JPS6245579A - Production of polymerizable isocyanurate - Google Patents

Abstract

PURPOSE:In reacting a specific organic halogen compound with an alkali cyanate in an acid amide type polar aprotic solvent, to obtain the titled compound in high yield, by adding a dehydrating solid acid and a tertiary amine compound to the reaction system. CONSTITUTION:A compound shown by the formula I [R and R' are H, alkyl, aralkyl, phenyl or substituted phenyl; A is alkylene, aralkylene or oxyalkylene; dotted line is optionally existing triple bond (R and R' do not exist); X is Cl, Br or I] is reacted with an alkali cyanate in the in an acid amide type polar aprotic solvent in the presence of both a dehydrating solid acid (dehydrated active powder or granules of silica gel, magnesium silicate, aluminum phosphate, zeolite, etc.,) and a tertiary amine compound (tertiary amine, its salt, quaternary ammonium salt or tertiary amine coordination compound), to give the aimed compound shown by the formula II useful as a crosslinking agent, etc., in 90-100% yield while suppressing by-products of substituted urea and tar-like polymer.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a new method for synthesizing polymerizable isocyanurate from an organic compound and an alkali cyanate, and Polymerizable isocyanurates have already been used as crosslinking agents, resin raw materials, heat-resistant resin additives, agricultural chemicals, and synthetic intermediates, and it has been desired that an industrially advantageous production method be developed.

<Prior Art> Modern methods of synthesizing incyanuric acid esters containing polymerizable isocyanurates and academic research thereof were discovered and developed by the present inventors and have continued to this day.

For example, ■Production method of cyanuric acid derivatives
b-3985), ■Production method of incyanuric acid ester (
1976-4376), ■Production method of isocyanuric acid ester (1976-6655), ■Purification method of trinisder isocyanurate (1976-9)
34s), ■ Purification method of isocyanuric acid ester (date and time, 1979-12915'), ■ Manufacturing method of isocyanic acid derivative C date and time, 1972-26766), ■ 12 manufacturing methods of incyanuric acid triester (date and time) minute, Showa 7-1a
395), ■Production method C of isocyanuric acid ester, Date and time, 163081-1981■ Method for removing impurities from isocyanuric acid ester (Date, time and minute, 2251-1981"tl"l)
and (9) Manufacturing method of triallyl isonanurate (Date/Time, 1972-26022) shows the basic manufacturing method, purification method, etc. <Problems to be solved by the invention> At present: 1. Although industrial production of isocyanurate is being carried out using this method, it cannot be said that sufficient detailed research has been conducted on the content of side reaction products and the unexplained decrease in isocyanurate yield. It is. In this regard, the present inventor has continued a lot of research in order to establish a more advanced method for synthesizing isocyanurate, and has finally completed the clever method of the present invention. .

<Means to solve the problem> Special action> As a result of detailed research by the present inventors on the reaction between an organic compound and an alkali cyanate, the general formula cHn= cR'p, x
(However, in the formula, R and R' represent either a hydrogen atom, an alkyl group, an aralkyl group, a phenyl group, or a substituted phenyl group, and A represents an alkyl group, an aralkylene group, or an oxyalkylene group, and R and R' may be the same or different. . . . may be present or absent. When present, it indicates a triple bond, and R5R1 is present from 1 to absent. Also, Indicates one of the atoms.

Hereinafter, the same symbols mean the same things. ) and an alkali cyanate in an acid amide type polar aprotic solvent, a polymerizable isocyanate characterized by the presence of a dehydrating solid acid and a tertiary amine compound. F-n production method of nurate 2
It is. The dehydrating solid acids mentioned here are silica gel,
Aluminum silicate, magnesium silicate, aluminum phosphate, zeolite, zirconium phosphate, zirconium silicate, zirconium phosphate silicate, rare earth silicate,
It is an activated dehydrate of at least one particulate material selected from the group consisting of rare earth phosphates, silicate minerals, and phosphate offerings, and tertiary amine-based compounds are still tertiary amine-based compounds. It refers to at least one compound selected from amines, tertiary amine salts, and quaternary ammonia.

