JPH0241525B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a method for producing a novel organic glass particularly excellent in transparency. Conventionally, various organic glasses have been proposed for use in place of inorganic glasses. Examples include polymethyl methacrylate and polystyrene. However, although these resins have transparency, they do not have a crosslinked structure, so they have poor mechanical properties and machinability in cutting and polishing, and they are also flammable. In contrast, the organic glass produced by the present invention is transparent and has a crosslinked structure, so it has excellent mechanical properties and processability such as cutting and polishing, and it also has flame retardancy because it contains halogen atoms. are doing. Therefore, the organic glass produced by the present invention is generally useful for building materials such as window glass and wood surface treatment, or for window glass and lenses as automobile parts. The present invention is based on nuclear halogens (but excluding fluorine).
Substituted aromatic ring via alkylene glycol group,
Copolymerization of a dimethylate or diacrylate compound bonded to a methacroyloxy group or acroyloxy group and a radically polymerizable aliphatic compound, alicyclic compound, or heterocyclic compound [However, if the general formula ( _R1 is H or a methyl group, X is a halogen other than fluorine, n+m is an integer of 1 to 8.) 10 to 30 equivalent % of the first monomer represented by the general formula (R ₂ is

【formula】

n ₁ is an integer from 6 to 20, n ₂ is an integer from 3 to 20, n ₃ is 3
Indicates an integer between ~20. ) When copolymerizing 1 to 15 equivalent % of the second monomer shown in the formula and 55 to 89 equivalent % of one or more radically polymerizable third monomers whose homopolymer has a refractive index of 1.55 or more except for. ] A method for producing organic glass characterized by the following. In addition, the above equivalent % is the total equivalent of each monomer to be copolymerized, when 1 equivalent is the number of grams obtained by dividing the molecular weight of the monomer by the number of unsaturated groups that the monomer has. It refers to the ratio of the number of equivalents of each monomer to the number expressed as a percentage. In the specific dimethacrylate or diacrylate compound used in the present invention, a nuclear halogen (excluding fluorine) substituted aromatic ring is bonded to a methacroyloxy group or an acroyloxy group, respectively, through the respective alkylene glycol group. This is the form in which it was created. That is, it has a structure in which an aromatic ring is connected to methacrylic acid or acrylic acid through at least one ether bond and an ester bond, respectively.
The halogen is not particularly limited to chlorine, bromine or iodine, but bromine is particularly preferred. Further, the number of halogens present in the aromatic ring is not particularly limited, but is generally 1 to 4. The specific dimethacrylates or diacrylates having a nuclear halogen (but excluding fluorine) substituted aromatic ring according to the present invention include, in particular, the following general formula: (In the formula, R ₁ is H or CH ₃ , R ₂ is -OCH ₂ CH ₂ -,

