JPH0144205B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polyol containing an aldehyde condensation polymer component, and particularly relates to a method for producing an aldehyde condensation polymer component by reacting an aldehyde condensation forming raw material in a polyol containing a specific addition polymer component. The present invention relates to a method for producing a polymer component-containing polyol containing a polymer. Conventionally, polyols called so-called polymer polyols or graft polyols have been known as polyols for polyurethane raw materials. This type of polyol can be produced by polymerizing addition-polymerizable monomers such as acrylonitrile or styrene in a substantially saturated or unsaturated polyol, or by adding addition polymers or other polymers into fine particles in a polyol. It can be obtained by a method of dispersion. The polyol obtained by the former method is thought to be one in which the addition polymer is grafted onto the molecular chain of the polyol or simply dispersed in the form of fine particles, and is a solid, fine particulate addition polymer with relatively high dispersion stability. It is a liquid dispersion in which components are dispersed. In addition, some of those obtained using unsaturated polyols are uniformly transparent and do not contain solid particulate components. Regarding this type of so-called polymer polyol, for example,
Publication No. 24737, Special Publication No. 3437, Special Publication No. 1973
-22108 Publication, Special Publication No. 46-20508, Special Publication Sho
They are described in Japanese Patent Publication No. 51-37228, Japanese Patent Publication No. 51-40914, Japanese Patent Publication No. 40915-1982, Japanese Patent Publication No. 3439-1982, Japanese Patent Publication No. 13834-1983, and other publications. Within the latter method of dispersing preformed polymers in polyols, it is also known to graft the polymers onto polyols. Examples of this type of polyol include, for example, Japanese Patent Publication No. 44-8230, Japanese Patent Publication No. 47-47597, Japanese Patent Publication No. 40788-1988, Japanese Patent Publication No. 55-40788,
There are publications such as Publication No. 135156. These so-called polymer polyols are suitable as raw materials for highly elastic polyurethane foams. However, these polymer polyols also have unresolved problems. For example, polymer polyols are not effective in making polyurethane flame retardant, but rather reduce the flame retardancy and make polyurethane more flammable. Hereinafter, the polyol containing the above addition polymer will be referred to as a polymer polyol, and the addition polymer grafted or simply dispersed or dissolved in this polymer polyol will be referred to as an addition polymer component. On the other hand, polyols in which an aldehyde condensation polymer is formed with a polyol and the aldehyde condensation polymer is dispersed in the polyol are known, such as those disclosed in JP-A-50-15832, JP-A-51-117793, It is described in Japanese Patent Application Laid-Open No. 51-122193. According to these publications, a polymer-dispersed polyol similar to the above polymer polyol can be produced by oligopolycondensing or polycondensing melamine, urea, or other compounds capable of forming aminoplasts with aldehydes in a polyol. In this case, the polyol is characterized in that it does not participate in this polycondensation reaction and merely acts as a reaction medium. It is said that the polyol in which the aldehyde condensation polymer referred to in the present invention is dispersed has better dispersion stability than that in which a pre-prepared aldehyde condensation polymer is dispersed in a polyol. However, the above-mentioned Japanese Patent Application Laid-Open No. 51-122193
As can be seen from the description in the publication, its dispersion stability was not necessarily sufficient and was inferior to the dispersion stability of the polymer polyol, and sedimentation separation was likely to occur. In addition, its characteristics include increasing the flame retardancy of the polyurethane obtained by using it, but it cannot match the above-mentioned polymer polyols in some performances such as the effect of increasing the elasticity of polyurethane foam. It was hot. In the present invention, we first investigated the improvement of the dispersion stability of polyols containing the above-mentioned aldehyde condensation polymer component. The reason why the addition polymer component in the polymer polyol has good dispersion stability is thought to be because some to all of the addition polymer component is grafted onto the molecular chain of the polyol as described above. This is because this grafting seems to occur even if the polyol is a substantially saturated polyol. Of course, this is not the only problem; the particle size of the addition polymer is small. Another possible reason is that the addition polymer has a high affinity with the polyol. On the other hand, even if the aldehyde condensation polymer is formed in a polyol, the bond between the polyol and the aldehyde condensation polymer is No