JPH0372520A - Production and use of polyol containing-condensed resin dispersed therein - Google Patents

Abstract

PURPOSE:To produce a polyol containing a condensed resin dispersed therein and excellent in the dispersion stability of condensed resin particles by reacting a mixture or precondensate of an aldehyde with a compd. condensable with the aldehyde in an active hydrogen compd. contg. a polyol with a hydroxyl number of a specified value or lower. CONSTITUTION:A mixture or precondensate of an aldehyde with a compd. condensable with the aldehyde (e.g. phenol or melamine) is dispersed in an active hydrogen compd. (e.g. polyether polyol) contg. a polyol having a hydroxyl number of 28 or lower, and is condensed to form solid particles of a condensed aldehyde resin. The obtained polyol containing a condensed resin dispersed therein is reacted with a polyisocyanate to give a polyurethane foam having excellent strengths, elongation, resilience, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a stable condensed resin-dispersed polyol, particularly a polyol suitable as a polyurethane raw material in which a solid condensed resin condensed with aldehydes is dispersed. The present invention also relates to a method for producing polyurethane using the condensed resin-dispersed polyol.

[Prior Art] Conventionally, polyols called so-called polymer polyols or graft polyols have been known as polyols for polyurethane raw materials. Polymer polyols are obtained by polymerizing vinyl monomers such as acrylonitrile and styrene in liquid polyols such as polyether polyols and unsaturated polyols.

The vinyl polymer in the polymer polyol is either grafted onto the molecular chain of the polyol or simply dispersed within the polyol. Other known methods for producing polymer polyols include a method in which a previously produced vinyl polymer is simply dispersed in a polyol, and a method in which the dispersed vinyl polymer is then grafted onto a polyol. However, the polymer in conventional polymer polyols is most often a vinyl polymer, which is a linear polymer and is a type of thermoplastic resin.

Exceptionally, linear polyesters are known as polymers other than vinyl polymers, and polymer polyols have been obtained by dispersing them in polyols.

[Problems to be Solved by the Invention] The present inventor has studied a dispersion in which a condensation resin is dispersed in an active hydrogen compound. Conventionally, it has been known to use amino resin initial condensates as polyols for polyurethane raw materials. In this case, the amino resin initial condensate has a hydroxyl group that can react with isomyanate groups such as methylol groups, and polyurethane such as polyurethane foam was obtained by reaction of this initial condensate with a polyisocyanate compound (Japanese Patent Application Laid-open No. 53-16798). Furthermore, it is also known to produce polyurethane foam using a polyol mixture obtained by mixing an amino resin initial condensate and a normal polyol for polyurethane raw materials (Japanese Unexamined Patent Publication No. 52-15).
3000), and in this case it is also known to produce an amino resin initial condensate in a polyol (Japanese Unexamined Patent Publication No. 5
4-101848). It is difficult to recognize that the polyol containing this amino resin initial condensate is a type of polymer polyol. That is, the amino resin initial condensate is a type of relatively low molecular weight polyol containing hydroxyl groups such as methylol groups, and is not a high molecular weight polymer that can be recognized as a polyol in polymer polyols.

Therefore, it is not only difficult to achieve the effects of increasing the elasticity of polyurethane foam, which is a characteristic of polymer polyols, but also its use is limited to raw materials for rigid polyurethane foams. Furthermore, it is known to fill polyurethane with powder of cross-linked high molecular weight condensation resin as a filler, but it is difficult to stably disperse this filler in polyol, and it is difficult to disperse it stably in polyol. It was not possible to form a stable dispersion. Of course, this filler has no effect as a filler, that is, an increase in weight or improves the physical properties of polyurethane beyond its effect as a flame retardant, and can be substituted for the target polymer polyol and used for newer or more improved polymer polyols. It was impossible to achieve this effect. In addition, the Tokko Sho 5
7-14708 describes a method for producing a dispersion of an aminoblast condensate by condensing a substance capable of forming an aminoblast in a polyhydroxy compound, but this method also does not make the resin particles completely stable. It is not possible to obtain a dispersion, and only those with a high particle size have been obtained.

[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems, and the present invention has been made in order to solve the above-mentioned problems. A method for producing a condensed resin-dispersed polyol, which is characterized by condensing it in an active hydrogen compound containing the following polyol to form solid fine particles of an aldehyde condensed resin, and a method for producing a polyurethane using the obtained condensed resin-dispersed polyol. A manufacturing method is provided.

One of the constituent units of the condensed resin in the present invention is aldehydes. As the aldehydes, aliphatic aldehydes, alicyclic aldehydes, heterocyclic aldehydes, or derivatives such as condensates thereof can be used alone or in combination. Preferred aldehydes are lower aliphatic aldehydes, particularly aliphatic aldehydes having 4 or less carbon atoms, and derivatives thereof such as polymers.

