JPH02134332A - Production of diarylmethane - Google Patents
Production of diarylmethaneInfo
- Publication number
- JPH02134332A JPH02134332A JP28776688A JP28776688A JPH02134332A JP H02134332 A JPH02134332 A JP H02134332A JP 28776688 A JP28776688 A JP 28776688A JP 28776688 A JP28776688 A JP 28776688A JP H02134332 A JPH02134332 A JP H02134332A
- Authority
- JP
- Japan
- Prior art keywords
- diarylmethane
- surfactant
- sulfuric acid
- formaldehyde
- reaction
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 58
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 12
- 238000009835 boiling Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003093 cationic surfactant Substances 0.000 abstract description 3
- 239000002736 nonionic surfactant Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012965 benzophenone Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 239000012044 organic layer Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/867—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an aldehyde or a ketone
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
- C07C2527/054—Sulfuric acid or other acids with the formula H2Sn03n+1
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は芳香族炭化水素とホルムアルデヒドとを硫酸触
媒存在下に反応させてジアリールメタンを製造する方法
の改良に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an improvement in a method for producing diarylmethane by reacting an aromatic hydrocarbon and formaldehyde in the presence of a sulfuric acid catalyst.
ジアリールメタンは高沸点溶媒、またはベンゾフェノン
ポリカルボン酸の原料として有用な物質である。Diarylmethane is a substance useful as a high-boiling point solvent or a raw material for benzophenone polycarboxylic acid.
芳香族炭化水素ドとホルムアルデヒドとを硫酸触媒存在
下に反応させてジアリールメタンを製造する方法（米国
特許第３．０４３．８８６等）は良く知られている。
しかしこれらの方法は同時に高縮合物が生成するという
欠点を有する。A method for producing diarylmethane by reacting an aromatic hydrocarbon and formaldehyde in the presence of a sulfuric acid catalyst is well known (eg, US Pat. No. 3,043,886).
However, these methods also have the disadvantage that high condensates are formed.
高縮合物の生成を少なくするための方法としてシリカゲ
ルを併用する方法（米国特許第２．９８１．７６５）や
脂肪族アルコールを添加する方法（Ｖｏｐｒ、Ｋｈ ｉ
ｍ、 Ｔｅｋｈｎｏ １．、７１．１１２−１１４ （
１９８３） 、 ＵＳＳＲ）が知られているが、前者は
反応性の低い芳香族炭化水素基串のジアリールメタンの
収率が低いきいう欠点がある。また後者は確かに脂肪族
アルコールの添加効果が認められるが、それでも依然と
して高縮合物が高い割合で生成するという欠点がある。Methods to reduce the formation of high condensates include a method of using silica gel (U.S. Pat. No. 2,981,765) and a method of adding aliphatic alcohol (Vopr, Kh i
m, Tekhno 1. , 71.112-114 (
1983), USSR), but the former has the disadvantage of a low yield of diarylmethane based on aromatic hydrocarbon groups with low reactivity. In the latter case, although the effect of adding an aliphatic alcohol is certainly observed, it still has the drawback of producing a high proportion of high condensates.
本発明者らは、硫酸を用いるジアリールメタンの製造に
おいて、高縮合物の生成を少なくしホルムアルデヒド基
準のジアリールメタンの収率（以下、ジアリールメタン
の収率と略す）を高めることを目的として鋭意研究し、
本発明に到達した。The present inventors have conducted extensive research with the aim of reducing the formation of high condensates and increasing the yield of diarylmethane based on formaldehyde (hereinafter abbreviated as diarylmethane yield) in the production of diarylmethane using sulfuric acid. death,
We have arrived at the present invention.
本発明は、芳香族炭化水素とホルムアルデヒドとを硫酸
触媒存在下に反応させてジアリールメタンを製造する方
法において、界面活性剤を存在させることを特徴とする
ジアリールメタンの製造法である。The present invention is a method for producing diarylmethane by reacting an aromatic hydrocarbon and formaldehyde in the presence of a sulfuric acid catalyst, which is characterized in that a surfactant is present.
本発明に用いられる芳香族炭化水素は、ベンゼン、トル
エン、キシレン、エチルベンゼン、トリメチルベンゼン
等、公知の硫酸触媒を用いる方法によりジアリールメタ
ンを合成することができる芳香族炭化水素である。本発
明に用いられるホルムアルデヒドはパラホルムアルデヒ
ド、ホルムアルデヒド水溶液およびトリオキサンのいず
れであってもよい。ホルムアルデヒド水溶液の場合には
少ｆｆｉのメチルアルコールが含まれてもよい。The aromatic hydrocarbons used in the present invention are aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene, which can be used to synthesize diarylmethane by a method using a known sulfuric acid catalyst. The formaldehyde used in the present invention may be any of paraformaldehyde, formaldehyde aqueous solution, and trioxane. In the case of an aqueous formaldehyde solution, a small amount of methyl alcohol may be included.
