JPH0216334B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a novel polyether polyol composition (hereinafter simply referred to as polyether) for use in rigid polyurethane foams. A large number of polyethers for use in rigid polyurethane foams have been commercially available. Among these, polyethers made by adding alkylene oxide to sucrose, sorbitol, pentaerythritol, glycerin, ethylenediamine, etc., were common. However, these polyethers have poor compatibility with polyisocyanates and freons, and it often occurs that good foams cannot be obtained. Furthermore, the polyether obtained by adding alkylene oxide to m-tolylene diamine has very good compatibility with polyisocyanate, freon, etc., and the resulting foam has narrow cells, making it a distinctive polyether. However, this polyether had the drawbacks of extremely high viscosity, poor workability, and high raw material costs. On the other hand, o-tolylene diamine, which is produced as a by-product during the synthesis of tolylene diamine, has been utilized. As is clear from its structure, o-tolylene diamine has very similar properties to m-tolylene diamine. However, the addition of alkylene oxide to amino groups is completely different from m-tolylene diamine, and conventional polymerization methods do not uniformly polymerize due to steric hindrance between amino groups. Japanese Patent Publications No. 48-32597 and No. 51-8676 report a method for producing polyether from o-tolylene diamine. However, these have problems such as poor compatibility with Freon, high friability of the obtained foam, and high deterioration under humid heat and high temperature. In view of these drawbacks, the present inventors conducted various studies and arrived at the present invention. That is, the present invention comprises: "() 95 to 50% by weight of 2,3-diaminotoluene, 3,4 diaminotoluene, or a mixture thereof; () a non-amine polyhydroxy compound having a functional group number of more than 3; and/or
Or a method for producing a polyether polyol composition, characterized in that ethylene oxide and propylene oxide are added to a mixture consisting of 5 to 50% by weight of ethylenediamine so that the weight ratio of ethylene oxide and propylene oxide is 10/90 to 18/82. . ”. The o-tolylene diamine used in the present invention is 2,
It is 3-diaminotoluene, 3,4-diaminotoluene, or a mixture thereof, and usually a mixture with a purity of 96% by weight or more (hereinafter % indicates weight%) is used. In the present invention, non-amine polyhydroxy compounds such as ethylene glycol, propylene glycol,
Particularly effective are glycerin, pentaerythritol, sorbitol, sucrose, etc. alone or in a mixture of two or more, with the number of functional groups or the average number of functional groups exceeding 3, and/or ethylenediamine. The mixing ratio of () o-tolylene diamine and () the non-amine polyhydroxy compound and/or ethylene diamine (hereinafter referred to as "base" when collectively described) is 95/5 to 50/
50 weight ratio. Outside this range, the properties of the polyether obtained, its compatibility with Freon and polyisocyanate, its foaming properties, and the properties of the obtained foam deteriorate. In the present invention, ethylene oxide (hereinafter simply referred to as EO) and propylene oxide (hereinafter referred to as PO) are generally used as alkylene oxides (hereinafter, when these oxides are collectively described, they will be referred to as alkylene oxide).
The addition ratio of EO and PO is usually 10/90 to 18/82 by weight, and if this number exceeds 20/80, scorch tends to occur in the foam. Although the method and order of addition of the alkylene oxide are not limited, preferably, the alkylene oxide is added to the base material without a catalyst, and then the alkylene oxide is further added after the addition of a catalyst, and the hydroxyl group of the target polyether is added. Add enough amount to make the value 300-600. Regarding the addition of ethylene oxide, there are no particular restrictions on the addition position or addition method, but preferably it is added to the alkylene oxide to be added without a catalyst, and either block addition or random addition of EO and PO is performed. good. The polyisocyanate used when producing the polyurethane foam that is harder than the polyether of the present invention is a conventionally known polyisocyanate and is not limited, but for example, 2,
4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate with an isomer ratio (weight ratio) of 80/20 and 65/35,
Crude tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, conventionally known modified 4,4'-diphenylmethane diisocyanate modified with carbodiimide, crude diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, o- , m- or p-xylylene diisocyanate, hexamethylene diisocyanate, etc.
