KR101400357B1 - New preparation method of allylcarbonate compound - Google Patents

Abstract

The present invention relates to a novel method for producing an allylcarbonate compound and an optical resin composition using the same, wherein an alcohol is added to a diallyl carbonate compound obtained by subjecting an alkylcarbonate and an unsaturated alcohol to a first ester exchange reaction under a catalyst, The present invention provides a process for producing a carbonate compound and an optical resin composition excellent in refractive index, Abbe number and APHA by mixing the obtained allyl carbonate alone or an unsaturated carboxylate or vinyl monomer.

Description

[0001] The present invention relates to a novel preparation method of an allylcarbonate compound,

The present invention relates to a process for producing a diallyl carbonate (DAC) compound by a primary ester exchange reaction from an organic carbonate and an unsaturated alcohol, performing a secondary ester exchange reaction with an alcohol and then subjecting the product to a vacuum distillation and concentration to produce an allyl carbonate .

The present invention also relates to providing an optical resin composition obtained by combining with an allyl carbonate compound alone or an unsaturated carboxylate compound or a vinyl monomer obtained by the above production method.

Particularly, the present invention relates to a method for producing an allyl carbonate compound, which comprises using a phosgene as a starting material to obtain a diallyl carbonate (DAC) compound having a high purity and a high yield, , The washing step can be omitted, and the process is simple. When the optical resin composition is prepared from the obtained allyl carbonate compound, the refractive index, Abbe number and color (APHA) are excellent.

Conventional methods for synthesizing polycarbonate include interfacial polycondensation, melt transterification and solution polycondensation, and interfacial polycondensation is frequently used. The interfacial polycondensation method is called a phosgene method and comprises polycondensation of chloropropromate produced by reaction of bisphenol A with phosgene in the presence of an oxidizing agent and a solvent by a decarboxylation reaction. The phosgene process, which is prepared by reacting chloroformate obtained from the reaction of alcohol with phosgene in the presence of an alcohol with an objective alcohol, is disclosed in US 2370565 and US 2592058.

Other methods include a carbonate method in which an organic halogen compound is reacted with an alcohol, a carbonate and carbon dioxide under high temperature and high pressure. This method is disclosed in Chinese Patent Publication CN 1974528A, Japanese Patent Laid-Open Nos. JP56-2937, JP56-5442 and JP56-5443 Is introduced.

An ester exchange method in which an allyl carbonate compound is subjected to an ester exchange reaction with two different alcohols is known from US 4512930 and the like.

Since the phosgene method described above is used in a limited manner due to the disadvantage of using poisonous phosgene gas (COCl ₂ ), the carbonate method requires a reaction at a high temperature and a high pressure, Has progressed.

The ester exchange reaction proposed in U.S. Patent No. 4512930 was able to obtain the target product, but there was a problem that the two compounds were azeotropically removed in the process of removing generated methanol. Also, by using an alkali catalyst, the color of the end product ) Was not good, the reaction time was long and by-products were produced, and there was a disadvantage in a process requiring a separate washing process to remove the catalyst in the post-process.

Disclosure of Invention Technical Problem [8] In order to solve the problems occurring in conventional organic carbonate compounds, the present invention provides a diallyl carbonate (DAC) compound by a primary ester exchange reaction from an organic carbonate and an unsaturated alcohol in the production of an allyl carbonate compound, A second ester exchange reaction with an alcohol, followed by concentration under reduced pressure distillation to produce an allyl carbonate compound represented by the following formula (II).

(II)

(R ₁ OCOO) _n -R ₂

N is an integer of 1 to 4,

R ₁ is an unsaturated alcohol residue,

R ₂ is a divalent or higher alcohol residue.

The present invention still further provides an optical resin composition obtained by combining the allyl carbonate compound alone or the unsaturated carboxylate compound or the vinyl monomer obtained by the above production method.

Hereinafter, the present invention will be described in more detail.

The present invention

Obtaining a diallyl carbonate compound represented by the following formula (I) by a first transesterification reaction of an alkyl carbonate compound and an unsaturated alcohol in a molar ratio of 1: 2 to 5;

Adding a polyhydric alcohol to the compound represented by Formula (I) at a molar ratio of 2 to 4: 1 to perform a second ester exchange reaction;

And then concentrating under reduced pressure distillation after the second transesterification reaction to obtain a compound represented by the following formula (II): < EMI ID = 2.0 >

(I)

R ₁ OCOOR ₁

[Formula II]

(R ₁ OCOO) _n -R ₂

Wherein n is an integer of 1 to 4,

R ₁ represents an unsaturated alcohol residue and may be selected from allyl alcohol, allylcarbitol, methallyl alcohol, crotyl alcohol, 3-butene-2-ol and 2-methyl-3-butene- Alcohols having unsaturated bonds may be included.

