CN116947698A - Synthesis method of ultraviolet absorber UV-3030 - Google Patents
Synthesis method of ultraviolet absorber UV-3030 Download PDFInfo
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- CVSXFBFIOUYODT-UHFFFAOYSA-N 178671-58-4 Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)=C(C#N)C(=O)OCC(COC(=O)C(C#N)=C(C=1C=CC=CC=1)C=1C=CC=CC=1)(COC(=O)C(C#N)=C(C=1C=CC=CC=1)C=1C=CC=CC=1)COC(=O)C(C#N)=C(C=1C=CC=CC=1)C1=CC=CC=C1 CVSXFBFIOUYODT-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000001308 synthesis method Methods 0.000 title claims abstract description 11
- 239000006097 ultraviolet radiation absorber Substances 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 37
- -1 rare earth carbonate Chemical class 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 16
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 13
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 33
- 230000002745 absorbent Effects 0.000 abstract description 8
- 239000002250 absorbent Substances 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 description 23
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- 238000004811 liquid chromatography Methods 0.000 description 16
- 239000012264 purified product Substances 0.000 description 15
- 238000001953 recrystallisation Methods 0.000 description 13
- 239000012043 crude product Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000013021 overheating Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- SXZIXHOMFPUIRK-UHFFFAOYSA-N diphenylmethanimine Chemical compound C=1C=CC=CC=1C(=N)C1=CC=CC=C1 SXZIXHOMFPUIRK-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing an ultraviolet absorbent UV-3030, which comprises the steps of dissolving UV-3035 and pentaerythritol in diethyl formamide, adding a supported mixed rare earth carbonate catalyst, carrying out reflux reaction, and filtering and purifying a reaction product to obtain UV-3030; the synthesis method has the advantages of high product yield, good selectivity, recyclable catalyst and the like, greatly reduces the process cost of the product, and has remarkable industrial application prospect.
Description
Technical Field
The invention relates to the technical field of ultraviolet absorber preparation, in particular to a synthesis method of an ultraviolet absorber UV-3030.
Background
UV-3030 (pentaerythritol tetra (2-cyano-3, 3-diphenyl acrylate)) is an ultraviolet absorber with wide application, and can be used in products of sun-screening cosmetics, plastics, resins, synthetic rubber and other high polymer materials, in particular to transparent products such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate and the like. Has the advantages of high temperature resistance, extraction resistance, low volatilization, low migration, good thermal stability, high absorption efficiency, good compatibility with various polymer materials, and the like.
The existing industrial production method of UV-3030 uses UV-3035 and pentaerythritol as a catalyst under the condition of no solvent, lithium hydroxide or organic tin oxide is used as a catalyst, the reaction is carried out for 10 to 15 hours at 175 ℃ under vacuum, and then toluene is used for extraction and recrystallization to obtain the product. The method has a plurality of defects which are difficult to overcome in the operation process: firstly, the reaction under the solvent-free condition is unfavorable for the mass transfer process of the intermediate with large molecular weight, the conversion rate is reduced due to the local overheating phenomenon, the byproducts are increased, the color of the product is very dark, the decolorization link of acid clay is required to be added in the refining process, the operation is troublesome, the refining yield is reduced, and the yield is calculated to be lower by using UV-3035 as the basis in the existing process; and secondly, the lithium hydroxide and the organotin catalyst are high in price, and the catalyst cannot be recovered under the existing process conditions, so that the post-treatment difficulty and the process cost are greatly increased.
In addition to the current commercial process, pentaerythritol tetracyanoacetate was reacted with benzophenone imine to synthesize UV-3030. The method has the advantages of mild reaction conditions, no need of catalysts, low synthesis yield of the two intermediates, no more than 50 percent, and high cost of products. Another disadvantage of this process is that the yield of the end product is also low, only 65%.
Disclosure of Invention
In order to solve the defects existing in the existing industrial production method, the invention provides a synthesis method of an ultraviolet absorbent UV-3030, and the synthesis route of the UV-3030 is improved: firstly, diethyl formamide (DEF) is used as a reaction medium, so that the mass transfer and heat transfer states of raw materials and intermediate molecules in the reaction process are improved, the reaction is more stable, the generation of byproducts is reduced, and the phenomenon of darkening of a system caused by overheating is reduced; the supported mixed rare earth carbonate with higher use efficiency is used as a catalyst, so that the selectivity of the reaction is higher, and almost no trisubstituted or disubstituted byproducts are generated; in addition, the catalyst can be recycled through simple filtration, so that the product cost generated by catalyst consumption is reduced.
