JPH0148273B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel compounds, 2-methylene-7,
It relates to 8-benzo-1,4,6-trioxaspiro[4,5]decene-9,10 (hereinafter referred to as compound [1]), and compound [1] is represented by the following formula [1]
For example, it is useful as a polymerizable monomer. Compound [1] is 2-halogenated methyl-7,8-benzo-1,4,6-trioxaspiro[4,5]decene-9,10 (hereinafter referred to as compound [2]) represented by the following formula [2]. It is produced by the dehydrohalogenation reaction of (Here, X represents a halogen atom such as Cl, Br, I, etc.) This reaction is shown below. Compound [2] is already known [K.
Bodenbenner . Compound [1] is synthesized by dehydrohalogenation by reaction with a sufficient amount of alkali such as sodium alcoholate. There is no particular restriction on the reaction temperature, but it is generally carried out at 0°C to 60°C. Further, the degree of progress of the reaction can be easily determined by analyzing the reaction solution using, for example, a gas chromatograph or a liquid chromatograph (abbreviated as HLC). Compound [1] can be separated and obtained from the reaction solution by, for example, pouring the reaction solution into water, separating the organic layer and the aqueous layer, and then performing an extraction operation on the aqueous layer with an organic solvent such as ether, chloroform, or toluene. The extract layer and the organic layer are combined, dehydrated and dried, and the solvent is distilled off.
This can be done by distilling the residue under reduced pressure. As a result of various studies regarding radical ring-opening polymerizable monomers, the present inventors have found that compound [1] not only undergoes cationic ring-opening polymerization, but also undergoes radical polymerization and radical ring-opening polymerization. Regarding spiroorthocarbonates, which have a somewhat similar chemical structure to spiroorthoesters,
Its radical ring-opening polymerizability is Endo, T., and
Bailey, W.J., J.Polym.Sci., Polym.Chem.Ed.,
14, 2525 (1975), etc., but the synthesis method for spiroorthocarbonates is complicated and requires the use of harmful CS2 with a low boiling point and expensive raw materials, making it difficult to manufacture. Not, but
It also has the disadvantage that the target product is expensive. However, the compound [1] of the present invention has the advantage that it can be easily synthesized by a simple reaction of dehydrohalogenation using the compound [2] synthesized from commercially available inexpensive epihalohydrin and coumarin as raw materials. have Among the polymerization of compound [1], for example, radical polymerization is thought to proceed by the following mechanism, and according to this, the radical polymer has the following formula [A],
A mixture of polymers represented by [B] and [C],
Ketone groups are created in the main chain of the polymer by radical polymerization.
It has the feature that ester groups and benzene rings can be easily introduced. As mentioned above, during radical polymerization, coumarin is produced along with the production of the polymer represented by formula [C]. If removal of coumarin from the polymer is desired, the polymer is dissolved in a good solvent for the polymer, such as methylene chloride, and the resulting solution is poured into a solvent that is a poor solvent for the polymer and dissolves the coumarin, such as methanol; This can easily be accomplished by a method of precipitating the polymer. As mentioned above, the compound [1] of the present invention can be easily and inexpensively produced, and can be polymerized by either radical polymerization or cationic polymerization, and the polymer has a main chain of It contains a ketone group, an ester group, and a benzene ring. Therefore, the compound [1] of the present invention is a molding material,
It is an extremely useful compound as a raw material for adhesives, paints, etc. Radical polymerization of compound [1] can be carried out by conventional radical polymerization means, such as ultraviolet rays, infrared rays, heat, electron beams, or microwaves. In ultraviolet radical polymerization, a photoinitiator is usually used. Suitable photoinitiators include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 4'-isopropyl-2-hydroxy-2
-Methylpropiophenone, 2-hydroxy-2
-methylpropiophenone, 4,4'-bis(diethylamino)benzophenone, benzophenone,
Methyl-(0-benzoyl)-benzoate, 1-
Phenyl-1,2-propanedione-2-(0-
ethoxycarbonyl)-oxime, 1-phenyl-1,2-propanedione-2-(0-benzoyl)-oxime, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, benzyl or carbonyl compounds such as diacetyl; anthraquinone or xanthone derivatives such as methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2-methylthioxanthone or 2-i-propylthioxanthone; diphenyl sulfide, diphenyl sulfide or dithiocarbamate, etc. Sulfur compounds; α-chloromethylnaphthalene, anthracene, etc. For polymerization using infrared rays, heat, or microwaves, any radical initiator can be used as long as it can generate radicals upon decomposition. For example, di-tert-butyl peroxide,
Organic peroxides such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl hydroperoxide, and tert-butyl peroxybenzoate; 2,2'-azobisisobutyro Azo compounds such as nitrile; ammonium persulfate,
Persalts such as potassium persulfate can be used. Further, polymerization using ionizing radiation such as an electron beam is usually carried out without a catalyst. When a catalyst is used, the amount used is generally 0.01 to 10 wt%, preferably 0.1% based on the total amount of monomers.
