JPH1143528A - Production of rigid polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rigid polyurethane foam having high compressive strength and high open cell content, by reacting a polyol having a specific aliphatic hydrocarbon side chain with an organic polyisocyanate. SOLUTION: This polyurethane foam is obtained by reacting (A) a polyol having mean HLB number of >=6 including (A1) a polyol (e.g. 1,2-alkanediol having 5-42C) having 5-85 wt.% of a 3-40C aliphatic hydrocarbon side chain and HLB number of <=4 (A2) a polyol other than (A1) (e.g. an alkylene adduct to a polyalcohol) having an active hydrogen equivalent of <=250 or including (A1), (A2) and (A3) a polyol having HLB number of >=250 (e.g. polyoxyethylene polyol) with (B) an organic polyisocyanate (e.g. an aromatic diisocyanate having 6-16C) in the presence of an expanding agent (e.g. a hydrocarbon with a low boiling point, water).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a rigid polyurethane foam. More specifically, the present invention relates to a method for producing a rigid polyurethane foam having a high compressive strength and a high communication rate.

[0002]

2. Description of the Related Art Conventional rigid polyurethane foams use a specific fluorocarbon represented by trichloromonofluoromethane as a foaming agent, and therefore have excellent dimensional stability and heat insulating properties, and are used as insulating materials for refrigerators, freezers, and construction. As widely used. However, the production of specified CFCs was stopped in December 1995 due to its large ozone depletion potential.
At present, instead of specific CFCs, halogenated hydrocarbons containing hydrogen atoms (alternative CFCs) and water are used. When substitute CFC is used as the foaming agent, the solubility in the urethane resin increases, and the resin strength decreases. When water is used, the pressure inside the foam is reduced because the generated carbon dioxide gas has a higher urethane resin permeability coefficient than air. For this reason,
Both of these blowing agents have the problem that the foam shrinks over time. In order to reduce shrinkage, a method of using rigid polyurethane foam as open cells is known. As a method of using water as a foaming agent to improve the communicability, a method of using a polyol composition comprising a high-molecular-weight polyol and a low-molecular-weight polyol (for example, Japanese Patent Application Laid-Open No.
No. 25375).

[0003]

However, the method disclosed in the above-mentioned publication improves the shrinkage of the foam, but has the problem that the mechanical strength is reduced due to the high molecular weight polyol. Furthermore, when the filling amount is increased in the mold,
There is also a problem that the communication rate is reduced. The purpose of the present invention is
When a hydrogen atom-containing halogenated hydrocarbon, water, or a mixture thereof is used as a foaming agent, the compression strength of the foam is large, and even when the filling amount is increased, a rigid polyurethane foam capable of obtaining a high communication rate is obtained. It is intended to obtain a manufacturing method.

[0004]

Means for Solving the Problems The present inventors have made intensive studies on a method for producing a rigid polyurethane foam capable of achieving the above object, and have found that a polyol having a specific aliphatic hydrocarbon side chain is used. As a result, the inventors have found that the above problems can be solved, and have reached the present invention.

That is, the present invention relates to a method for producing a polyol (A) and an organic polyisocyanate (B) by using at least one or more foaming agents selected from hydrogen atom-containing halogenated hydrocarbons, water, low-boiling hydrocarbons and liquefied carbon dioxide. In the method for producing a rigid polyurethane foam reacted in the presence of
(A) has an aliphatic hydrocarbon side chain having 3 to 40 carbon atoms of 5 to 5;
A polyol containing 85% by mass and having an HLB of 4 or less (A1)
And (A2) other than (A1) having an active hydrogen equivalent of 250 or less, or (A1) and (A2) and a polyol (A3) other than (A1) having an active hydrogen equivalent of more than 250. A method for producing a rigid polyurethane foam, wherein the average HLB is 6 or more.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the production process of the present invention, the aliphatic hydrocarbon side chain having 3 to 40 carbon atoms in the polyol (A1) may be linear, branched or alicyclic, saturated or unsaturated. Saturated hydrocarbon side chains are mentioned, and preferred are linear or branched saturated hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon side chain is usually 3 to 40, preferably 5 to 30.
It is. When the number of carbon atoms is less than 3, the continuity of the foam decreases, and when it exceeds 40, the mechanical strength of the obtained rigid urethane foam decreases.

The content of the aliphatic hydrocarbon side chain having 3 to 40 carbon atoms in the polyol (A1) is usually 5 to 85% by mass,
Preferably it is 10-80 mass%. If the amount is less than 5% by mass, the continuity of the foam is insufficient. On the other hand, if it exceeds 85% by mass, the foaming property of the obtained rigid urethane foam becomes too strong and collapses.

