CN104926599A - Method for preparing high-purity 4,4'-bis(chloromethyl)-1,1'-biphenyl under novel solvent system - Google Patents
Method for preparing high-purity 4,4'-bis(chloromethyl)-1,1'-biphenyl under novel solvent system Download PDFInfo
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- CN104926599A CN104926599A CN201510190914.3A CN201510190914A CN104926599A CN 104926599 A CN104926599 A CN 104926599A CN 201510190914 A CN201510190914 A CN 201510190914A CN 104926599 A CN104926599 A CN 104926599A
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- biphenyl
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- preparing high
- benzyl dichloride
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000002904 solvent Substances 0.000 title claims abstract description 19
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 title abstract description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000004305 biphenyl Substances 0.000 claims abstract description 17
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 17
- 238000007265 chloromethylation reaction Methods 0.000 claims abstract description 3
- 238000007670 refining Methods 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 12
- 229920002866 paraformaldehyde Polymers 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 235000011054 acetic acid Nutrition 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- FGKJLKRYENPLQH-UHFFFAOYSA-N isocaproic acid Chemical compound CC(C)CCC(O)=O FGKJLKRYENPLQH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 5
- IGIDLTISMCAULB-UHFFFAOYSA-N 3-methylvaleric acid Chemical compound CCC(C)CC(O)=O IGIDLTISMCAULB-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 4
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000009835 boiling Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 239000007789 gas Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000012264 purified product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- RAZKIGBWDJNTKX-UHFFFAOYSA-N 1-(dichloromethyl)-4-phenylbenzene Chemical group C1=CC(C(Cl)Cl)=CC=C1C1=CC=CC=C1 RAZKIGBWDJNTKX-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HSASKNPEYJOZHA-UHFFFAOYSA-N 2-[3-(carboxymethoxy)-5-(1-hydroxy-2-oxo-2-phenylethyl)phenoxy]acetic acid Chemical compound C(=O)(O)COC=1C=C(C(C(C2=CC=CC=C2)=O)O)C=C(C=1)OCC(=O)O HSASKNPEYJOZHA-UHFFFAOYSA-N 0.000 description 1
- 238000010464 Blanc reaction Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SFHGONLFTNHXDX-UHFFFAOYSA-N [4-[4-(hydroxymethyl)phenyl]phenyl]methanol Chemical group C1=CC(CO)=CC=C1C1=CC=C(CO)C=C1 SFHGONLFTNHXDX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
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Abstract
The invention relates to a method for preparing high-purity 4,4'-bis(chloromethyl)-1,1'-biphenyl under a novel solvent system, and belongs to the field of chemical synthesis, in particular to a method for preparing the high-purity 4,4'-bis(chloromethyl)-1,1'-biphenyl under the novel solvent system by using biphenyl as a raw material. Through the application of a novel solvent, the 4,4'-bis(chloromethyl)-1,1'-biphenyl is prepared through two steps of a chloromethylation reaction and refining by using the biphenyl as the raw material, the yield is greater than or equal to 80%, and the purity is greater than or equal to 99%. The product changes a traditional solvent system, the yield and purity of the product are obviously improved, the potential safety hazards of a low-boiling solvent in the production process are reduced, and the solvent is convenient for recycling.
Description
Technical field
The present invention relates to a kind of method preparing high purity biphenyl-benzyl dichloride at novel dissolvent, belong to technical field of chemical synthesis.
Background technology
4,4 '-bis-(chloromethyl) biphenyl (4,4 '-bis (chloromethyl) biphenyl, BCMB), also claiming biphenyl-benzyl dichloride, is a kind of fine-chemical intermediate, can be used as the monomer of synthetic resins, also can be used as the raw material of biphenyl analog derivative.Be mainly used at present synthesizing white dyes, have good whitening effect to tynex, thiozell; To cellulosic fibre, there is suitable affinity and good diffusion, can allow the whiteness that cellulosic fibre reaches rapidly very high at short notice; Simultaneously it has the perspiration fastness of excellent resistance to oxygen bleaching, chlorine-resistant drift, strong alkali-acid resistance performance and excellence; And its whiteness is very stable, washs, contaminate, to dry loss in process little, whitening effect is fairly obvious, and not easy to change in storage process, is described as super-fluorescent whitening agent by people.At present, for this fluorescent bleaches China mainly dependence on import, also have manufacturer production although domestic in recent years, there is sizable gap in quality compared with external product, and industrial scale is also smaller.The biphenyl-benzyl dichloride of high purity (99%) can be used for synthesizing compound of liquid crystal or polymkeric substance, also can as the intermediate of epoxy resin, polyvinyl chloride (PVC) RESINS, vibrin based flame retardant.This high-quality product, meets domestic needs mainly through import at present.Present Domestic generally adopts technique to be with biphenyl, paraformaldehyde for raw material outward, at catalyst Z nCl
2under effect, synthesized by Blanc chloromethylation.This preparation method is simple to operation, industrially has a wide range of applications.
