JPH082935B2 - Polymer polyol composition and method of use thereof - Google Patents

Description

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

Polymer polyols are usually produced by polymerizing monomers in polyols that do not contain substantially polymerizable unsaturated groups, but have been used in practice from the standpoint of dispersion stability, viscosity and physical properties of polyurethanes using them. It is said that the polymer polyol obtained by polymerizing acrylonitrile alone or a combination of a plurality of monomers having a large ratio of acrylonitrile (for example, acrylonitrile and styrene) is about 20% by weight.

However, even when acrylonitrile is used, when the polymer concentration becomes high (for example, 30% by weight or more), the viscosity increases sharply (when the amount of acrylonitrile is large) or particles are generated (when the amount of acrylonitrile is small, styrene is used as a comonomer). It was difficult to obtain a high-concentration polymer polyol having a low viscosity and excellent dispersion stability. A polymer polyol prepared by combining a monomer of glycidyl acrylate and acrylonitrile has also been proposed, but the physical properties (particularly rigidity) of the polyurethane obtained from this are poor.

The present inventors have conducted repeated studies for the purpose of obtaining a polyol in the case of giving a polyurethane having good dispersion stability even at a high concentration and having high physical properties (particularly high rigidity). As a result, a plurality of specific monomers are polymerized in the polyol. As a result, it is possible to obtain a polymer polyol having a low viscosity, good dispersion stability, and a high concentration (for example, 70% by weight) which cannot be seen by the conventional method.
Further, they have found that a polyurethane having an extremely high rigidity (high elastic modulus) can be produced by using this, and reached the present invention.

That is, the present invention has 20 to 75% by weight of a polyol having 2 to 8 hydroxyl groups and an OH equivalent of 200 to 4,000, and a polymer of an ethylenically unsaturated monomer dispersed in the polyol.
80% by weight of the composition, wherein the polymer is (A)
Glycidyl methacrylate 15 to 90% by weight, (B) acrylonitrile and / or methacrylonitrile 10 to 85% by weight, (C) other ethylenically unsaturated monomer 0 to 40% by weight
And a polymer polyol composition formed from the polyol.

In the present invention, it is essential to use both (A) glycidyl methacrylate and (B) both acrylonitrile and / or methacrylonitrile (A) and (B) monomers, but if necessary, (C) and others as optional components. These monomers can be used together.

Specific examples of the monomer (C) include butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-
Inexpensive hydrogen monomers such as octadiene, styrene, α-methylstyrene, methylstyrene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene; cyanostyrene, nitro styrene,
N, N-dimethylaminostyrene, acetoxystyrene, 4
-Substituted styrene such as methyl vinyl benzoate, phenoxystyrene, p-vinyl diphenyl sulfide, p-vinyl phenyl oxide; acrylic acid, methacrylic acid, methyl acrylate, 2-hydroxyethyl acrylate, methacryl Acid 2-hydroxyethyl, methyl methacrylate,
Cyclohexyl methacrylate, benzyl methacrylate,
Isopropyl methacrylate, octyl methacrylate, α
-Ethyl ethoxy acrylate, methyl α-acetamino acrylate, butyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, phenyl methacrylate, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, N-butyl Acrylic acid and substituted acrylic acid monomers such as acrylamide and methacrylformamide; vinyl acetate, vinyl alcohol, vinyl butyrate, isopropenyl acetate, vinyl formate, vinyl acrylate, vinyl methacrylate, vinyl methoxyacetate, vinyl benzoate, vinyl Toluene, vinyl naphthalene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-
Methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro-1,2-pyran, 2-butoxy-2'-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, vinyl methyl ketone, Vinyl ethyl ketone, vinyl phenyl ketone, vinyl ethyl sulfide, vinyl ethyl sulfone, N-methyl-N-vinyl acetamide, N-vinyl pyrrolidone, vinyl imidazole, divinyl sulfide, divinyl sulfoxide, divinyl sulfone, sodium vinyl sulfonate , Vinyl ethers such as methyl vinyl sulfonate and N-vinyl pyrrole, vinyl ethers,
Vinyl ketone, etc .; dimethyl fumarate, dimethyl maleate, maleic acid, crotonic acid, fumaric acid, itaconic acid,
Examples thereof include monomethyl itaconate, t-butylaluminoethyl methacrylate, dimethylaminoethyl methacrylate, allyl alcohol, glycol monoester of itaconic acid, vinyl pyridine and the like.

