JPS634852B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polyurethane by reacting a polyol and a polyisocyanate, and particularly relates to a method for producing polyurethane using a polyol containing a polymer component. It is known to produce polyurethanes, in particular polyurethane foams, using so-called polymer polyols (also called graft polyols). A typical polymer polyol is a polyol in which a finely divided solid polymer obtained by polymerizing acrylonitrile and/or styrene in a polyol is stably dispersed in the polyol. This dispersion stability is thought to be due to the polymer being grafted to the molecular chain of the polyol. However, the fine particle shape of the polymer also contributes to dispersion stability, and it is thought that in some polymer polyols, some or all of the polymer is simply dispersed in the polyol. . In fact, an example has been proposed in which a polymer polyol is produced by making a pre-made polymer into fine particles and dispersing it in a polyol. Polyurethanes obtained using polymer polyols have various characteristics. In particular, polyurethane foams obtained using polymer polyols have high elasticity, and it is considered difficult to obtain such highly elastic polyurethane foams without using polymer polyols. On the other hand, there are problems with polymer polyols.
In particular, a major drawback is that polyurethanes obtained using polymer polyols are more easily flammable than polyurethanes obtained using other polyols. It is known that flame retardant polyurethane can be made by adding a flame retardant or by using a so-called flame retardant polyol containing halogen or phosphorus. However, the addition of flame retardants deteriorates the physical properties of polyurethane and tends to have an adverse effect on polyurethanes using polymer polyols. On the other hand, flame-retardant polyurethane can be produced by using a combination of flame-retardant polyol and polymer polyol, but the proportion of polymer in the polymer polyol decreases by the amount of flame-retardant polyol, and this cannot be achieved by using a polymer polyol. In addition, in order to fully exhibit the effects of the polymer polyol, the amount of flame retardant polyol used is limited, and the desired flame retardancy tends to be insufficient. Therefore, it is difficult to impart flame retardant effects without reducing the inherent characteristics of polymer polyols, and no solution to this problem has hitherto been known. The present inventor conducted various studies in order to impart flame retardancy to polymer polyols. It is known to use halogen-containing polymers such as polyvinyl chloride as addition polymers in polymer polyols. However, polymer polyols containing halogen-containing polymers do not fully exhibit the original effects of polymer polyols, have insufficient flame retardant effects, and have low weather resistance. It was considered that it would be difficult to achieve this objective. Therefore, we investigated polyols and additives that can be used in combination with polymer polyols, have less reduction in the original effects of polymer polyols, and have flame retardant effects. As a result, it has been found that a polyol in which an aldehyde condensation polymer is dispersed can meet this purpose. Polyol in which aldehyde condensation polymer is dispersed is
Like polymer polyol, it is a polyol in which a polymer is dispersed, and polyurethane using it provides effects similar to polymer polyol. Moreover, this polyol imparts flame retardancy to polyurethane. Therefore, by using a conventional polymer polyol and a polyol containing an aldehyde condensation polymer component in combination, it is possible to reduce the reduction in the original effect of the polymer polyol and to exhibit the flame retardant effect. Of course, the polymer polyol and the aldehyde condensation polymer component-containing polyol can be used by mixing them in any ratio.
It is possible to manufacture and use a polyol having an addition polymer component and an aldehyde condensation polymer component in a polymer polyol without separately manufacturing both polyols, but rather from the viewpoint of dispersion stability etc. Preference is given to using polyols. The present invention is a method for producing polyurethane using this polyol, that is, a method for producing polyurethane by reacting a polyol and a polyisocyanate in the presence of a catalyst. an addition-polymerized polymer component formed by reacting a condensation-forming raw material capable of forming an aldehyde condensation polymer in a polyol; A polyol is an essential component, and the addition polymer component is 1 to 1% of the total amount of polyol.