Specific examples of preferred aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, paraformaldehyde, and paraacetaldehyde. These aldehydes can also be used dissolved in a solvent, and a particularly preferred solvent is water, but the solvent is not limited to this. A particularly preferred aldehyde in the present invention is formaldehyde, which is preferably used in aqueous solution (ie formalin).

Other constituent units of the condensed resin are compounds that can be condensed with aldehydes to form a solid condensed resin. This compound basically requires two positions (hereinafter referred to as reaction sites) that can react with aldehydes. Typical examples of the reaction site include, for example, a carbon atom to which hydrogen of an aromatic nucleus is bonded, or a nitrogen atom to which hydrogen of an amino group or an amide group is bonded. The reaction site of the aromatic nucleus is particularly preferably the ortho or para position of the aromatic nucleus to which a hydroxyl group or an amino group is bonded. Although the amino group has two reactive sites, a compound having a divalent amino group is preferably suitable. Preferred compounds that can react with aldehydes in the present invention include aromatic compounds such as phenolic compounds and aromatic amine compounds, and urea, melamine, and other polyamine compounds having two or more amine groups or amide groups. be.

The aromatic compound is preferably a compound having at least one phenolic hydroxyl group or amino group,
In particular, compounds having no substituents at at least two positions ortho or para to the functional group are preferred. Examples of phenolic compounds include phenol,
Cresol, xylenol, p-alkylphenol,
Examples include p-phenylphenol, bisphenol A, and resorcinol, which can be used alone or in combination with various phenolic compounds. Among these, a particularly preferred compound is phenol. Examples of aromatic amine compounds include aniline, diaminobenzene, p-alkylaniline, N-substituted alkylaniline, diphenylamine, and diaminodiphenylmethane, and as with phenolic compounds, two or more types can be used in combination. In aromatic or aliphatic amine compounds, the amino group or amide group itself also becomes a reactive moiety, so it may be considered as one type of diamine-based compound below; The number of parts may be one.

A particularly preferred aromatic amine compound is aniline. The aromatic compound is not limited to the above two types of compounds, and aromatic hydrocarbons such as benzene and xylene and other compounds can also be used. Furthermore, phenolic compounds and aromatic amine compounds can be used in combination,
Moreover, at least one of them can be further combined with other aromatic compounds.

The polyamine compound is a compound having two or more amino groups or amide groups, and particularly preferably a compound having two or more amino groups. One of the preferred polyamine compounds is a urea compound. Examples of urea-based compounds include urea, thiourea, and N-substituted urea, with urea being particularly preferred. Another preferred example of the polyamine compound is an s-triazine compound having two or more amino groups, representative examples of which are melamine compounds and guanamine compounds. Specific examples of the former include melamine and N-alkyl-substituted melamine, and the latter include benzoguanamine and acetoguanamine, with melamine and benzoguanamine being particularly preferred. Specific examples of various guanidine compounds that can be used include guanidine hydrochloride, aminoguanidine hydrochloride, and dicyandiamide. These polyamine compounds can be used in combination of two or more, and examples thereof include urea-thiourea, urea-melamine, urea-benzoguanamine, urea-melamine-benzoguanamine, and melamine-dicyandiamide.

The above aromatic compounds and polyamine compounds can also be used in combination. For example, phenol-urea, phenol-melamine, aniline-urea, aniline-melamine, phenol-aniline-urea, phenol-urea-melamine, and other combinations can be used.

Furthermore, compounds other than aromatic compounds and polyamine compounds can also be used as compounds capable of condensation with aldehydes. For example, there are ketone compounds known as raw materials for ketone resins.

Furthermore, initial condensates of aldehydes and compounds capable of condensation with aldehydes having the above-mentioned reactive sites and derivatives thereof can be used. This initial condensate can of course be used alone or in combination with the above-mentioned aldehydes and/or compounds that can be condensed with aldehydes. Examples of this initial condensate include methylol melamine such as hexamethylol melamine, methylol urea such as tetramethylol urea,
Examples include alkyl etherified methylolmelamine such as hexamethylolmelamine methyl ether, resol, and novolak.

