JPH06256448A - Production of modified polyisocyanurate foam - Google Patents

Abstract

PURPOSE:To obtain a low-density foam without using any evaporable blowing agent such as a chlorofluorocarbon by reacting an organic polyisocyanate with a polyol and water in the presence of a specified trimerization catalyst and a specified carbodiimidation catalyst. CONSTITUTION:This foam is obtained by reacting an organic polyisocyanate with a polyol and water in the presence of a trimerization catalyst comprising a hydroxyalkyl quat. ammonium compound of formula I (wherein R1, R2 and R3 are each alkyl; and R4 and R5 are each H or alkyl) and a carbodiimidation catalyst comprising a phospholene oxide of formula II or III (wherein R1 is (un)substituted alkyl, phenyl, naphthyl or benzyl; and R2 to R7 are each H, Cl or 1-4C alkyl).

Description

Detailed Description of the Invention

The present invention relates to a method for producing a modified polyisocyanurate foam, and more particularly to a modified polyisocyanate suitable for continuous production of laminated boards and siding boards, which does not require the use of an evaporative foaming agent such as Freon. It relates to a method for producing a nurate foam.

A method for producing a modified polyisocyanurate foam by using an organic polyisocyanate and a polyol together with an isocyanurate-forming catalyst and a carbodiimidating catalyst in the presence of a foaming agent is known (for example, Japanese Patent Publication No. 46-4).
591). Further, a modified polyisocyanurate foam is produced by using an organic polyisocyanate and a polyol together with methanol, furfuryl alcohol or phosfluorene oxide (carbodiimidization catalyst) and an alkali metal salt (trimerization catalyst) in the presence of a foaming agent. A method of doing so has also been proposed (see US Pat. No. 4,166,164, JP-A-2-245013). Furthermore, JP-A-50-95397 and JP-A-50-12499.
7, JP-A-51-75799, JP-A-51
-76395, JP-A-51-80393,
JP-A-51-102098 discloses a method of obtaining a modified polyisocyanate foam using a tertiary amine and an alcohol such as amino alcohol as a cocatalyst, and a method of catalytically using Mannich polyol, phosphorus-containing polyol and the like. ,
Methods using s-triazine and phenol have been reported.

In the production of these (modified) polyisocyanurate foams, it is general to use freon as a blowing agent, but freon has a problem of ozone layer depletion, and freon will not be used in the near future. It is in the direction of being totally banned. As a substitute for CFCs, a method of using carbon dioxide gas generated by the reaction of water and isocyanate can be considered, but if the amount of water used is increased to reduce the density of the foam (obtain high foam). , Generated urea bond (-NC
O + H ₂ O → -NH ₂ + CO ₂ ↑, -NH ₂ + OCN- →-
There is a problem that the amount of NHCONH-) becomes large, the strength is low, the dimensional stability is poor, and only a foam having poor adhesion to the face material can be obtained. Further, in the above-mentioned method of using a conventional isocyanurate-forming catalyst and a carbodiimidizing catalyst in combination, when water is used as a foaming agent, it is difficult to control the reaction, and it is particularly required for a laminate board or a siding board. It is not possible to produce cured high foams with densities below 30 kg / m ³ at economical rates.

The present inventors have developed a highly foamed modified polyisocyanurate foam having a density of 30 kg / m ³ or less from an organic polyisocyanate and a polyol without using an evaporative foaming agent represented by Freon. As a result of extensive studies on industrially applicable methods that can be produced, this time, when a certain combination of a specific trimerization catalyst and a carbodiimidization catalyst is used together with water, the polyisocyanate is trimerized. The reaction and carbodiimidization reaction, the reaction between water and polyisocyanate, etc. proceed rapidly in a well-balanced manner.
It was found that a modified polyisocyanurate foam having a low density of 0 kg / m ³ or less can be obtained in a short time, and the present invention has been completed.

