JPS61268711A - Polymeric polyol composition - Google Patents

Abstract

PURPOSE:To provide the titled composition containing pendant hydroxyl group and stably dispersed components, and suitable as a raw material of polyurethane, by polymerizing a glycol ester of an ethylenic unsaturated carboxylic acid and an unsaturated nitrile, etc., in a polyol. CONSTITUTION:The objective composition having a polymer content of 30-70wt% can be produced by (1) compounding (A) preferably 50-250pts.wt. of a composition composed of (i) 5-40wt% ethylenic unsaturated carboxylic acid glycol ester (e.g. ester of acrylic acid and ethylene glycol), (ii) 5-90wt% unsaturated nitrile (e.g. acrylonitrile) and (iii) 0-60wt% other ethylenic unsaturated monomer (e.g. methyl methacrylate) with (B) 100pts.wt. of a polyol having an OH-equivalent of 200-4,000 (e.g. adduct of glycerol and ethylene oxide), and (2) polymerizing the mixture e.g. at 60-180 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to polymeric polyol compositions, and more particularly to polymeric polyol compositions useful in the production of polyurethanes.

[Prior Art] As is well known, polymer polyols are usually produced by polymerizing ethylenically unsaturated monomers (hereinafter referred to as monomers) in polyols, and are considered to have higher practical value than before. is a polymer polyol containing 20 to 30% by weight of a polymer obtained by polymerizing acrylonitrile alone or a combination of monomers with a large proportion of acrylonitrile (for example, acrylonitrile and styrene). It is also a well-known fact that polyurethane foams and polyurethane elastomers obtained using such polymer polyols have better load bearing properties than polyurethanes obtained without using such polymer polyols.

[Object of the Invention] An object of the present invention is to provide a polymer polyol composition that provides a polyurethane with excellent physical properties such as rigidity and impact resistance.

[Structure of the Invention] The present invention comprises: 30-70% by weight of a polyol having an equivalent weight of 200-4000; (a) 5-50% by weight of a glycol ester of an ethylenically unsaturated carboxylic acid; (b) 5-50% by weight of an unsaturated nitrile. 90% by weight, and (c) 30 to 70% by weight of a polymer formed from a monomer mixture consisting of 0 to 60% by weight of other monomers and stably dispersed in the polyol. A polymer polyol composition having pendant hydroxyl groups, produced by polymerizing the monomer mixture in the polyol.

The pendant hydroxyl group-containing polymer polyol composition of the present invention comprises a monomer mixture consisting of (a) a glycol ester of an ethylenically unsaturated carboxylic acid, (b) an unsaturated nitrile, and (c) another monomer. , can be produced by polymerization in a polyol.

The glycol esters (a) of ethylenically unsaturated carboxylic acids used in the production of the pendant hydroxyl group-containing polymer polyol composition of the present invention include the following: (meth)acrylic acid, acrylic acid and methacrylic acid. represents. Similar expressions will be used below. ).

Crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, methylmalonic acid.

Ethylenically unsaturated mono- or poly-carboxylic acids such as aconitic acid, cinnamic acid, vinylbenzoic acid and alkylene glycols of 02-6 (ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-
butanediol, 1,6-hexanediol, etc.) and/or polyglycols [compounds having two active hydrogen atoms in the molecule (e.g. the above alkylene glycols,
Alkylene oxides [ethylene oxide, propylene oxide, starting materials for polyether polyols described below].

1.2-, 2.3-, 1.3- and 1,4-butylene oxide.

Styrene oxide, epichlorohydrin, etc., and combinations (random and/or block) of two or more of these (e.g. ethylene oxide and propylene oxide)] adducts (number of moles added is usually 1 to 20, preferably 1 to 10, particularly preferably Esters with glycols such as 2-10) and the above unsaturated polycarboxylic acids and the above glycols and monools [01-20 monohydric alcohols (e.g. aliphatic monohydric alcohols such as methanol and ethanol) or its alkylene oxide adduct (number of moles added is usually 1 to 20, preferably 1 to 1)
0, particularly preferably 2 to 10)]. [
These esters can be produced by reacting unsaturated carboxylic acids or their ester-forming derivatives (acid anhydrides, lower esters, etc.) with glycols or by reacting unsaturated carboxylic acids with alkylene oxides. ] Preferred among these esters are esters of (meth)acrylic acid, maleic acid, and fumaric acid. Most preferred are esters of (meth)acrylic acid (especially methacrylic acid), particularly those represented by the following general formula (1).