Acrylonitrile is preferable as the monomer (B), methyl methacrylate, ethyl methacrylate, styrene, and α-methylstyrene are preferable as the monomer (C), and methyl methacrylate and styrene are more preferable.

The polyol used in the present invention is a substantially saturated polyol, and typical examples thereof include a polyether polyol and a polyester polyol, both of which are usually used as a raw material for polyurethane and used alone or as a mixture. Can also be used as

The polyether polyol is a compound obtained by adding an alkylene oxide to an active hydrogen-containing compound having no polymerizable saturated group such as polyhydric alcohol, polyhydric phenol, amines and phosphoric acid. Water is a specific example of the active hydrogen-containing compound;
Glycols such as ethylene glycol, propylene glycol, 1,3 butylene glycol, 1,4 butanediol, hexylene glycol, 1,6 hexanediol; glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, α-methyl Glucoside, dipentaerythritol, sorbitol, xylitol, mannitol, glucose, fructose, sucrose, and other trivalent to octahydric alcohols; pyrogallol,
Polyvalent phenols such as hydroquinone, bisphenol A, bisphenol sulfone, condensation products of phenol and formaldehyde; ammonia; monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine and other alkanolamines; C ₁ ~ C ₂₀ saturated alkylaminos; ethylenediamine, diethylenetriamine, hexamethylenediamine and other saturated aliphatic amines; aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline, diphenyletherdiamine and other aromatic amines Isophoronediamine and other alicyclic amines; aminoethylpiperazine and other heterocyclic amines described in JP-B-55-21044

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin and styrene oxide. A preferred alkylene oxide is a combination system of propylene oxide, propylene oxide and ethylene oxide (random, block and mixed system of both). The addition reaction of the alkylene oxide can be carried out by a usual method, and is carried out in one step or multisteps under normal pressure or under pressure in the absence of a catalyst or a catalyst (alkali catalyst, amine catalyst, acidic catalyst). Examples of polyester polyol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolpropane, etc. Alcohol and /
Or the above polyether polyols and adipic acid,
Those produced by condensation reaction with aliphatic saturated or aromatic dicarboxylic acids such as sebamic acid, phthalic anhydride, dimethyl terephthalate, acid anhydrides and ester-forming carboxylic acid derivatives; and lactones (such as caprolactone) Examples thereof include those produced by ring-opening polymerization of

These polyols usually have 2 to 8 hydroxyl groups and 200 to
OH equivalent of 4,000, preferably 2-4 hydroxyl groups and 400-3,00
It has an OH equivalent weight of 0.

Of the polyether polyols and polyester polyols, polyether polyols are preferred. Preferred polyether polyols have 0 to 50% by weight of ethylene oxide chains, optionally distributed in the molecule, and 0 to 30% by weight.
The ethylene oxide chain of is chipped at the molecular end. Particularly preferred polyether polyols are those which contain 5-40% by weight of ethylene oxide chains optionally distributed in the molecule and 5-25% by weight of ethylene oxide chains are chipped at the ends of the molecule. The primary hydroxyl group content of the polyether polyol is usually 0 to 100%, preferably 30 to 1
00% More preferably 50-100%, most preferably 70-100%
Is.

By the way, the polyol which does not substantially contain an unsaturated group in the present invention means a polyol obtained from a saturated starting material, and a polyol which does not originate from the starting material and which contains a small amount of an unsaturated group produced by a side reaction is It is the subject of the present invention. As is well known, conventional polyether polyols which inevitably contain small amounts of unsaturated groups due to side reactions of propylene oxide are included in the present invention.