reaction occurs; the polyol merely serves as an inert medium for the reaction of aldehyde condensation polymer formation. Moreover, the affinity between the polyol and the aldehyde condensation polymer is not sufficient, and it is also not easy to freely adjust the particle size of the aldehyde condensation polymer. Therefore, the present inventors considered actively bonding an aldehyde condensation polymer and a polyol, thereby improving the dispersion stability of the aldehyde condensation polymer in the polyol. Therefore, it is necessary to introduce a reactive moiety (referred to as a reactive site as described below) into the polyol that can condense with aldehydes, but it is not easy to introduce such a reactive site into a normal polyol. Therefore, as a result of various research studies on this point, the inventor of the present invention found that it is possible to bond an aldehyde condensation polymer to the addition polymerization polymer in the polymer polyol, thereby indirectly bonding the polyol and the aldehyde condensation polymer. It was discovered that the purpose could be achieved by As mentioned above, it is thought that the addition polymer component in the polymer polyol is not necessarily grafted onto the polyol, but even if it is not grafted, the addition polymer component may have good properties. By introducing dispersion stability into the aldehyde condensation polymer component, the dispersion stability of the aldehyde condensation polymer component is improved.
What is more advantageous is that not only the dispersion stability of the polyol containing the aldehyde condensation polymer component is improved, but also the polyurethane foam obtained by using it can be improved by increasing the proportion of the addition polymer component. Physical properties such as elasticity are improved.
Conversely, when compared with conventional polymer polyols, polymer polyols with excellent flame retardancy can be obtained. The present invention relates to a method for producing the above polyol, that is, a method for producing a polyol containing an aldehyde condensation polymer component by reacting an aldehyde condensation forming raw material in a polyol.
At least a portion of the cyan groups of the polyol containing the addition polymer component having cyan groups are converted into amidoxime and/or hydroxam groups, and aldehyde is converted into the polyol containing the addition polymer component having cyan groups. This is a method for producing a polymer component-containing polyol containing an aldehyde condensation polymer component, which is characterized by reacting condensation forming raw materials. The polyol containing an addition polymer component having a cyan group in the present invention is equivalent to or similar to the polymer polyol described above, but requires at least a cyan group in the addition polymer component. For example, a polymerizable monomer having a cyan group and a polymerizable α,β-unsaturated group such as acrylonitrile or 2,4-dicyanobutene-1, or a substantially saturated polyol or a polymerizable unsaturated A method of polymerizing in a polyol having saturated groups, a method of dispersing a single or copolymer of these polymerizable monomers in a polyol, or a method of dispersing the preformed polymer in a polyol and then grafting the polymer to the polyol. An addition polymer component-containing polyol produced by a method such as that of In particular, a method in which a polymerizable monomer is polymerized in a substantially saturated or unsaturated polyol is preferred from the viewpoint of dispersion stability of the polymer component. Examples of the polymerizable monomer having a cyan group include, but are not limited to, acrylonitrile, methacrylonitrile, 2,4-dicyanobutene-1, and cyanoprene. A particularly preferred polymerizable monomer having a cyan group is acrylonitrile. At least one polymerizable monomer having a cyan group can be used alone to form an addition polymer, but at least one copolymerizable monomer not having a cyan group can be used to form a copolymer. You can also do that. Examples of copolymerizable monomers include, but are not limited to, the following compounds. Styrenic monomers: styrene, divinylbenzene. Acrylic monomers: methyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate. Vinyl acetate monomer: Vinyl acetate. Diene monomers: butadiene, isoprene,
Chloroprene. The proportion of the polymerizable monomer having a cyan group and other polymerizable monomers is not particularly limited, but the proportion of the polymerizable monomer having a cyan group in the total polymerizable monomers is 1 to 100 mol%, especially 5
Approximately 100% by mole is appropriate. As the polyol that can be used as a raw material for a polyol containing an addition polymer component having a cyan group, various polyols described in the above-mentioned known examples can be used. Substantially saturated polyols include, for example, polyether polyols, polyester polyols, polyether ester polyols,