芳香族炭化水素対ホルムアルデヒドのモル比は２．５：
１〜８：１の範囲から選ばれるのがよい。２．５対１以
下では高縮合物の生成量が増し、８対１以上では芳香族
炭化水素の基準のジアリールメタンの収率が著しく低く
なる。The molar ratio of aromatic hydrocarbon to formaldehyde is 2.5:
It is preferable to select from the range of 1 to 8:1. If it is less than 2.5:1, the amount of high condensate produced will increase, and if it is more than 8:1, the yield of diarylmethane based on aromatic hydrocarbons will be extremely low.
本発明に用いられる界面活性剤は、カチオン界面活性剤
、アニオン界面活性剤および非イオン界面活性剤のいず
れであってもよいが、好ましくはカチオン界面活性剤、
非イオン界面活性剤である。The surfactant used in the present invention may be a cationic surfactant, an anionic surfactant or a nonionic surfactant, but preferably a cationic surfactant,
It is a nonionic surfactant.
界面活性剤の添加量は、硫酸１００重量部に対して０．
０１〜５重量部、好ましくは０．０５〜３重量部の範囲
から選ばれるのがよい。０．０１重量部より小さいと界
面活性剤の添加効果は著しく低く、５重量部より大きい
と反応終了後の硫酸層の分離が困難になる。The amount of surfactant added is 0.00 parts by weight per 100 parts by weight of sulfuric acid.
0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight. If the amount is less than 0.01 parts by weight, the effect of adding the surfactant will be extremely low, and if it is more than 5 parts by weight, it will be difficult to separate the sulfuric acid layer after the reaction is completed.
本発明で使用する硫酸の濃度は、３０〜９５重量％、好
ましくは５０〜９０重量％の範囲から選ばれるのがよい
。９５重量％以上の濃硫酸を使用すると界面活性剤が有
効に作用せず、また３０重量％以下の濃度では反応速度
が著しく低下し、ジアリールメタンの収率が低下する。The concentration of sulfuric acid used in the present invention is preferably selected from the range of 30 to 95% by weight, preferably 50 to 90% by weight. If concentrated sulfuric acid is used in a concentration of 95% by weight or more, the surfactant will not work effectively, and if the concentration is less than 30% by weight, the reaction rate will drop significantly and the yield of diarylmethane will decrease.
さらに硫酸の使用量はホルムアルデヒド１モルに対し
て０．１〜８モル、好マシ＜は０．５〜６モルの範囲か
ら選ばれるのがよい。８モル以上では高縮合物の生成量
が増し、０゜１モル以下では反応速度が著しく低下し、
ジアリールメタンの収率が低下する。Further, the amount of sulfuric acid used is preferably selected from the range of 0.1 to 8 mol, preferably 0.5 to 6 mol, per mol of formaldehyde. If it is more than 8 mol, the amount of high condensate produced increases, and if it is less than 0.1 mol, the reaction rate will decrease significantly,
The yield of diarylmethane decreases.
本発明において、ホルムアルデヒドは連続的あるいは分
割して仕込まれる。ホルムアルデヒドの仕込み時間は、
１０分〜６時間、実際的には３０分〜４時間の範囲から
選ばれるのが好ましい。ホルムアルデヒドの仕込み時間
が１０分以下では高縮合物の生成量が多くなる。 反応
温度は１０〜２００℃、好ましくは５０〜１４０℃の範
囲から選ばれるのがよい。１０℃以下では反応速度が著
しく低下し、ジアリールメタンの収率が低下する。２０
０℃以上では高縮合物の生成量が増す。In the present invention, formaldehyde is charged continuously or in portions. The preparation time for formaldehyde is
It is preferably selected from the range of 10 minutes to 6 hours, practically 30 minutes to 4 hours. If the formaldehyde charging time is less than 10 minutes, the amount of high condensate produced will increase. The reaction temperature is preferably selected from the range of 10 to 200°C, preferably 50 to 140°C. At temperatures below 10°C, the reaction rate decreases significantly and the yield of diarylmethane decreases. 20
At temperatures above 0°C, the amount of high condensates produced increases.
