CN101928198B - Preparation method of high-purity 4,4'-dichloromethyl biphenyl - Google Patents
Preparation method of high-purity 4,4'-dichloromethyl biphenyl Download PDFInfo
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- CN101928198B CN101928198B CN200910053549.6A CN200910053549A CN101928198B CN 101928198 B CN101928198 B CN 101928198B CN 200910053549 A CN200910053549 A CN 200910053549A CN 101928198 B CN101928198 B CN 101928198B
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Abstract
The invention relates to a preparation method of high-purity 4,4'-dichloromethyl biphenyl, belongs to the field of chemical synthesis and particularly relates to the method for preparing the high-purity 4,4'-dichloromethyl biphenyl by taking biphenyl as a raw material. The purity of the 4,4'-dichloromethyl biphenyl which is prepared by taking the biphenyl as the raw material through two steps of chloromethylation reaction and refining can be more than 99%.
Description
Technical field
The present invention relates to a kind of highly purifiedly 4, the preparation method of 4 '-dichloromethyl biphenyl, belongs to the synthetic field of chemical industry, particularly relates to and prepares high purity 4, the method for 4 '-dichloromethyl biphenyl taking biphenyl as raw material.
Background technology
Biphenyl benzyl dichloride is a kind of fine-chemical intermediate, is widely used in synthetic white dyes, high-content can be used for electronic material.4,4 '-dichloromethyl biphenyl is the main raw material of synthesizing efficient fluorescent brightener CBS, is also synthetic medicine intermediate 4 simultaneously, the important source material of 4 '-'-bis (hydroxymethyl) biphenyl.And CBS is widely used in the industry such as plastics, fiber, coating, it brightens, brightening effect is fairly obvious.Though have minority manufacturer production domestic, its quality and quantity all can not meet market demand, need solve from external import every year. and the key that affects CBS quality and cost is purity and the yield of its raw material 4,4 '-dichloromethyl biphenyl.Common content is more than 95%.The quality of a lot of bibliographical informations is all at 80-95%.Seldom can accomplish more than 97%.Therefore, how to improve 4, the purity of 4 '-dichloromethyl biphenyl and yield, the production to CBS and the industrial production of related products are significant.
In document, report morely 4, the synthetic of 4 '-dichloromethyl biphenyl is taking biphenyl as raw material, and paraformaldehyde is methylating reagent, and under the effect of catalyzer, logical hydrogenchloride obtains.US3001975 has reported that biphenyl and paraformaldehyde in zinc chloride catalysis, prepare 4 under acetic acid and concentrated hydrochloric acid effect, the process of 4 '-dichloromethyl biphenyl, but the product finally obtaining contains a large amount of monosubstituted products, and document does not provide process for purification.Document dyestuffs industries, 2001,38 (3): 41-42 has reported with zinc chloride catalysis, mixed solvent preparation, but the purity of product is not high yet.Trifluoromethayl sulfonic acid scandium, trifluoromethayl sulfonic acid indium catalyzer in the document of some researches, are also mentioned, solvent is mainly methylene dichloride, trichloromethane, sherwood oil, hexanaphthene etc., also have and in solvent, add formic acid, Glacial acetic acid or trichoroacetic acid(TCA) (Huaihai Institute of Technology journal, 2006,15 (2): 41-43), but these reactions are because the difficulty that has used mixed solvent to cause solvent recuperation to apply mechanically, or used more expensive catalyzer, so be all not suitable for suitability for industrialized production.Also have other Chinese literatures to have similar research report, in CN1412193, by the recrystallization of benzene kind solvent, but long reaction time need to react 25 hours, and yield also only has below 40%.
Summary of the invention
The present invention relates to one and prepare highly purified 4, the method of 4 '-dichloromethyl biphenyl, can stably obtain more than 99% 4 of purity, 4 '-dichloromethyl biphenyl, and the quality index of metal ion reaches: Fe < 1mg/Kg, Na < 2mg/Kg, Ca < 3mg/Kg, Zn≤20mg/Kg, meet the requirement of electronic product intermediate, promoted quality product.Synthesis step is:
(1) chloromethylation: add biphenyl in a certain amount of alkane or chlorinated paraffin solvent, concentrated hydrochloric acid, stir, pass into dry hydrogen chloride, control certain temperature of reaction, then add paraformaldehyde and zinc chloride in batches, after HPLC follows the tracks of and reacted, filtration obtains 4, the crude product of 4 '-dichloromethyl biphenyl.