The following (a1) to (a5) are examples of compounds which give a side chain of an aliphatic hydrocarbon group in a polyol for obtaining (A1). (A1) a 1,2-alkanediol having 5 to 42 carbon atoms:
1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-octadecanediol and the like. (A2) Glycerin monoalkyl ether having 6 to 43 carbon atoms: glycerin monohexyl ether, glycerin monooctyl ether, glycerin mono-2-ethylhexyl ether, glycerin monodecyl ether, glycerin monododecyl ether, glycerin monooctadecyl ether and the like. (A3) glycerin fatty acid monoester having 7 to 44 carbon atoms: glycerin hexanoic acid monoester, glycerin octanoic acid monoester, glycerin-2-ethylhexanoic acid monoester, glycerin decanoic acid monoester,
Glycerin dodecanoic acid monoester, glycerin octadecanoic acid monoester and the like. (A4) Alkylamine having 3 to 40 carbon atoms: butylamine, hexylamine, 2-ethylhexylamine, octylamine, dodecylamine, stearylamine and the like. (A5) α-olefin oxide having 5 to 42 carbon atoms:
α-decene oxide, α-dodecene oxide, α-
Octadecene oxide and the like.

The 1,2-alkanediol (a1) and α-olefin oxide (a5) can be produced by a known method such as a method of reacting α-olefin with acetic acid and hydrogen peroxide in the presence of an acid catalyst. Glycerin monoalkyl ether (a2) can be produced by, for example, a method of reacting a long-chain alkyl alcohol with epichlorohydrin and then hydrolyzing it; a method of reacting glycerin with an alkyl halide. Glycerin fatty acid monoester (a3) can be produced by a method of esterifying glycerin and a fatty acid in the presence of an alkali catalyst.

Examples of (A1) obtained by using the above (a1) to (a5) include the following (A11) to (A11).
(A15). (A11) A 1,2-alkanediol having 5 to 42 carbon atoms (a1), a glycerin monoalkyl ether having 6 to 43 carbon atoms (a2) or a glycerin fatty acid monoester having 7 to 44 carbon atoms (a3), A diol having a structure obtained by adding 2 to 4 alkylene oxides (b). (A12) An alkylamine having 3 to 40 carbon atoms (a4)
Having a structure obtained by adding 2 mol or more of an alkylene oxide (b) having 2 to 4 carbon atoms to the diol. (A13) A polyol having a structure obtained by adding an alkylene oxide comprising an α-olefin oxide (a5) having 5 to 42 carbon atoms to a compound having two or more active hydrogens. (A14) (a1), (a2), (a3), (A1
1) A polyester polyol comprising a polyol component composed of at least one polyol selected from the group consisting of (A12) and (A13), and a polycarboxylic acid (c). (A15) (a1), (a2), (a3), (A1
1) A polylactone polyol having a structure obtained by adding a lactone monomer (d) to a polyol component comprising at least one polyol selected from the group consisting of (A12) and (A13).

The alkylene oxide (b) having 2 to 4 carbon atoms which can be used for (A11) and (A12)
Examples thereof include ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO), butylene oxide, and a combination thereof. (A11),
(A12) can be produced by a conventionally known alkylene oxide addition reaction. When two or more alkylene oxides are used, the addition form may be either block or random. The method for obtaining a diol having a structure obtained by adding an alkylene oxide (b) having 2 to 4 carbon atoms to a glycerin fatty acid monoester (a3) having 7 to 44 carbon atoms is not particularly limited. (B) may be added to (a3) as described above, or a polyol obtained by adding (b) to glycerin, and a polyol having 4 to 4 carbon atoms.
1 with a fatty acid (hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, dodecanoic acid, octadecanoic acid, oleic acid, etc.), the polyol is reacted with a lower alkyl of a fatty acid having 4 to 41 carbon atoms. Ester (methyl ester, ethyl ester, etc.) or 4-41 carbon atoms
May be transesterified with a triglyceride of a fatty acid.

(A13) is obtained by adding an α-olefin oxide (a5) to a compound having two or more active hydrogens. Further, if necessary, the alkylene oxide (b) may be added in combination. Examples of the active hydrogen compound include polyhydric alcohols, polyhydric phenols, and amines. Examples of polyhydric alcohols include dihydric alcohols [ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, etc.] and trihydric or higher alcohols [glycerin,
Trimethylolpropane, pentaerythritol, sorbitol, sucrose, etc.]. Examples of the polyhydric phenol include hydroquinone, bisphenols (such as bisphenol A and bisphenol F), and low-molar condensates of phenol compounds with formalin. Examples of amines include aliphatic amines [monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, etc.], aromatic amines [2,
4- and 2,6-diaminotoluene (TDA), crude TDA, 1,2-, 1,3-, and 1,4-phenylenediamine, 2,4'- and 4,4'-diaminodiphenylmethane (MDA) , Crude MDA, naphthylene-
1,5-diamine, 3,3'-dichloro-4,4'diaminodiphenylmethane, etc.]. In these,
The method of adding (a5) and, if necessary, (b) may be a known method, and the addition form when adding two or more kinds may be either block or random.

