JPS6333768B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyol composition containing an addition polymer component and an aldehyde condensation polymer component, and a method for producing the same. The present invention relates to a polyol composition with improved dispersion stability and a method for producing the same. 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 the addition polymer or other polymer into fine particles in a polyol. It is obtained by a method of dispersing. 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. It is a liquid dispersion in which the combined 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. 41-3437, Special Publication No.
43-22108 Publication, Special Publication No. 46-20508, Special Publication No. 51-37228, Publication No. 40914-1980, Publication No. 40914-1972, Publication No. 40915-1972, Publication No. 3439-1972,
It is described in Special Publication No. 52-13834 and other publications. Among the latter methods 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. 47597-1982, Japanese Patent Publication No. 40788-1988, Japanese Patent Publication No. 1987-40788,
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 retardance 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 are known in which an aldehyde condensation polymer is formed in a polyol, and the aldehyde condensation polymer is dispersed in the polyol.
It is described in Japanese Patent Application Publication No. 51-122193, etc. According to these publications, melamine, urea,
Polymer-dispersed polyols similar to the above polymer polyols can be produced by oligopolycondensing or polycondensing other aminoplast-forming compounds and aldehydes in polyols; It is characterized by simply acting as a reaction medium without participating in the reaction. 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 a polyol in which a pre-prepared aldehyde condensation polymer is dispersed. However, the above-mentioned Japanese Patent Application Publication No. 51-
As can be seen from the description in Publication No. 122193, its dispersion stability was not necessarily sufficient, inferior to the dispersion stability of the polymer polyol, and sedimentation separation was likely to occur. In addition, its characteristics are
Although it improves the flame retardancy of polyurethane obtained by using it, some of its performances, such as the effect of increasing the elasticity of polyurethane foam, are not as good as the polymer polyols described above. The present inventors first investigated the improvement of the dispersion stability of polyols containing the above 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, other possible reasons include the small particle size of the addition polymer and the high affinity between the addition polymer and the polyol. On the other hand, even if an aldehyde condensation polymer is formed in a polyol, the bond between the polyol and the aldehyde condensation polymer is No reaction occurs, and 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, a reactive part (referred to as a reactive part as described later) that can be condensed with aldehydes in a polyol
However, it is not easy to introduce such reactive sites into ordinary polyols.
Therefore, as a result of various research studies on this point, the present inventors have determined that an aldehyde condensation polymer may be bonded to the addition polymerization polymer in the polymer polyol, thereby indirectly bonding the polyol and the aldehyde condensation polymer. I discovered that I could achieve my goals by doing this. As mentioned above, it seems that the addition polymer component in the polymer polyol is not necessarily grafted to the polyol, but even if it is not grafted, the addition polymer component can be well dispersed. By introducing 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 the above-mentioned polyol composition, that is, a condensation polymer component capable of forming an aldehyde condensation polymer with an addition-polymerizable polymer component formed by addition-polymerizing an addition-polymerizable monool in a polyol. An aldehyde condensation polymer component formed by reacting raw materials in a polyol, and further comprising a functional group co-condensable with a part of the condensation-forming raw materials and an unsaturated group copolymerizable with the addition polymerizable monomer. A copolymerizable addition-polymerizable monomer having a co-condensable addition-polymerizable monomer is copolymerized with both the above-mentioned condensation-forming raw material and the addition-polymerizable monomer, and at least a portion of the above-mentioned two types of polymers are copolymerized, and the above-mentioned Polyol is an essential component, and based on the total of these three components, 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 A polyol composition for producing polyurethane, characterized in that: It is. The polyol of the present invention will first be explained using specific examples. For example, the aldehyde condensation polymer component is a polycondensate of melamine and formaldehyde,