【formula】

【formula】

[Formula] etc., where X is a chlorine, bromine or iodine atom, m and n are mutually independently integers of 1 to 4, and a and b are mutually independently integers of 1 to 4) ) diacrylate or bis(alkyleleneoxyphenyl) dimethacrylate is preferably used. The compound represented by the above general formula can be obtained by a known esterification reaction in which an alcohol component and an unsaturated carboxylic acid (methacrylic acid, acrylic acid, etc.) are heated in the presence of an acid catalyst and subjected to dehydration condensation. can. Further, an ester having a side chain hydroxyl group can be obtained by adding an unsaturated carboxylic acid to a corresponding terminal epoxy compound. Furthermore, in the present invention, the unsaturated compound (monomer) represented by the above general formula can be prepolymerized and used as a prepolymer. That is, since prepolymers have higher viscosities than corresponding unsaturated compounds, they generally
It has advantages such as being able to prevent unsaturated monomer from leaking from the mold, reducing shrinkage of the polymer due to polymerization, and increasing viscosity to make it easier to apply. Such prepolymers can be produced by polymerizing one or more unsaturated compounds (monomers) with heat or optionally in the presence of a radical polymerization initiator until the reaction system gels. can. As for the specific dimethacrylate or diacrylate having a nuclear halogen (excluding fluorine)-substituted aromatic ring of the present invention, representative examples that are preferably used include, for example, 1,4-dimethacryloxyethoxy -2,3,5,6-tetrachlorobenzene, 1,4-diacryloxyethoxy-2,3,5,6-tetrabenzene, di-(2-methacryloxyethyl) tetrabromophthalate, tetrabro Muftalic acid di(2-acryloxyethyl), 2,2-bis(4-methacryloxyethoxy-3,5-dichlorophenyl)propane, 2,2bis(4-acryloxyethoxy-
3-bromphenyl)propane, 2,2bis(4
-methacryloxyethoxy-3-chlorophenyl)propane, 2,2bis(4-methacryloxyethoxy-3-bromphenyl)propane, 2,
2bis(4-acryloxyethoxy-3-chlorophenyl)propane, 2,2bis(4-methacryloxyethoxy-3-bromphenyl)propane, 2,2bis(4-acryloxyethoxy-3)
-bromphenyl)propane, 2,2bis(4-
Methacryloxyethoxy-3,5-dibromphenyl)propane, 2,2bis(4-acryloxyethoxy-3,5-dibromphenyl)propane, polyoxyalkylated tetrabromobisphenol A dimethacrylate 1,5-dimethacryloxy Ethoxy-2,4,6,8-tetrabromnaphthalene, 1,5-diacryloxyethoxy-
2,4,6,8-tetrabromnaphthalene, and mixtures thereof. Further, as other unsaturated compounds among the aliphatic compounds, alicyclic compounds, and heterocyclic compounds that are radically polymerizable with the unsaturated compound used in the present invention, known ones can be used without particular restriction. One group that can be suitably used as aliphatic compounds is aliphatic diols, preferably having 2 to 2 carbon atoms.
Diester of alkylene glycol or polyalkylene glycol of No. 4 and acrylic acid or methacrylic acid, and diallyl ester of dicarboxylic acid. Examples of such compounds include ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate,
Aliphatic diols such as triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, propylene glycol diacrylate, 1,4-butanediol methacrylate, or diesters of polyalkylene glycol and acrylic acid or methacrylic acid; Examples include diallyl esters of dicarboxylic acids such as diallyl tartrate and diallyl maleate. Other examples include methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, 2-
Hydroxypropyl methacrylate, ethylene glycol bis[3-methacryloxy(2-hydroxy)propyl ether] (methacrylate compounds such as 3-chloro-2-hydroxypropyl methacrylate; diethylene glycose bis(allyl carbonate), etc.) Examples of suitable alicyclic compounds include acrylates and methacrylates such as cyclohexyl methacrylate and cyclopentadiene methacrylate. Suitable examples of the heterocyclic compound include methacrylates and acrylates such as glycidyl methacrylate, glycidyl acrylate, tetrahydrofurfuryl methacrylate, and triazine trimethacryloxyethyl. Among the above-mentioned radically polymerizable unsaturated compounds, , especially diesters of alkylene glycols or polyalkylene glycols with acrylic acid or methacrylic acid, diallyl esters of dicarboxylic acids, methyl methacrylate, 2-hydroxyethyl methacrylate, ethylene glycol bis[3
-methacryloxy(2-hydroxy)propyl ether), diethylene glycol bis(allyl carbonate), or tartrate diallyl ester, etc., have particularly excellent impact resistance, transparency, weather resistance, dyeability, or processability. A cured resin having various physical properties suitable as an organic glass can be obtained. In the present invention, a specific dimethacrylate or diacrylate having a nuclear halogen (but excluding fluorine) substituted aromatic ring and/or a prepolymer thereof, and the above-mentioned radically polymerizable unsaturated compound and/or a prepolymer thereof,
They can be used in amounts of 1 to 99% by weight and 99 to 1% by weight, respectively, preferably 5 to 95% by weight and 95 to 5% by weight, respectively, based on their total amount. The cured resin of the present invention is obtained by copolymerizing an intimate mixture consisting essentially of the unsaturated compounds described above in the presence of a radical polymerization initiator. The reaction proceeds simply by heating, but it can also be carried out by irradiation with actinic light such as ultraviolet rays or radiation. Any known radical polymerization initiator can be used without particular limitation. Typical examples include diacyl peroxides such as benzoyl peroxide, P-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, decanoyl peroxide, launoyl peroxide, and acetyl peroxide; Percarbonates such as pyrropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di-normal butyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, tert-butyl peroxydicarbonate, etc. - Compounds such as alkyl bar esters such as ethylhexanate and tert-butyl peroxypivalate, or azoisobutyronitrile. The amount of the radical polymerization initiator to be used varies depending on the polymerization mode, polymerization conditions, and type of monomer for the copolymerization component, and cannot be absolutely limited, but it is generally 0.0001 to 10% (by weight) based on the total monomers. Those used within the range are most suitable. The polymerization method in the present invention is not particularly limited, and any known polymerization method can be employed. A typical preferred polymerization method is a cast polymerization method. For example, an intimate mixture of the copolymer monomers containing a radical polymerization initiator is injected between molds held by elastomer gaskets or spacers, cured in an air oven, and then removed. It is also possible to preliminarily polymerize a mixture of copolymerization component monomers in the presence of a polymerization initiator to increase the viscosity of the mixture, and then perform cast polymerization. Among polymerization conditions, temperature in particular affects the properties of the resulting organic glass. This temperature condition cannot be determined unconditionally because it is affected by the type and amount of monomer and the type of polymerization initiator. Generally, it is preferable to carry out so-called two-stage polymerization, in which polymerization is started slowly at a relatively low temperature and then cured at a high temperature when the polymerization is completed. For example, it is preferable to polymerize slowly at room temperature to about 70°C and then terminate the polymerization at a high temperature of about 80 to 120°C. Moreover, it is preferable to determine the optimum polymerization time depending on various conditions. generally 3
It is preferable to select conditions such that polymerization is completed in ~40 hours. During the copolymerization, release agents, ultraviolet rays, absorbers,
Various stabilizers and additives such as antioxidants, color inhibitors, antistatic agents, fluorescent paints, etc. can also be appropriately present in the polymerization reaction system as required. The organic glass produced in the present invention is a colorless, transparent and flame-retardant resin with a light transmittance of generally 90% or more, particularly 95% or more. Further, resins having a refractive index of generally 1.5 or more can be easily obtained. Therefore, the organic glass of the present invention can also be used as a plastic lens. Further, since the organic glass produced by the present invention has a crosslinked structure, it can be cut and polished, and also has the advantage that it can be easily dyed with a dispersion paint. EXAMPLES Hereinafter, in order to specifically explain the present invention, examples will be shown below, but the present invention is not limited thereto. In addition, in the examples, various physical properties of organic glass are as follows:
It was measured by the following test method. (1) Refractive index The refractive index at 20°C was measured using an Atsube refractometer. Monobromnaphthalene was used as a contact liquid. (2) Transparency Transparency Tt (%) was measured using a fade meter using a sample of 30 x 30 x 2 m x m. Examples 1 to 14 The first monomer and the second monomer shown in Table 1 were mixed in the composition shown in Table 1 and sufficiently dissolved. Next, 1.0 part by weight of diisopropyl peroxydicarbonate was added as a radical polymerization initiator and thoroughly mixed. This mixed solution was poured into a mold consisting of a glass plate and a vinyl chloride spacer, and cast polymerization was performed. The temperature was gradually increased from 30°C using a polymerization air oven and raised to 80°C for 20 hours. Polymerization was further carried out at 80°C for 2 hours. After the polymerization was completed, the mold was taken out from the air furnace, the gasket was removed, and the polymer was peeled off from the glass mold after being allowed to cool. A transparent and tough polymer was obtained. The physical properties of the polymer are shown in Table 1.

