JPS6261034B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to aryl pyrophosphate derivatives, and more particularly to polymerizable monomers that have utility as restorative materials for dental treatment. Various cements have been the mainstream filling material for partially missing teeth, but heat- or photo-curable resin compositions are also attracting attention; for example, as described in U.S. Pat. , The compound represented by (glycidyl methacrylate derivative of bisphenol A: hereinafter referred to as bisGMA) has been proposed. This monomer is added with a suitable reactive diluent such as methyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, etc. to lower the viscosity, and
It is a mixture of tertiary amine and peroxide, which is filled into a defective tooth and then cured to perform restoration, and can give excellent evaluations in terms of physical properties such as strength. However, BisGMA
Unless a diluent like the one mentioned above is added, it has the disadvantage of being extremely viscous and difficult to handle, and has low moisture resistance, which causes it to absorb a large amount of water and reduce its strength after curing. A further fundamental problem is that the time from the start of gelation to the completion of hardening (gel time) is long, and patients are inconvenienced in having to keep their mouths open for long periods of time until hardening is complete. The above-mentioned reactive diluents are all low-molecular-weight compounds that have high permeability into the dental pulp tissue and are highly irritating to the patient. It is desired that The present invention was made in view of these circumstances, and aims to create a new polymerizable monomer that does not have the above-mentioned drawbacks. That is, the new polymerizable monomer provided in the present invention has the general formula (In the formula, A is aryl which may be substituted with one or more groups selected from lower alkyl, lower alkoxy or halogen; R ¹ means allyl, acryloyloxy (lower) alkyl or methacryloyloxy (lower) alkyl, respectively) death,
The (lower) alkyl in R ¹ may be substituted with a halogen). The compound represented by the above general formula () is produced according to the following reaction formula. However, the symbols A and R ¹ have the same meanings as before. Regarding the reaction mechanism in which compound () is produced from compound (), a part of compound () is hydrolyzed to produce compound (), which is then converted into unreacted compound () in the presence of an amine, which is a dehydrochlorination agent. ) to produce the compound (). The groups represented by the symbols A and R ¹ in each of the above general formulas are explained below. A is aryl such as phenyl, α-naphthyl, β-naphthyl or anthranyl, which may be substituted with one or more groups selected from lower alkyl, lower alkoxy or halogen. Lower alkyl mentioned here includes methyl, ethyl, propyl, isopropyl, butyl,
1 carbon number such as tertiary butyl, pentyl, hexyl, etc.
-6 alkyl is exemplified, and examples of lower alkoxy include alkyloxy having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tertiary butoxy, pentyloxy, and hexyloxy. Examples of halogen include fluorine, chlorine, bromine and iodine. Next, the group represented by R ¹ is allyl, acryloyloxy (lower) alkyl, or methacryloyloxy (lower) alkyl, and the vinyl group contained therein is responsible for imparting polymerizability to the compound (). . Examples of the above (lower) alkyl in R ¹ include the lower alkyls exemplified in A above, and such lower alkyls further include halogens such as fluorine, chlorine, bromine, and iodine. May be replaced with . Next, the manufacturing process for manufacturing compound () will be explained. Compound () → Compound () Under anhydrous conditions, compound () is reacted with phosphorus oxychloride. Although phosphorus oxychloride also serves as a reaction solvent, an appropriate organic solvent may be used in combination in some cases. Although the reaction temperature is not particularly limited, it is usually preferable to carry out the reaction with or under heating. Compound ()→Compound () An alcoholic compound represented by R ¹ OH is allowed to act on Compound () under anhydrous conditions. The reaction is usually carried out in a solvent, and preferred solvents are those that do not adversely affect the progress of the reaction, such as methylene chloride and chloroform. Although there are no particular restrictions on the reaction temperature, it is preferable to carry out the reaction under mild conditions, such as cooling or heating. Compound ()→Compound () The process proceeds via Compound (), and hydrolysis and dehydrochloric acid condensation are performed over time. For hydrolysis, simply adding water is sufficient, and it is desirable that the reaction temperature be moderate. Organic bases or inorganic bases are used to perform dehydrochloric acid condensation, but these are added at the same time as hydrolysis progresses, and the hydrolyzed products are used to dehydrolyze the unhydrolyzed products one after another. Thus, the compound () is given. Although the type of base used in combination is not limited, organic bases are preferably tertiary amines such as trialkylamine and pyridine, and inorganic bases are preferably weak bases such as carbonates. The target substance () thus obtained is a polymerizable monomer, and is polymerized by the vinyl group in ^R1 . Polymerization is progressed by light, heat, ultraviolet rays, etc., and a polymerization initiator or a polymerization accelerator is added as necessary. When used as a filling material for missing teeth etc., it may be used alone or in combination with a general-purpose filling material. When obtaining a polymer from the above-mentioned monomers, the duration of the gel state is short, so the time until it hardens after filling is short and there is less burden on the patient, and the viscosity during kneading is too high. Therefore, there is no need to mix low-molecular-weight reactive diluents, and there is less irritation to the dental pulp. After curing, physical properties such as compressive strength, hardness, and abrasion resistance show extremely favorable values, making it particularly useful as a dental filling material. It can be applied to various fields. Next, examples of the present invention will be shown. Example 1 A mixture of phenol (94g), phosphorus oxychloride (160g) and calcium chloride (25g) was heated at 150°C for 5 hours. After the reaction was completed, excess phosphorus oxychloride was distilled off under reduced pressure to obtain the following phosphoryl dichloride (204 g). Dissolve this product in methylene chloride (300ml) and
Then, 2-hydroxyethyl methacrylate (120 g) and pyridine (120 g) were added dropwise to a methylene chloride (200 ml) solution and stirred for 2 hours to obtain the following phosphoryl chloride. Next, add cold water and stir for another 2 hours.
After the hydrolysis was completed, the product was washed with 5% hydrochloric acid, a 5% aqueous potassium hydroxide solution, and water in this order, and dried with sodium sulfate. When the solvent was distilled off under reduced pressure, pyrophosphate (219 g) was obtained as a colorless and transparent oil. IR: ν _nax , cm ^-1 2900, 1720, 1630, 1600, 1365, 1160, 980 NMR (CDCl ₃ ): δ 7.35 (s.5H×2, aroma.protons) 6.10 (bs.1H×2, vinyl proton ) 5.55 (m.1H x 2, vinyl Proton) 4.25 (m.4H x 2, -CH ₂ CH ₂ -) 1.90 (d.3H x 2, vinyl CH ₃ ) Example 2 O-chlorophenol (12.8g) , phosphorus oxychloride (16 g) and calcium chloride (2.5 g) were reacted in the same manner as in Example 1 to obtain the following phosphoryl dichloride (24 g). This product was reacted with 2-hydroxypropyl methacrylate (14 g) and pyridine and treated in the same manner as in Example 1 to obtain the following pyrophosphate (25.7 g). IR: ν _nax , cm ^-1 2950, 1720, 1630, 1600, 1370, 1160, 980 NMR (CDCl ₃ ): δ 7.20 (m.4H×2, aroma.protons) 6.10 (bs.1H×2, vinyl proton ) 5.55 (m.1H×2, vinyl proton) 4.85 (m.1H×2,

【formula】) 4.15 (m.2H×2,

[Formula]) 1.90 (d.3H×2, vinyl CH ₃ ) 1.30 (m.3H×2,

[Formula]) Example 3 4-tertiary butylphenol (15 g), phosphorus oxychloride (16 g) and calcium chloride (2.5 g) were reacted in the same manner as in Example 1 to obtain the following phosphoryl dichloride (26 g). Ta. When this product was reacted with allyl alcohol (5.8 g) and pyridine (12 g) and treated in the same manner as in Example 1, the following pyrophosphate (21.3 g) was obtained.
was gotten. IR: ν _nax , cm ^-1 2950, 1630, 1600, 1365, 1160, 980 NMR (CDCl ₃ ): δ 6.95 (ABq, 4H×2, arom.protons) 5.62 (m.2H×2, vinyl proton) 4.10 (bs.1H×2, vinyl proton) 3.50 (t.2H×2, −CH ₂ −) 1.25 (s.9H×2, tert-butyl) Example 4 β-naphthol (14.4 g), phosphorus oxychloride ( 16
g) and calcium chloride (2.5 g) were reacted in the same manner as in Example 1 to obtain the following phosphoryl dichloride (25 g). This product was mixed with 2-hydroxyethyl acrylate (11.6 g) and pyridine (12 g) in the same manner as in Example 1.
By reacting with and treating in the same manner, the following pyrophosphate (19.5 g) was obtained. IR: ν _nax , cm ^-1 2900, 1720, 1630, 1600, 1365, 1160, 980 NMR (CDCl ₃ ): δ 7.80-7.05 (m.7H×2, aroma.protons) 6.35 (m.3H×2, vinyl proton) 4.25 (m.4H x 2, _-CH2CH2- ) Example 5 7-methoxy-α-naphthol ( _17.4g ), phosphorus oxychloride (16g) and calcium chloride (2.5g)
g) was reacted in the same manner as in Example 1 to obtain the following phosphoryl dichloride (28 g). This product was mixed with 2-hydroxyethyl methacrylate (13 g) and pyridine (12 g) in the same manner as in Example 1.
By reacting with and treating in the same manner, the following pyrophosphate (24.4 g) was obtained. IR: ν _nax , cm ^-1 2950, 1720, 1630, 1600, 1365, 1160, 980 NMR (CDCl ₃ ): δ 7.70 to 6.70 (m.6H×2, arom.protons) 6.10 (bs.1H×2, vinyl proton) 5.55 (m.1H x 2, vinyl proton) 4.25 (m.4H x 2, -CH ₂ CH ₂ - 3.90 (s.3H x 2, -OCH ₃ ) 1.90 (d.3H x 2, vinyl CH ₃ ) Example 6 O-cresol (10.8g), phosphorus oxychloride (16
g) and calcium chloride (2.5 g) were reacted in the same manner as in Example 1 to obtain the following phosphoryl dichloride (2.2 g). When this product was reacted with 2-chloro-3-hydroxypropyl methacrylate (17.8 g) and pyridine (12 g) and treated in the same manner as in Example 1,
The following pyrophosphate (14.7 g) was obtained. IR: ν _nax , cm ^-1 2950, 1720, 1630, 1600, 1370, 1160,
1000, 760 NMR (CDCl ₃ ): δ 6.85 (m.4H×2.arom.protons) 6.10 (bs.1H×2.vinyl proton) 5.55 (m.1H×2.vinyl proton) 3.65 (m.1H× 2.- _CH2CH ( _Cl )CH2-) 4.20(m.4H× _2. -CH2CH( Cl )CH2-) 2.20(s.3H × _2. - _CH3 ) 1.90(d .3H×2.vinyl CH ₃ ) Usage example Fused quartz sand was crushed in a porcelain ball mill to prepare a 200 mesh pass. γ-methacryloxypropyltrimethoxysilane in an amount equivalent to 0.5% by weight based on the quartz powder was added to an aqueous sodium hydroxide solution with a pH of 9.0 to 9.8, stirred and dissolved, and the above quartz powder was added to this. .
By thoroughly mixing and stirring this, a slurry was obtained. This slurry was dried at 130°C to obtain silane-treated quartz powder. Pyrophosphate obtained in Example 1 (70 parts by weight)
Ethylene glycol dimethacrylate (30 parts by weight) was mixed with the mixture to obtain a resin binder. The above quartz powder (80 parts by weight) was added to this binder (20 parts by weight) and thoroughly mixed to obtain a paste. This paste was divided into two parts, and to one part was added 0.6 parts by weight of N,N'-dimethyl-p-toluidine based on the paste (100 parts by weight) and thoroughly mixed to obtain a uniform dispersion. Paste (100 parts by weight) on the other side
Add 0.8 parts by weight of benzoyl peroxide to
A homogeneous dispersion was obtained in the same manner. When equal amounts of this uniform dispersion were mixed and kneaded and the operability and physical properties were examined, the results shown in the following table were obtained.

【table】

【table】

Claims (1)

[Claims] 1. General formula (In the formula, A is aryl which may be substituted with one or more groups selected from lower alkyl, lower alkoxy or halogen; R ¹ means allyl, acryloyloxy (lower) alkyl or methacryloyloxy (lower) alkyl, respectively) death,
The (lower) alkyl in R ¹ may be substituted with a halogen.