CN114605392B - Compound and ultraviolet absorber and application thereof - Google Patents

Compound and ultraviolet absorber and application thereof Download PDF

Info

Publication number
CN114605392B
CN114605392B CN202210166201.3A CN202210166201A CN114605392B CN 114605392 B CN114605392 B CN 114605392B CN 202210166201 A CN202210166201 A CN 202210166201A CN 114605392 B CN114605392 B CN 114605392B
Authority
CN
China
Prior art keywords
compound
mmol
ultraviolet
hydrogen
glass substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210166201.3A
Other languages
Chinese (zh)
Other versions
CN114605392A (en
Inventor
周英杰
张震
杨树斌
陈雪波
陈跃
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yantai Haisen Big Data Co ltd
Yantai Jingshi Materials Genomic Engineering Research Institute
Original Assignee
Yantai Haisen Big Data Co ltd
Yantai Jingshi Materials Genomic Engineering Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yantai Haisen Big Data Co ltd, Yantai Jingshi Materials Genomic Engineering Research Institute filed Critical Yantai Haisen Big Data Co ltd
Priority to CN202210166201.3A priority Critical patent/CN114605392B/en
Publication of CN114605392A publication Critical patent/CN114605392A/en
Application granted granted Critical
Publication of CN114605392B publication Critical patent/CN114605392B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat

Abstract

The application provides a compound of formula (I), which has a strong absorption effect on ultraviolet rays in a 280nm-380nm interval, wherein the absorption range covers a 360nm-380nm interval in a UVA wave band and a 280nm-315nm interval in a UVB wave band; and the absorption intensity is higher than that of T1600 in the range of 280nm-300nm and 340nm-380nm, and the ultraviolet resistance is better than that of T1600, so that the ultraviolet-resistant coating has wider application field. The present application also provides an ultraviolet absorber comprising a compound of formula (I) and uses thereof.

Description

Compound and ultraviolet absorber and application thereof
Technical Field
The application relates to the technical field of ultraviolet absorption, in particular to a compound, an ultraviolet absorber and application thereof.
Background
Ultraviolet light (also called ultraviolet) is electromagnetic wave with wavelength of 0.1-0.4 μm, accounting for 7% of total energy of solar radiation. The energy of ultraviolet light can break chemical bonds of most materials, causing the materials to fail, degrade or deteriorate. The ultraviolet absorber is a light stabilizer, has strong absorption in the ultraviolet region, has no obvious absorption in the visible region, and can release the absorbed ultraviolet in other low-energy forms, such as light or heat with longer wavelength, thereby protecting materials or dyes and the like; the ultraviolet absorber itself is not damaged by ultraviolet rays.
The ultraviolet absorber is benzotriazole, benzophenone, triazine and the like, wherein the triazine ultraviolet absorber TINUVIN1600 (hereinafter referred to as T1600) with good ultraviolet resistance effect is one of products with the best ultraviolet absorption effect in the sold products by BASF, the ultraviolet absorption main peak is 320nm, the absorption range is mainly concentrated in the range of 290nm-360nm, the absorption is weaker in the range of 280nm-300nm in the outdoor ultraviolet (hereinafter referred to as UVB) wave band, and the absorption is weaker in the range of 360nm-380nm in the long-wave black spot effect ultraviolet (hereinafter referred to as UVA) wave band.
Disclosure of Invention
The purpose of the application is to provide a compound which has a strong absorption effect on ultraviolet rays within a range of 280-380 nm and improves the ultraviolet resistance.
The present application provides in a first aspect a compound of formula (I):
wherein L is 1 Selected from single bonds, C 6 -C 50 Arylene or C 2 -C 50 A heteroarylene group, the hydrogen atoms on the arylene group and the heteroarylene group each independently may be substituted with Ra; the substituents Ra of the individual radicals are each independently selected from C 1 -C 12 Alkyl, halogen, hydroxy, cyano, sulfonyl, sulfo, phenyl, biphenyl, terphenyl, naphthyl, nitro, carboxyl, C 1 -C 12 Acyloxy or C 1 -C 12 An alkoxy group;
L 2 selected from hydrogen, C 1 -C 12 Alkyl, C 2 -C 6 Alkenyl, C 1 -C 18 Alkoxy, C 5 -C 12 Cycloalkoxy radicals C 2 -C 18 Alkenyloxy, cyano, C 1 -C 4 Haloalkyl, sulfo, hydroxy, C 2 -C 18 Amido, C 1 -C 12 Acyloxy radicals, C 6 -C 50 Aryl or C 2 -C 50 Heteroaryl, each hydrogen atom on the aryl and heteroaryl independently may be substituted with Rb; the substituents Rb of each group are each independently selected from C 1 -C 12 Alkyl, halogen, hydroxy, cyano, sulfonyl, sulfo, phenyl, biphenyl, terphenyl, naphthyl, nitro, carboxyl, C 1 -C 12 Acyloxy or C 1 -C 12 An alkoxy group;
R 1 、R 2 、R 3 、R 4 each independently selected from hydrogen, hydroxy, C 1 -C 20 Alkyl, C 6 -C 12 Cycloalkyl, C 1 -C 20 Alkoxy, C 6 -C 12 Cycloalkoxy, allyl, amino, C 6 -C 50 Aryl or C 2 -C 50 Heteroaryl; the hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted with Rc; the substituents Rc of the individual radicals are each independently selected from C 1 -C 12 Alkyl, halogen, hydroxy, cyano, sulfonyl, sulfo, phenyl, biphenyl, terphenyl, naphthyl, nitro, carboxyl or C 1 -C 12 An alkoxy group;
the heteroatoms on the heteroaryl or the heteroarylene are each independently selected from O, S or N;
R 5 、R 6 、R 7 、R 8 each independently selected from hydrogen orAnd R is 5 、R 6 、R 7 、R 8 At least one of is
In some embodiments, L 1 Selected from single bonds, C 6 -C 30 Arylene or C 2 -C 30 Heteroarylene, the arylene and the heteroaryleneThe hydrogen atoms on the radicals may each independently be substituted by Ra.
In some embodiments, L 1 Selected from the following groups:
in some embodiments, L 2 Selected from hydrogen, C 1 -C 8 Alkyl, allyl, C 1 -C 4 Alkoxy, C 6 -C 30 Aryl or C 2 -C 30 Heteroaryl, the hydrogen atoms on the aryl and the heteroaryl each independently may be substituted with Rb.
In some embodiments, L 2 Selected from the following groups:
x is selected from O, S, CR 5 R 6 Or NR (NR) 7 ；R 5 、R 6 Each independently selected from C 1 -C 10 Alkyl, C 6 -C 30 Aryl or C 3 -C 30 Heteroaryl, R 5 And said R 6 Can be connected into a ring; r is R 7 Selected from C 6 -C 30 Aryl or C 3 -C 30 Heteroaryl; when R is 7 Selected from C 3 -C 30 In the case of heteroaryl, the heteroatom of the heteroaryl is selected from O or S.
