JPS5857413A - Production of polymer polyol - Google Patents

Abstract

PURPOSE:To obtain a polymer polyol having good fluidity and being capable of providing polyurethane low in water absorption and excellent in weather resistance, by polymerizing an ethylenically unsaturated monomer in a polyol composition having a specified composition. CONSTITUTION:A polyol composition is prepared by blending 20-95wt% polyoxypropylene and/or polyoxyethylene polyol with 80-5wt% polybutadiene polyol and, if necessary, a polyol selected from the group consisting of polyester- polyol, polyester polyether polyol and OH-containing vinyl polymers. The purpose polymer polyol is obtained by polymerizing about 2-70pts.wt. ethylenically unsaturated monomer (e.g., acrylonitrile, styrene) in the presence of a polymerization catalyst in 100pts.wt. above-produced polyol composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polymer polyols. More specifically, it relates to a method for producing a polymer polyol with good fluidity, which provides a polyurethane with low water absorption and good weather resistance.

Conventionally, polymer polyols have been produced by polymerizing ethylenically unsaturated monomers in polyether polyols in the presence of radical generators. However, the polyurethane produced using this polymer polyol has the drawback of high water absorption, and its physical properties are not necessarily satisfactory.

The present inventors have arrived at the present invention as a result of extensive research into a method for producing a polymer polyol that does not have the above-mentioned problems.

That is, in producing a polymer polyol from a polyol and an ethylenically unsaturated monomer, the present invention includes (A) polyoxypropylene and/or polyoxyethylene polyol, (I3) polybutadiene polyol and 0 as the polyol. This is a method for producing a polymer polyol, which is characterized by using a polyol composition comprising at least one polyol selected from the group consisting of a polyvarnish polyol, a polyester/polyether polyol, and a hydroxyl group-containing vinyl polymer.

As the polybutadiene polyol (I3) used in the present invention, the hydroxyl group-terminated polybutadiene polyol is specifically manufactured by ABO3 Co., Ltd. (7) of the United States. Po1y Bd includes butadiene pomopolymer types and copolymer types (styrene butadiene copolymer, acrylonitrile butadiene copolymer). Its chemical structure is as follows.

Homopolymer type n: 55 (for R45M) 50 (for R-45HT) Copolymer type λ x,: C! 6H5 (OS-15) a=0.75. b=0.25. n=54X:
CN (CN-15) a = 0.85. b = 0.15. n = 7
8-87 molecular weight is usually 2500-4500. The number of functional groups is usually 2 to 8.

Further, the chemical structure of the Nl5SO-PBG series is as follows.

Specifically, G-1000, G-2000, G-8
000, and the molecular weight is usually 500 to 8,500.

Polybutadiene polyol is disclosed in JP-A No. 55-98220, Japan Rubber Association Journal, Vol. 45 (1972), 449-45.
0 pages 1. It is also described in -'i-Lantz (written by Tamsis, published by Reinhold Publishing, 1967). Furthermore, those described in Japanese Patent Application No. 162968/1988 can also be used.

The polyoxypropylene and/or polyoxyethylene polyol (A) used in the present invention includes active hydrogen atom-containing compounds such as polyhydric alcohols, amines, polyhydric phenols, and polycarboxylic acids, and propylene oxide and/or ethylene. Examples include compounds with a structure in which an oxide is added. The above polyhydric alcohols include ethylene glycol, propylene glycol, 1.4
-Butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, glycerin.

Trimethylolpropane, pentaerythritol.

Examples include sorbitol and sucrose.

Examples of amines include monoamines such as ammonia and butylamine; aliphatic polyamines such as ethylene diamine, trimethylene diamine, and diethylene triamine; alicyclic polyamines such as piperazine and N-aminoethylhyherazine; phenylene diamine, tolylene diamine, and xylylene diamine. Examples include aromatic polyamines such as amine, diphenylmethanediamine, and phoriphenylmethane polyamine, and alkanolamines such as monoethanolamine, jetanolamine, and triethanolamine.

Examples of polyhydric phenols include polyhydric phenols such as pyrogallol and hydroquinone, and bisphenols such as bisphenol A. Also, examples of polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid and adipic acid;
Phthalic acid.

