JPH0148274B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a novel compound, 2-methylene-
It provides 8,9-benzo-1,4,6-trioxaspiro[4,4]nonane (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 the desorption of 2-halogenated methyl-8,9-benzo-1,4,6-trioxaspiro[4,4]nonane (hereinafter referred to as compound [2]) represented by the following formula [2]. Produced by hydrogen halide reaction. (Here, X represents a halogen atom such as Cl, Br, I, etc.) This reaction is shown below. Compound [2] is already known [K.
Bodenbenner, Ann. 623, 183 (1959)] and a suitable solvent such as N,N-dimethylformamide,
The novel compound [1] is synthesized by dehydrohalogenation by reaction with a stoichiometric amount or an excess amount, preferably 1.1 to 5 times the molar amount, of an alkali such as sodium alcoholate in a solvent such as pyridine. Ru. 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 shown by Endo, T.
andBailey, 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. However, it has the disadvantage that it is not easy to manufacture and 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 phthalide as raw materials. have The polymerization of compound [1] is thought to proceed by the following mechanism, and according to this, radical polymers are polymers represented by formulas (A), (B), and (C), respectively. The cationic polymer is a mixture of polymers represented by formulas (D) and (E), respectively.
Furthermore, when forming the polymers represented by formulas (C) and (E), phthalide formation is observed in both cases. If removal of phthalide from the polymer is desired, the polymer is dissolved in a good solvent for the polymer, such as chloroform, and the solution is then poured into a solvent, such as n-hexane, that is a poor solvent for each polymer and in which the phthalide is soluble. Removal can be easily carried out by precipitating each polymer. Radical polymerization mechanism; Cationic polymerization mechanism; As mentioned above, the compound [1] of the present invention can be produced easily and inexpensively, and can be polymerized by either radical polymerization or cationic polymerization, and each polymerization can produce a polymer. It has the advantage of easily introducing an ester group and a benzene ring into the main chain, as well as a ketone group in radical polymerization. Therefore, the compound [1] of the present invention is an extremely useful compound as a raw material for molding materials, adhesives, paints, and the like. Radical polymerization of compound [1] can be carried out by conventional radical polymerization means, such as ultraviolet 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 disulfide or dithiocarbamate, etc. Sulfur compounds; α-chloromethylnaphthalene, anthracene, etc. In the polymerization using infrared rays, heat, or microwaves, any radical initiator can be used as long as it can generate radicals by 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. Cationic polymerization of the compound of formula [1] of the present invention is carried out by a generally well-known method, eg, by ultraviolet rays, infrared rays, heat or microwaves, 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;

【formula】 Aromatic onium salts of Group A elements of the periodic table, such as;

