CN101302137B - Preparation of 3, 3', 4,4' -tetramethyl diphenyl alkane - Google Patents
Preparation of 3, 3', 4,4' -tetramethyl diphenyl alkane Download PDFInfo
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- CN101302137B CN101302137B CN200810039710XA CN200810039710A CN101302137B CN 101302137 B CN101302137 B CN 101302137B CN 200810039710X A CN200810039710X A CN 200810039710XA CN 200810039710 A CN200810039710 A CN 200810039710A CN 101302137 B CN101302137 B CN 101302137B
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Abstract
The invention discloses a method for preparing 3, 3', 4, 4', -tetramethyldiphenylalkane. Any one of formaldehyde, aldehyde, paraformaldehyde and metaldehyde is mixed with ortho-xylene according to the mol ratio of between 1 to 2.5 and 5 under the existence of mixed acid catalyst formed by sulphuric acid and any one of methanoic acid, acetic acid or propanoic acid, wherein, the weight ratio of the sulphuric acid to fatty acid is between 1 to 0.5 and 2; the weight ratio of aldehyde to the mixed acid catalyst is between 1 to 5 and 10; the mixture reacts for 4 to 12 hours at a temperature of between 30 and 100 DEG C and is cooled, water and oil are separated, an oil phase is scrubbed by water for 3 times and is subject to the reduced pressure distillation to obtain the 3, 3', 4, 4', -tetramethyldiphenylalkane. The yield is between 78 and 80 percent, and the purity is between 95 and 98 percent by weight.
Description
One, technical field
The present invention relates to the preparation method of tetramethyl-diphenyl alkane, relate to 3,3 ', 4 or rather, the preparation method of 4 '-tetramethyl-diphenyl alkane.
Two, background technology
3,3 ', 4 of the present invention's preparation, 4 '-tetramethyl-diphenyl alkane has following general structure:
R=R ' in the formula=H or R=H, R '=CH
3
3,3 ', 4,4 '-tetramethyl-diphenyl alkane is 3,3 ', 4, and the initial feed of 4 '-benzophenone tetracarboxylic acid dianhydride.3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride is the raw material of preparation advanced composite material matrix resin, again can be as the raw material of curing agent for epoxy resin and high temperature resistance polyester, and thus 3,3 ', 4,4 ' one tetramethyl-diphenyl alkane is an important chemical material.
It is generally acknowledged o-Xylol by carbaldehyde alkylization, in alkylate, purpose product 3,3 ', 4,4 '-tetramethyl-ditan (TMDM) selection rate is low, and content is 78～84%.2,3,3 ', 4-TMDM, 2,3,2 ', 3 '-TMDM content of isomer is up to 13～27%.It is very difficult to separate them.Prior art U S Pat.No 5,254,768, Oct.19,1993 disclose: 425g (4mol) o-Xylol and 306g (2mol) 64% vitriolic stirred solution, be added dropwise to 81g (1mol) 37% formalin to it, refluxed 3 hours in 121 ℃.Reacted product cooling 30min, separating liquid, the oil phase of separating, water is given a baby a bath on the third day after its birth inferior, with anhydrous sodium sulfate dehydration, 427g oil phase reaction solution (R-1) is provided, and the compositional analysis result is 52.5 weight % o-Xylols, 38.1 weight % tetramethyl-ditans (TMDM) and 9.4 weight % miscellany materials.The TMDM of institute's output has following isomery and forms: 59.4%3,3 ', 4, and 4 '-TMDM, 37.4%2,3,3 ', 4-TMDM and 3.2%2,2 ' 3,3 '-TMDM.The yield that with formaldehyde is basic calculation TMDM is 72.6 moles of %, 3,3 ', 4, and 4 '-TMDM yield 43.1mol%, prior art is catalyzer with sulfuric acid, temperature of reaction is up to 121 ℃, product 3,3 ', 4, the yield of 4 '-TMDM is on the low side.These weak points are should be improved.
Three, summary of the invention
In order to overcome the shortcoming of prior art, present inventors have done particular study, propose to adopt mixed catalyst in low-temperature catalyzed alkylated reaction preparation 3,3 ', 4, the invention of 4 '-tetramethyl-diphenyl alkane.
The present invention organic aldehyde and o-Xylol 1: 2.5 in molar ratio～5 in the presence of mixed-acid catalyst, in 30～100 ℃ of reactions 4～12 hours, here temperature of reaction is 35～55 ℃ preferably, reaction times is to make 3 in 6～8 hours preferably, 3 ', 4,4 '-tetramethyl-diphenyl alkane, yield 75～80%, purity 〉=95 weight %.
Mixed-acid catalyst is that concentration is the mixture of choosing any one kind of them in 82～92 weight % sulfuric acid and the like formic acid of lipid acid, acetate or the propionic acid.The weight ratio of sulfuric acid and lipid acid is 1: 0.5～2.
Organic aldehyde is to choose any one kind of them from formaldehyde, acetaldehyde, Paraformaldehyde 96, Metaldehyde, and the weight ratio of aldehyde and mixed-acid catalyst is 1: 5～10.Paraformaldehyde 96 can be the ring-type trioxymethylene, the water-soluble Paraformaldehyde 96 of carbonatoms 4～7, C
8～100Water-insoluble Paraformaldehyde 96.Metaldehyde is C
4～8Metaldehyde.