Examples include aromatic polycarboxylic acids such as terephthalic acid and trimellitic acid. Two or more kinds of the above-mentioned active hydrogen atom-containing compounds can also be used.

Propylene oxide is a compound containing active hydrogen atoms.

The method for adding ethylene oxide may be any conventional method, and either block or random addition method may be used.

Preferred polyether polyols (A) are compounds having a structure in which propylene oxide or propylene oxide and ethylene oxide are added to a polyhydric alcohol, and particularly preferred are polyhydric alcohols (especially propylene glycol, glycerin, and trimethylolpropane). It is a compound having a structure in which propylene oxide and ethylene oxide are added to the polyol, especially polyoxypropylene/polyoxyethylene polyol (chipped type and balanced type) containing a terminal oxyethylene group.

The content of terminal oxyethylene groups is usually 8 to 30% by weight, preferably 10 to 25% by weight. If the terminal oxyethylene group content is less than 8% by weight, the curing properties during polyurethane production will be poor, and if it exceeds 80% by weight, the water absorption of the polyurethane will increase.

In addition, the oxyethylene group content in the whole (A) is usually 1
It is 0 to 35% by weight.

In the polyol composition, the hydroxyl value of the polyoxypropylene and/or polyoxyethylene polyol (A) is 150 or less, preferably 15-60, more preferably 20-45. If a polymer polyol obtained with a hydroxyl value exceeding 150 is used in a urethane molded product, the molded product will have poor elasticity.

Examples include condensed polyester polyols obtained by reacting dicarboxylic acid anhydrides, compounds, and alkylene oxides, and polyester polyols obtained by ring-opening polymerization of lactones.

The above-mentioned polyols include low-molecular polyols such as ethylene glycol and propylene glycol.

1.6-hexanediol, diethylene glyco, -ru.

Neopentyl glycol, di-lumitrimethylolpropanes such as bis(hydroxymethyl)cyclohexane, bis(hydroxyethyl)benzene, glycerin, etc.; polyether polyols (polyalkylene gelcols, etc.), and mixtures thereof.

Examples of dicarboxylic acids include succinic acid, gluta≠arrow acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, dimer acid, and mixtures thereof. Furthermore, examples of the polyester/polyengineered hydroxyl group-containing vinyl polymer obtained by reacting a polyoxyalkylene polyol with a polycarboxylic acid anhydride and a cyclic ether compound described in Japanese Patent Publication No. 10078 include acrylic polyols. Acrylic polyol is an acrylic (co)electropolymer into which a hydroxyl group is introduced, and includes a (co)polymer of a hydroxyl group-containing monomer and another polymerizable monomer. Examples of hydroxyl group-containing monomers include hydroxyalkyl (meth)acrylates [hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylic L/-), hydroxyalkyl (meth)acrylate, etc.], allyl alcohol, and polyhydric alcohols. Examples include monoallyl ether. Preferred is hydroxyalkyl (meth)acrylate. Examples of other polymerizable monomers include unsaturated carboxylic acid esters such as alkyl (meth)acrylates [methyl-; ethyl-; n-, iso,
or t-butyl; 2-ethylhexyl; lauryl (meth)acrylate], fumaric acid ester, maleic acid ester: aromatic vinyl monomer (styrene, alkylstyrene, etc.), vinyl halide (chlorinated Vinyl, vinyl esters (vinyl acetate, etc.), unsaturated nitriles ((meth)acrylonitrile, etc.).

Unsaturated amide ((meth)acrylamide).

Unsaturated carboxylic acids or anhydrides [(meth)acrylic acid,
Examples include maleic anhydride, crotonic acid, itaconic acid, etc. Preferred are alkyl (meth)acrylates.

Regarding acrylic polyols, see Journal of the Japan Rubber Association, Vol. 6, No. 5, 1972, pp. 77-79;
No. 1099; Special Publication No. 15417; Special Publication No. 15417-
No. 19278 Special Publication No. 6-15417; Special Publication No. 1989
-29879; It is described in US Pat. No. 8,028,867 and Japanese Patent Application No. 1983-65,767 and can be used. Furthermore, a vinyl acetate (co)polymer hydrolyzate can also be used.