In order to achieve the above object, the present invention is as follows:
a synthesis method of an ultraviolet absorber UV-3030 comprises the following steps: dissolving UV-3035 and pentaerythritol in diethyl formamide, adding a supported mixed rare earth carbonate catalyst, carrying out reflux reaction, and filtering and purifying a reaction product to obtain the UV-3030.
The technical principle of selecting DEF as a reaction medium has three aspects, namely, the boiling point of the DEF is 178 ℃, and the optimum temperature of the DEF is close to 175 ℃ for the transesterification between UV-3035 and pentaerythritol, so that the transesterification can be effectively carried out; the DEF is a good solvent, and the two reactants, the transesterification reaction intermediate and the product have good solubility, so that the formed solution has low viscosity, an effective homogeneous reaction micro-area can be formed on the surface of the catalyst, the reaction product can be quickly diffused out of the reaction micro-area, and the reaction efficiency is greatly improved; thirdly, the homogeneous reaction system with smaller viscosity is more beneficial to the heat transfer process, avoids the overheating phenomenon near the heating surface of the reaction vessel, makes the color of the product light and is beneficial to the post-treatment refining process.
Further, the supported mixed rare earth carbonate catalyst is prepared by suspending a ZSM-11 molecular sieve in a halogenated rare earth solution, adding ammonium bicarbonate to react under stirring, standing to obtain a precipitate, filtering the precipitate, washing with water, drying and roasting.
The rare earth metal salt has good catalytic effect on transesterification reaction as Lewis acid. According to the invention, the mixed rare earth carbonate is loaded on the ZSM-11 molecular sieve, so that on one hand, the catalytic activity of the rare earth carbonate is improved by increasing the surface area of the rare earth carbonate, and on the other hand, the catalyst has good shape stability, and is easy to recycle after the reaction is finished. Experimental results show that the reaction activity of the supported mixed rare earth carbonate catalyst is higher than that of lithium hydroxide and organic tin, the color of the reaction system is better than that of a catalytic system catalyzed by lithium hydroxide and organic tin, and the catalyst is a catalyst with excellent performance and recycling.
Preferably, the ZSM-11 molecular sieve has a particle size of from 0.5 to 2mm.
Preferably, the rare earth halide is rare earth chloride, a rare earth element selected from rare earth elements, preferably light rare earth elements; the mass ratio of the ZSM-11 molecular sieve to the rare earth chloride to the ammonium bicarbonate is 10:1:1.5.
further, the molar feed ratio of the UV-3035 to the pentaerythritol is (4-6): 1.
further, the volume of the diethyl formamide is 0.5-2 times of the mass of the UV-3035, the volume unit is mL, and the mass unit is g.
Further, the addition amount of the supported mixed rare earth carbonate catalyst is 0.5-2% of the mass of UV-3035.
Further, the reflux reaction time is 8-12 hours.
Further, the filtering process recovers the supported mixed rare earth carbonate catalyst and is recycled for catalytic reaction for more than 5 times.
Further, the purification process adopts a mixed solution of tetrachloroethylene and ethyl acetate for recrystallization, the volume ratio of the tetrachloroethylene to the ethyl acetate is 1:0.5, and the volume of the mixed solution is 2 times of the mass of UV-3035. The crude UV-3030 is refined by using a nonpolar tetrachloroethylene and polar ethyl acetate composite solvent, and the UV-3030 with the content of more than 99% can be obtained by one treatment, so that the method has better effect compared with toluene used in industry. The reason for achieving the effect is that tetrachloroethylene has good solubility to the reaction raw material UV3035, and ethyl acetate has good solubility to the trisubstituted and trisubstituted byproducts, and the solubility of the two solvents to UV-3030 is smaller, so that excessive UV-3035 and the trisubstituted and trisubstituted byproducts generated by the reaction can be well removed in the recrystallization treatment process, and the product with high purity can be obtained in high yield.
Compared with the prior art, the invention has the following beneficial effects:
1. the synthesis method of the invention adopts a solvent method to synthesize the UV-3030, has the advantages of mild reaction conditions, high product yield, good reaction selectivity and the like by combining with the supported mixed rare earth carbonate catalyst, and greatly reduces the process cost of the product.
