JP2002201252A - Method for producing rigid plastic foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a rigid polyurethane foam or a urethane modified rigid polyisocyanurate foam whereby a normal foam can be obtained even under conditions in which the atmospheric temperature during foam production is low in the case in which HFC-365mfc is used as a blowing agent. SOLUTION: There is provided a method for producing a rigid polyurethane foam or a urethane-modified rigid polyisocyanurate foam, which process comprises reacting an active-hydrogen-containing compound with a polyisocyanate compound in the presence of a low-boiling halohydrocarbon blowing agent, wherein the blowing agent used is a mixture of 0.1-30 wt.% at least one member selected from the group consisting of R-404A, R-407C, and R-410A with 99.9-70 wt.% HFC-365mfc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a rigid polyurethane foam or a urethane-modified rigid polyisocyanurate foam, and more particularly to a rigid polyurethane foam or a urethane-modified rigid foam characterized by using a specific blowing agent. The present invention relates to a method for producing a polyisocyanurate foam.

[0002]

2. Description of the Related Art A rigid polyurethane foam or a polyisocyanate compound is reacted with an active hydrogen-containing compound having two or more active hydrogen-containing functional groups capable of reacting with an isocyanate group in the presence of a foam stabilizer, a catalyst and a foaming agent. The production of urethane-modified rigid polyisocyanurate foams is widely practiced. Various compounds are known as foaming agents for producing the rigid polyurethane foam or urethane-modified rigid polyisocyanurate foam, but 1,1-dichloro-1-fluoroethane (HCFC-141b) is mainly used. . Usually, water is used together with HCFC-141b.

[0003]

When HCFC-141b is used as a foaming agent, it contains chlorine atoms in the molecule, and after reaching the ozone layer above the atmospheric layer, it is decomposed by the action of ultraviolet rays. It has recently been shown that decomposition products destroy the ozone layer. In order to solve this problem, it has been proposed to use 1,1,1,3,3-pentafluorobutane (HFC-365mfc) as a blowing agent. Since this halogenated hydrocarbon does not contain chlorine atoms in the molecule, it is thought that there is little risk of destruction of the ozone layer, and its boiling point is close to HCFC-141b, so it is a promising blowing agent in place of HCFC-141b. It is what is being watched.

[0004] However, when HFC-365mfc is used as a foaming agent, insufficient foaming may occur depending on the ambient temperature during production of a rigid polyurethane foam or a urethane-modified rigid polyisocyanurate foam due to the high boiling point of the foaming agent. And it becomes difficult to obtain a normal foam. SUMMARY OF THE INVENTION The present invention has been made to solve the problems at the time of producing this rigid polyurethane foam or urethane-modified rigid polyisocyanurate foam, and has solved the problems by using a specific foaming agent.

[0005]

That is, a first invention of the present application is to provide a polyisocyanate compound comprising an active hydrogen-containing compound having two or more active hydrogen-containing functional groups capable of reacting with an isocyanate group and a low boiling halogenated hydrocarbon. In the method for producing a rigid polyurethane foam or a urethane-modified rigid polyisocyanurate foam by reacting in the presence of a system-based foaming agent, R-404A, R-4
0.1C to 30% by weight of at least one member selected from the group consisting of 07C and R-410A and HFC-365mf
A method for producing a rigid polyurethane foam or urethane-modified rigid polyisocyanurate foam, characterized by using a mixture of c and 99.9 to 70% by weight,
A second invention is characterized in that 2 to 50% by weight of a foaming agent is mixed with an active hydrogen-containing compound containing a foam stabilizer and a catalyst, and the mixture is reacted with a polyisocyanate compound.
A method for producing a rigid polyurethane foam or a urethane-modified rigid polyisocyanurate foam according to the invention, wherein the third invention uses the reaction solution containing a foaming agent at a temperature of 10 ° C. or higher. This is a method for producing the rigid polyurethane foam or urethane-modified rigid polyisocyanurate foam of the second invention.