In some embodiments, R 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, hydroxy, C 1 -C 20 Alkyl, cyclohexyl, C 1 -C 20 Alkoxy, cyclohexoxy, allyl, amino, C 6 -C 30 Aryl or C 2 -C 30 Heteroaryl, the hydrogen atoms on the aryl and heteroaryl groups each independently can be substituted with Rc.
In some embodiments, L 1 Selected from single bonds, C 6 -C 18 Arylene or C 2 -C 18 A heteroarylene group, the hydrogen atoms on the arylene group and the heteroarylene group each independently may be substituted with Ra; the substituents Ra of the individual radicals are each independently selected from C 1 -C 3 Alkyl or hydroxy; l (L) 2 Selected from hydrogen, C 6 -C 18 Aryl or C 2 -C 18 Heteroaryl, each hydrogen atom on the aryl and heteroaryl independently may be substituted with Rb; the substituents Rb of each group are each independently selected from C 1 -C 3 Alkyl or hydroxy;
R 1 、R 2 、R 3 、R 4 each independently selected from hydrogen, C 6 -C 18 Aryl or C 2 -C 18 Heteroaryl; the hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted with Rc; the substituents Rc of each group are each independently selected from hydroxy;
the heteroatoms on the heteroaryl or the heteroarylene are each independently selected from N;
R 5 、R 6 、R 8 selected from hydrogen and R 7 Selected from the group consisting ofOr R is 5 、R 7 、R 8 Selected from hydrogen and R 6 Selected from the group consisting of
In some embodiments, L 1 Selected from single bonds orL 2 Selected from hydrogen, & lt & gt> R 1 、R 2 、R 4 Selected from hydrogen; r is R 3 Selected from hydrogen, & lt & gt>R 5 、R 6 、R 8 Selected from hydrogen and R 7 Selected from->Or R is 5 、R 7 、R 8 Selected from hydrogen and R 6 Selected from->
In some embodiments, the compound is selected from the group consisting of the compounds shown below as A1-A64:
in a second aspect the present application provides an ultraviolet light absorber comprising at least one of the compounds of the first aspect of the present application.
A third aspect of the present application provides a composition comprising: a) Organic substances susceptible to damage by light, oxygen and/or heat; and B) at least one of a compound provided in the first aspect of the present application or an ultraviolet absorber provided in the second aspect of the present application; wherein the mass ratio of the component A) to the component B) is 100:0.01-15.
In some embodiments, at least one of a thermoplastic polymer, a coating binder, or a photosensitive material is included as component a).
In some embodiments, the thermoplastic polymer is selected from at least one of polyethylene, polypropylene, polyvinyl chloride, a copolymer of vinyl chloride and vinyl acetate, polystyrene, a copolymer of styrene and acrylonitrile, polyamide, polyethylene terephthalate, the coating binder is selected from at least one of polyurethane, polyacrylate, natural rubber, silicone rubber, vinyl acetate, polyvinylidene chloride, and polyvinyl alcohol, and the photosensitive material is selected from at least one of color blind, positive color, full color, infrared, and color flakes.
A fourth aspect of the present application provides the use of a compound provided in the first aspect of the present application or an ultraviolet absorber provided in the second aspect of the present application or a composition provided in the third aspect of the present application to prevent light, oxygen and/or heat damage in an organic substance.
The compound provided by the application has a strong absorption effect on ultraviolet rays in a 280nm-380nm interval, and the absorption range covers a 360nm-380nm interval in a UVA wave band and a 280nm-315nm interval in a UVB wave band; and the absorption intensity is higher than that of T1600 in the range of 280nm-300nm and 340nm-380nm, and the ultraviolet resistance is better than that of T1600, so that the ultraviolet-resistant coating has wider application field.
Of course, not all of the above-described advantages need be achieved simultaneously in practicing any one of the products or methods of the present application.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following description will briefly introduce the drawings that are required to be used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other embodiments may also be obtained according to these drawings to those skilled in the art.
FIG. 1 is an ultraviolet-visible absorption spectrum of a glass substrate +Rh101 fluorescent film, a glass substrate +Rh101 fluorescent film +UV protective film (containing the compound A9 of example 1) and a glass substrate +Rh101 fluorescent film +UV protective film (containing the compound T1600 of comparative example 1);
FIG. 2 is an ultraviolet absorption spectrum of a glass substrate +Rh101 fluorescent film +UV protective film (containing the compound A9 of example 1), a glass substrate +Rh101 fluorescent film +UV protective film (containing the compound T1600 of comparative example 1);
FIG. 3 is a graph showing the relationship between absorbance at a wavelength of 580nm and ultraviolet light irradiation time of a glass substrate+Rh 101 fluorescent film, a glass substrate+Rh 101 fluorescent film+UV protective film (containing the compound A9 of example 1), and a glass substrate+Rh 101 fluorescent film+UV protective film (containing the compound T1600 of comparative example 1) at a temperature of 25 ℃;
FIG. 4 is a standard graph of absorbance versus mass concentration for methyl orange;
FIG. 5 is a graph of the mass concentration of methyl orange corresponding to different time points in different reactors.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. Based on the embodiments herein, a person of ordinary skill in the art would be able to obtain all other embodiments based on the disclosure herein, which are within the scope of the disclosure herein.
The first aspect of the present application provides a compound of formula (I):
wherein,
L 1 selected from single bonds, C 6 -C 50 Arylene or C 2 -C 50 A heteroarylene group, the hydrogen atoms on the arylene group and the heteroarylene group being independent of each otherOptionally substituted with Ra; the substituents Ra of the individual radicals are each independently selected from C 1 -C 12 Alkyl, halogen, hydroxy, cyano, sulfonyl, sulfo, phenyl, biphenyl, terphenyl, naphthyl, nitro, carboxyl, C 1 -C 12 Acyloxy or C 1 -C 12 An alkoxy group;
L 2 selected from hydrogen, C 1 -C 12 Alkyl, C 2 -C 6 Alkenyl, C 1 -C 18 Alkoxy, C 5 -C 12 Cycloalkoxy radicals C 2 -C 18 Alkenyloxy, cyano, C 1 -C 4 Haloalkyl, sulfo, hydroxy, C 2 -C 18 Amido, C 1 -C 12 Acyloxy radicals, C 6 -C 50 Aryl or C 2 -C 50 Heteroaryl, each hydrogen atom on the aryl and heteroaryl independently may be substituted with Rb; the substituents Rb of each group are each independently selected from C 1 -C 12 Alkyl, halogen, hydroxy, cyano, sulfonyl, sulfo, phenyl, biphenyl, terphenyl, naphthyl, nitro, carboxyl, C 1 -C 12 Acyloxy or C 1 -C 12 An alkoxy group;
R 1 、R 2 、R 3 、R 4 each independently selected from hydrogen, hydroxy, C 1 -C 20 Alkyl, C 6 -C 12 Cycloalkyl, C 1 -C 20 Alkoxy, C 6 -C 12 Cycloalkoxy, allyl, amino, C 6 -C 50 Aryl or C 2 -C 50 Heteroaryl; the hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted with Rc; the substituents Rc of the individual radicals are each independently selected from C 1 -C 12 Alkyl, halogen, hydroxy, cyano, sulfonyl, sulfo, phenyl, biphenyl, terphenyl, naphthyl, nitro, carboxyl or C 1 -C 12 An alkoxy group;
the heteroatoms on the heteroaryl or the heteroarylene are each independently selected from O, S or N;
R 5 、R 6 、R 7 、R 8 each independently selected from hydrogen orAnd R is 5 、R 6 、R 7 、R 8 At least one of is
In some embodiments of the present application, L 1 Selected from single bonds, C 6 -C 30 Arylene or C 2 -C 30 A heteroarylene group, the hydrogen atoms on the arylene group and the heteroarylene group each independently may be substituted with Ra.
