JPS5832625A - Preparation of rigid polyurethane foam - Google Patents

Abstract

PURPOSE:To obtain a rigid polyurethane foam having excellent dimensional stability, etc. in high efficiency, with reduced amount of catalyst, by reacting a polyisocyanate with a polyol obtained by the addition reaction of a specific four-component reaction product to an epoxide. CONSTITUTION:The objective foam is prepared by reacting (A) a polyol obtained by the addition reaction of (I) an epoxide (preferably propylene oxide, etc.) to (II) a reaction product of (i) a phenolic compound of formula A-OH (A is aromatic nucleus having two reactive sites) (preferably phenol), (ii) an aromatic amine of formula B-NH2 (B is A) (preferably aniline), (iii) an aldehyde (preferably formaldehyde), and (iv) an alkanolamine (preferably diethanolamine), with (B) a polyisocyanate (preferably tolylene diisocyanate, etc.), in the presence of a catalyst, a foaming agent, a foam stabilizer, etc. The reaction is carried out preferably by spraying.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a large hard polyurethane with a 70A OA using a novel polyol. Polyurethane is usually a polyol. A reaction between the active hydrogen-containing compound and the polyincyanate compound is obtained.

Polyol 0 Representative polyol is a polyether polyol produced by adding Inishekku kappa alkylene oxide.

The initiator is a compound having 2 or more 0 active hydrogens.
Typical examples of active hydrogen include hydrogen in mineral hydroxyl groups and hydrogen in adenate groups. Polyurethane 7-oh, which is polyurethane type 01, is divided into soft 7-oh and hard 7-oh by enlargement.
There is ohm. The 0 polyol for soft ▲ is mainly a polyol having hydroxyl groups of K2 to 4, but for hard 7 and 5. Polyols having three or more O hydroxyl groups, usually up to Fia, are used. As a special O initiator for producing O-boliol for A-quality foam, a mixture of bran, sugar, and O-4 alcohol such as glycerin is often used, but depending on the application, aromatic Initiation may also be used.

It is said that a rigid polyurethane foam using a polyol obtained by adding epoxide to an aromatic resin is said to have high rigidity and improved thermal printability. A typical example of aromatic inishes is the novolak resin-based inishes obtained by condensing phenol and formaldehyde.9 In addition to phenol and formaldehyde, aromatic amines such as aniline may also be used. . For example, in Japanese Patent Publication No. 39-1554t, inishekhu obtained by condensation of aldehyde-phenol-aniline is described in Japanese Patent Publication No. 1343-1973 KFi. An initiator obtained by condensing an aldehyde, phenol, or aniline with a non-aromatic amine is described. However, these initiators have various problems and there is still room for improvement.

9. For example, the former newsletter κ mentioned inishek κ
There is a problem of dehydration O and gelation O.

It is known that when epoxide is added to an initiator, if water is present as an impurity, a diol is formed between the water and the epoxide, and the presence of this diol is known to cause a decrease in the physical properties of the foam. On the other hand, the aldehyde-7-phenol-aniline condensate includes a compound in which a phenyl group is crosslinked with methylene, but also includes a compound having a methylol group in the crosslinked stage. Regardless of K%, it is difficult to completely eliminate K from this methyl group.
Dehydration occurs under the side addition reaction conditions in Evo. First, if the crosslinking by aldehyde is partially concentrated, a high molecular weight O condensate is likely to be formed, and gelation occurs, making it difficult to add ceboxide O. Furthermore, the 40-condensed metal product described in the latter publication not only has a sufficiently high functional group number, but also has a sufficiently high number of functional groups. There is also the problem that it is difficult to obtain initiators with t.