2. The supported catalyst used in the synthesis method has high catalytic efficiency and good selectivity, can be simply recycled after being used, reduces the production cost, and has no problems of separation and treatment of the spent catalyst.
3. The synthetic method has simple purification process, does not need an acid clay decoloring process, can reach the purity of more than 99 percent by using a mixed solvent of tetrachloroethylene and ethyl acetate for one-time recrystallization, and has low purification process cost and high yield.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with preferred embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Preparation example
The commercial ZSM-11 molecular sieve has the granularity range of 0.5-2mm, 50g of ZSM-11 molecular sieve is suspended in 500mL of lanthanum chloride solution with the concentration of 10g/L, 500mL of 15g/L ammonium bicarbonate solution is added under stirring to react for 30min, standing is carried out for precipitation, the obtained precipitate is filtered, washed and dried, and roasting is carried out at 200 ℃ for 2 hours, so that the supported mixed rare earth carbonate catalyst is obtained, and is used for preparing UV-3030 in the following examples.
Example 1
40g of UV-3035 and 3.8g of pentaerythritol (5.2:1, mol/mol) are dissolved in 40mL of diethyl formamide, 0.6g of supported mixed rare earth carbonate catalyst is added, the mixture is heated and refluxed for 12 hours, the catalyst is filtered and recovered after cooling, and the solvent is recovered under reduced pressure, so as to obtain a crude product of the ultraviolet absorbent UV-3030. The crude product was dissolved in 80mL of a mixed solvent of tetrachloroethylene and ethyl acetate (1:0.5, V/V), placed in an ice salt bath for crystallization for 12 hours, the solvent was removed by filtration, and heated to a molten state to remove the solvent, thereby obtaining 25.2g of a UV3030 purified product, the content of which was 99.6% as measured by liquid chromatography. The product yield calculated on the basis of UV-3035 was 85.1%.
Example 2
31g of UV-3035,3.8g of pentaerythritol (4.0:1 mol/mol) are dissolved in 30mL of diethyl formamide, 0.45g of supported mixed rare earth carbonate catalyst is added, the mixture is heated and refluxed for 12 hours, the catalyst is filtered and recovered after cooling, and the solvent is distilled off under reduced pressure to obtain a crude product of the ultraviolet absorbent UV-3030. The crude product was dissolved in 60mL of a mixed solvent of tetrachloroethylene and ethyl acetate (1:0.5, V/V), placed in an ice salt bath for crystallization for 12 hours, the solvent was removed by filtration, and heated to a molten state to remove the solvent, to obtain 21.2g of a UV3030 purified product, the content of which was 99.5% as measured by liquid chromatography. The product yield calculated on the basis of UV-3035 was 71.6%.
Example 3
34g of UV-3035,3.8g of pentaerythritol (4.4:1 mol/mol) are dissolved in 34mL of diethyl formamide, 0.5g of supported mixed rare earth carbonate catalyst is added, the mixture is heated and refluxed for 12 hours, the catalyst is filtered and recovered after cooling, and the solvent is distilled off under reduced pressure to obtain a crude product of the ultraviolet absorbent UV-3030. The crude product was dissolved in 70mL of a mixed solvent of tetrachloroethylene and ethyl acetate (1:0.5, V/V), placed in an ice salt bath for crystallization for 12 hours, the solvent was removed by filtration, and heated to a molten state to remove the solvent, to obtain 22.6g of a UV3030 purified product, the content of which was 99.7% as measured by liquid chromatography. The product yield calculated on the basis of UV-3035 was 76.3%.
Example 4
37. 37gUV-3035,3.8g pentaerythritol (4.8:1 mol/mol) is dissolved in 37mL diethyl formamide, 0.55g of supported mixed rare earth carbonate catalyst is added, the mixture is heated and refluxed for 12 hours, the catalyst is filtered and recovered after cooling, and the solvent is distilled off under reduced pressure to obtain a crude product of the ultraviolet absorbent UV-3030. The crude product was dissolved in 74mL of a mixed solvent (1:0.5, V/V) of tetrachloroethylene and ethyl acetate, placed in an ice salt bath for crystallization for 12 hours, and the solvent was removed by filtration and heated to a molten state to give 24.1g of a UV3030 purified product with a content of 99.2% as measured by liquid chromatography. The product yield calculated on the basis of UV-3035 was 81.4%.