In the above formula, R ₂ represents a divalent or higher alcohol residue. Examples of the divalent alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, Hexanediol, bisphenol A, and their EO and PO adducts. Examples of trihydric or higher alcohol include glycerol, trimethylolpropane, pentaerythritol, and EO and PO adducts thereof. Compounds having alcohol residues may be included.

The process for producing the allyl carbonate compound represented by the formula (II) according to the present invention is carried out in two steps. Firstly, a diallyl carbonate compound represented by the formula (I), which is a starting material for obtaining the allyl carbonate compound according to the present invention, In the first step reaction, an ester exchange reaction was carried out between an alkyl carbonate compound and an unsaturated alcohol.

Examples of the alkyl carbonate compound used in the present invention include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate and dibenzyl carbonate.

 The unsaturated alcohols used in the present invention may be selected from allyl alcohol, allylcarbitol, methallyl alcohol, crotyl alcohol, 3-butene-2-ol and 2-methyl- Alcohols having unsaturated bonds may be included.

For the first transesterification reaction, a catalyst may be used to improve the yield and purity. The catalyst used is a tin compound such as dibutyl tin oxide, dibutyl tin dilaurate, dibutyl tin dichloride, dibutyl tin diacetate and the like; Alkoxide compounds with metal complexes such as bisacetylacetonate zinc, bisacetylacetonate manganese, zinc acetate, and manganese acetonate; Carbonates or hydrogencarbonates of alkali metals such as sodium carbonate, sodium hydrogencarbonate and potassium carbonate; Hydroxides or oxides of alkali metals such as calcium hydroxide, calcium carbonate, magnesium hydroxide and barium hydroxide; Hydroxides or oxides of alkaline earth metals such as sodium carbonate, potassium carbonate, potassium chloride, sodium chloride, sodium sulfate, potassium sulfate, sodium carbonate, potassium carbonate and sodium hydrogen carbonate; A salt-combining catalyst of an inorganic acid or an organic acid of an alkali metal; Alkoxide alkoxides such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium methoxide, sodium isopropoxide; Alkaline earth metal alcoholate catalysts obtained by reaction of alkaline earth metal and alcohol, reaction of alkaline earth metal carbide with alcohol, reaction of alkaline earth metal hydride with alcohol, reaction of alkaline earth metal hydroxide with alcohol, reaction of alkaline earth metal oxide with alcohol, Any one of them or a mixture of two or more of them may be used.

For the smooth progress of the reaction, the molar ratio of the unsaturated alcohol required for the alkyl carbonate compound can be used more than 2 times, and 3 to 5 times of the unsaturated alcohol can be preferably used considering the capacity of the reactor.

Alternatively, urea may be used and the unsaturated alcohol and the unsaturated carbonate compound described above may be prepared in the presence of a catalyst.

The unsaturated carbonate compound obtained according to the production method of the present invention can be directly applied to an optical resin, but it is preferable to use it by growing the molecular weight through ester exchange reaction because the molecular weight is generally small and the shrinkage is serious.

Next, in order to obtain an allyl carbonate compound represented by the formula (II) according to the present invention, a secondary transesterification reaction is carried out.

At this time, the diallyl carbonate compound represented by the formula (I) is added to the alcohol represented by R ₂ in the formula (II) so that the molar ratio of the alcohol is 1: 2 or more, preferably 2 to 4: 1 relative to the diallylcarbonate compound And the reaction is completed after the atmospheric pressure or reduced pressure distillation is performed until the target unsaturated alcohol reaches the target value at a temperature in the range of 120 to 180 ° C.

The concentration under reduced pressure distillation according to the present invention is adjusted to be 5% or less.

The present invention further provides an optical resin composition using the allyl carbonate compound represented by the general formula (II).

The optical resin composition according to the present invention can be used in combination with an unsaturated carboxylate compound or a vinyl monomer in addition to the allyl carbonate compound alone represented by the above formula (II).

Examples of the unsaturated carboxylate (ester compound) include diaryl phthalate, diaryl isophthalate, diaryl terephthalate, diallyl adipate, diaryl succinate, etc., and they are subjected to transesterification using an alcohol to prepare an oligomer phase It is also possible to use them in combination with the compounds thus prepared, and in addition, they can be mixed with an ester compound having an unsaturated bond, and they can be used alone or in combination of two or more.

