JPH0410465B2 - - Google Patents
Info
- Publication number
- JPH0410465B2 JPH0410465B2 JP7008984A JP7008984A JPH0410465B2 JP H0410465 B2 JPH0410465 B2 JP H0410465B2 JP 7008984 A JP7008984 A JP 7008984A JP 7008984 A JP7008984 A JP 7008984A JP H0410465 B2 JPH0410465 B2 JP H0410465B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- methacrylate
- mol
- glycerol
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000006243 chemical reaction Methods 0.000 claims description 39
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 15
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims 3
- 230000018044 dehydration Effects 0.000 description 15
- 238000006297 dehydration reaction Methods 0.000 description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 10
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- MIHQWNKDHBLQEZ-UHFFFAOYSA-N 3-tert-butyl-2-methylphenol Chemical compound CC1=C(O)C=CC=C1C(C)(C)C MIHQWNKDHBLQEZ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明はグリセロールアクリレートまたはメタ
クリレートの製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing glycerol acrylate or methacrylate.
一般に、グリセロールアクリレートまたはメタ
クリレートは感光性樹脂を中心に原料モノマーと
して広い分野で使用されており、その製造法とし
ては、(1)グリシドールとアクリル酸またはメタク
リル酸との反応および(2)グリセリンとアクリル酸
またはメタクリル酸との反応が知られている。こ
れから従来から知られた製造法では、反応の際に
副生物が多量に生成するため、得られるグリセロ
ールアクリレートまたはメタクリレートは純度が
低く、しかも色相が悪いものであり、これらを使
用した樹脂製品の色相の悪化、品質の低下などの
問題点がある。 In general, glycerol acrylate or methacrylate is used in a wide range of fields as a raw material monomer, mainly for photosensitive resins, and its manufacturing methods include (1) reaction of glycidol with acrylic acid or methacrylic acid, and (2) reaction of glycerin with acrylic acid. Reactions with acids or methacrylic acid are known. In conventional production methods, large amounts of by-products are produced during the reaction, resulting in low purity glycerol acrylate or methacrylate and poor color, and the color of resin products using these products is poor. There are problems such as deterioration of quality and deterioration of quality.
本発明者らは上記の問題点の解決をめざして、
グリセロールアクリレートまたはメタクリレート
の製造法について鋭意研究した結果、グリシジル
アクリレートまたはメタクリレートを特定条件下
でエポキシ基の加水分解反応を行つて精製すれ
ば、高品質のグリセロールアクリレートまたはメ
タクリレートが高純度で得られることを見出して
本発明を完成するにいたつた。 The present inventors aim to solve the above problems,
As a result of intensive research into the production method of glycerol acrylate or methacrylate, we found that high-quality glycerol acrylate or methacrylate can be obtained with high purity by purifying glycidyl acrylate or methacrylate by performing a hydrolysis reaction of the epoxy group under specific conditions. This discovery led to the completion of the present invention.
すなわち本発明は、酸触媒、重合禁止剤および
水からなる混合液中にグリシジルアクリレートま
たはメタクリレート添加して反応させ、反応終了
後に酸価を0.3〜0.8に調整したのち低温で真空下
に脱水することを特徴とするグリセロールアクリ
レートまたはメタクリレートの製造法である。 That is, the present invention involves adding glycidyl acrylate or methacrylate to a mixed solution consisting of an acid catalyst, a polymerization inhibitor, and water, causing a reaction, and after the reaction is completed, the acid value is adjusted to 0.3 to 0.8, and then dehydration is performed under vacuum at a low temperature. A method for producing glycerol acrylate or methacrylate, characterized by:
本発明における酸触媒、重合禁止剤および水か
らなる混合液中へのグリシジルアクリレートまた
はメタクリレートの添加は、滴下方法を採用する
と便利である。 In the present invention, it is convenient to add glycidyl acrylate or methacrylate to a mixed solution consisting of an acid catalyst, a polymerization inhibitor, and water by a dropwise addition method.