Thus, according to the present invention, an organic polyisocyanate, a polyol and water are added to formula (a)

[0006]

[Chemical 4]

In the above formula, R ₁ , R ₂ and R ₃ each represent an alkyl group, and R ₄ and R ₅ each represent a hydrogen atom or an alkyl group. Catalyst and formula (b)

[0008]

[Chemical 5]

In the formula, R ₁ represents a substituted or unsubstituted alkyl, phenyl, naphthyl or benzyl group,
_{R 2, R 3, R 4} , R 5, R 6 and R ₇ each H, Cl or C ₁ represents an alkyl group -C _4, in the presence of a carbodiimidization catalyst consisting phosphorene off Oren oxide represented A method for producing a modified polyisocyanurate foam characterized by reacting is provided.

The present invention will be described in more detail below.

The organic polyisocyanate used as a raw material in the method of the present invention may be of any type such as an aliphatic type, an alicyclic type, an aromatic type and a mixed type thereof. Those used in the production of polyurethane and polyisocyanurate can be similarly used. Specifically, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
Aromatic diisocyanates such as crude tolylene diisocyanate, methylene diphenyl diisocyanate and crude methylene diphenyl diisocyanate; aromatic triisocyanates such as 4,4 ′, 4 ″ -triphenylmethane triisocyanate and 2,4,6-tolylene triisocyanate Isocyanate;
4,4'-Dimethyldiphenylmethane-2,2'-5,5'-
Aromatic tetraisocyanates such as tetraisocyanate; Aliphatic isocyanates such as hexamethylene-1,6-diisocyanate; Alicyclic isocyanates such as hydrogenated methylene diphenyl diisocyanate;
-Phenylene diisocyanate, naphthylene-1,5-diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, 4,4'-biphenylene diisocyanate, 3,
Examples thereof include 3'-dimethoxy-4,4'-biphenyldiisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, and among them, 2,4-tolylene diisocyanate and 2,6-tridiisocyanate. Diisocyanate, crude tolylene diisocyanate, methylene diphenyl diisocyanate, crude methylene diphenyl diisocyanate,
Hexamethylene-1,6-diisocyanate, hydrogenated methylenediphenyl diisocyanate and the like are preferable. The above organic polyisocyanates may be used alone or in combination of two or more.

As the polyol, compounds such as polyether polyol, polyester polyol, castor oil, etc., such as aliphatic series, sugar series, aromatic series and mixtures thereof having two or more hydroxyl groups in one molecule. And those conventionally used in the production of polyurethanes can be used as well. Such a polyol may have either a low molecular weight or a high molecular weight, and specifically, for example, as a polyether polyol, an alkylene is added to an active hydrogen-containing compound such as a polyhydric alcohol, a polyhydric phenol, amines and a polycarboxylic acid. An example is a compound having a structure to which oxide is added. As polyhydric alcohol,
For example, ethylene glycol, propylene glycol,
Dihydric alcohols such as 1,4-butanediol, 1,6-hexanediol, diethylene glycol and neopentyl glycol; 3 such as pentaerythritol and sucrose
Examples include polyhydric alcohols having a valency or more. Examples of polyvalent phenols include polyvalent phenols such as pyrogallol and hydroquinone, bisphenols such as bisphenol A, and condensation products of phenol and formaldehyde. Amines include ammonia, mono-, di-
-, And alkanolamines such as triethanolamine, isopropanolamine, aminoethylethanolamine; C ₁ -C ₂₂ alkylamines, C ₂ -C ₆
Aromatic amines such as alkylenediamine, polyalkylenepolyamine and aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline and diphenyletherdiamine, alicyclic amines such as isophoronediaminecyclohexylenediamine, hetero Examples thereof include cyclic amines. As the polycarboxylic acid, aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, maleic acid and dimer acid, aromatic polycarboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid, etc. Two or more of these active hydrogen-containing compounds can be used.
Examples of the alkylene oxide added to the active hydrogen-containing compound include propylene oxide, ethylene oxide, butylene oxide, and tetrahydrofuran. These alkylene oxides may be used alone or in combination of two or more kinds, and in the latter case, they may be those which are block-added or random-added.
Examples of polyester polyols include polyhydric alcohols (the above dihydric alcohols, trimethylolpropane, glycerin, etc.) and carboxylic acids (the above polycarboxylic acids, etc.)
A condensed polyester polyol obtained by reacting with
Examples thereof include a polyester polyol obtained by ring-opening polymerization of a lactone, and a recovered polyester to which an ethylene oxyd adduct of nonylphenol is added. Among these, in particular, aliphatic, aromatic, aliphatic or aromatic amine, pentaerythritol, sucrose polyether polyols; aromatic or aliphatic carboxylic acid polyester polyols; lactone polyester polyols and the like are preferable. Is. The above polyols can be used alone or in combination of two or more kinds.