Therefore, with the aim of improving the O condensate described in the latter publication, the present inventor replaced the first amine, which is one of the components in the O, with 7-lkanolamine, and used it as an initiator. Polyurethane foam was produced and the polyol was evaluated. Production of dehyde aniline-7-alkanolamine and O-reactant κ The reaction that occurs is mainly considered to be the Mannitz reaction, in which the reactant of alde-7d and alkanolamine reacts with aniline at the para- or ortho-position K to alkanolamine. It is expected that aniline with a methylene group will be formed. But this O! It turns out that the reaction does not occur efficiently enough, and the reaction that occurs is mainly an O-methylene cross-body reaction between aniline molecules, making it difficult to solve the above problem. On the other hand, initiate the reaction product of aldehyde phenol alkanol amine! This method is known by Voriol Co., Ltd., and is described, for example, in Japanese Patent Publication No. 48-12879. However, the condensate consisting of three components of ζ is still not sufficient. One reason is that the reactant-forming reaction is not fast enough, and the other reason is that the alkylene oxide addition reaction is not fast enough. Furthermore, when the physical properties of the polyurethane foam obtained by using a polyol obtained by adding alkylene oxide to this reaction product were investigated, it was found that the compressive strength and dimensional stability were not sufficiently high. In order to efficiently produce a polyol and to obtain a polyurethane foam with excellent physical properties, various research studies were carried out. As a result, it was found that a four-component reaction product of aldehyde-7-phenol-aromatic amine-alkanolamine was used as an initial shake, and a polyol to which κ eboxide was added was superior. That is, the present invention uses polyols and polyisocyanates as catalysts. Pond starter. In a method for producing rigid polyurethane foam by reacting in the presence of additives such as foam stabilizers O, at least a part of the polyol is a phenol (a) represented by ▲-ONli.
(▲: At least two reactive sites (aromatic nucleus), B
→ Eboxide is added to the reactants of at least 44 components of aromatic amines represented by This is a method for producing a rigid polyurethane foam, characterized in that the polyol is obtained by adding.

Phenols (a) Fi have at least 42 reactive sites that are not substituted on their aromatic nuclei. The reactive sites are usually at the para or ortho positions, preferably at least two of these are free of substitution #G. Specifically, phenol. Alkylphenol. Halophenol. Dialkyl ξnophenol. Alkoxyphenol. Dihydrogylebenzene and the like are preferred, particularly phenol having no substituents.

Aromatic amines, like phenols, have at least two unsubstituted reactive sites in their aromatic nucleus, and the O-reactive sites are usually at the para to ortho positions. good 4
These two do not have a stirrup substituent. Specific examples of K include aniline, diaminobenzene, alkyl monomerized aerin, M-alkyl dinoaniline, etc. 69.@Kaniline is preferred.

O aldehyde polymers such as formaldehyde, aldehyde, propionaldehyde, paraacetaldehyde in paraformaldehyde,
Chlorol and the like are suitable, with formaldehyde and hexabormaldehyde being particularly preferred. Any of these can be used as an aqueous solution or as a solution.

As alkanolamine II (+1), primary or 2@C) alkanolamines are used, and dialkanolamines are particularly preferred. Examples of alkanolamines include 9-epadiethanolamine. Diprobanolamine. Di(2-hydroxyprobyl)amine, etc.
Particularly preferred is diethanolamine.

Each of these four components may be used in an amount of 21 g or more. Two types of phenols and two aromatic amines can be used. Furthermore, in addition to these four components, a small amount of other component #r can be reacted. For example, amines other than aromatic amines can be further added to the above four components and reacted.

Aldehydes are phenols. Aromatic amines or the reactive sites of the aromatic nucleus between them are bridged with an alkylene group to form a nine-condensate in which the aromatic nucleus is bridged with an alkylene group.Aldehydes also combine with dialkanolamines and phenols. The reactive site of the aromatic nucleus of an aromatic compound M or a condensate thereof is bonded to a dialkanolamine using one alkylene group.The latter reaction is called the Mannitz reaction. In the present invention, it is referred to as a crosslinking reaction. ▼Reactions occur with both phenols and aromatic amines, but under normal conditions crosslinking reactions are likely to occur.The most common crosslinking reaction is between phenols, aromatic amines, and The O crosslinking reaction between similar compounds or between aromatic amines is thought to be slow. Therefore, in the above four component O reactions, phenols, aromatic amines, and aldehydes react as follows to form a condensate. Generate.

