JPH0420918B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound useful as a polymerizable monomer, for example, and the compound provided by the present invention has an acryloylamino group or a methacryloylamino group [hereinafter referred to as (meth)acryloylamino group] It is a bicycloorthoester compound represented by the following formula [1] containing:

(Here, R ¹ represents a hydrogen atom, a lower alkyl group, or a phenyl group, and R ² represents a hydrogen atom or a methyl group.) The compound represented by formula [1] of the present invention (hereinafter referred to as compound [1]) is , is produced from an amino group-containing bicycloorthoester represented by the following formula [2] and acrylic acid chloride or methacrylic acid chloride (hereinafter referred to as (meth)acrylic acid chloride).

(In the formula, R ¹ represents a hydrogen atom, a lower alkyl group, or a phenyl group.) A compound represented by formula [2] (hereinafter referred to as compound [2])
) is produced, for example, by the reduction reaction of a nitro group-containing bicycloorthoester represented by the following formula [3].

(In the formula, R ¹ represents a hydrogen atom, a lower alkyl group, or a phenyl group.) A compound represented by formula [3] (hereinafter referred to as compound [3])
) is produced, for example, by the dealkholization reaction of trialkyl orthoacylate represented by the following formula [4] (hereinafter referred to as compound [4]) and tris(hydroxymethyl)nitromethane.

R ¹ -C(-O-R') ₃ [4] (In the formula, R' represents an alkyl group, R ¹ is a hydrogen atom,
Represents a lower alkyl group or phenyl group. ) This reaction is shown below.

Regarding the method for producing the compound [4] in which R ¹ is a hydrogen atom in the above formula [4], see Ohme, Reland;
Schmitz, Ernst.Justus Liebigs Annalen der
Chemie, 716 , 207 (1968), etc.

Regarding the method for producing the compound [4] in which R ¹ is a lower alkyl group such as a methyl group, ethyl group, propyl group, or butyl group in the above formula [4], see SMMcElvain and J. Walter Nelson,
Journal of American Chemical Society, 64 ,
1825-1827 (1942), etc.

Regarding the method for producing a compound in which R ¹ is a phenyl group in formula [4], see SMMcElvain,
JTVenerable，Journal of American
It is described in Chemical Society, 72 , 1661 (1950), etc.

R' in formula [4] is preferably a lower alkyl group having about 1 to 4 carbon atoms. This is because the larger the alkyl group, the higher the boiling point of the compound, making isolation and purification by distillation more difficult.

Compound [3] is tris(hydroxymethyl)
Nitromethane and compound [4] are mixed in a suitable solvent,
For example, it is produced by dealcoholization in a solvent such as di-n-octyl phthalate or di-n-butyl phthalate in the presence of a catalyst such as p-toluenesulfonic acid. The degree of progress of the reaction can be determined not only by measuring the amount of alcohol distilled out, but also by analyzing the reaction solution using, for example, liquid chromatography.

The charging ratio of compound [4] and tris(hydroxymethyl)nitromethane may be equimolar or a slight excess of one of the two, and the reaction is generally carried out under heating in an inert gas atmosphere such as nitrogen gas.
It is appropriate to carry out the test at about 160°C. Compound [3] can be separated from the reaction product liquid by vacuum distillation or recrystallization depending on its physical properties.

Compound [2] is produced by reduction reaction of compound [3].

This reaction is shown below.

Compound [2] is produced by reacting compound [3] with hydrogen in a suitable solvent such as dioxane or diethyl ether in the presence of a catalyst such as platinum oxide. The degree of progress of the reaction can be determined by analyzing the reaction solution using, for example, a liquid chromatograph.

There is no particular restriction on the reaction temperature, but it is generally 0℃~
It is carried out at 100℃.

Compound [2] can be separated and obtained from the reaction solution by, for example, filtering the precipitate, distilling off the solvent, and then distilling the residue under reduced pressure or recrystallizing it depending on the physical properties of the target product. obtain.

The reaction for producing the compound [1] of the present invention by reacting the compound [2] with (meth)acrylic acid chloride is a dehydrochlorination reaction, and the reaction formula is as follows.

R ² in the compound [1] of the present invention represents a hydrogen atom or a methyl group, and R ¹ represents a hydrogen atom, a lower alkyl group, or a phenyl group, and the lower alkyl group in R ¹ is, for example, methyl, ethyl,
Examples include propyl or butyl groups.

The above reaction for producing compound [1] from compound [2] and (meth)acrylic acid chloride is carried out in a suitable organic solvent such as dioxane or methylene chloride in an amount equal to or more than equimolar amount to (meth)acrylic acid chloride. This can be carried out by adding (meth)acrylic acid chloride dropwise to compound [2] at a temperature of about 0°C to 100°C in the presence of a tertiary amine such as triethylamine or pyridine.

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.

Compound [1] can be separated and obtained from the reaction solution by, for example, washing the generated tertiary amine salt of hydrogen chloride with water,
After separating the aqueous layer and the organic layer, dehydrating the organic layer with magnesium sulfate, etc., distilling off the solvent in the presence or absence of a polymerization inhibitor, followed by distillation under reduced pressure or recrystallization. It can be done by

Compound [1] of the present invention has a (meth)acryloylamino group and a bicycloorthoester group in the molecule. The (meth)acryloyl group has radical polymerizability, and the bicycloorthoester group has cationic polymerizability. Therefore, after radical homopolymerization of the compound of the present invention [1], radical copolymerization of two or more types of the compound of the present invention [1], or radical copolymerization of the compound of the present invention and other monomers, cationic polymerization is performed. By polymerizing bicycloorthoester groups in the presence of a catalyst, etc.
It is also possible to obtain a cured product. Further, it is also possible to simultaneously polymerize both functional groups in the coexistence of a radical polymerization catalyst and a cationic polymerization catalyst.

As mentioned above, the compound of the present invention has a bicycloorthoester group, so it has a feature of small volumetric shrinkage during polymerization or curing, and therefore has no drawbacks associated with volumetric shrinkage during polymerization or curing. It has been improved and is extremely useful as a paint with good adhesion that does not cause voids, an adhesive that does not cause internal distortion, and as a component of composite materials and cast materials that require dimensional accuracy.

Alternatively, for example, a polymer having a bicycloorthoester group obtained by radical polymerization of the compound of the present invention may be dissolved in an appropriate solvent and applied to the substrate surface, and the formed coating film may be cured by an appropriate crosslinking means. It is also possible to obtain an excellent coating film.

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'-bisdi(ethylamino)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.

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.

Generally, when using a catalyst, the amount used is:
It generally ranges from 0.01 to 10 wt%, preferably from 0.1 to 5 wt%, based on the total amount of monomers.

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 catalyst is used during polymerization, examples of preferably used solvents include toluene, xylene, ethyl acetate, N,N-dimethylformamide, chloroform, and dioxane.

Generally, the amount of the catalyst used is preferably in the range of 0.001 to 10 wt% based on the monomer to be polymerized.

The cationic polymerization of the compound [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 Va elements of the periodic table, such as; Aromatic onium salts of Group VIa elements of the periodic table, such as; Dicarbonyl complex compounds of Group a-Va elements of the periodic table, such as, 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.

In this case, the amount of catalyst used is generally 0.001 to 10 wt%, preferably 0.1% to the monomer to be polymerized.
A range of ~5wt% 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 and 1,1-dichloroethane.

Next, the present invention will be further explained with reference to Examples and Reference Examples.

Reference Example 1 Production of 4-nitro-1-methyl-2,6,7-trioxabicyclo[2,2,2]octane Tris(hydroxy) methyl) nitromethane 90.6 g (0.6 mol), triethyl orthoacetate 107.0 g (0.66 mol), di-n
-400 g of octyl phthalate and p- as catalyst
0.3 g of toluenesulfonic acid was charged, and the temperature was gradually raised to 140° C. while stirring and passing nitrogen gas.
The reaction was continued at this temperature for 4 hours, and about 71 g of a distillate containing ethanol as a main component was obtained. 0.6 ml of triethylamine was added to this reaction solution to neutralize the catalyst.
Next, to prevent the precipitation of crystals, vacuum distillation is carried out while heating the distillation tube with a ribbon heater to form a pale yellow solid.
62.7g was obtained. Regarding this solid, acetone-n-
41.7g of white crystalline 4-nitro-1-methyl-2,6,7-trioxabicyclo[2,2,2]octane was purified by recrystallization using hexane system.
(yield 40%). The distillation temperature is 127℃/1mm
It was Hg.

Its physical property values are as follows.

Γ Boiling point: 127℃/1mmHg Γ Melting point: 128℃ Γ Specific gravity: 1.427/25℃ ΓIR: 1560cm ^-1 (-NO ₂ ) 1123cm ^-1 , 1027cm ^-1 (C-O-C) ΓNMR (in CDCl ₃ ) δ (ppm); 4.38 (6H, s, CH ₂ -O) 1.50 (3H, s, -CH ₃ ) The above specific gravity was measured using an air comparison hydrometer, type 930 [manufactured by Beckman Japan Co., Ltd.]. ] (The same applies to the following examples).

Reference Example 2 Production of 4-amino-1-methyl-2,6,7-trioxabicyclo[2,2,2]octane 4-nitro-1-methyl- obtained in Reference Example 1 was placed in a 500 ml stainless steel autoclave. 2,6,
Add 20.0 g (0.114 mol) of 7-trioxabicyclo[2,2,2]octane, 300 ml of dioxane, and 0.5 g of platinum oxide as a catalyst, and blow hydrogen into the mixture with stirring at a hydrogen pressure of 2.5 Kg/cm ² at about 30°C. The reaction was allowed to proceed for 24 hours.

After filtering the reaction solution and removing the solvent, recrystallization purification is performed using an acetone-n-hexane system,
White crystalline 4-amino-1-methyl-2,
13.8 g (yield: 83%) of 6,7-trioxabicyclo[2,2,2]octane was obtained.

The physical properties of this compound are as follows.

Γ Boiling point: 120℃ Γ Specific gravity: 1.392/25℃ ΓIR: 3370cm ^-1 , 3310cm ^-1 , 1620cm ^-1 (-NH ₂ ) 1123cm ^-1 , 1050cm ^-1 (C-O-C) ΓNMR (in CDCl ₃ ) ; δ (ppm); 3.74 (6H, s, C-CH ₂ -O) 1.5 (2H, -NH ₂ ) 1.28 (3H, s, -CH ₃ ) Example 1 Stirrer, condenser, dropping funnel, thermometer 10.1 g (0.1 mol) of triethylamine and 2.9 g (0.02 mol) of 4-amino-1-methyl-2,6,7-trioxabicyclo[2,2,2]octane obtained in Reference Example 2 were placed in a 4-necked 300 ml flask. mole)
Add 100ml of methylene chloride and add 10ml of ice water.
After cooling to ℃, add 2.61 g (0.025 mol) of methacrylic acid chloride to 10 ml of methylene chloride while stirring.
The solution was added dropwise over 1 hour. After further reacting at 40°C for 6 hours, the mixture was allowed to stand overnight. This reaction solution was washed three times with 50 ml of water and then dehydrated with magnesium sulfate. Next, the solvent was removed to obtain a solid product. This product was recrystallized in an acetone-n-hexane system to form a white solid of 4-methacryloylamino-1-methyl-2,
1.63 g (yield 38%) of 6,7-trioxabicyclo[2,2,2]octane was obtained.

Its physical property values are as follows.

Γ melting point: 104℃ ΓIR... (see Figure 1) 3350cm ^-1 (-NH-) 1660cm ^-1 , 1530cm ^-1 (-CONH-) 1133cm ^-1 , 1063cm ^-1 (C-O-C) ΓNMR (CDCl) ₃ )...(See Figure 2) δ (ppm); 5.3 to 5.8 (3H, CH ₂ = C, -NH
-) 4.22 (6H, s, CH ₂ -O) 1.91 (3H, s, =C-CH ₃ ) 1.46 (3H, s, C-CH ₃ ) Reference example 3 1-ethyl-4-nitro-2,6 , 7-trioxabicyclo[2,2,2]octane In an apparatus similar to Reference Example 1, 90.6 g (0.6 mol) of tris(hydroxymethyl)nitromethane, 116.2 g (0.66 mol) of triethyl orthopropionate, and 240 g of -n-octyl phthalate and 0.6 g of p-toluenesulfonic acid were charged, and the temperature was gradually raised to 140° C. while stirring and passing nitrogen gas. The reaction was continued at this temperature for 4 hours to obtain about 65 g of a distillate whose main component was ethanol.

After this reaction, 1.2 ml of triethylamine was added to neutralize the catalyst. Next, vacuum distillation was carried out while heating the distillation tube with a ribbon heater to prevent precipitation of crystals, yielding about 107 g of a pale yellow solid. This solid is n-
Recrystallization purification with hexane was performed to obtain 41.0 g (yield 36%) of white crystalline 1-ethyl-4-nitro-2,6,7-trioxabicyclo[2,2,2]octane.

Note that the distillation temperature was 110°C/1.5mmHg.

The physical properties of this compound are as follows.

Γ Melting point: 78℃ Γ Specific gravity: 1.440/25℃ ΓIR: 1558cm ^-1 (-NO ₂ ) 1120cm ^-1 , 1027cm ^-1 (C-O-C) ΓNMR (in CDCl ₃ ); δ (ppm); 4.29 ( 6H, s, C-CH ₂ -O) 1.72 (2H, q, C-CH ₂ ) 0.93 (3H, t, -CH ₃ ) Reference example 4 4-amino-1-ethyl-2,6,7-trio Production of xabicyclo[2,2,2]octane 1-ethyl-4-nitro-2,6,7-trioxabicyclo[2,2,2] obtained in Reference Example 3 was placed in the same apparatus as Reference Example 2. octane 5g (26 mmol),
100 ml of dioxane and 0.3 g of platinum oxide as a catalyst were added and reacted in the same manner as in Reference Example 2.

After filtering the reaction solution and removing the solvent, the solution was purified by recrystallization using an acetone-n-hexane system to obtain white crystalline 4-amino-1-ethyl-2,6,7-
trioxabicyclo[2,2,2]octane 2.8
g (68% yield) was obtained.

The physical properties of this compound are as follows.

Γ Melting point; 62°C ΓIR; 3370 cm ^-1 , 3300 cm ^-1 , 1610 cm ^-1 (-NH ₂ ) 1143 cm ^-1 , 1111 cm ^-1 , 1067 cm ^-1 (C-O-C) Γ NMR (in CDCl ₃ ); δ ( ppm); 3.72 (6H, C-CH ₂ -O) 2.0 (2H, -NH ₂ ) 1.56 (2H, q, C-CH ₂ ) 0.96 (3H, t, -CH ₃ ) Example 2 Example 1 and Triethylamine 10.1 in similar equipment
g (0.1 mol), 4-amino- obtained in Reference Example 4
Charge 3.18 g (0.02 mol) of 1-ethyl-2,6,7-trioxabicyclo[2,2,2]octane and 100 ml of methylene chloride, cool to 10°C with ice water, and add 2.26 g of acrylic acid chloride while stirring.
(0.025 mol) in methylene chloride (10 ml) was added dropwise over 1 hour. After further reacting at 40°C for 6 hours, the mixture was allowed to stand overnight. This reaction solution was washed twice with 30 ml of water and then dehydrated with magnesium sulfate. Next, the solvent was removed to obtain a solid product. This product was purified by recrystallization in an acetone-n-hexane system, and a white solid of 4-acryloylamino-1-
Ethyl-2,6,7-trioxabicyclo[2,
0.99 g (yield 23%) of 2,2]octane was obtained.

Its physical property values are as follows.

Γ melting point: 116℃ ΓIR... (see Figure 3) 3380cm ^-1 (-NH-) 1658cm ^-1 , 1552cm ^-1 (-CO-NH-) 1137cm ^-1 , 1067cm ^-1 (C-O-C) ΓNMR (in CDCl ₃ )... (see Figure 4) δ (ppm); 5.6 to 3.6 (4H, CH ₂ = CH-, -NH
−) 4.23 (6H, s, CH ₂ −O) 1.71 (2H, q, −CH ₂ −C) 0.95 (3H, t, C−CH ₃ ) Example 3 Triethylamine 10.1 was added to the same apparatus as in Example 1.
g (0.1 mol), 4-amino-1-ethyl-2,
3.18 g (0.02 mol) of 6,7-trioxabicyclo[2,2,2]octane and 100 g of methylene chloride
ml of methylene chloride was added dropwise over 1 hour while stirring and cooling to 10°C with ice water. After further reacting at 40°C for 6 hours, the mixture was allowed to stand overnight. After this reaction was washed three times with 50 ml of water,
Dehydrated with _MgSO4 . A solid product was obtained after subsequent solvent removal.

The product was purified by recrystallization in an acetone-n-hexane system, resulting in a white solid of 1-ethyl-4-
methacryloylamino-2,6,7-trioxysabicyclo[2,2,2]octane 2.02g (yield
45%).

The physical properties of this compound are as follows.

Γ Melting point: 116℃ ΓIR... (See Figure 5) 3290cm ^-1 (-NH-) 1664cm ^-1 , 1631cm ^-1 , 1561cm ^-1 (-CONH-) 1114cm ^-1 , 1077cm ^-1 (C-O-C ) ΓNMR (in CDCl ₃ )... (see Figure 6) δ (ppm); 5.3-5.7 (3H, CH ₂ = C, -NH-) 4.23 (6H, s, CH ₂ -O) 1.91 (3H, s , C-CH ₃ ) 1.73 (2H, q, C-CH ₂ ) 0.94 (3H, t, C-CH ₃ )

[Brief explanation of drawings]

Figure 1 is an IR diagram of 4-methacryloylamino-1-methyl-2,6,7-trioxabicyclo[2,2,2]octane obtained in Example 1, and Figure 2 is an NMR diagram of the same compound. FIG. 3 shows 4-acryloylamino-1-ethyl-2,6,7-trioxabicyclo(2,2,
2] An IR diagram of octane, Figure 4 is an NMR diagram of the same compound, and Figure 5 is an IR diagram of 1-octane obtained in Example 3.
Ethyl-4-methacryloylamino-2,6,7
-trioxabicyclo[2,2,2]octane
This is an IR diagram, and FIG. 6 is an NMR diagram of the same compound.

Claims (1)

[Claims] 1. A picycloorthoester compound represented by the following general formula [1]. (Here, R ¹ represents a hydrogen atom, a lower alkyl group, or a phenyl group, and R ² represents a hydrogen atom or a methyl group.)