The hydroxyl value of the hydroxyl group-containing vinyl polymer is usually 20 to 200.
, preferably 80-150. Molecular weight is usually 100
0 to io, ooo, preferably 1000 to 5000.

The number of functional groups is usually 2 or more, preferably 2 to 4.

Two or more types of 0 may be used in combination. For example, a combination of a polyester polyol and a hydroxyl group-containing vinyl polymer may be used.

GA) in the polyol composition is usually 20 to 95% (wt%
represents. (same below) preferably 80 to 90%, particularly preferably 50 to 80%. If GA) is less than 20%, the fluidity of the polyol will be poor and the physical properties of polyurethane (
In particular, temperature characteristics) become worse. If it exceeds 95%, the water absorbency and physical properties of polyurethane will not be satisfactory.

The content in the polyol composition is usually 5 to 8,096%, preferably 20 to 50%. If the direction is less than 596, the fluidity of the polyurethane and polyol will be poor, and the physical properties of the polyurethane will be poor.

The ratio of (b) and (q is usually 1:9 to 1o: on a weight basis)
0, preferably 3:0 to 10:0.

The hydroxyl value of the polyol composition is usually 200 or less, preferably 10-180, more preferably 15-110.

The ethylenically unsaturated monomers used in the present invention include the following.

(a) Acrylic acid, methacrylic acid and their derivatives: acrylonitrile, methacrylate trile.

Acrylic acid, methacrylic acid and their salts.

Methyl acrylate, methyl methacrylate, dimethylaminoethyl methacrylate, acrylamide, methacrylic acid amide, etc.

(b) Aromatic vinyl monomer K: styrene, α-methylstyrene, etc. (C) Olefinic hydrocarbon monomer: ethylene.

propylene, butadiene, isobutylene, isoprene,
1.4-pentagene, etc.

(d) Vinyl ester monomer: vinyl acetate etc. (e
) Vinyl halide monomers: vinyl chloride, vinylidene chloride, etc. (f) Vinyl ether monomers: vinyl methyl ether, etc. Among these, preferred is acrylonitrile.

Methyl methacrylate, styrene, and butadiene are particularly preferred, and particularly preferred is acrylonitrile, and a combination of tolyl and styrene is also preferred.

In the production of polymer polyols, the ratio of the polyol composition to the monomer (or polymer) used can be varied over a wide range, but usually the ethylenically unsaturated monomer (or polymer) is used per 100 parts by weight of the polyol composition. 2-7
0 parts by weight, preferably 5 to 40 M parts. When polymerizing a mixture of styrene and acrylonitrile, the blending ratio of styrene:acrylonitrile is 10:9.
0-60:40 (weight ratio) is preferable.

A known method may be used to produce a polymer polyol from a polyol composition and an ethylenically unsaturated monomer. Method of polymerization in the presence of
No. 7, Special Publication No. 47-47999, Japanese Patent Publication No. 158-1973
No. 94).

The reaction (polymerization) temperature is usually 50 to 170°C, preferably 90 to 150°C. Polymerization catalysts (radical generators) used in polymerization reactions include azo compounds, peroxides,
Persulfate salts, perborate salts, etc. can be used, but azo compounds are practically preferred. The amount used is not particularly limited, and for example, 0.1 parts by weight per 100 parts by weight of the ethylenically unsaturated monomer.
~2oN parts, preferably 0.1 to 15 parts by weight. The above polymerization can also be carried out in the presence of a solvent such as toluene, xin, etc.

The polymer polyol obtained by the present invention has 1) a reduced oxygen concentration in the molecule compared to a polymer polyol obtained from polyoxypropylene rice/or polyoxyethylene polyol or a polymer polyol obtained from polybutadiene polyol; 2) The lower oxygen concentration reduces the degree of UV degradation and improves weather resistance. 3) It is not compatible with polyoxypropylene and/or polyoxyethylene polyol. By using polybutadiene polyol or polyester polyol as a polymer polyol, a uniform solution can be obtained. 4) When polyurethane is produced, it has excellent strength properties (tensile strength, elongation), water absorption, and weather resistance. It has the effect of making you feel like you are there. The polymer polyols obtained according to the invention are suitable as raw materials for the production of polyurethanes.

