JPH0148909B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel compound, and the compound provided by the present invention is a 2-vinyl-1,4,6-trioxaspiro[4,m]alkane (herein m) represented by the general formula [1]. is 4, 5 or 6
), and more specifically 2-vinyl-1,4,6-trioxaspiro[4,4]
nonane, 2-vinyl-1,4,6-trioxaspiro[4,5]decane and 2-vinyl-1,
These compounds of the present invention (hereinafter collectively referred to as compounds [1]), which are 4,6-trioxasspiro[4,6]undecane, are useful as, for example, polymerizable monomers. Compound [1] can be produced by an addition reaction between lactones selected from γ-butyrolactone and δ-valerolactone and butadiene monoxide. The reaction formula is shown below. (Here, an integer of 3, 4 or 5) When producing compound [1], the reaction is preferably carried out with an excess of lactone of 1 mol or more, more preferably 1.2 to 2 mol, per 1 mol of butadiene monoxide. are suitable, and these are mixed with acids such as BF ₃ .Et ₂ O, SnCl ₄ , TiCl ₄ , etc. in a solvent such as methylene chloride or tetrahydrofuran.
Compound [1] is synthesized by reaction using a Lewis acid such as FeCl ₃ as a catalyst. In general, there is no particular restriction on the reaction temperature, but it ranges from 0°C to 60°C.
Perform at ℃. An example of a desirable production method is to charge lactones and approximately equal weight of a solvent into a reactor, maintain the liquid temperature at a predetermined temperature, and add 0.1 to 0.1 to 0.1% of the required amount of a solution usually consisting of lactone and solvent. This is a method in which 3% by weight of a catalyst is added, and then butadiene monoxide is added dropwise either alone or as a solution with a solvent up to about the same weight. The degree of progress of the reaction can be easily determined by analyzing the reaction solution using, for example, a gas chromatograph (abbreviated as GC) or a liquid chromatograph (abbreviated as HLC). The required reaction time is generally around 3 hours, and 5 to 6 hours is sufficient. At the end of the reaction, an alkali is added to the reaction solution to neutralize the acid catalyst. Compound [1] is separated and obtained from the reaction solution as follows. For example, an alkaline aqueous solution, such as a dilute aqueous sodium hydroxide solution, is added to the reaction solution while cooling it with ice water, and after stirring and mixing, the mixture is separated into an aqueous layer and an organic layer. After repeating the above operation until the amount of unreacted lactone compound in the organic layer was reduced to almost zero, the organic layer was washed with a 10% NaCl aqueous solution, and then the organic layer was dehydrated over magnesium sulfate, followed by atmospheric distillation. Compound [1] is obtained by removing low-boiling substances and distilling the residue under reduced pressure. Regarding the cationic polymerization of spiro-orthoester compounds, Journal of Macromolecular Science
Chemistry, A9 (5), 849-865 (1975), but the following compounds are currently known for the cationic polymerization of spiro-orthoester compounds (Journal of Polymer Science
Polymer Letters Edition, vol.18, 25-27
(1980), Japanese Unexamined Patent Publication No. 56-45481, etc.). However, the following compounds have the property that the spiroolester ring opens even in radical polymerization. (m is an integer of 3 to 5) On the other hand, as a result of intensive research, the present inventors have found that not only cationic polymerization occurs, but also radical polymerization occurs without ring opening of the spiro-orthoester ring.
They have discovered a compound [1] that has properties different from those of the above compounds. Furthermore, compound [1]
It also has the feature of extremely small volumetric shrinkage during polymerization. Compound [1] has the industrial advantage that it can be easily synthesized by addition reaction between commercially available butadiene monoxide and lactones, and can be produced in a simple process. The polymerization reaction of compound [1] is understood as follows. Radical polymerization: Cationic polymerization: Compound [1] is radically polymerized using a radical polymerization initiator, and at this time, as shown in the above reaction formula [2], the terminal vinyl group is polymerized and the spiro-orthoester ring is retained. In addition, compound [1] undergoes cationic polymerization using a cationic polymerization initiator, and at this time, as shown in reaction formula [3] above, the ring opening of the spiro-orthoester ring and ester bond are generated, giving a viscous polymer. . As mentioned above, the compound [1] of the present invention not only undergoes cationic polymerization but also radical polymerization while retaining the spiro-orthoester ring, and has the advantage of having small volumetric shrinkage during polymerization. Compound [1] is a novel compound that has both a vinyl group, which is a radically polymerizable functional group, and a spiro-orthoester group, which is a cationically polymerizable functional group, in one molecule, and is therefore a post-crosslinking monomer. It is also useful as Conventional radically polymerizable monomers or cationically polymerizable monomers undergo extremely large volumetric contraction during polymerization, as shown in Table 1 below.