The reaction of ζ usually proceeds further to form a condensate in which phenols and aromatic amines combine 7 alkylene groups and are arranged alternately. As the molecular weight of this metal shrinkage increases, the system O viscosity increases. However, it is thought that as the molecular weight of the metal shrinkage increases, the rate of crosslinking reaction decreases, and gradually the rate of K▼Nnitz reaction O also decreases. Therefore, aldehyde @
(cross-linking reaction) also participates in the reaction, which reduces the success of increasing the molecular weight of the condensate. In the preferred reaction temperature range described below, Oj'J1! in one molecule of the O condensate.
The number of nuclei is 2-10% special K2-61I! It is thought that there is a degree.

The above condensation compound, aldehydes and alkanolamines are then reacted in a Mannitz reaction.

When the condensate is a condensate of pentafunctional compounds such as phenol and aniline, aromatic nuclei 1d2' at both ends of the condensate:)0
An aromatic nucleus within a molecular chain that has a reactive site has one reactive site. Condensation of difunctional compounds 11[) In the case of both ends O
It has a κ-reactive site. ! If the reaction is mourning, it will be the following reaction.

m, O: O to 20 integer m+nm1 to 4in, and the number of alkanolaminomethylene groups O produced by the reaction Σ is preferably one or less on average per one aromatic nucleus κ of the condensate O. Condensation reaction! The grinning reaction is a competitive reaction, so
The reaction product is a mixture of various compounds. However, since the O condensation reaction is likely to occur initially, it is difficult for phenols and aromatic agents to cause the reaction alone when they are present. I don't think so.

Alkanolamines) Otri. The amount used may be small compared to other OS components κ. 0 Phenol Iik) One aromatic amine 1 m(1)) One Aldehyde II
(6)II! ) This is because even if a condensation product is produced as a by-product, the O condensation product reacts with the epoxide and forms a polyol. On the other hand, the amount of alkanosylua<7@#)t)41μ is relatively large and remains as an unreacted product, which is good.

This is because it itself reacts with epoxide and becomes a polyol.

Normally, the polyol obtained by reacting at least 44 components of the reactant with epoxide, the O viscosity, the reaction, and the OS in the reaction product.
The higher the ratio of e10, the higher the viscosity.

Generally, the lower the viscosity of the polyol, the better. Therefore, it is considered that the lower the condensation ratio of the condensate O in the reactant, the better, as long as the number of functional groups does not fall below the required number. Therefore, the amounts of the four components used and reaction conditions are comparative! It is preferable to choose conditions where it is easy to insult someone.

The usage ratio of phenols (-) and aromatic amines (b) is not limited to 4GK, but the molar ratio is about 1/4 to 4/4GK.
1, especially about 172 to 2/1 degrees. Aldehydes (C) and alkanolamines (salmon) O ratio molar ratio is approximately C/+1-2/α1-1/2, %K15/1-1/t
5a degree is preferred. Furthermore, aldehydes (
c) Cl1 is preferably about (a+b)/C=1/2 to 2/1, particularly 1/t5 to t5/1 degrees. In particular, phenols (a) and aromatic amines φ) are used in mol. It is also preferable to use aldehydes (C), 7-phenols (1), aromatic compounds (1), and the same amount of t1 for the total molar amount of O.

The reaction of these four components is usually carried out by adding components 1 to 5 and the other 5 to 1 components.

Normally, add Ojg of residual oil to the 5-component c1 mixture.
Therefore, one component to be added is usually an aldehyde. The S component of the residue, in which no aldehydes are present, shows that almost no reaction occurs.

The reaction of this 04 component occurs even in the absence of a catalyst.

The reaction temperature is suitably 30 to 120°C, especially 50 to 1%.
00°C is preferred. If the reaction temperature is high, the condensation reaction is likely to occur, and it is preferable to carry out the reaction at this temperature even in the case of zero dehydration after the reaction is completed. The -O reaction can also be carried out in an inert solvent. As the inert solvent, polyols that can be used as raw materials for polyurethane, such as polyether polyols and polyester polyols, are preferred.