In some embodiments of the present application, L 1 Selected from the following groups:
in some embodiments of the present application, L 2 Selected from hydrogen, C 1 -C 8 Alkyl, allyl, C 1 -C 4 Alkoxy, C 6 -C 30 Aryl or C 2 -C 30 Heteroaryl, the hydrogen atoms on the aryl and the heteroaryl each independently may be substituted with Rb.
In some embodiments of the present application, L 2 Selected from the following groups:
x is selected from O, S, CR 5 R 6 Or NR (NR) 7 ；
R 5 、R 6 Each independently selected from C 1 -C 10 Alkyl, C 6 -C 30 Aryl or C 3 -C 30 Heteroaryl, R 5 And said R 6 Can be connected into a ring;
R 7 selected from C 6 -C 30 Aryl or C 3 -C 30 Heteroaryl; when R is 7 Selected from C 3 -C 30 In the case of heteroaryl, the heteroatom of the heteroaryl is selected from O or S.
In some embodiments of the present application, R 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, hydroxy, C 1 -C 20 Alkyl, cyclohexyl, C 1 -C 20 Alkoxy, cyclohexoxy, allyl, amino, C 6 -C 30 Aryl or C 2 -C 30 Heteroaryl, the hydrogen atoms on the aryl and heteroaryl groups each independently can be substituted with Rc.
In some embodiments of the present application, L 1 Selected from single bonds, C 6 -C 18 Arylene or C 2 -C 18 A heteroarylene group, the hydrogen atoms on the arylene group and the heteroarylene group each independently may be substituted with Ra; the substituents Ra of the individual radicals are each independently selected from C 1 -C 3 Alkyl or hydroxy;
L 2 selected from hydrogen, C 6 -C 18 Aryl or C 2 -C 18 Heteroaryl, each hydrogen atom on the aryl and heteroaryl independently may be substituted with Rb; the substituents Rb of each group are each independently selected from C 1 -C 3 Alkyl or hydroxy;
R 1 、R 2 、R 3 、R 4 each independently selected from hydrogen, C 6 -C 18 Aryl or C 2 -C 18 Heteroaryl; the hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted with Rc; the substituents Rc of each group are each independently selected from hydroxy;
the heteroatoms on the heteroaryl or the heteroarylene are each independently selected from N;
R 5 、R 6 、R 8 selected from hydrogen and R 7 Selected from the group consisting ofOr R is 5 、R 7 、R 8 Selected from hydrogen and R 6 Selected from the group consisting of
In some embodiments of the present application, L 1 Selected from single bonds or
L 2 Selected from hydrogen,
R 1 、R 2 、R 4 Selected from hydrogen; r is R 3 Selected from hydrogen,
R 5 、R 6 、R 8 Selected from hydrogen and R 7 Selected from the group consisting ofOr R is 5 、R 7 、R 8 Selected from hydrogen and R 6 Selected from the group consisting of
For example, the compound of formula (I) may be selected from the group consisting of the compounds represented by A1-A64, and the specific chemical structural formulas of the compounds represented by A1-A64 are described in detail above.
The compound of the formula (I) has a strong absorption effect on ultraviolet rays in a 280nm-380nm interval, and the absorption range covers a 360nm-380nm interval in a UVA wave band and a 280nm-315nm interval in a UVB wave band; and the absorption intensity is higher than that of T1600 in the range of 280nm-300nm and 340nm-380nm, and the ultraviolet resistance is better than that of T1600, so that the ultraviolet-resistant coating has wider application field.
A second aspect of the present application provides an ultraviolet absorber comprising at least one of the compounds provided in the first aspect of the present application. The ultraviolet absorbent provided by the application can comprise other substances and/or additives capable of absorbing ultraviolet, and the additives can be at least one selected from antioxidants, metal deactivators and phosphites. Wherein the antioxidant can be at least one selected from 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butyl-4-methoxyphenol and N-isopropyl-N' -phenyl-p-phenylenediamine; the metal passivating agent can be at least one selected from N, N' -diphenyl formamide and 3-salicylamide-1, 2, 4-triazole; the phosphite ester may be at least one selected from triphenyl phosphite and tris (2, 4-di-t-butylphenyl) phosphite. The other substance capable of absorbing ultraviolet rays may be at least one selected from benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and triazine-based ultraviolet absorbers.
The specific kind and amount of the other substances and/or additives capable of absorbing ultraviolet rays to be added are not limited in the present application, as long as the objects of the present application can be achieved.
A third aspect of the present application provides a composition comprising: a) Organic substances susceptible to damage by light, oxygen and/or heat; and B) at least one of a compound provided in the first aspect of the present application or an ultraviolet absorber provided in the second aspect of the present application; wherein the mass ratio of the component A) to the component B) is 100:0.01-15.
The method for preparing the composition of the present application is not particularly limited, and any method known in the art may be employed, for example, directly mixing component a) and component B) in proportion uniformly. The compound or the ultraviolet absorber of the formula (I) is added into organic substances which are sensitive to light, oxygen and/or heat damage, and can absorb ultraviolet rays in the range of 280nm-380nm, so that the organic substances which are sensitive to light, oxygen and/or heat damage are prevented from being damaged by the ultraviolet rays in the range, and the effect of protecting the organic substances which are sensitive to light, oxygen and/or heat damage is achieved.
In some embodiments of the present application, at least one of a thermoplastic polymer, a coating binder, or a photosensitive material is included as component a).