~5wt% range. Radical polymerization proceeds even at room temperature when irradiated with ultraviolet rays or ionizing radiation, but in other cases it proceeds smoothly under heating or heating conditions. When a solvent is used during polymerization, examples of preferably used solvents include toluene, xylene, ethyl acetate, N,N-dimethylformamide, chloroform, and dioxane. Further, the cationic polymerization of compound [1] is carried out by a generally well-known method, that is, by using ultraviolet rays, infrared rays, heat, microwaves, etc. in the presence of a cationic polymerization initiator. As a cationic polymerization catalyst in the case of ultraviolet irradiation,
For example, aromatic diazonium salts such as φ−N ⁺ ≡N・PF ⁻ ₆ and φ−N≡N ⁺・BF ⁻ ₄ ; aromatic halonium salts such as φ−I ⁺ −φ・BF ⁻ ₄ ; Aromatic onium salts of Group A elements of the Periodic Table, such as; Aromatic onium salts of Group A elements of the Periodic Table, such as [Formula]; Dicarbonyl of Group a-a elements of the Periodic Table, such as [Formula]; Complex compounds can be used. In addition, other cationic polymerization catalysts include, for example, Lewis acids such as BF ₃ , FeCl ₃ , SnCl ₄ , SbF ₃ , TiCl ₄ ; Lewis acids such as BF ₃ OEt ₂ , BF ₃ -aniline complex, and O, S, Compounds with compounds containing N, etc.; oxonium salts, diazonium salts, carbonium salts of Lewis acids; halogen compounds, mixed halogen compounds, perhalogen acid derivatives, and the like. The amount of catalyst used is generally 0.001 to 10 wt%, preferably 0.1 to 5 wt%, based on the monomer to be polymerized.
A range of is suitable. Although there are no particular restrictions regarding the polymerization temperature, it is usually carried out at room temperature to 200°C. When using a solvent during polymerization, it is desirable to choose a compound that does not react with the growing cation and reduce its activity. Suitable solvents for use include aliphatic hydrocarbons such as hexane and octane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride, 1,1-dichloroethane, and others. Example: Put 108 g (2 mol) of sodium methylate and 500 ml of DMF (dimethylformamide) into a 4-neck flask equipped with a stirrer, condenser, thermometer, and dropping funnel, and add 120 g while stirring.
(0.5 mol) of 2-chloromethyl-7,8-benzo-1,4,6-trioxaspiro[4,5]decene-9,10 was added dropwise over 80 minutes. During this time, the reaction solution was kept at 15°C to 20°C. Thereafter, the reaction was carried out at 40°C for 10 hours, and the reaction solution was poured into water from Step 1 to separate the aqueous layer and the organic layer. Next, the operation of adding 400 ml of toluene to the aqueous layer for extraction was repeated three times, and each toluene layer was combined with the organic layer and washed twice with 500 ml of water. This was dehydrated with magnesium sulfate, desolventized with a rotary evaporator, and then distilled under reduced pressure.