O CH2=C, -C-0-fA-〇 +-n)-1(1)
(In the formula, R is H or a methyl group, A is an ethylene group and/or a propylene group, and n is an integer of 1 to 20.) Specific examples of the monomer of general formula (1) include hydroxyethyl (meth) Examples include acrylate, hydroxypropyl (meth)acrylate, polyoxyethylene (meth)acrylic acid, polyoxypropylene (meth)acrylic acid, and polyoxyethylene-polyoxypropylene (meth)acrylic acid. It can also be used as a mixture. Among these monomers, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, polyoxypropylene (meth)acrylic acid (the number of repeating n of oxypropylene groups is 2)
~20> is preferred, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and polyoxypropylene methacrylic acid (n is 2 to 20) are more preferred, and polyoxypropylene methacrylic acid (n is 2 to 10) is particularly preferred.

Examples of the unsaturated nitrile (b) used in combination include (meth)acrylonitrile, with acrylonitrile being particularly preferred.

Other ethylenically unsaturated monomers (c
), for example, patent application aB58-2308428ct>
Examples include monomers other than those described in Yohi Patent Application No. 76,890/1988. Among (c), preferred are methyl methacrylate, ethyl methacrylate, and styrene.

α-methylstyrene and methyl methacrylate.

Styrene is more preferred.

In the pendant hydroxyl group-containing polymer polyol composition of the present invention, the proportion of each monomer to the total monomers is (
a) is usually (wt%, the same applies hereinafter) 5 to 50%, preferably 5 to 40%, particularly preferably 10 to 30%, and (b) is usually 35 to 90%, preferably 35 to 80%, particularly preferably 40 to 80%. %, (c) is usually θ to 60%, preferably 0 to 50%, more preferably 0 to 40%.

Examples of polyols that can be used for producing the polymer polyol composition of the present invention include Japanese Patent Application No. 59-199160
Examples include those described in the specification (polyether polyols, polyester polyols, polymer polyols thereof, modified polyols thereof, etc.).

These polyols usually have 2 to 8 hydroxyl groups and 200 to
4.000 OH equivalents, preferably 2 to 4 hydroxyl groups and 4
It has an OH equivalent weight of 00 to 3.000.

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. A generally preferred polyether polyol has 0 to 50% by weight of ethylene oxide chains randomly 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 5-40% by weight of ethylene oxide chains arbitrarily distributed in the molecule, with 5-25% 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 O~100.
% preferably 30-100% more preferably 50-10
0%, most preferably 70-100%.

The amount of monomer used in the production of the polymer polyol composition of the present invention is 100 parts (parts by weight, same hereinafter) of the polyol.
The amount is usually 50 to 250 parts, preferably 70 to 160 parts, and more preferably 85 to 125 parts per part (however, when the polyol is a polymer polyol, the polymer portion is calculated as a 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-(2,4-dimethylvaleronitrile) (AVN); dibenzoyl peroxide, dicumyl peroxide and patent application 1986-19
Although peroxides, persulfates, perborates, persuccinct salts, etc. other than those described in the specification of No. 9160 can be used, azo compounds, particularly AIBN and AvN, are preferred for practical purposes.

The amount of polymerization initiator used is 0.1 based on the total amount of monomers.
~20% by weight, preferably 0.2~10% 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 polymer concentration is high. Examples of organic solvents include benzene, toluene, xylene, acetonitrile, ethyl acetate,
Hexane, heptane.

Dioxane, N,N-dimethylformamide, N,N
-Dimethylacetamide, inpropyl 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 180
℃ Preferably 90-160℃ Particularly preferably 100-1
It can be carried out at 50°C, and it can also be carried out under atmospheric pressure or under reduced pressure.