Examples include hydroxyl group-containing hydrocarbon polymers and polycarbonate polyols. In particular, polyether polyols obtained by adding epoxides or other cyclic ether compounds to various initiators are preferred. Among these, polyether polyols obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an initiator such as a polyhydric alcohol, a polyphenol, an alkanolamine, or a polyamine are preferred. Two or more types of initiators and epoxides can be used in combination. When two or more epoxides are used in combination, for example, when ethylene oxide and propylene oxide are used together, they can be added to the initiator as a mixture, or they can be added sequentially. Furthermore, polyols having unsaturated groups copolymerizable with polymerizable monomers are also preferred raw materials. For example, unsaturated polyester polyol obtained by reacting a polyol with an unsaturated polycarboxylic acid, unsaturated polyether ester polyol obtained by further adding an epoxide to an ester of a polyol and an unsaturated polycarboxylic acid, Unsaturated polyether polyols obtained by adding a saturated epoxide and other epoxides, polyether polyols, unsaturated polyhydric alcohols, and urethanized unsaturated polyols obtained by reacting polyisocyanates can be used. The proportion of the addition polymer component in the polyol containing the addition polymer component having cyan groups is not particularly limited. When the main objective is to stabilize the dispersion of the aldehyde condensation polymer component described below, a sufficient effect can be obtained even if the proportion of the addition polymer component is extremely small.
Further, if the purpose is to further add the effects of conventional polymer polyols, the proportion of the addition polymer component can be set to be about the same as that of conventional polymer polyols. That is, for example, when the purpose is to increase the elasticity of polyurethane foam, the proportion of the addition polymer component can be increased. The preferred proportion of the addition polymer component in the polyol containing the addition polymer component having cyan groups is from 0.1 to 40% by weight, especially from 1 to 30% by weight. In addition, after or before converting the cyanide groups described below into amidoxime groups and/or hydroxam groups, a compound or substance inactive against this conversion is added to the polyol containing this addition polymer component. You can leave it there. For example, various polyols may be added, such as polyether polyols, and polyols containing addition polymer components without cyan groups may be added. Hydroxylamine is used to convert the cyan groups of polyols containing addition polymer components having cyan groups into amidoxime and/or hydroxam groups. When an addition polymer component having a cyan group is represented by A--CN, an amidoxime group is generated by the following reaction with hydroxylamine. This amidoxime group becomes a hydroxyme group due to the presence of water. Of course, the hydroxylamine used is
It can be used by dissolving it in water or in an acid aqueous solution such as hydrochloric acid water. The reaction usually occurs under heating and first amidoxime groups are produced, but due to the presence of water, a portion of these usually becomes hydroxam groups. Generally, amidoxime groups are rarely all hydroxam groups due to the presence of water, and in many cases both are present. The amount of hydroxylamine relative to the cyan groups may be less than or equal to more than the equivalent. Even if the amount of hydroxylamine is excessive relative to the cyan groups, it is unlikely that all of the cyan groups will react with the hydroxylamine. In the present invention, the amount of cyanide groups reacted may be extremely small. Although not particularly limited, it is sufficient that the amount of hydroxylamine is 0.01 equivalent or more relative to the cyan group, and about 0.1 to 1.5 equivalent is particularly suitable. Both the generated amidoxime and hydroxam groups react with aldehydes. Therefore, when an aldehyde condensation-forming raw material is reacted in a polyol containing an addition polymer component having an amidoxime group and/or a hydroxam group, the resulting aldehyde condensation polymer grafts onto the addition polymer, and forms a polymer with which both are bonded. It becomes a combination. Therefore, by using a polyol containing an addition polymer component with good dispersion stability, the dispersion stability of the aldehyde condensation polymer component is also improved. In particular, when the addition polymer component is grafted onto the polyol, the aldehyde condensation polymer component is also indirectly grafted onto the polyol, resulting in high dispersion stability. It is considered that the addition polymer component-containing polyol obtained by addition polymerizing a polymerizable monomer in a polyol having an unsaturated group has the addition polymer component grafted onto the polyol. It has also been speculated that in polyols containing addition polymer components obtained by addition polymerizing a polymerizable monomer containing at least acrylonitrile in a polyether polyol, the addition polymer component is grafted onto the polyol.
