CN102267870A - Production process of 4,4'-bis(chloromethyl)-biphenyl - Google Patents
Production process of 4,4'-bis(chloromethyl)-biphenyl Download PDFInfo
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- CN102267870A CN102267870A CN2011102004484A CN201110200448A CN102267870A CN 102267870 A CN102267870 A CN 102267870A CN 2011102004484 A CN2011102004484 A CN 2011102004484A CN 201110200448 A CN201110200448 A CN 201110200448A CN 102267870 A CN102267870 A CN 102267870A
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Abstract
The invention discloses a production process of 4,4'-bis(chloromethyl)-biphenyl and belongs to the technical field of chemical synthesis. The production process comprises: sequentially adding petroleum ether, biphenyl, by-products, paraformaldehyde and zinc chloride to a reactor, stirring uniformly, introducing dry HCl gas, and performing chloromethylation reaction at normal pressure at the reaction temperature of 25-35 DEG C for 22-26 hours; and after the reaction is finished, washing the material with water, performing solid-liquid separation to obtain a crude product, then recrystallizing with toluene, draining and drying to obtain 4,4'-bis(chloromethyl)-biphenyl, wherein the molar ratio of biphenyl to the by-products to paraformaldehyde to zinc chloride is 1.0:0.4:2.3:0.6. In the production process disclosed by the invention, the waste residue by-products generated during the production of 4,4'-bis(chloromethyl)-biphenyl are recycled to participate in the chloromethylation reaction, thereby changing the concentration balance between the original reactants and products, inhibiting side reactions, being beneficial to the generation of a main reactant and improving the yield of 4,4'-bis(chloromethyl)-biphenyl.
Description
Technical field
The invention discloses a kind of production technique of biphenyl benzyl dichloride, belong to technical field of chemical synthesis.
Background technology
The biphenyl benzyl dichloride has another name called 4,4'-dichloromethyl biphenyl, 4,4'-Bis (chloromethyl)-Diphenyl, molecular formula C
14C
12Cl
2, relative molecular weight 251, the white solid powder, 136 ℃ of fusing points, structural formula is:
The biphenyl benzyl dichloride is to produce fluorescent brightener CBS-X(C.I white dyes 351) and white dyes FP(C.I white dyes 378) important intermediate, also be that synthetic electronic chemical product material is 4, two (methoxymethyl) biphenyl of 4'-also can be used as the intermediate of Resins, epoxy, polyvinyl chloride (PVC) RESINS, vibrin based flame retardant.
The production technique of biphenyl benzyl dichloride, current what generally adopt both at home and abroad is to be raw material with biphenyl, Paraformaldehyde 96, gas HCL, is solvent with the sherwood oil, at ZnCl
2Effect makes through chloromethylation down.In the reaction, except that generating main reaction thing biphenyl benzyl dichloride, also generate materials such as side reaction thing biphenyl monochloro benzyl, behind the refining decon of solvent recrystallization, get finished product, yield (in biphenyl) the weight yield 83-85% of general finished product, molar yield 51-52%, the raffinate of the filtrate of recrystallizing and refining after reclaiming solvent make waste residue and handle.Product yield is low in the existing technology, and the production technique of existing biphenyl benzyl dichloride is needed improvement badly.
Summary of the invention
The objective of the invention is existing technology is improved, a kind of production technique of biphenyl benzyl dichloride is provided, the by product of disposing as waste residue that produces in the production of biphenyl benzyl dichloride is carried out recycled, participate in chloromethylation, change the concentration balance relation between original reactant and the resultant, suppress side reaction, make reaction help the main reaction thing and generate, improve biphenyl benzyl dichloride yield.
The objective of the invention is to be achieved through the following technical solutions, a kind of production technique of biphenyl benzyl dichloride, it is characterized in that, add sherwood oil in the reaction unit successively, biphenyl, by product, Paraformaldehyde 96, zinc chloride, stir, feed exsiccant HCL gas, chloromethylation, temperature of reaction 25-35 ℃, reaction times 22-26 hour take place down in normal pressure, reaction finishes, material is through washing, solid-liquid separation gets crude product, uses the toluene recrystallization again, and filter is done, dry the biphenyl benzyl dichloride, described biphenyl, by product, Paraformaldehyde 96, the mol ratio of zinc chloride is 1.0:0.4:2.3:0.6.
Described by product comprises the biphenyl monochloro benzyl of 16-18wt%, the biphenyl benzyl dichloride of 46-47wt%, the organic polymer of 22-25wt% and other impurity of 11-14wt%, and the molecular-weight average of described by product is 250.
Mol ratio between described sherwood oil and the biphenyl is 2:1.
