JPS6247207B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a polymer polyol used as a raw material for polyurethane, and in particular a method for producing a vinyl monomer in an unsaturated group-containing polyether polyol obtained by adding an alkylene oxide to a specific unsaturated bisphenol compound. The present invention relates to a method for producing a polymer polyol by polymerization. Polyurethanes such as polyurethane foams and polyurethane elastomers are obtained by reacting organic polyisocyanates and polyols. Various types of polyols are known, one of which is polymer polyols.
Polymer polyols are polyols having polymer chains of polymerizable vinyl monomers, in particular polyether polyols having polymer chains. These polymer polyols are produced by polymerizing vinyl monomers in polyether polyols that do not have unsaturated groups, by polymerizing vinyl monomers in polyether polyols containing unsaturated groups, and by polymerizing vinyl monomers in polyether ester polyols containing unsaturated groups. and various other methods are known. However, polymerization of vinyl monomers in polyether polyols without unsaturated groups does not result in sufficient grafting, and polymer polyols with ester groups have high hydrolyzability. The method of polymerizing vinyl monomers in ether polyols is believed to be preferred. Unsaturated group-containing polyether polyols are produced by adding alkylene oxide to an active hydrogen-containing compound (initiator) containing unsaturated groups, and by introducing unsaturated groups into polyether polyols. There is. In the latter case, for example, a polyether polyol having an unsaturated group at a terminal is produced by reacting a polyether polyol with allyl chloride or allyl glycidyl ether. However, compared to the former method, this method has problems such as complicated production and changes in the properties of the polyether polyol, such as the hydroxyl value. The method of adding alkylene oxide to an initiator having an unsaturated group to produce a polyether polyol having an unsaturated group is almost the same as the method of adding an alkylene oxide to an initiator having no unsaturated group. It has the characteristics that it is easy to control the amount of unsaturated groups in the polyether polyol by using an unsaturated group-containing initiator alone or a mixture of it and other conventional initiators as an initiator. However, if the unsaturated group-containing initiator is easily polymerized, during the alkylene oxide addition reaction, the unsaturated group-containing initiator and the unsaturated group-containing polyether polyol to which the alkylene oxide is added may be homopolymerized. There's a lot of fear. Therefore, the unsaturated group of the unsaturated group-containing initiator is preferably one that is difficult to polymerize by itself, and is also preferably one that is easily copolymerized with a vinyl monomer during the production of a polymer polyol. In addition to the polymerizable unsaturated group, the unsaturated group-containing initiator requires active hydrogen to which at least two alkylene oxides can be added, and this active hydrogen is hydrogen such as a hydroxyl group or an amino group. The present inventor conducted various research studies in order to find a compound that has at least two hydroxyl groups and has an unsaturated double bond that is difficult to polymerize by itself and is easy to copolymerize with other vinyl monomers. . As a result, an unsaturated bisphenol compound represented by the following formula was discovered. This compound is difficult to homopolymerize, and unsaturated polyether diol in which alkylene oxide is added to the hydroxyl group is also difficult to homopolymerize. Therefore, this unsaturated group is stable and difficult to change during the alkylene oxide addition reaction. On the other hand, this unsaturated group is easily copolymerized with other polymerizable vinyl monomers. The present invention is a method for producing an unsaturated group-containing polyether polyol using this unsaturated bisphenol compound as an initiator, and producing a polymer polyol from this, that is, the formula: An unsaturated bisphenol compound represented by or at least two unsaturated bisphenol compounds
A method for producing a polymer polyol, which comprises polymerizing a polymerizable vinyl monomer in an unsaturated group-containing polyether polyol obtained by adding an alkylene oxide to a mixture with an active hydrogen-containing compound having active hydrogens. be. The above-mentioned unsaturated bisphenol compound is a known commercially available compound and can be easily obtained. The reaction of adding alkylene oxide to this compound can be carried out under the same conditions as the reaction of adding alkylene oxide to a common active hydrogen-containing compound such as a polyhydric alcohol. That is, the reaction can be carried out using an alkali metal hydroxide or other catalyst under normal pressure or increased pressure at a temperature of 80 to 150°C. Of course, this addition reaction is not limited to these conditions. The addition reaction of alkylene oxide to the unsaturated group-containing bisphenol compound may be carried out in the presence of another active hydrogen-containing compound. For example, an unsaturated group-containing polyether polyol mixture can be produced by adding an alkylene oxide to a mixture with polyhydric alcohols, amines, or other active hydrogen-containing compounds having at least two active hydrogens. The unsaturated group-containing polyether diol obtained by adding alkylene oxide to the unsaturated group-containing bisphenol compound is also mixed with an active hydrogen compound, which is a raw material for other polyurethanes, to create an unsaturated group-containing polyether polyol mixture. You can also use it as For example, there are active hydrogen compounds such as polyether polyols and polyester polyols having other unsaturated groups, polyether polyols and polyester polyols having no unsaturated groups, and other polyols. Furthermore, in the case of alkylene oxide addition to the unsaturated group-containing bisphenol compound or in the unsaturated group-containing polyether diol, other compounds may be present. for example,