Polyols such as those mentioned above are generally 20-60.
0 mgKOH / g, preferably 25-500 mgKOH
/ G, more preferably 50 to 400 mg KOH / g.

According to the method of the present invention, a polyisocyanurate foam is produced by reacting the above-mentioned organic polyisocyanate and polyol with water as a foaming agent. In this reaction, the use ratios of the organic polyisocyanate, the polyol and the water are not strictly limited, and can be varied over a wide range depending on the desired physical properties and intended use of the modified polyisocyanurate foam of the final product. However, in general, NCO / O
Isocyanate index shown by H equivalent ratio is 1.8 or more,
It is preferable to mix and react the above components so that the amount is preferably in the range of 1.8 to 5.0, particularly 2.0 to 4.0.

The amount of water used as a foaming agent can be adjusted depending on the desired density of the modified polyisocyanurate foam of the final product. In particular, the method of the present invention is characterized in that a product having a high expansion ratio can be produced only with water without using an evaporative foaming agent such as CFC. According to the method of the present invention, for example, , 0.3-1.8% by weight, preferably 0.8-1.5% by weight, based on the total weight of the organic polyisocyanate, polyol and water
By adding an amount of water within the range, the free foam density is generally 30 kg / m ³ or less, and particularly 20 to 28 kg / m ^3.
It is possible to easily manufacture a foam having a high expansion ratio without using an evaporative foaming agent.

The method of the present invention is characterized in that the reaction for producing a modified polyisocyanurate foam from the above-mentioned organic polyisocyanate, polyol and water is carried out according to the formula (a)

[0017]

[Chemical 6]

In the formula, R ₁ , R ₂ and R ₃ each represent an alkyl group, and R ₄ and R ₅ each represent a hydrogen atom or an alkyl group. Catalyst and formula (b)

[0019]

[Chemical 7]

In the formula, R ₁ represents a substituted or unsubstituted alkyl, phenyl, naphthyl or benzyl group,
_{R 2, R 3, R 4} , R 5, R 6 and R ₇ each H, Cl or C ₁ represents an alkyl group -C _4, in the presence of a carbodiimidization catalyst consisting phosphorene off Oren oxide represented There is a point to implement.

In the above formula (I), "alkyl group"
May be linear or branched, for example, methyl, ethyl, n-propyl, iso-propyl,
n-butyl, tert-butyl, n-pentyl, isoamyl, n-hexyl, n-heptyl, 1-ethylpentyl,
Examples include n-octyl and 2-ethylhexyl. R ₁
An alkyl group represented by R ₃ has 6 or less carbon atoms,
It is preferably a lower one of 4 or less, while R ₄
The alkyl group represented by R ₅ and R ₅ may be not only lower one but also higher one having up to 18 carbon atoms.