(2) refining: crude product is dissolved in a certain amount of benzene kind solvent and alcohols mixed solvent, adds gac reflux decolour, crystallisation by cooling after heat filtering, suction filtration obtains pure di-benzyl chloride.Total recovery reaches more than 80%.
Wherein, in chloromethylation, the alkane solvent that reaction is used is pentane, hexane, heptane, sherwood oil, and chloroparaffin is methylene dichloride, trichloromethane, preferably sherwood oil.The consumption of solvent is biphenyl 1-5 times, and preferably 2-3 doubly.Temperature of reaction is 25-60 DEG C, preferably 40-45 DEG C.The feeding mode of raw material paraformaldehyde and zinc chloride is for add in batches, preferably divides 3-5 to criticize to add best.
In treating process, described benzene kind solvent is benzene,toluene,xylene, and alcoholic solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, and wherein the ratio of alcohol and benzene kind solvent is volume ratio 1: 20-1: 5, preferably 1: 12-1: 9; 4, the ratio of 4 '-dichloromethyl biphenyl crude product and mixed solvent is 1: 1-1: 10, preferably 1: 2-1: 5.
Specific implementation method
Embodiment 1
In 3L reaction flask, add 308g biphenyl (2mol), 120ml concentrated hydrochloric acid, 800ml sherwood oil, stirs; Dry hydrogen chloride gas is passed into, control temperature to 40 DEG C, after temperature-stable, add fast 70g paraformaldehyde, 245g zinc chloride; Afterwards, add remaining paraformaldehyde and zinc chloride in batches, react 8 hours.After end, filter out solid, wash solid with water, dry 4,4 '-dichloromethyl biphenyl crude product.
With the mixed solvent dissolving soluble solids of 800ml toluene and 100ml ethanol, add 15 grams of gacs, reflux 30 minutes, heat filtering is removed gac.The filtrate Slow cooling crystallization filtering out, filters, is dried to obtain 430g4,4 '-dichloromethyl biphenyl, yield 80.0%, purity 99.3%, metal ion conformance with standard.
Embodiment 2
In 3L reaction flask, add 308g biphenyl (2mol), 120ml concentrated hydrochloric acid, 800ml sherwood oil, stirs; Dry hydrogen chloride gas is passed into, control temperature to 20 DEG C, after temperature-stable, add fast 65g paraformaldehyde, 240g zinc chloride; Afterwards, add remaining paraformaldehyde and zinc chloride in batches, react 9 hours.After end, filter out solid, wash solid with water, dry 4,4 '-dichloromethyl biphenyl crude product.
With the mixed solvent dissolving soluble solids of 750ml toluene and 150ml ethanol, add 15 grams of gacs, reflux 30 minutes, heat filtering is removed gac.The filtrate Slow cooling crystallization filtering out, filters, is dried to obtain 410g4,4 '-dichloromethyl biphenyl, yield 82.0%, purity 99.2%, metal ion conformance with standard.
Embodiment 3
In 3L reaction flask, add 308g biphenyl (2mol), 120ml concentrated hydrochloric acid, 800ml sherwood oil, stirs; Dry hydrogen chloride gas is passed into, control temperature to 20 DEG C, after temperature-stable, add fast 65g paraformaldehyde, 240g zinc chloride; Afterwards, add remaining paraformaldehyde and zinc chloride in batches, react 9 hours.After end, filter out solid, wash solid with water, dry 4,4 '-dichloromethyl biphenyl crude product.
With the mixed solvent dissolving soluble solids of 1385ml toluene and 115ml ethanol, add 15 grams of gacs, reflux 30 minutes, heat filtering is removed gac.The filtrate Slow cooling crystallization filtering out, filters, is dried to obtain 415g 4,4 '-dichloromethyl biphenyl, and yield 82.7%, purity is greater than 99.2%, metal ion conformance with standard.