As the polyol component in (A14), (a1), (a2), (a3), (A11), (A
In addition to one or more polyols selected from the group consisting of 12) and (A13), other polyols may be used in combination. Examples of other polyols include the polyhydric alcohols exemplified as the active hydrogen compound in the above (A13), and alkylene oxide adducts of bisphenols.

The polycarboxylic acids (c) in (A14) include, for example, the following (c1) and (c2) and combinations of two or more of them. (C1) An aliphatic dicarboxylic acid having 4 to 10 carbon atoms (eg, adipic acid, succinic acid, sebacic acid, azelaic acid, fumaric acid, maleic acid) or an ester-forming derivative thereof (anhydride, lower alkyl ester, etc.). (C2) An aromatic dicarboxylic acid (phthalic acid, terephthalic acid, isophthalic acid, etc.) or an ester-forming derivative thereof. Among these, preferred are aliphatic or aromatic dicarboxylic acids having 6 to 10 carbon atoms, especially adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid and ester-forming derivatives thereof.

(A14) can be produced by a conventionally known method,
For example, it can be obtained by a method in which a dehydration condensation polymerization or transesterification reaction is carried out from an excess molar amount of a polyol component and a polycarboxylic acid (c) to obtain a polyester having a terminal hydroxyl group.

The lactone monomer (d) used in (A15) includes ε-caprolactone, δ-valerolactone and the like. (A15) can be produced by a conventionally known method of adding a lactone monomer to a polyol component.

The average HLB (HYDROPHILE-LIP) of the polyol (A1) used in the production method of the present invention
OPHILE BALANCE) is usually 4 or less, preferably 1 to 3.5. When the average HLB exceeds 4,
The continuity of the obtained polyurethane foam decreases. The HLB used here is a numerical value calculated by the method of Oda et al. [Source: Oda, Teramura "Synthesis of Surfactant and Its Application", page 501, published by Maki Shoten (1957)]. HLB
Is used as a numerical value representing hydrophilicity, and 0 to 40
And the larger the value, the higher the hydrophilicity.

The active hydrogen equivalent of (A1) is preferably from 200 to 3000, more preferably from 250 to 25.
00. When the active hydrogen equivalent is less than 200, the continuity of the foam decreases, and when it exceeds 3000, the compressive strength decreases.

Polyol (A2) used in combination with (A1)
Is a polyol other than (A1) having an active hydrogen equivalent of 250 or less, and a known polyol used for a usual rigid polyurethane foam can be used. For example, the above-mentioned polyhydric alcohols, polyhydric phenols, these compounds, and alkylene oxide adducts such as amines and polycarboxylic acids are exemplified. Preferred among these are alkylene oxide adducts of polyhydric alcohols because of their low viscosity and good mixing with isocyanate (B).

The active hydrogen equivalent of (A2) is usually 250
It is the following, Preferably it is 30-230. When the active hydrogen equivalent exceeds 250, the mechanical strength of the foam decreases.

The mass ratio of (A1) / (A2) in (A) is preferably from 0.5 / 99.5 to 60/40,
Particularly preferably, it is 1/99 to 55/45. (A
If the ratio of 1) is less than 0.5, the communicability will be low, and if it exceeds 60, the compressive strength will be low.

As the polyol component (A), if necessary, a polyol (A3) other than (A1) having an active hydrogen equivalent exceeding 250 may be used in combination. The active hydrogen equivalent of (A3) is preferably from 260 to 3000.
The use amount of (A3) is preferably 50% by mass or less, particularly preferably 40% by mass or less, based on the total mass of (A1) and (A2).

As (A3), for example, the following (A3)
1), (A32) and combinations of two or more of these. (A31) Polyether polyol: polyoxyethylene polyol, polyoxypropylene polyol, polyoxyethylene propylene polyol, EO and / or PO adducts of bisphenols, and the like. (A32) Polyester polyol: polyethylene adipate diol, polybutylene adipate diol,
Polyethylene butylene adipate diol, polyneopentyl adipate diol, poly 3-methylpentylene adipate diol, polycaprolactone diol, polyvalerolactone diol, polyhexamethylene carbonate diol, and the like.