These include inert solvents and fillers. The type of alkylene oxide is not particularly limited, but preferably alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, epichlorohydrin, and butylene oxide. Particularly preferred is propylene oxide alone or a combination of propylene oxide and ethylene oxide. In the case of a combination, a mixture of both may be reacted, or both may be reacted sequentially. at least two to which an alkylene oxide is added by mixing with an unsaturated group-containing bisphenol compound;
As the active hydrogen-containing compound having active hydrogen, active hydrogen-containing compounds used as initiators in the production of ordinary polyether polyols, ie, polyhydric alcohols, polyhydric phenols, and amines are preferred. Particularly preferred are polyhydric alcohols, such as dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols such as glycerin, hexanetriol, and trimethylolpropane, and tetrahydric or higher alcohols such as pentaerythritol, diglycerin, sorbitol, and dextrose. These include polyhydric alcohols. In the present invention, the type of polymerizable vinyl monomer to be polymerized in the unsaturated group-containing polyether diol alone or in the polyol mixture containing the same is not particularly limited. For example, acrylonitrile, acrylamide, styrene, acrylic ester,
There are methacrylic acid esters, olefins, vinyl acetate, maleic esters, fumaric acid esters, vinyl halides, and others, and these can be polymerized by mixing two or more types, or by polymerizing two or more types sequentially. You can also do it. Particularly preferably,
Acrylonitrile, styrene, vinyl acetate, methyl methacrylate and mixtures thereof.
Polymerization of these polymerizable vinyl monomers in polyols can be carried out under the same conditions as in conventional polymerizations in unsaturated group-containing polyols. That is,
50 in the presence of peroxide or other radical polymerization catalyst
Polymerization is carried out by mixing or dissolving a polymerizable vinyl monomer at a temperature of ~150°C. As the polymerization catalyst, in addition to benzoyl peroxide, di-t-butyl peroxide, azobisisobutyronitrile, persulfate, diisopropyl peroxydicarbonate, and other radical catalysts, metal compounds such as cerium compounds can also be used. The hydroxyl value of the polymer polyol of the present invention is not particularly limited, but is preferably about 16 to 150. This polymer polyol is suitable as a raw material for high modulus polyurethane foams and polyurethane elastomers, but can also be used as a raw material for other polyurethanes. EXAMPLES The present invention will be specifically explained below using Examples and Comparative Examples, but the present invention is not limited to these Examples. Reference example 1 (Production of unsaturated group-containing polyether polyol) Unsaturated bisphenol compound Mix 270g and 90g of glycerin and add caustic potassium.
After mixing 14.0 g, the temperature was raised to 120°C and dehydration was performed under reduced pressure. Then propylene oxide
3500 g was introduced over 5.5 hours. The reaction proceeded while the autoclave internal pressure was maintained at 2.9 Kg/cm ² G. Thereafter, it was aged at 120°C for 2 hours. Next, 700g of ethylene oxide was heated to 120℃.
After being introduced for 2 hours, it was aged for 30 minutes. After the reaction was completed, 150g of magnesium silicate was added and the temperature was heated to 110°C.
The mixture was stirred for 3.5 hours to adsorb the catalyst, filtered and dried to obtain a polyol. The OH value of the obtained product is 35.1
It was mgKOH/g. Reference example 2 (Production of unsaturated group-containing polyether polyol) Unsaturated bisphenol compound After mixing 240 g of polyol with a molecular weight of 1000 by adding PO to propylene glycol and 12 g of caustic potassium, the temperature was raised to 110° C. and dehydration was performed under reduced pressure. Then propylene oxide
3150 g was introduced over 3.8 hours. Further 110℃
Aging was carried out for 2 hours. Subsequently, 850 g of ethylene oxide was introduced at 120° C. for 2 hours, and the mixture was aged for 30 minutes. The OH value of the product obtained through purification is 28.2 mg.
It was KOH/g. Examples 1 to 7, Comparative Examples 1 to 2 (Manufacture of polymer polyol) A method for manufacturing a polymer polyol composition according to the present invention and its manufacturing results will be described. A predetermined amount of the unsaturated group-containing polyether polyols or normal polyoxyalkylene polyols produced in Reference Examples -1 and -2 shown in Table 1 was charged into the autoclave No. 5 in advance, and a reduced pressure/nitrogen purging operation was carried out. After repeating this at a specified temperature, as shown in Table 1, a mixture of the remaining unsaturated group-containing polyol or normal polyoxyalkylene polyol, a monomer having a polymerizable unsaturated group, and a polymerization initiator was added to the specified mixture. was introduced into the autoclave while stirring at a speed of . Unreacted polymerizable unsaturated monomers were removed under reduced pressure to obtain the desired polymer polyol. As a comparison, when only a normal polyoxyalkylene polyol was used, when styrene was used as a monomer, no homogeneous dispersion was obtained due to separation. On the other hand, according to the present invention, an extremely uniform and fine dispersion was obtained even when styrene was used as a monomer.