Here, R-404A is HFC-125 /
143a / 134a is a mixture of 44/52/4,
R-407C is HFC-32 / 125 / 134a 23
/ 25/52, and R-410A is HFC-
32/125 is a 50/50 mixture and HFC
-125 is (CHF_TwoCF_ThreeThe hide represented by the structural formula
HFC-143a is (CH)
_ThreeCF_Three) Hydrofluorocarbon represented by the structural formula
And HFC-134a is (CH_TwoFCF _Three)
A hydrofluorocarbon represented by the formula
-32 is (CH _TwoF_Two) The hydrofur represented by the structural formula
HFC-365mfc is (CF)_Three
CH_TwoCF_TwoCH_Three) The hydrofluoro represented by the structural formula
Locarbon.

Hereinafter, the present invention will be described in detail. HFC-
When 365 mfc is used as the foaming agent, the rise of foaming tends to be slow when the ambient temperature during the production of the rigid polyurethane foam or urethane-modified rigid polyisocyanurate foam is low. This is thought to be due to the high boiling point of the blowing agent. In the production of a rigid polyurethane foam or a urethane-modified rigid polyisocyanurate foam, the role of a physical foaming agent such as HFC-365mfc is to cause the foaming agent to vaporize due to heat of reaction during polymerization of the active hydrogen compound and the polyisocyanate compound. This is to promote foaming of the hard plastic.

However, if the ambient temperature is lowered, a time lag occurs before the reaction heat required for vaporization is generated in the initial stage of the reaction, during which the resinification reaction proceeds, and it is considered that a normal foam cannot be obtained. The present inventors have added HFC-365mfc as a physical blowing agent to R-404A and R-407C which are low boiling halogenated hydrocarbon blowing agents.
And that at least one selected from the group consisting of R-410A is used in combination to promote the foaming reaction, which is effective for producing a rigid polyurethane foam or a urethane-modified rigid polyisocyanurate foam at a low atmospheric temperature. Heading, the present invention has been reached.

It has also been found that when the temperature of the reaction solution is 10 ° C. or higher, preferably 20 ° C. or higher, the effect of the low boiling halogenated hydrocarbon is remarkably exhibited. In the present invention, the mixing amount of at least one selected from the group consisting of R-404A, R-407C and R-410A, which are low boiling halogenated hydrocarbon blowing agents used as one component of the blowing agent, is 0.1 to 30% by weight, preferably 0.2 to 15
%, More preferably 0.3 to 10% by weight. If the mixing amount is less than 0.1% by weight, the foaming effect as a foaming agent cannot be exhibited, and if it exceeds 30% by weight, foaming of the foam is inhibited by bumping of the low boiling point foaming agent.

The active hydrogen-containing compound having two or more active hydrogen-containing functional groups capable of reacting with an isocyanate group includes a compound having two or more active hydrogen-containing functional groups such as a hydroxyl group and an amino group, or two kinds of the compounds. A mixture of the above is mentioned. Particularly, a compound having two or more hydroxyl groups or a mixture thereof, or a mixture containing the compound as a main component and further containing a polyamine or the like is preferable. As the compound having two or more hydroxyl groups, a polyol widely used is preferable. Examples of the polyol include a polyether-based polyol, a polyester-based polyol, a polyhydric alcohol, a polyamine, and an alkanolamine. A combination use of these polyols and other active hydrogen compounds is preferable.

The polyether polyols include polyhydric alcohols, sugars, alkanolamines, polyamines,
A polyether polyol obtained by adding a cyclic ether, particularly an alkylene oxide such as propylene oxide or ethylene oxide, to another initiator is preferable. Examples of the polyester-based polyol include a polyol of a polyhydric alcohol-polycarboxylic acid condensation type and a polyol of a cyclic ester ring-opening polymer type. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and glycerin. , Trimethylolpropane, pentaerythritol, diethanolamine, triethanolamine and the like.

Examples of the polyisocyanate compound include aromatic, alicyclic and aliphatic polyisocyanates having two or more isocyanate groups, mixtures of two or more thereof, and modified poly obtained by modifying them. Isocyanates. Specifically, for example, polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and their prepolymer-modified, nurate-modified, and urea-modified products And the like.