本発明において用いる酸触媒としては、硫酸、
硝酸、パラトルエンスルホン酸、スルホン酸型イ
オウ交換樹脂などがあげられ、それら触媒の使用
量はグリシジルアクリレートまたはメタクリレー
ト１モルに対して0.0001〜0.05モル、好ましくは
0.0005〜0.02モルである。使用量が0.0001モルよ
り少ないと触媒としての作用が不十分であり、
0.05モルより多いと副生物を生成し易くなる。 The acid catalyst used in the present invention includes sulfuric acid,
Examples include nitric acid, paratoluenesulfonic acid, and sulfonic acid type sulfur exchange resins, and the amount of these catalysts used is 0.0001 to 0.05 mol, preferably 0.0001 to 0.05 mol per mol of glycidyl acrylate or methacrylate.
It is 0.0005 to 0.02 mole. If the amount used is less than 0.0001 mol, the catalyst action will be insufficient,
When the amount is more than 0.05 mol, by-products are likely to be generated.
重合禁止剤としては、フエノチアジン、ヒドロ
キノン、ヒドロキノンモノメチルエーテル、ｔ−
ブチルクレゾールなどが用いられ、その使用量は
グリシジルアクリレートまたはメタクリレートに
対して50〜１，000ppmが適している。これより
少ない使用量では重合禁止効果が認められず、逆
に多量に使用しても顕著な改善はみられず経済的
に不利である。 As the polymerization inhibitor, phenothiazine, hydroquinone, hydroquinone monomethyl ether, t-
Butyl cresol or the like is used, and the appropriate amount is 50 to 1,000 ppm relative to glycidyl acrylate or methacrylate. If the amount used is less than this, no polymerization inhibiting effect will be observed, and if it is used in a larger amount, no significant improvement will be observed, which is economically disadvantageous.
混合液に用いる水の量は特に限定されないが、
反応の効率や反応後の精製を考慮すると、グリシ
ジルアクリレートまたはメタクリレート１モルに
対して８〜30モル、好ましくは10〜20モルであ
り、反応促進剤を添加する場合には３〜20モル、
好ましくは５〜15モルである。 The amount of water used in the mixed solution is not particularly limited, but
Considering reaction efficiency and post-reaction purification, the amount is 8 to 30 mol, preferably 10 to 20 mol, per 1 mol of glycidyl acrylate or methacrylate, and 3 to 20 mol when a reaction accelerator is added.
Preferably it is 5 to 15 moles.
本発明においては、反応の促進をはかる目的で
混合液中にグリシドール、グリセロールアクリレ
ート、グリセロールメタクリレートまたはグリセ
リンを添加することが好ましい。これらの添加量
はグリシジルアクリレートまたはメタクリレート
１モルに対して0.1〜0.5モルが適している。添加
量が0.1モルより少ない場合には反応促進の効果
がみられず、逆に0.5モルより多い場合には反応
促進効果はほぼ一定となり、多量に用いても工業
的なメリツトがない。 In the present invention, it is preferable to add glycidol, glycerol acrylate, glycerol methacrylate, or glycerin to the mixed solution for the purpose of promoting the reaction. The appropriate amount of these additives to be added is 0.1 to 0.5 mol per mol of glycidyl acrylate or methacrylate. If the amount added is less than 0.1 mol, no effect of promoting the reaction is observed, and conversely, if the amount added is more than 0.5 mol, the reaction promoting effect is almost constant, and there is no industrial advantage even if it is used in a large amount.
混合液中にグリシジルアクリレートまたはメタ
クリレートを添加して反応する温度は60〜90℃が
好ましい。反応温度が60℃より低いと反応速度が
遅く、また90℃より高いと副生物が生成し易くな
り好ましくない。 The temperature at which glycidyl acrylate or methacrylate is added to the mixed solution and reacted is preferably 60 to 90°C. If the reaction temperature is lower than 60°C, the reaction rate is slow, and if it is higher than 90°C, by-products are likely to be produced, which is not preferable.
また、添加物に要する時間は３〜８時間であ
り、反応促進剤を用いる場合には1.5〜５時間で
ある。添加終了後反応を完結させるために、さら
に0.5〜２時間反応を続けることが好ましい。し
たがつて反応は通常２〜10時間で終了する。 Further, the time required for additives is 3 to 8 hours, and when using a reaction accelerator, it is 1.5 to 5 hours. In order to complete the reaction after the addition is completed, it is preferable to continue the reaction for an additional 0.5 to 2 hours. Therefore, the reaction is usually completed in 2 to 10 hours.