Examples of the vinyl monomers which can be mixed include aromatic vinyl compounds such as styrene, alpha-methylstyrene, alpha-chlorostyrene, methylstyrene, vinylnaphthalene and divinylbenzene; Vinyl esters such as vinyl acetate, vinyl benzoate, allyl benzoate and divinyl phthalate; Acrylic acid and methacrylic acid, glycidyl acrylate and methacrylate, methyl acrylate and methacrylate, ethyl acrylate and methacrylate, isopropyl acrylate and methacrylate, n-propyl acrylate and methacrylate, Isobutyl acrylate and methacrylate, sec-butyl acrylate and methacrylate, n-butyl acrylate and methacrylate, allyl acrylate and methacrylate, methallyl acrylate and methacrylate, vinyl acrylate and Methacrylate, 2-hydroxyethyl acrylate and methacrylate, 2-hydroxypropyl acrylate and methacrylate, cyclohexyl acrylate and methacrylate, phenyl acrylate and methacrylate, benzyl acrylate and methacrylate Acrylic Diethylene glycol diacrylate and dimethacrylate, triethylene glycol acrylate and methacrylate, 2-hydroxy-3-phenoxy-2-hydroxypropyl methacrylate, Acryloyloxyglycerol monomethacrylate, 2,2-bis- (acryloyloxy-ethoxyphenyl) propane, 2,2-bis- (acryloyloxy- (2'-hydroxypropyloxy) phenyl] propane, 2,2-bis- (methacryloyloxy-diethoxyphenyl) propane, , Acrylic or methacrylic monomers such as 2-bis- [methacryloyloxy (2'-hydroxypropyloxy) phenyl] propane, 2-acryloyloxyethylsuccinic acid and 2-methacryloyloxyethyl- ; And unsaturated acids such as diisopropyl fumarate, dicyclohexyl fumarate, dibenzyl maleate, dibenzyl itaconate, dibenzyl mesaconate, maleic anhydride and itaconic anhydride, and esters thereof. have. These vinyl monomers may be used singly or as a mixture.

The production of the optical resin composition according to the present invention can simultaneously carry out the polymerization reaction of the compound represented by the formula (II) and the optional unsaturated compound.

That is, the allyl carbonate compound represented by the formula (II) is prepared by mixing the unsaturated compound alone or with a curing agent.

The curing agent available in this case is preferably an organic peroxide having a temperature at which the selected 10 hour half-life temperature is not higher than 120 占 폚. Preferred examples of such organic peroxides include, for example, peracid, perhydroxy compounds and peroxyesters and azo-bis-nitriles. These compounds are conventionally known and commercially available. Exemplary curing agents are, for example, lauroyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicar T-butyl peroxybenzoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, azo-bis-iso Butyronitrile, and mixtures thereof.

The curing agent is used in an amount of 0.05 to 5% by weight, preferably 0.1 to 4% by weight, based on the total amount of the polymerizable component and the optional vinyl monomer. If the amount of the curing agent is lower than 0.05% by weight, various physical properties of the resultant resin are deteriorated. On the other hand, when the weight ratio is more than 5%, it is difficult to control the polymerization reaction, and there is a high possibility that cracks on the surface of the resulting resin are generated.

The optical resin composition is put into a mold having a predetermined shape, and the air of the mold is preferably replaced with an inert gas such as nitrogen, helium and carbon dioxide, and polymerization reaction is carried out under heating.

As another example, it is preferable to preliminarily heat the optical resin composition to a temperature of preferably 30 to 70 占 폚 in a suitable container for a prepolymerization reaction to form a prepolymer, and then to preliminarily heat the optical resin composition in a mold. The preferred temperature range for the polymerization reaction of the polymerizable composition varies depending on the kind of the curing agent used, but is generally in the range of 20 to 130 占 폚. Moreover, it is preferred that the polymerization reaction of the composition is carried out slowly at a temperature 20 占 폚 lower than the 10 hour half-life temperature of the curing agent used. The temperature can be suitably raised for shortening the curing time or for treating unreacted monomers. The polymerization reaction time in the above-mentioned temperature range is preferably within 5 to 48 hours. The obtained molding resin can be used directly on the desired optical article. Since the resin obtainable by the thermal polymerization reaction contains internal strain due to heat, the resin is heated at a temperature of 110 to 140 캜, preferably 110 to 130 캜 for at least 30 minutes to 6 hours, It can be annealed for 4 hours.

When preparing the molding resin for the use of the optical element, the polymerizable composition or the viscous prepolymer thereof, if required, may be mixed with one or more various additives to increase the availability of the optical element.

Examples of such additives include colorants such as dyes and pigments, various protectants such as ultraviolet absorbers, antioxidants, various stabilizers such as antistatic agents, photochromes, optical brighteners, release agents and the like. These materials may be used in combination in amounts that are well known in the relevant industry for the purposes desired.