【table】

[Table] Reference Examples 3 to 6, Comparative Example 1 of Reference Example (High elastic foam foaming test) High elastic foam molds using the polymer polyols produced in Examples 1, 2, 5, and 6 of Table 1. Foaming was performed. For comparison, the results of foaming using polyoxypropylene ethylene triol (polyol A) with a molecular weight of 5000 will also be described. Polymer polyol (Polyol A in the case of Comparative Example-1) 160g, Polyol A 240g, Silicone
L5305 4.4g, Dabco33LV2.4g, water 12g, TDI
-80/PAPI-135 (chemical addition, crude phenylene diisocyanate) = 80/20 mixed isocyanate was mixed to give an index of 105, and the temperature was quickly adjusted to 50℃.
It was put into a mold of mm x 400 mm x 100 mm, and after being left at room temperature for 10 minutes, the mold form was taken out. The physical properties of the foam are shown in Table 2. Compared to Comparative Example-1 of Reference Example, Reference Examples 3, 4,
It can be seen that the physical properties of the forms 5 and 6 are particularly excellent for ILD.

[Table] Reference Examples 7 to 9, Comparative Example 2 of Reference Example The polymer polyols produced in Examples 3, 4, and 7 in Table 1 were used to mold elastomers. For comparison, the results of molding using polyoxypropylene ethylene diol (polyol B) with a molecular weight of 4000 will also be described. 64 g of polymer polyol (Polyol B in the case of Comparative Example-2 of Reference Example), 97 g of Polyol B, 1.4 butanediol
39g, Dabco33LV1.4g, dibutyltin dilaurate 0.24g and Mondur E-451 (Mobay) were mixed to give an index of 102, and quickly
Pour into an aluminum flat mold heated to 60°C.
After 3 minutes at room temperature, the elastomer molded article was taken out. The physical properties are shown in Table 3. It can be seen that the elastomer properties of Reference Examples 7, 8, and 9 are superior to that of Comparative Example 2, especially in terms of bending modulus.

【table】

Claims (1)

[Claims] 1 formula An unsaturated bisphenol compound represented by or at least two unsaturated bisphenol compounds
A method for producing a polymer polyol, which comprises polymerizing a polymerizable vinyl monomer in an unsaturated group-containing polyether polyol obtained by adding an alkylene oxide to a mixture with an active hydrogen-containing compound having active hydrogens. 2. The method according to claim 1, wherein the active hydrogen-containing compound is a polyhydric alcohol. 3. The method according to claim 1, wherein the alkylene oxide is propylene oxide alone or a combination of propylene oxide and ethylene oxide. 4 The polymerizable vinyl monomer is acrylonitrile,
Claim 1 characterized in that it is styrene, methyl methacrylate and mixtures thereof.
the method of.