In the present invention, a modified polyol such as a urethane polyol produced from a large excess of polyol and polyisocyanate can also be used.

In the present invention, it is usually 35 per 100 parts by weight of polyol.
~ 400, preferably 50-250, preferably 70-200, most preferably 85-150 parts by weight of monomer can be used.

A polymerization initiator is usually used to polymerize these monomers. The polymerization initiator is of a type that generates free radicals to initiate polymerization, such as 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis- (2,4
Azo compounds such as dimethyl valeronitrile); dibenzoyl peroxide, lauroyl peroxide, di-t
-Butyl peroxide, dicumyl peroxide, t-butyl-hydroperoxide, diisopropyl peroxide carbonate, t-butylperoxy-2-ethylhexanoate, t-butylperpivalate, 2,5-dimethylhexane -2,5-di-per-2-ethylhexoate, t-
Butyl percarbonate, t-butyl perisobutyrate, di-t-butyl perphthalate, or other peroxides or persulfates, perborates, persuccinic acids, etc. can be used, but practically they are azo compounds. Particularly, 2,2'-azobisisobutyronitrile is preferable. The amount of the polymerization initiator used is 0.1 to 20, preferably 0.2 to 10% by weight, based on the total amount of the monomers. Further, a method of generating free radicals by a physical method, that is, a method of generating free radicals by irradiation of ultraviolet rays or electron beams can also be used.

The polymerization reaction in the polyol can be carried out without a solvent, but when the polymer concentration is high, it is preferably carried out in the presence of an organic solvent. Examples of the organic solvent include benzene, toluene, xylene, acetonitrile, ethyl acetate, hexane, heptane, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, isopropyl alcohol, n-butanol and the like.

Known chain transfer agents (carbon tetrachloride, carbon tetrabromide, chloroform,
Enol ethers described in JP-A-55-31880)
The polymerization can be carried out in the presence of

 The polymerization can be carried out batchwise or continuously.

Polymerization reaction is above the decomposition temperature of the polymerization initiator, usually 60 to 180
C., preferably 90 to 160.degree. C., particularly preferably 100 to 150.degree. C., and can be carried out under atmospheric pressure, under pressure, or under reduced pressure.

After the completion of the polymerization reaction, the obtained polymer polyol can be used as it is as a polyurethane raw material or an epoxy resin raw material without any post-treatment. It is desirable to remove the impurities in Step 1 by conventional means.

In the polymer polyol composition thus obtained,
The proportion of all the monomers polymerized is (A) 15 to 90% by weight,
(B) 10 to 85% by weight, (C) 0 to 40% by weight.
If the proportions of (A), (B) and (C) deviate from the above range, the obtained polymer polyol composition has a high viscosity and tends to form particles.

The polymer polyol composition of the present invention is usually 25 to 80% by weight.
Preferably from 30 to 70% by weight, more preferably from 40 to 65% by weight, most preferably from 45 to 60% by weight, of a semi-transparent to opaque white or tan dispersion in which the total polymerized monomer or polymer is stably dispersed in the polyol. It is the body. When the polymer content exceeds 80%, the viscosity becomes high and the fluidity deteriorates,
When it is lower than 25%, the rigidity of polyurethane becomes low.

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

The composition of the present invention can be used for producing a foamed or non-foamed polyurethane by reacting with a polyisocyanate, optionally in the presence of a foaming agent, a catalyst and other auxiliary agents.