Examples of the ultraviolet absorber in the present invention include ethyl-2-cyano-3,3-diphenylacrylate, 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole; 2- (2-hydroxy-3,5-di-t-butylphenyl) -5-chloro-2H-benzotriazole; 2- (2-hydroxy-3-t-butyl-5-methylphenyl) -5-chloro-2H-benzotriazole; 2- (2-hydroxy-3,5-di-t-amylphenyl) -2H-benzotriazole; 2- (2-hydroxy-3,5-di-t-butylphenyl) -2H-benzotriazole; 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole; 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole; 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-octyloxybenzophenone; 4-dodecyloxy-2-hydroxybenzophenone; 4-benzooxy-2-hydroxybenzophenone; 2,2,4,4-tetrahydroxybenzophenone; 2,2-dihydroxy-4,4-dimethoxybenzophenone, and the like, or a mixture of two or more thereof.

2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, which has good ultraviolet light absorbing ability in a wavelength range of 400 or less and has good solubility in the composition of the present invention, 2-cyano-3,3-diphenylacrylate, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole, 2,2- Hydroxy-3,5-di-t-amylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3,5-di (2-hydroxy-3-t-butyl-5-methylphenyl) -5-chloro-2H- benzotriazole, 2,2- Dihydroxy-4,4-dimethoxybenzophenone and the like can be used.

In the present invention, the heat stabilizer may be, for example, a metal fatty acid salt type calcium stearate; Barium stearate; Zinc stearate; Cadmium stearate; Lead stearate; Magnesium stearate; Aluminum stearate; Potassium stearate; Zinc octoate, and the like can be used, and phosphoric acid triphenyl phosphite; Diphenyldecyl phosphite; Phenyldodecyl phosphite; Diphenyldodecyl phosphite; Trinoryl phenyl phosphite; Diphenyl isooctyl phosphite; Tributyl phosphite; Tripropyl phosphite; Triethyl phosphite; Trimethyl phosphite; Tris (monodecyl phosphite); Tris (monophenyl) phosphite such as one species or two or more kinds of compounds and are available in, lead-sealed 3PbO.PbSO4.4H ₂ O; _{2PbO.Pb (C 8 H 4 O 4} ); _{3PbO.Ph (C 4 H 2 O 4} ) .H be one species or two or more kinds of the compounds, such as O ₂ is used, and sealed organotin dibutyltin diahwoo rate; Dibutyl tin maleate; Dibutyltin bis (isooctyl maleate); Dioctyl maleate; Dibutyltin bis (monomethyl maleate); Dibutyltin bis (lauryl mercaptide); Dibutyl bis (isoxyl mercaptoacetate); Monobutyltin tris (isooctyl mercaptoacetate); Dimethyltin bis (isooctyl mercaptoacetate); Tris (isooctyl mercaptoacetate); Fertile tiltin bis (isooctyl mercaptoacetate); Dibutyltin bis (2-mercaptoethylolate); Monobutyltintris (2-mercaptoethanolate); Dimethyltin bis (2-mercaptoethylol); Monomethyl tin tris (2-mercaptoethylolate), and the like can be used.

