JPS5922916A - Manufacture of aliphatic polyisocyanurate polymer - Google Patents

Abstract

PURPOSE:To readily obtain titled polymer of low viscosity using only a little catalyst, which gives high heat resistance and weatherability, by carrying out a polymerization of an aliphatic polyisocyanate, using a specific catalyst, into its isocyanurate derivative. CONSTITUTION:The objective polymer can be obtained by carrying out the reaction, pref. at 20-80 deg.C, of an aliphatic polyisocyanate (e.g. hexamethylene, diisocyanate) and/or an isocyanate group-terminated aliphatic polyisocyanate polyol adduct, in the presence or absence of a solvent (e.g. ethyl acetate) using as a catalyst a coordinated compound of a metal belonging to the III or IV group in the periodic table (e.g. titanium acetyl acetonate) plus, if required, an accelerator such as phenol.

Description

[Detailed description of the invention] The present invention relates to aliphatic polyisocyanate polymers.

More specifically, the present invention relates to a method for producing an aliphatic polyisocyanurate polymer having at least one incyanurate ring in the molecule, which has low viscosity and excellent heat resistance and weather resistance.

Aliphatic polyisocyanates are widely used in applications such as paints, adhesives, leather, elastomers, foams, etc., and are often used in the form of terminal polyisocyanate compounds reacted with various active hydrogen compounds while taking advantage of their non-yellowing property. . Furthermore, its rigidity and toughness make it suitable for these main uses.

Many methods are known for these incyanurate reactions.

For example, British Patent No. 1001746 describes a method using ethyleneimine, and a German patent describes a method of producing incyanurate by using ethyleneimine or an ethyleneimine derivative together with a tertiary amine using an aliphatic incyanate as a catalyst. No. 2325826.

However, while these catalysts are somewhat effective for in-annulation reactions, the reactions are either very slow or require some co-catalyst. It has also been pointed out that these catalysts are unfavorable in terms of safety and health.

Further, in U.S. Patent No. 3,487,080, quaternary ammonium hytrokind and phenol, oxy/mu,
Isocyanuration of organic borisonanate has been carried out by using a combination of methanol and the like. However, the specification (Table 3) discloses that the catalytic effect is small when hexamethylene diisonanate (hereinafter abbreviated as HDI) is used as an incyanurate catalyst.

As a similar example, U.S. Pat. No. 4,040,992 discloses that carboxylic acid N-
A method of producing polyisone annulate using hydroxypropyltrimethylammonium salt is disclosed.

However, since this catalyst is very active, it is used in the one-shot process for forming foams, but because the side effects of the reaction are not easy, the product has a high viscosity. It is stated that it is suitable.

Furthermore, the incyanurate catalysts described in British Patent Nos. 952931 and 809809 are characterized by the use of alkali metal salts (aliphatic carboxylic acid salts), but these catalysts are difficult to react with. This occurs so violently that a product with a high viscosity and a partially heterogeneous inocyanate content is formed.

Furthermore, when the catalyst is inactivated to improve stability, the catalyst tends to form an insoluble precipitate when the reaction is carried out without a solvent.

As mentioned above, these various catalysts have been applied to the production of isocyanurate polymers. Such incyanurate polymers are widely used as curing agents for paints, adhesives, elastomers, foams, plastics, and the like. However, while these known catalysts are effective for aromatic incyanates, they are highly selective for aliphatic incyanates; Many incyanates are not effective.

Among aliphatic incyanates, isocyanurate polymerization of HDI (l-limethylhexamethylene diisocyanate) (hereinafter abbreviated as TMDI) is particularly difficult, and the resulting polymer has low compatibility with other resins and solvents. There were drawbacks such as.

The present inventors have overcome these drawbacks and provided a new catalyst for producing aliphatic polyisocyanurate and a method for producing an aliphatic polyisocyanurate polymer using the same. It has been found that by the method of the present invention, an incyanurate polymer can be produced easily, stably, in a short period of time, and with a small amount of catalyst.