Polyisocyanate used for polyurethane production has 6 to 20 carbon atoms (excluding carbon in NCO group), aromatic polyisocyanate having 2 to 18 carbon atoms, alicyclic group having 4 to 15 carbon atoms Polyisocyanate,
Aroaliphatic polyisocyanates having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product Etc.) can be used. Specific examples of such polyisocyanate include
1,3- and 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), diphenylmethane-2,4'- and / or 4,4'-diisocyanate (MDI) , Naphthylene-1,5-diisocyanate,
Aromatic aromatics such as triphenylmethane-4,4 ', 4 "-triisocyanate, polyphenylene polyisocyanate (PAPI) obtained by anigen-formaldehyde condensation followed by phosgenation, m- and p-isocyanatophenylsulfonyl isocyanate Polyisocyanate; ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,6-11-undecane triisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate, 2,6-diisocyanate methylcaproate , Bis (2-isocyanatoethyl) fumarate, bis (2-isocyanateethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanate hexanoate Cyanate; alicyclic polyisocyanate such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) 4-cyclohexene-1,2-dicarboxylate; xylylene diisocyanate, Aroaliphatic polyisocyanates such as diethylbenzene diisocyanate; modified polyisocyanates such as urethane-modified DMI, carbodiimide-modified MDI, and urethane-modified TDI, and mixtures of two or more thereof. Available polyisocyanates such as 2,4- and 2,6-
TDI and mixtures of these isomers, crude TDI, 4,4'- and
Containing 2,4'-MDI and mixtures of these isomers, PAPI also called crude MDI and urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups and isocyanurate groups derived from these polyisocyanates Modified polyisocyanates are preferred.

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

The low molecular weight active hydrogen-containing compound is usually called a cross-linking agent or a chain extender, and at least two, preferably 2 to 5, active hydrogens and an equivalent weight of 30 to less than 200 (molecular weight per active hydrogen-containing group). Compounds having a) can be used. Specific examples thereof include dihydric and trihydric alcohols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin and trimethylolpropane; diethanolamine, triethanol. Amines such as amine, triisopropanolamine, diaminotoluene, diethyltoluenediamine, methylenedianiline, and methylenebislusochloroaniline; and the above-mentioned 2- to 3-hydric alcohols, 4- to 8-hydric alcohols (pentaerythritol,
(Methyl glucoside, sorbitol, sucrose, etc.)
A small amount of alkylene oxide such as ethylene oxide and / or propylene oxide is added to polyvalent phenols (bisphenol A, hydroquinone, etc.), the above amines, and other amines (ethylenediamine, diethylenetriamine, aminoethylpiperazine, aniline, etc.) Polyhydroxy compounds having an equivalent weight of less than 200 can be mentioned. These low molecular weight active hydrogen-containing compounds are usually used in an amount of 0-100 per 100 parts by weight of the polymer polyol composition.
Parts by weight are used, preferably 0 to 50 parts by weight and particularly preferably 0 to 30 parts by weight.

As the polymer active hydrogen-containing compound, at least 2
A compound having an equivalent number of active hydrogen of 200 to 4,000, for example, polyether polyol, polyester polyol, and polyether polyol having most of the molecular terminals which are amino groups produced by reacting ammonia under high pressure. And polyols obtained from natural oils such as castor oil. As the polyether polyol and the polyester polyol, the same polyols as those mentioned above for producing the polymer polyol can be used.

Among these, ethylene oxide, propylene oxide, butylene oxide and any mixture thereof, particularly propylene oxide alone or a mixture of propylene oxide and ethylene oxide, are added to the starting material.
Polyether polyols having 8 hydroxyl groups and 200-4,000 OH equivalents, especially 2-4 hydroxyl groups and 400-3,000 OH equivalents, are preferred.

These macromolecular 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 component is usually 20 to 100% by weight. The content of polymer in the total active hydrogen-containing component is usually 5 to 80%.

The following known substances can be used as a foaming agent, a catalyst and other auxiliaries which are optionally used in the production of polyurethane.

(1) Examples of the foaming agent include methylene chloride,
Halogenated hydrocarbons such as chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorofluoromethane; low boiling point hydrocarbons such as butane, hexane, heptane; acetone, ethylene acetate, diethyl ether, etc. Examples thereof include a volatile organic solvent containing no halogen, a reactive blowing agent such as water that reacts with an isocyanate to generate carbon dioxide, and a combination system thereof. The amount of blowing agent used can vary depending on the desired density of the polyurethane (eg 0.01 to 1.4 g / cm ³ ).