In the present invention, the inner mold release agent includes, for example, (mono, di) methylphosphoric acid; (Mono, di) ethylphosphoric acid; (Mono, di) (n-propyl) phosphoric acid; (Mono, di) isopropyl phosphoric acid; (Mono, di) (n-butyl) phosphoric acid; (Mono, di) (n-pentyl) phosphoric acid; (Mono, di) (n-hexyl) phosphoric acid; (Mono, di) (n-heptyl) phosphoric acid; (Mono, di) (n-octyl) phosphoric acid; (Mono, di) (2-ethylhexyl) phosphoric acid; (Mono, di) (n-nonyl) phosphoric acid; (Mono, di) (n-decyl) phosphoric acid; (Mono, di) (isodecyl) phosphoric acid; (Mono, di) (n-undecyl) phosphoric acid; (Mono, di) (n-dodecyl) phosphoric acid; (Mono, di) (tridecyl) phosphoric acid; (Mono, di) (n-tetradecyl) phosphoric acid; (Mono, di) (n-pentadecyl) phosphoric acid; (Mono, di) (n-hexadecyl) phosphoric acid; (Mono, di) (n-octadecyl) phosphoric acid; (Mono, di) (o-methyldecyl) phosphoric acid; (Mono, di) (p-methylphenyl) phosphoric acid; (Mono, di) (p-ethylphenyl) phosphoric acid; (Mono, di) (p-propylphenyl) phosphoric acid; (Mono, di) (p-butylphenyl) phosphoric acid; (Mono, di) (p-nonylphenyl) phosphoric acid; (Mono, di) (p-methyl methyl) phosphoric acid; (Mono, di) (2-phenylethyl) phosphoric acid; (Mono, di) (4-phenylbutyl) phosphoric acid; (Mono, di) (3-oxabutyl) phosphoric acid; (Mono, di) (3-oxapentyl) phosphoric acid; (Mono, di) (3-oxahexyl) phosphoric acid; (Mono, di) (3-oxaheptyl) phosphoric acid; (Mono, di) (3-oxaoctyl) phosphoric acid; (Mono, di) (3-oxanonyl) phosphoric acid; (Mono, di) (3-oxoundecyl) phosphoric acid; (Mono, di) (3-oxatridecyl) phosphoric acid; (Mono, di) (3-oxapentadecyl) phosphoric acid; (Mono, di) (3-oxaheptadecyl) phosphoric acid; (Mono, di) (3-oxanonadecyl) phosphoric acid; (Mono, di) (3-oxahenicosyl) phosphoric acid; (Mono, di) (1-methyl-3-oxabutyl) phosphoric acid; (Mono, di) (1-methyl-3-oxapentyl) phosphoric acid; (Mono, di) (1-methyl-3-oxaheptyl) phosphoric acid; (Mono, di) (1,2-dimethyl-3-oxacetyl) phosphoric acid; (Mono, di) (1-methyl-3-oxatridecyl) phosphoric acid; (Mono, di) (1-methyl-2- (o-methylphenoxy) ethyl) phosphoric acid; (Mono, di) (3-methyl-2- (p-nonylphenoxy) (3,6-dioxadecyl) phosphoric acid, (mono, di) (3,6-dioxaoctyl) phosphoric acid, (3,6-dioxahexadecyl) phosphoric acid, (3,6-dioxahexadecyl) phosphoric acid, (mono, di) (Mono, di) (3,6-dioxadecosyl) phosphoric acid, (mono, di) ), (Mono, di) (3,6,9-trioxadecyl) phosphoric acid, (mono, di) (Mono, di) (3,6,9-trioxanecenyl) phosphoric acid, (mono, di) (3,6,9-trioxaheptadecyl) phosphoric acid, (Mono, di) (1,4,7-trimethyl-3,6,9-trioxatridecyl) phosphoric acid, (mono, di) 3,6,9,12-tetraoxaheptadecyl) phosphoric acid; (Mo (Mono, di) (3,6,9,12-tetraoxaoctyldecyl) phosphoric acid, (mono, di) Tetraoxadecosyl) phosphoric acid, (mono, di) (3,6,9,12-tetraoxatetracosyl) phosphoric acid, (mono, di) (1,4,7,10-tetramethyl 3,6,9,12-tetraoxahexadecyl) phosphoric acid, triisopropyl acid phosphate, tributyl acid phosphate, trioctyl acid phosphate, triisodecyl acid phosphate, tridecanolic acid phosphate, bis (tridecanolic acid) phosphate A polyoxyethylene nonylphenol ether phosphate, a tri polyoxyethylene nonylphenol ether phosphate, a bis (tridecanedioic acid) phosphate, a polyoxyethylene nonylphenol ether phosphate, Oleic acid phosphate, ethylene glycol monoethyl phosphate, diethylene glycol monoethylphosphate Triethylene glycol monoethyl phosphate, diethylene glycol monobutyl diphosphate, diethylene glycol monobutyl phosphate; Isopropylene glycol monoethyl phosphate; Diisopropylene glycol monoethyl phosphate; Triisopropylene glycol monoethyl phosphate, and the like, or a mixture of two or more thereof. The specifically exemplified compounds are mixtures and do not need to be defined as compounds with a single composition.

Further, a silicon-based surfactant and a fluorine-based surfactant may be further added as a mold release agent.

Further, a hard coat film may be provided on the outer surface of the molding resin to increase the abrasion resistance characteristics of the surface. Furthermore, by inserting a primer layer between the surface of the resin and the hard coat film, the adhesion of the resin to the hard coat film can be improved. In order to apply the hard coat agent on the resin outer surface in order to provide the hard coat film on the surface, the fully cured and annealed resin is first coated with the primer solution, and then coated by a conventional method such as dipping method, spin- Hard-coating is applied according to the method of flow-coating, spraying and other methods. In addition, a reflection-preventing film may be provided on the molding resin surface to prevent surface reflection on the surface of the optical element, thereby increasing the transmittance of the visible light.

The optical resin composition according to the present invention is a colorless resin having a refractive index of 1.35 or more, preferably 1.48 to 1.58, an Abbe number of at least 30, preferably 30 to 58, and a color (APHA) of 10 to 16 It has a transparent feature.

By having excellent impact resistance, heat resistance and adhesion to a hard coat film, the optical resin composition according to the present invention is particularly useful for lens manufacturing industries such as glasses, various optical element industries, and various high refractive index resin related industries Do.