When reacting an active hydrogen compound with a polyisocyanate compound, it is usually necessary to use a catalyst. As the catalyst, a metal compound catalyst such as an organotin compound which promotes the reaction between the active hydrogen-containing group and the isocyanate group, or a tertiary amine catalyst such as triethylenediamine is used. In addition, a multimerization catalyst such as a metal carboxylate for reacting isocyanate groups with each other is used depending on the purpose. In addition, foam stabilizers to form good cells are often used. As the foam stabilizer, a silicone-based foam stabilizer is mainly exemplified. Other optional additives include, for example, fillers, stabilizers, coloring agents, and flame retardants.

Using these raw materials, a rigid polyurethane foam and a rigid urethane-modified isocyanurate foam can be obtained. The present invention is a rigid polyurethane foam which is a field in which a large amount of a halogenated hydrocarbon-based blowing agent is used,
Particularly useful in the production of urethane-modified rigid polyisocyanurate foams. Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

[0015]

EXAMPLES The evaluation of the blowing agent according to the invention in rigid polyurethane foams was carried out using examples and comparative examples.
The polyols used are as follows. Polyol A: Polyol having a hydroxyl value of 400 obtained by reacting propylene oxide with triethanolamine Polyol B: Polyol having a hydroxyl value of 450 obtained by reacting propylene oxide with shoe rose The evaluation of the foaming state was performed according to the following evaluation criteria. . ：: Good foaming, good foam rising ○ △: Good foaming, slightly delaying foam rising △: Long foaming, slow foam rising △ ×: Long foaming time , Form rises slowly

[0016]

Example 1 To a mixture of 50 parts by weight of polyol A and 50 parts by weight of polyol B, 2 parts by weight of a silicone foam stabilizer, 1 part by weight of water, and a DPG solution of triethylenediamine as a catalyst: 1 part by weight Table as parts by weight and blowing agent
The reaction solution obtained by mixing the foaming agent shown in No. 1 with polymethylene polyphenyl isocyanate (commonly called Crude MDI) was mixed at a predetermined liquid temperature, and 200 mm × 20 at an ambient temperature of 10 ° C.
It was put into a 0 mm × 100 mm wooden box and foamed to obtain a foam. Table 1 shows the evaluation results of the obtained foam.

[0017]

Example 2 A foam was obtained in the same manner as in Example 1 except that the blowing agent was changed as shown in Table 1. Table 1 shows the obtained results.

Example 3 A foam was obtained in the same manner as in Example 1 except that the foaming agent was changed as shown in Table 1. Table 1 shows the obtained results.

Comparative Example 1 A foam was obtained in the same manner as in Example 1 except that the foaming agent was changed as shown in Table 1. Table 1 shows the obtained results.

[0018]

[Table 1]

[0019]

According to the present invention, a normal rigid polyurethane foam or urethane-modified rigid polyisocyanurate foam can be produced even at a low ambient temperature.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F074 AA78 BA34 BA53 BC05 CA12 CA23 CC22Y DA02 4J034 DA01 DA03 DF01 DF16 DF32 DG14 HA01 HA02 HA06 HA07 HB09 HB11 HC03 HC12 HC17 HC22 HC46 HC61 HC64 HC67 HC71 HC73 JA24 KA01 KB05 K NA05 QB01 QC01

Claims (3)

[Claims] 1. A hard polyurethane comprising reacting an active hydrogen-containing compound having two or more active hydrogen-containing functional groups capable of reacting with an isocyanate group with a polyisocyanate compound in the presence of a low-boiling halogenated hydrocarbon-based blowing agent. In a method for producing a foam or a urethane-modified rigid polyisocyanurate foam, R-404 is used as a blowing agent.
A, R-407C and R-410A, at least one selected from the group consisting of HFC-
A method for producing a rigid polyurethane foam or a urethane-modified rigid polyisocyanurate foam, comprising using a mixture of 365 mfc and 99.9 to 70% by weight. 2. The hard material according to claim 1, wherein a foaming agent is mixed with an active hydrogen-containing compound containing a foam stabilizer and a catalyst in an amount of 2 to 50% by weight, and the mixture is reacted with a polyisocyanate compound. A method for producing a polyurethane foam or a urethane-modified rigid polyisocyanurate foam. 3. The temperature of a reaction solution containing a foaming agent is 10 ° C.
The method for producing a rigid polyurethane foam or a urethane-modified rigid polyisocyanurate foam according to claim 1 or 2, which is used as described above.