After the polymerization reaction is complete, the obtained polymer polyol can be used as is for producing polyurethane without any post-treatment. It is desirable to remove it by conventional means.

The polymer polyol composition of the present invention is a translucent to opaque white to tan dispersion of polymerized monomers or polymers dispersed in a polyol.

The polymer content of the polymer polyol composition of the present invention is usually 30 to 70%, preferably 40 to 60%, more preferably 4
5-55%, most preferably 50-55%.

If the content of the polymer exceeds 70%, the viscosity will become high and the fluidity will be poor.If the content of the polymer is lower than the above range (30%), the improvement in the physical properties of the polyurethane will be small.

The hydroxyl value of the polymer polyol composition of the present invention is usually 10.
~300 preferably 20~250 more preferably 30~
It is 200.

The polymer polyol compositions of the present invention are useful in the production of polyurethanes.

The polyincyanate used when using the polymer polyol composition of the present invention for polyurethane production includes:
Aromatic polyinsocyanate with 6 to 20 carbon atoms (excluding carbon in the NGO group), aliphatic polyisocyanate with 2 to 18 carbon atoms, alicyclic polyisocyanate with 4 to 15 carbon atoms, aromatic with 8 to 15 carbon atoms Aliphatic polyisocyanates and modified products of these polyisocyanates (modified products containing urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone groups, etc.) can be used. , Specific examples of these include patent application No. 59-19916.
Examples include those described in the specification of No. 0. Preferred are commercially readily available polyisocyanates such as 2,
4- and 2,8-TDI and mixtures of these isomers, crude TDI, 4,4°- and 2,4°-)I
DI and mixtures of these isomers, polyarylene polyisocyanate (, PAP), also called crude MDI
I) and urethane groups, carbodiimide groups, allophanate groups derived from these polyisocyanates,
These are modified polyisocyanates containing urea groups, biuret groups, and polyisocyanurate groups.

Furthermore, when used for producing polyurethane, the polymer polyol composition of the present invention can be used in combination with other polyols, if necessary.

As such polyols, polymeric polyols having at least two water M groups and an OH equivalent weight of 200 to 4,000 can be used, examples of which include the same polyols used to produce the polymer polyols already mentioned. That is, polyether polyols, polyester polyols, modified polyols, polymer polyols, and the like can be mentioned. Polyols obtained from natural oils such as polybutadiene polyols and castor oil can also be used. Among these, starting materials include ethylene oxide, propylene oxide, butylene oxide, and any mixture thereof, especially propylene oxide alone or propylene oxide and ethylene oxide added.
Polyether polyols having 8 hydroxyl groups and an OH equivalent of 200 to a, ooo (especially 2 to 4 hydroxyl groups and an OH equivalent of 400 to 3.000), and their polymer polyols [the monomers in the polyether polyol] (b
) (especially acrylonitrile) and if necessary (c)
(Especially those made by polymerizing styrene and methyl methacrylate) are suitable.

These polymeric polyols are generally used in an amount of 0 to 500 parts, preferably 0 to 300 parts, particularly preferably 0 to 200 parts, per 100 parts of the pendant hydroxyl group-containing polymer polyol.

In addition to the pendant hydroxyl group-containing polymer polyol and polymer polyol, the polymer polyol composition of the present invention may optionally contain other polymeric active hydrogen-containing compounds (for example, two or more active hydrogens and an equivalent amount of 200 to 4,000). (e.g. polyether polyamine with , methylene dianiline, diethyltoluenediamine, an alkylene oxide adduct of aniline having an equivalent weight of less than 200, etc.). These low-molecular active hydrogen-containing compounds are usually 0 to 100 parts, preferably 0 to 50 parts, particularly preferably 0 to 30 parts, per ioo part of the above polyol (pendant hydroxyl group-containing polymer polyol and optionally other polymer polyol). amount is used.