Total reaction formula can be expressed as:
US3001975 reports biphenyl and paraformaldehyde prepares 4 under zinc chloride catalysis, acetic acid and concentrated hydrochloric acid effect, the process of 4 '-dichloromethyl biphenyl, but the product finally obtained contains a large amount of mono-substituted products, and document does not provide process for purification.
The people such as Ma Weixing are at document " 4,4 '-bis-(chloromethyl) biphenyl new synthetic process " in have set forth by biphenyl be raw material, first synthesize 4,4 '-bis-(methylol) biphenyl, biphenyl-benzyl dichloride is synthesized again by thionyl chloride, reaction is made up of four steps, and reaction process is comparatively loaded down with trivial details, and yield only reaches 61.5%.
Chinese patent CN101928198 discloses a kind of production technique of biphenyl-benzyl dichloride, it is raw material that this technique adopts sherwood oil to be solvent, biphenyl, paraformaldehyde and zinc chloride, and the by product as Solid state fermentation produced in biphenyl-benzyl dichloride production is carried out recycled, pass through activated carbon decolorizing, obtain biphenyl-benzyl dichloride, yield.But there is a large amount of by product to generate in production process, and with sherwood oil or these lower boiling reagent of hexanaphthene as solvent, in actual industrial production, there is huge potential safety hazard.
Summary of the invention
The invention discloses a kind of method preparing high purity biphenyl-benzyl dichloride at novel dissolvent.By improveing the solvent of existing technological reaction, use novel dissolvent, in reaction process, the impurity such as a chlorine substituent or many chlorine substituent is separated with product biphenyl-benzyl dichloride, not only drastically increase production security, and effectively improve the quality of product, yield (>80%), purity (>99%), improve the value of product, meet the demand of high-tech product; By carrying out compressive reaction to reaction system, significantly reducing the input amount of raw material, improve feed stock conversion significantly; By strictly controlling temperature of reaction, fully suppressing the generation of side reaction, significantly enhancing the selectivity of product, meet the principle of Atom economy.
Below main technical schemes of the present invention:
In reaction unit, add novel dissolvent I, biphenyl, paraformaldehyde and catalyzer successively, temperature of reaction control 25 ~ 80 DEG C, 25 ~ 35 hours reaction times, pass into dry HCL gas condition under carry out chloromethylation, HPLC following response; After reaction terminates, because the impurity such as a chlorine substituent or many chlorine substituent are dissolved in solvent I, coarse fodder is directly through washing, filtering and solvent II recrystallization, solid-liquid separation, without desolventing technology, convection drying obtains highly purified biphenyl-benzyl dichloride (HPLC>99%).
Described solvent I is toluene, chlorobenzene, dimethylbenzene, methyl alcohol, ethanol, ethylene glycol, formic acid, acetic acid, propionic acid, butyric acid, isopropylformic acid, isovaleric acid, valeric acid, 3 methylvaleric acid, 4-methylvaleric acid, caproic acid, enanthic acid, sad, one or more in the middle of isocaprylic acid, n-nonanoic acid, methylene dichloride, chloroform, tetracol phenixin.
In the middle of described solvent I, the mol ratio of each component is 1:0 ~ 15:0 ~ 7.
Described catalyzer is one or both in the middle of aluminum chloride, tin chloride, cupric chloride, phosphoric acid, hydrochloric acid, sulfuric acid, zinc chloride.
The mol ratio of described biphenyl, paraformaldehyde, catalyzer is 1:0 ~ 3:0 ~ 2.