The case where the addition polymerization type polymer component is a copolymer of acrylamide and acrylonitrile will be described. The important point is that acrylamide is a monomer that can undergo addition polymerization, and that it can also be condensed with formaldehyde. For example, when melamine and formaldehyde are reacted in the polymer polyol containing an addition copolyol of acrylamide and acrylonitrile, a so-called melamine polycondensate is formed, and formaldehyde and the amide group of the acrylamide structural unit are condensed. , an addition polymerization copolymer and a melamine polycondensate are combined. When the addition copolymer in the polymer polyol is grafted to the polyol, the melamine polycondensate is bonded to the addition copolymer, so it is bonded to the polyol via the addition copolymer. . Therefore, compared to conventional melamine-based polycondensates which are merely dispersed in polyols, the dispersion stability in polyols is significantly improved. On the other hand, even if the addition copolymer is not grafted onto the polyol, the dispersion stability of the addition copolymer is imparted to the melamine polycondensate, thereby stabilizing the dispersion of the melamine polycondensate. Improves sex. Thus, in the present invention, the addition polymer component requires a functional group capable of reacting with the aldehyde condensation polymer and bonding the two. This functional group is either an amino group, an amide group, or a functional group that has at least one reactive site (described later) that can be condensed with aldehydes, or a methylol group, an aldehyde group, etc. that can be condensed with a compound that has these reactive sites. It is a functional group. As mentioned above, the polyol composition of the present invention can be produced by forming an aldehyde condensation polymer in the presence of an addition polymer component having these functional groups in a polyol; It can also be produced by other methods, such as a method in which addition polymerization of an addition polymerizable monomer having these functional groups and formation of an aldehyde condensation polymer are carried out almost simultaneously, or addition polymerization having these functional groups. It can be produced by, for example, a method in which a polyester monomer is reacted with at least one type of raw material capable of forming an aldehyde condensation polymer (hereinafter referred to as a condensation-forming raw material), and then this reaction product is subjected to addition polymerization. Using the same example as above, for example, after mixing melamine, acrylamide, and formaldehyde into a polyol and heating and dissolving the mixture, adding or adding a mixture of the polyol, acrylonitrile, and an addition polymerization initiator, and performing addition polymerization and polymerization. The polyol composition of the present invention can be produced by condensation. In this case, when melamine, acrylamide and formaldehyde are heated and dissolved in the polyol, some condensation reaction may occur. Therefore, if this part of the reaction is performed intentionally, a similar polyol composition of the present invention can also be produced by addition polymerizing an initial condensate or condensate of melamine, acrylamide, and formaldehyde together with acrylonitrile in a polyol. be able to. The present invention also relates to a method for producing the above polyol composition, that is, an addition polymer component formed by addition polymerizing an addition polymer synthesis monomer in a polyol, and an aldehyde condensation polymer. An aldehyde condensation polymer component formed by reacting condensation forming raw materials that can be formed in a polyol, and the above polyol as essential components, and the addition polymer component is 1 to 50% of the total of these three components. When producing a polyol composition in which the aldehyde condensation polymer component is 1 to 50% by weight and the total of both components is 60% by weight or less, a functional cocondensable with a part of the condensation forming raw materials is used. Using a co-condensable addition-polymerizable monomer having a group and an unsaturated group copolymerizable with the above-mentioned addition-polymerizable monomer, addition polymerization of it with another addition-polymerizable monomer, the co-condensable addition-polymerizable monomer or A method for producing a polyol composition for producing polyurethane, characterized in that a condensation reaction between the polymer and a condensation-forming raw material and a polycondensation of the condensation-forming raw material are carried out simultaneously or sequentially in a polyol. It is. The order in which the above three reactions are performed is not particularly limited. Furthermore, two reactions can be performed simultaneously and then the remaining reactions can be performed, or one reaction can be performed and then the remaining two reactions can be performed simultaneously. Of course, the three reactions can also be carried out simultaneously. However, these reactions usually occur together, and it is often impossible to distinguish one reaction from another. In particular, the reaction between the condensation-forming raw