Example 5
43.3. 43.3gUV-3035,3.8g pentaerythritol (5.6:1 mol/mol) is dissolved in 44mL diethyl formamide, 0.65g of supported mixed rare earth carbonate catalyst is added, the mixture is heated and refluxed for reaction for 12 hours, the catalyst is filtered and recovered after cooling, and the solvent is distilled off under reduced pressure to obtain a crude product of the ultraviolet absorbent UV-3030. The crude product was dissolved in 87mL of a mixed solvent (1:0.5, V/V) of tetrachloroethylene and ethyl acetate, placed in an ice salt bath for crystallization for 12 hours, filtered to remove the solvent, and heated to a molten state to remove the solvent, thereby obtaining 25.5g of a UV3030 refined product, the content of which was 99.3% as measured by liquid chromatography. The product yield calculated on the basis of UV-3035 was 86.1%.
Example 6
46.4g of UV-3035 and 3.8g of pentaerythritol (6:1 mol/mol) are dissolved in 47mL of diethyl formamide, 7g of supported mixed rare earth carbonate catalyst is added, the mixture is heated and refluxed for reaction for 12 hours, the catalyst is filtered and recovered after cooling, and the solvent is distilled off under reduced pressure to obtain a crude product of the ultraviolet absorbent UV-3030. The crude product was dissolved in 93mL of a mixed solvent of tetrachloroethylene and ethyl acetate (1:0.5, V/V), left to crystallize in an ice salt bath for 12 hours, the solvent was removed by filtration, and heated to a molten state to remove the solvent, thereby obtaining 25.4g of a UV3030 purified product, the content of which was 99.1% as measured by liquid chromatography. The product yield calculated on the basis of UV-3035 was 85.8%.
Example 7
The same amount and operation procedure as in example 1 were followed except that the amount of diethylformamide was changed to 20mL, and the mixture was recrystallized to give 23.8g of a UV-3030 purified product, the content of which was 99.2% as determined by liquid chromatography. The product yield calculated on the basis of UV-3035 was 80.4%.
Example 8
The same amount and operation procedure as in example 1 were followed except that the amount of diethylformamide was changed to 60mL, and 25.5g of a UV-3030 purified product was obtained after recrystallization, the content being 99.6% as determined by liquid chromatography. The product yield calculated on the basis of UV-3035 was 86.1%.
Example 9
The same amount and operation procedure as in example 1 were followed except that the amount of diethylformamide was changed to 80mL, and 25.8g of a UV-3030 purified product was obtained after recrystallization, the content being 99.7% as determined by liquid chromatography. The product yield calculated on the basis of UV-3035 was 87.1%.
Example 10
The same amount and operation procedure as in example 1 were followed except that the amount of the supported mixed rare earth carbonate catalyst was changed to 0.2g, and 20.3g of a UV-3030 purified product was obtained after recrystallization, with a liquid chromatography detection content of 99.1%. The product yield calculated on the basis of UV-3035 was 68.6%.
Example 11
The same amount and operation procedure as in example 1 were followed except that the amount of the supported mixed rare earth carbonate catalyst was changed to 0.4g, and 23.9g of a UV-3030 purified product was obtained after recrystallization, with a liquid chromatography detection content of 99.3%. The product yield calculated on the basis of UV-3035 was 80.7%.
Example 12
The same amount and operation procedure as in example 1 were followed except that the amount of the supported mixed rare earth carbonate catalyst was changed to 0.8g, and 25.6g of a UV-3030 purified product was obtained after recrystallization, with a liquid chromatography detection content of 99.5%. The product yield calculated on the basis of UV-3035 was 86.5%.
Example 13
The same amount and operation procedure as in example 1 were followed except that the reflux reaction time was changed to 8 hours, and 22.4g of a UV-3030 purified product was obtained after recrystallization, the content being 98.3% as determined by liquid chromatography. The product yield calculated on the basis of UV-3035 was 75.7%.
Example 14
The same amount and operation procedure as in example 1 were followed except that the reflux reaction time was changed to 10 hours, and 24.2g of a UV-3030 purified product was obtained after recrystallization, the content being 99.0% as measured by liquid chromatography. The product yield calculated on the basis of UV-3035 was 81.8%.