The production of polyurethane is carried out by reacting the above polymer polyol alone or in combination with other polymeric polyols and/or crosslinking agents with an organic polyisocyanate.

As the organic polyisocyanate used for polyurethane production, those conventionally used for polyurethane production can be used. For example, aliphatic polyisocyanates (hexamethylene diisocyanate, lysine diisocyanate, etc.), alicyclic polyisocyanates (hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, etc.), aromatic polyisocyanates (tolylene diisocyanate) (TDI)
, diphenylmethane diisocyanate), (MDI), naphthylene diisocyanate, xylylene diisocyanate), and mixtures thereof. Among these, preferred are aromatic diisocyanates,
Particularly preferred is TDI.

It is MDI. These polyisocyanates are crude polyisocyanates, such as crude TDI j crude MDI
(crude $1J diaminodiphenylmethane (41 product diaminodiphenylmethane of formalhydrogen and aromatic I-group amine or mixture thereof) and a small amount (e.g. 5-20% by weight) of octafunctional or higher polyamine) Phosgenide: polyallyl polyisocyanate (PAPI))
, or modified polyisocyanates such as liquefied MDI (carbodiide modified, trihydrocarbyl phosphate modified, etc.) or excess polyisocyanate (T
It can also be used as a free isocyanate-containing prepolymer obtained by reacting (DI, MDI, etc.) with a polyol, or they can be used in combination (for example, a modified polyisocyanate and a prepolymer are used together). The polyols used in the production of the prepolymer include polyols having an equivalent weight of 80 to 200, such as ethylene glycol and fluoropylene gellicol.

Glycols such as diethylene glycol and dipropylene glycol; triols such as trimethylolpropane and glycerin; high-functional polyols such as pentaerythritol and sorbitol; and alkylene oxide (ethylene oxide and/or propylene oxide) adducts thereof. Among these, preferred are those having 2 to B functional groups. The free isocyanate group content of the modified polyisocyanate and prepolymer is usually 10 to 83%, preferably 15 to 80%.
, especially f is preferably from 25 to 3096.

As the crosslinking agent that may be used in combination, low-molecular polyols and polyamines can be used. Examples of low-molecular polyols include triethanolamine, jetanolamine, ethylene glycol, diethylene glycol, butanediol, trimethylo-J-repropane, and glycerin. Examples of polyamines include tolylene diamine, xylylene diamine, diaminodiphenylmethane, and methylenebis-〇-chloroaniline. The amount of crosslinking agent used can be varied depending on the required degree of rigidity, etc. In the case of low-molecular polyols, usually 5 out of all polyols
An amount of up to 0% by weight, preferably 5 to 40%, is used.

If a polyamine is used, it is used in a smaller amount than above, for example 1096 or less, preferably 2 to 5%, based on the total of polyol and amine.

If the amount of crosslinking agent is increased above the above, the urethane becomes too rigid and the temperature characteristics deteriorate.

Other polymeric polyols that may be used include polyether polyols, polyester polyols, other polymer polyols, and the like. The types commonly used as polyether polyols may be used.
Compound having at least 2 active hydrogen atoms [φ)
The polyhydric alcohols and amines mentioned as starting materials for
polyhydric phenol, polycarboxylic acid, etc.] and alkylene oxide (propylene oxide, ethylene oxide, butylene oxide, etc.) adducts. When used in combination with other polymer polyols, the polymer polyol accounts for usually 5% by weight or more, preferably 20% or more, and more preferably 50% by weight of the total polymer polyol (total of the polymer polyol and other polymer polyols). % or more is used.

When producing polyurethane using a polymer polyol, it may be foamed to produce polyurethane foam, or polyurethane resin (elastomer, sealant, sheet, paint, adhesive) may be produced without foaming. .

Foaming is usually carried out using a single blowing agent, but foaming can also be carried out by introducing a gas such as air during molding.

