CN106986839B - A kind of ultra-violet absorber UVT 150 preparation method - Google Patents
A kind of ultra-violet absorber UVT 150 preparation method Download PDFInfo
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- 239000006097 ultraviolet radiation absorber Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 59
- 150000002148 esters Chemical group 0.000 claims abstract description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 18
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 238000009413 insulation Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- LZXXNPOYQCLXRS-UHFFFAOYSA-N methyl 4-aminobenzoate Chemical compound COC(=O)C1=CC=C(N)C=C1 LZXXNPOYQCLXRS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- JGUMTYWKIBJSTN-UHFFFAOYSA-N 2-ethylhexyl 4-[[4,6-bis[4-(2-ethylhexoxycarbonyl)anilino]-1,3,5-triazin-2-yl]amino]benzoate Chemical compound C1=CC(C(=O)OCC(CC)CCCC)=CC=C1NC1=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=N1 JGUMTYWKIBJSTN-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 230000008676 import Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000005809 transesterification reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000008025 crystallization Effects 0.000 abstract description 6
- 238000004821 distillation Methods 0.000 abstract 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 9
- 229960004050 aminobenzoic acid Drugs 0.000 description 6
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 150000000182 1,3,5-triazines Chemical class 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 2
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NCSHGROOCJHAFK-UHFFFAOYSA-N [Cl].N#CC#N Chemical compound [Cl].N#CC#N NCSHGROOCJHAFK-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000000475 sunscreen effect Effects 0.000 description 2
- 239000000516 sunscreening agent Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- QMNWYGTWTXOQTP-UHFFFAOYSA-N 1h-triazin-6-one Chemical compound O=C1C=CN=NN1 QMNWYGTWTXOQTP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- -1 carboxyl phenyl Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001506 immunosuppresive effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a kind of ultra-violet absorber UVT 150 preparation method, it is made up of following processing steps：1. fragrant aminoization is reacted：Add methyl p-aminobenzoate and organic solvent into reactor, heating is slowly added dropwise Cyanuric Chloride, after insulation reaction, distills, crystallization, obtains intermediate methyl triazon；2. ester exchange reaction：Toluene, catalyst and isooctanol are added into reactor, heating, the toluene solution of methyl triazon is added dropwise, insulation reaction, distillation crystallization obtain the products of ultra-violet absorber UVT 150；Present invention process route is simple, and raw material are easy to get, and easy to operate, high income, is easy to industrialized production.
Description
Technical field
The present invention relates to a kind of synthetic method of ultra-violet absorber, specifically a kind of ultra-violet absorber UVT-150's
Preparation method.
Background technology
UVT-150（Also known as octyl triazone）Belong to triazine-based ultraviolet absorbent, to UVB（275-320 nm）Wave band
Specific absorption function, its chemical entitled 4,4', 4''-（The imino groups of 1,3,5- triazines -2,4,6- three）Three benzoic acid three
（2- ethylhexyls）Ester, the immunosuppressive action for possessing high photostability and preventing UV-B from inducing, water resistance is strong, to skin
Keratoprotein have preferable affinity.The advantages of with high-absorbility few additive, only needed generally in Sun Care Products
Want few dosage, it is possible to reach higher spf value, and have excellent waterproof effect.
Relevant 4,4', 4''- are reported both at home and abroad at present（The imino groups of 1,3,5- triazines -2,4,6- three）Three benzoic acid three（2- second
Base hexyl）Ester（UVT-150）Synthetic method mainly have it is following two：
Method one：The A of Chinese patent CN 104860893 are reported with melamine, parachlorobenzoic-acid, isooctanol within 2015
For initiation material, be substituted reaction and obtain 2,4,6- tri- [(to carboxyl phenyl) amino] -1,3,5- triazines, then again with it is different
Octanol occurs esterification and is prepared for ultra-violet absorber UVT-150, and synthetic route is as follows：
Method two：Disclosed in the patent application that International Patent Publication No. Ws in 2012 are WO2012/127425A1 with trimerization
Chlorine cyanogen and the different monooctyl ester of p-aminobenzoic acid are raw material, synthesize to obtain ultra-violet absorber UVT-150 products by three substitution reactions,
Synthetic route is as follows：
The problem of above method one, is, in the substitution reaction of melamine and parachlorobenzoic-acid, chlorine substitutes on phenyl ring
Base and the amino generation substitution in melamine are more difficult, make yield be difficult to improve;Intermediate 2,4,6- tri- is [(to carboxyl simultaneously
Phenyl) amino] -1,3,5- triazines obtained with isooctanol three esterifications yield it is also not high, so the industrial cost of the technique
It is higher.