Typical organic halogen compounds represented by the general formula (ARI CR' A These include α-benzyl allyl chloride, cinnamyl chloride, crotyl chloride, flopargyl chloride, β-chloroethyl vinyl ether, β-chloroethyl propargyl ether, etc. All representative examples are shown as chlorides, but bromides may also be used. It may be iodide or a mixture thereof. All of these are raw materials that are easy to synthesize and are industrially advantageous compounds. Alkali cyanate refers to sodium cyanate, potassium cyanate, or a mixture thereof. Refers to either a mixture or an industrial product containing 7n% or more of these (containing 5 to 60 cycles of alkali carbonate).Acid amide type polar aprotic solvents include dimethylformamide, diethylformamide, and 7-formylformyl-sulfate. Ruho 1
1, N N'-diformylpiperazine, dimethylacetamide, diethylacetamide, acetylpiperidine,
Acetylmorpholine, N,N'-diacetylpiperazine, N-methyldiacetimide, N-methylmaleimide,
N-methylsuccinimide, N-methylphthalimide, N
-Methylpyrrolidone, N-ethylpyrrolidone, N, N'
- Dimethylethylene urea or tetramethylurea alone or a mixture of two or more thereof. A dehydrating solid acid refers to a substance that has acidic points on its solid surface and has the ability to dehydrate. In general, there are some types of properties on the surface of a solid that can be predicted from the properties of the solid itself, and some special types that cannot be predicted.
This also applies to acids and bases.

For example, there are surprisingly strong acidic points on the surface of a substance called silica-alumina catalyst, but these acidic points are difficult to predict based only on the properties of the solid. The surface acidity of a solid is unevenly distributed and spreads from very strong acid sites to very weak acid sites, so it is difficult to treat it theoretically. A uniformly distributed solid acid has been well studied. For example, catalysts containing ion exchange resins and phosphoric acid are well known. However, the dehydrating solid acids referred to in the present invention include silica gel, aluminum silicate, magnesium silicate penta-aluminum phosphate,
At least one powder or granule selected from the group consisting of zeolite, zirconium phosphate, zirconium silicate, zirconium phosphate silicate, rare earth silicate, rare earth phosphate, GgrQK silicate, and phosphate mineral. A dehydration activated product having acidic points such as activated alumina, activated red sea bream,
I don't like Shia. Next, let's take a look at some representative substances.

Namely, silica gel, silica/alumina catalyst, silica/magnesia catalyst, silica/alumina/magnesia catalyst, semisynthetic silica/alumina catalyst, aluminum phosphate,
Synthetic zeolites (molecular sieve, etc.), natural zeolites (balmuchite, philipsite, chabasite, erionite, clinotaylolite, mordenite, etc.), zirconium phosphate, zirconium hyrophosphate,
Zirconium silicate, zirconium silicate phosphate, synthetic silicates or synthetic phosphates of rare earth elements (including thorium), mono-nonite, nacrite, dietskite,
Halloysite, f-jugami, monmo I noronite, beidellite, nontronite, sabonite.

rib Kt white clay, Fuller's earth, bentonite, sericite, pyrophyllite, chlorite, vivianite, bosphorite, cacoxenite, phosphoric acid panshian, phosphoric acid ±C phosphorite), etc. alone or 1 to 2 Powder and granules with a relatively large specific surface edge (5n to 5nOTn''/') ') sufficiently dehydrated with a mixture of F and Kl.
It refers to powder or granular material whose particle size is between 0.5 and 10 nO microns. Even if the pH of these powders and granules when placed in water may be 7 to 12, there are acidic active sites dotted on the solid surface. In a solvent, the Kokuai granules act in a 1-7 manner with the solid acid for dehydration, and act to strongly attract the alkali IJ ions in the alkali cyanate. Chiru. This effect can be further enhanced by the coexistence of a tertiary amine compound. Tertiary amine compounds and l-Lm
Tertiary amines, i.e. trialkylamines, dialkylaralkylamines, dialkylaralkylamines, alkyldialkylamines, alkyldialkenylamines,
Trialkylamines, trialkenylamines, dialkylarylamines, dialkenylarylamines, dialkylarylamines, and amine-based compounds that do not contain active hydrogen atoms, which can be substituted in some of these hydrocarbon processes. These salts, quaternary ammonium salts based on these salts, or the Lewis acid coordination 9-position compounds (charge transfer complexes) of these tertiary amines, singly or as a mixture of two or more thereof, are referred to. 1. The reaction targeted by the present invention is generally expressed by the following formula using sodium cyanate.