本発明は一般的には次のように実施される。すなわち、
撹拌器、温度計および冷却器を備えた反応容器に、芳香
族炭化水素、硫酸および界面活性剤を入れ、撹拌しなが
ら反応温度まで昇温する。The invention is generally practiced as follows. That is,
An aromatic hydrocarbon, sulfuric acid, and a surfactant are placed in a reaction vessel equipped with a stirrer, a thermometer, and a condenser, and the temperature is raised to the reaction temperature while stirring.
反応液の温度を反応温度にコントロールしながらホルム
アルデヒドを連続的または分割して仕込み、仕込み終了
後５〜３０分間撹拌して反応を完結させる。反応終了後
硫酸層を分離し、アルカリ水溶液で中和した有機層から
蒸留により、まず未反応の芳香族炭化水素を回収し、続
いてジアリールメタンを得る。Formaldehyde is charged continuously or in portions while controlling the temperature of the reaction solution to the reaction temperature, and after completion of the charging, the reaction is completed by stirring for 5 to 30 minutes. After the reaction is completed, the sulfuric acid layer is separated, and the unreacted aromatic hydrocarbons are first recovered by distillation from the organic layer neutralized with an aqueous alkaline solution, and then diarylmethane is obtained.
以下、実施例および比較例をあげて説明する。 Examples and comparative examples will be described below.
実施例１
撹拌棒、温度計および冷却器を備えた２Ｉ！フラスコに
トルエン３６９ｇ （４モル）、７５％硫酸２６３ｇ
（２モル）および界面活性剤としてドデシルトリメチル
アンモニウムクロライド０．３９ｇ（硫酸１００重量部
に対して０．１５重量部）を入れ、ＩＯＱ ｔに昇温し
た。Example 1 2I with stir bar, thermometer and cooler! 369 g (4 moles) of toluene and 263 g of 75% sulfuric acid in a flask.
(2 mol) and 0.39 g of dodecyltrimethylammonium chloride (0.15 parts by weight per 100 parts by weight of sulfuric acid) as a surfactant were added, and the temperature was raised to IOQ t.
反応液温度を１００℃にコントロールしながら、３７％
ホルムアルデヒド水溶液を１５０分かけて滴下し、滴下
終了後、５分間撹拌を続けた。反応終了後３０分間静置
放冷して分液し、有機層を１５％炭酸ナトリウム水溶液
で中和した後、減圧蒸留を行い先ず、トルエン１７３ｇ
を回収した。続いて沸点１５１℃＜５ｍｍｌ１ｇ）の留
分としてジトリルメタンを１８１ｇ （収率９２．３％
）を得た。なお、高縮合物は蒸留残香として５ｇで、次
式で定義される高縮合物の割合は２．７％であった。37% while controlling the reaction solution temperature at 100℃.
The formaldehyde aqueous solution was added dropwise over 150 minutes, and after the addition was completed, stirring was continued for 5 minutes. After the reaction was completed, the organic layer was left to cool for 30 minutes to separate the layers, and the organic layer was neutralized with a 15% aqueous sodium carbonate solution, followed by distillation under reduced pressure. First, 173 g of toluene was added.
was recovered. Subsequently, 181 g of ditolylmethane (yield 92.3%) was obtained as a fraction with a boiling point of 151°C
) was obtained. The amount of high condensate was 5 g as distillation residual aroma, and the proportion of high condensate defined by the following formula was 2.7%.
高縮合物の割合
＝高縮合物の重量／（高縮合物の重量＋ジアリールメタ
ンの重量） Ｘ１００ （％）
比較例１
実施例１の反応を界面活性剤無添加で行ったところ、ト
ルエンの回収ｆｆ１１７１ｇ、ジトリルメタンの収量１
５５ｇ （収率７９．１％）、高縮合物２３ｇ（高縮合
物の割合１２．９％）という結果であった。Ratio of high condensate = weight of high condensate / (weight of high condensate + weight of diarylmethane) ff1171g, yield of ditolylmethane 1
The results were 55 g (yield 79.1%) and 23 g of high condensate (ratio of high condensate 12.9%).
実施例２
実施例１と同じ反応容器にｍ−キシレン４２５ｇ （４
モル）、７５％硫酸２６３ｇ （２モル）および界面活
性剤としてポリオキシエチレン（７）ラウリルエーテル
１゜３ｇ（硫酸１００重量部に対して０．５０重量Ｒ）
を入れ、８０℃に昇温した。反応液温度を８０℃にコン
トロールしながら、３７％ホルムアルデヒド水溶液を１
５０分かけて滴下し、滴下終了後５分間撹拌を続けた。Example 2 425 g of m-xylene (4
mol), 263 g (2 mol) of 75% sulfuric acid and 1°3 g of polyoxyethylene (7) lauryl ether as a surfactant (0.50 weight R per 100 parts by weight of sulfuric acid).
was added and the temperature was raised to 80°C. While controlling the temperature of the reaction solution at 80°C, 1 liter of 37% formaldehyde aqueous solution was added.