The present invention relates to a process for producing an allyl carbonate compound represented by the above formula (II), wherein a starting material of a diallyl carbonate (DAC) having a high purity and a high yield is first synthesized and then subjected to a two- The washing step can be omitted. Thus, it is possible to shorten the processing time and the refractive index, the Abbe number and the color (APHA) when the optical lens is manufactured using the obtained allyl carbonate compound.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples.

Example

The raw material used in the present invention was purified and a high purity substance was used, and the physical properties of the optical resin were measured as follows.

The refractive index and the Abbe number were measured by Atago Co., Ltd. And the DR-M4 model. The APHA value was obtained by comparing the concentration of the standard solution prepared by dissolving the reagents of platinum and cobalt using Hunterlab's ColorQuest XE instrument and comparing it with the embedded program and sample APHA value was measured.

Synthesis Example)

 Synthesis of Diaryl Carbonate (DAC)

A distillation tower was placed in a 1 L four-necked flask, and 90.08 g (1.0 mol) of dimethyl carbonate (DMC) and 232.32 g (4.0 mol) of allyl alcohol were added, and 1.50 g of potassium carbonate was added and the mixture was heated to 120 ° C and refluxed. After about 4 hours of reflux, the temperature of the distillation column was kept below 65 ° C and recovery began. After about 20 hours, the temperature of the distillation column began to increase. As a result, the content of the DMC was eliminated and the content of DAC was 99% or more. The excess AA and DAC were then fractionally distilled to obtain 136.40 g (96% theoretical yield) of DAC.

Synthesis Example 1)

 Synthesis of diethylene glycol bisallyl carbonate (DEGDC)

568.60 g (4.0 mol) of diaryl carbonate (DAC) and 106.12 g (1.0 mol) of diethylene glycol were added and reacted at 160 DEG C for 6 hours to obtain about 60% of the reaction. After slowly depressurizing, The alcohol was recovered. The reaction was further continued for 4 hours, and the excessive amount of DAC was distilled under reduced pressure at about 85 캜 to be less than 5%. The target product, DEGDC, was subjected to a filtration process without additional washing step to obtain about 240.00 g (theoretical yield of about 88%, APHA 12).

Synthesis Example 2)

 Synthesis of diethylene glycol bisallyl carbonate (DEGDC)

28.03 g (2.0 mol) of DAC and 106.12 g (1.0 mol) of diethylene glycol were charged and reacted at 160 DEG C for 6 hours to conduct about 60% of reaction. After that, the reaction was induced slowly under reduced pressure to recover allyl alcohol. The reaction was further continued for 4 hours, and the excess DAC was cooled to about 85 캜 and concentrated to 5% or less. The target product, DEGDC, was obtained through filtration without additional washing step to give 230.00 g (84% of theory, APHA 14). The yield was lower than that of Synthesis Example 1) and the amount of oligomer was increased.

Synthesis Example 3)

Synthesis of bisphenol A (2EO) diallyl carbonate

(1.0 mol) of alcohol in which EO (2.0 mol) of bisphenol A was added instead of diethylene glycol was used instead of the reagent used in Synthesis Example 1), and bisphenol A 2EO) diallylcarbonate (theoretical yield of about 90%, APHA 10) was obtained by filtration only without washing.

Example 1)

DEGDC Using 88.90 g of DEGDC prepared in Synthesis Example 1, 11.10 g of diisopropylperoxy dicarbonate (product diluted in diethylene glycol bisallyl carbonate: product of Nippon Oil and Fats Co., Ltd.) was mixed and stirred for about 1 hour After sufficiently mixing, vacuum degassing was performed for 10 minutes at 1 torr or less. After filtering through 3 filter paper, it was injected into a flat 2mm glass mold and -6.0 diopter glass mold. The polymerization was carried out at 35 DEG C for 1 hour, then the temperature was raised to 40 DEG C over 4 hours, then the temperature was elevated to 60 DEG C over 9 hours, the temperature was elevated to 85 DEG C over 3 hours, Respectively. After about 19 hours, it was demolded, washed, and washed.

Thereafter, the annealing was further continued at 120 ° C for 2 hours, and after cooling to room temperature, the refractive index was confirmed. The refractive index was 1.499, Abbe number was 58, and APHA was 18.