Example 15
The same amount and operation procedure as in example 1 were followed except that the reflux reaction time was changed to 14 hours, and 25.4g of a UV-3030 purified product was obtained after recrystallization, the content being 99.4% as measured by liquid chromatography. The product yield calculated on the basis of UV-3035 was 85.8%.
Example 16
The same amount and operation procedure as in example 1 were followed except that the reflux reaction time was changed to 16 hours, and 25.1g of a UV-3030 purified product was obtained after recrystallization, the content being 99.2% as determined by liquid chromatography. The product yield calculated on the basis of UV-3035 was 84.8%.
It is apparent from the above examples that the molar ratio of UV-3035 to pentaerythritol is (4-6): 1, the using volume of the diethyl formamide is 0.5-2 times of the mass of the UV-3035, and under the condition that the using volume of the supported mixed rare earth carbonate catalyst is 0.5-2% of the mass of the UV-3035, the reflux time is 8-16 hours, so that a product with higher yield can be obtained, and the purification process is simple and is suitable for industrial production. The reflux reaction time is preferably 8 to 12 hours in view of productivity. Compared with the prior art that the product yield of the UV-3030 prepared by using lithium hydroxide or organic tin oxide as a catalyst is below 70% under the condition of no solvent and vacuum, the method has various remarkable advantages.
Experimental example
The same amount of the mixture and the operation process of example 1 are adopted, the filtered and recovered supported mixed rare earth carbonate catalyst is recycled to prepare UV-3030, and the experimental results are shown in Table 1.
Table 1: catalyst recovery test results
| Catalyst | Refined product quantity (g) | Purity (%) |
| Novel catalyst | 25.2 | 99.6 |
| Recovery of the primary catalyst | 25.1 | 99.4 |
| Recovery of secondary catalyst | 25.3 | 99.5 |
| Catalyst recovery for three times | 25.0 | 99.4 |
| Four times catalyst recovery | 25.1 | 99.6 |
| Five times catalyst recovery | 24.9 | 99.3 |
As can be seen from Table 1, the supported mixed rare earth carbonate catalyst can still have higher catalytic activity and selectivity when being respectively recycled for different times, and compared with the lithium hydroxide or organic tin oxide catalyst with high price in the prior art, the supported mixed rare earth carbonate catalyst can avoid the defect of difficult recovery and has obvious industrial application prospect.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A method for synthesizing an ultraviolet absorber UV-3030, which is characterized by comprising the following steps: dissolving UV-3035 and pentaerythritol in diethyl formamide, adding a supported mixed rare earth carbonate catalyst, carrying out reflux reaction, and filtering and purifying a reaction product to obtain the UV-3030.
2. The synthesis method according to claim 1, wherein the supported mixed rare earth carbonate catalyst is prepared by suspending a ZSM-11 molecular sieve in a rare earth halide solution, adding ammonium bicarbonate under stirring for reaction, standing to obtain a precipitate, filtering the precipitate, washing with water, drying and roasting.
3. The synthesis of claim 2, wherein the ZSM-11 molecular sieve has a particle size of 0.5-2mm.
4. The synthetic method of claim 2, the rare earth halide being rare earth chloride; the mass ratio of the ZSM-11 molecular sieve to the rare earth chloride to the ammonium bicarbonate is 10:1:1.5.
5. the method of claim 1, wherein the molar ratio of UV-3035 to pentaerythritol is (4-6): 1.
6. the method of claim 1, wherein the diethyl formamide is used in an amount of 0.5 to 2 times (V/W) the amount of UV-3035.
7. The synthesis method according to claim 1, wherein the amount of the supported mixed rare earth carbonate catalyst added is 0.5 to 2% by mass of UV-3035.
8. The synthetic method of claim 1 wherein the reflux reaction time is 8-12 hours.
9. The synthesis process according to claim 1, wherein the filtration process recovers the supported mixed rare earth carbonate catalyst and is recycled for catalytic reaction more than 5 times.
10. The synthesis method according to claim 1, wherein the purification process is performed by recrystallizing a mixed solution of tetrachloroethylene and ethyl acetate in a volume ratio of tetrachloroethylene to ethyl acetate of 1:0.5, the mixed solution volume being 2 times the mass of UV-3035.
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