In some embodiments of the present application, the thermoplastic polymer is selected from at least one of polyethylene, polypropylene, polyvinyl chloride, a copolymer of vinyl chloride and vinyl acetate, polystyrene, a copolymer of styrene and acrylonitrile, polyamide, polyethylene terephthalate, the coating binder is selected from at least one of polyurethane, polyacrylate, natural rubber, silicone rubber, vinyl acetate, polyvinylidene chloride, and polyvinyl alcohol, and the photosensitive material is selected from at least one of color blinder sheet, positive color sheet, full color sheet, infrared sheet, and color sheet.
A fourth aspect of the present application provides the use of a compound provided in the first aspect of the present application or an ultraviolet absorber provided in the second aspect of the present application or a composition provided in the third aspect of the present application to prevent light, oxygen and/or heat damage in an organic substance.
The method for synthesizing the compound of the present application is not particularly limited, and may be synthesized by any method known to those skilled in the art. The following illustrates the synthesis of the compounds of the present application.
The silica gel column used in the following examples was a silica gel column available from Qingdao Spectroscopy separation materials Co., ltd. And having a model of coarse pore (zcx-II); yield = actual synthetic product mass/theoretical synthetic product mass x 100% in the examples below.
Example 1: synthesis of Compound A9
1-3: compound 1-1 (925 mg,4 mmol), compound 1-2 (1.4 g,4.4 mmol), tetraphenylphosphine palladium (231 mg,0.2 mmol), potassium carbonate (2.2 g,16 mmol), 35mL anhydrous THF (tetrahydrofuran) and 15mL deionized water were added to a reaction flask, reflux reaction was performed at 80℃under nitrogen atmosphere for 14h, after the reaction was completed, the reaction system was concentrated, and silica gel column chromatography (eluent: petroleum ether: ethyl acetate=10:1, v/v) was used to obtain product 1-3 in 80% yield.
1-4 preparation: compounds 1-3 (1.3 g,3 mmol) and 10mL of anhydrous DCM (dichloromethane) were added to a 50mL reaction flask, then a dichloromethane solution (570mg,3.2mmol NBS) of NBS (N-bromosuccinimide) was added dropwise to the flask under ice bath, the reaction was allowed to proceed to room temperature for 12h, after the reaction was completed, the reaction system was concentrated, and silica gel column chromatography (eluent: petroleum ether: dichloromethane=5:1, v/v) was used to give products 1-4 in 77% yield.
1-5 preparation: compounds 1-4 (1.1 g,2 mmol), pinacol diboronate (53 mg,2.1 mmol), potassium acetate (490 mg,5 mmol) and 20mL anhydrous DMF (N, N-dimethylformamide) were added to a 50mL reaction flask followed by PdCl 2 (dppf) (73 mg,0.1 mmol), 15h at 85℃and after completion of the reaction, 50mL of water was added to the system, extracted with ethyl acetate (3X 50 mL), the organic phases were combined, dried over anhydrous sodium sulfate, and the organic phase was concentrated and chromatographed on a silica gel column (eluent petroleum ether: ethyl acetate=30:1, v/v) to give the product 1-5 in 60% yield.
1-8 preparation: compounds 1 to 7 (685 mg,5 mmol), compounds 1 to 6 (1.4 g,5 mmol), potassium carbonate (1.0 g,7.5 mmol), 40mL toluene, 16mL absolute ethanol and 8mL deionized water were added to a 250mL reaction flask, and then tetrakis triphenylphosphine palladium (289 mg,0.25 mmol) was added, reacted at 85℃for 20 hours, after the reaction was completed, the reaction system was concentrated, and silica gel column chromatography (eluent: petroleum ether: ethyl acetate=15:1, v/v) was used to obtain products 1 to 8, yield 78%.
Preparation of A9: compounds 1 to 5 (560 mg,1 mmol), compounds 1 to 8 (276 mg,1.1 mmol), potassium carbonate (196 mg,2 mmol), toluene 10mL, absolute ethanol 6mL and 2mL of water were added to a 50mL reaction flask, and then tetrakis triphenylphosphine palladium (57 mg,0.05 mmol) was added, followed by an oil bath at 85℃for 9 hours, after the reaction was completed, the reaction system was concentrated, and silica gel column chromatography (eluent: petroleum ether: ethyl acetate=15:1, v/v) was used to obtain product A9 in 65% yield.
Compound A9 1 H NMR results: 1 H NMR(400MHz,Chloroform-d)δ13.14(d,J＝16.1Hz,1H),9.12(d,J＝9.1Hz,2H),8.55(dd,J＝8.0,1.7Hz,1H),8.40(d,J＝1.3Hz,1H),8.37–8.33(m,1H),8.24(d,J＝7.8Hz,1H),7.93(d,J＝8.4Hz,2H),7.86(d,J＝7.8Hz,1H),7.81–7.75(m,2H),7.73–7.63(m,5H),7.62–7.56(m,1H),7.54–7.48(m,2H),7.44–7.35(m,4H),7.08(d,J＝8.2Hz,1H),7.01(t,J＝7.5Hz,1H),1.60(s,6H).
example 2: synthesis of Compound A26
2-2 preparation: compound 2-1 (2.0 g,5 mmol), pinacol diboronate (3.1 g,12 mmol), potassium acetate (2.0 g,20 mmol) and 50mL anhydrous DMF are added to a 250mL reaction flask, nitrogen is bubbled for 30min and PdCl is added 2 (dppf) (290 mg,0.4 mmol), was reacted at 85℃for 25h, after the reaction was completed, 400mL of water was added to the system, extracted with ethyl acetate (3X 200 mL), the organic phases were combined, dried over anhydrous sodium sulfate, and the organic phase was concentrated, and the product was obtained in a yield of 2-2 by column chromatography on silica gel (eluent: petroleum ether: ethyl acetate=15:1, v/v).
1-8 preparation: compounds 1 to 7 (685 mg,5 mmol), compounds 1 to 6 (1.4 g,5 mmol), potassium carbonate (1.0 g,7.5 mmol), 40mL toluene, 16mL absolute ethanol and 8mL deionized water were added to a 250mL reaction flask, and then tetrakis triphenylphosphine palladium (289 mg,0.25 mmol) was added, reacted at 85℃for 20 hours, after the reaction was completed, the reaction system was concentrated, and silica gel column chromatography (eluent: petroleum ether: ethyl acetate=15:1, v/v) was used to obtain products 1 to 8, yield 78%.
Preparation of A26: compound 2-2 (99mg, 2 mmol), compound 1-8 (1.1 g,4.2 mmol), potassium carbonate (1.1 g,8 mmol), toluene 20mL, absolute ethyl alcohol 10mL and 6mL deionized water were put into a 100mL reaction bottle, then tetrakis triphenylphosphine palladium (288 mg,0.25 mmol) was added, the reaction was carried out at 85℃in an oil bath for 9 hours, after the reaction was completed, the reaction system was concentrated, and silica gel column chromatography (eluent: petroleum ether: ethyl acetate=5:1, v/v) was used to obtain product A26, yield 63%.
