WO2013015055A1 - 芳香族ジオールモノ(メタ)アクリレートの製造方法 - Google Patents
芳香族ジオールモノ(メタ)アクリレートの製造方法 Download PDFInfo
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- the present invention relates to a method for obtaining a highly pure aromatic diol mono (meth) acrylate with little coloring and solvent insolubles, and an economically advantageous production method.
- an aromatic diol mono (meth) acrylate As a method for producing an aromatic diol mono (meth) acrylate, a method of reacting an aromatic diol with (meth) acrylic anhydride or (meth) acrylic acid chloride is known (see, for example, Patent Document 1). ). As a method for obtaining a high-purity aromatic diol mono (meth) acrylate, an aromatic diol mono (meth) acrylate and a by-product fragrance are reacted by reacting an aromatic diol with (meth) acrylic anhydride.
- a high-purity aromatic diol mono (meth) acrylate comprising a step of preparing a solution, and a step of removing the aromatic diol di (meth) acrylate in the solution by bringing the solution into contact with a poor solvent has been reported (Patent Document 2).
- Patent Document 3 The method of Patent Document 3 has been reported as an economically advantageous method.
- an aromatic diol is heated and refluxed together with (meth) acrylic acid in a hydrophobic solvent in the presence of a strong acid, and reacted while separating and removing water distilled off at a reflux temperature of 110 to 160 ° C. It has succeeded in the dehydration esterification reaction of aromatic diol and (meth) acrylic acid directly without using a halide.
- the amount of water removed is measured, and when the amount of water removed reaches an amount corresponding to 40 to 100% of the number of moles of aromatic diol, the heating and refluxing is terminated, whereby the aromatic diol (Meth) acrylate is obtained at a much higher ratio than aromatic diol di (meth) acrylate.
- the aromatic diol mono (meth) acrylate obtained by this method is more colored than the product obtained by the method described in Patent Document 2, and tends to generate a solvent-insoluble component, which is satisfactory in terms of purity. It is not a thing.
- a synthesized aromatic diol mono (meth) acrylate is polymerized and used for a photoresist or the like, it is fatal that a solvent-insoluble component is generated.
- the present invention is economical and colored by obtaining aromatic diol (meth) acrylate at a much higher ratio than aromatic diol di (meth) acrylate without using (meth) acrylic acid chloride.
- An object of the present invention is to provide a high-purity aromatic diol mono (meth) acrylate with little solvent-insoluble content.
- the present inventors have produced an aromatic diol mono (meth) acrylate by esterifying an aromatic diol and (meth) acrylic acid in the presence of a strong acid.
- the reaction In carrying out the reaction at 100 ° C. to 140 ° C. in the presence of a solvent-free or aprotic organic solvent, and further by carrying out an esterification reaction while removing moisture in the reaction system by heating under reduced pressure, the above-mentioned problems are solved. I found that it can be solved.
- the present invention relates to (1) a method for producing an aromatic diol mono (meth) acrylate by esterifying an aromatic diol and (meth) acrylic acid in the presence of a strong acid. Is carried out at 100 to 140 ° C. in the presence of a solvent-free or aprotic organic solvent, and includes a step of carrying out an esterification reaction while removing water in the reaction system by heating under reduced pressure.
- Production method (2) The method for producing an aromatic diol mono (meth) acrylate according to (1), wherein the strong acid is a liquid in the reaction system, (3) The method for producing an aromatic diol mono (meth) acrylate according to (2), wherein the strong acid is selected from p-toluenesulfonic acid, sulfuric acid, or methanesulfonic acid, (4) The molar ratio in the esterification reaction of aromatic diol and (meth) acrylic acid is 3.0 to 4.0 mol of (meth) acrylic acid with respect to 1.0 mol of aromatic diol.
- a highly pure aromatic diol mono (meth) acrylate with little coloring and solvent insolubles can be produced economically advantageously.
- the problem of corroding the reaction vessel and the treatment of the waste liquid containing halide, which are generated when (meth) acrylic acid chloride is used can be solved.