The condensation resin dispersed in the polyol after the condensation of aldehydes and a compound that can be condensed with aldehydes is a cured resin that is conventionally known as a condensation thermosetting resin such as phenol resin, urea resin, and melamine resin. expected to be similar or identical to the object. Therefore, it is thought that the reaction for producing the condensed resin is also similar or the same. For example, in the initial stage of the reaction between a compound that can react with aldehydes and formaldehyde, various methylol group-containing compounds are generated by addition condensation, and then the methylol group-containing compounds are condensed by dehydration condensation etc. to form three-dimensionally cross-linked insoluble compounds. It is thought that it becomes an infusible condensation resin. The present invention is characterized in that when these reactions are carried out in a polyol to obtain a polyol in which a solid condensation resin is dispersed, the hydroxyl value of the polyol is 28 or less. The condensed resin in the condensed resin-dispersed polyol of the present invention is considered to have almost no hydroxyl groups due to residual methylol groups and the like. In addition, during its production, it is preferable to carry out a sufficient dehydration reaction so that no methylol groups remain. This condensation resin production reaction can be carried out in the presence of various additives if necessary. for example,
These include catalysts such as acid catalysts and alkali catalysts, curing agents such as hexamethylenetetramine, dispersion stabilizers, colorants, and other additives. Surfactants and solvents can be added to stabilize the particles.

A polyol is preferable as the active hydrogen compound used as a dispersion medium. Examples of polyols include polyether polyols, polyester polyols, hydroxyl group-containing polydiene polymers, polycarbonate polyols, etc.
In particular, there are polyols having 2 to 4 hydroxyl groups.

In particular, it is preferable to use only one or more types of polyether polyols, or to use them as the main component in combination with a small amount of polyester or hydroxyl group-containing polydiene polymers.

Examples of polyether polyols include polyhydric alcohols,
Preferred are polyether polyols obtained by adding a cyclic ether, particularly propylene oxide or ethylene oxide, to an initiator such as a sugar, an alkanolamine, or a polyhydric phenol.

In the present invention, at least a part of the active hydrogen compound needs to be a polyol having a hydroxyl value of 28 or less. By reacting the compound capable of condensing with the aldehyde and the aldehyde in the presence of this polyol having a low hydroxyl value, a finely divided condensation resin having excellent dispersion stability is formed.

The hydroxyl value of the more preferable low hydroxyl value polyol is 2 to 2.
20, especially 5-18. This polyol is
Polyoxyalkylene polyols and derivatives thereof are preferred. This polyol with a hydroxyl value of 28 or less can be used as the total amount of active hydrogen compounds, but other active hydrogen compounds,
In particular, it can be used in combination with the above-mentioned polyols. As the polyol used in combination with this low hydroxyl value polyol, polyoxyalkylene polyols are preferable, and among them, polyoxyalkylene polyols with a low hydroxyl value (80 or less), particularly polyoxyalkylene polyols with a hydroxyl value of 60 or less. Polyols are preferred. The average hydroxyl value of the above-mentioned low hydroxyl value polyol and the mixture thereof with the polyoxyalkylene polyol used in one well is preferably 60 or less, particularly preferably 5 to 34. As these polyoxyalkylene polyols, including polyols with low hydroxyl values, those commonly used as raw materials for polyurethane can be used.

However, it is difficult to synthesize polyoxyalkylene polyols with a particularly low hydroxyl value using ordinary alkali catalysts, so polyoxyalkylene polyols with a hydroxyl value of at least 28 or less include diethyl zinc, iron chloride, metal porphyrin, double metal cyanogen, etc. Those synthesized using a catalyst such as a compound complex are preferred. The polyoxyalkylene polyol is preferably a polyoxyalkylene polyol containing oxypropylene groups (oxypropylene group content of 70% by weight or more), but is not limited thereto. Examples of oxyalkylene groups other than oxypropylene include oxyethylene and oxybutylene, with oxyethylene being particularly preferred.

A compound capable of reacting with aldehydes and aldehydes react at room temperature to heating or under pressure.

Reactions at relatively low temperatures tend to produce compounds to which aldehydes such as methylol groups are added, as well as low molecular weight condensates, while at relatively high temperatures, methylene crosslinks and dimethylene ether bonds are likely to occur due to the dehydration reaction of methylol groups. Conceivable. Of course, the compounds produced are not related only to the reaction temperature, but also to the charging ratio of each constituent unit and the presence of additives such as catalysts.
Varies depending on H. However, considering only the reaction temperature, it is preferable in the present invention to carry out the reaction at a relatively low temperature in the first stage of the reaction and at a relatively high temperature in the second stage of the reaction. In particular, the latter reaction is often necessary to carry out the condensation reaction of hydroxyalkyl groups such as methylol groups. The upper limit of the reaction in the latter stage is preferably a temperature at which side reactions other than the decomposition of the polyol and the production reaction of the condensed resin are unlikely to occur, and is usually preferably 80 to 200°C. In order to proceed with the condensation at a relatively low temperature, acids such as hydrochloric acid, acetic acid, NaO
A base such as H, triethylamine can also be used as a catalyst.

The amount of condensation resin in the condensation resin-dispersed polyol to be produced is not particularly limited, but is preferably 5 to 80% by weight, particularly 5 to 60% by weight.