The mixture was added dropwise over 50 minutes, and stirring was continued for 5 minutes after the addition was completed.
反応終了後３０分間静置放冷して分液し、有機層を１５
％炭酸すｌ−ＩＪウム水溶液で中和した後、減圧蒸留を
行い、先ずｍ−キシレン２０２ｇを回収した。After the reaction was completed, the organic layer was cooled for 30 minutes to separate the organic layer.
After neutralization with an aqueous solution of % Sourium-IJ carbonate, vacuum distillation was performed to first recover 202 g of m-xylene.
続いて沸点１６５℃（５ｍｍＨｇ）の留分としてジメタ
キシリルメタン１９７ｇ （収率８７．９％）を得た。Subsequently, 197 g (yield: 87.9%) of dimethaxylylmethane was obtained as a fraction with a boiling point of 165° C. (5 mmHg).
なお、高縮合物は１２ｇ（高縮合物の割合５．７％）で
あった。The amount of high condensate was 12 g (ratio of high condensate: 5.7%).
比較例２
実施例２の反応を界面活性剤無添加で行ったところ、ｍ
−キシレンの回収ｆｆｔ２２７ｇ、ジメタキシリルメタ
ンの収量１３５ｇ （収率６０．３％）、高縮合物５０
ｇ（高縮合物の割合２７．０％）であった。Comparative Example 2 When the reaction of Example 2 was carried out without adding surfactant, m
- Recovery of xylene fft 227 g, yield of dimethaxylylmethane 135 g (yield 60.3%), high condensate 50
g (proportion of high condensate: 27.0%).
実施例３
実施例１と同じ反応容器にＯ−キシレン４２５ｇ （４
モル）、７５％硫酸２６３ｇ （２モル）および界面活
性剤としてテトラデシルジメチルベンジルアンモニウム
クロライド０．３９ｇ （硫酸１００重量部に対して０
．１５重量部）を入れ、１００℃に昇温した。反応液温
度を１００℃にコントロールしながら、３７％ホルムア
ルデヒド水溶液を１５０分かけて滴下し、滴下終了後５
分間撹拌を続けた。反応終了後３０分間静置して分液し
、有機層を１５％炭酸ナトリウム水溶液で中和した後、
減圧蒸留を行い先ず、Ｏ−キシレン１９７ｇを回収した
。続いて沸点１６９℃（５ｍｍ）Ｉｇ）の留分としてジ
オルツキシリルメタンを２０４ｇ （収率９１，１％）
を得た。なお、高縮合物は８ｇ（高縮合物の割合３゜８
％）であった。Example 3 425 g of O-xylene (4
mol), 263 g (2 mol) of 75% sulfuric acid and 0.39 g of tetradecyldimethylbenzylammonium chloride as a surfactant (0 per 100 parts by weight of sulfuric acid).
．． 15 parts by weight) and the temperature was raised to 100°C. While controlling the temperature of the reaction solution at 100°C, 37% formaldehyde aqueous solution was added dropwise over 150 minutes.
Stirring was continued for a minute. After the reaction was completed, the mixture was allowed to stand for 30 minutes to separate the layers, and the organic layer was neutralized with a 15% aqueous sodium carbonate solution.
First, 197 g of O-xylene was recovered by vacuum distillation. Subsequently, 204 g of diortoxylylmethane (yield 91.1%) was obtained as a fraction with a boiling point of 169°C (5 mm) Ig).
I got it. In addition, the high condensate is 8g (ratio of high condensate is 3°8
%)Met.
実施例４
実施例３の界面活性剤をステアリン酸力１月、３ｇ（硫
酸１００重量部に対して０．５０重量部）に変えて反応
を行ったところ、０−キシレンの回収量２１０ｇ。Example 4 When the surfactant of Example 3 was changed to 3 g (0.50 parts by weight per 100 parts by weight of sulfuric acid) of stearic acid and a reaction was carried out, 210 g of 0-xylene was recovered.
ジオルツキシリルメタンの収ｆｆｉ１９２ｇ（収率８５
．７％）、高縮合物１９ｇ（高縮合物の割合９．０％）
という結果であった。Diortoxylylmethane yield: 192 g (yield: 85
．． 7%), high condensate 19g (ratio of high condensate 9.0%)
That was the result.