(2) Examples of the catalyst include triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ', N'-tetramethylethylenediamine, 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-diethanolamine, N-ethyl-diethanolamine, N, N-dimethyl-ethanolamine, and other alkanolamines; tetramethylammonium hydroxide, Benzyltrimethylammonium hydroxide and other tetraalkyls Ammonium hydroxides; alkali metal phenolates such as sodium phenolate; hydroxides of alkali metals such as potassium hydroxide; alkali metal alkoxides such as sodium methoxide; potassium acetate, sodium acetate, 2-
Alkali metal salts of carboxylic acids such as potassium ethylhexanoate; phosphinic acids such as triethylphosphine; metal chelate compounds such as potassium salicylaldehyde; stannas acetate, stannas octoate (stannas 2-ethylhexoate) and others Organotin (II) compounds of dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dioctyltin diacetate and other organotin (IV) compounds; other organometallics such as dialkyl titanates A compound can be mentioned. Tris (dimethylaminomethyl)-
It is also possible to use isocyanurate-promoting catalysts such as phenol, N, N ', N "-tris (dimethylaminopropyl) hexahydro-s-triazine. These catalysts are, for example, from about 0.001 to about 5 based on the weight of the reaction mixture. Used in small amounts of%.

(3) As other auxiliaries, an emulsifier and a surface-active agent as a foam stabilizer can be used.
Polyoxyalkylene copolymers are important.

Other auxiliary agents that can be used in the present invention include flame retardants, reaction delay agents, colorants, internal mold release agents, antioxidants, antioxidants, plasticizers, bactericides and carbon black, participating titanium, diatomaceous earth, and cut glass. Well-known auxiliaries such as milled glass, tanks, mica and other fillers can be used.

The polymerized polyol composition of the present invention contains an epoxy group derived from the monomer (A). When the composition is used for producing a polyurethane, the epoxy group is subjected to a ring-opening reaction (for example, a coupling reaction or a polymerization reaction between epoxy groups) in the presence of a known catalyst and / or a curing agent simultaneously with or before or after the urethanization reaction. A reaction with an active hydrogen-containing compound; a reaction with an acid anhydride; a reaction with an isocyanate (formation of oxazolidone), and the like.

When the polymer polyol composition of the present invention is used for producing polyurethane, the isocyanate index is usually 80 to 120.
(Preferably 100 to 110), but the isocyanate index can be made higher than the above range (for example, 300 to 1000) to produce polyisocyanurate.

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, the semi-prepolymer method, the prepolymer method and the like. Polyurethane can be manufactured. Polyurethane is usually produced by mixing and reacting raw materials using a low-pressure or high-pressure mechanical device. Especially RIM
Non-foaming or low-foaming RIM by (reaction injection molding) method
Molded polyurethane ethanone Sutoma (density 0.8 to 1.4 g / cm ³⁾
Also, high hardness, high elasticity soft or semi-rigid polyurethane foams for energy absorption or cushioning of automobiles, furniture, etc. are conveniently manufactured.

The characteristics of the polymer polyol composition of the present invention are that it has a low viscosity and an excellent dispersion stability even in a high polymer concentration region. Contrary to the fact that the conventional polymer polyol impairs practicality in terms of dispersion stability and fluidity at a polymer concentration of 30%, especially 40% by weight or more, the polymer polyol composition of the present invention contains 50% by weight and 70% by weight. Not only does fluidity not be lost even at a polymer concentration of 1, the dispersion stability is good, and its practical value is high.

Further, the polymer polyol composition of the present invention provides polyurethane having excellent rigidity as compared with conventional polymer polyols (for example, acrylonitrile-glycidyl acrylate polymer polyol).

Therefore, the polymer polyol composition of the present invention is useful for various polyurethanes such as soft, semi-rigid and rigid polyurethane foams or polyurethane elastomers, and particularly suitable for RIM molded polyurethane elastomers (hereinafter referred to as RIM urethane).