As the blowing agent, water and/or a halogen-substituted aliphatic hydrocarbon blowing agent (fluorocarbons such as trichloromonofluoromethane) can be used. The amount of the blowing agent to be used can be varied depending on the required physical properties, use, etc., but in general, in the case of water, it is usually 6 parts or less, preferably 4 parts or less, based on 100 parts of polyol. In the case of fluorocarbons, the amount is usually less than 1 part (capital), preferably 15 parts or less. RIM
When manufacturing polyurethane molded products by the method, the amount of blowing agent is 0.5 parts or less for water per 100 parts of polyol;
In the case of Freon, it is preferably 10 parts or less. Both blowing agents can also be used in combination.

The ratio of the polyisocyanate and the active hydrogen atom-containing compound (polymer polyol, crosslinking agent, water) may be the same as that of ordinary polyurethane (resin, foam) (NCO index, for example, 95 to 120, particularly 100 to 110). Also, excess isocyanate (for example, 120 to 1 as an index)
000, especially 150 to 500) can also be used to form a polyisocyanurate (resin, foam).

Further, if necessary, the reaction can be carried out in the presence of catalysts (tertiary amines, organic tin compounds, organic lead compounds, etc.), surfactants (silicone surfactants, etc.), and other auxiliaries. If necessary, pigments, fillers, flame retardants, solvents, thixotropic agents, etc. can also be added.

The polyurethane manufacturing method may be the same as conventional methods, and either the one-shot method or the prepolymer method (quasi-prepolymer method) can be applied. For example, Special Publication No. 89-24787, Special Publication No. 4
Foam manufacturing methods described in JP-A No. 7-15108, JP-A-55-13:9417, JP-A-46-5750, etc., JP-A-50-28497, JP-A-49-99597,
The elastomer, sheet or sealant production methods described in JP-A-58-42294, JP-A-58-16796, etc. can be used, and the catalysts, surfactants and other auxiliary agents, equivalent ratios, amounts added, etc. to be used are also based on these. Those listed can be used.

The polyurethane manufacturing method is particularly useful for molding using the RIM method, but other methods such as molding using an open mold, integral molding with composite materials, etc.
cold cure and hot cure), slab method,
On-site construction, spray method.

It can also be applied to various methods such as injection, coating, and impregnation.

A polyurethane molded product can be produced by molding using the RIM method using a conventional method. For example, a polyol, a crosslinking agent, a catalyst, if necessary a blowing agent (water and/or fluorocarbons), a pigment, and a foam stabilizer are added and mixed uniformly to form part A, and part B is an organic isocyanate prepared in advance. , fill the A and B liquid tanks of the high-pressure foaming machine. The injection nozzle of the high-pressure foaming machine is connected to the injection port of the mold in advance, and liquids A and B are mixed with a mixing head and injected into the mold, and after curing, the mold is demolded.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. Parts in the examples are parts by weight.

Example 1 30 parts of polyether polyol (obtained by adding 3466 parts of propylene oxide and then 400 parts of ethylene oxide to 184 parts of trimethylolpropane) and 70 parts of polybutadiene polyol with a hydroxyl value of 37 to Kolben. Add 1 part each and add 1 part while stirring.
After the temperature was raised to 20 to 140°C, 1 part of azobisisobutyronitrile dissolved in 10 parts of acrylonitrile was added dropwise little by little over 8 hours. After the dropwise addition, the mixture was aged for 1 hour at the same temperature to obtain the polymer polyol (+) of the present invention.

Example 2 Polyether polyol with hydroxyl value (glycerin 92
4,828 parts of propylene oxide and then 1,080 parts of ethylene oxide) (capital) parts;
The test was carried out using 5 parts of acrylonitrile and 1 part of azobisisobutyronitrile in a polyol composition prepared by mixing 20 parts of polybutadiene polyol-J with a hydroxyl value of 46 and 20 parts of polybdR-45HT manufactured by Idemitsu Petrochemical Co., Ltd. (hereinafter the same shall apply). The reaction was carried out in the same manner as in Example 1 to obtain the polymer polyol (It) of the present invention.