Therefore, the hydroxyalkyl quaternary ammonium compound of the formula (I) used as a trimerization catalyst in the method of the present invention is used in the production of polyurethane, polyisocyanurate, polyurethane-polyisocyanurate resin and the like. The catalyst is known per se (see, for example, Japanese Patent Publication No. 61-23214), and specific examples thereof include the following:

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

[0026]

[Chemical 11]

[0027]

[Chemical 12]

[0028]

[Chemical 13]

[0029]

[Chemical 14]

[0030]

[Chemical 15]

[0031]

[Chemical 16]

[0032]

[Chemical 17]

Of these hydroxyalkyl quaternary ammonium compounds, the compounds described above and above are preferably used.

On the other hand, the above formula (II) used in combination with the above hydroxyalkyl quaternary ammonium compound
Alternatively, in (III), the alkyl group represented by R ₁ may be linear or branched and may be partially substituted with halogen or another functional group. Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl,
t-butyl, 2-phenylethyl, 2-chloroethyl, 2-
Examples include methoxyethyl group. Examples of the substituted or unsubstituted phenyl, naphthyl and benzyl groups include benzyl, phenyl, o-, p- or m-tolyl, xylyl, naphthyl, 4-diphenyl, o-, p- or m-chlorophenyl. To be R ₁ may preferably be a C ₁ -C ₄ alkyl group, a phenyl group and a benzyl group. Examples of R _{2 to} R ₇ in the formula (II) or (III) include hydrogen, chlorine, methyl, ethyl, propyl, isopropyl and butyl, and hydrogen and methyl are preferable.

The following are specific examples of the phosfluorene oxide of the formula (II) or (III).

1-Methylphosphorus oxide, 3-methyl-1-phenylphosphorus oxide, 3-methyl-
1-benzylphosphorus oxide, 3-methyl-1-ethylphosphorus oxide, 3-methyl-1-ethylphenylphosphorus oxide, 1-phenyl-3- (4-
Methyl-3-pentenyl) phosphorene oxide, 1-
Phenyl-3-chlorophosphylene oxide etc. Among these phosphorene oxides, especially 3-methyl-1-
Phenyl-2-phosfluorene oxide and 3-methyl-1
-Phenyl-3-fuosfluorene oxide is preferably used. These phosfluorene oxides are known per se as catalysts for accelerating the reaction of forming a carbodiimide compound from an organic isocyanate (see, for example, Japanese Patent Publication No. 46-4591).

In the present invention, as a catalyst for producing a modified polyisocyanurate foam from an organic polyisocyanate, a polyol and water, a hydroxyalkyl quaternary ammonium compound of the above formula (I) (trimerization catalyst) and the above-mentioned are used. It is characterized by the fact that it uses a specific combination with a phosfluorene oxide of formula (II) or (III) (carbodiimidization catalyst). As a result, the modified polyisocyanurate foam having a high expansion ratio was successfully produced by an industrially applicable method without using a problematic effervescent foaming agent such as CFC.

A hydroxyalkyl quaternary ammonium compound of the formula (I) (trimerization catalyst) and a formula (II) or (I
The amount of each of the phosphorene oxides (carbodiimidization catalysts) of II) used is not strictly limited and may be changed according to the reaction conditions to be used, but based on the weight of the organic polyisocyanate, the former The trimerization catalyst (1) is generally used in the range of 0.1 to 10% by weight, particularly 0.5 to 5% by weight, and the latter carbodiimidization catalyst is generally 0.05 to 5% by weight, and particularly preferably 0.5 to 5% by weight. It is suitable to use within the range of 1 to 2% by weight.

The relative proportions of the trimerization catalyst and the carbodiimidization catalyst can be varied within a wide range depending on the desired physical properties of the final product, but usually the weight ratio of trimerization catalyst / carbodiimidization catalyst is 0. It is preferably in the range of 0.5 to 20, particularly 1 to 10.