The mol ratio of described biphenyl and solvent I is 1:0 ~ 3.
Described recrystallization solvent for use II is one or both in toluene, chlorobenzene, dimethylbenzene, benzene, ethanol, methyl alcohol, butanols, formic acid, acetic acid, ethyl acetate, propyl acetate.
Compared with prior art, the beneficial effect that the present invention has is:
(1) the present invention is the industrial method of preparation high purity biphenyl-benzyl dichloride;
(2) reaction solvent system is improved, improve quality and the production security of product;
(3) solvent for use is convenient to recovery;
(4) by the control to temperature of reaction, obviously suppress the generation of side reaction, improve the selectivity of product;
(5) raw-material transformation efficiency is significantly improved.
Accompanying drawing explanation
Fig. 1 is FB(flow block) of the present invention.
Embodiment
Below in conjunction with specific examples, set forth the present invention further.
Embodiment 1
A kind of method preparing high purity biphenyl-benzyl dichloride under novel dissolvent system: drop into 2.00mol toluene, 0.50mol butyric acid, 1.00mol biphenyl, 2.00mol paraformaldehyde, 0.55mol aluminum chloride in reactor successively, stir, pass into dry HCL gas, control temperature 30 ~ 50 DEG C, reacts 30 hours.Reaction terminates, and is carried out by the material in reactor washing, filters and to obtain thick product, then carry out recrystallization with toluene, dry purified product after filtering.Testing product purity is 99.15%, and yield is 82.2%.
Embodiment 2
A kind of method preparing high purity biphenyl-benzyl dichloride under novel dissolvent system: drop into 1.50mol chlorobenzene, 1.00mol formic acid, 1.00mol biphenyl, 2.00mol paraformaldehyde, 0.70mol zinc chloride in reactor successively, stir, pass into dry HCL gas, control temperature 25 ~ 55 DEG C, reacts 28 hours.Reaction terminates, and is carried out by the material in reactor washing, filters and to obtain thick product, then carry out recrystallization with benzene and ethanol, dryly after filtering obtains purified product.Testing product purity is 99.26%, and yield is 84.1%.
Embodiment 3
A kind of method preparing high purity biphenyl-benzyl dichloride under novel dissolvent system: drop into 6.00mol ethanol, 1.50mol propionic acid, 3.00mol biphenyl, 6.00mol paraformaldehyde, 1.65mol aluminum chloride in reactor successively, stir, pass into dry HCL gas, control temperature 35 ~ 55 DEG C, reacts 30 hours.Reaction terminates, and is carried out by the material in reactor washing, filters and to obtain thick product, then carry out recrystallization with dimethylbenzene, dry purified product after filtering.Testing product purity is 99.42%, and yield is 84.7%.
Embodiment 4
A kind of method preparing high purity biphenyl-benzyl dichloride under novel dissolvent system: drop into 1.00mol toluene, 0.25mol isocaprylic acid, 0.50mol biphenyl, 1.00mol paraformaldehyde, 0.3mol zinc chloride in reactor successively, stir, pass into dry HCL gas, under pressurization 50kpa condition, control temperature 40 ~ 65 DEG C, reacts 30 hours.Reaction terminates, and is carried out by the material in reactor washing, filters and to obtain thick product, then carry out recrystallization with acetic acid, dry purified product after filtering.Testing product purity is 99.17%, and yield is 83.5%.
Embodiment 5
A kind of method preparing high purity biphenyl-benzyl dichloride under novel dissolvent system: drop into 6.00mol toluene, 1.50mol 4-methylvaleric acid, 3.00mol biphenyl, 6.00mol paraformaldehyde, 1.65mol aluminum chloride in reactor successively, stir, pass into dry HCL gas, control temperature 55 ~ 80 DEG C, reacts 25 hours.Reaction terminates, and is carried out by the material in reactor washing, filters and to obtain thick product, then carry out recrystallization with toluene and methyl alcohol, dryly after filtering obtains purified product.Testing product purity is 99.25%, and yield is 80.7%.