Reaction equation of the present invention is:
The present invention has following beneficial effect: first, technology of the present invention is simple, the production efficiency height, it is low to consume energy, the product yield height, (by product comprises the biphenyl monochloro benzyl of 16-18wt% the by product of disposing as waste residue that produces in the production of biphenyl benzyl dichloride, the biphenyl benzyl dichloride of 46-47wt%, other impurity of the high boiling substance of 22-25wt% and 11-14wt%) carry out recycle, participate in chloromethylation, change the concentration balance relation between original reactant and the resultant, suppress side reaction, make reaction help the main reaction thing and generate, improve biphenyl benzyl dichloride yield, this technology makes biphenyl dichlorobenzene yield (in biphenyl), and weight yield reaches 100%-105%, improves 15%-20% than former technology, molar yield reaches 62-65%, improve 11-13% than former technology, quality product is identical with former technology, and by product waste residue amount obviously reduces; The second, the present invention reacts under the normal pressure and temperature condition, reaction conditions gentleness, operational safety; The 3rd, the present invention carries out recycle with the by product of disposing as waste residue that produces in the production of biphenyl benzyl dichloride, and the science environmental protection has solved the problem of the waste residue processing that produces in the biphenyl benzyl dichloride production process, reduce the disposal costs of waste residue, realized cleaner production, cyclic production.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment 1
A kind of production technique of biphenyl benzyl dichloride: drop into 2.00mol sherwood oil, 1.00mol biphenyl, 0.40mol by product, 2.3mol Paraformaldehyde 96,0.60mol zinc chloride in the reactor successively, stir, feed exsiccant HCL gas, chloromethylation takes place down in normal pressure, 25 ℃ of temperature of reaction, in 26 hours reaction times, reaction finishes, material in the reactor is washed, material after the washing leaves standstill, and solid-liquid separation gets crude product, uses the toluene recrystallization again, filter is done, dry the biphenyl benzyl dichloride.By product comprises the biphenyl monochloro benzyl of 16wt%, the biphenyl benzyl dichloride of 46wt%, the organic polymer of 22wt% and other impurity of 11wt%, and the molecular-weight average of by product is 250, and organic polymer mainly comprises polyethylene and polyvinyl chloride.The massfraction of biphenyl is 99%, and the massfraction of Paraformaldehyde 96 is 96%, and the massfraction of zinc chloride is 94.7%.More than Fan Ying reaction equation is:
Embodiment 2
A kind of production technique of biphenyl benzyl dichloride: drop into 3.0mol sherwood oil, 1.5mol biphenyl, 0.6mol by product, 3.45mol Paraformaldehyde 96,0.9mol zinc chloride in the reactor successively, stir, feed exsiccant HCL gas, chloromethylation takes place down in normal pressure, 30 ℃ of temperature of reaction, in 24 hours reaction times, reaction finishes, material in the reactor is washed, material after the washing leaves standstill, and solid-liquid separation gets crude product, uses the toluene recrystallization again, filter is done, dry the biphenyl benzyl dichloride.By product comprises the biphenyl monochloro benzyl of 18wt%, the biphenyl benzyl dichloride of 47wt%, the organic polymer of 25wt% and other impurity of 14wt%, and the molecular-weight average of by product is 250, and organic polymer mainly comprises polyethylene and polyvinyl chloride.The massfraction of biphenyl is 99%, and the massfraction of Paraformaldehyde 96 is 96%, and the massfraction of zinc chloride is 94.7%.More than Fan Ying reaction equation is with embodiment 1.
Embodiment 3
A kind of production technique of biphenyl benzyl dichloride: drop into 6mol sherwood oil, 3mol biphenyl, 1.2mol by product, 6.9mol Paraformaldehyde 96,1.8mol zinc chloride in the reactor successively, stir, feed exsiccant HCL gas, chloromethylation takes place down in normal pressure, 35 ℃ of temperature of reaction, in 22 hours reaction times, reaction finishes, material in the reactor is washed, material after the washing leaves standstill, and solid-liquid separation gets crude product, uses the toluene recrystallization again, filter is done, dry the biphenyl benzyl dichloride.By product comprises the biphenyl monochloro benzyl of 16wt%, the biphenyl benzyl dichloride of 47wt%, the organic polymer of 23wt% and other impurity of 13wt%, and the molecular-weight average of by product is 250, and organic polymer mainly comprises polyethylene and polyvinyl chloride.The massfraction of biphenyl is 99%, and the massfraction of Paraformaldehyde 96 is 96%, and the massfraction of zinc chloride is 94.7%.More than Fan Ying reaction equation is with embodiment 1.
Claims (3)
1. the production technique of a biphenyl benzyl dichloride, it is characterized in that, add sherwood oil, biphenyl, by product, Paraformaldehyde 96, zinc chloride in the reaction unit successively, stir, feed exsiccant HCL gas, chloromethylation takes place down in normal pressure, temperature of reaction 25-35 ℃, reaction times 22-26 hour, reaction finished, and material gets crude product through washing, solid-liquid separation, use the toluene recrystallization again, filter is done, dry the biphenyl benzyl dichloride, the mol ratio of described biphenyl, by product, Paraformaldehyde 96, zinc chloride is 1.0:0.4:2.3:0.6.