Example 2)

80.00 g of an oligomer obtained by adding 0.4 mol% propyleneglycol to diallyl isophthalate and transesterification reaction, 20.00 g of DEGDC prepared in Synthesis Example 1 were mixed, and 27% of diisopropyl peroxydicarbonate And 12.50 g of a product diluted in diethylene glycol bisallyl carbonate) were thoroughly mixed for about 1 hour, and vacuum defoaming was performed for 10 minutes at 1 torr or less. After filtering through 3 filter paper, it was injected into a flat 2mm glass mold and -6.0 diopter glass mold. The polymerization was carried out at 35 DEG C for 1 hour, then the temperature was raised to 40 DEG C over 4 hours, then the temperature was elevated to 60 DEG C over 9 hours, the temperature was elevated to 85 DEG C over 3 hours, Respectively. After about 19 hours, it was demolded, washed, and washed.

Thereafter, the annealing was further continued at 120 ° C for 2 hours, and after cooling to room temperature, the refractive index was confirmed. The physical properties are listed in Table 1.

Example 3)

80.00 g of an oligomer obtained by carrying out transesterification reaction by adding propylene glycol at 0.4 mol% to diallyl isophthalate and 20.00 g of DEGDC prepared in Synthesis Example 2 were mixed and 27% of diisopropyl peroxydicarbonate (di Manufactured by Nippon Oil & Fats Co., Ltd.) diluted in ethylene glycol bisallyl carbonate) were mixed, sufficiently mixed for about 1 hour, and vacuum degassed for 10 minutes at 1 torr or less. After filtering through 3 filter paper, it was injected into a flat 2mm glass mold and -6.0 diopter glass mold. The polymerization was carried out at 35 DEG C for 1 hour, then the temperature was raised to 40 DEG C over 4 hours, then the temperature was elevated to 60 DEG C over 9 hours, the temperature was elevated to 85 DEG C over 3 hours, Respectively. After about 19 hours, it was demolded, washed, and washed.

Thereafter, the annealing was further continued at 120 ° C for 2 hours, and after cooling to room temperature, the refractive index was confirmed. The physical properties are listed in Table 1.

Example 4)

Bisphenol A diallyl carbonate of Synthesis Example 3) was highly viscous and was diluted with 25.00 g of dibutyl malate to 75.00 g. Then, 27% diisopropylperoxy dicarbonate (diethylene glycol bisallyl carbonate Manufactured by Nippon Oil & Fats Co., Ltd.) were mixed and thoroughly mixed for about 1 hour, followed by vacuum degassing for 10 minutes at 1 torr or less. After filtering through 3 filter paper, it was injected into a flat 2mm glass mold and -6.0 diopter glass mold. The polymerization was continued for 35 hours, then the temperature was raised to 40 占 폚 over 4 hours, then the temperature was raised to 60 占 폚 for 9 hours, the temperature was raised to 85 占 폚 for 3 hours, . After about 19 hours, it was demolded, washed, and washed.

Thereafter, the annealing was further continued at 120 ° C for 2 hours, and after cooling to room temperature, the refractive index was confirmed. The physical properties are listed in Table 1.

Comparative Synthesis Example)

A distillation tower was placed in a 1 L four-necked flask, and 180.16 g (2.0 mol) of dimethyl carbonate (DMC) and 232.32 g (4.0 mol) of allyl alcohol were added and 17.00 g of diethylene glycol 0.1%, and the mixture is heated to 120 ° C and refluxed. After about 4 hours of reflux, the temperature of the distillation column was kept below 65 ° C and recovery began. After about 48 hours, the temperature of the distillation column began to increase. As a result, the content of the DMC disappears and the DAC is more than 85%. After removing excess AA and DAC by fractional distillation, the target product, DEGDC layer, was washed twice with 100 g of ultrapure water, distilled under reduced pressure to remove water, and filtered through a membrane filter to obtain about 220.00 g (theoretical yield: about 81% Of the target product.

Comparative Example

Comparative Example 1)

Using 88.90 g of DEGDC prepared in Comparative Synthesis Example 1, 11.10 g of diisopropylperoxy dicarbonate (product diluted in diethylene glycol bisallyl carbonate: product of Nippon Oil and Fats Co., Ltd.) was mixed and stirred for about 1 hour After sufficiently mixing, vacuum degassing was performed for 10 minutes at 1 torr or less. After filtering through 3 filter paper, it was injected into a flat 2mm glass mold and -6.0 diopter glass mold. The polymerization was carried out at 35 DEG C for 1 hour, then the temperature was raised to 40 DEG C over 4 hours, then the temperature was elevated to 60 DEG C over 9 hours, the temperature was elevated to 85 DEG C over 3 hours, Respectively. After about 19 hours, it was demolded, washed, and washed.

Thereafter, the annealing was further continued at 120 ° C for 2 hours, and after cooling to room temperature, the refractive index was confirmed. The refractive index was 1.499, the Abbe number was 58, and the APHA was 65.