The proportion of the pendant hydroxyl group-containing polymer polyol in the total active hydrogen-containing components is usually 20 to 100%. The content of polymer in the total active hydrogen-containing component is usually from 5 to 70%, preferably from 25 to 60%, particularly preferably from 30 to 55%.

In addition, when producing polyurethane, if necessary, for example, known blowing agents (for example, methylene chloride, monofluorotrichloromethane, water, etc.) described in Japanese Patent Application No. 199160, known catalysts (for example, triethylenediamine, etc.), Tertiary amines; metal catalysts such as tin octylate, dibutyltin dilaurate, lead octylate, etc.) can be used.

The amount of blowing agent used depends on the desired density of the polyurethane (e.g. 0
．． 01 to 1.49/Cd), and the catalyst can vary, e.g.
It is used in small amounts of about 5%. Other additives that can be used in polyurethane production include surfactants as emulsifiers and cell stabilizers, especially polysiloxanes.
Polyoxyalkylene copolymers are important.

Additives that can be used in the compositions of the Ikensui invention include flame retardants, reaction retarders, colorants, internal mold release agents, anti-aging agents, antioxidants, plasticizers, fungicides and carbon black, zinc oxide, Calcium, lead dioxide, titanium oxide, diatomaceous earth, glass fiber and its crushed products (cut glass, milled glass, glass flakes, etc.), tartar,
Known additives include mica and other fillers.

When using the polymer polyol composition of the present invention for producing polyurethane, the isocyanate index is usually 65 to 1.
20 (preferably 75-100, particularly preferably 85-1
00). In addition, polyisocyanurate is introduced into polyurethane by making the isocyanate index significantly higher than the above range (polyisocyanate index 300 to i
, ooo >.

Polyurethane can be produced by a known method such as a one-shot method, a semi-prepolymer method, or a prepolymer method. Various types of unfoamed or foamed polyurethanes can be produced in closed or open molds. Polyurethane is usually produced by mixing and reacting raw materials using low or high pressure mechanical equipment.

Furthermore, before and after mixing raw materials (especially before mixing raw materials).

Polyurethane can also be produced by removing dissolved air in the raw materials or gases such as air mixed in during mixing using a vacuum method.

The polymer polyol composition of the present invention is particularly suitable for non-foaming or low foaming (density 0.8 to low foaming) by RIM (reaction injection molding) method.
R of 1.49/CII, especially 0.95 to 1.4 g/d)
It is useful in the production of IM molded polyurethane elastomers (hereinafter referred to as RIM urethanes).

Molding by the RIM method can be carried out under the same conditions as conventional methods.

For example, raw materials (2 to 4 components) whose temperature is usually controlled at 25 to 90°C are collision-mixed at a pressure of 100 to 200 K'j/criG, and the mixture is mixed in advance at 30 to 200°C (preferably 60 to 90°C).
This can be carried out by casting the mold into a mold whose temperature is controlled at 0.011°C (°C) and then removing it from the mold within 0.11 to 5 minutes. The molded product obtained after molding can be made into a product as is, but it is preferable to perform rough annealing (after-curing) before making it into a product. The annealing conditions in this case are usually 6
0 to 180℃ x 0.3 to 100 hours, 80 degrees
~160'cX0.3~100 hours more preferably io
o to 150' CX O for 3 to 100 hours, particularly preferably at 120 to 140°C for 1 to 30 hours.

[Examples] The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples. The compositions of the raw materials used in Examples, Usage Examples, and Comparative Examples are as follows. Note that parts and % represent parts by weight and % by weight, respectively.

(1) Polyol A: 76 parts of propylene glycol and 2,000 parts of propylene oxide (hereinafter abbreviated as PO')
parts, 500 parts of ethylene oxide (hereinafter abbreviated as EO), P
o 2,000 parts of EOTQO part, a difunctional polyol with a water base value of 28.

(2) Polyol C: PO5,10 in 92 parts of glycerin
After adding a mixture of 0 parts and 800 parts of EO,
A trifunctional polyol with a hydroxyl value of 28 to which 1,000 parts of O is added.

