700 parts of EO were added in that order.

t2+ Polyol B: 92 parts of glycerin and PO5,
A trifunctional polyol with a hydroxyl value of 28, to which a mixture of 100 parts of EO and 800 parts of EO was added, and then 000 parts of EOL was added thereto.

(3) Polymer polyol C: A polymer polyol obtained by radical polymerization of acrylonitrile in polyol A and having a polymer content of about 20%. Viscosity (A5
°C) is 2,600 cps 0 (A) Polymer polyol D: Polymer polyol obtained by radical polymerization of acrylonitrile in polyol B and having a polymer content of about 20%. Viscosity (A5℃) is 6,200 cp
s.

(A) Monomethacryloxypropyl-modified polydimethylsiloxane of structure 820 parts of monomer (6) Monomethacryloxypropyl-modified polydimethylsiloxane of structure m of 820 parts of monomer, where 18. m, n is /, m,
It is a positive number satisfying n≧1 and g+m+n=20.

(7) Millionate MTL: Carbodiimide-modified liquid MDI (NCO28.8%) manufactured by Nippon Polyurethane Kogyo Co., Ltd.

+81 DBTDL dibutyl tin dilaurate.

+9) DABCOA81. v: 38% dipropylene glycol solution of triethylenediamine.

αQ black toner: 50% carbon black mixed into polyoxypropylene diol (molecular weight 2,000).

Example 1 Polyol A2 in a pressure-resistant reaction vessel for stirring and temperature control material
00 parts were added, and the temperature was raised to about 120°C.

A mixture of 350 parts of polyol A, 20 parts of monomer A, 180 parts of acrylonitrile, and 4 parts of AIBN was continuously fed into the reaction vessel over 2 hours using a pump. During this time, the reaction temperature was controlled at 115 to 120°C while stirring. 8 at the same temperature
After continuing stirring for 0 minutes, 1 part of AIBN dispersed in 50 parts of polyol A was added, and stirring was continued for another 30 minutes at the same temperature. Finally, low volatile matter was removed using a vacuum pump, and a pale yellow-brown polymer polyol composition with a polymer concentration of 19.8% was obtained by pouring.

Viscosity (A5℃) 2,800 cps, hydroxyl value 22.
It was 5 mg KOH/g.

Example 2 200 parts of polyol A was charged into the same reaction vessel as in Example 1, and the temperature was raised to about 120°C. 450 parts of polyol A,
A mixture of 170 parts of acrylonitrile and 8.5 parts of AIBN was fed into the reaction vessel in a continuous manner by means of a pump over a period of 2 hours. Next, 100 parts of polyol A, 820 parts of monomer,
A mixture of 10 parts of acrylonitrile and 5 parts of AIB No. was continuously fed into the reaction vessel by a pump over a period of 80 minutes. After continuing stirring at the same temperature for 30 minutes, polyol A
Supply 1 part of AIBN dispersed in 50 parts, and add 3 parts of AIBN.
Stirring was performed at the same temperature for 0 minutes.

Finally, low volatile matter was removed using a vacuum pump, and a pale yellow-brown polymer polyol composition with a polymer concentration of 19.7% was obtained by pouring. Viscosity (A5°C): 2,200 CpS + hydroxyl value: 22.5 mg KOH/g.

Example 3.4 A polymer polyol composition of the present invention was produced in the same manner as in Example 1 using xylene as a solvent. The results are shown in Table-1.

Table 1 Example 5.6; Comparative Example 1 After applying an external mold release agent B-511 (manufactured by Middle East Yushi Co., Ltd.) to a flat iron mold with an inner diameter of 200 x 150 x 1 (thickness) m/m, the mold was heated to approximately 70°C. Temperature control 1. 6 ingredients of the recipe listed in Table-2.
The mixture was poured into a mold with vigorous stirring for 5 seconds, and taken out from the mold after 5 minutes. A similar operation was carried out without applying an external mold release agent to the lower surface of the mold (the mold recess (the upper surface was simply a flat plate)), and was repeated until the polyurethane adhered to the lower surface of the mold. Table 2 shows the number of sheets of polyurethane that could be successfully released from the mold without adhesion.

Examples 7 and 8: Comparative Example 2 R-RIM machine (Krauss-Maffei PU40
/40) and the raw materials are 1.0OQXI, 0OOX2.5
(Thickness) m/m Cast into a mold.

RIM urethane was obtained. The raw material formulation, molding conditions,
Table 3 shows the physical properties of the elastomer.