Compound A26 1 H NMR results: 1 H NMR(400MHz,Chloroform-d)δ9.62(s,2H),9.24(s,4H),8.31(dd,J＝7.2,1.6Hz,1H),8.13(d,J＝7.2Hz,1H),7.99(dd,J＝7.0,1.5Hz,1H),7.89(d,J＝8.1Hz,2H),7.76(d,J＝8.1Hz,1H),7.70–7.59(m,5H),7.52–7.49(m,2H),7.34–7.28(m,2H),7.13–7.02(m,4H).
example 3: synthesis of Compound A44
4-3 preparation: compound 4-2 (1.2 g,5 mmol), pinacol diboronate (3.0 g,12 mmol), potassium acetate (1.9 g,20 mmol) and 50mL anhydrous DMF are added to a 250mL reaction flask followed by PdCl 2 (dppf) (183 mg,0.25 mmol), was reacted at 85℃for 25 hours, after the reaction was completed, 50mL of water was added to the system, extracted with ethyl acetate (3X 50 mL), the organic phases were combined, dried over anhydrous sodium sulfate, and the organic phase was concentrated, and the product 4-3 was obtained in 79% yield by silica gel column chromatography (eluent: petroleum ether: ethyl acetate=10:1, v/v).
1-8 preparation: compounds 1 to 7 (685 mg,5 mmol), compounds 1 to 6 (1.4 g,5 mmol), potassium carbonate (1.0 g,7.5 mmol), 40mL toluene, 16mL absolute ethanol and 8mL deionized water were added to a 250mL reaction flask, and then tetrakis triphenylphosphine palladium (289 mg,0.25 mmol) was added, reacted at 85℃for 20 hours, after the reaction was completed, the reaction system was concentrated, and silica gel column chromatography (eluent: petroleum ether: ethyl acetate=15:1, v/v) was used to obtain products 1 to 8, yield 78%.
4-5 preparation: compound 4-3 (879 mg,3 mmol), compound 1-8 (800 mg,3.2 mmol), potassium carbonate (589 mg,6 mmol), toluene 30mL, absolute ethanol 15mL and 8mL of water were added to a 100mL reaction flask, and then tetrakis triphenylphosphine palladium (173 mg,0.15 mmol) was added, reacted at 85℃for 9 hours in an oil bath, after the reaction was completed, the reaction system was concentrated, and silica gel column chromatography (eluent: petroleum ether: ethyl acetate=3:1, v/v) was used to obtain product 4-5 in a yield of 68%.
4-6 preparation: compound 4-5 (6754 mg,2 mmol), p-bromophenylboronic acid (480 mg,2.4 mmol), pd 2 (dba) 3 (46mg，0.05mmol)、P(t-Bu) 3 (Tri-tert-butylphosphine, 24mg,0.12 mmol), sodium t-butoxide (576 mg,6 mmol) and 30mL of toluene were added to a 250mL reaction flask, reacted at 110℃for 10 hours under nitrogen atmosphere, after the reaction was completed, 50mL of water was added to the system, extracted with ethyl acetate (3X 50 mL), the organic phase was combined, and anhydrous sodium sulfate was driedThe organic phase was dried and concentrated and chromatographed on a silica gel column (eluent petroleum ether: ethyl acetate=3:1, v/v) to give the product 4-6 in 71% yield.
Preparation of A44: compounds 4 to 6 (457 mg,1 mmol), compounds 1 to 8 (300 mg,1.2 mmol), potassium carbonate (200 mg,1.5 mmol), 10mL toluene, 4mL absolute ethanol and 2mL deionized water were added to a 250mL reaction flask, and then tetrakis triphenylphosphine palladium (58 mg,0.05 mmol) was added, reacted at 85℃for 20 hours, after the reaction was completed, the reaction system was concentrated, and silica gel column chromatography (eluent: petroleum ether: ethyl acetate=10:1, v/v) was used to obtain product A44 in 74% yield.
Compound A44 1 H NMR results: 1 H NMR(400MHz,Chloroform-d)δ9.61(s,1H),9.60(s,1H),9.25(s,2H),9.23(s,2H),8.62(d,J＝7.6Hz,1H),8.25–8.13(m,2H),7.93–7.90(m,4H),7.74(d,J＝1.8Hz,1H),7.61–7.55(m,3H),7.52–7.49(m,1H),7.34–7.29(m,2H),7.22–7.19(m,1H),7.10–6.93(m,4H)。
example 4: synthesis of Compound A58
2-2 preparation: compound 2-1 (1.6 g,5 mmol), pinacol diboronate (1.55 g,6 mmol), potassium acetate (2.0 g,10 mmol) and 40mL anhydrous DMF are added to a 100mL reaction flask, nitrogen drum for 30min and PdCl 2 (dppf) (182 mg,0.25 mmol), after completion of the reaction, 30mL of water was added to the system, extracted with ethyl acetate (3X 30 mL), the organic phases were combined, dried over anhydrous sodium sulfate, and the organic phase was concentrated and chromatographed on a silica gel column (eluent petroleum ether: ethyl acetate=30:1, v/v) to give product 2-2 in 79% yield.
1-8 preparation: compounds 1 to 7 (685 mg,5 mmol), compounds 1 to 6 (1.4 g,5 mmol), potassium carbonate (1.0 g,7.5 mmol), 40mL toluene, 16mL absolute ethanol and 8mL deionized water were added to a 250mL reaction flask, and then tetrakis triphenylphosphine palladium (289 mg,0.25 mmol) was added, reacted at 85℃for 20 hours, after the reaction was completed, the reaction system was concentrated, and silica gel column chromatography (eluent: petroleum ether: ethyl acetate=15:1, v/v) was used to obtain products 1 to 8, yield 75%.
2-3 preparation: compound 2-2 (1.1 g,3 mmol), compound 1-8 (838 g,3.2 mmol), potassium carbonate (690 mg,5 mmol), toluene 20mL, absolute ethanol 10mL and 6mL deionized water are added into a 100mL reaction bottle, then tetrakis triphenylphosphine palladium (272 mg,0.15 mmol) is added, the reaction is carried out for 9h at 85 ℃ in an oil bath, after the reaction is completed, the reaction system is concentrated, and silica gel chromatographic column chromatography (eluent is petroleum ether: ethyl acetate=10:1, v/v) is adopted to obtain product 2-3, and the yield is 71%.
2-4 preparation: compound 2-3 (826 mg,2 mmol) and 10mL of anhydrous DCM are added into a 50mL reaction bottle, under ice bath condition, a DCM solution of NBS (310mg,2.1mmol NBS is dissolved in 6mL of DCM) is added dropwise, the reaction is continued for 12h at room temperature after the addition, after the reaction is completed, the reaction system is concentrated, and silica gel chromatographic column chromatography (eluent is petroleum ether: ethyl acetate=20:1, v/v) is adopted to obtain product 2-4, and the yield is 78%.