The average HLB of (A) is usually 6 or more,
If the average HLB is less than 6, preferably 6-16,
Compressive strength decreases. On the other hand, if it exceeds 16, the continuity is reduced and the obtained foam tends to shrink. The average number of functional groups of (A) is preferably 2.5 or more, particularly preferably 3 to 6. When the number of functional groups is less than 2.5, the mechanical strength of the foam decreases. Also, if you go over 6,
The viscosity of (A) increases and the miscibility with isocyanate (B) deteriorates. The average active hydrogen equivalent of (A) is
Preferably from 30 to 3000, more preferably from 40 to 25
00, particularly preferably 50 to 2000. When the active hydrogen equivalent is less than 30, the viscosity of (A) increases,
Mixability with isocyanate (B) is poor. Also, 3
If it exceeds 000, the mechanical strength of the foam decreases.

As the organic polyisocyanate (B),
For example, the following (B1) to (B5) and a mixture of two or more of them are exemplified. (B1) 6 to 16 aromatic diisocyanates [2,4- and / or 2,6-tolylene diisocyanate (TDI), 4,4 ′ (B2) aliphatic diisocyanate having 6 to 10 carbon atoms [hexamethylene diisocyanate (HDI), lysine diisocyanate, etc.]; (B3) alicyclic diisocyanate having 6 to 16 carbon atoms [isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MD
(B4) araliphatic diisocyanate having 8 to 12 carbon atoms [xylylene diisocyanate (XDI), α, α,
αB, α′-tetramethylxylylene diisocyanate (TMXDI) etc.]; (B5) Crude or modified form of these organic diisocyanates [crude TDI, crude MDI
(Polymethylene polyphenylisocyanate) such as isocyanurate-modified MDI, burette-modified MDI, carbodiimide-modified MDI, and sucrose-modified T
DI and the like]; preferred among these are MDI, crude MDI,
Carbodiimide-modified MDI and sucrose-modified TDI.

In the production method of the present invention, the ratio between the polyol (A) and the polyisocyanate (B) can be variously changed. Is usually 40 to 500, preferably 50 to 500.
300, particularly preferably 60 to 200.

As the blowing agent (C) in the production method of the present invention, at least one or more blowing agents selected from hydrogen atom-containing halogenated hydrocarbons, water, low-boiling hydrocarbons and liquefied carbon dioxide are used. Specific examples of the hydrogen atom-containing halogenated hydrocarbon include those of the HCFC type (for example, H
CFC-123, HCFC-141b, HCFC-22
And HCFC-142b); of the HFC type (eg, HFC-134a, HFC-152a, HFC-3)
56mff, HFC-236ea, HFC-245c
a, HFC-245fa and HFC-365mcf)
And the like. Preferred of these are HC
FC-141b, HFC-134a, HFC-356m
ff, HFC-236ea, HFC-245ca, HF
C-245fa, HFC-365mcf and a mixture of two or more thereof. The amount of the hydrogen atom-containing halogenated hydrocarbon-based blowing agent to be used is generally 0 to 60 parts by mass, preferably 0 to 50 parts by mass, per 100 parts by mass of the polyol (A). Also, water can be used as a blowing agent. The amount of water to be used is generally 0 to 18 parts by mass, preferably 0.5 to 15 parts by mass, per 100 parts by mass of (A).

As the low-boiling hydrocarbon, the boiling point is usually from 0 to
A hydrocarbon at 50 ° C. is mentioned, and specific examples thereof include propane, butane, pentane and a mixture thereof. The amount of the low boiling point hydrocarbon to be used is generally 0 to 40 parts by mass, preferably 0 to 30 parts by mass, per 100 parts by mass of (A). The amount of liquefied carbon dioxide gas used is (A) 1
Usually 0 to 30 parts by mass, preferably 0
２５25 parts by mass.

In the production method of the present invention, if necessary, a catalyst usually used for a polyurethane reaction, for example, an amine catalyst (triethylenediamine, N, N-tetramethylhexamethylenediamine, N, N-tetramethylethylenediamine, N-ethyl) Morpholine, diethylethanolamine, 1-isobutyl-2-methylimidazole,
For example, 1,8-diazabicyclo- [5,4,0] -undecene-7) and / or metal catalysts (such as stannous octylate, dibutylstannic dilaurate, lead octylate, etc.) can be used. The amount of catalyst used is (A)
It is usually 0 to 5 parts by mass with respect to 100 parts by mass.