The advantage of using the polymer polyol composition of the present invention is that an extremely high-rigidity polyurethane can be produced easily and inexpensively. Therefore, a reinforced RIM molded polyurethane elastomer (hereinafter referred to as R-RIM urethane) containing about 20% crushed glass fiber is added. It is also possible to obtain RIM urethane having a rigidity equal to that of (abbreviated as) without adding glass fiber. Contrary to the fact that R-RIM urethane has fatal problems such as equipment damage due to glass abrasion, adverse effects on paintability and aesthetics due to glass on the surface of molded products, and directionality inherent in molded products, Since RIM urethane from the polymer polyol composition of the present invention has no such problems, it is promising as an exterior material for automobile bumpers, fenders, door panels, etc. or a housing material for electric equipment.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The compositions of the raw materials used in Examples and Comparative Examples are as follows. In the following, "part" and "%" represent "part by weight" and "% by weight", respectively.

1. Polyol A Propylene glycol 76 parts, propylene oxide (hereinafter abbreviated as PO) 1,700 parts, and then ethylene oxide (hereinafter abbreviated as EO) 300 parts are added, and the hydroxyl value is approximately 56 mg KOH / g and the degree of unsaturation is 0.02 meq / g. Property polyol.

2. Polyol B Propylene glycol 76 parts, PO2,000 parts, EO500 parts, PO2,
A difunctional polyol with a hydroxyl value of about 28 and an unsaturation degree of about 0.07 added in the order of 000 parts and EO700 parts.

3. Polyol C Approximately 5 hydroxyl groups with 3,000 parts PO added to 92 parts glycerin
6, Trifunctional polyol with an unsaturation of about 0.02.

4. Polyol D A trifunctional polyol having a hydroxyl value of about 55 and a degree of unsaturation of about 0.02, in which 700 parts of PO2 and 700 parts of EO are added to 92 parts of glycerin.

5. Polyol E A trifunctional polyol having a hydroxyl value of about 55 and a degree of unsaturation of about 0.02, in which 92 parts of glycerin, 300 parts of PO2 and 600 parts of EO are added.

6. Polyol F 20 parts of polyol C, 40 parts of polyol D, E40 of polyol
A trifunctional polyol having a hydroxyl value of about 55 and a degree of unsaturation of about 0.02, mixed in parts.

7. Polyol G A trifunctional polyol having a hydroxyl value of about 33 and an unsaturation degree of 0.04, which is obtained by adding 5,000 parts of PO and then 800 parts of EO to 92 parts of glycerin.

8. Polyol H A trifunctional polyol having a hydroxyl value of about 28 and an unsaturation degree of about 0.06, which is obtained by adding a mixture of 100 parts of PO5 and 800 parts of EO to 92 parts of glycerin and further adding 1,000 parts of EO.

9. Polyol I Pentaerythritol 136 parts EO400 parts, PO6000 parts, EO70
4 with a hydroxyl value of about 36 and an unsaturation degree of about 0.04 with 0 parts added sequentially
Functional polyol.

10. Polyisocyanate Coronate C-1055 ... Carbodiimide modified liquid MDI
NCO2.88% Millionate MR-200 manufactured by Nippon Polyurethane Industry Co., Ltd .... Crude MDI NCO 31% T-80 manufactured by Nippon Polyurethane Industry Co., Ltd. Tolylene diisocyanate consisting of 80% 2,4TDI and 20% 2,6TDI 11. Foam stabilizer Polysiloxane-polyoxyalkylene copolymer SRX-274C, SRX-294A is manufactured by Toray Silicone Co., Ltd. L-520, L-5307 is manufactured by Nippon Unicar Co., Ltd. 12. Tin catalyst DBTDL ... Dibutyltin dilaurate T-9 ... Stannas 2-Ethylhexoate 13. Black toner Polyoxypropylene diol (molecular weight 2,000) with 50% carbon black kneaded.