[Table] Examples 15 to 17 Using the first and second monomers shown in Table 2, 0.5 parts by weight of dimyristyryl peroxydicarbonate was added as an initiator and thoroughly mixed. The rest was carried out in the same manner as Examples 1 to 14. The results are shown in Table 2.

[Table] Example 18 Same as Examples 1 to 14, as the first monomer
₃₀ % by weight of Br4.BMEPP and 70% by weight of glycidyl methacrylate as the second monomer were polymerized. The obtained polymer has a refractive law n _D of 1537 and a transparency T _t of 96.
It was %. Example 19 In Example 3, instead of using diisopropyl peroxydicarbonate, irradiation was performed with a high pressure mercury lamp at room temperature to obtain a polymer. A transparent and tough polymer was obtained. The transparency Tt of the polymer was 95.

Claims (1)

[Claims] 1. Radically polymerizable with a dimethacrylate or diacrylate compound in which a nuclear halogen (excluding fluorine) substituted aromatic ring is bonded to a methacroyloxy group or an acroyloxy group via an alkylene glycol group. Copolymerization with aliphatic compounds, alicyclic compounds, or heterocyclic compounds [However, if the general formula ( _R1 is H or a methyl group, X is a halogen other than fluorine, n+m is an integer of 1 to 8.) 10 to 30 equivalent % of the first monomer represented by the general formula (R ₂ is n ₁ is an integer from 6 to 20, n ₂ is an integer from 3 to 20, n ₃ is 3
Indicates an integer between ~20. ) When copolymerizing 1 to 15 equivalent % of the second monomer shown in the formula and 55 to 89 equivalent % of one or more radically polymerizable third monomers whose homopolymer has a refractive index of 1.55 or more except for. ] A method for producing organic glass characterized by the following.