Implement 3,3 ', 4 of preparation according to the inventive method, 4 '-tetramethyl-diphenyl alkane, 3 among the present invention, 3 ', 4,4 '-tetramethyl-diphenyl alkane means 3,3 ', 4,4 '-tetramethyl-ditan (TMDM) or 3,3 ', 4,4 '-tetramethyl-diphenylethane (DXE), its yield is 75～80%, in the reaction product 3,3 ', 4, the selection rate of 4 '-TMDM or DXE 〉=95%, other isomer 2,3 that is to say, 3 ', 4-TMDM or DXE, 2,3,2 ', 3 '-TMDM or DXE total amount≤5%.
Four, specific embodiments
Especially exemplified by example it is described in order to implement the present invention better, but is not restriction invention.
Embodiment 1
Containing 371g (3.5mol) o-Xylol and 304g concentration in 3 liters of round-bottomed flasks that are equipped with agitator, thermometer and prolong is sulfuric acid and the 304g acetate of 86 weight %, after mixing 5min, then add the 120g Paraformaldehyde 96, in 50 ℃ of reactions 8 hours.Then reaction solution is cooled to 30 ℃ of following temperature, separates water, wash oil phase three times with 300ml, continue it, 140 ℃/1mmHg of cut is got in underpressure distillation, obtains 306g3, and 3 ', 4,4 '-tetramethyl-ditan, yield is 78%, purity is 97 weight %.
Embodiment 2
Except that containing 530g (5mol) o-Xylol, sulfuric acid (concentration 82 weight %) 135g, formic acid 270g, formaldehyde (37% concentration) 81g in 30 ℃ of reactions 12 hours, other prescription, operation steps are the same with embodiment 1, the result obtains 420g3,3 ', 4,4 '-tetramethyl-ditan, yield are 75%, and purity is 95 weight %.
Embodiment 3
Remove and contain o-Xylol 265g (2.5mol), concentration is that 92 weight % sulfuric acid 540g, propionic acid 270g, acetaldehyde 44g are outside 100 reactions 4 hours, other prescription is the same with embodiment 1 with operation steps, the result obtains 224g3,3 ', 4,4 '-tetramethyl-diphenylethane, yield is 80%, and purity is 98 weight %.
Claims (3)
1.3,3 ', 4, the preparation method of 4 '-tetramethyl-diphenyl alkane is characterized in that organic aldehyde and o-Xylol mol ratio are 1: 2.5～5 in the presence of mixed-acid catalyst, obtains 3 in 4～12 hours in 30～100 ℃ of reactions, 3 ', 4,4 '-tetramethyl diphenyl alkane, its purity 〉=95 weight %, yield are 75～80%; Mixed-acid catalyst is that concentration is the mixture of 82～92 weight % sulfuric acid and lipid acid, and the mixed weight ratio is 1: 0.5～2; Lipid acid is to choose any one kind of them from formic acid, acetate or propionic acid; Described 3,3 ', 4,4 '-tetramethyl-diphenyl alkane is 3,3 ', 4,4 '-tetramethyl-ditane or 3,3 ', 4,4 '-tetramethyl-diphenylethane.
2. described 3,3 ', 4 according to claim 1, the preparation method of 4 '-tetramethyl-diphenyl alkane is characterized in that organic aldehyde is to choose any one kind of them from formaldehyde, Paraformaldehyde 96, acetaldehyde, Metaldehyde, and the weight ratio of organic aldehyde and mixed-acid catalyst is 1: 5～10.
3. according to claim 13,3 ', 4, the preparation method of 4 '-tetramethyl-diphenyl alkane is characterized in that temperature of reaction is 35～55 ℃, and the reaction times is 6～8 hours.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210353A (en) * | 1990-11-30 | 1993-05-11 | Amoco Corporation | Aromatic transformation process |
| US5254768A (en) * | 1991-03-01 | 1993-10-19 | Mitsubishi Gas Chemical Company, Inc. | Process for producing 3,3',4,4'-tetramethyldiphenylmethane |
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2008
- 2008-06-27 CN CN200810039710XA patent/CN101302137B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210353A (en) * | 1990-11-30 | 1993-05-11 | Amoco Corporation | Aromatic transformation process |
| US5254768A (en) * | 1991-03-01 | 1993-10-19 | Mitsubishi Gas Chemical Company, Inc. | Process for producing 3,3',4,4'-tetramethyldiphenylmethane |
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Address after: 200235 No. 36, Shanghai, Caobao Road Patentee after: SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS CO., LTD. Address before: 200235 Xuhui District, Caobao Road, No. 36, Patentee before: Shanghai Inst. of Synthetic Resin |
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Effective date of registration: 20210203 Address after: No. 1251, Zhulu West Road, Xujing Town, Qingpu District, Shanghai, 201702 Patentee after: SHANGHAI PLASTICS RESEARCH INSTITUTE Co.,Ltd. Address before: 200235 No. 36, Shanghai, Caobao Road Patentee before: SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS Co.,Ltd. |