50% by weight, the aldehyde condensation polymer component is 1~
50% by weight, and the total of both components is 60% by weight or less. It is. Conventional polymer polyols are produced by polymerizing addition-polymerizable monomers such as acrylonitrile or styrene in substantially saturated or unsaturated polyols, or by forming addition polymers or other polymers into fine particles in polyols. It is obtained by a method of dispersing. The addition polymer component in the present invention is one obtained by the former method, that is, a component formed by polymerizing a monomer capable of addition polymerization in a polyol. In polyols containing this addition polymer, it is thought that the addition polymer component is grafted to the molecular chain of the polyol or simply dispersed in fine particles, and is a solid fine particle with relatively high dispersion stability. It is a liquid dispersion in which addition polymer components of . In addition, some products obtained using unsaturated polyols are uniformly transparent and do not contain solid particulate components. Regarding this type of so-called polymer polyol, for example, Japanese Patent Publication No. 39-24737, Japanese Patent Publication No. 41-3437,
Special Publication No. 43-22108, Publication No. 46-20508, Publication No. 37228-1980, Publication No. 40914-1980, Publication No. 40914-1972, Publication No. 40915-1971, Publication No. 40915-1971, Publication No. 3439-1977
No. 52-13834, and other publications. If I explain these outlines,
As the substantially saturated polyol, a substantially saturated polyether polyol is preferable, and a polyether polyol obtained by adding a nipoxide such as an alkylene oxide to an initiator such as a polyhydric alcohol or amine is particularly preferable. This will be discussed further later. As unsaturated polyols, for example, in addition to those described in the above-mentioned Japanese Patent Publication No. 46-20508 and the following six publications, unsaturated polyols containing nitrogen-containing bonds according to the invention of the present inventors −90818 Publication, Japanese Patent Application Laid-Open No. 1983-
93724, JP-A-56-93729), etc. Specific examples include unsaturated polyester polyols obtained from unsaturated polycarboxylic acids and polyhydric alcohols, unsaturated polyols obtained by reacting polyether polyols with unsaturated polycarboxylic acids, and further reacting with epoxides if necessary. Ether ester polyol, unsaturated polyether polyol obtained by adding an unsaturated epoxide such as allyl glycidyl ether to an initiator together with alkylene oxide, polyether polyol and unsaturated polyhydric (and/or monohydric) alcohol Examples include nitrogen-containing bond-containing unsaturated polyols bonded via isocyanate compounds. The addition polymerizable monomer forming the addition polymer is preferably a vinyl monomer, but is not limited thereto, and vinylidene monomers, diene monomers, and other monomers can be used alone or in combination. Specific examples include acrylonitrile, styrene, vinyltoluene, acrylic ester, methacrylic ester, vinyl halide, olefin, vinylidene halide, divinylbenzene, butadiene, chloroprene, diallyl phthalate, and the like. Particularly preferred are vinyl monomers consisting of acrylonitrile, styrene, or a combination of the two. When polymerizing addition-polymerizable monomers in polyols, a polymerization initiator is usually used, such as an azo compound such as azobisisobutyronitrile or a peroxide such as benzoyl peroxide. Appropriate for use. The proportion of the addition polymer in the addition polymer component-containing polyol is 1 to 50% by weight, especially 5% by weight.
~40% by weight is suitable. Its hydroxyl value is preferably 200 or less, particularly 5 to 100. This hydroxyl value is
When the addition polymerization type polymer does not contain a hydroxyl group, it is determined by the hydroxyl value of the original polyol and the addition polymerization type polymer. Similarly, the number of hydroxyl groups matches the number of hydroxyl groups in the original polyol, preferably 2 to 2.
8, especially 2 to 4 is suitable. From the viewpoint of dispersion stability, it is preferable that at least a part of the addition polymer is grafted onto the polyol;
Therefore, the polyol used is preferably an unsaturated polyol, and when a substantially saturated polyol is used, the addition polymerizable monomer preferably contains at least acrylonitrile. Next, the aldehyde condensation polymer component-containing polyol will be explained. This polyol is publicly known, and is disclosed in Japanese Patent Application Laid-open Nos. 15832-1983 and 1983-15832,
It is described in Japanese Patent Application Laid-open No. 117793 and Japanese Patent Application Laid-Open No. 122193/1983. The aldehyde condensation polymer component-containing polyol in the present invention may be of this known type, or may be of other types or obtained by other methods. For example, a compound that can be polycondensed with aldehydes (for example, urea) and an aldehyde (for example, formaldehyde) are reacted in advance to produce a reactant (such as dimethylol urea) or an initial condensate, and this is then reacted in a polyol. A polyol containing an aldehyde condensation polymer component can be produced. As mentioned above, the aldehyde condensation polymer-containing polyol is produced by reacting a compound that can be polycondensed with aldehydes (hereinafter referred to as a polycondensable compound) and aldehydes in a polyol, or by reacting an initial condensate of both of them. If necessary, it can be obtained by further reacting it with a polycondensable compound or aldehyde in a polyol. Hereinafter, condensation forming raw materials refer to compounds and combinations thereof that can form these aldehyde condensation polymers. One of the raw materials for condensation formation is aldehydes. Examples of aldehydes include aliphatic, alicyclic, aromatic,