Tsukinokatsu 1〆outUoγa, tertiary amine compound organic
Rogen compound ACR' :: CHR ■ The reaction can proceed at filtration polymerizable isocyanurate ~170'C, but the reaction is easier when the above-mentioned dehydrating solid acid and tertiary amine compound are used together as a catalyst for the reaction. In order for the reaction to proceed smoothly and in the same amount of time, for example, the reaction temperature may be increased by 10°C.
The temperature can be lowered by as much as ~20°C. Advantageously, the by-products of substituted r and l elements and polymers (tar-like substances) from organic halogen compounds are significantly suppressed, and 90 to 100 It promises to produce polymerizable isocyanurator in high yield. Moreover, the method of the present invention can quickly solve the purpose even when using an industrial product in which the cyan ffF alkali contains a small amount of alkali carbonate, alkali oxide, alkaline earth metal carbonate, or alkaline earth metal oxide as impurities. The reaction can proceed.

Furthermore, if the yield of the target product is 95% or more using the powder method, the water content in the reaction system (this can be easily determined by analyzing the water content in the supernatant liquid of the reaction mixture using the Karl Fischer method) is 20 nppm or less. This can be achieved without any special efforts. Collection of polymerizable isocyanurate from the reaction-completed mixture is as follows:
This is carried out by applying ordinary organic synthesis operations such as filtration, centrifugation, distillation, and recrystallization, and the reaction solvent can be recovered and reused. Dehydrating solid acids are usually mixed with alkali halides and produced as a by-product, but this can be easily separated from the alkali halides, and can also be used as is in other industries that require alkali halides. is also possible. The tertiary and amine compounds may be recovered and reused, and if the amount used is small, the water-washed compound may be removed by pickling or the like during the purification of the radically polymerizable isocyanurate.

Polymerizable isocyanurates obtained by the method of the present invention include, for example, triallylisocyanurate, tricrotylisocyanurate, trimetaallylisocyanurate,
Tripropargyl isocyanurate, tris(p-vinylbenzyl)isocyanurate, tris(β-vinyloxyethyl)isocyanurate.

As shown by bis(β-vinyloxyethyl)allyl isocyanurate, bis(β-vinyloxyethyl)metallic isocyanurate, dimethalylisocyanurate, or allyldimethallyl isocyanurate, the organic It can be synthesized by a powder method using a halogen compound or two types of organic halogen compounds as raw materials.

Of course, in the method of the present invention, the reaction can be carried out by changing a part of the organic halogen compound to an alkyl halide or an aralkyl halide, and in this case, the following polymerizable isocyanurate can be obtained. Typical examples are methyl diallyl isocyanurate, dimethyl aryl isocyanurate, ethyl diallyl isocyanurate, diethylallyl isocyanurate, butyl diallyl isocyanurate, dibutylallyl isocyanurate,
Butyl dimethallyl isocyanurate, dibutylmethallyl isocyanurate, benzyl diallyl isocyanurate, dibenzylallyl isocyanurate, benzyl dimetaallyl isocyanurate, dibenzylallyl isocyanurate, benzyl dicrotyl isocyanurate, penzyl dibrohargyl isocyanurate nurate, bis(β-vinyloxyethyl)ethyl isocyanurate, diethyl
Examples include β-vinyloxyethyl isocyanurate, dibenzylcinnamyl isocyanurate, and the like.

As described above, the polymerizable isocyanurate of the present invention is composed of a substituent on the nitrogen atom of the isocyanuric ring and a hydrocarbon group having one double bond, a hydrocarbon group having one triple bond, or a double bond. A compound containing at least one atomic group (7) in which the methylene group of a hydrocarbon group having one bond is replaced with an oxygen atom, and can be polymerized or copolymerized under various conditions. It is something that can be done.

Additionally, these compounds are useful for hydrogenation, hydrogenhalide addition, sulfuric acid addition, halogenation, epoxidation, mercaptan addition, Friedel-Krach reaction, Prins reaction, Ziels-Alder reaction, or other reactions. It is used as a raw material, and the isocyanuric ring is not changed in such polymerization or various reactions. In order to start the reaction of this polymerizable isocyanurate, radical reagents, cationic reagents, anionic reagents, complex reagents, ultraviolet rays, electron beams, gamma rays, etc. are used, and the desired reaction can also be controlled.
If the reaction temperature, pressure, etc. are considered in order to accelerate the reaction, the purpose of each use can be achieved.

The inventors of the present invention have conducted numerous experiments regarding the present invention as described above, and have clearly demonstrated the superiority of the present invention. It is.

〈Example〉 We will clarify the technical contents of representative examples from Shiroka. In the following examples, potassium cyanate is a 999.8% pure synthetic product as KNCO.

Purity 99.5 as sodium cyanate NaNC0
% synthetic product, industrial sodium cyanate NaNC05
These are the results using 8% Na2CO (1% or less H2O) in Section 1. The acid amide type polar solvent was rectified immediately before use and used as a high-grade product (a2o 200-4nnppm). Further, the dehydrating solid acid was used after being sufficiently dehydrated and activated according to the method described in the literature. For water in the reaction system, collect the supernatant of the reaction mixture from time to time and analyze it using the Karl Fischer method. Take care to ensure that the concentration of H2O is 50 to 200 ppm. If this exceeds 2[101)111m, The experiment was continued with the addition of some dehydrating solid acid. The total amount of the dehydrating solid acid used in the method of the present invention is in the range of 5 to 50% by weight of the alkali cyanate, and the amount of the NX 5th class amine compound used is 0.5 to 10% by weight of the organic halogen compound. % Particularly preferably '41 to 5% by weight
It has been confirmed from many preliminary experiments that

Examples 1 to 12 0.5 mol of the organic halogen compound shown in Table 1, 10 mol of an acid amide type polar solvent, and 60 g of potassium cyanate powder were placed in a flask equipped with a moisture-proof L-type stirrer and a backflow condenser.

10 g of dehydrating solid acid and 2 to 3 tertiary amine compounds
After reacting for 2.5 hours at 140 to 15 n'C with stirring, the reaction mixture was filtered to remove inorganic compounds, and the residue was distilled under reduced pressure to recover the solvent. The extract was extracted with ether, washed with water, dried over anhydrous sodium sulfate, and distilled to determine the yield of isocyanurate. In some cases, the ether extract (dry product) was subjected to chromatographic analysis and NMR analysis to determine the yield of isocyanate. These results, expressed as f, are as shown in Table 1.

Table 1 Example Organic Norogen Compound Solvent 1
Allyl chloride dimethylformamide 2
Allyl bromide dimethylacetamide 5
Methyl chloride 1 nor dimethylformamide 4
Bromide metaa 1 nor formyl piperidino 5 α
- Chlormemethis image Acetylmorpholine 6 Cinnamyl chloride N, N'- Chill diagnosis (U〃7
Croquel bromide N-methylpyrrolidone 8 Propargyl bromide Tetramethylurea 9 Propargyl iodide Tetramethylurea 10 p-Chlormethyls 9 Dimethylformamide 11 α-Benzyl allyl bromide Dimethylformamide silica gel
Triethylamine/EE3r salt 97 silica gel Triethylamine 98 silica gel
Triethylamine・)Br Salt 96 Aluminum Phosphate N-Methylmorpho-1-None 95+<o',
"Ruconium N-Methylmorpholine 91 Aluminum phosphate Triethylenediamine 93 Aluminum silicate Trimethylamine FJ3r salt
95 Aluminum silicate tributylamine
90 aluminum silicate tributylamine
88 Magnesium silicate Tribenzylamine 92 Psium Tribenzylamine 86 Cerium silicate N-Mesa L-Siretphosphorus 94 Examples 16-17 In a closed reaction vessel, organic halogen compounds shown in Table 2 were added. ), dimethylformamide 2 onml. Add 511 g of cyanic acid powder, 59 g of solid acid, and 4 q of Asahi tertiary amine (hypolysate) and heat to 145°C with stirring.
-Co2 [Volume reaction After cooling, the reaction was carried out in the same manner as in Examples 1 to 12, and the results shown in Table 2 were obtained.