Therefore, in the present invention, it is preferable to use a polyol containing an addition polymer component, in which these addition polymer components are considered to be grafted onto the polyol. The aldehyde condensation forming raw materials for forming the aldehyde condensation polymer component in polyol are combinations of aldehydes and compounds that can be polycondensed with aldehydes (hereinafter referred to as condensable compounds), and combinations of polycondensable compounds and aldehydes. or a combination of the initial condensate and a polycondensable compound and/or an aldehyde. A polycondensable compound is a compound that has at least two reactive sites that can be condensed with aldehydes, and the reactive sites include, for example, the ortho and para positions of aromatic nuclei to which phenolic hydroxyl groups and amino groups are directly bonded, Examples include hydrogen atoms bonded to nitrogen atoms such as amino groups and amide groups. Examples of polycondensable compounds include, but are not limited to, the following compounds. (1) Phenol, p-alkylphenol, cresol, xylenol, bisphenol A, resorcinol, dihydroxydiphenylmethane, and other phenols. (2) Aniline, p-alkylaniline, N-substituted alkylaniline, diaminobenzene, diaminodiphenylmethane, and other aromatic amines. (3) Urea, thiourea, N-substituted urea, guanidine, N-substituted guanidine, dicyandiamide,
Other amino group-containing compounds. (4) Melamine, N-substituted melamine, benzoguanamine, acetoguanamine, N-substituted guanamine, and other amino-s-triazine compounds. Two or more of these compounds can be used in combination, and they can also be used in combination with monoamines, alkanolamines, and other compounds having one reactive site. In addition, initial condensates of these and the following aldehydes can be used. The initial condensate may not only be a conventional initial condensate such as novolak, but also a single compound such as methylol urea or hexakismethoxymethylmelamine. These initial condensates can of course be used alone,
It can also be used in combination with polycondensable compounds and aldehydes. As the aldehyde, a compound having an aldehyde group or a compound capable of producing an aldehyde group can be used. Examples include formaldehyde, paraformaldehyde, glyoxal, acetaldehyde, paraacetaldehyde, hexamethylenetetramine, and the like. Particularly preferred aldehydes are aliphatic aldehydes having 6 or less carbon atoms and derivatives thereof, and among these, formaldehyde and paraformaldehyde are most preferred. These can be used by being dissolved in a solvent, and in particular, an aqueous solution can be used. The reaction ratio between the polycondensable compound and the aldehyde, the reaction temperature, and other reaction conditions are not particularly limited.
However, usually a ratio of 0.3 to 3.0 mol, particularly 0.8 to 2.5 mol of aldehyde is employed per mol of polymerizable compound. A particularly preferred proportion is 0.9 to 1.5 mol. The reaction temperature is usually above room temperature, especially 40~
It is carried out at 200℃. In order to obtain a good polymer, it is preferable to carry out the reaction at a relatively low temperature and the latter half at a relatively high temperature. For example, the first half is carried out at a temperature of 80°C or lower, particularly preferably about 60°C or lower, and the second half is carried out at a temperature of at least about 10°C or higher, particularly preferably about 70°C or higher. This is because it is preferable to carry out the dehydration reaction, which is the latter stage of the reaction, more fully. Further, the reaction is carried out under neutral to acidic conditions, but it is also preferable to carry out the reaction under alkaline conditions in the first half and neutral to acidic conditions in the second half.