In the production method of the present invention, a foam stabilizer can be used if necessary. Specific examples of the foam stabilizer used include SZ-1306 and L-5 manufactured by Nippon Unicar Co., Ltd.
309, L-520, L-540, L-5420, L-
5340, L-580, SZ-1666 and SZ-1
127; SH manufactured by Dow Corning Toray Silicone Co., Ltd.
-190, SH-193, SF-8410, SF-84
27, SRX-294A and SRX-274C dimethylsiloxane-based foam stabilizers. The amount of the foam stabilizer to be used is generally 0 to 5 parts by mass with respect to 100 parts by mass of (A).

If necessary, known additives such as coloring agents (dyes and pigments), plasticizers, fillers, flame retardants, antioxidants, antioxidants and the like can also be used.

An example of a method for producing a rigid polyurethane foam according to the method of the present invention is as follows. First,
A polyol component, a foaming agent and, if necessary, a foam stabilizer, a catalyst, and other additives are mixed in predetermined amounts. This mixture is then rapidly mixed with the polyisocyanate component using a polyurethane foamer or stirrer. The obtained mixture is poured into a mold. After curing, the mold is released to obtain a rigid polyurethane foam.

The rigid polyurethane foam obtained by the method of the present invention has high mechanical strength and excellent dimensional stability, and thus can be widely used as a filler for building members.

[0034]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In addition, below, a part shows a mass part. [Synthesis of Polyol (A1)] Synthesis Example 1 254 parts of 1-dodecene, 159 parts of acetic acid, and 3 parts of sulfuric acid were charged into a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer. Keeping at 85 ° C gradually 60
% Hydrogen peroxide solution was dropped. Then, toluene 2
Add 71 parts, sodium hydroxide 90 parts, water 200 parts,
Neutralization and hydrolysis were performed, and 11 parts of hydrochloric acid was further added. Then, liquid separation was performed using a separating funnel to obtain 520 parts of a supernatant toluene solution. This was transferred to another four-necked flask, toluene was removed, and then purified by distillation under reduced pressure to obtain 220 parts of 1,2-dodecanediol. In a separate four-necked flask, 202 parts of the above 1,2-dodecanediol and 131 parts of adipic acid were charged, and nitrogen gas was passed therethrough under normal pressure to obtain a 190-190 flask.
Esterification was carried out at 210 ° C. while distilling off water. When the acid value of the produced polyester became 1 or less, the degree of reduced pressure was increased to complete the reaction, and a polyol (A1-1) [active hydrogen equivalent = 1500, average HLB = 3.5] was obtained.

Synthesis Example 2 A four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer was charged with 381 parts of 1-octadecene and 159 acetic acid.
And 3 parts of sulfuric acid, and a 60% aqueous hydrogen peroxide solution was gradually added dropwise while maintaining the temperature at 85 ° C. Thereafter, 271 parts of toluene, 90 parts of sodium hydroxide, and 200 parts of water were added to neutralize and hydrolyze. Further, 11 parts of hydrochloric acid was added, and then liquid separation was performed using a separating funnel, and 520 parts of a supernatant toluene solution was added. Obtained. This was transferred to another four-necked flask, toluene was removed, and then purified by distillation under reduced pressure to obtain 340 parts of 1,2-octadecanediol. In another four-necked flask, 286 parts of the above 1,2-octadecanediol and 117 parts of adipic acid were charged, and esterification was carried out at 190 to 210 ° C. while distilling water at 190 to 210 ° C. through a nitrogen gas under normal pressure. When the acid value of the produced polyester became 1 or less, the degree of vacuum was increased to complete the reaction, and the polyol (A1
-2) [Active hydrogen equivalent = 1000, average HLB = 3.
0] was obtained.

Synthesis Example 3 An autoclave was charged with 268 parts of octadecylamine, and 116 parts of PO was injected at a reaction temperature of 100 to 110 ° C. to cause a reaction. 3 parts of potassium hydroxide was added as a catalyst, and the mixture was dehydrated under reduced pressure to 130 ° C. to perform alcoholation. Further, at a reaction temperature of 100 to 110 ° C., PO 278
Four parts were press-fitted and allowed to react, followed by aging at 130 ° C.
After dehydration, polyol (A1-3) [active hydrogen equivalent = 15
80, average HLB = 2.7].

Synthesis Example 4 In an autoclave, 3 parts of potassium hydroxide was added as a catalyst to 92 parts of glycerin, followed by dehydration at 130 ° C. under reduced pressure to carry out alcoholation. After cooling to 40 ° C., 2355 parts of α-octadecene oxide were charged, and then 555 parts of PO were injected at a reaction temperature of 100 to 110 ° C. to cause a reaction, followed by aging at 130 ° C. After neutralization, dehydration was carried out at 130 ° C. to obtain polyol (A1-4) [active hydrogen equivalent =
1000, average HLB = 1.7].

Synthesis Example 5 In an autoclave, 3 parts of potassium hydroxide was added as a catalyst to 92 parts of glycerin, followed by dehydration at 130 ° C. under reduced pressure to carry out alcoholation. After cooling to 40 ° C., 1450 parts of α-dodecene oxide were charged, and then the reaction temperature was 1
1450 parts of PO were injected under pressure at 00 to 110 ° C to cause a reaction, and aging was performed at 130 ° C. After neutralization, the mixture was dehydrated at 130 ° C., and polyol (A1-5) [active hydrogen equivalent = 1
000, average HLB = 2.5].

Comparative Synthesis Example 1 In an autoclave, 1 part of potassium hydroxide was added as a catalyst to 286 parts of 1,2-octadecanediol obtained in Synthesis Example 2, and the mixture was alcoholated by dehydration under reduced pressure at 130 ° C. . PO 580 at a reaction temperature of 100 to 110 ° C.
The reaction was carried out by press-fitting a part, and aging was performed at 130 ° C.
After neutralization and activated clay treatment, the mixture was dehydrated at 130 ° C. to obtain polyol (A1′-6) [active hydrogen equivalent = 433, average H
LB = 4.3].

Example 1 20 parts of the polyol (A1-1) of Synthesis Example 1 and a polyol (A2) having an active hydrogen equivalent of 134 to which PO was added to sucrose were added.
-1) a mixture with 80 parts [average HLB of (A) = 11.
1], 10 parts of "Phirol PCF" (manufactured by Akzo Japan Co., Ltd., flame retardant), 2 parts of "Silicone L-5420" (manufactured by Nippon Unicar, foam stabilizer), 3 parts of water, "HCFC-
141b ”and 2.0 parts of“ U-CAT1000 ”(an amine catalyst manufactured by San Apro Co.)
The temperature was adjusted to 25 ° C., and 128 parts of “Millionate MR-100” (manufactured by Nippon Polyurethane Co., Ltd., crude MDI) (isocyanate index: 100) adjusted to 25 ° C. was added thereto. ) 3000r
After stirring at pm for 10 seconds, the temperature was adjusted to 40.degree.
It was poured into a mold of mm (length) x 100 mm (width) x 50 (height) mm, and was demolded after 10 minutes to obtain a rigid polyurethane foam.

Example 2 35 parts of the polyol (A1-2) of Synthesis Example 2 and “Fantol PL-402” (manufactured by Toho Rika Co., Ltd., active hydrogen equivalent: 1)
30 polyester polyol) (A2-2) in a mixture with 65 parts [Average HLB of (A) = 10.8], 10 parts of “Phirol PCF” and 10 parts of “Silicone SH-193”
(Toray Dow Corning, foam stabilizer) 2 parts, water 3
Part, “HCFC-141b” 40 parts and “DABCO
"33LV" (Amine catalyst, manufactured by Sankyo Air Products Co., Ltd.) 1.5 parts in advance, and the temperature was adjusted to 25C, and "Millionate MR-20" was adjusted to 25C.
0 "(Nippon Polyurethane Co., crude MDI) (152 parts) (isocyanate index: 130) and the same operation as in Example 1 was carried out to obtain a rigid polyurethane foam.

Example 3 10 parts of polyol (A1-3) of Synthesis Example 3, 70 parts of active hydrogen equivalent of 167 with sorbitol and PO added, and 70 parts of active hydrogen equivalent of glycerin with PO added to glycerin In a mixture with 300 parts of polyol (A3-1) 20 parts [average HLB of (A) = 8.2], 10 parts of “Phirol PCF” and 10 parts of “silicone SF-8410”
(Toe Dow Corning, foam stabilizer) 2 parts, water 2
, "HCFC-141b" 29 parts and "DABCO
33 LV "was previously blended and the temperature was adjusted to 25 ° C, and the“ Millionate MR ”was adjusted to 25 ° C.
The same operation as in Example 1 was performed except that 106 parts (isocyanate index 110) was added to obtain a rigid polyurethane foam.

Example 4 A mixture of 3 parts of the polyol (A1-4) of Synthesis Example 4 and 97 parts of a polyol (A2-4) having an active hydrogen equivalent of 140 to which pentaerythritol was added with PO [average H of (A)]
LB = 9.8], 10 parts of “Phirol PCF”,
3 parts of "Silicone SZ-1666" (manufactured by Nippon Unicar, foam stabilizer), 3 parts of water, 25 parts of "HCFC-141b" and 2.0 parts of "TOYOCAT-TE" (Tosoh Corp., amine catalyst) in advance. "Lupranate M-12" which was blended and the temperature was adjusted to 25 ° C, and the temperature was adjusted to 25 ° C.
The same operation as in Example 1 was performed by adding 111 parts (isocyanate index: 80, crude MDI, manufactured by BASF) to obtain a rigid polyurethane foam.