比較例３
実施例３の反応を界面活性剤無添加で行ったところ、叶
キシレンの回収量２１０ｇ、ジオルツキシリルメタンの
収量１７６ｇ （収率７８．６％）、高縮合物３４ｇ（
高縮合物の割合１６．２％）であった。Comparative Example 3 When the reaction of Example 3 was carried out without adding surfactant, the amount of recovered xylene was 210 g, the yield of diortoxylylmethane was 176 g (yield 78.6%), and the amount of high condensate was 34 g (yield: 78.6%).
The proportion of high condensates was 16.2%).
本発明によれば高縮合物の生成量を少なくし、ジアリー
ルメタンを高収率で得ることができる。According to the present invention, the amount of high condensate produced can be reduced and diarylmethane can be obtained in high yield.
特許出願人 三菱瓦斯化学株式会社Patent applicant: Mitsubishi Gas Chemical Co., Ltd.
Claims (1)
に反応させてジアリールメタンを製造する方法において
、界面活性剤を存在させることを特徴とするジアリール
メタンの製造法A method for producing diarylmethane by reacting an aromatic hydrocarbon and formaldehyde in the presence of a sulfuric acid catalyst, characterized by the presence of a surfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28776688A JPH02134332A (en) | 1988-11-16 | 1988-11-16 | Production of diarylmethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28776688A JPH02134332A (en) | 1988-11-16 | 1988-11-16 | Production of diarylmethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02134332A true JPH02134332A (en) | 1990-05-23 |
Family
ID=17721479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28776688A Pending JPH02134332A (en) | 1988-11-16 | 1988-11-16 | Production of diarylmethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02134332A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6207866B1 (en) | 1997-07-11 | 2001-03-27 | Nippon Petrochemicals Company, Limited | Method for producing diarylmethane or its derivatives |
| US6300534B1 (en) | 1998-07-01 | 2001-10-09 | Nippon Petrochemicals Company, Limited | Process for producing dehydrogenated compounds of m-ethyldiphenylalkane |
| US6586362B1 (en) | 1999-09-20 | 2003-07-01 | Nippon Petrochemicals Company, Limited | Hydrocarbon solvent and pressure-sensitive copying material made with the same |
| WO2003055927A1 (en) * | 2001-12-27 | 2003-07-10 | Nippon Steel Chemical Co., Ltd. | Process for production of aromatic oligomers |
| WO2009063860A1 (en) * | 2007-11-16 | 2009-05-22 | Mitsubishi Gas Chemical Company, Inc. | Polyfunctional dimethylnaphthalene formaldehyde resin, and process for production thereof |
| DE102010062804A1 (en) | 2010-01-12 | 2011-07-14 | Evonik Degussa GmbH, 45128 | Process for the preparation of 1,1-diarylalkanes and derivatives thereof |
-
1988
- 1988-11-16 JP JP28776688A patent/JPH02134332A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6207866B1 (en) | 1997-07-11 | 2001-03-27 | Nippon Petrochemicals Company, Limited | Method for producing diarylmethane or its derivatives |
| US6300534B1 (en) | 1998-07-01 | 2001-10-09 | Nippon Petrochemicals Company, Limited | Process for producing dehydrogenated compounds of m-ethyldiphenylalkane |
| US6586362B1 (en) | 1999-09-20 | 2003-07-01 | Nippon Petrochemicals Company, Limited | Hydrocarbon solvent and pressure-sensitive copying material made with the same |
| WO2003055927A1 (en) * | 2001-12-27 | 2003-07-10 | Nippon Steel Chemical Co., Ltd. | Process for production of aromatic oligomers |
| WO2009063860A1 (en) * | 2007-11-16 | 2009-05-22 | Mitsubishi Gas Chemical Company, Inc. | Polyfunctional dimethylnaphthalene formaldehyde resin, and process for production thereof |
| US8648152B2 (en) | 2007-11-16 | 2014-02-11 | Mitsubishi Gas Chemical Company, Inc. | Polyfunctional dimethylnaphthalene formaldehyde resin, and process for production thereof |
| KR101533862B1 (en) * | 2007-11-16 | 2015-07-03 | 미츠비시 가스 가가쿠 가부시키가이샤 | Polyfunctional dimethylnaphthalene formaldehyde resin, and process for production thereof |
| DE102010062804A1 (en) | 2010-01-12 | 2011-07-14 | Evonik Degussa GmbH, 45128 | Process for the preparation of 1,1-diarylalkanes and derivatives thereof |
| US8093438B2 (en) | 2010-01-12 | 2012-01-10 | Evonik Degussa Gmbh | Process for producing 1,1 diaryl alkanes and derivatives thereof |
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