These polyols do not undergo a condensation reaction during the above-mentioned ▼Nnitz reaction. However, it may react with the next eboxide. Therefore, if there is a risk of reaction with eboxide, it is necessary to take into account in advance the increase in molecular weight due to the reaction. However, as will be described later, when the epochide reaction is carried out without a catalyst, this risk is extremely small, and even in the presence of catalysts, if the solvent is a relatively high molecular weight polyol, There is little reaction with eboxide.

As shown in Section 11g, aldehydes-phenols-alkanolamines O reactants are known.

However, this reaction is not fast enough and when the reaction temperature is raised, the condensation reaction of the 7 enols tends to occur. In contrast, in the present invention, the aromatic amine O catalytic effect K
Since the reaction is less likely to occur, the condensation rate of the condensate can also be reduced due to the use of oxygen which can be used under milder reaction conditions. The catalytic effect of any aromatic amine O affects the epoxide addition reaction and even the polyurethane production reaction, making these reactions more likely to occur. Furthermore, the low condensation ratio is one of the reasons why it is difficult for water to be produced as a by-product in the addition reaction of epoxyde. It is preferable to dehydrate the resulting at least four-component reactant and use the water produced from the aqueous reaction K used as a solvent for the aldehyde.

Of course, if O bath #[ other than polyol exists, its O
Preferably, the solvent is removed. The obtained good reactant κ is. Eboxide is then added. As eboxide. ，
Ethylene oxide. Propylene oxide. butylene oxide. Typical alkylene oxides with 2 to 407 carbon atoms, such as shrimp chlorohydrin, are alkylene oxides with 5 or more carbon atoms. Aromatic or alicyclic epoxides such as sterene oxide. Glycidyl ether. Glycidyl esters and odopts are used as epoxides with epoxy groups.

Preferably, propylene oxide alone or a combination of propylene oxide and ethylene oxide is used; in the case of a combination O, a mixture of both O may be added.
You may add the following:

The addition reaction of eboimaside to reactant κ occurs without a catalyst up to a certain amount of O. However, it is necessary to add Sara K Engineering I Oxide! o In some cases, it is preferable to use a catalyst.
The typical catalyst is an alkali metal hydroxide, but any known catalyst can be used. The reaction temperature is not specified, but is usually 70-200℃,
In particular, a temperature of about 90 to 130°C is preferable. By increasing the amount of epoxide added, the hydroxyl value of the obtained polyol decreases. The hydroxyl value of this polyol is soO~7
It is preferable that it be about 00, especially κ 400-400. ``The polyol in the present invention is used as a raw material for rigid polyurethane foam.'' ? This polyol can be used as it is as a raw material for rigid polyurethane foam, or it can be mixed with other polyols. In order to produce rigid polyurethane foams, the basic raw materials are the above-mentioned polyols or polyols mixed with other polyols and polyisocyanate compounds, which are usually combined with the presence of additives such as catalysts, blowing agents and foam stabilizers. React below. Crosslinking agent in some cases. filler. Coloring agent. Stabilizer, reinforcing fiber. Seventy-
60 Additives may be added. When using the above polyol and other O polyols together, the other O polyols are usually O hard polyurethane! Polyols used as raw materials for the foam are preferred, but are not limited thereto. Examples of the polyisocyanate F compound include tolylene diisocyanate (TD Engineering). Diphenylmethane diisocyanate (MDI), 11MDI, polymethylene polyphenyl isocyanate, aromatic polyisocyanates, and their O-modified products are preferred. In addition, it can also be used as ζ, in which non-aromatic polyisocyanates such as inphorone diisocyanate in hexamethylene diinocyanate are used. As a catalyst, an organometallic catalyst and a 5th grade acetic acid catalyst are usually used in combination, and as a blowing agent, water, foam, etc. are used. Halogenated hydrocarbons such as medelene chloride are used, and silicon compounds are usually used as foam stabilizers. The manufacturing method for hard polyurethane 7 ohm is the one-shot F method. Prepoli! One law. Although a spray method or the like can be used, the mv-ol of the present invention is suitable as a hard polyurethane foam Dig material produced by the special K spray method. The present invention #i also provides a method for producing fcζO-retaining polyurethane foam using the above polyol.

In method K of the present invention, the polycrete-forming reaction is more likely to occur in O, which has many nitrogen-containing bonds fr in the polyol, than in other polyols. Therefore, the amount of the 5th class amine catalyst used can be made smaller than when other O polyols are used. Furthermore, it is clear that the rigid polyurethane foam obtained using the above-mentioned polyol has excellent dimensional stability compared to the rigid polyurethane foam obtained using other polyols.

The present invention will be specifically explained below using Example K, but the present invention is not limited to these Examples.

Reference Example-1 [Production of polyol ▲O] Phenol 94f (1 mol). Aniline 93F (1 mol). 210f (2 mol) of diethanolamine was placed in an autoclave, and 151 t ('L 7 mol) of an aqueous opsa-formalin solution mixed with 1/2 K was introduced and reacted at 30°C for 2 hours, then the humidity was raised to 100'CK for 2 hours. held.

j! The system was dehydrated by reducing pressure at 100° C. until the water content in the system became less than a1. Next, Bribylene Oxide ssot was press-injected for about 2 hours while maintaining the internal pressure at SK47cm'' or less, and the reaction was completed by keeping the temperature at Kts%@100CK9.Subsequently, the volatile matter was removed under reduced pressure.

The obtained polyol O analysis values are as follows. In addition, and O polyol is hereinafter referred to as polyol▲ (hereinafter O
The 9-boliol produced in Reference Example κ is also referred to as INK Alphapet) on value (QIKOil/f: the same hereinafter) 542 pH 1 (
L8 H Snow Oα05 Viscosity (same below 25℃) 51.800ap Reference Example-2
[Boriol B4! ) 3m construction] Phenol! 4t. Aniline qs. t. Diethanolamine jIQf was charged into an autoclave, and after mixing, 71 t of paraformaldehyde (purity 8591) was added and reacted at 60°C for 2 hours, then the temperature was raised to 100°C and held for 1 hour. 100
Moisture in the system was removed at ℃. Then, tetrapylene oxide 380f was reacted.

The analytical values of the obtained polyol were as follows.

OH value 54tOpi! 1t2 H=Oaos@ Viscosity 2tjOOap Reference Example-5 [Made with polyol oog] Phenol 1.41? ．． Aniline 47t. Diethanolic acid 7210f was charged into an autoclave, and after mixing, 71 t of paraformaldehyde (purity 85%) was added and reacted at 60° C. for 2 hours. The reaction was completed at 100° C. After completion, water was removed. Next, p-pylene oxy? Do 350
9. React f. The analytical values of the nine polyols obtained were as follows: 0 and 9.

OH number 54αS pigtα7 ■ 0α04 viscosity 11500cp Reference example-4 [Boriol Do#! ] Phenol 122F. Aniline 112f. Diimp tetrapanolamine S'20f was charged in an autoclave and mixed thoroughly, then 1 tot of s8s hol▼9y aqueous solution was introduced and reacted at 50°C for 1 hour, then raised to 115°C and held for 2 hours. Furthermore, water in the system was sufficiently removed under reduced pressure at KIIO°C. Next, 450 f of tetrapylene oxide was increased in pressure for about 2 hours while maintaining an internal pressure of SK4/amKm, and then kept at 110°C for an additional 6 cts to complete the reaction. Subsequently, volatile components were removed under reduced pressure.

The obtained product analysis value was O and O.

ON value 53α2 pm1tO・H Dew 0α04T Viscosity 24% 400cp Reference Example-5 [Manufacture of Polyol 1] Phenol 94t. Aniri 7951. 210 t of diethanolamine was charged in an autoclave K, mixed, and then 71 t of paraformaldehyde (purity 8S1j) was added and reacted at 60°C for 2 hours. After the reaction was completed at 100°C, BS% KOH Belet}2-41F was added. After dissolving the mixture, water in the system was removed under reduced pressure at 100°C. Then, 410 tons of propylene oxide was reacted.

The analytical value of 9-boliol O obtained by adding a certain amount of phosphoric acid to [011] is as follows: phenol 18
8f. Autoclave 210t of diethanolia
After preparation and mixing, paraformaldehyde (purity 851
G) Example-2 with addition of 71F. React with Doroku K, and after dehydration, react with propylene oxide 530f. The analytical values of the desired polyol were as follows.