2. the production technique of a kind of biphenyl benzyl dichloride according to claim 1, it is characterized in that, described by product comprises the biphenyl monochloro benzyl of 16-18wt%, the biphenyl benzyl dichloride of 46-47wt%, the organic polymer of 22-25wt% and other impurity of 11-14wt%, and the molecular-weight average of described by product is 250.
3. the production technique of a kind of biphenyl benzyl dichloride according to claim 1 is characterized in that, the mol ratio between described sherwood oil and the biphenyl is 2:1.
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| CN2011102004484A CN102267870A (en) | 2011-07-18 | 2011-07-18 | Production process of 4,4'-bis(chloromethyl)-biphenyl |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880741A (en) * | 2014-02-28 | 2014-06-25 | 安徽国星生物化学有限公司 | Preparation method of 2-chloromethyl-3,5-dimethyl-4-alkoxypyridyl-N-oxide |
| CN104926599A (en) * | 2015-04-21 | 2015-09-23 | 青岛科技大学 | Method for preparing high-purity 4,4'-bis(chloromethyl)-1,1'-biphenyl under novel solvent system |
| CN105085159A (en) * | 2015-08-25 | 2015-11-25 | 陕西省石油化工研究设计院 | Preparation method of 4, 4'-bis(chloromethyl)-1, 1'-biphenyl |
| CN105503513A (en) * | 2015-12-08 | 2016-04-20 | 天津利安隆新材料股份有限公司 | Method for catalytically synthesizing 4,4'-bischloromethylbiphenyl by using silicon dioxide-loaded phosphotungstic acid |
| CN112573993A (en) * | 2020-11-20 | 2021-03-30 | 河北星宇化工有限公司 | Production process of 4, 4' -dichloromethyl biphenyl |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10139699A (en) * | 1996-11-08 | 1998-05-26 | Ube Ind Ltd | Production of 4,4'-bischloromethylbiphenyl |
| JPH1180047A (en) * | 1997-09-12 | 1999-03-23 | Ube Ind Ltd | Production of 4,4'-bis(chloromethybiphenyl) |
| JPH11130706A (en) * | 1997-10-31 | 1999-05-18 | Ube Ind Ltd | Production of 4,4'-bischloromethylbiphenyl |
| JP2005298356A (en) * | 2004-04-07 | 2005-10-27 | Nippon Kayaku Co Ltd | Method of purifying 4,4'-bischloromethylbiphenyl |
-
2011
- 2011-07-18 CN CN2011102004484A patent/CN102267870A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10139699A (en) * | 1996-11-08 | 1998-05-26 | Ube Ind Ltd | Production of 4,4'-bischloromethylbiphenyl |
| JPH1180047A (en) * | 1997-09-12 | 1999-03-23 | Ube Ind Ltd | Production of 4,4'-bis(chloromethybiphenyl) |
| JPH11130706A (en) * | 1997-10-31 | 1999-05-18 | Ube Ind Ltd | Production of 4,4'-bischloromethylbiphenyl |
| JP2005298356A (en) * | 2004-04-07 | 2005-10-27 | Nippon Kayaku Co Ltd | Method of purifying 4,4'-bischloromethylbiphenyl |
Non-Patent Citations (3)
| Title |
|---|
| 《淮海工学院学报》 19980930 季锡平 4,4'-二(氯甲基)联苯的合成 46-51 1-3 , 第3期 * |
| 季锡平: "4,4’-二(氯甲基)联苯的合成", 《淮海工学院学报》 * |
| 方奇等: "联苯氯甲基化反应的研究", 《精细与专用化学品》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880741A (en) * | 2014-02-28 | 2014-06-25 | 安徽国星生物化学有限公司 | Preparation method of 2-chloromethyl-3,5-dimethyl-4-alkoxypyridyl-N-oxide |
| CN104926599A (en) * | 2015-04-21 | 2015-09-23 | 青岛科技大学 | Method for preparing high-purity 4,4'-bis(chloromethyl)-1,1'-biphenyl under novel solvent system |
| CN105085159A (en) * | 2015-08-25 | 2015-11-25 | 陕西省石油化工研究设计院 | Preparation method of 4, 4'-bis(chloromethyl)-1, 1'-biphenyl |
| CN105503513A (en) * | 2015-12-08 | 2016-04-20 | 天津利安隆新材料股份有限公司 | Method for catalytically synthesizing 4,4'-bischloromethylbiphenyl by using silicon dioxide-loaded phosphotungstic acid |
| CN112573993A (en) * | 2020-11-20 | 2021-03-30 | 河北星宇化工有限公司 | Production process of 4, 4' -dichloromethyl biphenyl |
| CN112573993B (en) * | 2020-11-20 | 2023-03-14 | 河北星宇化工有限公司 | Production process of 4,4' -dichloromethyl biphenyl |
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Application publication date: 20111207 |