【table】

[Table] If the volumetric shrinkage during polymerization is large, for example, when used as a molding material, dimensional accuracy may be poor, when used as a casting material, there may be distortion due to shrinkage in the filled object, or the adhesive strength with the mold may be reduced. There are problems such as a drop gap occurring. In addition, when used as a paint, the internal strain causes a decrease in adhesion to the painted plate, causing warping, and when used as an adhesive, the internal strain causes a decrease in adhesive strength, causing problems in use such as warping and deformation. . On the other hand, compound [1] is used as a radical polymerization catalyst.
10.6%, and the volumetric shrinkage rate during cationic polymerization was approximately 2.7%, confirming that general radically polymerizable vinyl monomers are much smaller than cationically polymerizable monomers. Here, the volumetric shrinkage rate (%) is expressed as [1-(specific gravity of compound [1]/specific gravity of polymer)]×100. As mentioned above, the compound [1] of the present invention can be easily and inexpensively produced, can be polymerized by either radical polymerization or cationic polymerization, and has low volume shrinkage during polymerization. It has the characteristic of having a very low rate. Therefore, the compound [1] of the present invention is an extremely useful compound for use in molding materials, composite materials, adhesives, casting materials, 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-pwapanedione-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; methylanthraquinone, chloroanthraquinone, crothioxanthone, 2-methylthioxanthone or 2
- Anthraquinone or xanthone derivatives such as i-propylthioxanthone; sulfur compounds such as diphenyl sulfide, diphenyl disulfide or dithiocarbamate; 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 by decomposition. For example, di-tert-butyl peroxide, 2,5-
Organic peroxides such as dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl hydroperoxide, and tert-butyl peroxybenzoate; Compounds: Persalts such as ammonium persulfate and 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, for example, 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 _, aromatic diazonium salts such as φ-N ⁺ ≡N・PF ^- ₆ and φ _- N≡N+・BF ^- ₄ ; Group haloronium salts; Aromatic onium salts of element a of the periodic table, such as;

Aromatic onium salts of Group A elements of the periodic table such as [Formula];