Claims (9)
1. under novel dissolvent system, prepare a method for high purity biphenyl-benzyl dichloride, comprise the steps:
(1) joined in reaction unit with novel dissolvent I by a certain amount of biphenyl and mix, paraformaldehyde and catalyzer join in reaction unit in batches according to certain mol proportion, and under the condition passing into dry HCL gas, chloromethylation is carried out in heating;
(2) refining: the material system after reaction being terminated obtains high purity biphenyl-benzyl dichloride product after washing, filtration, recrystallization, drying.
2. a kind of method preparing high purity biphenyl-benzyl dichloride under novel dissolvent system as claimed in claim 1, it is characterized in that: novel dissolvent I is toluene, chlorobenzene, dimethylbenzene, methyl alcohol, ethanol, ethylene glycol, formic acid, acetic acid, propionic acid, butyric acid, isopropylformic acid, isovaleric acid, valeric acid, 3 methylvaleric acid, 4-methylvaleric acid, caproic acid, enanthic acid, sad, one or more in the middle of isocaprylic acid, n-nonanoic acid, methylene dichloride, chloroform, tetracol phenixin.
3. a kind of method preparing high purity biphenyl-benzyl dichloride as claimed in claim 1, is characterized in that: in the middle of the novel dissolvent I described in step (1), the mol ratio of each component is 1:0 ~ 15:0 ~ 7.
4. a kind of method preparing high purity biphenyl-benzyl dichloride under novel dissolvent system as claimed in claim 1, is characterized in that: the mol ratio of the biphenyl described in step (1), paraformaldehyde, catalyzer is 1:0 ~ 3:0 ~ 2.
5. a kind of method preparing high purity biphenyl-benzyl dichloride under novel dissolvent system as claimed in claim 1, is characterized in that: the biphenyl described in step (1) and the mol ratio of novel dissolvent I are 1:0 ~ 3.
6. a kind of method preparing high purity biphenyl-benzyl dichloride under novel dissolvent system as claimed in claim 1, is characterized in that: the catalyzer described in step (1) is one or both in the middle of aluminum chloride, tin chloride, cupric chloride, phosphoric acid, hydrochloric acid, sulfuric acid, zinc chloride.
7. a kind of method preparing high purity biphenyl-benzyl dichloride under novel dissolvent system as claimed in claim 1, is characterized in that: the heating and temperature control described in step (1) is 25 ~ 80 DEG C.
8. a kind of method preparing high purity biphenyl-benzyl dichloride under novel dissolvent system as claimed in claim 1, is characterized in that: the recrystallization solvent for use II described in step (2) is toluene, one or both in chlorobenzene, dimethylbenzene, benzene, ethanol, methyl alcohol, butanols, formic acid, acetic acid.
9. a kind of method preparing high purity biphenyl-benzyl dichloride as claimed in claim 1, is characterized in that: in the middle of the solvent II described in step (2), the mol ratio of each component is 1:0 ~ 3:0 ~ 7.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510190914.3A CN104926599A (en) | 2015-04-21 | 2015-04-21 | Method for preparing high-purity 4,4'-bis(chloromethyl)-1,1'-biphenyl under novel solvent system |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510190914.3A CN104926599A (en) | 2015-04-21 | 2015-04-21 | Method for preparing high-purity 4,4'-bis(chloromethyl)-1,1'-biphenyl under novel solvent system |
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| CN104926599A true CN104926599A (en) | 2015-09-23 |
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| CN201510190914.3A Pending CN104926599A (en) | 2015-04-21 | 2015-04-21 | Method for preparing high-purity 4,4'-bis(chloromethyl)-1,1'-biphenyl under novel solvent system |
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| CN110028379A (en) * | 2019-04-04 | 2019-07-19 | 三峡大学 | A kind of preparation method of 4,4 '-dichloromethyl biphenyl |
| 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 |
| CN114057540A (en) * | 2021-12-10 | 2022-02-18 | 西安凯立新材料股份有限公司 | Method for preparing 2, 5-dimethyl benzyl chloride |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN114057540A (en) * | 2021-12-10 | 2022-02-18 | 西安凯立新材料股份有限公司 | Method for preparing 2, 5-dimethyl benzyl chloride |
| CN114057540B (en) * | 2021-12-10 | 2023-11-10 | 西安凯立新材料股份有限公司 | Method for preparing 2, 5-dimethyl benzyl chloride |
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