- production of the aromatic diol di (meth) acrylate which byproduces many can be suppressed.
- Aromatic diol di (meth) acrylate as an impurity causes a problem of lowering the solvent solubility of the polymer, and in some cases causing gelation during polymerization.
- the present invention is an economically advantageous production method because an aromatic diol mono (meth) acrylate can be obtained without using an expensive (meth) acrylic anhydride.
- the process for producing an aromatic diol mono (meth) acrylate according to the present invention comprises an aromatic diol and (meth) acrylic acid in the presence of a strong acid, in the absence of a solvent or an aprotic organic solvent, from 100 ° C to 140 ° C. And the esterification reaction is carried out while removing water in the reaction system by heating under reduced pressure.
- aromatic diol used in the method of the present invention refers to a compound having two hydroxyl groups in one benzene ring. Specifically, hydroquinone, resorcin, and catechol. Further, these compounds may have a substituent such as an alkyl group having 1 to 4 carbon atoms or an alkoxy group.
- (Meth) acrylic acid used in the present invention is acrylic acid or methacrylic acid.
- the molar ratio when the aromatic diol is reacted with (meth) acrylic acid is 1.0 to 10.0 mol of (meth) acrylic acid, preferably 1.0 mol to 1.0 mol of aromatic diol. 2.0 to 5.5 moles. More preferably, it is 3.0 to 4.0 mol.
- the amount of (meth) acrylic acid is less than 1.0 mol with respect to 1.0 mol of the aromatic diol, the solubility of the aromatic diol as a raw material is poor, which is not preferable for uniform stirring.
- an aprotic polar organic solvent such as dioxane or tetrahydrofuran can be used. It is better to avoid using water as a solvent.
- the amount of the solvent used is about 0 to 500 parts by mass with respect to 100 parts by mass of the aromatic diol, and can be added for the purpose of improving the solubility of the raw material aromatic diol or for easy control of the reaction temperature.
- hydrophobic solvents such as toluene and xylene are not used. Hydrophobic solvents are effective for the purpose of removing condensed water, but tend to reduce the solubility of aromatic diols and consequently increase the generation of by-product aromatic diol di (meth) acrylates.
- the solvent-insoluble component is a component having a relatively large molecular weight and is a polymer.
- Examples of the strong acid used in the present invention include sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and ion exchange resins such as styrene / divinylbenzene copolymer having a sulfonic acid group as a functional group.
- the amount of strong acid used is preferably 1 to 10 parts by mass with respect to 100 parts by mass of (meth) acrylic acid. When the amount of strong acid used is less than 1 part by mass, the progress of the reaction is slow, which is not preferable. When the amount exceeds 10 parts by mass, a large amount of a basic substance necessary for neutralization is required, which is not preferable.
- solid strong acids such as strongly acidic ion exchange resins such as styrene / divinylbenzene copolymer must be removed by filtration from the reaction system before the purification step after the reaction is completed, which increases the number of reaction steps. Economically unfavorable.
- aromatic diol and aromatic diol mono (meth) acrylate precipitate from the reaction solution, so the solid strong acid must be filtered off from the reaction system. It becomes difficult.
- strong acids that do not require a filtration step that is, strong acids that are liquid in the reaction system are preferred.
- the strong acid include sulfuric acid, p-toluenesulfonic acid, and methanesulfonic acid.
- the reaction is preferably carried out in the presence of a strong acid at 100 to 140 ° C., preferably at 110 to 130 ° C. for about 1 to 24 hours. If the reaction temperature is less than 100 ° C., the progress of the reaction is slow, which is not preferable. Moreover, when reaction temperature exceeds 140 degreeC, there exists a problem which a reaction liquid will color extremely. This is considered to be promoted when the by-product of impurities derived from coloring exceeds 140 ° C.
- hydrolysis is preferential when it exceeds 1.3% by mass. It is preferable to keep the water in the reaction system at 0.5% by mass or less.
- the concentration of water in this case is the concentration relative to the total mass of substances present in the reaction system at the time of measurement.
- an aprotic polar organic solvent is used for the reaction, the mass of the solvent is not considered.
- the timing for starting the removal of condensed water by heating under reduced pressure is not particularly limited. However, when distillation under heating under reduced pressure is performed at the same time as the esterification reaction is started, the main component of the distillate is (meth) acrylic acid as a raw material. Absent. In that respect, it is preferred to start after the esterification has reached the initial equilibrium.
- the reaction is preferably terminated when the production rate of the aromatic diol mono (meth) acrylate is 30 to 70 mol% with respect to the charged aromatic diol, and more preferably 40 to 70 mol%. is there.
- a gas containing oxygen such as air
- a polymerization inhibitor are generally used, and those that do not inhibit the reaction are preferably selected.
- Examples of the method for blowing a gas having a polymerization inhibiting action include a method for blowing into a gas phase of a reaction tank and a method for blowing directly into a liquid phase.
- the flow rate of blowing is not particularly limited as long as it is an amount that can prevent polymerization. For example, in the case of air, an amount of 50 mL / min or less is sufficiently effective for 1 L of reaction liquid.
- the strong acid After completing the esterification reaction, it is preferable to neutralize the strong acid with a basic substance.
- a basic substance for neutralization, for example, triethylamine, tributylamine, triethanolamine or the like can be used.
- the neutralized reaction solution contains unreacted aromatic diol, aromatic diol mono (meth) acrylate, and by-product aromatic diol di (meth) acrylate.
- the content of the unreacted aromatic diol can be reduced.
- crude crystals are precipitated in water.
- water is used until the unreacted aromatic diol becomes 1.0 mol% or less with respect to 100 mol% in total of the unreacted aromatic diol, aromatic diol mono (meth) acrylate and aromatic diol di (meth) acrylate. It is preferable to repeat the washing.
- unreacted aromatic diol remains in excess of 1.0 mol%, the purity of the aromatic diol mono (meth) acrylate finally obtained is lowered, and when this is used as a raw material, the aromatic diol is polymerized. Is not preferable because it acts as a polymerization inhibitor.
- the aromatic diol di (meth) acrylate can be removed by washing the reaction solution with a hydrophobic solvent.
- a hydrophobic solvent used for washing include hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, and the like, and at least one of them can be used.
- the hydrophobic solvent here is a solvent for the aromatic diol di (meth) acrylate and a poor solvent for the aromatic diol mono (meth) acrylate. Therefore, the aromatic diol mono (meth) acrylate is precipitated as a crude crystal by adding a hydrophobic solvent, and this is collected.
- the total amount of unreacted aromatic diol, aromatic diol mono (meth) acrylate and aromatic diol di (meth) acrylate is 100 mol%, until the aromatic diol di (meth) acrylate is 1.0 mol% or less. It is preferable to repeat the washing with an ionic solvent.
- the aromatic diol di (meth) acrylate remains in excess of 1.0 mol%, the purity of the finally obtained aromatic diol mono (meth) acrylate is lowered, and when this is used as a raw material for polymerization, the aromatic diol di (meth) acrylate is reduced. Since (meth) acrylate is a cross-linking component, the molecular weight of the polymer becomes abnormally large, or in some cases, gelation may occur, or solvent solubility may be deteriorated.
- Either washing with water or washing with a hydrophobic solvent may be performed first as the washing order, but an optimum method can be selected depending on the composition when the reaction is completed.
- the water washing is performed first, it is preferable to dissolve the crude crystals precipitated in water with a solvent after the water washing is completed.
- the solvent used for dissolution include toluene, xylene, or a mixture thereof. These are poor solvents for the starting aromatic diol, but they are a solvent for the crude crystals after the completion of water washing. By using such a solvent, the yield of the aromatic diol mono (meth) acrylate composition finally obtained is improved.
- the solvent is preferably dissolved in 50 to 300 parts by mass, more preferably 100 to 200 parts by mass, with heating as necessary, with respect to 100 parts by mass of the crude crystal. Good.
- the water contained in the crude crystals is preferably separated and removed from the solvent layer containing the crude crystals. Thereafter, the solvent layer is washed with the hydrophobic solvent.
- a method in which the solvent layer in which the crude crystals are dissolved is put into the hydrophobic solvent, or a method in which the hydrophobic solvent is added to the solvent layer in which the crude crystals are dissolved.
- crystallization of aromatic diol mono (meth) acrylate is deposited by dissolving a crude crystal with a solvent and making a hydrophobic solvent contact the solvent in which this crude crystal dissolved.
- the purity of the aromatic diol mono (meth) acrylate finally obtained is improved.
- the reaction solution and the hydrophobic solvent are brought into contact with each other to produce a crude crystal containing an aromatic diol mono (meth) acrylate and an unreacted aromatic diol.
- the crude crystals are washed with water to obtain aromatic diol mono (meth) acrylate crystals.
- the aromatic diol mono (meth) acrylate obtained by the production method of the present invention is solid at normal temperature, is relatively stable to heat and light, and has a general polymerization property (meth) acrylate. It has the feature that it is equivalent.
- a polymer When a polymer is synthesized using the aromatic diol mono (meth) acrylate obtained by the production method of the present invention, it is excellent in solvent solubility, alkali solubility, transparency, heat discoloration, etc., high Tg, and high thermal decomposition temperature. A polymer with a high refractive index is obtained. Therefore, it can be applied to alkali developing type photoresists used for semiconductor manufacturing, display members, printing plate making materials, and the like, and protective films requiring transparency and heat discoloration. It is also useful as a curing agent such as an epoxy resin.
- the aromatic diol mono (meth) acrylate obtained by the production method of the present invention has good copolymerizability with not only a homopolymer but also other unsaturated group-containing polymerizable compound.
- unsaturated group-containing polymerizable compounds include, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, maleic anhydride, fumaric anhydride, Citraconic anhydride, mesaconic anhydride, itaconic anhydride, vinyl benzoic acid, o-carboxyphenyl (meth) acrylate, m-carboxyphenyl (meth) acrylate, p-carboxyphenyl (meth) acrylate, o-carboxyphenyl (meth) Acrylamide, m-carboxyphenyl (meth) acrylamide, p-carboxyphenyl
- Styrene ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, 1,3-butadiene, isoprene, 2,3-dimethyl -1,3-butadiene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, o-hydroxyphenyl (meth) acrylamide, m-hydroxyphenyl (meth) acrylamide, p-hydroxyphenyl ( (Meth) acrylamide, 3,5-dimethyl-4-hydroxybenzyl (meth) acrylamide, phenylmaleimide, hydroxyphenylmaleimide, cyclohexylmaleimide, benzylmaleimide, trifluoromethyl
- Polymerization uses azo initiators typified by azobisisobutyronitrile, organic peroxides typified by benzoyl peroxide, etc., using methanol, ethanol, 1-propanol, isopropyl alcohol, butanol, ethylene glycol , Acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, toluene, xylene, ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, acetic acid 3-methoxybutyl, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether In organic solvents such as diacetate, diethylene glycol monobutyl
- composition ratio By 1 H-NMR measurement, each component was calculated with the total of aromatic diol, aromatic diol mono (meth) acrylate, and aromatic diol di (meth) acrylate being 100 mol%.
- Hue The degree of coloring at the end of the reaction was visually observed. ⁇ : Slightly colored, ⁇ : Very colored (turbidity) The reaction solution at the end of the reaction was diluted 4 times by mass with propylene glycol monomethyl ether acetate and visually observed. ⁇ : Transparent, ⁇ : Cloudy
- Example 1 Synthesis of 4-hydroxyphenyl methacrylate A 1 L separable flask equipped with a condenser, thermometer, and stirring blades was charged with 100 parts by mass of hydroquinone, 235 parts by weight of methacrylic acid, and 4 parts by weight of p-toluenesulfonic acid. The reaction was started at ° C. When the reaction reached equilibrium and the product composition became constant, the reaction was continued while distilling off under reduced pressure at ⁇ 80 kPa so that the water content in the system was maintained at 0.2 mass% or less.
- Example 2 Synthesis of 4-hydroxyphenyl methacrylate 100 parts by mass of hydroquinone, 235 parts by mass of methacrylic acid in a 1 L separable flask equipped with a condenser, a thermometer, and stirring blades. 10 parts by mass of DRY was charged and the reaction was started at 120 ° C. When the reaction reached equilibrium and the product composition became constant, the reaction was continued while distilling off under reduced pressure at ⁇ 80 kPa so that the water content in the system was maintained at 0.2 mass% or less. When the proportion of 4-hydroxyphenyl methacrylate reached 56.8% of the number of moles charged with hydroquinone, the system was returned to normal pressure and cooled to complete the esterification reaction. The composition ratio, hue, and turbidity are as shown in Table 1.
- Example 3 Synthesis of 4-hydroxyphenyl methacrylate A 1 L separable flask equipped with a condenser, thermometer and stirring blade was charged with 100 parts by mass of hydroquinone, 86 parts by weight of methacrylic acid, and 4 parts by weight of p-toluenesulfonic acid, and reacted at 125 ° C. Started. When the reaction reached equilibrium and the composition of the product became constant, the reaction was continued while distilling off under reduced pressure at ⁇ 80 kPa. When the proportion of 4-hydroxyphenyl methacrylate reached 34.4% of the number of moles charged with hydroquinone, the system was returned to normal pressure and cooled to complete the esterification reaction. The composition ratio, hue, and turbidity are as shown in Table 1.
- the obtained polymer solution was filtered through a 0.1 ⁇ m Teflon (registered trademark) filter.
- the film was applied to a glass plate with a 50 ⁇ m applicator and dried on a 110 ° C. hot plate for 90 seconds to obtain a coating film having a thickness of 3 ⁇ m.
- permeability in wavelength 400nm when it heat-processes in 230 degreeC oven for 0, 1, 2, 3 hours was measured with the ultraviolet visible spectrophotometer, respectively.
- the results are shown in FIG. A polymer using uncolored hydroxyphenyl methacrylate as a raw material is good with little change in transmittance even when heated.
- Comparative Reference Example 1 The reaction solution obtained in Comparative Example 1 was purified in the same manner as in Reference Example 1 to obtain a brown powder. Polymerization was performed in the same manner as in Reference Example 1 using the obtained brown powder to obtain a polymer solution. Subsequently, the obtained polymer solution was filtered with a 0.1 ⁇ m Teflon (registered trademark) filter, but could not be filtered due to clogging. This is considered due to the high turbidity.
- Teflon registered trademark
- Comparative Reference Example 2 The reaction solution obtained in Comparative Example 3 was treated and purified in the same manner as in Reference Example 1 to obtain a brown powder. Polymerization was performed in the same manner as in Reference Example 1 using the obtained brown powder to obtain a polymer solution. Subsequently, the transmittance of the coating film was measured in the same manner as in Reference Example 1 using the obtained polymer solution. The results are shown in FIG. A polymer using colored hydroxyphenyl methacrylate as a raw material has a large change in transmittance when heated, and cannot be applied to uses requiring transparency.
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Abstract
Description
また、高純度の芳香族ジオールモノ(メタ)アクリレートを得る方法として、芳香族ジオールと(メタ)アクリル酸無水物とを反応させて、芳香族ジオールモノ(メタ)アクリレートと副生成物である芳香族ジオールジ(メタ)アクリレートとを含有する反応液を調製する工程、前記反応溶液中の未反応芳香族ジオールを水洗浄により除去して粗結晶を調製する工程、前記粗結晶を溶媒で溶解させて溶解液を調製する工程、及び前記溶解液を貧溶媒と接触させることにより前記溶解液中の前記芳香族ジオールジ(メタ)アクリレートを除去する工程を含む、高純度の芳香族ジオールモノ(メタ)アクリレートを得る方法が報告されている(特許文献2)。
さらに、芳香族ジオールを、疎水性溶剤中強酸触媒存在下(メタ)アクリル酸と加熱還流させ、溜出水を除去し、除去水の量が芳香族ジオールのモル数の40~100%に達したとき終了する芳香族ジオールモノ(メタ)アクリレートの製造方法が報告されている(特許文献3)。
(2)前記強酸は反応系内で液体である、(1)の芳香族ジオールモノ(メタ)アクリレートの製造方法、
(3)前記強酸が、p-トルエンスルホン酸、硫酸、またはメタンスルホン酸から選択される(2)の芳香族ジオールモノ(メタ)アクリレートの製造方法、
(4)芳香族ジオールと(メタ)アクリル酸とをエステル化反応させる際のモル比が、芳香族ジオール1.0モルに対し、(メタ)アクリル酸が3.0~4.0モルである、請求項(1)~(3)のいずれかに記載の芳香族ジオールモノ(メタ)アクリレートの製造方法、
(5)仕込みの芳香族ジオールに対する、芳香族ジオールモノ(メタ)アクリレートの生成率が40~70モル%になった時点でエステル化反応を終了させる、(1)~(4)のいずれかに記載の芳香族ジオールモノ(メタ)アクリレートの製造方法、
(6)前記加熱減圧は、前記エステル化反応と、反応系内の水分とエステル化物との加水分解反応が平衡状態となった後に開始する、(1)~(5)のいずれかに記載の芳香族ジオールモノ(メタ)アクリレートの製造方法、
(7)空気を吹き込みながらエステル化反応させる(1)~(6)のいずれかに記載の芳香族ジオールモノ(メタ)アクリレートの製造方法である。
本発明による芳香族ジオールモノ(メタ)アクリレートの製造方法は、芳香族ジオールおよび(メタ)アクリル酸を、強酸の存在下に、無溶剤又は非プロトン性有機溶剤の存在下で100℃から140℃で反応を行い、更に反応系内の水分を加熱減圧により除去しながらエステル化反応させることを特徴とする。
また、疎水性溶剤での洗浄を先に行った場合は、反応溶液と疎水性溶剤を接触させて、芳香族ジオールモノ(メタ)アクリレートおよび未反応の芳香族ジオールを含む粗結晶を生成させて、この粗結晶を水で洗浄することで、芳香族ジオールモノ(メタ)アクリレートの結晶を得る。
1H-NMR測定により、芳香族ジオール、芳香族ジオールモノ(メタ)アクリレート、及び芳香族ジオールジ(メタ)アクリレートの合計を100モル%として、各成分を算出した。
(色相)
反応終了時点での着色具合を目視で観察した。
○:僅かに着色、×:かなり着色
(濁度)
反応終了時点の反応液をプロピレングリコールモノメチルエーテルアセテートにより4質量倍に希釈して目視で観察した。
○:透明、×:濁り
4-ヒドロキシフェニルメタクリレートの合成
冷却器、温度計、攪拌羽を取り付けた1Lセパラブルフラスコにヒドロキノン100質量部、メタクリル酸235質量部、p-トルエンスルホン酸4質量部を仕込み、空気を吹き込みながら120℃で反応を開始した。反応が平衡に達し、生成物の組成が一定になったところで、系内の水分が0.2質量%以下を維持するように、-80kPaで減圧留去しながら反応を継続した。4-ヒドロキシフェニルメタクリレートの割合がヒドロキノンを仕込んだモル数の49.9%になったところで系内を常圧に戻し、冷却してエステル化反応を終了した。組成比、色相、濁度は表1に示すとおりである。
4-ヒドロキシフェニルメタクリレートの合成
冷却器、温度計、攪拌羽を取り付けた1Lセパラブルフラスコにヒドロキノン100質量部、メタクリル酸235質量部、オルガノ(株)製強酸性イオン交換樹脂アンバーリスト15.DRY10質量部を仕込み、120℃で反応を開始した。反応が平衡に達し、生成物の組成が一定になったところで、系内の水分が0.2質量%以下を維持するように、-80kPaで減圧留去しながら反応を継続した。4-ヒドロキシフェニルメタクリレートの割合がヒドロキノンを仕込んだモル数の56.8%になったところで系内を常圧に戻し、冷却してエステル化反応を終了した。組成比、色相、濁度は表1に示すとおりである。
4-ヒドロキシフェニルメタクリレートの合成
冷却器、温度計、攪拌羽を取り付けた1Lセパラブルフラスコにヒドロキノン100質量部、メタクリル酸86質量部、p-トルエンスルホン酸4質量部を仕込み、125℃で反応を開始した。反応が平衡に達し、生成物の組成が一定になったところで-80kPaで減圧留去しながら反応を継続した。4-ヒドロキシフェニルメタクリレートの割合がヒドロキノンを仕込んだモル数の34.4%になったところで系内を常圧に戻し、冷却してエステル化反応を終了した。組成比、色相、濁度は表1に示すとおりである。
4-ヒドロキシフェニルメタクリレートの合成
還流冷却器、水分離器、温度計及び撹拌羽を取り付けた1Lセパラブルフラスコに、ヒドロキノン100質量部、メタクリル酸86質量部、p-トルエンスルホン酸4質量部、トルエン100質量部を仕込み、還流させて反応を行った。120℃でトルエンと水の共沸混合物の留出が始まり、水分離器で分離した水を系外へ除去しながら、120℃で5時間反応させた。4-ヒドロキシフェニルメタクリレートの割合がヒドロキノンを仕込んだモル数の37.0%になったところで系内を常圧に戻し、冷却してエステル化反応を終了した。組成比、色相、濁度は表1に示すとおりである。
4-ヒドロキシフェニルメタクリレートの合成
還流冷却器、水分離器、温度計及び撹拌羽を取り付けた1Lセパラブルフラスコに、ヒドロキノン100質量部、メタクリル酸86質量部、オルガノ(株)製強酸性イオン交換樹脂アンバーリスト15.DRY10質量部、トルエン100質量部を仕込み、還流させて反応を行った。120℃でトルエンと水の共沸混合物の留出が始まり、水分離器で分離した水を系外へ除去しながら、120℃で16時間反応させた。4-ヒドロキシフェニルメタクリレートの割合がヒドロキノンを仕込んだモル数の51.3%になったところで、冷却してエステル化反応を終了した。組成比、色相、濁度は表1に示すとおりである。疎水性溶剤のトルエンを使用した場合、ヒドロキノンジメタクリレートの割合が多くなり、精製工程で大量の洗浄溶剤を必要とすることから経済的ではない。
4-ヒドロキシフェニルメタクリレートの合成
冷却器、温度計、攪拌羽を取り付けた1Lセパラブルフラスコにヒドロキノン100質量部、メタクリル酸86質量部、p-トルエンスルホン酸4質量部を仕込み、145℃で1.5時間反応したところ、反応生成物の割合が一定になったため、-80kPaで減圧蒸留して系内の水分を除去した。再び、常圧下、145℃で1.5時間反応したところ、反応生成物の割合が一定になったため、-80kPaで減圧蒸留して系内の水分を除去した。この時、系内の水分は0.5~1.0%質量%で推移した。この操作を繰り返し行い、4-ヒドロキシフェニルメタクリレートの割合がヒドロキノンを仕込んだモル数の35.1%になったところでエステル化反応を終了した。組成比、色相、濁度は表1に示すとおりである。
4-ヒドロキシフェニルメタクリレートの精製
実施例1で得た反応液をトリエチルアミンで中和して、メチルシクロヘキサンでの洗浄を繰り返し行い、p-フェニレンジメタクリレートのモル分率が0.1%になったところで、メチルシクロヘキサンでの洗浄を終了した。ここで、p-フェニレンジメタクリレートが除去された粗結晶が得られた。次に、水によるこの粗結晶の洗浄を繰り返し行い、未反応の芳香族ジオールのモル分率が0.2%になったところで、水洗浄を終了した。引き続き脱液、乾燥することで52.6質量部(収率:32.5%)の白色結晶を得た。
ヒドロキノン:4-ヒドロキシフェニルメタクリレート:p-フェニレンジメタクリレートのモル分率は、0.2:99.7:0.1であった。
冷却器、温度計、攪拌羽を取り付けた1Lセパラブルフラスコに、得られた白色結晶100質量部、プロピレングリコールモノエチルエーテルアセテート300質量部、アゾビスイソブチロニトリル4.0質量部を仕込み、70℃で6時間反応し、ポリマー溶液を得た。
得られたポリマー溶液を0.1μmのテフロン(登録商標)フィルターで濾過を行った。ガラス板に50μmのアプリケーターで塗布し、110℃のホットプレートで90秒、乾燥して膜厚3μmの塗膜を得た。更に230℃のオーブンで0、1、2、3時間加熱処理したときの波長400nmでの透過率を紫外可視分光光度計でそれぞれ測定した。結果を図1に示す。着色のないヒドロキシフェニルメタクリレートを原料に使用したポリマーは、加熱しても透過率の変化が少なく良好である。
比較例1で得られた反応液を参考例1と同様に処理して精製を行い、褐色粉末を得た。得られた褐色粉末を用いて参考例1と同様に重合を行い、ポリマー溶液を得た。引き続き、得られたポリマー溶液を0.1μmのテフロン(登録商標)フィルターで濾過を試みたが、目詰まりのため濾過が出来なかった。これは、濁度が高いためと考えられる。
比較例3で得られた反応液を参考例1と同様に処理して精製を行い、褐色粉末を得た。得られた褐色粉末を用いて参考例1と同様に重合を行い、ポリマー溶液を得た。引き続き、得られたポリマー溶液を用いて参考例1と同様に塗膜の透過率を測定した。結果を図1に示す。着色のあるヒドロキシフェニルメタクリレートを原料に使用したポリマーは、加熱すると透過率の変化が大きく、透明性を必要とする用途への適用が出来ない。
Claims (7)
- 芳香族ジオールおよび(メタ)アクリル酸を、強酸の存在下にエステル化反応させて芳香族ジオールモノ(メタ)アクリレートを製造する方法であって、該方法が無溶剤又は非プロトン性有機溶剤の存在下で100から140℃で行われ、反応系内の水分を加熱減圧により除去しながらエステル化反応させる工程を含む、芳香族ジオールモノ(メタ)アクリレートの製造方法。
- 前記強酸は反応系内で液体である、請求項1に記載の芳香族ジオールモノ(メタ)アクリレートの製造方法。
- 前記強酸が、p-トルエンスルホン酸、硫酸、またはメタンスルホン酸から選択される請求項2に記載の芳香族ジオールモノ(メタ)アクリレートの製造方法。
- 芳香族ジオールと(メタ)アクリル酸とをエステル化反応させる際のモル比が、芳香族ジオール1.0モルに対し、(メタ)アクリル酸が3.0~4.0モルである、請求項1~3のいずれか一項に記載の芳香族ジオールモノ(メタ)アクリレートの製造方法。
- 仕込みの芳香族ジオールに対する、芳香族ジオールモノ(メタ)アクリレートの生成率が40~70モル%になった時点でエステル化反応を終了させる、請求項1~4のいずれか一項に記載の芳香族ジオールモノ(メタ)アクリレートの製造方法。
- 前記加熱減圧は、前記エステル化反応と、反応系内の水分とエステル化物との加水分解反応が平衡状態となった後に開始する、請求項1~5のいずれか一項に記載の芳香族ジオールモノ(メタ)アクリレートの製造方法。
- 空気を吹き込みながらエステル化反応させる請求項1~6のいずれか一項に記載の芳香族ジオールモノ(メタ)アクリレートの製造方法。
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JP7367761B2 (ja) | 2019-05-30 | 2023-10-24 | 株式会社レゾナック | 樹脂組成物および樹脂膜 |
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