CN101928198A - A kind of preparation method of high-purity 4,4'-dichloromethyl biphenyl - Google Patents
A kind of preparation method of high-purity 4,4'-dichloromethyl biphenyl Download PDFInfo
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- CN101928198A CN101928198A CN2009100535496A CN200910053549A CN101928198A CN 101928198 A CN101928198 A CN 101928198A CN 2009100535496 A CN2009100535496 A CN 2009100535496A CN 200910053549 A CN200910053549 A CN 200910053549A CN 101928198 A CN101928198 A CN 101928198A
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Abstract
本发明涉及到一种高纯度的4，4’-二氯甲基联苯的制备方法，属化工合成领域，特别是涉及以联苯为原料制备高纯度4，4’-二氯甲基联苯的方法。以联苯为原料经氯甲基化反应、精制两步制备4，4’-二氯甲基联苯，纯度达到99％以上。The invention relates to a method for preparing high-purity 4,4'-dichloromethyl biphenyl, which belongs to the field of chemical synthesis, in particular to the preparation of high-purity 4,4'-dichloromethyl biphenyl using biphenyl as raw material. Benzene method. Using biphenyl as raw material, 4,4'-dichloromethylbiphenyl is prepared through two steps of chloromethylation and refining, with a purity of over 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, and particularly relating to biphenyl is feedstock production high purity 4, the method for 4 '-dichloromethyl biphenyl.
Background technology
The biphenyl benzyl dichloride is a kind of fine-chemical intermediate, is widely used in synthetic white dyes, the high-load electronic material that can be used for.4,4 '-dichloromethyl biphenyl is the main raw material of synthesizing efficient fluorescent brightener CBS, also is simultaneously synthetic medicine intermediate 4, the important source material of 4 '-'-bis (hydroxymethyl) biphenyl.And CBS is widely used in the industry such as plastics, fiber, coating, and it brightens, brightening effect is fairly obvious.Though domestic have a minority manufacturer production, its quality and quantity all can not satisfy market demand, and annual the need solves from external import. and the key that influences CBS quality and cost is the 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, significant to the industrial production of the production of CBS and related products.
Report is more 4 in the document, and the synthetic of 4 '-dichloromethyl biphenyl is to be raw material with biphenyl, and Paraformaldehyde 96 is a methylating reagent, and under the effect of catalyzer, logical hydrogenchloride obtains.US3001975 has reported biphenyl and Paraformaldehyde 96 in zinc chloride catalysis, prepare 4 under acetic acid and concentrated hydrochloric acid effect, the process of 4 '-dichloromethyl biphenyl, but the product that obtains at last contains a large amount of single substitution products, and document does not provide process for purification.The 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, have also been 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 of having used mixed solvent to cause solvent recuperation to apply mechanically has perhaps been used more expensive catalyzer, so all be not suitable for suitability for industrialized production.Also have other Chinese literatures that similar research report is arranged, the recrystallization by benzene kind solvent among the CN1412193, but long reaction time needs reaction 25 hours, and yield also has only below 40%.
Summary of the invention
The present invention relates to a kind of preparation highly purified 4, the method of 4 '-dichloromethyl biphenyl, can stably obtain purity 4 more than 99%, 4 '-dichloromethyl biphenyl, and the quality index of relevant 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: in a certain amount of alkane or chlorinated paraffin solvent, add biphenyl, concentrated hydrochloric acid, stir, feed dry hydrogen chloride, control certain temperature of reaction, add Paraformaldehyde 96 and zinc chloride then in batches, after HPLC tracking reaction is finished, 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 the gac reflux decolour, the crystallization of heat filtering postcooling, and suction filtration gets pure di-benzyl chloride.Total recovery reaches more than 80%.
Wherein, in chloromethylation, reacting employed alkane solvent is pentane, hexane, heptane, sherwood oil, and chloroparaffin is methylene dichloride, trichloromethane, preferred sherwood oil.The consumption of solvent is biphenyl 1-5 times, and preferred 2-3 doubly.Temperature of reaction is 25-60 ℃, preferred 40-45 ℃.The feeding mode of raw material Paraformaldehyde 96 and zinc chloride is for add in batches, and it is best preferably to divide 3-5 to criticize adding.
In treating process, described benzene kind solvent is a benzene,toluene,xylene, and alcoholic solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, and wherein the ratio of pure and mild benzene kind solvent is volume ratio 1: 20-1: 5, preferred 1: 12-1: 9; 4, the ratio of 4 '-dichloromethyl biphenyl crude product and mixed solvent is 1: 1-1: 10, preferred 1: 2-1: 5.
Specific implementation method
Embodiment 1
In the 3L reaction flask, add 308g biphenyl (2mol), the 120ml concentrated hydrochloric acid, the 800ml sherwood oil stirs; The exsiccant hydrogen chloride gas is fed, and controlled temperature to 40 ℃ behind the temperature-stable, adds the 70g Paraformaldehyde 96, the 245g zinc chloride fast; Afterwards, add remaining Paraformaldehyde 96 and zinc chloride in batches, reacted 8 hours.Finish after-filtration and go out solid, wash solid with water, dry 4,4 '-dichloromethyl biphenyl crude product.
With 800ml toluene and 100ml ethanol mixed solvent dissolving soluble solids, add 15 gram gacs, refluxed 30 minutes, heat filtering is removed gac.The slow crystallisation by cooling of the filtrate that filters out, filtration, dry 430g4,4 '-dichloromethyl biphenyl, yield 80.0%, purity 99.3%, the metal ion conformance with standard of getting.