(3) Polyol C: 92 parts of glycerin and 3,000 parts of PO
A trifunctional polyol with a hydroxyl value of 56 to which 0 parts have been added.

(4) Polyol D: A tetrafunctional polyol with a hydroxyl value of 36, in which 400 parts of EO, 6,000 parts of Po, and 700 parts of EO were sequentially added to 136 parts of pentaerythritol.

(5) Monomer: HEA: Hydroxyethyl acrylate.

HEMA: Hydroxyethyl methacrylate.

HPMA: Hydroxypropyl methacrylate.

TPMA: Trioxypropylene methacrylic acid.

HOPMA: Hexaoxypropylene methacrylic acid.

to N: Acrylonitrile.

MMA: Methyl methacrylate.

(6) Millionate MTL: Carbodiimide modified liquid M
DI (NGO28.8%) Japan Polyurethane Industry■
Made.

(7) Catalyst DBTDL Nidibutyl tin dilaurate.

NMM: N-methylmorpholine.

, DABCO33LV: 3 of triethylenediamine
3% dipropylene glycol solution.

(8) Polymer polyol E: Polymer content 2 obtained by radical polymerization of AN in polyol B
0% polymer polyol (hydroxyl value 22.4>.

(9) Polymer polyol ■: Polymer polyol with a polymer content of 20% (hydroxyl value 22.4>) obtained by radical polymerization of monomers (AN: styrene - 80:20>) in polyol A.

(10) E G : Ethylene glycol Example 1 Polyol B1 was added to a pressure-resistant reaction vessel with stirring and temperature control.
50 parts of xylene and 150 parts of xylene were added, and the temperature was raised to about 120°C. 3300 parts of polyol, 100 parts of HEMA,
A mixture of 355 parts of AN, 55 parts of MMA, and 4 parts of AIBN was continuously fed into the reaction vessel by a pump over a period of 2 hours.

During this time, the reaction temperature was controlled at 115-120°C while stirring. After continuing stirring at the same temperature for 30 minutes, 1.6 parts of AIBN dispersed in 50 parts of polyol B was added,
Stirring was continued at the same temperature for an additional 30 minutes. Finally, remove low volatile matter using a vacuum pump.

A light brown polymer polyol composition with a polymer concentration of SO, 0% [viscosity (25°C) 11,300c] was collected and obtained.
ps.

A hydroxyl value of 56 mg and OH/g were obtained.

Examples 2 to 16 Polymer polyols according to the present invention were produced in the same manner as in Example 1. Table 1 shows the raw materials used and the properties of the obtained polyonyl polymer.

Usage Examples 1 to 10: Comparative Examples 1 and 2 The raw materials listed in Table 2 were mixed vigorously for 10 seconds and cast into an iron mold with a size of 127 x 100 x 12.7 m (thickness) whose temperature was controlled to about 70°C. After a few minutes, it was taken out of the mold and after-cured at 120°C for 2 hours, and then at 135°C for 5 hours to obtain a polyurethane molded product. The physical properties are shown in Table 2.

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

Tensile strength, Kg/cr/l: JIS K-6
301 elongation rate 2%: JIS K-6301
Bending strength, g/ci: JIS K-7203
Flexural modulus, KQ/cti: JIS K-72
03 Impact strength, 'fQcm/cm: JIS K
-7110 Heat distortion temperature, 'C:' JISK-720
7 (Method A) Usage Example 11.12 90 parts of the polymer polyol of Example 1, 10 parts of black toner,
EG15 parts (use example 11) or 30 parts (use example 12)
), DABCO33LV O, 5 parts, DBTDL O
, 02 parts (more than A component); Millionate MT1 76
．． 6 parts (NGO index: 90) Mata Gt 14 parts (
NGO index: 95), Freon - 113 parts (more than B component)
The prescription raw materials for ingredients A and B are processed using an R-RIM machine (Claus-
Matsufai Pυ40/40) was heated to about 70°C in advance.
A mold whose temperature is controlled to (1,0OOx 1,0OOx 2.
5m> [Discharge pressure 150kg/cdG, injection time 4
．． 5 seconds), and after 30 seconds, it was taken out and after-cured in an oven at 120°C for 2 hours and 130°C for 5 hours to obtain RIM urethane.