2-5 preparation: compounds 2-4 (539 mg,1 mmol), pinacol diboronate (310 mg,1.2 mmol), potassium acetate (400 mg,2 mmol) and 8mL anhydrous DMF were added to the reaction flask, after 30min nitrogen drum PdCl 2 (dppf) (37 mg,0.05 mmol), after completion of the reaction, 6mL of water was added to the system, extracted with ethyl acetate (3X 8 mL), the organic phases were combined, dried over anhydrous sodium sulfate, and the organic phase was concentrated and chromatographed on a silica gel column (eluent petroleum ether: ethyl acetate=10:1, v/v) to give the product 2-5 in 77% yield.
Preparation of a 58: compounds 2 to 5 (491 mg,0.5 mmol), compounds 1 to 8 (129 mg,0.65 mmol), potassium carbonate (134 mg,1 mmol), 5mL toluene, 2mL absolute ethanol and 1mL deionized water were added to a 250mL reaction flask, and then tetrakis triphenylphosphine palladium (29 mg,0.025 mmol) was added, reacted at 85℃for 16 hours, after the reaction was completed, the reaction system was concentrated, and silica gel column chromatography (eluent: petroleum ether: ethyl acetate=10:1, v/v) was used to obtain product A58 in 75% yield.
Compound A58 1 H NMR results: 1 H NMR(400MHz,Chloroform-d)δ9.63(s,1H),9.62(s,1H),9.28(s,4H),8.62(d,J＝7.1Hz,1H),8.22(dd,J＝7.4,1.7Hz,1H),7.98(dd,J＝7.5,1.6Hz,1H),7.88(d,J＝1.7Hz,1H),7.80–7.71(m,2H),7.69–7.54(m,5H),7.52–7.45(m,2H),7.39–7.26(m,2H),7.13–6.93(m,4H)
example 5: synthesis of Compound A60
/>
2-2 preparation: compound 2-1 (1.6 g,5 mmol), pinacol diboronate (1.55 g,6 mmol), potassium acetate (2.0 g,10 mmol), 40mL anhydrous DMF were added to a 100mL reaction flask, nitrogen drum for 30min and PdCl was added 2 (dppf) (182 mg,0.25 mmol), after completion of the reaction, 30mL of water was added to the system, extracted with ethyl acetate (3X 30 mL), the organic phases were combined, dried over anhydrous sodium sulfate, and the organic phase was concentrated and chromatographed on a silica gel column (eluent petroleum ether: ethyl acetate=30:1, v/v) to give product 2-2 in 79% yield.
1-8 preparation: compounds 1 to 7 (685 mg,5 mmol), compounds 1 to 6 (1.4 g,5 mmol), potassium carbonate (1.0 g,7.5 mmol), 40mL toluene, 16mL absolute ethanol and 8mL deionized water were added to a 250mL reaction flask, and then tetrakis triphenylphosphine palladium (289 mg,0.25 mmol) was added, reacted at 85℃for 20 hours, after the reaction was completed, the reaction system was concentrated, and silica gel column chromatography (eluent: petroleum ether: ethyl acetate=15:1, v/v) was used to obtain products 1 to 8, yield 75%.
2-3 preparation: compound 2-2 (1.1 g,3 mmol), compound 1-8 (838 g,3.2 mmol), potassium carbonate (690 mg,5 mmol), toluene 20mL, absolute ethanol 10mL and 6mL deionized water are added into a 100mL reaction bottle, then tetrakis triphenylphosphine palladium (272 mg,0.15 mmol) is added, the reaction is carried out for 9h at 85 ℃ in an oil bath, after the reaction is completed, the reaction system is concentrated, and silica gel chromatographic column chromatography (eluent is petroleum ether: ethyl acetate=10:1, v/v) is adopted to obtain product 2-3, and the yield is 71%.
2-4 preparation: compound 2-3 (826 mg,2 mmol) and 10mL of anhydrous DCM are added into a 50mL reaction bottle, under ice bath condition, a DCM solution of NBS (310mg,2.1mmol NBS is dissolved in 6mL of DCM) is added dropwise, the reaction is continued for 12h at room temperature after the addition, after the reaction is completed, the reaction system is concentrated, and silica gel chromatographic column chromatography (eluent is petroleum ether: ethyl acetate=20:1, v/v) is adopted to obtain product 2-4, and the yield is 78%.
Preparation of A60: compounds 2 to 4 (491 mg,1 mmol), compounds 2 to 5 (257 mg,1.3 mmol), potassium carbonate (200 mg,1.5 mmol), 8mL toluene, 4mL absolute ethanol and 2mL deionized water were added to a 250mL reaction flask, and then tetrakis triphenylphosphine palladium (58 mg,0.05 mmol) was added, reacted at 85℃for 20 hours, after the reaction was completed, the reaction system was concentrated, and silica gel column chromatography (eluent: petroleum ether: ethyl acetate=10:1, v/v) was used to obtain product A60 in 69% yield.
Compound A60 1 H NMR results: 1 H NMR(400MHz,Chloroform-d)δ9.63(s,1H),9.26(s,2H),8.62(d,J＝7.4Hz,1H),8.22(dd,J＝7.2,1.6Hz,1H),7.95(dd,J＝7.3,1.8Hz,1H),7.89(d,J＝1.8Hz,1H),7.77–7.74(m,4H),7.62–7.58(m,4H),7.50–7.43(m,4H),7.41–7.25(m,6H),7.12–6.98(m,2H).
other compounds of the present application can be synthesized by selecting appropriate raw materials according to the concept of synthesizing the compounds A9, a26, a44, a58 or a60, or by selecting any other appropriate methods and raw materials.
Comparative example 1
T1600 has a structural formula shown as a formula (II):
the following performance measurements were performed on the compounds synthesized in the above examples and on T1600 of comparative example 1.
1. Ultraviolet protective coating performance test
0.7mol of tetraethyl orthosilicate (hereinafter abbreviated as TEOS), 0.3mol of phenyltriethoxysilane (hereinafter abbreviated as PhTES) and 1mol of ethanol were mixed, and then 1.4mol of water and 0.003L of nitric acid having a molar concentration of 14mol/L were added thereto, followed by stirring at room temperature for hydrolysis for 24 hours to obtain an alkoxide solution. 1mL of an ethanol solution containing 0.001mol of rhodamine 101 dye was added to the above alkoxide solution to obtain a mixed solution. The above mixed solution was spin-coated on a glass substrate at 2000rpm, dried at room temperature for 2 days, and dried at 50℃for 24 hours to obtain a glass substrate (hereinafter referred to simply as glass substrate + Rh101 fluorescent film) covered with rhodamine 101 dye-doped organically modified silicate gel glass coating, wherein the Rh101 fluorescent film had a thickness of 0.8. Mu.m.