material and the condensable addition-polymerizable monomer or its polymer is difficult to distinguish from the polycondensation of the condensation-forming raw material, and is generally thought to occur simultaneously. Therefore, the reaction can be broadly classified into two reactions: addition polymerization and condensation reaction (including polycondensation), and the above-mentioned production method can be broadly classified into whether these two reactions are performed simultaneously or separately. A preferred method is to carry out at least part of the addition polymerization and condensation reaction simultaneously, and then to carry out the addition polymerization and then the condensation reaction. The remaining method of first carrying out a condensation reaction and then carrying out addition polymerization is not a particularly preferable method, but as described below, an initial condensate is produced by the first condensation reaction, this is subjected to addition polymerization, and then the next step is carried out. Preferred among these methods are a method in which a condensation reaction is further carried out, or a method in which an initial condensate is produced and then the remaining condensation reaction and addition polymerization are carried out. The most preferred method is one in which addition polymerization and at least part of the condensation reaction are carried out simultaneously. The above-mentioned specific examples of the above-mentioned manufacturing method are shown below in order of preference. (1) A method in which melamine, formaldehyde, acrylamide, and acrylonitrile are reacted by heating in a polyol in the presence of an addition polymerization initiator. In this case, the reaction may be carried out while adding acrylonitrile gradually as described above. In this method, addition polymerization and condensation reaction proceed almost simultaneously. However, producing the final melamine-formaldehyde condensation polymer usually requires a post-reaction, which is carried out to complete the condensation reaction, such as dehydration of the methylol group. It is also preferable to remove simultaneously generated water or mixed water. (2) Acrylamide and acrylonitrile are first subjected to addition polymerization in a polyol, and then melamine and formaldehyde are added to perform a condensation reaction. As described above, this corresponds to a conventional method for producing an aldehyde condensation polymer, in which a polyol containing an addition polymer capable of reacting with an aldehyde-forming raw material is used as the polyol. (3) A method in which an initial condensate of melamine, formaldehyde, and acrylamide is addition-polymerized together with acrylonitrile in a polyol, and the condensation reaction is carried out simultaneously or thereafter with or without the addition of at least one of melamine and aldehyde. Initial condensate refers to a relatively low molecular weight condensate whose molecular structure is difficult to clearly determine. In the present invention, compounds such as N-methylolacrylamide, which is a condensate of acrylamide and formaldehyde, are one of the condensable addition polymerizable monomers. Considered a seed. In the present invention, the condensable addition-polymerizable monomer includes functional groups and addition-polymerizable groups that can be bonded to the condensation-forming raw materials described below through a condensation reaction, particularly α,β-unsaturated groups such as vinyl groups and vinylidene groups. It is called a compound that has . Specific examples include acrylamide, N-methylolacrylamide,
Examples include acrolein, hydroxyethyl methacrylate, aminoethyl methacrylate, vinylpyridine, vinylphenol, vinylaniline, etc., and addition polymerizable monomers having an amino group or an amide group are particularly preferred. These condensable addition-polymerizable monomers can be used alone or in combination of two or more thereof, but are more preferably used in combination with other addition-polymerizable monomers. In this case, the proportion of the condensable addition-polymerizable monomer in all the addition-polymerizable monomers is preferably 2% by weight or more, particularly 10% by weight or more. Various addition polymerizable monomers can be used in combination, including acrylonitrile monomers such as acrylonitrile and methacrylonitrile, styrene monomers such as styrene and divinylbenzene, and methyl methacrylate and ethyl acrylate. Examples include acrylic monomers, vinyl acetate monomers, halogenated vinyl monomers, diene monomers such as butadiene, and others. Particularly preferred are acrylonitrile monomers, styrene monomers, and acrylic monomers, with acrylonitrile and styrene being most preferred. Two or more of these addition-polymerizable monomers can be used in combination, and combinations containing acrylonitrile or styrene as main components, and combinations of both are particularly preferred. When polymerizing these addition-polymerizable monomers, an addition polymerization initiator is usually used, such as an azo compound such as azobisisobutyronitrile or a peroxide such as benzoyl peroxide. Appropriate. Addition polymerization can also be carried out using ultraviolet rays or other radiation. Aldehyde condensation polymers are produced from synthetic raw materials, and the condensation raw materials are at least a combination of aldehydes and compounds that can be polycondensed with aldehydes (hereinafter referred to as polycondensable compounds), or at least an initial condensation product of both of them. Consisting of As the initial condensate,
Particularly preferred are reaction products of a polycondensable compound having a methylol group and formaldehyde, such as novolak, methylol urea, dimethylol urea, polymethylol melamine, and alkyl etherified polymethylol melamine. These initial condensates can be reacted alone to form an aldehyde condensation polymer, but they can also be reacted together with aldehydes or polycondensable compounds. As the aldehydes, aliphatic, alicyclic, aromatic, and other aldehydes, condensates thereof, and derivatives such as compounds capable of generating aldehydes can be used. Preferred aldehydes are aliphatic aldehydes having 6 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. The condensable addition-polymerizable monomer can be regarded as a compound having only one reactive site, and the condensable addition-polymerizable monomer having two or more reactive sites is regarded as one type of polycondensable compound herein. You can also do that. Examples of the aromatic compounds mentioned above include phenol, cresol, xylenol, P-alkylphenol, bisphenol A, resorcinol,
Dihydroxydiphenylmethane, other phenols, and aromatic amines such as aniline, diaminobenzene, P-alkylaniline, N-substituted alkylaniline, and diaminodiphenylmethane are suitable, and aromatic amines are particularly preferred. Since the amino group of the aromatic amine is also a reactive site, the aromatic nucleus may have one or less reactive sites. Examples of polyamine compounds include:
Ureas such as urea, thiourea and N-substituted urea, guanidines such as guanidine and N-substituted guanidine, S-triazines such as melamine, N-substituted melamine, benzoguanamine, acetoguanamine and N-substituted guanamine are suitable. It is. Among these, particularly preferred are urea, guanidine,
Melamine, benzoguanamine, dicyandiamide, and the combination of two or more of these;
Alternatively, it is also preferable to use these together with phenol and/or aniline. Furthermore, as mentioned above, it is also preferable to use monoamines, alkanolamines, and other compounds having one reactive site together with these. The formation of the addition polymerization type polymer and the formation of the aldehyde condensation type polymer are carried out in a polyol. As these polyols, unsaturated polyols or substantially saturated polyols can be used, and unsaturated polyols are particularly preferred. Examples of unsaturated polyols include those described in the six publications listed below, as well as the nitrogen-containing unsaturated polyol (Japanese Unexamined Patent Application Publication No. 56-1988) according to the invention of the present inventors. -90818, JP-A-56-93724, and JP-A-56-93729).
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. As a substantially saturated polyol,
Examples include polyether polyol, polyester polyol, polyether ester polyol, polycarbonate polyol, and hydroxyl group-containing hydrocarbon polyol. Particularly preferred are polyether polyols, such as polyhydric alcohols, polyamines,
Preferred are other polyether polyols obtained by adding an epoxide, particularly an alkylene oxide having 2 to 4 carbon atoms, to an initiator having two or more active hydrogens, and polyether polyols obtained by ring-opening polymerization of a cyclic ether. The most preferred is a polyether polyol obtained by adding propylene oxide or propylene oxide and ethylene oxide to a divalent to tetravalent initiator. Two or more of these polyols may be used in combination. Further, these polyols preferably have a hydroxyl value of 800 or less and a number of 2 to 8 hydroxyl groups, and particularly preferably a hydroxyl value of 20 to 200 and a number of hydroxyl groups of 2 to 4. These unsaturated or substantially saturated polyols are preferably liquid at room temperature; Melting point polyols may also be used. Addition polymerization in polyols is usually carried out under heating. This temperature is preferably higher than the temperature at which the addition polymerization initiator can become radicals by decomposition or the like. The addition-polymerizable monomer can be polymerized by charging the entire amount into a reactor filled with polyol, or can be polymerized by gradually adding a portion thereof to the reactor. Thus, addition polymerization in polyols can be carried out using conventional methods for producing polymer polyols. Furthermore, a polyol containing an addition polymer component can also be produced by dispersing a pre-prepared addition polymer in a polyol, or by grafting it onto a polyol. As for the method for producing an aldehyde condensation polymer in a polyol, the method described in the above-mentioned Japanese Patent Application Laid-Open No. 50-15832 and subsequent publications can be directly applied to the production method of the present invention, but this known method It is not limited to only. The reaction rate of the condensation forming raw materials is preferably not particularly limited as long as a solid, particulate polymer can be formed. However, the ratio of the aldehyde to 1 mole of the polycondensable compound is usually preferably 0.5 to 3.0 moles, particularly 0.8 to 2.5 moles, and more preferably 0.9 to 1.5 moles. The reaction of both polyols is usually carried out under heating; if addition polymerization is not performed, the temperature is below 60°C in the first half, and above 70°C in the second half, and if addition polymerization is carried out simultaneously, addition polymerization occurs in the first stage. It is preferable that the reaction is carried out at a temperature higher than the above temperature and at a relatively low temperature, with the subsequent reaction being carried out at a higher temperature. 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 (e.g., 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 As mentioned above, it is preferable that the aldehyde condensation polymer component in the polyol composition of the present invention has few, particularly substantially no, hydroxyl groups resulting from aldehydes. If the polyol does not contain an addition polymer component, the hydroxyl value of the polyol containing an aldehyde condensation polymer component is as follows:
The hydroxyl value of the original polyol decreases in proportion to the amount of 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 polyol containing the aldehyde condensation type polymerization component is preferably 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. In the case of the polyol composition of the present invention containing an addition polymer component, if the addition polymer does not contain hydroxyl groups, the apparent hydroxyl value of the polyol similarly decreases as its proportion increases. . The polyol composition of the present invention is preferably a dispersion in which finely divided solids are dispersed in a polyol. It is presumed that the fine particulate solid is composed of an addition polymer, an aldehyde condensation polymer, and a combination or mixture of the two. From the viewpoint of dispersion stability, it is preferable that part to all of the addition polymer is grafted onto the polyol. It is thought that when unsaturated polyols are used, the proportion of grafting occurring is high. In some cases, the particulate solid may not contain only one polymer. For example, it is known that transparent polymer polyols containing no particulate solids can be obtained from known polymer polyols using unsaturated polyols, and according to the studies of the present inventors, aldehyde condensation polymers formed in polyols can be obtained. This is because it is possible to produce a product evenly mixed with a polyol. Therefore, some polyol compositions of the present invention may not contain particulate solids. The aldehyde condensation polymer dispersed in the polyol as a fine particulate solid is a relatively high molecular weight condensate polycondensed in a two-dimensional or three-dimensional shape such as a linear to network shape, and more preferably a three-dimensional condensation product. It is a condensate and does not dissolve in ordinary resin-soluble solvents. Also, although it does not melt when heated, it becomes molten and decomposes when heated at high temperatures. Therefore, such a condensate is considered to correspond to a cured product of a conventional thermosetting aldehyde condensation resin such as a melamine resin or a urea resin. The appearance of the polyol composition of the present invention is usually a white to colored translucent to opaque viscous liquid. Although its viscosity may vary depending on various conditions, it is preferably 20,000 centipoise or less at 25°C. Since the polyol composition of the present invention can be diluted with a polyol or other liquid, compositions with higher viscosities than this can also be diluted and used. The proportion of each component in the polyol composition of the present invention is not particularly limited, but the addition polymer component is 1 to 50% by weight, and the aldehyde condensation polymer component is 1 to 50% by weight. The total amount of both components is preferably 60% by weight or less. Of course, if there are no restrictions such as viscosity, the proportion of each component can be further increased. In addition, the relative proportions of both components can be changed depending on the purpose. For example, when the purpose is to make polyurethane flame retardant or to improve the dispersion stability of the aldehyde condensation polymer component, the aldehyde condensation polymer component The proportion of the addition polymer component can be increased, and it is effective even if the proportion of the addition polymer component is 10% by weight or less based on the polyol composition. More preferably, the proportion of both components in the polyol composition is 2 to 40% by weight of the addition polymer component, 5 to 40% by weight of the aldehyde condensation polymer component, and the total of both is 7 to 40% by weight.
It is appropriate that the weight ratio of both components is 1 to 1 of the addition polymer component to 0.2 to 10 of the aldehyde condensation polymer component. Also,
The hydroxyl value of the polyol composition of the present invention is 200 or less,
In particular, it is preferably 5 to 100. The polyol composition of the present invention is used as a raw material for polyurethane. That is, it is suitable as part to all of the polyol that is the main raw material for polyurethane. The polyol composition of the present invention is as effective as conventional polymer polyols in improving the hardness, modulus, etc. of polyurethane. Moreover, whereas conventional polymer polyols actually lower the flame retardance of polyurethane, the present invention The polyol composition improves the flame retardancy of polyurethane. In particular, those obtained using phenols, ureas, guanidines, and S-triazines are particularly effective in improving flame retardancy. Polyurethane can be roughly divided into foam polyurethane and non-foam polyurethane. Non-foam polyurethane includes, for example, elastomers, hard resins, waterproof materials, sealants,
Some are used for paints and other purposes. The polyol composition of the present invention is particularly suitable as a raw material for polyurethane foam, particularly for flexible polyurethane foam and semi-rigid polyurethane foam. These polyurethanes can be manufactured by using polyols such as the above-mentioned polyether polyols together with the polyol composition of the present invention. Further, as a chain extender or crosslinking agent, a relatively low molecular weight polyol, especially a polyhydric alcohol, a compound having active hydrogen such as a polyamine, or a compound having an active hydrogen such as a polyol composition can be mixed or used separately. In the production of polyurethane foam, a blowing agent such as water or a halogenated hydrocarbon is usually used, and in some cases, an inert gas such as air is mixed into the foam. As a halogenated hydrocarbon blowing agent,
Trichloroolomethane, dichlorodifluoromethane, methylene chloride, etc. are suitable. Further, a foam stabilizer is usually used, and organosilicon compounds such as poly(dialkylsilane) and polyoxyalkylene chain-containing silane are suitable as the foam stabilizer. Furthermore, in many cases, it is essential to use a catalyst, and typical catalysts include tertiary amine catalysts and organometallic compound catalysts. In addition, various additives can be optionally used when producing polyurethane foam.
Examples include fillers, reinforcing agents, stabilizers, colorants, flame retardants, mold release agents, foam breakers, crosslinking agents, chain extenders, and the like. These catalysts and other additives may also be used in the production of non-foam polyurethanes, in particular catalysts are usually essential raw materials. Other basic raw materials for polyurethanes 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, isophorone diisocyanate, etc. .
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 for example, methods such as the one-shot method, prepolyol method, quasi-prepolyol 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. The polyether polyols used in the examples are as follows. Polyol A: Polyoxypropylene ethylene triol with a molecular weight of 3000, which is 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. Example 1 8 parts of urea (parts by weight, the same applies below), 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. After cooling the system to 30°C, 80 parts of polyol B, 6 parts of acrylonitrile, and 2 parts of styrene were added.
1 part and 0.5 part of α,α'-azobisisobutyronitrile were added at the same time and heated to 80°C. 35% at 80℃
6 parts of formaldehyde aqueous solution is fed to the reactor every hour or so. After supply is finished, keep at 80℃ for another 1 hour.
After a post-reaction, the system was heated to 100°C and reacted 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. The hydroxyl value was 26.5, and the viscosity at 25°C (the same applies hereinafter) was 2920 cps. The resin component in this polyol composition is stably dispersed,
No separation was observed over two months. The obtained polyol composition was diluted 10 times with methanol, and a centrifugation test (the same applies hereinafter) for the dispersed resin was performed at 3000 rpm using a centrifuge. The resin content recovered was 21% of the resin content contained in the polyol composition. Example 2 5 parts of urea, 7 parts of 80% acetaldehyde aqueous solution,
Charge 3 parts of acrolein and 10 parts of water into a reactor, and
Incubate at ℃ for 2 hours. Charge 90 parts of polyol C into a reactor and raise the temperature to 100°C. α,α′-Azobisisobutyronitrile in 5 parts of methyl methacrylate
Dissolve 0.5 part of the solution and feed for 5 hours or more. Next, add 7 parts of 80% acetaldehyde aqueous solution to 1 part.
Supply once or twice. After the supply was completed, the temperature was raised to 140°C and degassed under reduced pressure to obtain a white viscous polyol composition. It had a hydroxyl value of 23.4 and a viscosity of 2530 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 23% of the resin content contained in the polyol composition. Example 3 70 parts of polyol A, 10 parts of acrylonitrile, 5 parts of methyl methacrylate, 3 parts of N-methylolacrylamide, and 0.6 parts of α,α'-azobisisobutyronitrile were charged into a reactor and reacted at 100°C for 5 hours. Cool to 60℃, add 6 parts of urea and 6 parts of melamine.
2 parts, 32 parts of 40% glyoxal aqueous solution,
The mixture was allowed to react for an hour, then the temperature was raised to 80°C, and the reaction was continued for an additional 2 hours. In order to remove water in the system and complete the condensation reaction, dehydration was performed under reduced pressure at 140°C to obtain a yellow-white viscous liquid. It had a hydroxyl value of 37.8 and a viscosity of 4290 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 is the resin content contained in the polyol composition.