Dicarbonyl complex compounds of elements of groups a-a of the periodic table, such as the formula: [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 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 1 74 g (0.65 mol) of ε-caprolactone and 150 ml of methylene chloride were placed in a four-neck flask equipped with a stirrer, condenser, thermometer, and dropping funnel, and the mixture was cooled to 5° C. with ice water. While stirring the pot liquid, 2 ml of BF ₃ ·Et ₂ O was added. 35 g (0.5 mol) of butadiene monoxide and 100 ml of methylene chloride
into the dropping funnel, and while stirring the pot liquid, add about
A solution of butadiene monoxide in methylene chloride was added dropwise over 1.5 hours. During the dropping, the solution in the pot was cooled with ice water. After stirring at room temperature for 5 hours, 5 ml of triethylamine was added to neutralize the catalyst. Next, in order to remove unreacted ε-caprolactone, the reaction solution was cooled with ice water, and while stirring, 10%
Gradually add 300ml of NaOH aqueous solution, and after the addition is complete,
After continuing stirring for a minute, the alkaline aqueous solution layer and the organic layer were separated. Add 10% of the above to the separated organic layer
After repeating the washing operation with NaOH aqueous solution two more times, the organic layer was washed with 300 ml of 10% NaCl aqueous solution.
The organic layer was dried with magnesium sulfate. Next, the organic layer was subjected to simple distillation at normal pressure to remove the solvent, and then distilled under reduced pressure to obtain 2-vinyl-1,4,6-trioxaspiro[4,6] at a boiling point of 72°C/1.5mmHg.
46.9 g (yield 51%) of undecane was obtained. Its physical property values are as follows. Γ Specific gravity: 1.060 (25℃) Γ Refractive index: n ²⁰ _D = 1.470 Γ Boiling point: 72℃/1.5mmHg Γ IR (infrared absorption spectrum): 1645cm ^-1 (-CH=CH ₂ ) ... (see Figure 1) ) 1125cm ^-1 , 1070cm ^-1 , (C-O-C), 955cm ^-1 Γ NMR (Nuclear Magnetic Resonance Spectrum) (in CDCl ₃ )
...(See Figure 2) δ (ppm) 4.95 to 5.9 (3H, CH ₂ = CH-) 4.2 to 4.7 (1H, -CH-O-) 3.3 to 4.2 (4H, -CH ₂ -O-, - _CH2 -O
―) 1.8 to 2.2 (2H, C―CH ₂ ) 1.3 to 1.8 (6H, ―(CH ₂ ―) ₃ Example 2 γ― in a four-necked 500 ml flask equipped with a stirrer, condenser, thermometer, and dropping funnel. Charge 60.2g (0.7mol) of butyrolactone and 100ml of methylene chloride, and add 35ml of butadiene monoxide to the dropping funnel.
(0.5 mol) and 70 ml of methylene chloride.
After cooling the pot liquid to 10℃ with ice water, add 0.7ml of BF ₃ · Et ₂ O.
Added. For about an hour while stirring the pot liquid,
Butadiene monoxide solution was added dropwise. During the dropping, the solution in the pot was cooled with ice water and kept at about 10°C.
After the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour, and then 1.5 ml of triethylamine was added to neutralize the catalyst. Next, the reaction solution was cooled with ice water, and while stirring, 100 ml of a 10% NaOH aqueous solution was gradually added. After the addition was completed, the mixture was stirred for 10 minutes, and then the alkali aqueous solution layer and the organic layer were separated. After repeating the above alkaline washing until there is no unreacted γ-butyrolactone in the organic layer, 10% NaCl
The organic layer was washed with 200 ml of aqueous solution. Next, the organic layer dehydrated with magnesium sulfate was subjected to simple distillation at normal pressure to remove the solvent, and then distilled under reduced pressure to obtain a boiling point of 70.
2-vinyl-1,4,6- at °C/2mmHg
Trioxaspiro[4,4]nonane 17.9g (yield
23%). Mass spectrum (GC-MS) analysis of the product revealed that the parent peak was (70ev) m/e=156. Moreover, its physical property values are as follows. Γ Boiling point: 70℃/2mmHg Γ Refractive index; n ²⁵ _D = 1.457 Γ IR; 1645cm ^-1 (CH ₂ = CH-), 1130cm ^-1 , 1050cm ^-1 , 952cm ^-1 (C-O-C) Γ NMR (in CDCl ₃ ) ... (see Figure 3) δ (ppm); 5.5 to 6.2 (1H, C=CH-) 5.0 to 5.5 (2H, CH ₂ = C-) 4.3 to 4.8 (1H, -CH- O-) 3.4-4.3 (4H, -CH ₂ -O-) 1.7-2.3 (4H, γC-CH ₂ -CH ₂ -) Reference Example 1 2-vinyl-1,4,6- obtained in Example 1 To trioxaspiro[4,6]undecane, 3 mol% of di-tert-shari-butyl peroxide was added as a polymerization catalyst, and the mixture was reacted in a sealed tube at 120°C for 40 hours. The polymer was purified by dissolving the reaction in methylene chloride and then pouring into n-hexane for precipitation. A white powdery polymer was obtained with a yield of about 40%. By HLC analysis, the weight average molecular weight of the polymer was
It was 6700. In addition, the IR spectrum of the polymer is as shown in Figure 3, and the peak at 1645 cm ^- ₁ almost disappears.
The peaks at 955 cm ^-1 , 1125 cm ^-1 and 1070 cm ^-1 (C—O—C) remain. According to the NMR spectrum, δ (ppm) = 4.95~5.9
The peak of (CH ₂ =CH-) had disappeared. The specific gravity of this polymer is 1.186 (25℃), and the volumetric shrinkage rate during polymerization calculated from this value is 10.6.
%. Reference example 2 Add 1wt% of benzoin ethyl ether to 2-vinyl-1,4,6-trioxaspiro[4,6]undecane, sandwich it between Mylar films, and make a 30W/cm ozone-less type diffused high-pressure mercury lamp. Using a high-pressure mercury lamp H-2000TQ manufactured by Matsushita Electric Industrial Co., Ltd., at a conveyor speed of 10 m/min at an irradiation distance of 20 cm,
It was irradiated with ultraviolet light 20 times. HCL analysis of the irradiated material revealed that it mainly consisted of polymers. Reference Example 3 BF ₃ was added to 2-vinyl-1,4,6-trioxaspiro[4,6]undecane as a polymerization catalyst.
3 mol % of Et ₂ O was added and polymerization was carried out at 80° C. for 4 hours.
As a result, a black and colored viscous polymer and a small amount of gelled product were produced. The weight average molecular weight of these polymers was approximately 7,600 according to HCL analysis. IR spectrum analysis of this polymer shows that 1735cm
A strong peak was observed at ^-1 (-CO-O-), 1645
The peak of cm ^-1 (-CH=CH ₂ ) remained. In addition, in NMR spectrum analysis, δ (ppm) = 4.95
A peak of ~5.9 (-CH=CH ₂ ) remains, and δ
(ppm)=4.0~4.2

The peak of [Formula] is the main component. As mentioned above, in the polymer obtained by cationic polymerization, the spiro-orthoester group is ring-closed, and the ester group,
Methylene groups are generated. The specific gravity of this polymer is
1.089 (25°C), and the volumetric shrinkage during polymerization calculated from this value is only 2.7%. Reference Example 4 After completely dissolving 1 g of the polymer obtained in Reference Example 1 in 20 ml of 1,1-dichloroethane, BF ₃ .
25 mg of Et ₂ O was added and the mixture was reacted at 70°C for 8 hours. The product was a gel insoluble in 1,1-dichloroethane. IR spectrum analysis of gelled product purified by removing low boiling point substances by vacuum drying revealed that 1735
A strong peak is generated at cm ^-1 (-COO-). The specific gravity of this gelled product was 1.165 (25°C), and it had expanded by 1.8% due to polymerization.

[Brief explanation of drawings]

Figure 1 is an infrared absorption spectrum diagram of 2-vinyl-1,4,6-trilioxaspiro[4,6]undecane, Figure 2 is a nuclear magnetic resonance spectrum diagram of the same compound, and Figure 3 is a diagram of 2-vinyl-1,4,6-trilioxaspiro[4,6]undecane. FIG. 1 is a nuclear magnetic resonance spectrum diagram of -1,4,6-trioxaspiro[4,4]nonane.

Claims (1)

[Claims] 1. A spiroorthoester compound represented by the following general formula. In the above formula, l is an integer of 3, 4 or 5.