Comparative Example 2)

80.00 g of an oligomer obtained by carrying out transesterification reaction by adding 0.4 mol% propylene glycol to diallyl isophthalate and 20.00 g of DEGDC prepared in Synthesis Example 1 were mixed, and then 27% diisopropyl peroxydicarbonate (di Manufactured by Nippon Oil & Fats Co., Ltd.) diluted in ethylene glycol bisallyl carbonate) were mixed, sufficiently mixed for about 1 hour, and vacuum degassed for 10 minutes at 1 torr or less. After filtering through 3 filter paper, it was injected into a flat 2mm glass mold and -6.0 diopter glass mold. The polymerization was carried out at 35 DEG C for 1 hour, then the temperature was raised to 40 DEG C over 4 hours, then the temperature was elevated to 60 DEG C over 9 hours, the temperature was elevated to 85 DEG C over 3 hours, Respectively. After about 19 hours, it was demolded, washed, and washed.

Thereafter, the annealing was further continued at 120 ° C for 2 hours, and after cooling to room temperature, the refractive index was confirmed. The physical properties are listed in Table 1.

division Refractive index Abe number APHA Example 1 1.499 58 15 Example 2 1.547 36 13 Example 3 1.546 35 16 Example 4 1.545 37 15 Comparative Example 1 1.498 57 65 Comparative Example 2 1.546 35 42

The method for producing an allyl carbonate compound according to the present invention solves the problem of toxic gas by the use of phosgene, and the reaction is divided into two stages and the transesterification reaction is carried out, whereby the economical efficiency due to the shortening of the process is excellent and the obtained allyl carbonate compound The resin composition for optical use is excellent in refractive index and Abbe number as well as in color (APHA) and can be usefully used in lenses manufacturing industries such as glasses, various optical industries, and high refractive index resin industries.

Claims (9)

Obtaining a diallyl carbonate compound represented by the following formula (I) by primary ester exchange reaction in a molar ratio of alkylcarbonate compound and unsaturated alcohol at a molar ratio of 1: 2 to 5;
Adding a polyhydric alcohol to the compound of formula (I) at a molar ratio of 2: 4: 1 to effect a second ester exchange reaction;
And then concentrating under reduced pressure distillation after the second transesterification reaction to obtain an allyl carbonate compound represented by the following formula (II).
(I)
R ₁ OCOOR ₁
[Formula II]
(R ₁ OCOO) _n -R ₂
In the above general formulas (I) and (II), R ₁ is an unsaturated alcohol residue,
In the above formula (II), R ₂ is an alcohol residue having a valence of 2 or more, and n is an integer of 1 to 4. The method of claim 1, wherein the alkyl carbonate compound is selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, and dibenzyl carbonate. The method according to claim 1, wherein the R ₁ unsaturated alcohol residue is selected from the group consisting of allyl alcohol, allylcarbitol, methallyl alcohol, crotyl alcohol, 3-butene- ≪ / RTI > wherein the alcohol is selected from the group consisting of alcohols having the formula < RTI ID = 0.0 > The composition of claim 1, wherein R ₂ is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, pentanediol, hexanediol, Divalent alcohols selected from PO adducts; Wherein the alcohol is an alcohol selected from the group consisting of glycerol, trimethylol propane, pentaerythritol, and trivalent alcohol selected from EO and PO adducts thereof. The process according to claim 1, wherein, in the first transesterification reaction,
Tin compounds selected from dibutyl tin oxide, dibutyl tin dilaurate, dibutyl tin dichloride, dibutyl tin diacetate; Metal complexes and alkoxide compounds selected from bisacetylacetonate zinc, bisacetylacetonate manganese, zinc acetate, manganese acetonate; Carbonates or hydrogencarbonates of alkali metals selected from sodium carbonate, sodium hydrogencarbonate and potassium carbonate; Hydroxides or oxides of alkali metals selected from calcium hydroxide, calcium carbonate, magnesium hydroxide and barium hydroxide; Hydroxides or oxides of an alkaline earth metal selected from sodium carbonate, potassium carbonate, potassium chloride, sodium chloride, sodium sulfate, potassium sulfate, sodium carbonate, potassium carbonate and sodium hydrogencarbonate; A salt-combining catalyst of an inorganic acid or an organic acid of an alkali metal; An alkoxide of an alkali metal selected from sodium methoxide, potassium methoxide, sodium ethoxide, potassium methoxide, sodium isopropoxide; An alcohol selected from the reaction of an alkaline earth metal and an alcohol, the reaction of an alkaline earth metal carbide with an alcohol, the reaction of an alkaline earth metal hydride with an alcohol, the reaction of an alkaline earth metal hydroxide with an alcohol, the reaction of an alkaline earth metal oxide with an alcohol, Wherein at least one catalyst selected from the group consisting of catalysts selected from the group consisting of catalysts, catalysts, and catalysts is used.

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