Further, in the method of the present invention, if necessary, a urethanization catalyst (eg, triethylenediamine, dimethylethanolamine, triethylamine, trimethylaminoethylethanolamine, dimethylaminoethyl ether, pentamethyldiethylenetriamine, N-methyl) is used. Morpholine, dibutyltin dilaurate,
Tin octoate, lead octoate, etc.), foam stabilizer (eg,
Dimethylsiloxane-polyether block copolymer, etc.), cross-linking agent (for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethanolamine, diethanolamine, ethylenediamine, toluenediamine, etc.), Flame retardant (e.g., triphenyl phosphite, triethyl phosphate, trimethyl phosphate, cresyl diphenyl phosphite, tris cresyl phosphate, tris chloroethyl phosphate, tris dichloropropyl phosphite,
Tris-β-chloropropylphosphonate, Tris-β-
Chloroethyl Phosphate, Tris (2,3-dibromopropyl) Phosphate, Tris (Bromocresyl)
Phosphite, melamine, antimony trioxide, etc.),
Coloring agents and other additives can be used together in the amounts usually used.

As a method for producing a modified polyisocyanurate foam from the above-mentioned components, for example, an isocyanate component composed of the above-mentioned organic polyisocyanate or an isocyanate prepolymer obtained by previously reacting an organic polyisocyanate with a polyol is used. A component and a polyol component obtained by further adding a urethanization catalyst, a foam stabilizer, a cross-linking agent, a flame retardant, a colorant and other additives to the above-mentioned polyol, water, trimerization catalyst and carbodiimidization catalyst, if necessary. One method is to prepare, combine both components at the time of use, rapidly stir and mix, and then foam and cure.

The reaction temperature is usually room temperature, but in some cases, it may be heated up to about 90 ° C.

Hereinafter, the present invention will be described in more detail with reference to Examples.

[0044]

【Example】

Examples 1 to 14 and Comparative Examples 1 to 6 25 g of a polyol component prepared by mixing predetermined amounts of polyol, water, catalyst, foam stabilizer and flame retardant shown in Table 1 below (however, in the case of Example 14). Is 50g),
Crude MDI (diphenylmethane diisocyanate) 75 g
(However, 50 g in the case of Example 14) was mixed and stirred with a hand drill (2200 rpm, stirring blade 30 mmφ) for 5 seconds. 80g of the mixture is added to 150x150x15
It was poured into a 0 mm wooden box and the cream time and rise time were measured. The time from the liquid state to the start of foaming was defined as the cream time, and the time when the foaming was completed was defined as the rise time. After 1 minute, the foam was touched to determine the cured state of the surface. About 1 at the center of the cured foam
It was cut into 00 × 100 × 100 mm, and the free foam density was calculated from its volume and weight.

The results are shown in Table 1 below.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

Note (1): Polyol Polyol A: Phthalate ester type polyol, hydroxyl value = 315 (APP-315 manufactured by Union Carbide Co.) Polyol B: Pentaerythritol type polyol, hydroxyl value = 410 (410NE manufactured by Asahi Glass Co., Ltd.) Polyol C: Schieger aromatic amine polyol, hydroxyl value = 410 (manufactured by Sanyo Kasei Co., RX-403) Polyol D: Aliphatic polyol, hydroxyl value = 400 (manufactured by Sanyo Kasei Co., GP-400) Polyol E: Aliphatic System polyol, hydroxyl value = 28.
5 (manufactured by Sanyo Kasei Co., FA-718) Note (2): Catalyst DABCO TMR:

[0050]

[Chemical 18]

DABCO TMR2:

[0052]

[Chemical 19]

DMEA:

[0054]

Embedded image (CH ₃ ) ₂ NCH ₂ CH ₂ OH (urethane-forming catalyst) TEDA:

[0055]

[Chemical 21]

KAO No. 1:

[0057]

[Chemical formula 22]

3-Methyl-1-phenyl-2-phosfluorene oxide:

[0059]

[Chemical formula 23]

3-Methyl-1-phenyl-3-phosfluorene oxide:

[0061]

[Chemical formula 24]

Kiryusen 52:

[0063]

[Chemical 25]

DMP-30:

[0065]

[Chemical formula 26]

TAP:

[0067]

[Chemical 27]

Note (3): Foam stabilizer dimethylsiloxane-polyale block copolymer (SZ-1627 manufactured by Nippon Unicar) Note (4): Flame retardant tris (β-chloropropyl) phosphate (Faureol PCF manufactured by Stofar Chemical) ) Further, the results of measuring the physical properties of the modified polyisocyanurate foam obtained in Example 1 were as shown in Table 2 below.