Mixing 1mol TEOS and 1mol PhTES, adding into 100mL ethanol, fully dissolving, adding 2mol water and 6mL nitric acid with the molar concentration of 14mol/L, and stirring at room temperature for hydrolysis for 24 hours; 0.4mol of each of the compounds of the examples and comparative examples was added separately; and spin coating the glass substrate and the Rh101 fluorescent film at 2000rpm, drying at room temperature for 2 days, and drying at 50 ℃ for 2 hours to obtain the glass substrate (hereinafter referred to as glass substrate, rh101 fluorescent film and UV protective film) sequentially covered with the rhodamine 101 dye doped organic modified silicate gel glass coating and the ultraviolet light absorbing layer, wherein the film thicknesses of the two layers are 0.8 mu m respectively.
(1) Ultraviolet visible absorption spectrum test
The testing method comprises the following steps: the ultraviolet-visible absorption spectra of the glass substrate+rh 101 fluorescent film, the glass substrate+rh 101 fluorescent film+uv protective film (containing the compound A9 of example 1), the glass substrate+rh 101 fluorescent film+uv protective film (containing T1600 of comparative example 1) were measured in the range of 300nm to 700nm using an ultraviolet-visible spectrophotometer as a sample to be measured.
Test results: the ultraviolet-visible absorption spectra of the glass substrate+rh 101 fluorescent film, the glass substrate+rh 101 fluorescent film+uv protective film (containing the compound A9 of example 1), and the glass substrate+rh 101 fluorescent film+uv protective film (containing the compound T1600 of comparative example 1) are shown in fig. 1, in which: rh101 corresponds to the glass substrate +Rh101 fluorescent film, T1600 corresponds to the glass substrate +Rh101 fluorescent film +UV protective film (T1600 is used as an ultraviolet absorber), and A9 corresponds to the glass substrate +Rh101 fluorescent film +UV protective film (A9 is used as an ultraviolet absorber). As can be seen from fig. 1: in the interval of 300nm-400nm, the absorbance of the glass substrate, the Rh101 fluorescent film, the UV protection film (A9) and the glass substrate, the Rh101 fluorescent film and the UV protection film (T1600) is far greater than that of the glass substrate, the Rh101 fluorescent film (Rh 101); the difference between the absorbance of the glass substrate +Rh101 fluorescent film +UV protective film (A9) and the absorbance of the glass substrate +Rh101 fluorescent film (Rh 101) is small in the range of 400nm to 650 nm. Without being bound by any theory, the inventors believe that the absorption peak occurring in the 400nm-650nm interval is mainly due to the absorption effect of Rh101 on visible light.
The above results show that compounds A9 and T1600 have no significant absorption of visible light (400 nm-650 nm) and strong absorption of ultraviolet light (300 nm-400 nm). Therefore, the UV protective film containing the compounds A9 and T1600 of example 1 was coated on the surface of the Rh101 fluorescent film, and the ultraviolet light reaching the Rh101 fluorescent film could be significantly reduced, thereby reducing the degree of degradation of the Rh101 fluorescent film by ultraviolet light.
(2) Ultraviolet absorbance spectroscopy test
Ultraviolet absorption spectra of the glass substrate + Rh101 fluorescent film + UV protective film (containing the compound A9 of example 1) and the glass substrate + Rh101 fluorescent film + UV protective film (containing the compound T1600 of comparative example 1) were measured in the range of 280nm to 400nm using an ultraviolet-visible spectrophotometer.
Test results: the ultraviolet absorption spectra of the glass substrate + Rh101 fluorescent film + UV protective film (containing the compound A9 of example 1), the glass substrate + Rh101 fluorescent film + UV protective film (containing the compound T1600 of comparative example 1) are shown in fig. 2, in which: a9 corresponds to the glass substrate+rh101 fluorescent film+uv protective film (containing the compound A9 of example 1), and T1600 corresponds to the glass substrate+rh101 fluorescent film+uv protective film (containing the compound T1600 of comparative example 1). As can be seen from fig. 2: the absorption range of the glass substrate +Rh101 fluorescent film +UV protective film (A9) is wider than that of the glass substrate +Rh101 fluorescent film +UV protective film (T1600), and the absorbance of the glass substrate +Rh101 fluorescent film +UV protective film (A9) is larger than that of the glass substrate +Rh101 fluorescent film +UV protective film (T1600) in the intervals of 280nm-300nm and 340nm-380 nm.
The result shows that the compound A9 in the UV protective film has a strong absorption effect on ultraviolet rays in the range of 280nm-380nm, has higher absorption intensity than T1600 in the ranges of 280nm-300nm and 340nm-380nm, and has better anti-ultraviolet performance than T1600.
(3) Photodegradation Rate test
The testing method comprises the following steps: the glass substrate + Rh101 fluorescent film, the glass substrate + Rh101 fluorescent film + UV protective film (each containing the compound of each example and comparative example) were placed in a QUV-Spray ultraviolet aging oven at 25deg.C, with a UVA band optical power of 0.4 W.m -2 。
The absorbance of each sample to be measured was measured for the change in ultraviolet irradiation time at the maximum absorption wavelength (580 nm) of the Rh101 fluorescent dye using an ultraviolet-visible spectrophotometer.
Test results: the graph of absorbance at a wavelength of 580nm versus ultraviolet irradiation time for the glass substrate+rh 101 fluorescent film, the glass substrate+rh 101 fluorescent film+uv protective film (containing the compound A9 of example 1), and the glass substrate+rh 101 fluorescent film+uv protective film (containing the compound T1600 of comparative example 1) at a temperature of 25 ℃ is shown in fig. 3, in which: a9 corresponds to the glass substrate+rh101 fluorescent film+uv protective film (containing the compound A9 of example 1), T1600 corresponds to the glass substrate+rh101 fluorescent film+uv protective film (containing the compound T1600 of comparative example 1), and the blank corresponds to the glass substrate+rh101 fluorescent film. As can be seen from fig. 3: the rate of decrease in absorbance of the glass substrate+rh 101 fluorescent film+uv protective film (A9) was much smaller than the rate of decrease in absorbance of the glass substrate+rh 101 fluorescent film (blank) with the increase in the ultraviolet irradiation time, and slightly smaller than the rate of decrease in absorbance of the glass substrate+rh 101 fluorescent film+uv protective film (containing compound T1600 in comparative example). The above results indicate that A9 has better UV resistance than T1600.