本発明においては反応終了後にアルカリ水溶液
を加えて反応液の酸価を0.3〜0.8に調整する。酸
価を0.3より低くすると後の工程において色相が
悪くなり、また0.8より高くすると系内に触媒が
残存して副生物の顕著な生成が起こつてしまう。
この際に用いるアルカリとしては、水酸化ナトリ
ウム、水酸化カリウム、炭酸ナトリウムなど通常
アルカリ性物質として知られるものを用いること
ができる。そのアルカリ水溶液の濃度としては、
後の工程での脱水、副生物の生成などを考慮して
0.1〜30％の濃度が好ましい。アルカリ水溶液を
添加する温度は30℃以下がよく、これより高温だ
と副生物が生成し易くなり好ましくない。 In the present invention, after the reaction is completed, an aqueous alkaline solution is added to adjust the acid value of the reaction solution to 0.3 to 0.8. If the acid value is lower than 0.3, the hue will deteriorate in subsequent steps, and if it is higher than 0.8, the catalyst will remain in the system, resulting in significant production of by-products.
As the alkali used in this case, those commonly known as alkaline substances such as sodium hydroxide, potassium hydroxide, and sodium carbonate can be used. The concentration of the alkaline aqueous solution is
Considering dehydration, by-product generation, etc. in later processes.
Concentrations of 0.1-30% are preferred. The temperature at which the alkaline aqueous solution is added is preferably 30°C or lower; higher temperatures are undesirable because by-products tend to form.
酸価を調整した後に10〜40℃、好ましくは15〜
35℃の低温で２〜40mmHgの減圧下に脱水を行う。
脱水温度が10℃より低い場合には脱水効率が悪
く、また40℃より高い場合には副生物である二量
体、三量体などが生成し易くなる。脱水は上記条
件を満足できる普通に使用される方法および装置
を用いて行うことができる。例えば薄膜蒸留器や
減圧脱水器を用いることができる。脱水が進行す
ると中和による生成塩が析出してくることがあ
る。塩が析出してくる場合には30℃以下の低温で
別して取り除いて本発明のグリセロールアクリ
レートまたはメタクリレートを得る。 10~40℃, preferably 15~40℃ after adjusting the acid value
Dehydration is performed at a low temperature of 35°C under reduced pressure of 2 to 40 mmHg.
If the dehydration temperature is lower than 10°C, the dehydration efficiency is poor, and if it is higher than 40°C, by-products such as dimers and trimers are likely to be produced. Dehydration can be carried out using commonly used methods and equipment that meet the above conditions. For example, a thin film distiller or a vacuum dehydrator can be used. As dehydration progresses, salts produced by neutralization may precipitate. If salt precipitates, it is removed separately at a low temperature of 30° C. or lower to obtain the glycerol acrylate or methacrylate of the present invention.
本発明の方法により得られるグリセロールアク
リレートまたはメタクリレートは純度が高く、か
つ色相が良好なだけでなく、保存安定性にもすぐ
れているので、感光性樹脂をはじめとする巾広い
分野における原料モノマーとして利用できるもの
である。 Glycerol acrylate or methacrylate obtained by the method of the present invention not only has high purity and good hue, but also has excellent storage stability, so it can be used as a raw material monomer in a wide range of fields including photosensitive resins. It is possible.
つぎに、本発明を実施例により説明する。 Next, the present invention will be explained by examples.
実施例 １
温度計、撹拌器、還流管および滴下ロートを備
え付けた500ml四つ口フラスコに水270ｇ（15モ
ル）、硫酸0.1ｇ（0.001モル）およびヒドロキノ
ン0.014ｇをとり、グリシジルメタクリレート
142.2ｇ（１モル）を滴下しながら70〜80℃で５
時間反応を行い、さらに１時間反応を続けた。次
に30℃に温度を下げて15％水酸化ナトリウム水溶
液を加え、反応液の酸価を0.5に調整した。ヒド
ロキノン0.014ｇを添加した後、少量の空気を通
気しながら20〜25℃，３〜40mmHgの低温減圧下
で脱水した。中和により生成塩が析出してきたの
で25℃にて過して取り除いた。得られた反応生
成物は153.8ｇであり、ガスクロマトグラフイー
による純度測定の結果はグリセロールメタクリレ
ートが95.6％であつた。この反応生成物の色相は
APHA50であつた。Example 1 In a 500 ml four-necked flask equipped with a thermometer, stirrer, reflux tube, and dropping funnel, 270 g (15 mol) of water, 0.1 g (0.001 mol) of sulfuric acid, and 0.014 g of hydroquinone were added, and glycidyl methacrylate was added.