Example 5 A mixture of 30 parts of the polyol (A1-5) of Synthesis Example 5 and 70 parts of a polyol (A2-5) having an active hydrogen equivalent of 110 obtained by adding PO to monoethanolamine [average of (A)] HLB = 9.7], 10 parts of “Phirol PCF”,
3 parts of "Silicone L-5340" (manufactured by Nippon Unicar, foam stabilizer), 2 parts of water, 30 parts of "HCFC-141b" and 0.5 parts of "TOYOCAT-TE" are blended in advance to obtain 2 parts.
The temperature was adjusted to 5 ° C, and 120 parts of “Millionate MR-100” (isocyanate index: 100) adjusted to 25 ° C was added thereto, and the same operation as in Example 1 was performed to obtain a rigid polyurethane foam.

Example 6 50 parts of a polyol (A1-1) and a polyol (A2-6) 5 having an active hydrogen equivalent of 84 obtained by adding PO to glycerin were added.
0 parts [average HLB of (A) = 8.5]
"Phiroll PCF" 10 parts, "Silicone L-54"
20 "2 parts, water 7 parts and" U-CAT1000 "2.
0 parts in advance, and the temperature is adjusted to 25 ° C.
“Millionate MR-200” 172 temperature-controlled to ℃
Then, the same operation as in Example 1 was performed except for adding a part (isocyanate index: 90) to obtain a rigid polyurethane foam.

Example 7 1 part of polyol (A1-4) and polyol (A2-
4) mixture with 99 parts [average HLB of (A) = 10.
1], 10 parts of “Phirol PCF”, 3 parts of “Silicone SF-8410”, 8 parts of water, and “DABCO 3
3LV ”1.5 parts in advance and temperature adjusted to 25 ° C,
In this, “Lupranate M-1” whose temperature was adjusted to 25 ° C.
2 "173 parts (isocyanate index 80) was added, and the same operation as in Example 1 was performed to obtain a rigid polyurethane foam.

Example 8 20 parts of the polyol (A1-5) and 20 parts of the polyol (A2-
4) mixture with 80 parts [average HLB of (A) = 8.4]
In addition, 10 parts of "Phirol PCF", "Silicone SZ"
-1666 "3 parts, water 6 parts and" DABCO 33L
V "was previously blended and the temperature was adjusted to 25C, and" Millionate MR-10 "was adjusted to 25C.
“0” (170 parts) (isocyanate index: 100) and the same operation as in Example 1 was carried out to obtain a rigid polyurethane foam.

Comparative Example 1 A mixture of 20 parts of the polyol (A1'-6) of Comparative Synthesis Example 1 and 80 parts of the polyol (A2-1) [average HLB of (A) = 10.5] was added to "Phyrol". PCF "10
Parts, "Silicone SF-8410" 2 parts, water 3 parts, "H
25 parts of "CFC-141b" and "DABCO 33L
V) was previously blended and the temperature was adjusted to 25 ° C, and “Millionate MR-20” was adjusted to 25 ° C.
0 "(106 parts of isocyanate index) and the same operation as in Example 1 was carried out to obtain a rigid polyurethane foam.

Comparative Example 2 A mixture of 10 parts of the polyol (A1-3) of Synthesis Example 3 and 90 parts of a polyol (A2-7) having an active hydrogen equivalent of 253 obtained by adding PO to pentaerythritol [average of (A)] HLB = 7.1], 10 parts of “Phirol PCF”,
"Silicone SH-193" 2 parts, water 3 parts, "HCFC
-141b "and 30 parts of" TOYOCAT-TE "
1.0 part was previously blended and the temperature was adjusted to 25 ° C., and “Millionate MR-100” 1 was adjusted to 25 ° C.
Example 1 with the addition of 21 parts (isocyanate index 120)
The same operation as described above was performed to obtain a rigid polyurethane foam.

Comparative Example 3 100 parts of polyol (A2-4) [Average HLB of (A)]
= 10.2], 10 parts of "Phirol PCF", 2 parts of "Silicone L-5340", 2 parts of water, "HCFC-1
30 parts of "41b" and 2.0 parts of "UCAT-1000" are preliminarily blended and the temperature is adjusted to 25C, and 127 parts of "Millionate MR-100" (isocyanate index: 100) adjusted to 25C is added thereto. The same operation as in Example 1 was performed to obtain a rigid urethane foam.