Example 3 Acrylonitrile and styrene were mixed in advance in a weight ratio of 8:2 to a polyol composition prepared by mixing the polyether polyol recess with a hydroxyl value of 28 obtained in Example 2 and 50 parts of a polybutadiene polyol with a hydroxyl value of 46. Polymer polyol (III) of the present invention was obtained by reacting in the same manner as in Example 1 using 15 parts of monomer and 1 part of azobisisobutyronitrile.

Example 4 70 parts of a polyether polyol with a hydroxyl value of 22 (obtained by adding 7,664 parts of propylene oxide and then 2,200 parts of ethylene oxide to 136 parts of pentaerythritol) and 30 parts of a polybutadiene polyol with a hydroxyl value of 112. A polyol composition containing 20 parts of acrylonitrile and 1 part of azobisisobutyronitrile was reacted in the same manner as in Example 1 to obtain the polymer polyol of the present invention.

Example 5 70 parts of the polyether polyol with a hydroxyl value of 22 obtained in Example 4 and the polybutadiene polyol 2 with a hydroxyl value of 46
0 parts, and further 10 parts of a hydroxyl group-containing vinyl polymer with a hydroxyl value of 150 (manufactured by Nippon Carbide Kogyo, Dicalide H480, hydroxyl value 150).
The polymer polyol (V) of the present invention was obtained by reacting in the same manner as in Example 1.

Example 6 70 parts of the polyether polyol with a hydroxyl value of 28 obtained in Example 2 and 20 parts of the polybutadiene polyol with a hydroxyl value of 46
and 10 parts of polyester with a hydroxyl value of 45 (obtained by reacting a mixture of 200 parts of ethylene glycol, 4 parts of 1,4-butanediol, and 755 parts of adipic acid at 150 to 200°C for about 20 hours). The obtained polyol composition was reacted with 20 parts of acrylonitrile and 1 part of azobisisobutyronitrile in the same manner as in Example 1 to obtain the polymer polyol (VI) of the present invention.

Example 7 70 parts of the polyether polyol with a hydroxyl value of 28 obtained in Example 2 and 10 parts of the polybutadiene polyol with a hydroxyl value of 46
Furthermore, 2 parts of polyether ester with a hydroxyl value of 46 (polypropylene glycol with a hydroxyl value of 56 (1 mol) and phthalic anhydride (2 mol) were added at about 150°C under an alkali catalyst.
Obtained by adding ethylene oxide at about 120°C after a time reaction. ) A polyol composition containing 20 parts of acrylonitrile and 1 part of azobisisobutyronitrile was reacted in the same manner as in Example 1 to obtain the polymer polyol (b) of the present invention.

Comparative Example 1 A comparative polymer polyol (A) was prepared by reacting 100 parts of a polybutadiene polyol having 46 hydroxyl groups with 20 parts of acrylonitrile and 1 part of azobisisobutyronitrile in the same manner as in Example 1. Obtained.

Comparative Example 2 Example 2 was used instead of the polybutadiene polyol of Comparative Example 1.
A comparative polymer polyol (I3) was obtained by reacting in the same manner using the hydroxyl value 28/) obtained in Example 1 and polyether polyol.

Example 8 Polymer polyol obtained in Examples 1 to 7 and Comparative Example 1 ■
The appearance and analytical values of ~■, A, and B are as shown in Table 1. Table 1: Appearance and analytical values of each polymer polyol. With the polyol composition excluding the polybutadiene polyol or polyester polyol used in
When H polymer polyol was prepared and compared with a polyol in which a polybutadiene polyol or a polyester polyol was later mixed, the polyol in Example 1 and a polyol in which a polyol was later mixed was compared. separated.

Reference Examples 1 to 4 and Comparative Example 1 Polyurethane molded products were produced using polymer polyols I to ① and B under the following formulation and molding conditions.

[Molding prescription]

Polymer polyol 1001.4-butanediol 80 black toner
4 Diflon-11u7 DABCOB3LV
O,5DTD
O,05z! J 4th
- t'MTL Nad tRbckx IAIIL
X105 (Note) Black toner; carbon black dispersed in polyether polyol.