Embodiment 2
In the 3L reaction flask, add 308g biphenyl (2mol), the 120ml concentrated hydrochloric acid, the 800ml sherwood oil stirs; The exsiccant hydrogen chloride gas is fed, and controlled temperature to 20 ℃ behind the temperature-stable, adds the 65g Paraformaldehyde 96, the 240g zinc chloride fast; Afterwards, add remaining Paraformaldehyde 96 and zinc chloride in batches, reacted 9 hours.Finish after-filtration and go out solid, wash solid with water, dry 4,4 '-dichloromethyl biphenyl crude product.
With 750ml toluene and 150ml ethanol mixed solvent dissolving soluble solids, add 15 gram gacs, refluxed 30 minutes, heat filtering is removed gac.The slow crystallisation by cooling of the filtrate that filters out, filtration, dry 410g4,4 '-dichloromethyl biphenyl, yield 82.0%, purity 99.2%, the metal ion conformance with standard of getting.
Embodiment 3
In the 3L reaction flask, add 308g biphenyl (2mol), the 120ml concentrated hydrochloric acid, the 800ml sherwood oil stirs; The exsiccant hydrogen chloride gas is fed, and controlled temperature to 20 ℃ behind the temperature-stable, adds the 65g Paraformaldehyde 96, the 240g zinc chloride fast; Afterwards, add remaining Paraformaldehyde 96 and zinc chloride in batches, reacted 9 hours.Finish after-filtration and go out solid, wash solid with water, dry 4,4 '-dichloromethyl biphenyl crude product.
With 1385ml toluene and 115ml ethanol mixed solvent dissolving soluble solids, add 15 gram gacs, refluxed 30 minutes, heat filtering is removed gac.The slow crystallisation by cooling of the filtrate that filters out filters, dry 415g 4,4 '-dichloromethyl biphenyl, and yield 82.7%, purity is greater than 99.2%, the metal ion conformance with standard.
Claims (13)
- One kind highly purified 4, the preparation method of 4 '-dichloromethyl biphenyl may further comprise the steps:(A) add biphenyl in a certain amount of alkane or chlorinated hydrocarbon solvent, concentrated hydrochloric acid stirs, and feeds dry hydrogen chloride, controls certain temperature of reaction, adds Paraformaldehyde 96 and zinc chloride then in batches, after the tracking reaction is finished, filters and obtains crude product;(B) refining: crude product is dissolved in a certain amount of benzene kind solvent and alcohols mixed solvent, and add gac and decolour at a certain temperature, the crystallization of heat filtering postcooling, it is highly purified 4 that suction filtration gets, 4 '-dichloromethyl biphenyl.
- 2. preparation method according to claim 1 is characterized in that the alkane solvent in the 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 the step (A) is a sherwood oil.
- 4. preparation method according to claim 1, the consumption that it is characterized in that solvent in the step (A) is 1-5 a times of biphenyl.
- 5. preparation method according to claim 4, the consumption that it is characterized in that solvent in the step (A) is biphenyl 2-3 times.
- 6. preparation method according to claim 1, the temperature of reaction that it is characterized in that step (A) is 1-60 ℃,
- 7. preparation method according to claim 6, the temperature of reaction that it is characterized in that step (A) is 30-50 ℃.
- 8. preparation method according to claim 1 is characterized in that in the step (A), and the feeding mode of raw material Paraformaldehyde 96 and zinc chloride preferably divides 3-5 to criticize for add in batches.
- 9. preparation method according to claim 1 is characterized in that step (B) benzene kind solvent is a benzene,toluene,xylene, and alcoholic solvent is methyl alcohol, ethanol, propyl alcohol, Virahol.
- 10. preparation method according to claim 1 is characterized in that in the step (B), the ratio of pure and mild benzene kind solvent is volume ratio 1: 20-1: 5.
- 11. preparation method according to claim 10 is characterized in that in the step (B), the ratio of pure and mild benzene kind solvent is volume ratio 1: 12-1: 9.
- 12. preparation method according to claim 1 is characterized in that in the step (B), 4, and the ratio of 4 '-dichloromethyl biphenyl crude product and mixed solvent is 1: 1-1: 10.
- 13. preparation method according to claim 1 is characterized in that in the step (B), 4, and the ratio of 4 '-dichloromethyl biphenyl crude product and mixed solvent is 1: 2-1: 5.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN110028379A (en) * | 2019-04-04 | 2019-07-19 | 三峡大学 | A kind of 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 |
| CN117430789A (en) * | 2023-10-13 | 2024-01-23 | 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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| JPH1180047A (en) * | 1997-09-12 | 1999-03-23 | Ube Ind Ltd | Method for producing 4,4'-bischloromethylbiphenyl |
| JPH11130706A (en) * | 1997-10-31 | 1999-05-18 | Ube Ind Ltd | Method for producing 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 |
| 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 |
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2009
- 2009-06-22 CN CN200910053549.6A patent/CN101928198B/en not_active Expired - Fee Related
Patent Citations (4)
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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 |
| JPH1180047A (en) * | 1997-09-12 | 1999-03-23 | Ube Ind Ltd | Method for producing 4,4'-bischloromethylbiphenyl |
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Non-Patent Citations (1)
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| 陈红飙等: "4,4，-二氯甲基联苯的合成研究", 《染料工业》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN110028379A (en) * | 2019-04-04 | 2019-07-19 | 三峡大学 | A kind of preparation method of 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 |
| CN117430789A (en) * | 2023-10-13 | 2024-01-23 | 安徽觅拓材料科技有限公司 | Preparation method and application of high-purity colorless transparent biphenyl phenolic resin |
| 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 and transparent biphenyl phenol-formaldehyde resin |
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