Those with a high proportion of condensed resin can be diluted with the above-mentioned polyoxyalkylene polyol when used as a raw material for polyurethane.

The condensed resin-dispersed polyol obtained in the present invention is used as a polyol for polyurethane raw materials, either as it is or diluted with a polyol or the like.

As the polyurethane, polyurethane foams such as flexible polyurethane foams are particularly preferred, and polyurethane foams with excellent flame retardancy can be obtained. Polyurethane is obtained by reacting the above-mentioned polyol and polyirisyanate compound in the presence of auxiliary agents such as catalysts, and when producing foam, it is reacted in the presence of auxiliary agents such as catalysts, blowing agents, and even foam stabilizers. Obtained by reaction.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Example 1) Starting glycerin in a 5I2 pressurized reaction tank with a molecular weight of 10,000
(hydroxyl value 16.8), ethylene oxide content 10%
Polyoxybrobyleneoxyethylene polyol 24
00 parts by weight, 600 parts by weight of melamine, and 800 parts by weight of 35% formalin aqueous solution were added, and while stirring, 100 parts by weight of melamine was added.
After reacting at °C for 4 hours, dehydration was performed under reduced pressure to obtain a white viscous polyol dispersion.

(Example 2) In a 5β pressurized reaction tank, starting with glycerin, molecular weight 8000 (
Hydroxyl value 21) 1500 parts by weight of polyoxypropylene oxyethylene triol with an ethylene oxide content of 10%, 1000 parts by weight of trimethylolmelamine, 500 parts by weight of dicyandiamide, 500 parts by weight of water, and 500 parts by weight of ethanol were charged, and the mixture was heated at 80°C with continuous stirring. After reacting for 4 hours, water and ethanol were degassed under reduced pressure while gradually heating the mixture to 140° C. to obtain a blue-white paste-like polyol dispersion. This dispersion was diluted to 1/2 concentration with polyoxypropyleneoxyethylene triol having a molecular weight of 5,000 and an ethylene oxide content of 15% starting with glycerin to obtain a polyol dispersion having low viscosity and good particle dispersion stability.

(Comparative Example 1) A reaction was carried out under the same reaction conditions as in Example 1 using polyoxypropyleneoxyethylene triol starting with glycerin, having a molecular weight of 3000 (hydroxyl value 56.1), and an ethylene oxide content of 15%. A stable polyol dispersion with coarse particles could not be obtained.

Table 1 shows the urethane foam properties of the polyol dispersion obtained by the above method.

(Example 3) [Foam manufacturing method] 100 parts by weight of a mixture of polyol and polyol dispersion, 7 parts by weight of water, 43 parts by weight of D A B CO33-LVO, 0.3 parts by weight of N-ethylmorpholine, silicone foam stabilizer L A mixture of 2 parts of -574O3 (manufactured by Nippon Unica), 0.2 parts by weight of stannous octoate (T-9) and tolylene diisocyanate (T-80) with an index of 105
After stirring and mixing so that
The mixture was poured into a mold (mold temperature: 40°C) and cured for 12 minutes in Oats 2 at 180°C.

Table 1 shows the urethane foam properties of the polyol dispersion obtained by the above method.

Table 1 [Effects of the invention] The present invention relates to a method for producing a polyol composition in which particles of an aldehyde condensation resin are dispersed in a polyol,
The method of allowing the condensation reaction to proceed in the presence of a polyol having a hydroxyl value of 28 or less to precipitate fine particles has the effect that a polyol composition with excellent particle dispersion stability can be obtained. Furthermore, the urethane foam using the polyol dispersion based on the high molecular weight polyol obtained in this way has higher hardness, strength, and strength compared to the system based on the low molecular weight polyol.
It also has the effect of improving physical properties such as elongation, impact resilience, and flame retardancy.

These results show that the physical properties of urethane foams using polyol dispersions with high molecular weight polyols as the base polyol are not only improved in hardness and strength, but also in elongation, impact resilience, flame retardancy, etc. compared to low molecular weight based foams. It can be seen that the physical properties of are also improved.

Claims (1)

[Claims] 1. Compounds that can be condensed with aldehydes and aldehydes,
or a method for producing a condensed resin-dispersed polyol, which comprises condensing an initial condensate of both in an active hydrogen compound containing a polyol having a hydroxyl value of 28 or less to form solid fine particles of an aldehyde condensed resin. 2. The method according to claim 1, wherein the polyol having a hydroxyl value of 28 or less is a polyether polyol. 3. A method for producing polyurethane, which comprises reacting a condensed resin-dispersed polyol obtained by the method according to claim 1 or a polyol containing the same with a polyisocyanate compound as a main raw material. 4. The method according to claim 3, wherein the polyurethane is polyurethane foam.