0.5 mol of the organic halogen compound shown in Table 3, N-
Methylpyrrolidone 150 stomach Otsu industrial cyanide 1 role sodium powder 607, dehydrated solid acid 20p: b-, hbi7shin =, completed treatment Add 1g of min-based compound q and p, while stirring 'i
After reacting at s n 'C for 2 hours, it was cooled, and then the yield of isocyanurate C was determined by the same operation as in Examples J, F, 6 p111-12. The results are shown in Table 6.

Table 3 Examples Organic/logen compounds Dehydrating solid acid 18 Allyl chloride Zirconium phosphate silicate 19 Metaallyl chloride Intervening zeolite Comparative example 1
Metaallyl chloride - Comparative example 2 Metaallyl chloride - Comparative example 3 Metaallyl chloride Synthetic zeolite comparative example 4 Metaallyl chloride Activated alumina tertiary amine compound Isocyanurate yield @) N-ethylpiperazine 96 Triethylamine/HBr salt 94 N-ethylpiperazine 7 Atethylamine/HBr salt 79 In Table 3, Comparative Examples 1 to 4 were those in which either a dehydrating solid acid or a tertiary amine compound was not added, and in particular, activated alumina was added as a dehydrating solid acid. It was recognized that the method had a poor yield of isocyanurate and was not suitable as an industrial method.

<Effects of the Invention> As described above, according to the present invention, polymerizable insia slate can be obtained in high yield. Further, the object compound of the present invention contains a double bond or a triple bond and is rich in polymerizability and chemical reactivity. Therefore, it is expected to be used as a crosslinking agent, resin raw material, heat-resistant resin additive, and also as a flame retardant for resins by adding bromine. In addition, it is highly valuable as a raw material for organic synthesis because it can easily undergo epoxidation, Friedel-Krach reaction, Prins reaction, and Ziels-Argout reaction, and these reactions can be used to create biochemically active compounds. Alternatively, induction into reactive oligomers is expected. Therefore, it is expected that the products obtained by the method of the present invention will make a large contribution to various industries.

Claims (3)

[Claims] (1) General formula CHR■CR'AX (wherein R, R'
represents a hydrogen atom, an alkyl group, an aralkyl group, a phenyl group, or a substituted phenyl group, A represents an alkylene group, an aralkylene group, or an oxyalkylene group, and R and R' may be the same or different. good.・・・
* may be present or absent; when present, it indicates a triple bond, and R and R' are absent. Moreover, X represents either a chlorine atom, a bromine atom or an iodine atom. ) is reacted with an alkali cyanate in an acid amide type polar aprotic solvent, and a dehydrating solid acid and a tertiary amine compound are present in the polymerizable isocyanurate. Manufacturing method. (2) The dehydrating solid acid is silica gel, aluminum silicate, magnesium silicate, aluminum phosphate, zeolite, zirconium phosphate, zirconium silicate, zirconium phosphate silicate, rare earth silicate, rare earth phosphate, silicic acid A method for producing a polymerizable isocyanurate according to claim (1), which is a dehydration activated product of at least one powder selected from the group consisting of salt minerals and phosphate minerals. . (3) The tertiary amine compound is at least one compound selected from the group consisting of tertiary amines, tertiary amine salts, quaternary ammonium salts, and tertiary amine coordination compounds. A method for producing polymerizable isocyanurate according to claim (1).