142.2g (1 mol) was added dropwise at 70-80°C.
The reaction was carried out for an hour and continued for an additional hour. Next, the temperature was lowered to 30°C, and a 15% aqueous sodium hydroxide solution was added to adjust the acid value of the reaction solution to 0.5. After adding 0.014 g of hydroquinone, dehydration was carried out at a low temperature of 20 to 25° C. and a reduced pressure of 3 to 40 mmHg while a small amount of air was passed through. The salts formed during neutralization precipitated and were removed by filtration at 25°C. The obtained reaction product weighed 153.8 g, and its purity was determined by gas chromatography to be 95.6% glycerol methacrylate. The hue of this reaction product is
It was APHA50.
比較例 １
実施例１と同じ反応容器にグリシジルメタクリ
レート142.2ｇ（１モル）、水270ｇ（15モル）、硫
酸0.1ｇ（0.001モル）およびヒドロキノン0.014ｇ
をとり、70〜80℃で６時間反応を行つた。反応終
了後、実施例１と同様に酸価を調整して低温減圧
脱水した。得られた反応生成物は154.0ｇであり、
グリセロールメタクリレートが89.5％含まれてい
た。Comparative Example 1 In the same reaction vessel as in Example 1, 142.2 g (1 mol) of glycidyl methacrylate, 270 g (15 mol) of water, 0.1 g (0.001 mol) of sulfuric acid, and 0.014 g of hydroquinone were added.
The reaction was carried out at 70-80°C for 6 hours. After the reaction was completed, the acid value was adjusted in the same manner as in Example 1, and dehydration was performed at low temperature under reduced pressure. The reaction product obtained was 154.0g,
It contained 89.5% glycerol methacrylate.
比較例 ２
実施例１と同様に反応を行い、反応終了後に反
応液の酸価を０に調整し、実施例１と同様に脱水
を行つた。得られた反応生成物の色相はガードナ
ー３であつた。Comparative Example 2 A reaction was conducted in the same manner as in Example 1, and after the reaction was completed, the acid value of the reaction solution was adjusted to 0, and dehydration was performed in the same manner as in Example 1. The color of the reaction product obtained was Gardner 3.
比較例 ３
反応終了後の反応液の酸価を1.0に調整する以
外は実施例１と同様に行つたところ、グリセロー
ルメタクリレート82.3％を含む反応生成物が得ら
れた。Comparative Example 3 The same procedure as in Example 1 was conducted except that the acid value of the reaction solution was adjusted to 1.0 after completion of the reaction, and a reaction product containing 82.3% of glycerol methacrylate was obtained.
比較例 ４
実施例１と同様に反応を行い、反応液の酸価の
調整も同様に行つて、45〜50℃で脱水したとこ
ろ、得られた反応生成物中のグリセロールメタク
リレートは85.5％であつた。Comparative Example 4 The reaction was carried out in the same manner as in Example 1, the acid value of the reaction solution was adjusted in the same way, and dehydration was performed at 45 to 50°C. The glycerol methacrylate in the obtained reaction product was 85.5%. Ta.
実施例 ２
実施例１と同じ反応容器に水90ｇ（５モル）、
グリシドール14.8ｇ（0.2モル）、61％硝酸0.5％
（0.005モル）およびヒドロキノン0.014ｇをとり、
グリシジルメタクリレート142.2ｇ（1.0モル）を
滴下しながら70〜80℃で２時間反応を行い、さら
に30分間反応を続けた。ついで実施例１と同様に
酸価を0.4に調整して実施例１の条件で脱水した。
反応生成物167.1ｇが得られ、その中にグリセロ
ールメタクリレートが94.0％含まれていた。Example 2 In the same reaction vessel as in Example 1, 90 g (5 mol) of water,
Glycidol 14.8g (0.2mol), 61% nitric acid 0.5%
(0.005 mol) and 0.014 g of hydroquinone,
The reaction was carried out at 70 to 80°C for 2 hours while 142.2 g (1.0 mol) of glycidyl methacrylate was added dropwise, and the reaction was continued for an additional 30 minutes. Then, the acid value was adjusted to 0.4 in the same manner as in Example 1, and dehydration was carried out under the conditions of Example 1.