2-methylene-7,8 at 125℃/0.45mmHg
-benzo-1,4,6-trioxaspiro [4,
5] Decene-9,10 80.2 g (yield 79%) was obtained. The physical properties of this product are as follows. Γ Specific gravity: 1.300 (25℃) (Measured by Beckman air comparison type specific gravity measuring device) Γ Melting point: 45-48℃ Γ Boiling point: 120-125℃/0.45mmHg Γ Infrared absorption spectrum (hereinafter referred to as IR); 1690cm ^-1 ( CH ₂ = C) 1640 cm ^-1 (CH = CH) (see Figure 1) Γ nuclear magnetic resonance spectrum (in CDCl ₃ ); δ (ppm) (see Figure 2) 6.7~7.3 5.6~5.9 5H 1Ha 4.5~ 5.0 2H b 3.9〜4.1 2H c In addition, 2-chloromethyl-7,8 used above
-benzo-1,4,6-trioxaspiro [4,
5] Decene-9,10 was produced by the following method. That is, in one flask similar to the above, 300 ml of methylene chloride, 175 g (1.2 mol) of coumarin, and
Take 10ml of _BF3・_OEt2 and add 288g (3.1mol) of epichlorohydrin to 100ml of methylene chloride while stirring.
ml solution was added dropwise over 90 minutes. During this time, the temperature of the reaction solution was maintained at 20-25°C. After further reaction at 30-35℃ for 7 hours, _BF3・
10 ml of OEt ₂ was added and the reaction was further carried out at 30 to 35°C for 10 hours. Next, 25 ml of triethylamine was added to deactivate the catalyst. The reaction solution was washed twice with 250 ml of 8% NaOH aqueous solution, and the organic layer was washed twice with 300 ml of distilled water and then dehydrated with anhydrous magnesium sulfate. Next, after removing the solvent using a rotary evaporator, it was distilled under reduced pressure to obtain 2
-chloromethyl-7,8-benzo-1,4,6-
trioxaspiro[4,5]decene-9,10 243
g (yield 85%) was obtained. Reference Example 1 3 mol% of 2,2'-azobisisobutyronitrile was added as a polymerization initiator to compound [1], and the mixture was reacted in a sealed tube at 70°C for 16 hours. Production of coumarin was observed in the reaction product. The reactants were dissolved in methylene chloride and then poured into methanol with stirring to precipitate the polymer. The precipitate was purified twice using methylene chloride-methanol, resulting in a yield of 9%.
A white powdery polymer was obtained. The weight average molecular weight of the polymer based on polystyrene based on HLC analysis is 15,000.
It was hot. Infrared absorption spectrum (IR) analysis of the above radical polymer showed that the peak at 1640 cm ^-1 (CH=CH in the spiro-orthoester group) became smaller.
A peak at 1710 cm ^-1 (C=O) was generated. Compound [1] was subjected to radical polymerization, and part of its spiro-orthoester group was ring-opened to generate a ketone and an ester group, and a polymer containing a spiro-orthoester group was also formed. Reference Example 2 Compound [1] was heated and melted, 5 wt% of benzoin ethyl ether was added, and the mixture was sandwiched between Mylar films to a thickness of 8μ.
Ultraviolet radical polymerization was carried out by irradiating ultraviolet light for 8 minutes using a high-pressure mercury lamp at a height of 20 cm. HLC analysis of the irradiated material confirmed the formation of a polymer. Reference Example 3 When 3 mol% of BF ₃ .OEt ₂ was added as a polymerization initiator to a 1,1-dichloroethane solution of compound [1], a dark brown solid was immediately produced. The polymer obtained by this cationic polymerization was gelled and was not soluble in organic solvents such as methylene chloride and acetone. Further, the IR analysis revealed a peak at 1710 cm ^-1 (C=0).

[Brief explanation of drawings]

Figure 1 is an infrared absorption spectrum diagram of compound [1], Figure 2 is a nuclear magnetic resonance spectrum diagram of compound [1], and Figure 3 is a polymer obtained by radical polymerization of compound [1] in Reference Example 1. It is an infrared absorption spectrum diagram of.

Claims (1)

[Claims] 1 2-methylene-7,8-benzo-1,4,6
-trioxaspiro[4,5]decene-9,10.