The problem of above method two, is, substitution directly occurs instead by raw material and Cyanuric Chloride of the different monooctyl ester of aminobenzoic acid
Ultra-violet absorber UVT-150 products should be prepared, but because the different monooctyl ester raw material country of aminobenzoic acid does not produce, and import is former
Expect fairly expensive, therefore each production UVT-150 enterprises are all that esterification first occurs with paranitrobenzoic acid and isooctanol to prepare
Paranitrobenzoic acid isooctanol, then carry out catalytic hydrogenation and obtain the different monooctyl ester of p-aminobenzoic acid, because catalytic hydrogenation process needs
Carry out under high pressure, build the investment of catalytic hydrogenation workshop greatly, safety in production requires high, and risk is big, and general enterprises are reluctant self-built;And
The contaminated wastewater of iron powder reducing technique is again serious；If esterification occurs with p-aminobenzoic acid and isooctanol to prepare to amino
Benzoic acid isooctanol, and the esterification is difficult to carry out, yield is not high, and integrated cost is higher.Therefore, it is badly in need of exploitation one kind to prepare
Route is simple, and raw material are easy to get, and easy to operate, high income, is easy to the new technology of industrialized production, to meet domestic UVT-
The production requirement of 150 products.
The content of the invention
The purpose of the present invention is exactly for overcome the deficiencies in the prior art, there is provided a kind of syntheti c route is simple, and raw material are easy
, and easy to operate, high income, it is easy to the ultra-violet absorber UVT-150 of industrialized production preparation method.
A kind of ultra-violet absorber UVT-150 of present invention preparation method, is made up of following processing steps：
1. fragrant aminoization is reacted：Methyl p-aminobenzoate and organic solvent are added into reactor, is warming up to 60-150
DEG C stirring and dissolving, and the pre- Cyanuric Chloride being first dissolved in organic solvent is slowly added dropwise on this condition, it is added dropwise, in 60-
150 DEG C of insulation reaction 5-6h, the hydrogen chloride gas generated in course of reaction import alkali liquor absorption device, and reaction is finished, distilled back
Solvent is received, crystallisation by cooling, intermediate methyl triazon is obtained, is not required to refine, be directly used in lower step ester exchange reaction；
The fragrant amino reaction raw materials weight ratio is Cyanuric Chloride：Methyl p-aminobenzoate：Organic solvent=1：1~
3.0：2.5~9.0；
2. ester exchange reaction：Toluene, catalyst and isooctanol, heating stirring dissolving are added into reactor, and is warming up to
100-150 DEG C, the toluene solution of methyl triazon is slowly added dropwise, is added dropwise, insulation reaction 8-10h, in course of reaction constantly
Caused methanol is distilled off, reaction finishes, and is distilled to recover solvent, and solvent adds absolute ethyl alcohol after being evaporated, crystallization separates out pungent
Base triazinone, filtering, respectively with absolute ethyl alcohol and water washing, that is, obtains ultra-violet absorber UVT-150 products, total recovery is more than
96%, through liquid chromatographic detection, purity is more than 99.0%；
The ester exchange reaction raw material weight ratio is methyl triazon：Catalyst：Isooctanol：Toluene：Ethanol=1：0.05~
0.15：0.6~1.0：2.0~3.0：1.0~2.0.
The organic solvent used in the fragrant aminoization reaction is one in benzene,toluene,xylene, hexamethylene, petroleum ether
Kind.
The preferred dimethylbenzene of organic solvent used in the fragrant aminoization reaction.
The fragrant amino reaction raw materials preferred weight ratio is Cyanuric Chloride：Methyl p-aminobenzoate：Organic solvent=1：
2.5：8.0.
Catalyst used in the ester exchange reaction is sulfuric acid, one kind in p-methyl benzenesulfonic acid, sodium methoxide.
Catalyst used in the ester exchange reaction is preferably sodium methoxide.
The ester exchange reaction raw material preferred weight ratio is methyl triazon：Catalyst：Isooctanol：Toluene：Ethanol=1：
0.1：0.97：2.9：2.0.
It is former as starting using Cyanuric Chloride and methyl p-aminobenzoate instant invention overcomes domestic and international the deficiencies in the prior art
Material, is reacted to obtain intermediate methyl triazon through fragrant amino, then ester exchange reaction is carried out under catalyst action with isooctanol,
Only needing two-step reaction, not only syntheti c route is simple, and raw material are easy to get, and operation side with regard to that can prepare target product UVT-150
Just, high income, it is easy to industrialized production.Its reaction equation is as follows：
Present invention process compared with prior art, has following features：
1. carrying out the reaction of three fragrant aminoizations using Cyanuric Chloride and methyl p-aminobenzoate, reaction condition is gentle, fragrant ammonia
Base high income, yield >=98% of intermediate methyl triazon is obtained, is not required to refine, be directly used in lower step ester exchange reaction,
And simple production process, and raw material are easy to get；
2. the present invention carries out ester exchange reaction using sodium methoxide or sulfuric acid or p-methyl benzenesulfonic acid as catalyst, purple is obtained
Ultraviolet absorbers UVT-150, target product impurity is few, synthetic yield is high, and industrial cost is low；
3. ultra-violet absorber UVT-150 products prepared by the inventive method, total recovery is more than 96%, and chromatographic purity reaches
More than 99.0%, cosmetic industry requirement is fully met, is more suitably applied to oil-soluble sunscreen product.
Brief description of the drawings
Fig. 1 is the ultra-violet absorber UVT-150 liquid chromatograms prepared by the embodiment of the present invention 1.
The testing conditions of liquid chromatogram shown in Fig. 1 are：Liquid chromatograph model：Shimadzu LC-1000/LC-
15C, detector：LC-1000UV/SPD-15C, work station：N2000/LCsolution 15C, chromatographic column：Kromasil-C18,
5 μm, 4.6nm*250mm, Detection wavelength：295nm, flow velocity：1.0ml/min, mobile phase：Tetrahydrofuran：Acetonitrile：Water=38：34：
28, sample size：20 μ l, sample：0.005g is dissolved in 25ml mobile phases, records time 30min.
Embodiment
Embodiment 1
1. fragrant aminoization is reacted：950g methyl p-aminobenzoates and the mL of dimethylbenzene 2000, heating are added into reactor
To 60-150 DEG C of stirring and dissolving, and the 380g trimerizations being first dissolved in advance in 1500 mL dimethylbenzene are slowly added dropwise on this condition
Chlorine cyanogen, is added dropwise, and the hydrogen chloride gas generated in 120 ~ 125 DEG C of insulation reaction 5-6h, course of reaction imports alkali liquor absorption
Device, reaction finish, and are distilled to recover solvent, crystallisation by cooling, obtain intermediate methyl triazon 1036g, yield 98%, be not required to essence
System, is directly used in lower step ester exchange reaction.
2. ester exchange reaction：2000 mL toluene, sodium methoxide 103.6g and 1210 mL isooctanol are added into reactor, are added
Thermal agitation is dissolved, and is warming up to 110 ~ 115 DEG C, and the 1500mL toluene solutions containing 1036g methyl triazons are slowly added dropwise, and is added dropwise
Finishing, insulation reaction 8-10h, caused methanol is constantly distilled off in course of reaction, reaction finishes, and is distilled to recover solvent,
Solvent adds 2500mL absolute ethyl alcohols after being evaporated, crystallization separates out octyl triazone（UVT-150）Product, filtering, uses absolute ethyl alcohol
And water washing, obtain ultra-violet absorber（UVT-150）Product 1549g, by the UVT-150 products of gained through liquid chromatographic detection
Its analysis result is as shown in the table：
Each raw material dosage and process conditions in embodiment 1 be the present invention best-of-breed technology scheme, resulting UVT-150
Product yield is 96%, through liquid-phase chromatographic analysis, purity 99.74%, fully meets cosmetic industry requirement, is suitably applied oil
The sunscreen product of dissolubility.
Embodiment 2
1. fragrant aminoization is reacted：850g methyl p-aminobenzoates and the mL of benzene 1500 are added into reactor, is warming up to
60-150 DEG C of stirring and dissolving, and the polychlorostyrene of 369g tri- being first dissolved in advance in 800 mL dimethylbenzene is slowly added dropwise on this condition
Cyanogen, it is added dropwise, the hydrogen chloride gas generated in 120 ~ 125 DEG C of insulation reaction 5-6h, course of reaction imports alkali liquor absorption dress
To put, reaction finishes, and is distilled to recover solvent, crystallisation by cooling, obtains intermediate methyl triazon 951g, yield 90%, be not required to refine,
It is directly used in lower step ester exchange reaction.
2. ester exchange reaction：1000 mL toluene, 80g sulfuric acid and 800 mL isooctanol, heating stirring are added into reactor
Dissolving, and 110 ~ 115 DEG C are warming up to, the 1200mL toluene solutions of 951g methyl triazons are slowly added dropwise, are added dropwise, insulation is anti-
8-10h is answered, caused methanol is constantly distilled off in course of reaction, reaction finishes, and is distilled to recover solvent, and solvent adds after being evaporated
Enter 1500mL absolute ethyl alcohols, crystallization separates out octyl triazone（UVT-150）Product, filtering, with absolute ethyl alcohol and water washing, is obtained
Ultra-violet absorber（UVT-150）Product 1318g, yield 89%, through liquid-phase chromatographic analysis, purity 99.63%.
Embodiment 3
1. fragrant aminoization is reacted：800g methyl p-aminobenzoates and the mL of toluene 1800 are added into reactor, is warming up to
60-150 DEG C of stirring and dissolving, and the polychlorostyrene of 369g tri- being first dissolved in advance in 900 mL dimethylbenzene is slowly added dropwise on this condition
Cyanogen, it is added dropwise, the hydrogen chloride gas generated in 120 ~ 125 DEG C of insulation reaction 5-6h, course of reaction imports alkali liquor absorption dress
To put, reaction finishes, and is distilled to recover solvent, crystallisation by cooling, obtains intermediate methyl triazon 850g, yield 80%, be not required to refine,
It is directly used in lower step ester exchange reaction.
2. ester exchange reaction：1000 mL toluene, 70g toluene sulfonic acides and 800mL isooctanol are added into reactor, is added
Thermal agitation is dissolved, and is warming up to 110 ~ 115 DEG C, and the 1000mL toluene solutions of 850g methyl triazons are slowly added dropwise, are added dropwise,
Insulation reaction 8-10h, caused methanol is constantly distilled off in course of reaction, reaction finishes, and is distilled to recover solvent, and solvent steams
1200mL absolute ethyl alcohols are added after dry, crystallization separates out octyl triazone（UVT-150）Product, filtering, with absolute ethyl alcohol and washing
Wash, obtain ultra-violet absorber（UVT-150）Product 1205g, yield 91%, through liquid-phase chromatographic analysis, purity 99.70%.
Claims (7)
1. a kind of ultra-violet absorber UVT-150 preparation method, by step, 1. fragrant aminoization is reacted and 2. ester exchange reaction group
Into；Wherein fragrant aminoization, which is reacted, is：Methyl p-aminobenzoate and organic solvent are added into reactor, is warming up to 60-150 DEG C
Stirring and dissolving, and the pre- Cyanuric Chloride being first dissolved in organic solvent is slowly added dropwise on this condition, it is added dropwise, in 60-150
DEG C insulation reaction 5-6h, the hydrogen chloride gas generated in course of reaction import alkali liquor absorption device, and reaction finishes, and is distilled to recover molten
Agent, crystallisation by cooling, intermediate methyl triazon is obtained, be not required to refine, be directly used in lower step ester exchange reaction；The fragrant amino
Reaction raw materials weight ratio is Cyanuric Chloride：Methyl p-aminobenzoate：Organic solvent=1：1~3.0：2.5~9.0；Its feature exists
In：The trans-esterification processes step is that toluene, catalyst and isooctanol are added into reactor, heating stirring dissolving, and
100-150 DEG C is warming up to, the toluene solution of methyl triazon is slowly added dropwise, is added dropwise, insulation reaction 8-10h, course of reaction
In caused methanol is constantly distilled off, reaction finishes, and is distilled to recover solvent, and solvent adds absolute ethyl alcohol after being evaporated, and crystallizes
Octyl triazone is separated out, filtering, respectively with absolute ethyl alcohol and water washing, that is, obtains ultra-violet absorber UVT-150 products, it is total to receive
Rate is more than 96%, and through liquid chromatographic detection, purity is more than 99.0%；The ester exchange reaction raw material weight ratio is methyl triazon：
Catalyst：Isooctanol：Toluene：Ethanol=1：0.05~0.15：0.6~1.0：2.0~3.0：1.0~2.0.
A kind of 2. ultra-violet absorber UVT-150 according to claim 1 preparation method, it is characterised in that：The virtue
The organic solvent used in ammoxidation is one kind in benzene,toluene,xylene, hexamethylene, petroleum ether.
A kind of 3. ultra-violet absorber UVT-150 according to claim 2 preparation method, it is characterised in that：The virtue
The organic solvent used in ammoxidation is dimethylbenzene.
A kind of 4. ultra-violet absorber UVT-150 according to claim 1 preparation method, it is characterised in that：The virtue
Ammoxidation raw material weight ratio is Cyanuric Chloride：Methyl p-aminobenzoate：Organic solvent=1：2.5：8.0.
A kind of 5. ultra-violet absorber UVT-150 according to claim 1 preparation method, it is characterised in that：The ester
Catalyst used in exchange reaction is sulfuric acid, one kind in p-methyl benzenesulfonic acid, sodium methoxide.
A kind of 6. ultra-violet absorber UVT-150 according to claim 5 preparation method, it is characterised in that：The ester
Catalyst used in exchange reaction is sodium methoxide.
A kind of 7. ultra-violet absorber UVT-150 according to claim 1 preparation method, it is characterised in that：The ester
Exchange reaction raw material weight ratio is methyl triazon：Catalyst：Isooctanol：Toluene：Ethanol=1：0.1：0.97：2.9：2.0.
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