Its physical properties are shown in Table 3.

Table 3 Usage Example 13.14 Two-component prescription raw materials (50
℃) into a mold (400 x 300 x 3 parts wr1) pre-adjusted to about 70 ℃ using R-RIMa (MINIRIHHC-102 manufactured by Polyurethane Engineering ■) (discharge pressure 150-180 K! j/c
iG, discharge amount 1501 minutes, injection time 1.8 seconds),
The mold was demolded after 60 seconds. [The raw material tank of the R-RIM machine was evacuated to remove dissolved air, etc., and then cast into a mold to obtain a polyurethane molded product. ] The obtained RIM urethane was heated at 120°C for 1 hour.

After-cure was carried out in an oven at 130° C. for 5 hours. Its physical properties are shown in Table 4.

Table 4 [Effects of the Invention] The polymer polyol according to the present invention has pendant hydroxyl groups in the main chain of the polymer, so by reacting (polyurethanization) this, the polymer portion and the polyurethane portion can be bonded. It is also possible to connect (crosslink) polymer parts to each other, and it is possible to produce polyurethane with particularly excellent impact resistance.

As is clear from Table 3, the polyurethane obtained according to the present invention has superior rigidity, impact resistance, and heat resistance compared to polyurethane obtained from conventional non-crosslinked polymer polyols. In particular, it is characterized by low temperature dependence of impact resistance (excellent low-temperature impact resistance), [Notched Izot impact strength at 23°C is 10! j cm /
cm or more], it is of great significance to the Institute of Technology.

The polymer polyol according to the present invention has a relatively low viscosity even though the polymer concentration is high. Above especially 10, oooKg/c
rA or higher) polyurethane molded products (density 0.8 to 1.4
9/cIII, in particular 0.95 to 1.4 g/cn), can be produced more advantageously and without problems than when using conventional polymer polyols.

As described above, the polymer polyol composition of the present invention provides polyurethane with excellent rigidity and impact resistance, so R
In addition to IM urethane (exterior materials such as automobile bumpers, fenders, and door panels, and housings for electrical equipment), high hardness and high elasticity soft or semi-rigid polyurethane foams are used for energy absorption and cushioning of automobiles, furniture, etc. Also, foamed or non-foamed rigid polyurethane sheets are useful for producing polyurethane suitable for adhesives and coating materials, and their practical value is high.

Claims (1)

[Claims] 1, a polyol having an equivalent weight of 200 to 4000;
(a) 5-50% by weight of glycol esters of ethylenically unsaturated carboxylic acids, (b) 5-90% by weight of unsaturated nitriles, and (c) 0-60% by weight of other monomers. A polymer formed from a monomer mixture consisting of 30 to 70% by weight of the polymer stably dispersed in the polyol, and produced by polymerizing the monomer mixture in the polyol. Also, a polymer polyol composition having pendant hydroxyl groups. 2. (a) is the general formula (1): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R is H or a methyl group, A is an alkylene group with 2 to 4 carbon atoms, and n is 1 represents an integer of 20 to 20.) The composition according to claim 1, which is a monomer represented by: 3. The composition according to claim 2, wherein n is an integer of 2 to 10. 4. The composition according to claim 1, wherein (a) is hydroxyethyl (meth)acrylate and/or hydroxypropyl (meth)acrylate. 5. The composition according to any one of claims 1 to 4, wherein (b) is acrylonitrile. 6. The composition according to any one of claims 1 to 5, wherein (c) is methyl methacrylate, styrene, or a mixture thereof. 7. The proportion of monomers in all polymerized monomers is (a)
(b) 35-80% by weight, and 0-50% by weight of other ethylenically unsaturated monomers. 8. The composition according to any one of claims 1 to 7, wherein the polyol is a polyether polyol. 9. The content of the polymer in the polymer polyol is 40 to 60
9. A composition according to any one of claims 1 to 8, which is % by weight.