Table-2 Table-3 The method for measuring the physical properties of polyurethane is as follows.

0 tensile strength, elongation r): ratio: JISK-63010 bending strength 1 bending modulus: sample size 25x70x
2.5mm (thickness), span 40m/m, measured at 25℃.

0 falling weight distance: DuPont impact test MFi! Use i.

A 1kg weight is naturally placed in an atmosphere of -80℃. It was measured by dropping it. sample broken Minimum loss distance. The longer the falling weight distance Impact resistance is good.

[Effects of the Invention] The polymer polyol of the present invention has pendant polyorganosiloxane groups in the main chain of the polymer, and when used in the production of polyurethane, a unique surface-active effect can be expected.

In other words, the self-P-type ability of polyurethane molded products is improved by more than 2 to 3 times compared to conventional polymer polyols (Table 1).
2), and the moldability is also good (see Table 3).

Furthermore, when the polymer polyol composition of the present invention is used, it is possible to obtain a polyurethane that has excellent physical properties, particularly impact resistance, as compared to conventional polymer polyols (see Table 3).

As described above, when the composition of the present invention is used, mold releasability is improved.

Since polyurethane with excellent moldability and impact resistance can be obtained, RIM urethane (used in automobile bumpers) is used.

Highly efficient molded products of high-hardness, high-elasticity, soft or semi-rigid polyurethane foam are used not only for exterior materials such as fenders and door panels, or housings for electrical equipment, but also for energy absorption and cushioning of automobiles, furniture, etc. You can make it. The composition of the present invention is also useful as foamed or non-foamed rigid polyurethane, and polyurethane suitable for adhesives and coating materials, and has high practical value.

Claims (1)

[Claims] 1. Consists of a polymer of a polyol and an ethylenically unsaturated monomer dispersed in the polyol, and is produced by polymerizing the ethylenically unsaturated monomer in the polyol. A polymer polyol composition characterized in that (A) a polyorganosiloxane having one ethylenically unsaturated group in the molecule is used as at least a part of the monomer. 2. The monomer contains (A) monoacryloxypolyorganosiloxane and/or monomethacryloxypolyorganosiloxane, (B) acrylonitrile and/or methacrylonitrile, and optionally (C) other ethylenically unsaturated monomers. 2. The composition according to claim 1, which comprises a mercury. 3. The proportion of monomers in all polymerized monomers is (A) 1
~100% by weight, (B) 0-99% by weight, (C) 0-8
2. A composition according to claim 2, which contains 0% by weight. 4. The composition according to claim 1, 2 or 3, wherein (A) is a monoacryloxy group-containing polydimethylsiloxane and/or a methacryloxy group-containing polydimethylsiloxane. 5. The composition according to claim 2, 3 or 4, wherein (B) is acrylonitrile. 6. The composition according to any one of claims 2 to 5, wherein (C) is methyl methacrylate, styrene, glycidyl methacrylate, or a mixture thereof. 7. The composition according to any one of claims 1 to 6, wherein the amount of total polymerized monomers in the polymer polyol composition is 5 to 70% by weight. 8. The composition according to any one of claims 1 to 7, wherein the polyol is a polyether polyol. 9. A polyorganosiloxane consisting of a polyol and an ethylenically unsaturated monomer dispersed in the polyol, and (A) a polyorganosiloxane having one ethylenically unsaturated group in the molecule, or this and other ethylenically unsaturated monomers. A polyol containing a polymer polyol composition produced by polymerizing a saturated monomer in the polyol as an essential component is reacted with a polyisocyanate, if necessary in the presence of a blowing agent, a catalyst, and other additives. A method of using a polymeric polyol composition for use in producing foamed or non-foamed polyurethane. 10. The polymer polyol contains (A) monoacryloxypolyorganosiloxane and/or methacryloxypolyorganosiloxane, (B) acrylonitrile and/or methacrylonitrile, and optionally (C)
10. The method of claim 9, which is a polymeric polyol prepared by polymerizing other ethylenically unsaturated monomers in the polyol. 11. The ratio of (A) in all polymerized monomers is 5 to 95
11. A method according to claim 10, in which the amount is % by weight. 12. The method according to claim 9, 10 or 11, wherein (A) is a monoacryloxy group-containing polydimethylsiloxane and/or a methacryloxy group-containing polydimethylsiloxane. 13. The method according to any one of claims 9 to 12, wherein the polyol is reacted with the polyisocyanate by a reaction injection molding method. 14. The method according to any one of claims 9 to 13, wherein the other additive is glass fiber and/or crushed glass fiber.