Guiflon-11u; Daikin Industries a [Flon-11 DABC! 088LVi Amine catalyst DTD manufactured by Sankyoko Arprotak Co., Ltd.
f Tiltin dilaurate millionate MTL, modified MD manufactured by Nippon Polyurethane Co., Ltd.
I [Molding conditions for urethane molded product] A polyol component, which is a mixture of a polymer polyol and auxiliary agents such as a crosslinking agent and a catalyst, and an isocyanate component are respectively charged into the raw material tank of a high-pressure foaming machine, and liquids A and B are mixed using a high-pressure foaming machine. Back thickness 2.5ff width 800ff length 1000 m
A urethane molded product was created by injecting it into a closed mold that allows temperature control.

Discharge rate (Kg/min) Approx. 40 Discharge pressure (Kg/d) Approx. 160 Injection time (sec) Approx. 1.8 Raw material temperature (°C) Polyol component/Isocyanate component
50/40 Molded temperature ('C) 70±2
Mold release time (seconds) 80 Reference Examples 5 to 8 and Comparative Example 2 Polyurethane molded products were manufactured using the polymer polyols V to ■ and A according to the following formulation under the same molding conditions as above.

[Molding prescription]

Polymer polyol 100 ethylene glycol 20 black toner
4 Freon-11u7 DTD O,10
Millionaire) BfI'L NCOftulNUOL M x 105 Tables 2 and 8 show the physical property measurement results of the polyurethane molded products obtained in the above reference examples and comparative examples. The physical property measurement method is as follows. Immediately after mold release, the molded polyurethane was annealed at 120°C for 1 hour, and then left at room temperature for 3 days or more before measurement.

Tensile strength: According to JIS K-6402.

Elongation diplane upward bending modulus: Sample size 25mm x 7QII
Measured with ff x 2.5m (t), span 40ff, punch diameter 5R.

Heat sag: sample size 25ff x 1
5 (NfllX2.5fi(t) with 100fl overhang, leave at 120°C for 1hr, then 8 at room temperature
Measure the sagging distance after cooling for 0 minutes.

Brittleness temperature: According to JIS K-6801.

Water absorption: Sample size 100m + 1
2001ffX2.5ff (t), weight change rate after immersion in a water tank at 40°C for 10 days.

Table-2 Physical property values of urethane molded products 7-day procedure Correction The book was revised from 1937 to 1970. nlA day! Mr. Haruki Shimada, Director-General of the Office, 2. Title of the invention: Process for producing polymer polyol 5. Relationship with the case of the person making the amendment. Sponsored by the patent applicant. 5. Increased coverage of the invention by the amendment. 6. Subject of the amendment. Detailed description of the invention (1) “Hydroxy group 4
6" is corrected to "Hydroxyl value 46."

(2) Table 2 on page 32 and Table 3 on page 33 of the specification
``Embrittlement temperature'' is corrected to ``Embrittlement temperature ℃)''.

Claims (1)

[Claims] 1. In producing a polymer polyol from a polyol and an ethylenically unsaturated monomer, the polyol is (A) polyoxypropylene and/or polyoxyethylene polyol, (B ) A polymer polyol characterized by using a polyol composition consisting of a polybutadiene polyol and optionally at least one polyol selected from the group consisting of a polyester polyol, a polyester/polyether polyol, and a hydroxyl group-containing vinyl polymer. Manufacturing method. 2. The manufacturing method according to claim 1, wherein the polyol composition is a polyol composition containing 20 to 95% by weight of (A). 8. Claim 1 or 2, wherein the polyol composition is a polyol composition containing 5 to 80% by weight of
Manufacturing method described in section. 4. The manufacturing method according to any one of claims 1 to 8, wherein (A) of the polyol composition is a polyoxypropylene/polyoxyethylene polyol containing a terminal oxyethylene group. 5. Polyoxypropylene containing terminal oxyethylene group
5. The manufacturing method according to claim 4, wherein the polyoxyethylene polyol has a terminal oxyethylene group content of 8 to 80% by weight. 6. The manufacturing method according to any one of claims 1 to 5, wherein the polyol composition has a hydroxyl value of 10 to 180.