In the present invention, an aliphatic polyisocyanate is converted into incyanurate using a specific catalyst, and has a low viscosity, thermal stability, and weather resistance, and contains at least one incyanurate ring in the molecule. This invention relates to a method for producing an aliphatic polyisocyanurate polymer. That is, the method of the present invention involves converting an aliphatic polyisocyanate polyol adduct having a terminal isocyanate group into isocyanurate in the presence or absence of a solvent. In producing an aliphatic polyisocyanurate polymer containing at least one incyanurate group in the molecule, metal coordination compounds of metals belonging to Groups I and E of the Periodic Table are used as catalysts. This is a method for producing an octa-aliphatic polyisocyanurate polymer.

In the present invention, examples of the organic polyisocyanate used include tetramethylene diisocyanate, HDl, hexyldiisonanate, dichloromethane 44
1 diisocyanate, inphorone diisocyanate, T
MDll 4.4'methylenebis(cyclohexylisocyanate χ diisocyanate cyclohexylmethane,
Nib-diiso7anate, lysine diisocyanate, 1.5 diisocyanate 2-2 dimethylpentane,
Hydrogenated xylylene diisocyanate, cyclohexylylene diisocyanate, 1, 3.5 triisonanetone chlorhexane.

These may be used alone or in combination of two or more.

It can also be applied to other aromatic polyisocyanates.

Further, the aliphatic polyisocyanate polyol adduct used in the present invention is a product of the urethanization reaction between the aliphatic polyisocyanate compound and a polyol, and is prepared by a conventional method. Heboriol was added and the reaction temperature was 100℃
It can be obtained by carrying out the reaction preferably at 60°C to 90°C for about 3 hours.

At temperatures above 100°C, the product may become colored, side reactions may occur, and the viscosity of the product after the trimerization reaction may become extremely high, and in some cases, a gelatinous substance may be formed.
Undesirable.

By introducing a urethane group into the aliphatic polyisonoanate, the urethane group exhibits a cocatalytic effect, and therefore the incyanurate reaction proceeds easily. This is thought to be because a hydrogen bond is formed between the active hydrogen in the urethane group and the oxygen atom in the yn7anate group, which significantly activates the isocyanate group. The incyanurate polymer thus obtained has further improved compatibility with other resins and solvents, and is particularly preferred as the aliphatic polyisocyanate derivative in the present invention.

As polyols for urethanization that can be used in the present invention,
Polyols having a molecular weight of 3.000 or less and a functional group number of 2 to 4 are suitable.

Examples of polyols include ethylene glycol, 1-
3 Butanediol (hereinafter abbreviated as 1.3 B G), 1
-4 Butanediol, propylene glycol, dipropylene glycol, neopentyl glycol, 1-6 hexane glycol, 2-ethylhexanediol, 2-
2-4 Dihydric alcohol such as trimethylpenotanediol, trimethylolpropane (hereinafter abbreviated as TMP),
Examples include tri- to tetrahydric alcohols such as glycerin and pentaerythritol, polyester polyols, and polyether polyols, either singly or in a mixture of two or more.

The urethane group concentration is not particularly limited, but in the presence of a catalyst, the incyanurate reaction rate exhibits a first-order reactivity with the urethane group concentration, so an increase in the urethane group concentration will affect the incyanurate reaction rate. promote. Due to the cocatalytic effect of this urethane group, the urethane group concentration is therefore selected together with the amount of catalyst added.

However, an increase in the urethane group concentration tends to impede the thermal stability, which is a characteristic of the isocyanate groups subsequently produced. Therefore, the urethane group concentration should be selected depending on the application.

The urethanation reaction and the isocyanation reaction described later can be carried out in the presence or absence of a solvent.

When using a solvent, use one that is inert to incyanate groups and that dissolves the formed polymer, i.e., acetic acid esters such as ethyl acetate, butyl acetate, seronulpacetate acetate (hereinafter abbreviated as Fzu Shichikuchi). , aromatic hydrocarbons such as toluene, xylene, etc., and all solvents that can generally be used in urethanization reactions can be used.

Examples of the catalyst used in the incyanurate polymerization include metal coordination compounds of Group 1 and Group 1V metals. Examples of these representative compounds are as follows.

Titanium acetylacetonate-1, titanium octylene glycolate, titanium lactate ammonium salt, titanium lactate, titanium lactate ethyl ester, titanium triethyl 7-ruaminate, titanium triisostearate, titanium diacrylate, titanium dimethacrylate, titanium di(cumyl) ferulate) oxyacetate,
For diisostearoyl ethylene titanate, zirconium tetraethylacetylacetonate, zirconium butoxide, tetramethylzilfnium, zirconium tributoxymonoethylacetoacetate, zirconium ammonium lactate, and aluminum alcoholade, aluminum chelate, etc., for example, aluminum dibutquindomonoethyl acetoacetate-h
, aluminum dibutkind monomethyl acetoacetate, aluminum trisacetylacetonate, aluminum diisopropoxide monoethylacetoacetate, ethyl acetate aluminum diisopropylate, and similar compounds thereof.

Further, a co-catalyst can be used simultaneously with these catalysts, if necessary.

Examples of co-catalysts include phenolic hydroquine compounds such as phenol, cresol, and i-lymethylphenol; alcoholic hydroquine compounds such as ethanol, cyclohexanol, and ethylene glycol; and tertiary amines such as triethylamide, methylpyridine, and pendel. Examples include dimethylamine.

In the method of the present invention, the amount of catalyst is generally 0.001 to 10% by weight, preferably 0.01 to 4% by weight, based on the polyincyanate compound. The most effective amount of catalyst to be used can be varied depending on the type of metal coordination compound used and the purpose.

The method of the present invention generally ranges from 10 to 100°C, preferably from 20 to 100°C.
It is carried out in a temperature range of 80°C.

When the catalyst is used according to the present invention, the incyanurate reaction proceeds homogeneously and stably with high selectivity in the preferred temperature range of 20 to 80°C, and a very good product can be obtained in high yield. Therefore, unreacted incyanate can be easily removed by known methods such as evaporation or extraction, resulting in high economical effects.

That is, it has been found that incyanurate formation can be stably performed up to a polymerization rate of 50 to 60 (g) of all incyanate groups. This is a high polymerization rate that has not been achieved with known catalysts.

The incyanurate reaction according to the method of the present invention is generally carried out by a solvent-free method, and if necessary, it can also be carried out in the presence of a solvent.

In addition, when a single incyanate with two isocyanate groups having the same activity as conventional HDI is polymerized to form an incyanurate, the compatibility between the incyanurate polymer and the single incyanate is not good, so no solvent is used. There were times when turbidity occurred inside. For this reason, methods have been taken to improve solubility by introducing urethane groups, but in the method of the present invention, incyanurate can be converted to incyanurate in a solvent-free manner, both in cyanate alone and incyanate polyol adduct. Polymerization is achieved and an incyanurated polymer is obtained that is stable, free of turbidity, and with less formation of non-uniform high molecular weight polymers.

According to the present invention, the reaction after addition of the catalyst and co-catalyst in the preferred temperature range of 20 to 80 DEG C. is an exothermic polymerization reaction, and the exothermic rate is slow. Therefore, this reaction can be easily produced using conventional production equipment, and reaction adjustment is also possible.

Further, the reaction time, yield, and quality of the incyanurated polymer can be effectively controlled and adjusted by controlling the type and amount of the catalyst used.

In the method of the present invention, by selecting a suitable amount of catalyst and a suitable reaction temperature, N
GO content decreases linearly and gradually. Therefore, the reaction can be arbitrarily stopped when the desired NCO content is reached while being measured by the commonly used titration analysis. Can be adjusted.

In producing the aliphatic polyisocyanurate polymer of the present invention, an acidic compound is used as a terminator.

Acidic compounds include hydrochloric acid, phosphoric acid, dimethyl phosphate,
Trimethyl phosphate, triethyl phosphate, tricresyl phosphate, triphenyl phosphate, phosphorus, butyl phosphate, P-
Toluenesulfonic acid, methyl P-toluenesulfonate,
Xylene sulfonic acid, benzenesulfonic acid, methanesulfonic acid, alkylbenzenesulfonic acid, sinaphthalene disulfonic acid, dinaphthalene monosulfonic acid, dinonylnaphthalene disulfonic acid, dinonylnaphthalene monosulfonic acid, aminophenolsulfonic acid, nonafluorobutanesulfonic acid , acetyl chloride, hendiyl chloride, and similar compounds thereof.

The amount of stopper is 0 per mole of metal content in the catalyst.
．． A 5-5 times molar amount is used, preferably a 1.0-3 times molar amount. In the method of the present invention, by adding it during the isocyanurate reaction, the reaction solution does not become cloudy.
Stabilization of aliphatic polyisocyanurate polymers can be achieved.

In the method of the present invention, a product of the same quality can be obtained both in the presence of a solvent and in the absence of a solvent.
It is widely useful not only as an adhesive but also as a raw material for elastomers, plastic foams, etc., and has the advantage of exhibiting excellent performance in yellowing resistance, heat resistance, water resistance, weather resistance, etc.

The present invention will be further explained in detail with reference to Examples, but the present invention is not limited thereto. In the examples, all parts and percentages mean parts by weight and percentages by weight unless otherwise specified.

Example 1.2.5.6.7.8.9゜Under the conditions shown in Table 1, a 10100O capacity glass four-eye flask with a sliding lid was equipped with a thermometer, a stirrer, a nitrogen seal tube, and a cooling tube. Add inocyanate, catalyst, co-catalyst (no co-catalyst was added in Example 5), solvent (Example 9 only),
The air in the flask was replaced with nitrogen, heated to the reaction temperature while stirring, and reacted at the same temperature for a predetermined time. The NGO content and viscosity were measured. The reaction liquid was a pale yellow transparent liquid (Example 7 was a yellow liquid). )Met.

A terminator was added to this reaction solution, and after stirring at the reaction temperature for 1 hour,
Free incyanate was removed using a molecular distillation apparatus to obtain a pale yellow transparent liquid (yellow liquid in Example 7).

The NGO content, viscosity, and free incyanate of this liquid were measured, and the results are shown in Table 1.

In the infrared absorption spectrum of the Kono liquid, a strong absorption characteristic of the incyanurate ring was observed at 1680 cm.

Example 3.4.10.11 Under the conditions shown in Table 1, incyanate and polyol were placed in a four-eye glass flask similar to Example 1, the air in the flask was replaced with nitrogen, and the reaction was carried out with stirring. The mixture was heated to a certain temperature and reacted at the same temperature for a predetermined time to measure the NGO content.

The soybean liquid was a colorless and transparent liquid.

Next, a catalyst and co-catalyst were added and heated to a reaction temperature of t.
The reaction was carried out in the same manner.

The results are shown in Table 1.0 Comparative Example 1.2 A reaction was carried out in the same manner as in Example 1 under the conditions shown in Table 1, using isocyanate, catalyst, and co-catalyst (not added in Comparative Example 2). . The results are shown in Table 1.

Comparative Example 2 has an infrared absorption spectrum of 1680
Absorption +i specific to the incyanurate ring of crn-' was not observed.

Comparative Example: 34 Under the conditions shown in Table 1, incyanate 1. + (Riolu,
A reaction was carried out in the same manner as in Example 3 using a catalyst and a co-catalyst. The results are shown in the table below.

All of the obtained polymers had poor compatibility by 2.

Compatibility Test Compatibility tests were conducted on the polymers obtained in Examples 1 to U and Comparative Example 3.4 with Desmofene 800 (manufactured by Nippon Polyurethane Industries) and Hiepiko 1001 (Shell Chemicals).

Test method Polyol (Desmofene 800, Epicote 100
1)) is a mixed solvent of ethyl acetate: butyl acetate: toluene: acid cello = 1:1:1:1 (weight ratio), each with a solid content of 4
200 m at room temperature 25°C using
Use a bee force of l to convert the polymer and polyol into NCO:0H=
t: 1.

judgement By naked eye.

Results Examples 1 to 11 were transparent, but Comparative Example 3. No. 4 was slightly cloudy, and No. 4 was cloudy. See table l.

Claims (1)

[Scope of Claims] ■ As an in-cyanurate catalyst in in-cyanurate polymerization of an aliphatic polyisocyanate and/or an aliphatic polyisocyanate polyol adduct having a terminal isocyanate group in the presence or absence of a solvent. A method for producing an aliphatic polyisocyanurate polymer, which comprises using a coordination compound of a metal belonging to Groups 1II and 2 of the Periodic Table. 2. As an aliphatic polyisonanate polyol adduct having a terminal isocyanate group, an aliphatic incyanate polyol 4 obtained by reacting an aliphatic polyisocyanate with a polyol having a molecular weight of 3.000 or less and a functionality of 2 to 4. The method according to claim 1, characterized in that a filler is used.