14. Amine catalyst DABCO33LV ... 33% dipropylene glycol solution of triethylenediamine DMEA ... Dimethylethanolamine TMED ... Tetramethylethylenediamine NiaxA-1 ... Union Carbide Company amine catalyst 15. Glass fiber crushed product Fuji Fiber Glass Co., Ltd. Cut glass FESS-041
3 I Polymer Polyol Production Example It is shown that the present invention is superior in terms of lower viscosity and dispersion stability to the prior art (acrylonitrile / styrene = 78/22) which gives a low viscosity polymer polyol. Further, while it is difficult to raise the polymer concentration to 30% by the conventional technique in which the monomer is acrylonitrile alone, the present invention illustrates that a polymer polyol composition having a concentration of about 70% can be obtained.

Example 1 300 parts of xylene was charged into a reaction vessel equipped with a dropping device, a reflux cooling device, a gas introduction pipe, a temperature recorder and a stirring device, and heated to 120 ° C. under a nitrogen stream. Temperature 120 ~ 130 ℃
While controlling to 1, the mixture of 1,200 parts of polyol F, 365 parts of glycidyl methacrylate, 365 parts of acrylonitrile, and 10 parts of AIBN was added within 4 hours. After the addition was completed, stirring was continued at 120 ° C. for 2 hours. Then dispersed in 100 parts of polyol F
Add 25 parts of AIBN and stir for another 2 hours. Finally, a low volatile component was removed and collected by a vacuum pump, and a polymer polyol composition having a polymer concentration of 35.3% and good gloss dispersion stability was obtained by calculating from the obtained amount. The viscosity (25 ° C) was 3,100 cps.

Example 2 Polyol F 1,200 parts to 1,100 parts, glycidyl methacrylate 365 parts to 420 parts, acrylonitrile 365 parts to 420 parts
The procedure of Example 1 was repeated, substituting parts. As a result, a polymer polyol composition having a polymer concentration of 40.6% and good dispersion stability and good dispersion stability was obtained. The viscosity (25 ° C) was 4,600 cps.

Comparative Example 1 The method of Example 1 was repeated except that the monomer was replaced by 570 parts of acrylonitrile and 160 parts of styrene. Polymer concentration 35.1%
A polymer polyol having a glossy and good dispersion stability was obtained. The viscosity (25 ° C) was 4,700 cps.

Comparative Example 2 The method of Example 2 was repeated except that the monomer was replaced with 655 parts of acrylonitrile and 185 parts of styrene. Polymer concentration 40.5%
A low-gloss polymer polyol containing the above particulate matter was obtained. The viscosity of this product (25 ° C) was 8,300 cps.

Example 3 Polyol H500 was added to a reaction vessel equipped with two dropping devices, a reflux cooling device, a gas introduction pipe, a temperature recorder and a stirring device.
Parts were charged and heated to 120 ° C. under a nitrogen stream. Temperature 120
A mixture of 800 parts of Polyol H, 450 parts of Glydyl Methacrylate and 450 parts of Acrylonitrile and 600 parts of Polyol H and 12 parts of AIBN was simultaneously added from separate dropping lines while controlling at ~ 130 ℃. At the same time, the addition of all the amount was completed. After continuing stirring at 120 ° C. for 2 hours, a dispersion prepared by dispersing 3 parts of AIBN in 100 parts of polyol H was added and further stirred at 120 ° C. for 2 hours. Finally, the volatile components were removed by a vacuum pump to obtain a polymer polyol composition having a polymer concentration of 30.6% and having gloss and good dispersibility. The viscosity (25 ° C) was 5,900 cps.

Comparative Example 3 Example 3 with the monomer being replaced by 900 parts of acrylonitrile
The method was repeated. The resistance of the stirrer became larger than when about 700 parts of acrylonitrile was added, which was difficult. Since a large amount of solids adhered to the wall of the reaction vessel,
The content that could be taken out was only about 70%, and the property after cooling was a solid clay-like substance with no gloss, which was a mixture of glass-like substances and had no luster.

Reference Example 1 Example 3 was repeated except that 260 parts of glycidyl methacrylate and 260 parts of acrylonitrile were used as the monomers. A glossy polymer polyol having a polymer concentration of 20.3% and good dispersion stability was obtained. The viscosity (25 ° C) was 3,300 cps.