167.1 g of reaction product was obtained, which contained 94.0% glycerol methacrylate.
実施例 ３
実施例１と同様にして、水126ｇ（７モル）、グ
リセロールメタクリレート32.0ｇ（0.2モル）、硫
酸0.1ｇ（0.001モル）およびヒドロキノンモノメ
チルエーテル0.028ｇをとり、グリシジルメタク
リレート142.2ｇ（1.0モル）を滴下しながら70〜
80℃で2.5時間反応を行い、さらに30分間反応を
続けた。実施例１と同様に酸価の調整ならびに脱
水を行つた。反応生成物186.5ｇが得られ、その
中にグリセロールメタクリレート97％が含まれて
いた。Example 3 In the same manner as in Example 1, 126 g (7 mol) of water, 32.0 g (0.2 mol) of glycerol methacrylate, 0.1 g (0.001 mol) of sulfuric acid and 0.028 g of hydroquinone monomethyl ether were taken, and 142.2 g (1.0 mol) of glycidyl methacrylate was prepared. ) while dropping 70~
The reaction was carried out at 80°C for 2.5 hours and continued for an additional 30 minutes. The acid value was adjusted and dehydration was carried out in the same manner as in Example 1. 186.5 g of reaction product was obtained, which contained 97% glycerol methacrylate.
実施例 ４
実施例１と同様にして、水90ｇ（５モル）、グ
リセリン18.4ｇ（0.2モル）、パラトルエンズルホ
ン酸1.9ｇ（0.01モル）およびヒドロキノン0.014
ｇをとり、グリシジルメタクリレート142.2ｇ
（1.0モル）を滴下しながら70〜80℃で2.5時間反
応を行い、さらに30分間反応を続けた。実施例１
と同様に酸価の調整ならびに脱水を行つて反応生
成物169.7ｇを得た。グリセーロールメタクリレ
ートが92.5％であつた。Example 4 In the same manner as in Example 1, 90 g (5 moles) of water, 18.4 g (0.2 moles) of glycerin, 1.9 g (0.01 moles) of paratoluenesulfonic acid and 0.014 g of hydroquinone
Take g and 142.2 g of glycidyl methacrylate
(1.0 mol) was added dropwise at 70 to 80°C for 2.5 hours, and the reaction was continued for an additional 30 minutes. Example 1
The acid value was adjusted and dehydration was performed in the same manner as above to obtain 169.7 g of a reaction product. Glycerol methacrylate was 92.5%.
実施例 ５
実施例１と同様にして、水270ｇ（15モル）、硫
酸0.1ｇ（0.001モル）およびヒドロキノン0.014ｇ
をとり、グリシジルアクリレート128.2ｇ（1.0モ
ル）を滴下しながら70〜80℃で５時間反応を行
い、さらに１時間反応を続けた。実施例１と同様
に酸価の調整ならびに脱水を行い、反応生成物が
139.6ｇを得た。グリセロールアクリレートが95
％含まれていた。Example 5 270 g (15 mol) of water, 0.1 g (0.001 mol) of sulfuric acid and 0.014 g of hydroquinone as in Example 1.
was taken, and 128.2 g (1.0 mol) of glycidyl acrylate was added dropwise to react at 70 to 80°C for 5 hours, and the reaction was continued for an additional hour. Adjustment of acid value and dehydration were carried out in the same manner as in Example 1, and the reaction product was
139.6g was obtained. Glycerol acrylate is 95
% was included.
Claims (1)
中にグリシジルアクリレートまたはメタクリレー
トを添加して反応させ、反応終了後に酸価を0.3
〜0.8に調整したのち10〜40℃で減圧下に脱水す
ることを特徴とするグリセロールアクリレートま
たはメタクリレートの製造法。 ２ 混合液中にグリシドールを存在させる特許請
求の範囲第１項記載の製造法。 ３ 混合液中にグリセロールアクリレートまたは
メタクリレートを存在させる特許請求の範囲第１
項記載の製造法。 ４ 混合液中にグリセリンを存在させる特許請求
の範囲第１項記載の製造法。[Claims] 1. Glycidyl acrylate or methacrylate is added to a mixed solution consisting of an acid catalyst, a polymerization inhibitor, and water and reacted, and after the reaction is completed, the acid value is reduced to 0.3.
