JP2002003565A - Polyol composition for rigid polyurethane foam - Google Patents

Abstract

(57) [Summary] [Problem] Although water is used as a foaming agent, in a reaction with isocyanate, the viscosity is increased only to an extent that does not hinder the reaction, and the dimensional stability and difficulty of urethane foam are reduced. Provided is a polyol composition having excellent flammability. SOLUTION: (a) 30 to 80% by weight of an alkylene oxide adduct of a polyamine (hydroxyl value 400 to 800);
(B) 5-40% by weight of an alkylene oxide adduct of chlorendic acid (hydroxyl value 100-500), (c) 3-60% by weight of an alkylene oxide adduct of dihydric or higher polyhydric alcohol (hydroxyl value 20-800) Polyol composition for rigid polyurethane foam comprising

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 polyol composition for rigid polyurethane foam which is excellent in liquid viscosity, dimensional stability of urethane foam, flame retardancy and the like even when only water is used as a blowing agent without using fluorocarbon.

[0002]

2. Description of the Related Art A rigid polyurethane foam is usually obtained by reacting a polyol component and an isocyanate component in the presence of auxiliary agents such as a foaming agent, a reaction catalyst and a foam stabilizer. However, in recent years, environmental pollution such as destruction of the ozone layer in the stratosphere and global warming due to the influence of Freon gas as a foaming agent has become a problem, and CFCs (11, 12,
13, 112, 113, 114, 115, etc.) have been completely abolished. In the urethane foam industry, where the impact of this regulation is greatest, switching to HCFC for the time being,
141b is the mainstay, but it is also decided to abolish it in 2003 because its ODP (ozone depletion potential) is not 0.

As blowing agents other than chlorofluorocarbons, chlorinated hydrocarbon compounds such as methylene chloride (toxic), carbon tetrachloride (toxic), chloroform (toxic), ethane dichloride (toxic and flammable), and n- Hydrocarbon compounds such as pentane (flammable), cyclopentane (flammable), and n-hexane (harmful, flammable) can also be used as blowing agents in place of chlorofluorocarbons, but still safety and environmental concerns There is. For this reason, in the field of producing rigid polyurethane foam, attention has been paid to a method of using water alone as a foaming agent. However, when water and the polyol composition are mixed, there is a disadvantage that the viscosity rises and the progress of the urethane reaction is hindered, and when urethane foam is formed, this method uses carbon dioxide gas generated by a chemical reaction between water and an isocyanate component. When foaming is actually attempted with water alone, the inside of the urethane foam bubbles is once filled with carbon dioxide gas, but the diffusion rate of carbon dioxide gas from the bubbles is 5 times the diffusion rate of air into the bubbles. Since it is 10 to 10 times, the internal pressure of the air bubbles decreases over time, and as a result, foam shrinkage, particularly at high temperature and high humidity, occurs, and as a result, there is a problem that the dimensional stability is poor. Therefore, in the field of polyurethane foam production, there is a demand for the development of a polyurethane foam production technique that uses water as a foaming agent and has excellent dimensional stability.

[0004]

In the present invention, despite the use of water as a foaming agent, in the reaction with water or the reaction with isocyanate, the viscosity increases only to such an extent that the reaction is not hindered. An object is to provide a polyol composition used for producing a rigid polyurethane foam. It is a second object of the present invention to provide a foam polyol composition having excellent dimensional stability. A third object is to provide a polyol composition having excellent flame retardancy.

[0005]

That is, the polyol composition for a rigid polyurethane foam of the present invention is characterized by containing the following components (a), (b) and (c). (a) 30 to 80% by weight of an alkylene oxide adduct of a polyamine (hydroxyl value 400 to 800). (B) 5 to 40% by weight of an alkylene oxide adduct of chlorendic acid (hydroxyl value 100 to 500). (C) An alkylene oxide adduct of a dihydric or higher polyhydric alcohol (hydroxyl value 20 to 800) 3 to 60% by weight.

The polyol composition for a rigid polyurethane foam of the present invention further comprises the following (d-1) or (d-
2) A component can be contained. (D-1) An alkylene oxide adduct of sorbitol (having a hydroxyl value of 50) with respect to 100 parts by weight of the polyol composition.
To 200) by 5 to 20 parts by weight. (D-2) 0.01 to 0.1 part by weight of polybutene based on 100 parts by weight of the polyol composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyol composition referred to in the present invention is a mixture of a foam stabilizer, a catalyst, a flame retardant, and other auxiliary materials using water as a foaming agent, and then reacting with a polyisocyanate to obtain mechanical properties, It means a polyol composition for rigid polyurethane foam having excellent foam properties such as dimensional stability.

The (a) alkylene oxide adduct of a polyamine of the present invention includes, for example, ethylenediamine, propylenediamine, hexamethylenediamine, xylenediamine, tolylenediamine, etc.
It is obtained by adding an alkylene oxide such as propylene oxide. Of these, alkylene oxide adducts of ethylenediamine, propylenediamine and tolylenediamine are preferred.

(B) The alkylene oxide adduct of chlorendic acid conforms to the production method of JP-A-11-228803. Chlorendic acid is represented by the molecular formula C ₉ H ₄ O ₄ Cl ₆ and has a chemical name of 1,4,5,6,7,7-hexachlorobicyclo- (2,2,1) -5-heptene-2. , 3
-Dicarboxylic acid, represented by the following chemical formula (I).

[0010]

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The alkylene oxide added to the component (A) includes ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and the like.
One or a mixture of two or more of these can be used. Preferred alkylene oxides include ethylene oxide, 1,2-propylene oxide and mixtures thereof.

(C) Alkylene oxide adducts of dihydric or higher polyhydric alcohols include alkylene oxides such as propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, diglycerin, pentaerythritol and ethylene oxide and propylene oxide. Is added. Of these, dipropylene glycol, glycerin, and alkylene oxide adducts of diglycerin are preferred. The polyhydric alcohol (c) does not include the polyhydric alcohol derived from the polyamine (a).

The polyol component used in the present invention is prepared by adding (a) an alkylene oxide adduct of a polyvalent amine (having a hydroxyl value of 400) to 100 parts by weight of the total polyol component.
To 800) is from 30 to 80 parts by weight, preferably 4 parts by weight.
0 to 60 parts by weight. (B) The content of the alkylene oxide adduct of chlorendic acid (hydroxyl value 100 to 500) is 5 to 40 parts by weight, preferably 10 to 30 parts by weight. (C) The content of the alkylene oxide adduct of dihydric or higher polyhydric alcohol (hydroxyl value 20 to 800) is 3 to
60 parts by weight, preferably 5 to 50 parts by weight. It is essential that the mixing ratio be within these ranges so as not to cause separation of the polyol composition over time and to improve the properties of the desired polyurethane foam.

Further, in order to obtain a urethane foam having good dimensional stability without causing shrinkage of the foam used in the present invention, (d-
1) 5 to 20 parts by weight, preferably 7 to 10 parts by weight of an alkylene oxide adduct of sorbitol (hydroxyl value 50 to 200)
15 parts by weight or (d-2) polybutene in an amount of 0.01 to
It is preferable to add 0.1 part by weight, preferably 0.02 to 0.05 part by weight. Polybutene has a molecular weight of 300
To 1000 are preferred.

When an alkylene oxide adduct of sorbitol is added, an alkylamine ethylene oxide adduct (for example, Esodoomin T / 13; manufactured by Lion Akzo) is used as a compatibilizer so as not to cause separation of the polyol composition. It is preferable to use benzyl ether in combination.

The amount of water of the blowing agent used in the present invention is 2 to 10 parts by weight, preferably 3 to 8 parts by weight, based on 100 parts by weight of the total polyol component. As the polyisocyanate used in the present invention, those conventionally used for rigid polyurethane foams can be used. Examples of such an isocyanate include an aromatic polyisocyanate, an aliphatic polyisocyanate, and an alicyclic polyisocyanate.

Specific examples of aromatic polyisocyanates include 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate (TDI), 2,4'- and 4,4 '-Diphenylmethane diisocyanate (MDI), polymethylene polyphenylisocyanate (crude MDI), naphthylene-
1,5-diisocyanate, triphenylmethane-4,
4 ′, 4 ″ -triisocyanate, xylylene diisocyanate, α, α, α ′, α-tetramethylxylylene diisocyanate and the like.

Specific examples of the aliphatic polyisocyanate include 1,6-hexamethylene diisocyanate,
2,4-trimethylhexamethylene diisocyanate,
Examples include lysine diisocyanate and xylylene diisocyanate. Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and 1,4-cyclohexane diisocyanate. Of these, preferred are crude MDI and TDI.

The rigid polyurethane foam is preferably produced by reacting a mixture of the polyol composition of the present invention, water, a catalyst, a foam stabilizer and a flame retardant with a polyisocyanate. As the catalyst, a catalyst usually used for a rigid polyurethane foam is used. Specifically, tertiary amines such as triethylenediamine, pentamethyldiethylenetriamine, tetramethylhexanediamine, dimethylalkylamine and dibutyltin dilaurate,
Metal catalysts such as stannas octoate and lead octanoate,
Catalysts for trimerizing isocyanates (isocyanuration catalysts) such as potassium octylate and quaternary ammonium salts are preferred.

As the foam stabilizer, those commonly used in rigid polyurethane foams are used. Specifically, an alkylene oxide-modified polydimethylsiloxane having an alkoxy group or an active OH group at the terminal is preferable. As the flame retardant, phosphate esters, chlorine-containing phosphate esters, and the like are preferable.

The polyol composition of the present invention is mainly used for the production of rigid polyurethane foams such as injection foaming and spray foaming, and has a high flame retardant nullate foam having an NCO / OH equivalent ratio of 2 to 10 or more. And a polyol compound in the production of polyurethane foam or semi-rigid foam by injection molding.

[0022]

According to the present invention, in spite of the fact that water is used as a blowing agent, in the reaction with isocyanate,
It is advantageously used as a polyol composition having a viscosity increase that does not hinder the reaction and having excellent dimensional stability and flame retardancy of urethane foam.

[0023]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples. Unless otherwise specified, "parts" and "%" are by weight. 100 parts of the polyol component shown in Table 1 (provided that E
O = ethylene oxide, PO = propylene oxide),
A predetermined amount of ion-exchanged water as a blowing agent, 3 parts of dimethylhexadecylamine (Armine DM16D; manufactured by Lion Akzo) and 3 parts of pentamethyldiethylenetriamine (TOYOCAT-DT; manufactured by Tosoh) and 3 parts of lead octanoate (Nikkaoctix) as a catalyst Pb 20% product; Nippon Kagaku Sangyo Co., Ltd. 3 parts, silicone foam stabilizer (L-5)
420; Nippon Unicar Co., Ltd.) 2 parts, tris (β-chloropropyl) phosphate (Phirol PCF; Akzokashima) as a flame retardant, dibenzyl ether (Daiwa Kasei) as an compatibilizer, alkyl Amine ethylene oxide adduct (Esodyomin T / 13;
(Lion Akzo Co., Ltd.) in a predetermined amount, and this mixture is mixed with N
Polymethylene polyphenyl isocyanate as an isocyanate component at a CO / OH equivalent ratio of 1.1; crude MDI
Using (Millionate MR-100; manufactured by Nippon Polyurethane Industry Co., Ltd.), the liquid temperature was adjusted to 5 ° C., followed by high-speed mixing (mixing time: 3 seconds) with a homomixer to conduct a foaming test. At this time, the reactivity (free foaming) and the appearance and physical properties of the foam were evaluated.

The reactivity was measured for the following times. Cream time; time from the start of liquid mixing until the reaction mixture rises to creamy turbidity. Gel time; time from the start of liquid mixing to the start of stringing due to thickening. Rise time; The time from the start of mixing until the foam reaches its maximum height. Tack-free time; the time when the liquid is no longer sticky when it comes into contact with the foam surface after mixing

Basically, physical properties were measured one day after the urethane reaction, on the core portion from which the skin was removed. The dimensional stability was measured by measuring the dimensional change after 48 hours at 70 ° C. and 95%.
JIS K 7201, oxygen index as an index of flame retardancy,
Core density is JIS A9526, compressive strength is JIS
K 7220, the closed cell rate was measured based on the test method specified in ASTM D 2856. Core density is 0.0
35 g / cm ³ or less, compressive strength 0.5-2.0 kgf
/ Cm ² , oxygen index 23.0 or more, closed cell rate 65
% Is a preferable range. The results are shown in Tables 1 and 2. As shown in Table 1, this example shows that the polyol composition of the present invention has excellent urethane foam properties.

[0026]

[Table 1]

[0027]

[Table 2]

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J034 BA05 CA03 CA04 CA05 CA15 CA24 CB03 CB04 CB05 CB08 CC15 CC26 CC55 CD04 DA01 DA03 DA05 DB04 DB05 DB08 DC05 DC12 DC40 DG02 DG08 DG15 DG23 DP02 DP12 HA01 HA07 HA08 HC03 HC12 HC17 HC22 HC52 HC61 HC64 JA01 KA01 KC02 KC17 KC18 KD12 KE02 NA03 QB16 QC01

Claims (2)

[Claims] 1. An alkylene oxide adduct of a polyamine (hydroxyl value 400 to 800) 30 to 80% by weight, and (b) an alkylene oxide adduct of chlorendic acid (hydroxyl value 100 to 500) 5 to 40% by weight. (C) 3 to 60% by weight of an alkylene oxide adduct of a dihydric or higher polyhydric alcohol (having a hydroxyl value of 20 to 800), which is a polyol composition for rigid polyurethane foams. 2. 100 parts by weight of the polyol composition, 5 to 20 parts by weight of (d-1) an alkylene oxide adduct of sorbitol (hydroxyl value 50 to 200), or (d-2) polybutene. 0.01-0.1
The polyol composition for a rigid polyurethane foam according to claim 1, wherein the polyol composition is blended in parts by weight.