Reference Example 2 Example 3 with the monomer being replaced by 520 parts of acrylonitrile.
Was repeated. Polymer concentration 20.1%, viscosity (25 ℃) 6,200c
A polymer polyol having a ps gloss and good dispersion stability was obtained.

Reference Example 3 Example 3 was repeated substituting 520 parts of glycidyl methacrylate for the monomer. Large amounts of granules were formed and only phase separated polymer polyols were obtained.

Tables showing the results of Examples 1 to 3, Comparative Examples 1 to 3 and Reference Examples 1 to 3
It is shown in FIG.

Examples 4 to 20 In Examples 1 and 2, when the type of polyol was changed, when the polymer concentration was changed, when the ratio of (A) and (B) of the monomer was changed, and when methacrylic acid was used as the monomer (C). The production example of the polymer polyol composition of the present invention in the case of using methyl acid or styrene is shown, and the polymer polyol composition of the present invention is excellent in dispersibility and low viscosity even at a high polymer concentration. Indicates that. The results are shown in Table-2.

II Production Example of Polyurethane Elastomer The production of a polyurethane elastomer is illustrated by using the polymer polyol compositions shown in Table-1, Table-2-1 and Table-2-2, and the rigidity of the elastomer according to the present invention is excellent. Indicates that

Examples 21-35, Reference Example 4 100 parts of polymer polyol composition, ethylene glycol 1
Using 5 parts, DBTDL 0.025 parts and Coronate C-1055 in an amount such that the equivalent ratio of isocyanate group / hydroxyl group is 1.05,
250 preheated to 60-70 ° C with vigorous stirring and mixing for seconds
Cast into an iron mold with a size of × 200 × 2.5 m / m (thickness),
After 5 minutes, it was taken out from the mold and further annealed at 120 ° C. for 1 hour to obtain a polyurethane elastomer molded article.

Table 3-1 and Table 3-2 show the physical properties of the elastomer.

Examples 36-39, Comparative Examples 5-7, Reference Example 5 R-RIM machine (Krauss-Maffei PU40 / 40) was used to prepare 1,000 raw materials.
RIM urethane and R-RIM urethane were obtained by casting in a mold of × 1,000 × 2.5 m / m (thickness). Table 4 shows the raw material formulation and molding conditions in that case, and Table 5 shows the physical properties of the elastomer.

The method of the present invention is more cost-effective than the prior art method of hypermodulation by increasing the amount of a chain extender or a cross-linking agent because less expensive MDI is used. Further, the method of the present invention is superior in the reinforcing effect to the reinforcing method using the glass fiber broken frame.

III Soft polyurethane foam manufacturing example (Examples 40 to 4
5) For the production examples of high-elasticity mold foam, hot mold foam, and slab foam foam, the foaming recipe is shown in Table-6, and the molding conditions and foam physical properties are shown in Table-7.

The load-bearing capacity of these flexible polyurethane foams according to the method of the invention is very good.

The methods for measuring the physical properties of polyurethane elastomers and soft polyurethane foams are as follows.

Claims (5)

[Claims] 1. Has 2 to 8 hydroxyl groups and has an OH equivalent of 200 to
A composition comprising 20 to 75% by weight of 4,000 polyols and 25 to 80% by weight of a polymer of ethylenically unsaturated monomers dispersed in the polyol, wherein the polymer is (A) glycidyl methacrylate. 15-90% by weight, (B) acrylonitrile and / or methacrylonitrile 10-85% by weight,
(C) A polymer polyol composition comprising 0 to 40% by weight of another ethylenically unsaturated monomer and formed in the polyol. 2. The composition according to claim 1, wherein (B) is acrylonitrile. 3. A composition according to claim 1 or 2, wherein (C) is methyl methacrylate, styrene or a mixture thereof. 4. The method according to claim 1, wherein the amount of total polymerized monomers in the polymer polyol composition is 30 to 70% by weight.
The composition according to any one of 1 to 3. 5. The composition according to any one of claims 1 to 4, wherein the polyol is a polyether polyol.