Other aldehydes, condensates thereof, and derivatives such as compounds capable of generating aldehydes may be used. Preferred aldehydes are aliphatic aldehydes having 4 or less carbon atoms and derivatives thereof, such as formaldehyde, acetaldehyde, paraformaldehyde, paraacetaldehyde, glyoxal, and hexamethylenetetramine. Particularly preferred are formaldehyde and formaldehyde derivatives such as paraformaldehyde. These aldehydes can be used by being dissolved in a solvent, and the preferred solvent is water. Another condensation-forming raw material is a polycondensable compound, which requires at least two sites (hereinafter referred to as reaction sites) that can react with aldehydes. The reactive site is typically a carbon atom to which hydrogen is bonded in an aromatic nucleus, or a nitrogen atom to which hydrogen is bonded in an amino group, an amide group, or the like. The reaction site of the aromatic nucleus is preferably the ortho or para position of the aromatic nucleus to which a hydroxyl group or amino group is bonded, and it is appropriate to use an aromatic compound having two or more of these reaction sites, and has an amino group or an amide group. Suitable compounds are polyamine compounds having two or more of these groups. It may be particularly preferable to use two or more types of these polycondensable compounds, and a compound having only one reactive site can also be used together with these. Examples of the aromatic compounds include phenol, cresol, xylenol, P-alkylphenol, bisphenol A, resorcinol, dihydroxydiphenylmethane, other phenols, aniline, diaminobenzene, P-alkylaniline, N- Aromatic amines such as substituted alkylanilines and diaminodiphenylmethane are suitable, and aromatic amines are particularly preferred. Since the amino group of aromatic amines is also a reactive site,
The aromatic nucleus may have one or less reactive sites in some cases. Examples of polyamine compounds include ureas such as urea, thiourea, and N-substituted ureas, guanidines such as guanidine and N-substituted guanidine, melamine, N-substituted melamine, benzoguanamine, acetoguanamine, and N-substituted guanamine. S-triazines and the like are suitable. Among these, particularly preferred are urea, guanidine,
These are melamine and benzoguanamine, and it is also preferable to use two or more of these in combination, or to use them together with phenol and/or aniline. Moreover, as mentioned above, it is also preferable to use monoamines, alkanolamines, and other compounds having one reactive site together with these. Other initial condensates that are raw materials for condensation formation include:
In particular, a reaction product of the above-mentioned polycondensable compound having a methylol group and formaldehyde is preferred. for example,
Examples include methylol urea, dimethylol urea, polymethylol melamine, and partially alkyl etherified polymethylol melamine. In addition to these single compounds, it may also be an initial condensate with further condensation such as novolak. There are no particular limitations on the amount of condensation-forming raw materials used, such as the reaction ratio between the polycondensable compound and the aldehyde, as long as a solid, particulate polymer can be produced in the polyol. However, usually 0.5 to 3.0 mol of aldehydes, especially 0.8 to 3.0 mol, per 1 mol of polycondensable compound.
A proportion of 2.5 mol is preferred, more preferably 0.9
~1.5 mol. The reaction of both in polyol is usually carried out under heating, especially in the first half below 60°C.
It is preferable that the reaction is carried out at a temperature of 70° C. or higher in the latter half. 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. Especially in the latter half of the reaction, hydroxyl groups (e.g. methylol groups) caused by aldehydes
It is preferable to carry out the reaction sufficiently until no residue remains, and it is preferable that the dehydration treatment is 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 As mentioned above, the aldehyde condensation polymer component in the aldehyde condensation polymer-containing polyol is preferably one with few, particularly substantially no hydroxyl groups resulting from aldehydes. 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 1.2 times or less of the hydroxyl value of the original polyol,
In particular, it is preferable that it is equal to or lower than that. 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 a polyol containing an aldehyde condensation polymer component obtained by sufficient dehydration using the above reaction conditions is the hydroxyl value of the original polyol when calculated by subtracting the aldehyde condensation polymer component. substantially match. Therefore, it is presumed that such an aldehyde condensation polymer component does not substantially contain hydroxyl groups resulting from aldehydes. When producing a polyol containing only this aldehyde condensation polymer component, it is preferable to use a substantially saturated polyol.
Examples of the substantially saturated polyol include polyether polyols, polyester polyols, polyether ester polyols, polycarbonate polyols, and hydroxyl group-containing hydrocarbon polymers, which are usually used as raw materials for polyurethane. Particularly preferred are polyether polyols, such as polyhydric alcohols, polyamines,
Polyether polyols obtained by adding alkylene oxides having 2 to 4 carbon atoms to epoxides, etc. to initiators having two or more active hydrogens, and polyether polyols obtained by ring-opening polymerization of cyclic ethers are preferred. . A particularly preferred polyether polyol is a polyether polyol obtained by adding propylene oxide or propylene oxide and ethylene oxide to a divalent to tetravalent initiator. These polyols such as polyether polyols may be a mixture of two or more types of polyols. The hydroxyl value of these polyols is preferably 800 or less, particularly 20 to 200, and the number of hydroxyl groups is 2 to 8, particularly preferably 2 to 4. The aldehyde condensation polymer-containing polyol produced using the above-mentioned condensation forming raw materials and polyols is usually a polyol in which finely granular aldehyde condensation polymers are dispersed, but in some cases, aldehyde condensation polymers are dispersed in the polyol. In some cases, the mixture becomes a uniform transparent liquid that is uniformly dissolved or dispersed in the polyol. Particularly preferred in the present invention is one in which finely divided solid aldehyde condensation polymers are dispersed in polyol. The aldehyde condensation polymer dispersed in fine particles in polyol is a relatively high molecular weight condensation product polycondensed in a two-dimensional or three-dimensional shape such as a linear or network shape, and more preferably a three-dimensional condensation product. It does not dissolve in ordinary resin-soluble solvents. Also, although it does not melt when heated, it may become molten and decompose during decomposition. Therefore, such polymers are considered to correspond to cured products of ordinary thermosetting aldehyde condensation resins such as melamine resins and phenol resins. Polyols in which such solid aldehyde condensation polymers are dispersed are
Like the addition polymer-containing polyol, it is a white to colored translucent to opaque viscous liquid.
The proportion of the aldehyde condensation polymer in this aldehyde condensation polymer-containing polyol is 1 to 50% by weight.
is appropriate, particularly preferably 5 to 40% by weight. If there are no restrictions such as viscosity, or if it is used diluted with other polyols, the ratio may be even higher. The viscosity is not particularly limited, but it is preferably 20,000 centipoise or less at 25°C. The polyol containing the addition polymer component and the polyol containing the aldehyde condensation polymer component can be mixed in any ratio, and this mixed polyol can be used to produce the polyurethane of the present invention. Both polyols can also be prepared separately and mixed immediately before mixing with the polyisocyanate, or simultaneously with the polyisocyanate. Further, in the case of a prepolymer or a quasi-prepolymer, they can be reacted separately with a polyisocyanate and then mixed. Apart from these methods, an addition polymer and an aldehyde condensation polymer can be formed in a polyol almost simultaneously or sequentially to form a polyol containing an addition polymer component and an aldehyde condensation polymer component. Can be manufactured directly. This method includes a method in which the addition-polymerizable monomer and the condensation-forming raw material are reacted almost simultaneously in a polyol, a method in which the condensation-forming raw material is reacted in a polyol containing an addition polymer component, and a method in which the condensation-forming raw material is reacted in a polyol containing an aldehyde condensation polymer component. Among them, there is a method of polymerizing an addition-polymerizable monomer, and the first two methods are particularly preferred. Including the method of simply mixing the addition polymer component-containing polyol and the aldehyde condensation polymer component-containing polyol, the total ratio of both components in the polyol containing both components obtained by these methods is 1 to 1. Preferably it is 50% by weight, especially 5 to 40% by weight. The relative proportions of both components can be changed arbitrarily depending on the purpose. For example, if the purpose is to make polyurethane flame retardant, the proportion of the aldehyde condensation polymer component can be increased. Therefore, the relative proportions of both components are not particularly limited, but the weight ratio is 1 to 1 of the addition polymer component to 0.1 to 50 of the aldehyde condensation polymer,
In particular, a ratio of 0.2 to 10 is suitable. Among the methods for producing a polyol having both of the above components, the method of reacting a condensation forming raw material in a polyol containing an addition polymer component is a method for producing a polyol containing an aldehyde condensation polymer component. This method corresponds to the method using component-containing polyols.
For example, a polyol having both components can be obtained by polymerizing acrylonitrile and/or styrene in an unsaturated polyol or a substantially saturated polyol, then adding melamine and formaldehyde and polycondensing the polymer. Similarly, by using a polyol containing an aldehyde condensation polymer component as the polyol and polymerizing an addition polymerizable monomer therein, a polyol having both components can be similarly obtained. Furthermore, a similar polyol can be obtained by reacting an addition-polymerizable monomer and a condensation-forming raw material almost simultaneously in a polyol. Addition-polymerizable monomers are formed in the presence of an addition-polymerization initiator by heating above the decomposition temperature of the addition-polymerization initiator, and condensation-polymerization of ordinary condensation-forming raw materials also occurs at this temperature. Therefore, for example, a polyol having both components can be obtained by adding acrylonitrile and/or an addition polymerization initiator such as styrene, melamine, formaldehyde and an azo compound to a polyol and heating the mixture. In this case, the addition-polymerizable monomer such as acrylonitrile can be decomposed and added gradually, and it is also preferable to raise the temperature in the latter stages of the reaction to perform the dehydration. Among the methods for producing a polyol having both of these components, preferred are a method in which a condensation-forming raw material is reacted in a polyol containing an addition polymer component, and a method in which an addition-polymerizable monomer and a condensation-forming raw material are reacted almost simultaneously in a polyol. These methods are advantageous in that they have relatively higher dispersion stability than the case where the addition polymer component-containing polyol and the aldehyde condensation polymer component-containing polyol are used as a mixture. As mentioned above, the dispersion stability of polyols containing aldehyde condensation polymer components is usually lower than that of polyols containing addition polymerization polymer components, and this can sometimes pose a problem during polyurethane production. For example, polyols containing the aldehyde condensation polymer component may have to be used with stirring to prevent sedimentation of the aldehyde condensation polymer component. The reason why the polyol containing an addition polymer component has good dispersion stability is thought to be that part to all of the addition polymer is grafted onto the polyol. On the other hand, as described in the above-mentioned known examples, the aldehyde condensation polymer does not react with the polyol, but is simply dispersed in the polyol, and therefore is considered to have insufficient dispersion stability.
Therefore, the present inventors investigated a method of bonding an aldehyde condensation polymer to a polyol, and found that
It has been found that they can be combined in various ways. One method is to use a monomer (hereinafter referred to as
A method for producing a polyol having a component in which an aldehyde condensation polymer and an addition polymerizable polymer are combined using a method such as the method for producing a polyol having both components described above. It is. For example, when acrylamide, N-methylolacrylamide, hydroxyethyl methacrylate, aminoethyl methacrylate, vinylpyridine, vinylphenol, vinylaniline, acrolein, etc. are used as the condensable addition polymerizable monomer, these monomers or their polymers or copolymers A polymer in which both components are bonded together is obtained through coalescence. Also, another method is
Taking advantage of the fact that acrylonitrile polymers and copolymers can be modified to change nitrile groups to groups that can react with aldehydes such as hydroxams, after modifying polyols containing acrylonitrile (co)polymer components, A polyol in which both components are combined can be obtained by reacting the condensation forming raw materials.
In a polyol having a component in which both components are bonded, when the addition polymer is grafted to the polyol, the aldehyde condensation polymer is also indirectly bonded to the polyol, so the dispersion stability is improved. An excellent polyol containing both components is obtained, and the problem of dispersion stability of the aldehyde condensation polymer component is solved. The polyurethane of the present invention uses two types of polyols having at least each component as described above, or using a polyol having at least both components,
It is obtained by reacting this with polyisocyanate. This reaction typically requires a catalyst, but other additives can optionally be used as desired. A combination of these two types of polyols or a polyol containing both components can also be used in combination with other polyols. Even in that case,
The proportion of each component in the total polyol is at least 1
Preferably, it is % by weight. In particular, it is preferred that the total proportion of each component in the total polyol is at least 5% by weight, especially at least 10% by weight. In addition,
This polyol is a relatively high molecular weight polyol, and does not contain the following chain extender or crosslinking agent. As mentioned above, the polyurethane obtained by the present invention has excellent physical properties as well as the polyurethane obtained using conventional polymer polyols, and at the same time has flame retardancy depending on the amount of the aldehyde condensation polymer component. The characteristics are improved. Polyurethane obtained by the method of the present invention can be broadly classified into foam polyurethane and non-foam polyurethane. Non-foam polyurethane is used for, for example, elastomers, hard resins, waterproof materials, sealants, paints, and other uses. It is something that The method of the present invention is particularly suitable as a method for producing polyurethane foam, and particularly for producing flexible polyurethane foam or semi-rigid polyurethane foam. Catalysts such as tertiary amine catalysts and organometallic compound catalysts are used in the production of these polyurethanes, but the catalysts are not limited to these. Blowing agents such as water and halogenated hydrocarbons are usually used in the production of polyurethane foam, and
It may also be manufactured by mixing an inert gas such as air. Suitable halogenated hydrocarbon blowing agents include trichlorofluoromethane, dichlorodifluoromethane, and methylene chloride. Further, a foam stabilizer is usually used, and organosilicon compounds such as poly(dialkylsilane) polyoxyalkylene chain-containing silane are suitable as the foam stabilizer. Polyurethane foams usually require the use of these catalysts, blowing agents, and foam stabilizers, but can also contain a variety of optional additives, such as fillers, reinforcing agents, stabilizers, colorants, and flame retardants. , mold release agent, foam breaker,
These include crosslinking agents and chain extenders. These additives may also be used to make non-foam polyurethanes. Other basic raw materials for polyurethanes are polyisocyanate compounds. As the polyisocyanate compound, aromatic, aliphatic, or heterocyclic compounds having at least two isocyanate groups can be used alone or in combination, and aromatic polyisocyanate compounds are particularly preferred. preferable. If specific polyisocyanate compounds are listed,
Examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate group, xylylene diisocyanate group, naphthalene diisocyanate, hexamethylene diisocyanate group, 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, for example. EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples. The polyols used in the reference examples are as follows. Polyol A: Polyoxypropylene ethylene triol with a molecular weight of 3000, obtained by adding propylene oxide to a glycerin initiator and then adding 13% by weight of ethylene oxide. Polyol B: Polyoxypropylene ethylene triol with a molecular weight of 5000, which is obtained by adding propylene oxide to a glycerin initiator and then adding 15% by weight of ethylene oxide. Polyol C: Polyoxypropylene ethylene triol with a molecular weight of 6500, which is obtained by adding propylene oxide to a glycerin initiator and then adding 15% by weight of ethylene oxide. Polyol D: Polyoxypropylene ethylene hexanol with a molecular weight of 9600, prepared by adding propylene oxide to a sorbitol initiator and then adding 10% by weight of ethylene oxide. Reference Example 1 80 parts (by weight, hereinafter the same) of polyol C was charged into a reactor and heated to 100°C. A solution of 0.6 parts of α,α'-azobisisobutyronitrile dissolved in 15 parts of acrylonitrile and 5 parts of methyl methacrylate was fed into the reactor over 3 hours. After the supply was completed, aging was carried out for 30 minutes, the temperature was raised to 120°C, and unreacted monomers were degassed under reduced pressure to obtain a yellowish-white polyol composition. 95 parts of this polyol composition,
5 parts of urea and 35 parts of a 40% glyoxal aqueous solution were charged into a reactor and reacted at 50°C for 2 hours, then heated to 70°C and further reacted for 3 hours. In order to remove water in the system and complete condensation, vacuum dehydration was performed at 120°C to obtain a yellowish white viscous polyol composition. The hydroxyl value was 19.0, and the viscosity at 25°C (hereinafter the same) was 3400 cps. The resin component in this polyol composition was stably dispersed, and no separation was observed for more than two months. The obtained polyol composition was diluted 10 times with methanol and centrifuged.
A centrifugation test of the dispersed resin fraction was conducted at 3000 rpm. The resin content recovered was 17% of the resin content contained in the polyol composition. Reference Example 2 97 parts of polyol D, 1 part of maleic anhydride, and 2 parts of ethylene oxide were charged into a reactor and reacted at 150°C for 5 hours, and then unreacted components were degassed under reduced pressure. This modified polyol contains 32 parts of acrylonitrile and 11 parts of styrene contains α,α′-masobisisobutyronitrile.
A solution containing 0.7 part of the solution was fed into the reactor over a period of 3 hours. After the supply was completed, aging was carried out at 120° C. for 30 minutes, and unreacted monomers were degassed under reduced pressure to obtain a yellowish-white viscous polyol composition. 85 parts of this polyol composition, 15 parts of dimethylol urea, and 15 parts of water were charged into a reactor and reacted at 50°C for 2 hours and at 70°C for 2 hours, then heated to 140°C and dehydrated under reduced pressure. . The obtained polyol composition was a yellowish white viscous liquid with a hydroxyl value of 18.3 and a viscosity of 4120 cps. The resin in this polyol composition was stably dispersed, and no separation was observed for over two months. The resin content separated and recovered by the methanol dilution centrifugation test was 15% of the resin content contained in the polyol composition. Reference example 3 40 parts of polyol A, 10 parts of urea, and 28.5 parts of a 35% formaldehyde aqueous solution were charged into a reactor, and the mixture was heated at 50℃ for 2 hours.
After reacting for a period of time, α,
A monomer/initiator polyol solution in which 0.2 part of α'-azobisisobutyronitrile is dissolved is fed at 100° C. over 5 hours. Aging was performed at 100°C for 1 hour, and vacuum degassing was performed at 1400°C to remove moisture and unreacted monomers in the system and complete condensation. The obtained polyol composition was a yellowish white viscous liquid with a hydroxyl value of 48.1 and a viscosity of 2880 cps. The resin component in this polyol composition was stably dispersed, and no separation was observed for more than two months. The resin content separated and recovered by the methanol dilution centrifugation test was 19%. Reference Example 4 80 parts of polyol B, 8 parts of melamine, 26.5 parts of 80% glyoxal aqueous solution, and 2 parts of acrylamide were charged into a reactor and reacted at 50°C for 2 hours. 100℃
The temperature was raised to 1.5 parts, and a solution of 0.6 parts of α,α'-azobisisobutyronitrile dissolved in 5 parts of acrylonitrile and 5 parts of styrene was supplied for 3 hours. moreover
After post-reaction for 30 minutes, unreacted monomers and residual water were removed, and vacuum dehydration was performed at 140°C to complete condensation. The obtained polyol composition was a yellowish white viscous liquid with a hydroxyl value of 26.5 and a viscosity of 2870 cps. The resin component in this polyol composition was stably dispersed, and no separation was observed for more than two months. The resin content recovered by the methanol dilution centrifugation test is 5% of the resin content contained in the polyol composition.
It was hot. Reference Example 5 90 parts of polyol A, 5 parts of urea, 2 parts of N-methylolacrylamide, and 28 parts of a 35% formaldehyde aqueous solution were charged into a reactor and reacted at 70°C for 3 hours. After reaction, 3 parts of methyl methacrylate, α, α′-
0.3 part of azobisisobutyronitrile was introduced into the reactor, heated to 100°C, and reacted for 3 hours. Unreacted monomers and residual water were removed, and in order to complete the condensation reaction, dehydration was performed under reduced pressure at 120°C to obtain a white viscous polyol composition. Hydroxyl value 50.4, viscosity 1950cps
It was hot. The resin component in this polyol composition was stably dispersed, and no separation was observed for more than two months. The resin content recovered by the methanol dilution centrifugation test is 5% of the resin content contained in the polyol composition.
It was %. Reference Example 6 80 parts of Polyol D, 0.8 parts of maleic anhydride, and 1.6 parts of ethylene oxide were placed in a reactor and heated at 150°C.
After reacting for a period of time, unreacted components are removed by degassing. To this modified polyol, 5 parts of melamine, 5 parts of urea, 80
% acetaldehyde aqueous solution was introduced, and the reaction was further carried out at 60°C for 2 hours. The temperature was raised to 100°C, and 5 parts of acrylonitrile, 5 parts of methyl methacrylate, 3 parts of acrolein, and 0.6 parts of α,α'-azobisisobutyronitrile were fed over 5 hours. at 100℃
After post-reaction for 30 minutes, in order to remove unreacted monomers and residual water and complete the condensation reaction,
Vacuum degassing was performed at 140°C. The obtained polyol composition was a yellowish white viscous liquid with a hydroxyl value of 24.7 and a viscosity of 4160 cps. The resin component in this polyol composition was stably dispersed, and no separation was observed for more than two months. The resin content recovered and separated by the methanol dilution centrifugation test was 3% of the resin content contained in the polyol composition. Reference Example 7 80 parts of polyol A was charged into a reactor and heated to 100°C. A mixed monomer/initiator solution containing 0.6 parts of α,α'-azobisisobutyronitrile dissolved in 15 parts of acrylonitrile and 5 parts of styrene was fed into the reactor over a period of 5 hours. After the supply was completed, aging was carried out for 30 minutes, and after the temperature was raised to 120° C., unreacted monomers were degassed under reduced pressure to obtain a yellowish-white viscous polyol composition. 80 parts of polyol B, 20 parts of urea, and 57 parts of a 35% formaldehyde aqueous solution were charged into a reactor and heated at 60°C for 2 hours, then the temperature was raised to 80°C and reacted for 2 hours.
To remove water in the system and complete condensation
Deaeration was performed under reduced pressure at 140°C to obtain a white viscous polyol composition. Fifty parts of the polyol composition obtained in each batch were mixed using a mechanical stirrer to obtain a yellowish white viscous polyol composition. The hydroxyl value is
It was 45.1, 2150cps. The resin component in this polyol composition was stably dispersed, and no separation was observed for more than two months. The resin content separated and recovered by the methanol dilution centrifugation test was 65% of the resin content contained in the polyol composition. Reference example 8 90 parts of polyol B, 5 parts of urea, 5 parts of melamine,
32 parts of a 35% formaldehyde aqueous solution was charged into a reactor and reacted at 100°C for 3 hours. Moisture in the system was then removed and dehydration was performed under reduced pressure at 140°C to complete condensation. The obtained polyol composition was a white viscous liquid. 80 parts of this polyol composition was charged into a reactor and heated at 120°C. A mixed monomer/initiator solution containing 10 parts of acrylonitrile and 0.6 parts of α,α'-azobisisobutyronitrile dissolved in 10 parts of styrene was fed into the reactor over a period of 5 hours.
After the supply was completed, aging was carried out for 30 minutes and unreacted monomers were degassed under reduced pressure to obtain a yellowish white viscous polyol composition. The hydroxyl value was 23.8 and the viscosity was 2570 cps.
The resin component in this polyol composition was stably dispersed, and no separation was observed for more than two months. The resin content separated and recovered by the methanol dilution centrifugation test was 45%. Reference Example 9 60 parts of polyol B was charged into a reactor and heated to 100°C. A solution of 1.0 part of α-α′-azobisisobutyronitrile dissolved in 20 parts of methyl methacrylate and 20 parts of urea in a 35% formaldehyde aqueous solution.
A 28.5 part aqueous solution is fed into the reactor simultaneously from separate feed tanks for 5 hours. 100
After aging at .degree. C. for 2 hours, vacuum degassing was performed to remove unreacted monomers and water and to complete condensation. The obtained polyol composition was a white viscous liquid with a hydroxyl value of 20.2 and a viscosity of 5360 cps. The resin component in this polyol composition was stably dispersed, and no separation was observed for more than two months. The resin content separated and recovered by the methanol dilution centrifugation test was 21%. Reference Example 10 8 parts of urea, 2 parts of benzoguanamine, 2 parts of acrylamide, and 15 parts of a 35% formaldehyde aqueous solution are charged into a reactor and reacted at 80°C for 1 hour. 30 systems
After cooling to 80°C, 80 parts of polyol B, 6 parts of acrylonitrile, 2 parts of styrene, and 0.5 part of α,α'-azobisisobutyronitrile were charged at the same time.
Heat until. 6 parts of a 35% formaldehyde aqueous solution at 80° C. is fed into the reactor for one hour or so. After the supply was completed, post-reaction was carried out for another hour at 80°C, and the system was heated to 100°C.
The temperature was raised to ℃ and allowed to react for 2 hours. In order to remove water in the system and complete the reaction, vacuum degassing was performed at 140°C to obtain a yellowish white viscous polyol composition. Hydroxyl value 26.5, viscosity at 25℃ 2920cps
It was hot. The resin component in this polyol composition was stably dispersed, and no separation was observed for more than two months. The resin content separated and recovered by the methanol dilution centrifugation test was 21% of the resin content contained in the polyol composition. Reference example 11 75 parts of polyol C, 10 parts of acrylonitrile, 5 parts of urea, 5 parts of benzoguanamine, 17 parts of 80% aqueous acetaldehyde solution, 5 parts of acrolein, α, α′-
Charge 0.6 part of azobisisobutyronitrile into a reactor and react at 60°C for 2 hours. After raising the temperature to 100°C and reacting for 3 hours, vacuum degassing was performed at 140°C to remove residual moisture and unreacted monomers and complete the condensation reaction. The obtained polyol composition was a yellowish white viscous liquid with a hydroxyl value of 18.8 and a viscosity of 5120 cps. The resin component in this polyol composition was stably dispersed, and no separation was observed for more than two months. The resin content recovered by the methanol dilution centrifugation test was 8% of the resin content contained in the polyol composition.
It was hot. Reference Example 12 (Known Polymer Polyol) 80 parts of polyol B was charged into a reactor and heated to 100°C. A solution of 0.6 part of α,α'-azobisisobutyronitrile dissolved in 20 parts of acrylonitrile was fed into the reactor over 5 hours. After supply ends,
After aging for 30 minutes and raising the temperature to 120°C, unreacted monomers were degassed under reduced pressure to obtain a yellowish brown viscous polyol composition. Hydroxyl value 28.3, viscosity 3520cps
It was hot. The resin component in this polyol composition was stably dispersed, and no separation was observed for more than two months. The resin content separated and recovered by the methanol dilution centrifugation test was 14% of the resin content contained in the polyol composition. Examples 1 to 11, Comparative Example 1 Hot-molded polyurethane foam was manufactured using polyol A and the polyol composition synthesized by the method shown in Reference Example. The composition of the raw materials used and the physical properties of the foam are shown in Table 1 below.

【table】

[Table] Examples 12 to 22, Comparative Example 2 Highly elastic polyurethane foam was manufactured using the polyol composition synthesized by the method shown in Reference Example and polyol B. The raw material formulation and the physical properties of the obtained foam are shown in Table 2 below.

【table】

Claims (1)

[Claims] 1. In a method for producing polyurethane by reacting a polyol and a polyisocyanate in the presence of a catalyst, an addition polymer component formed by polymerizing an addition polymerizable monomer in a polyol as the polyol , an aldehyde condensation polymer component formed by reacting a condensation-forming raw material capable of forming an aldehyde condensation polymer in a polyol, and the polyol used as the polymer medium as essential components, and the sum of these components In contrast, it is recommended to use a polyol composition in which the addition polymer component is 1 to 50% by weight, the aldehyde condensation polymer component is 1 to 50% by weight, and the total of both components is 60% by weight or less. Characteristic polyurethane manufacturing method. 2. The method of claim 1, wherein each polymer component is dispersed in fine particles in the polyol. 3. The method of claim 1, wherein at least a portion of the addition polymer component is grafted onto the polyol. 4. The method of claim 1, wherein at least a portion of the aldehyde condensation polymer is bonded to an addition polymer component. 5. The method of claim 1, wherein the polyurethane is a flexible or semi-rigid polyurethane foam.