A method for producing glycerol acrylate or methacrylate, which comprises adjusting the glycerol acrylate to 0.8 and then dehydrating it under reduced pressure at 10 to 40°C. 2. The manufacturing method according to claim 1, wherein glycidol is present in the mixed liquid. 3 Claim 1 in which glycerol acrylate or methacrylate is present in the mixed liquid
Manufacturing method described in section. 4. The manufacturing method according to claim 1, wherein glycerin is present in the mixed liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7008984A JPS60215650A (en) | 1984-04-10 | 1984-04-10 | Preparation of glycerol acrylate for methacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7008984A JPS60215650A (en) | 1984-04-10 | 1984-04-10 | Preparation of glycerol acrylate for methacrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60215650A JPS60215650A (en) | 1985-10-29 |
| JPH0410465B2 true JPH0410465B2 (en) | 1992-02-25 |
Family
ID=13421462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7008984A Granted JPS60215650A (en) | 1984-04-10 | 1984-04-10 | Preparation of glycerol acrylate for methacrylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60215650A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4730081A (en) * | 1986-01-14 | 1988-03-08 | Halliburton Company | Vicinal diol containing monomers and methods of preparing |
| FR2664272B3 (en) * | 1990-07-06 | 1992-11-27 | Norsolor | PROCESS FOR THE SELECTIVE EPOXIDATION OF UNSATURATED (METH) ACRYLATES, NEW FUNCTIONAL (METH) ACRYLATES OBTAINED AND THEIR APPLICATION TO THE SYNTHESIS OF NEW POLYMERS. |
| KR970042452A (en) * | 1995-12-29 | 1997-07-24 | 황선두 | Purification and recovery method of 2-hydroxyalkyl methacrylate |
-
1984
- 1984-04-10 JP JP7008984A patent/JPS60215650A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60215650A (en) | 1985-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0410465B2 (en) | ||
| US6162946A (en) | Processing for producing allyl 2-hydroxyisobutyrate | |
| CN115572272A (en) | Preparation method of febuxostat and aldehyde ester intermediate thereof | |
| JPH02193944A (en) | Production of (meth)acrylic acid ester | |
| JP4662026B2 (en) | Method for producing glycidyl methacrylate | |
| JPH09249657A (en) | Purification of glycidyl (meth)acrilate | |
| US4611088A (en) | Process for preparing D-α-(6-methoxy-2-naphtyl) propionic acid | |
| JPS63190862A (en) | Recovery method of N-vinylformamide | |
| JPS62255450A (en) | Production of glycerin monoacrylate or methacrylate | |
| JPH11279121A (en) | Production of alkyl beta-alkoxypropionate | |
| JPH0825991B2 (en) | Method for producing dithiol di (meth) acrylate | |
| SU571473A1 (en) | Method of preparing lythium acrylate | |
| JPS6338983B2 (en) | ||
| SU1664783A1 (en) | Method of purifying concentrated acetic acid from iron ion admixtures | |
| JPH0710798B2 (en) | Method for producing methacrylic acid ester | |
| SU1198073A1 (en) | Method of producing 3,4-benzocoumarin | |
| KR0173545B1 (en) | Method for preparing isopropyl thioxanthone using solid acid | |
| SU1567565A1 (en) | Method of obtaining 1-chlor-4-methylpentan 2-ol | |
| JP4246447B2 (en) | Process for producing deuterated methyl methacrylate | |
| SU1482913A1 (en) | Method sodium methanothiolate | |
| JPS6168472A (en) | Production of unsaturated hydantoin | |
| JPH03251555A (en) | Production of alkyl alkoxypropionate | |
| SU1616895A1 (en) | Method of producing benzylacetate | |
| JPH05140039A (en) | Production of lactic acid ester | |
| KR930002277B1 (en) | Method for preparing 5- (4-hydroxyphenyl) hydantoin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |