JP3197513B2 - Flame retardant polyester polyol composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polyester polyol composition, and more particularly, to a flame-retardant rigid urethane foam (hereinafter, also simply referred to as a foam).
The present invention relates to a polyester polyol composition which can be used as a raw material for producing a polyester polyol.

[0002]

2. Description of the Related Art Conventionally, rigid urethane foam has been widely used as a heat insulating material for buildings and houses due to its excellent heat insulating performance. As a raw material for producing a rigid urethane foam, main components of an aromatic polyisocyanate and a polyol component and various additives such as a foaming agent, a catalyst, and a foam stabilizer are used.

[0003] Among them, the polyol component is composed of polyether polyol, polyester polyol and the like, and is used alone or in combination of two or more.

[0004] Originally, since rigid urethane foam is a combustible material, it is necessary to make it hard to burn when used as a heat insulating material for buildings and houses. Conventionally, as a method of making hard urethane foam hard to burn, it is common to use an organic phosphate ester-based flame retardant. Regarding the polyol component, a method of using a polyester polyol as the polyol component and increasing the proportion of the polyester polyol, that is, a polyester polyol having an aromatic introduced in the molecule, and a polyester polyol having a high aromatic concentration is used. It is a common method to use.

[0005] As a method for introducing an aromatic compound into the molecule of a polyester polyol, it is generally known to use an aromatic polybasic acid as the polybasic acid used as the acid component of the raw material.

[0006]

However, the method of improving the polyester polyol by the above-mentioned method increases the viscosity of the polyol, so that the compatibility with the aromatic polyisocyanate which is a raw material of the rigid urethane foam,
Problems such as on-site workability and limitations of the foam body manufacturing machine occur. In addition, the method of increasing the amount of the organic phosphate ester-based flame retardant causes problems such as a decrease in physical properties of the foam and an increase in cost. Therefore, there is a limit in improving the flame retardancy of the rigid urethane foam.

Accordingly, an object of the present invention is to improve a conventional polyester polyol to have low viscosity physical properties and flame retardancy, and to use the raw material as a raw material to form a rigid urethane foam so that the foam becomes flame retardant. An object of the present invention is to provide a polyester polyol composition that can be produced.

[0008]

In order to achieve the above object, the polyester polyol composition according to the first aspect of the present invention is characterized in that one or more compounds selected from phenoxy alcohols are replaced with one or more compounds selected from polybasic acids. Is obtained by reacting with a compound of formula (I) and at least one compound selected from polyhydric alcohols;

Embedded image (Where R represents an aliphatic hydrocarbon having 2 to 16 carbon atoms and / or an oxygen-containing aliphatic hydrocarbon, A represents a phenyl group and / or an alkylene group , and X represents 1 to 5 The above hydroxyl groups and / or phenoxy groups are shown, and P is hydrogen and / or a group represented by -CO-ORX, and / or

Embedded image Wherein n represents 1 to 5 and m represents 1 to 4
Is shown. ).

This polyester polyol composition has a low viscosity, and when used as a raw material for rigid urethane foam, the foam can have excellent flame retardancy.

[0010] In order to achieve the above object, the polyester polyol composition according to the second aspect of the present invention is the polyester polyol composition according to the first aspect, wherein the phenoxy alcohol is reacted at a ratio of 1 to 60% by weight based on the weight of the reaction mixture. It is characterized by having been obtained.

The polyester polyol composition has physical properties that do not degrade the foam properties when used as a raw material for rigid urethane foam.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The present invention is a polyester polyol having a hydroxyl group at a terminal obtained by esterification reaction with various polybasic acids using a polyhydric alcohol and phenoxy alcohol as alcohol components. By performing an esterification reaction with the terminal carboxylic acid of the molecular chain, it is possible to suppress the increase in the molecular weight, to realize a low viscosity of the polyol, and to increase the aromatic concentration in the molecule. A polyester polyol having excellent flame retardancy when used as a raw material can be obtained.

The phenoxy alcohol used to exhibit the above performance in the present invention includes methylene glycol monophenyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, polyethylene glycol monophenyl ether, and polypropylene glycol monophenyl. Polyoxyalkylene monophenyl ether represented by ether, methylene glycol nonyl phenyl ether,
Polyoxyalkylene alkyl phenyl ethers typified by ethylene glycol nonyl phenyl ether, propylene glycol nonyl phenyl ether, polyethylene glycol nonyl phenyl ether, and the like, and one or more kinds are used.

[0014] The ratio of the phenoxy alcohol to the weight of the reaction mixture is as described in claim 2.
At less than 1%, no improvement in flame-retardant performance is observed and at 60%
If the ratio exceeds, not only does the improvement in flame retardancy level off, but also the physical properties of the foam when it is made into a foam body are significantly reduced. Therefore, it is desirably 3 to 40%.

The polybasic acids used simultaneously include phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic anhydride, adipic acid, sebacic acid, fumaric acid, maleic anhydride and the like. One or two or more are used.

Examples of the polyhydric alcohol to be esterified with the acid component include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and 1,4-butanediol. , 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, trimethylolpropane, triethanolamine, diglycerin, pentaerythritol, methylglycoside and the like. And used alone or in combination of two or more.

The reaction between the above-mentioned phenoxy alcohol, polybasic acid and polyhydric alcohol is carried out by a usual esterification reaction. That is, an esterification reaction is performed between an acid component and an alcohol component using an esterification catalyst to obtain a polyester polyol. Further, as a method other than esterification, when a polyester resin represented by a fiber, a PET bottle, or the like is subjected to a transesterification reaction with a polyhydric alcohol, a part of the polyhydric alcohol is replaced with phenoxy alcohol to perform a transesterification reaction. Thus, the polyester polyol of the present invention can be obtained.

As the esterification catalyst described above, paratoluenesulfonic acid, sulfuric acid, hydrochloric acid, Lewis acid, organotin compounds, organotitanium compounds, activated clay, acidic ion exchange resins and the like can be used.

The phenoxy alcohol is preferably ethylene glycol monophenyl ether, propylene glycol monophenyl ether, or polyethylene glycol monophenyl ether, depending on the ease of the reaction. Of the polybasic acids, phthalic anhydride, isophthalic acid, terephthalic acid and adipic acid are preferred. Among polyhydric alcohols, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, glycerin, and trimethylolpropane are desirable.

Regarding the resin properties of the polyester polyol of the present invention, the hydroxyl value can be varied from high to low depending on the molar ratio of the acid component and the alcohol component, but is preferably 50 to 500 (KOH mg / g). . The acid value is 4.0 (KOHmg / g) or less, and the water content is 0.4.
1 (%) or less is desirable.

Further, the present invention can be in the following modes. (A) The phenoxy alcohol according to claim 1 or 2, wherein at least one compound selected from the group consisting of ethylene glycol monophenyl ether, propylene glycol monophenyl ether and polyethylene glycol monophenyl ether is used. Polyester polyol composition. When these compounds are used, the reactivity is good and the production time is shortened to obtain a good polyester polyol composition.

(2) The polyester according to claim 1 or 2, wherein at least one compound selected from the group consisting of phthalic anhydride, isophthalic acid, terephthalic acid and adipic acid is used as the polybasic acid. A polyol composition. When these compounds are used, a good polyester polyol can be obtained by shortening the reaction time.

(C) As the polyhydric alcohol, at least one compound selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, glycerin and trimethylolpropane is used. The polyester polyol composition according to claim 1 or 2, which comprises: When these compounds are used, a good polyester polyol composition can be obtained by shortening the reaction time.

(D) The polyester polyol composition according to claim 1 or 2, which is based on (a), (b) and (c). In such a case, a favorable polyester polyol composition can be obtained by making the reaction time very short.

Next, examples and comparative examples of the present invention will be described.

Example 1 49 g of propylene glycol monophenyl ether was placed in a 1-liter four-necked flask connected to a Dimroth condenser.
(5% by weight), 622 g of terephthalic acid, 464 g of ethylene glycol, and 1.5 g of a catalyst (organotin compound), and the mixture was heated and dehydrated under a nitrogen stream while stirring. The heat dehydration reaction is carried out under a nitrogen stream at a normal pressure of 220 to 230.
Heated at <RTIgt; C </ RTI> for 3-4 hours. As a result, polyester polyol A shown in the examples of Table 1 was obtained.

Example 2 298 g of propylene glycol monophenyl ether
(30% by weight), 459 g of terephthalic acid, 343 g of ethylene glycol, and 1.5 g of a catalyst (organotin compound) were obtained in the same reactor and method as in Example 1 to obtain a polyester polyol B shown in Examples of Table 1.

Example 3 88 g of propylene glycol monophenyl ether (1
0% by weight), 595 g of PET resin (polyethylene terephthalate), 350 g of triethylene glycol, and 1.5 g of catalyst were subjected to a transesterification reaction using the same reactor as in Example 1, and as a result, polyester polyol C shown in Examples of Table 1 was obtained. Obtained.

Example 4 298 g (30% by weight) of ethylene glycol nonylphenyl ether and 432 of terephthalic acid were placed in a 1-liter four-necked flask connected to a Dean-Stark water separator.
g, 370 g of ethylene glycol, and 1.5 g of a catalyst (paratoluenesulfonic acid), and toluene was added thereto to cause a thermal dehydration reaction. This heat dehydration reaction is carried out at 150 ° C. under normal pressure for 3 hours.
Heated for ~ 4 hours. Next, the treated product was subjected to toluene removal to obtain a polyester polyol D shown in the examples of Table 1.