A dicarbonyl complex compound of an element of group a-a of the periodic table, such as [Formula] may be used. 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, etc., and O, S , N, etc.; oxonium salts, diazonium salts, and carbonium salts of Lewis acids; halogen compounds, mixed halogen compounds, and perhalogen acid derivatives. 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. The present invention will be explained in more detail by showing Examples and Reference Examples below. Example 54 g (1 mol) of sodium methylate and 300 ml of DMF were placed in a four-necked flask equipped with a stirrer, condenser, thermometer, and dropping funnel, and while cooling to 15°C with ice water and stirring, 2-chloromethyl was added. 113.3 g (0.5 mol) of -8,9-benzo-1,4,6-trioxaspiro[4,4]nonane was added dropwise over about 1 hour. Thereafter, the mixture was stirred at room temperature for about 3 hours, and then reacted at 40° C. for 6 hours. Subsequently, the reaction solution was poured into water from Step 1, and the aqueous layer and organic layer were separated. Then add 200 methylene chloride to the aqueous layer.
ml was added and extracted three times, each methylene chloride layer was combined with the organic layer, washed twice with 300 ml of water, and then the organic layer was dehydrated with magnesium sulfate. Next, after removing the solvent using a rotary evaporator, the 2-methylene-8,9-benzo-1,4,6
-Trioxaspiro[4,4]nonane 72.3g (yield 76%) was obtained. Its physical property values are as follows. Γ Specific gravity: 1.207 (25℃) Γ Boiling point: 87℃/0.2mmHg Γ Infrared absorption spectrum (hereinafter abbreviated as IR);
(See Figure 1) 1690cm ^-1 (C=C), 1120cm ^-1 , 1070cm ^-1 (C-O-C) Γ Nuclear Magnetic Resonance Spectrum (hereinafter abbreviated as NMR) (in CDCl ₃ ) (Figure 2) Reference) δ (ppm); 6.9 to 7.3 (4H, φ-H), 4.95 (2H, φ-CH ₂ -O), 4.65 (2H, CH ₂ =C), 4.40, 3.93 (2H, C-O- CH ₂ ) 2-chloromethyl-8,9 used above
-benzo-1,4,6-trioxaspiro [4,
4] Nonane was produced by the following method.
That is, in one flask similar to the above, 300 ml of methylene chloride, 134 g (1 mol) of phthalide, and
Take 10ml of BF ₃ OEt ₂ and cool it to 20℃ in a water bath.
While stirring, add 138.8 g (1.5 g) of epichlorohydrin.
A solution prepared by dissolving mol) in 100 ml of methylene chloride was added dropwise over about 1 hour. The reaction mixture was further reacted at 20 to 23°C for 7 hours and left at room temperature overnight. Next, 20 ml of triethylamine was added to deactivate the catalyst. The reaction solution was washed once with 300 ml of 6% NaOH aqueous solution, and the organic layer was washed twice with 300 ml of distilled water, followed by MgSO ₄
I dehydrated it. Next, the solvent was removed using a rotary evaporator and then distilled under reduced pressure. At a boiling point of 112-115℃/0.14mmHg,
2-chloromethyl-8,9-benzo-1,4,6
-Trioxaspiro[4,4]nonane 175g (yield 78%) was obtained. Reference Example 1 3 mol% of 2,2'-azobisisobutyronitrile was added as a polymerization catalyst to compound [1], and the mixture was reacted in a sealed tube at 70°C for 18 hours. Formation of phthalide was observed in the reaction product. The reaction product was dissolved in chloroform and then poured into n-hexane with stirring to precipitate the polymer. The precipitate was dissolved in chloroform again and n-
The polymer was precipitated by pouring into hexane. Precipitation purification was performed once again using chloroform-n-hexane to obtain a white powdery polymer with a yield of about 18%. HLC analysis revealed that the weight average molecular weight of the polymer was 7,500 in terms of polystyrene. In addition, IR analysis of the polymer revealed that 1690 cm ^-1 (C=
The peak of C) almost disappeared, 1120 cm ^-1 and 1070 cm ^-1
(C-O-C) peak remains, 1710 cm ^-1 (C=
A peak of O) was generated (see Figure 3). Compound [1] undergoes partial ring opening of its spiro-orthoester group by the above radical polymerization,
A ketone group and an ester group were formed in the polymer, and the polymer contained these groups and a spiro-orthoester group. Reference example 2 Adding benzoin ethyl ether to compound [1]
Add 5wt% and sandwich it between mylar films,
At a thickness of about 8 μm, ultraviolet rays were irradiated for 8 minutes at a height of 20 cm using a 60 W/cm high-pressure mercury lamp manufactured by Ushio Inc. to cause ultraviolet radical polymerization. HLC analysis of the irradiated material confirmed the formation of a polymer. Reference example 3 Adding 2 BF ₃ OEt ₂ to compound [1] as a polymerization catalyst
% by mole was added and polymerized at 70°C for 2 hours. As a result, a black and viscous polymer was produced. This polymer was separated under the following separation conditions,
The polymer component was separated as a polymer. Separation conditions: Equipment: HLC-807 manufactured by Toyo Soda Kogyo Co., Ltd. Column: TSK Gel G-3000HG + G-2000HG Eluent: Chloroform Flow rate: 4 ml/min HLC analysis showed that the weight average molecular weight of the polymer was approximately 4900 in terms of polystyrene. . IR analysis of the separated polymer showed that 1720 cm ^-1 (C
=O) and 1610-1620 cm ^-1 (C=C) peaks were generated, and the 970 cm ^-1 peak disappeared. The spiro-orthoester group of compound [1] was ring-opened by the above cationic polymerization, and an ester group was produced in the polymer.

[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 polymerizing compound [1] in Reference Example 1. It is an infrared absorption spectrum diagram of an object.

Claims (1)

[Claims] 1 2-methylene-8,9-benzo-1,4,6
-trioxaspiro[4,4]nonane.