[0069]

[Table 4]

Example 15 The operation of Example 1 was applied to an actual siding board continuous production line.

Foaming machine: low-pressure foaming machine (forced stirring system), G
-05 type (made in-house), discharge rate 2.0 kg / min.

Double conveyor: conveyor length 18 m, conveyor speed 10 m / min.

Cutter: traveling type circular saw cutter, cut 2 minutes and 20 seconds after injection.

Molded product: Face material (front) aluminum decorative board 0.32
mmt, (back) aluminum kraft paper.

Molded product (width) 350 mm, (thickness) 18 m
m.

Temperature conditions: polyol component 25 ° C., isocyanate component 40 ° C., face material temperature 20 ° C., conveyor temperature 7
5 ° C.

When continuous molding was carried out under the above conditions, there were no problems with respect to filling properties, curability and cutting properties, and there were no particular problems regarding warpage, shrinkage, adhesion to paper, aluminum, etc. regarding the molded products.

Main physical properties of serially manufactured product: Form density 3
2 kg / m ³ Peel strength (paper) 2.4 kg / 10 cm Oxygen index 24 Compressive strength 1.4 kg / cm ²

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 15, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0068

[Correction method] Change

[Correction content]

[0068] Note (3): Foam stabilizer dimethylsiloxane - Porie Te le block copolymer (manufactured by Nippon Unicar Co., SZ-1627) Note (4): a flame retardant tris (beta-chloropropyl) phosphates (Stowe Sulfur Chemical Co., Fuairoru PCF) The results of measuring the physical properties of the modified polyisocyanurate foam obtained in Example 1 were as shown in Table 2 below.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0070

[Correction method] Change

[Correction content]

[0070] was applied to the procedure of Example 15 Example 1 to the actual Saide I Ngubodo continuous production line.

Claims (9)

[Claims] 1. An organic polyisocyanate, a polyol and water are added according to the formula (a): In the formula, R ₁ , R ₂ and R ₃ each represent an alkyl group, and R ₄ and R ₅ each represent a hydrogen atom or an alkyl group, and a trimerization catalyst comprising a hydroxyalkyl quaternary ammonium compound and ( b) Formula [2] In the formula, R ₁ represents a substituted or unsubstituted alkyl, phenyl, naphthyl or benzyl group, and R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each H, Cl or C ₁ -C ₄ The method for producing a modified polyisocyanurate foam, which comprises reacting in the presence of a carbodiimidization catalyst consisting of phosfluorene oxide represented by: 2. A hydroxyalkyl quaternary ammonium compound is represented by: The method of claim 1, wherein 3. Phosphorene oxide is 3-methyl-1.
-The method according to claim 1, which is phenylphosphorus fluorene oxide. 4. The polyol is 20 to 600 mg KOH /
The method according to claim 1, which is at least one polyol having a hydroxyl value within the range of g. 5. The method according to claim 1, wherein the compounding ratio of the organic polyisocyanate, the polyol and the water is 1.8 or more in terms of isocyanate index represented by the NCO / OH equivalent ratio. 6. A process according to claim 1, wherein water is used in an amount of 0.3 to 1.8% by weight, based on the total weight of organic polyisocyanate, polyol and water. 7. The free-foaming density of the resulting modified polyisocyanurate foam is 30 kg / m ³ or less.
The method described. 8. A hydroxyalkyl quaternary ammonium compound represented by formula (I) according to claim 1, and a compound of formula (I
A catalyst system for isocyanate polymerization, which comprises a phosphorene oxide represented by I) or (III). 9. A polyol composition comprising a polyol, water and the catalyst system of claim 8.