Comparative Example 1 5 g of propylene glycol monophenyl ether (0.
5% by weight), 655 g of terephthalic acid, 488 g of ethylene glycol, and 1.5 g of a catalyst were obtained in the same reactor and method as in Example 1 to obtain a polyester polyol E shown in Comparative Examples in Table 1.

Comparative Example 2 680 g of propylene glycol monophenyl ether
(63% by weight), 264 g of terephthalic acid, 199 g of ethylene glycol, and 1.5 g of a catalyst were obtained in the same reactor and method as in Example 1 to obtain a polyester polyol F shown in Comparative Examples in Table 1.

Comparative Example 3 654 g of terephthalic acid, 488 g of ethylene glycol,
Using 1.5 g of the catalyst and the same reaction apparatus and method as in Example 1, polyester polyol G shown in Comparative Example in Table 1 was obtained.

The above Examples 1 to 4 and Comparative Examples 1 to 3
Table 1 shows the resin properties of each polyester polyol obtained in
Was as shown in FIG.

[Table 1]

A hard urethane foam was prepared from each of the polyester polyols obtained in Examples 1 to 4 and Comparative Examples 1 to 3, and a combustion test was performed on each of the obtained urethane foams. In the method for producing the urethane foam, an isocyanate, a polyol, a catalyst, a foaming agent and a foam stabilizer were blended according to the formulation shown in Table 2, and foamed in a mold to obtain a foam.

[Table 2]

Materials used Polyester polyol; Examples 1-4 and Comparative Examples 1
The polyester polyol obtained in 3. Polyether polyol A: EL-455AR (a polyether polyol manufactured by Asahi Glass Co., Ltd.). Polyether polyol B; EL-455S (a polyether polyol manufactured by Asahi Glass Co., Ltd.). Catalyst: POLYCAT-43 (manufactured by San Apro Co., Ltd.) Foam stabilizer: SH-193 (manufactured by Dow Corning Toray Silicone Co., Ltd.) Blowing agent: Freon HCFC-141b (manufactured by Daikin Industries, Ltd.) Isocyanate: MILLIONATE MR -100
(Nippon Polyurethane Industry Co., Ltd.) The results of the combustion test of this urethane foam are as shown in Table 3.

[Table 3] The combustion performance was evaluated in accordance with JIS A 1321, and the CA value (smoke emission coefficient), tdθ (temperature time area),
The combustion performance was determined from the measured value of the afterflame.

In Table 1, a comparison between the conventional polyester polyol (Comparative Example G) and the polyester polyol using the phenoxy alcohol of Examples A to D is shown.
It can be seen that the polyester polyols of the examples all have the same hydroxyl value but low viscosity.

In Table 3, in the polyester polyol (E) of Comparative Example 1, the effect of improving the flame retardancy and lowering the resin viscosity was small, and in the polyester polyol (F) of Comparative Example 2, the flame retardancy was improved. Although effective in reducing the viscosity of the resin, the foam physical properties are clearly reduced in shrinkage and strength at normal temperature of the foam, and the performance is poor when the phenoxy alcohol is out of the range of 1 to 60% by weight based on the weight of the composition. It was confirmed that no improvement could be expected. Regarding the foam shrinkage, the one that shrank by 5% or more in volume change at room temperature after foaming was evaluated as x. The polyester polyol foams of the examples were good with little shrinkage.

[0038]

The polyester polyol according to the first and second aspects of the present invention improves the combustion performance of rigid urethane foam reacted with isocyanate by partially using phenoxy alcohol for the alcohol component of the raw material, and And a low viscosity polyol. Therefore, it can be used as a raw material of rigid urethane foam used as a heat insulating material for buildings and houses requiring flame retardant performance.

According to the second aspect of the invention, when used as a raw material for a rigid urethane foam, flame retardancy can be ensured without deteriorating the physical properties of the foam.

Claims (2)

(57) [Claims] 1. A compound obtained by reacting one or more compounds selected from phenoxy alcohols with one or more compounds selected from polybasic acids and one or more compounds selected from polyhydric alcohols, Is (Where R represents an aliphatic hydrocarbon having 2 to 16 carbon atoms and / or an oxygen-containing aliphatic hydrocarbon, A represents a phenyl group and / or an alkylene group , and X represents 1 to 5 Represents a hydroxyl group and / or a phenoxy group, wherein P is hydrogen,
And / or a group represented by -CO-ORX, and / or
Or Wherein n represents 1 to 5 and m represents 1 to 4
Is shown. A polyester polyol composition represented by the formula: 2. The polyester polyol composition according to claim 1, wherein the polyester polyol composition is obtained by reacting phenoxy alcohol at a ratio of 1 to 60% by weight based on the weight of the reaction mixture.