It is preferable to carry out dehydration treatment after the completion of the reaction or together with the latter half of the reaction. This is done to remove water used as a solvent for aldehydes and water produced by the reaction. In particular, the latter half of the reaction is preferably carried out sufficiently until no hydroxyl groups (for example, methylol groups) remain due to aldehydes, and the dehydration treatment is preferably carried out at a temperature that allows the dehydration reaction to proceed further. Furthermore, a treatment for blocking methylol groups and the like as described in the above-mentioned publication can also be performed. In this way, it is preferable to produce an aldehyde condensation polymer that is substantially free of hydroxyl groups caused by aldehydes, and the above reaction conditions are also used for the same purpose when reacting the initial condensate in a polyol. It is preferable that The polymer component-containing polyol obtained by the present invention is usually a viscous dispersion in which a solid polymer component is stably dispersed. A part of the polymer consisting of an aldehyde condensation polymer and an addition polymer may be dissolved in the polyol. Furthermore, a product in which most of the polymer components are dissolved in the polyol may be produced. Particularly preferred is a dispersion in which finely divided solid polymers are stably dispersed. The proportion of the polymer component in this polymer component-containing polyol is not particularly limited, but is 1 to 50% by weight, particularly 5% by weight.
~30% by weight is preferred. The ratio of the addition polymer component and the aldehyde condensation polymer component in this polymer component is also not particularly limited, but the former is
0.1-90% by weight, especially 1-60 parts by weight, the latter being 10-90% by weight
99.9% by weight, especially 40-99% by weight is suitable. In addition, if the purpose is to impart flame retardancy to the polyol containing an addition polymer component without reducing its properties, the proportion of the addition polymer component should be at least 10% by weight or more of the total polymer component. Preferably, it is a component. The viscosity of this polymer component is 2 at 25°C.
It is preferably less than 10,000 centipoise. However, in cases where the polyol is later diluted with other polyols and used as a raw material for polyurethane, a polyurethane with a higher viscosity may be used. The aldehyde condensation polymer in the polymer component-containing polyol is a linear or network polymer with a relatively high molecular weight, similar to ordinary aldehyde condensation polymers. Normally, this polymer does not melt when heated, but it may become molten during thermal decomposition.
This aldehyde condensation polymer is preferably one that has been sufficiently dehydrated as described above and has few, particularly substantially no, acid group-containing groups such as methylol groups.
When the aldehyde condensation polymer does not have a hydroxyl group, the hydroxyl value of the polyol containing the aldehyde condensation polymer component is lower than the hydroxyl value of the original polyol in proportion to the amount of the aldehyde condensation polymer present. The greater the number of hydroxyl groups in the aldehyde condensation polymer, the lower the rate of decrease, and when the hydroxyl value of the original polyol matches the hydroxyl value of the aldehyde condensation polymer, the hydroxyl value no longer decreases. In the present invention, the hydroxyl value of the aldehyde condensation polymer component-containing polyol is preferably at most 1.2 times, particularly at most the same as, the hydroxyl value of the original polyol. As an exception, there are cases where a compound having a hydroxyl group itself, such as a phenol, is used as a polycondensable compound, and in this case, a polyol with a hydroxyl value higher than that of the original polyol may be produced. However, even in this case, it is preferable that the hydroxyl value of the aldehyde condensation polymer component-containing polyol is 1.2 times or less, particularly the same or less, as the original polyol, as described above. In fact, the hydroxyl value of the aldehyde condensation polymer component-containing polyol obtained by sufficient dehydration using the above reaction conditions is essentially the same as the hydroxyl value of the original polyol when calculated by subtracting the aldehyde condensation polymer component. match exactly. Therefore, it is presumed that such an aldehyde condensation polymer component does not substantially contain hydroxyl groups resulting from aldehydes. As mentioned above, the dispersion stability of the polymer component-containing polyol obtained by the present invention is better than that of conventional aldehyde condensation type polymer component-containing polyols. In particular, when this type of polymer component-containing polyol is allowed to stand still, it is preferred that the polymer component does not substantially settle for at least two weeks, preferably at least one month. This condition is fully satisfied. Also,
In order to measure dispersion stability in a shorter period of time, it can be estimated from the amount of polymer that precipitates by diluting it and centrifuging it for a certain period of time. In the examples below, a polymer component-containing polyol was diluted with methanol for 10 min.
Dilute it twice and centrifuge at 3000 rpm for 60 minutes.
The dispersion stability is compared based on the percentage of sediment recovered. The ratio of this precipitate to the total aldehyde condensation polymer components is preferably 20% by weight or less, more preferably 5% by weight or less. The polymer component-containing polyol containing an addition polymer component and an aldehyde condensation polymer component obtained by the present invention is particularly suitable as a raw material for producing a polyurethane polymer. That is, by reacting this polymer component-containing polyol alone or together with other polyols or polyamines with a polyisocyanate compound having two or more isocyanate groups, a polyurethane-based, polyurethaneurea-based, or polyisocyanurate-based polymer is produced. can be manufactured. Other polyols and polyamines that can be used in combination include polyether polyols obtained by adding epoxides to various initiators,
Polyester polyols, polyether ester polyols, hydroxyl group-containing hydrocarbon polymers, polyhydric alcohols, alkanolamines, aromatic cyamines, and other polyols used as main raw materials for polyurethane, polyols used as crosslinking agents or chain extenders, etc. There are polyamines, etc. By using the aldehyde condensation polymer component-containing polyol obtained by the present invention,
Flame retardancy can be imparted to polyurethane polymers. Moreover, it is also effective in improving hardness and modulus. In particular, the aldehyde condensation polymer component-containing polyol obtained by the present invention is most suitable as a raw material for polyurethane foam. The production of polyurethane foam requires a catalyst and a blowing agent in addition to the main raw materials polyol and polyisocyanate compound, and in many cases a foam stabilizer is also used. As the polyol, the aforementioned polyol containing the aldehyde condensation polymer component or a polyol mixture containing the same is used. Suitable blowing agents include water, low-boiling halogenated hydrocarbons, and inert gases such as air. Examples of low-boiling halogenated hydrocarbons include trichlorofluoromethane, dichlorodifluoromethane, and methylene chloride. As the catalyst, a tertiary amine catalyst or an organometallic compound catalyst such as an organic tin compound is generally used. As the foam stabilizer, organosilicon compounds such as polyoxyalkylene chain-containing silanes and poly(dialkylsilanes) are used. Other optional additives include fillers, reinforcing agents, stabilizers, colorants, flame retardants, mold release agents,
These include foam-breaking agents, cross-linking agents, and chain extenders. The catalyst and these other additives are non-foamed polyurethane,
For example, it is also used in elastomers, sealants, and paints. Other main raw materials for polyurethane are polyisocyanate compounds. As the polyisocyanate compound, aromatic, aliphatic, alicyclic, heterocyclic, etc. compounds having at least two isocyanate groups can be used alone or in combination. Preference is given to using isocyanate compounds. Specific polyisocyanate compounds include, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate, xylylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
The polyisocyanate compound can also be used as a modified polyisocyanate compound modified by various methods or compounds, and can also be used as a blocked isocyanate compound blocked with various compounds. The method for producing polyurethane using these raw materials is not particularly limited, and methods such as the one-shot method, prepolymer method, quasi-prepolymer method, and RIM method can be used. EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples. Example 1 Polyols used in the examples of the present invention were produced by the method described below. In addition, below, % is weight%, part is weight part, viscosity is 25
It represents the viscosity at °C. Polyol A: 475 parts of polyoxypropylene ethylene triol having a molecular weight of 3000 and having 15% ethylene oxide added to the terminals was charged into a reactor and heated to 120°C. A mixed monomer and initiator solution prepared by dissolving 2.5 parts of α,α'-azobisisobutyronitrile in 25 parts of acrylonitrile was fed into the reactor over a period of 5 hours. After completion of the supply, aging was carried out for 30 minutes to complete the reaction, and unreacted monomers were degassed under reduced pressure. A 50% aqueous solution of 16 parts of hydroxylamine hydrochloride was added to the obtained polyol composition and reacted at 98°C for 3 hours. Water in the reaction system was removed under reduced pressure to obtain a brown polyol composition. Polyol B: 425 parts of polyoxypropylene ethylene triol having a molecular weight of 5000 and having 15% ethylene oxide added to the terminals was charged into a reactor and heated to 100°C. A mixed monomer initiator solution containing 2.5 parts of α,α'-azobisisobutyronitrile dissolved in 50 parts of acrylonitrile and 25 parts of styrene was fed into the reactor over a period of 5 hours. After completion of the supply, aging was carried out for 30 minutes to complete the reaction, and unreacted monomers were degassed under reduced pressure. Hydroxylamine hydrochloride is added to the resulting polyol composition.
22 parts of 50% aqueous solution was added and reacted at 80°C for 6 hours. Water in the reaction system was removed under reduced pressure to obtain a yellow-white polyol composition. Polyol C: 448 parts of polyoxypropylene ethylene triol with a molecular weight of 5000 and 15% ethylene oxide added to the terminal, 1 part of 2-hydroxyethyl methacrylate, and 1.5 parts of tolylene diisocyanate were mixed well, 2 parts of triethylamine was added, and the mixture was heated at 50°C. Allowed time to react. After the reaction was completed, unboiled components were degassed under reduced pressure. The obtained modified polyol was heated to 120°C.
40 parts of acrinonitrile, 2,4-dicyano-1-
A mixed solution of monomer and initiator prepared by dissolving 2.5 parts of α,α'-azobisisobutyronitrile in 10 parts of butene was fed into the reactor over 5 hours. 30 after supply ends
After completing the reaction by aging for a minute, unreacted monomers were degassed under reduced pressure. A 50% aqueous solution of 33 parts of hydroxylamine hydrochloric acid was added to the obtained polyol composition, and the mixture was reacted at 98°C for 3 hours. Water in the reaction system was removed under reduced pressure to obtain a brown polyol composition. Charge 350 parts of the above polyol A, 150 parts of urea, and 320 parts of 35% formaldehyde aqueous solution into a reactor and
React at ℃ for 3 hours. Next, the temperature was raised to 100°C and the mixture was reacted for an additional 3 hours, followed by dehydration under reduced pressure at 120°C to obtain a yellowish white polyol composition. The hydroxyl value is
35.4, and the viscosity was 3300 cps. It was found that the resin component in this polyol composition was stably dispersed without any separation for more than two months. The obtained polyol composition was diluted 10 times with methanol and centrifuged at 3000 rpm for 1 hour using a centrifuge. As a result, the resin content recovered was 2 times the resin content contained in the polyol composition. It was %. Comparative Example 1 350 parts of polyol composition before hydroxylamine treatment with polyol A obtained in Example 1, urea
150 parts and 320 parts of a 35% formaldehyde aqueous solution were charged into a reactor and reacted at 45°C for 3 hours. then
After raising the temperature to 100°C and reacting for an additional 3 hours, dehydration was performed under reduced pressure at 120°C to obtain a yellowish-white polyol composition. The hydroxyl value was 37.1 and the viscosity was 3010 cps.
It was found that the resin component in this polyol composition was stably dispersed without any separation for more than two months. The obtained polyol composition was subjected to a methanol dilution centrifugation test, and as a result, the resin content recovered was 23% of the resin content contained in the polyol composition. Example 2 400 parts of polyol A obtained in Example 1, urea
A reactor was charged with 75 parts of benzoguanamine, 25 parts of benzoguanamine, and 142 parts of a 35% formaldehyde aqueous solution, and the mixture was reacted at 55°C for 3 hours and at 100°C for 5 hours, followed by dehydration under reduced pressure. The obtained polyol composition was a yellowish white viscous liquid with a hydroxyl value of 41.6 and a viscosity of 2100 cps. It was found that the resin component in this polyol composition was stably dispersed without any separation for more than two months. As a result of a methanol dilution centrifugation test, the resin content recovered was 3% of the resin content contained in the polyol composition. Example 3 425 parts of polyol B obtained in Example 1, 75 parts of melamine, and 102 parts of 35% formaldehyde aqueous solution were charged into a reactor and heated at 30°C for 2 hours and at 70°C for 3 hours.
After reacting at 100°C for 5 hours, dehydration was performed at 140°C under reduced pressure. The obtained polyol composition was a white viscous liquid with a hydroxyl value of 23.5 and a viscosity of 4050 cps.
It was found that the resin component in this polyol composition was stably dispersed without any separation for more than two months. As a result of a methanol dilution centrifugation test, the resin content recovered was 1% of the resin content contained in the polyol composition. Example 4 400 parts of polyol B obtained in Example 1, 80 parts of melamine, 20 parts of aniline, and 109 parts of 35% formaldehyde aqueous solution were charged into a reactor and heated at 60°C for 5 hours.
The reaction was carried out at 100°C for 3 hours. Thereafter, dehydration was performed under reduced pressure at 120°C to obtain a yellowish-white viscous polyol composition. It had a hydroxyl value of 23.5 and a viscosity of 4530 cps.
It was found that the resin component in this polyol composition was stably dispersed without any separation for more than two months. As a result of a methanol dilution centrifugation test, the resin content recovered was 3% of the resin content contained in the polyol composition. Example 5 400 parts of polyol C obtained in Example 1, 50 parts of melamine, 50 parts of urea, and 1405 parts of a 35% formaldehyde aqueous solution were charged into a reactor, reacted at 45°C for 5 hours, and then heated to 110°C. Allowed time to react. Dehydration was carried out under reduced pressure at 120°C to obtain a yellowish white viscous polyol composition. It had a hydroxyl value of 21.8 and a viscosity of 3680 cps. It was found that the resin component was stably dispersed in this polyol composition without any separation for more than two months. As a result of a methanol dilution centrifugation test, the resin content recovered was 2% of the resin content contained in the polyol composition. Example 6 425 parts of polyol C obtained in Example 1, urea
50 parts of dicyandiamide, 25 parts of dicyandiamide, and 116 parts of 35% formaldehyde aqueous solution were charged into a reactor and heated at 60°C for 2 hours.
The reaction was carried out at 80°C for 2 hours and at 100°C for 3 hours. 140℃
Dehydration was carried out under reduced pressure to obtain a yellowish white viscous polyol composition. It had a hydroxyl value of 23.2 and a viscosity of 3180 cps. It was found that the resin component in this polyol composition was stably dispersed without any separation for more than two months. As a result of a methanol dilution centrifugation test, the resin content recovered was 1% of the resin content contained in the polyol composition. Reference Example Table 1 shows the physical property results when the polyol compositions obtained in Examples 1 to 6 were foamed. 【table】

Claims (1)

[Scope of Claims] 1. A method for producing a polyol containing an aldehyde condensation polymer component by reacting an aldehyde condensation forming raw material in a polyol, in which a polyol containing an addition polymer component having cyan groups has a small amount of cyan groups. An aldehyde condensation polymer characterized by converting a portion of both into amidoxime groups and/or hydroxam groups, and reacting an aldehyde condensation forming raw material in a polyol containing an addition polymer component having the amidoxime groups and/or hydroxam groups. A method for producing a polyol containing a polymer component. 2. The method according to claim 1, wherein the cyan group-containing addition polymer component is a component containing a single or copolymer of acrylonitrile. 3. The method according to claim 1, characterized in that the conversion of the cyan group into an amidoxime group and/or a hydroxam group is carried out using hydroxylamine. 4. The method according to claim 1, wherein the polymer component-containing polyol is a polyol in which finely particulate solid polymer components are dispersed.