OR value 5357 pli1α7 11,0103% Viscosity 149OOap Comparative reference example-2 [BORIOL GD production] Aniline 11k
41F. 210f of diethanolamine was charged in an autoclave, 71f of mixed 0chinokurahol▲alde and de (purity 85Is) was added and reacted in the same manner as in Example 2. After dehydration, propylene oxide S'1st was reacted. .

The obtained polyol O analysis value was 9 as follows.

OH value 5491 ．． B115 n,oα0311 Viscosity 54500ap It can be seen that the viscosity is extremely high compared to Boliol 1.

Examples 1-4. Comparative Examples 5-4 Physical property tests were conducted on rigid polyurethane foams using the polyols ▲-D and 1-G obtained in Reference Examples 1-4 and Comparative Reference Examples 1-2.

Silipun foam stabilizer 8H19 per 100 parts of Boliol
3 (Toray Siri: ry) 10 copies, 7v on Im-115
Add 0 parts, 2 parts water, triethylene diisocyanate (L 7 parts, tOS times the amount of active hydrogen), stir well, and foam in a cardboard box measuring 2051 cm long and 25 cm high. Let's make it nine.

The results are shown in Table 1.

It can be seen that the combination of phenol and aniline has excellent compressive strength and dimensional stability.

Examples 5-6. Comparative Examples 3-5 Boliol ▲. B. Using F, Q and a general-purpose sorbitol/monoethanolamine/ethylenediamine ternary initiator, add pyrene oxide, add 9-bolyol H (Oil number 540), and spray. A spray foaming test was conducted on rigid polyurethane foam ▲ using lI-v Synth.

Foaming conditions> Spray machine Propler (Landsparg) discharge pressure 4
0114/tar/Face, wood veneer plywood formulation> Boliol 100-Silicone foam stabilizer to dibutyltin! Rate to Freon R-11 blowing agent SO- triethylenedia. Min α5 flk@20℃ Bolihuenylene Boliisoindex [105] Siku C
Mohito (Takuin ID engineer) Spray! After mixing, spray foam onto the veneer plywood. Appearance of the obtained foam. Physical properties, etc. [Table 2 shows]

As is clear from the results shown, when the polyol according to the present invention is used, the smoothness is . The front picture is excellent, t
It can be seen that the cross-flow phenomenon, which is a highly praised performance of nine spray foams, has very good adhesion strength, and also voids. Excellent results were also obtained for flame retardancy κ.

Claims (1)

[Claims] t-potuol and polyisocquanate are used as a catalyst. Foaming agent. In the method of manufacturing rigid polyurethane foam by reacting in the presence of additives such as foam stabilizers, at least a part of the polyol contains phenols (Xu) represented by ▲-OR (▲: at least 2 (aromatic nucleus with two reactive sites)
, B-11. Aromatic amines (6) represented by (B=
It must be a polyol obtained by adding oxide t to a reactant of at least 44 components, such as an aromatic nucleus having at least two O-reactive sites, an aldehyde II (C), and an alkanoane (C). Hard polyurethane 7O▲OS manufacturing method with slight variations. 1. The method according to item 1 of the scope of the patent application, characterized in that phenol or phenol is used. The method according to item 1 of the scope of the application, characterized in that the pentaaromatic amine is aniline. Pre-aldehydes are formaldehyde or paraform.
▲The method according to claim 1, wherein the aldehyde is an aldehyde. ζ The method according to claim WJ1, wherein the alkanolamine is a dialkanolamine. - The molar ratio of melon phenols (IL) and aromatic amines Φ is 1/b-1/4 to 4ha, and the molar ratio of aldehydes (C) to alkanolamines ■ and O is a/a# 2/α1~1/
2 and phenols (&) and aromatic amines (b) 0
The ratio of 11 imol to aldehyde III(0) is (a
+b)/a-17z to 2c. 1 epoxide is an alkaline lene oxide having 2-1-40 carbon atoms. Characteristics of patent clearance I! l first term O
Method. 1. O method of patent claim 1, characterized in that the polyol has a hydroxyl value of 500 to 70G.