Claims (10)
- One kind highly purified 4, the preparation method of 4 '-dichloromethyl biphenyl, comprises the following steps:(A) in a certain amount of alkane or chlorinated hydrocarbon solvent, add biphenyl, concentrated hydrochloric acid, stirs, and passes into dry hydrogen chloride, controls certain temperature of reaction, then adds paraformaldehyde and zinc chloride in batches, after tracking has been reacted, filters and obtains crude product;(B) refining: crude product is dissolved in a certain amount of benzene kind solvent and alcohols mixed solvent, add gac and decolour at a certain temperature, crystallisation by cooling after heat filtering, it is highly purified 4 that suction filtration obtains, 4 '-dichloromethyl biphenyl;Doubly, described temperature of reaction is 1-60 DEG C to the 1-5 that in step (A), the consumption of solvent is biphenyl;In step (B), the ratio of alcoholic solvent and benzene kind solvent is volume ratio 1:20-1:5; Wherein, benzene kind solvent is benzene,toluene,xylene, and alcoholic solvent is methyl alcohol, ethanol, propyl alcohol, Virahol;Described " high purity " refers to that purity is more than 99%.
- 2. preparation method according to claim 1, is characterized in that the alkane solvent in step (A) is pentane, hexane, heptane, sherwood oil; Hydrochloric ether is methylene dichloride, trichloromethane.
- 3. preparation method according to claim 2, is characterized in that the alkane solvent in step (A) is sherwood oil.
- 4. preparation method according to claim 1, the consumption that it is characterized in that solvent in step (A) is biphenyl 2-3 times.
- 5. preparation method according to claim 1, is characterized in that the temperature of reaction in step (A) is 30-50 DEG C.
- 6. preparation method according to claim 1, is characterized in that in step (A), the feeding mode of raw material paraformaldehyde and zinc chloride is for add in batches.
- 7. preparation method according to claim 1, is characterized in that, in step (B), the ratio of alcohol and benzene kind solvent is volume ratio 1:12-1:9.
- 8. preparation method according to claim 1, is characterized in that in step (B), 4, and the ratio of 4 '-dichloromethyl biphenyl crude product and mixed solvent is 1:1-1:10.
- 9. preparation method according to claim 1, is characterized in that in step (B), 4, and the ratio of 4 '-dichloromethyl biphenyl crude product and mixed solvent is 1:2-1:5.
- 10. preparation method according to claim 6, is characterized in that the feeding mode of raw material paraformaldehyde and zinc chloride adds for a point 3-5 criticizes.
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| 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 |
| CN105061137A (en) * | 2015-07-23 | 2015-11-18 | 韦海棉 | Synthetic method for 4, 4'-bis(chloromethyl) biphenyl |
| CN105503513B (en) * | 2015-12-08 | 2018-04-24 | 天津利安隆新材料股份有限公司 | The method of silicon dioxide carried catalysis of phosphotungstic acid synthesis 4,4 '-dichloromethyl biphenyl |
| CN110028379B (en) * | 2019-04-04 | 2022-03-18 | 三峡大学 | Preparation method of 4, 4' -dichloromethyl biphenyl |
| CN110078585A (en) * | 2019-04-18 | 2019-08-02 | 山东省计量科学研究院 | A kind of method of purification and device of octafluoro naphthalene |
| CN117430789B (en) * | 2023-10-13 | 2024-05-17 | 安徽觅拓材料科技有限公司 | Preparation method and application of high-purity colorless transparent biphenyl phenolic resin |
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| JP3784865B2 (en) * | 1995-09-19 | 2006-06-14 | 新日鐵化学株式会社 | Method for producing 4,4'-bis (chloromethyl) biphenyl |
| JP3845977B2 (en) * | 1997-09-12 | 2006-11-15 | 宇部興産株式会社 | Method for producing 4,4'-bischloromethylbiphenyl |
| JPH11130706A (en) * | 1997-10-31 | 1999-05-18 | Ube Ind Ltd | Production of 4,4'-bischloromethylbiphenyl |
| CN1412193A (en) * | 2002-11-07 | 2003-04-23 | 大庆开发区新世纪精细化工有限公司 | Method for preparing 4,4'-bis (diethoxyphosphorylmethyl) biphenyl |
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