It was 18%. Example 4 85 parts of polyol B and 3 parts of acrylamide were charged into a reactor and heated to 120°C. α,α′-Azobisisobutyronitrile in 8 parts of acrylonitrile
A solution containing 0.6 parts was fed for 3 hours. After post-reaction was carried out at 120°C for 30 minutes, unreacted monomers were degassed under reduced pressure. Cool to 90° C. and feed an aqueous solution of 9 parts of urea dissolved in 26 parts of a 35% formaldehyde aqueous solution to the reactor for 3 hours. After the supply is finished, the temperature is raised to 100°C and post-reaction is carried out for 1 hour. Water in the system was removed and dehydration was performed under reduced pressure to complete the condensation reaction to obtain a yellowish brown viscous polyol composition. Hydroxyl value
27.6, and the viscosity was 2610 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 15% of the resin content contained in the polyol composition. Example 5 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. Example 6 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. Example 7 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 carried out 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 %. Example 8 80 parts of polyol D, 0.8 parts of maleic anhydride, and 1.6 parts of ethylene oxide are charged into a reactor, and after reacting at 150°C for 5 hours, unreacted components are removed by degassing.
This modified polyol contains 5 parts of melamine, 5 parts of urea,
Introduce 10 parts of 80% acetaldehyde aqueous solution and heat at 60°C.
The reaction was continued for an additional 2 hours. Raise the temperature to 100℃ and add 5 parts of acrylonitrile and 5 parts of methyl methacrylate.
1 part, 3 parts of acrolein, and 0.6 part of α,α'-azobisisobutyronitrile were fed for 5 hours.
After post-reaction was carried out at 100°C for 30 minutes, deaeration was carried out under reduced pressure at 140°C in order to remove unreacted monomers and residual water and complete the condensation reaction. The obtained polyol composition is a yellowish white viscous liquid with a hydroxyl value.
24.7, and the viscosity was 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 Examples 1 to 6 The polyol compositions of Examples and polyol A were mixed to produce polyurethane foams by hot molding. The raw material formulation used and the physical properties of the obtained foam are shown in Table 1 below. 【table】

Claims (1)

[Scope of Claims] 1. An addition-polymerizable polymer component formed by addition-polymerizing an addition-polymerizable monomer in a polyol and a condensation-forming raw material capable of forming an aldehyde condensation-based polymer are reacted in a polyol. A cocondensable addition polymerizable monomer which is an aldehyde condensation polymer component and further has a functional group cocondensable with a part of the above condensation forming raw materials and an unsaturated group copolymerizable with the above addition polymerizable monomer. Two components in which at least a portion of the two types of polymers are copolymerized, which are copolymerized with both the condensation forming raw material and the addition-polymerizable monomer, and the above polyol as essential components, and these three components 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
A polyol composition for producing polyurethane, characterized in that the content is 60% by weight or less. 2 The co-condensable functional group is an amino group, an amide group,
The composition of claim 1, wherein the functional group is selected from a methylol group and an aldehyde group. 3. An addition polymer component formed by addition polymerizing an addition polymerizable monomer in a polyol, an aldehyde condensation polymer formed by reacting a condensation forming raw material capable of forming an aldehyde condensation polymer in a polyol. component, and the above-mentioned polyol as essential components, and based on the total of these three components, 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, a co-condensable addition having a functional group co-condensable with a part of the above-mentioned condensation forming raw materials and an unsaturated group co-polymerizable with the above-mentioned addition-polymerizable monomer. Using a polymerizable monomer, addition polymerization with another addition polymerizable monomer, condensation reaction of the co-condensable addition polymerizable monomer or its polymer with a condensation forming raw material, and polycondensation of the condensation forming raw material in a polyol. A method for producing a polyol composition for producing polyurethane, characterized in that the steps are carried out simultaneously or sequentially. 4 The co-condensable functional group is an amino group, an amide group,
4. The method of claim 3, wherein the functional group is selected from a methylol group and an aldehyde group. 5. The method of claim 3, wherein the addition polymerization, condensation reaction and polycondensation are carried out substantially simultaneously in the polyol. 6. The method according to claim 3, wherein addition polymerization of a co-condensable addition polymerizable monomer and another addition polymerizable monomer is performed in a polyol, and then a condensation forming raw material is added to perform a condensation reaction and polycondensation.