In addition, these dimers, trimers, and polyisocyanates partially modified with known low-molecular-weight polyols or known polyethers may be used alone or in combination. The amount of polyisocyanate used is such that NCO/H (active hydrogen) is 0.7 to 1.4 (equivalent ratio). As the foaming aid, a foaming catalyst, a foaming agent, and a foam stabilizer are used. As the blowing catalyst, conventionally known amine compounds, organic tin compounds, etc. are used, and as the blowing agent, water, trichloromonofluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane, monochlorodifluoromethane, methylene chloride, etc. are used. It will be done. As the foam stabilizer, a conventionally known silicone foam stabilizer is used. When a rigid polyurethane foam is obtained from the polyether of the present invention, foaming can be carried out by a one-shot method, a prepolymer method, or a semi-prepolymer method. The polyether of the present invention has a relatively low viscosity;
It has good compatibility with Freon and polyisocyanate, and the resulting foam has good scorch properties regardless of the hydroxyl value, low flyability, and good physical properties with little deterioration under humid heat or high temperatures. is obtained. The polyether of the present invention is useful as a raw material for rigid polyurethane foam in a wide range of fields such as electric refrigerators, freezers, cold storage boxes, cold/heat insulation materials for buildings, sound absorbing materials, synthetic wood, and structural materials. EXAMPLES Next, the present invention will be specifically explained using Examples, Reference Examples, and Comparative Examples, but the present invention is not limited by these in any way. Example 1 o-Tolylene diamine (2,3-tolylene diamine 51.9%, 3,4-tolylene diamine 45.5%,
2,4-tolylenediamine 0.4%, 2,6-tolylenediamine 2.2%) (hereinafter referred to as o-TDA) 80
Charge g and 20 g of pentaerythritol into an autoclave, raise the temperature to 70°C, add 21 g of PO and then 32 g of EO while stirring under pressure, and when the reaction pressure becomes constant, form hydroxylated flakes. After adding 1.42g of sodium, the reaction temperature was raised to 110℃, and 202g of PO was introduced. After the reaction was completed, the reaction solution temperature was lowered to 70℃, and after neutralization using 85% phosphoric acid, I did some filtration. The properties of the obtained polyether (A) are as follows: hydroxyl value 396, viscosity 6000 cps (25℃),
PH11.2, the theoretical addition amount of EO and PO was 12.5/87.5. Example 2 7000 g of o-TDA, 1500 g of glycerin, and 1500 g of sucrose used in Example 1 were placed in an autoclave, and after raising the temperature to 70°C, PO was added while stirring under pressure.
After feeding 9650g and adding 143g of flaky potassium hydroxide when the internal pressure became constant, EO was added.
Feed 4540g and further PO11750g at reaction temperature 110℃
After the reaction was completed, neutralization filtration was performed using 85% phosphoric acid. The properties of the obtained polyether (B) are as follows: hydroxyl value 468, viscosity 18000 cps (25℃) PH 10.2,
The theoretical addition amount of EO and PO was 17.5/82.5. Example 3 7000 g of o-TDA, 1500 g of glycerin, and 1500 g of sucrose used in Example 1 were placed in an autoclave, heated to 110°C and melted, and then 10,000 g of PO was introduced while stirring under pressure until the internal pressure became constant. After adding 167g of flaked potassium hydroxide,
16000g of PO, then 3750g of EO, after the reaction is complete
Neutralization and filtration were performed using 85% phosphoric acid. The properties of the obtained polyether (c) were a hydroxyl value of 425, a viscosity of 9000 cps (at 25°C), a pH of 11.8, and a theoretical addition amount of EO and PO of 12.6/87.4. Example 4 850 g of o-TDA used in Example 1 and 150 g of pentaerythritol were placed in an autoclave, and the
After raising the temperature to 110°C, 414g of EO and 265g of PO were added, and 17.0g of flaky potassium hydroxide was added.The reaction temperature was raised to 110°C, and 2370g of PO was added.
g was sent. After the reaction is complete, neutralize with 85% phosphoric acid.
Filtered. The properties of the obtained polyether (D) were a hydroxyl value of 405, a viscosity of 6,700 cps, a pH of 11.8, and a theoretical addition amount of EO and PO of about 16/84. Reference Examples 1-4, Comparative Examples 1-5 Table 1 shows the results of box foaming using the polyethers synthesized in Examples 1 and 3-5.

【table】

【table】

[Table] Reference Example 7, Comparative Example 4 Table 2 shows the spray foaming results using the Viking Mark 5A foaming machine using the polyether synthesized in Example 3. Materials and test methods that have already been explained have been omitted.

【table】

【table】

Claims (1)

[Claims] 1 ()2,3-diaminotoluene, 3,4-
Ethylene oxide and propylene oxide are added to a mixture consisting of 95 to 50% by weight of diaminotoluene or a mixture thereof, and () 5 to 50% by weight of a non-amine polyhydroxyl compound having a functional group of more than 3 and/or ethylenediamine. A method for producing a polyether polyol composition, which comprises adding the polyether polyol composition at a weight ratio of 10/90 to 18/82. 2. The method for producing a polyether polyol composition according to claim 1, wherein the non-amine polyhydroxyl compound is pentaerythritol, glycerin, or sucrose.