Comparative Example 4 A mixture of 10 parts of the polyol (A1′-6) of Comparative Synthesis Example 1 and 90 parts of a polyol (A2-8) having an active hydrogen equivalent of 117 to which PO was added to glycerin [(A) average HL
B = 11.6], 10 parts of “Phirol PCF”,
"Silicone SF-8410" 2 parts, water 6 parts and "T
2.0 parts of OYOCAT-TE was previously blended and the temperature was adjusted to 25 ° C, and 153 parts of “Millionate MR-200” adjusted to 25 ° C therein (isocyanate index: 9).
0) and the same operation as in Example 1 was carried out to obtain a rigid polyurethane foam.

Comparative Example 5 20 parts of polyol (A1-4) and polyol (A2-
7) Mixture with 80 parts [average HLB of (A) = 5.7]
In addition, 10 parts of "Phirol PCF", "Silicone SZ"
-1666 "2 parts, water 8 parts and" DABCO 33L
V "was previously blended and the temperature was adjusted to 25C, and" Millionate MR-10 "was adjusted to 25C.
0 "(isocyanate index: 100) and the same operation as in Example 1 was carried out to obtain a rigid polyurethane foam.

Test Example The communication rate was measured in accordance with ASTM: D2856-70 (unit:%). The compressive strength was measured based on the compressive strength test method of JIS A 9511 (unit: Kg / c).
m ² ). Table 1 shows the measurement results of the foam density (Kg / m ³ ), the communication ratio and the compressive strength of the urethane foams obtained in Examples 1 to 8, and the measurement results of the urethane foams obtained in Comparative Examples 1 to 5. It is shown in Table 2.

[0054]

[Table 1]

[0055]

[Table 2]

As is clear from Tables 1 and 2, the rigid urethane foams obtained in Examples 1 to 8 have a high communication rate and a high compressive strength. In comparison with this, Comparative Examples 1 to
The foam obtained in No. 5 cannot achieve both high communication ratio and compressive strength.

[0057]

According to the method for producing a polyurethane foam of the present invention, even when a hydrogen atom-containing halogenated hydrocarbon or water is used as a foaming agent, a rigid urethane having a high communication rate and a high compressive strength can be obtained. You can get the form. Due to the above effects, the rigid polyurethane foam obtained by the method of the present invention is extremely useful as a high-strength filler for building members.

Claims (3)

[Claims] 1. A method comprising the steps of: converting a polyol (A) and an organic polyisocyanate (B) into a hydrogen atom-containing halogenated hydrocarbon;
In the method for producing a rigid polyurethane foam which is reacted in the presence of at least one or more foaming agents selected from water, low-boiling hydrocarbons, and liquefied carbon dioxide, (A) has a carbon number of 3
Containing 5 to 85% by mass of an aliphatic hydrocarbon side chain of
A polyol (A1) having an LB of 4 or less and an active hydrogen equivalent of 2
Polyol (A2) other than (A1) of 50 or less, or (A1) and (A2) and polyol (A3) other than (A1) having an active hydrogen equivalent exceeding 250, and the average HLB of (A) is 6 or more. A method for producing a rigid polyurethane foam, characterized in that: 2. (A1) is the following (A11) to (A1)
2. The composition according to claim 1, which is one or more polyols selected from 5).
Production method as described. (A11) A 1,2-alkanediol having 5 to 42 carbon atoms (a1), a glycerin monoalkyl ether having 6 to 43 carbon atoms (a2) or a glycerin fatty acid monoester having 7 to 44 carbon atoms (a3), A diol having a structure obtained by adding 2 to 4 alkylene oxides (b). (A12) An alkylamine having 3 to 40 carbon atoms (a4)
Having a structure obtained by adding 2 mol or more of an alkylene oxide (b) having 2 to 4 carbon atoms to the diol. (A13) A polyol having a structure obtained by adding an alkylene oxide comprising an α-olefin oxide (a5) having 5 to 42 carbon atoms to a compound having two or more active hydrogens. (A14) (a1), (a2), (a3), (A1
1) A polyester polyol comprising a polyol component composed of at least one polyol selected from the group consisting of (A12) and (A13), and a polycarboxylic acid (c). (A15) (a1), (a2), (a3), (A1
1) A polylactone polyol having a structure obtained by adding a lactone monomer (d) to a polyol component comprising at least one polyol selected from the group consisting of (A12) and (A13). 3. The method according to claim 1, wherein the mass ratio of (A1) / (A2) in (A) is 0.5 / 99.5 to 60/40.