Without being limited to any theory, the inventors believe that: since ultraviolet light degrades Rh101 fluorescence, the UV protective film covering the surface of the Rh101 fluorescent film contains the compound A9 of example 1, and the compound A9 can absorb ultraviolet light, thereby reducing ultraviolet light reaching the Rh101 fluorescent film, further reducing degradation of Rh101 fluorescence by ultraviolet light, slowing down the rate of decrease in absorbance of Rh101 fluorescent dye, and finally making the rate of decrease in absorbance of the glass substrate+rh 101 fluorescent film+uv protective film (containing the compound A9 of example 1) much smaller than the rate of decrease in absorbance of the glass substrate+rh 101 fluorescent film. The ultraviolet absorber T1600 of comparative example 1 also has the same tendency that the rate of decrease in absorbance is also much smaller than that of the glass substrate+rh101 fluorescent film.
The photodegradation rate v of the Rh101 fluorescent dye in the glass substrate +Rh101 fluorescent film +UV protective film (containing the compounds of the examples and comparative examples, respectively) was calculated from the absorbance at 580nm wavelength of the glass substrate +Rh101 fluorescent film +UV protective film (containing the compounds of the examples and comparative examples, respectively) and the absorbance at 580nm wavelength of the glass substrate +Rh101 fluorescent film at 25℃temperature 1 Photo degradation rate v of Rh101 fluorescent dye in glass substrate +Rh101 fluorescent film 2 The method comprises the steps of carrying out a first treatment on the surface of the Photodegradation Rate v 1 And v 2 By the formula v= (a 0 -a)/a 0 Calculated, wherein a 0 The initial absorbance, a, after 12 hours of aging; further, the ratio v of the photodegradation rate of the Rh101 fluorescent dye in the glass substrate +Rh101 fluorescent film to the photodegradation rate of the Rh101 fluorescent dye in the glass substrate +Rh101 fluorescent film +UV protection film (containing the compounds of each example and comparative example, respectively) was obtained 2/ v 1 Specific results are shown in table 1 below.
TABLE 1 photodegradation Rate test results
As is clear from the results in Table 1, under ultraviolet irradiation, the ratio v of the photodegradation rate of Rh101 fluorescent dye in the glass substrate +Rh101 fluorescent film to the photodegradation rate of Rh101 fluorescent dye in the glass substrate +Rh101 fluorescent film +UV protective film (each containing the compound of each example) 2/ v 1 Can reach more than 5, which indicates that the compounds of each embodiment included in the UV protection film covered on the surface of the Rh101 fluorescent film can effectively absorb the ultraviolet rays, thereby reducing the ultraviolet rays reaching the Rh101 fluorescent film and further reducing the fluorescence of the Rh101 by the ultraviolet raysIs a degradation rate of (a). Whereas the ratio v of the photodegradation rate of the Rh101 fluorescent dye in the glass substrate +Rh101 fluorescent film to the photodegradation rate of the Rh101 fluorescent dye in the glass substrate +Rh101 fluorescent film +UV protection film (compound T1600 of comparative example 1) 2/ v 1 From the photodegradation rate ratio, the compound provided in the examples is better than the compound provided in the comparative example T1600, and can better protect the product and reduce the photodegradation rate of the product. The results show that the compound provided by the application can bear long-time solar radiation, can improve the durability of outdoor products when being used for preparing the outdoor products, and has wide application prospects.
2. Photodegradation methyl orange test
(1) Drawing of a Standard Curve
0.5g of methyl orange is weighed, dissolved in N-methylpyrrolidone (NMP) solvent, transferred into a 500mL constant volume bottle, added with NMP for constant volume and uniformly shaken to obtain 1g/L of methyl orange solution.
20mL of the 1g/L methyl orange solution is measured in a 1L volumetric flask, NMP is added for constant volume and shaking is carried out, and 20mg/L methyl orange solution is obtained.
Taking 5 colorimetric tubes with 10mL, respectively transferring 0mL, 2.5mL, 5mL, 7.5mL and 10mL of 20mg/L methyl orange solution into the colorimetric tubes by using a 10mL pipette, and adding NMP to prepare 0mg/L, 5mg/L, 10mg/L, 15mg/L and 20mg/L methyl orange standard solutions respectively.
And measuring the absorbance of the methyl orange in the methyl orange standard solution with different mass concentrations at the wavelength of 470nm by adopting an ultraviolet-visible light spectrophotometer, and drawing a standard curve of the relationship between the absorbance and the mass concentration of the methyl orange according to the measurement result. The absorbance results of methyl orange in methyl orange standard solutions of different mass concentrations are shown in table 2 below.
TABLE 2 absorbance of methyl orange in methyl orange solutions of different mass concentrations
Concentration by mass (mg/L) 0 5 10 15 20
Absorbance of light 0.000 0.371 0.692 1.029 1.350
According to the results of Table 2, a standard curve of the relationship between the absorbance and the mass concentration of methyl orange is drawn, and the obtained standard curve is shown in FIG. 4, wherein the regression equation of the standard curve is y=0.0676x+0.0006, and the correlation coefficient R 2 = 0.99858, where y is absorbance and x is methyl orange mass concentration.
(2) Photocatalytic degradation methyl orange test
150mL of the 20mg/L methyl orange solution was measured and poured into a reactor to which 2mg of the compounds of each of the examples and comparative examples were added, respectively; 150mL of the 20mg/L methyl orange solution was additionally measured and directly poured into the reactor as a control group. The reactor is put into a QUV-spray ultraviolet aging box, and the optical power of UVA wave band is set to be 0.4W.m -2 To photo-catalyze the methyl orange solution.
10mL of each of the reaction vessels corresponding to the control group, the reaction vessel containing 2mg of the compound A9 of example 1 and the reaction vessel containing 2mg of the compound T1600 of comparative example 1 was sampled at 0h, 1h, 3h, 5h and 9h, respectively, and absorbance at 470nm was measured.
The absorbance of the methyl orange measured at different time points is substituted into the regression equation y=0.0676x+0.0006 of the standard curve, and the mass concentration of the methyl orange at different time points is calculated, and specific results are shown in the following table 3 and fig. 5.
TABLE 3 mass concentration of methyl orange measured at different time points
Note that: "blank" means no compound added
Fig. 5 is a graph of the mass concentration of methyl orange corresponding to different time points in different reactors, wherein: a9 corresponds to a reactor to which 0.2g of compound A9 of example 1 was added, T1600 corresponds to a reactor to which 0.2g of compound T1600 of comparative example 1 was added, and "blank" corresponds to a control reactor. As can be seen from table 3 and fig. 5, the mass concentration of methyl orange in each of the three reaction vessels gradually decreased with the increase of the ultraviolet irradiation time, but the mass concentration of methyl orange in the corresponding reactor of the control group decreased at the fastest rate; the rate of decrease in the mass concentration of methyl orange in the reactor (A9) to which the compound A9 of example 1 was added was the slowest and gradual; the rate of decrease in the mass concentration of methyl orange in the reactor (T1600) to which compound T1600 of comparative example 1 was added was intermediate to the above two. The above results indicate that: the compound A9 can absorb ultraviolet rays, so that the degradation of methyl orange is effectively inhibited; and compound A9 absorbs ultraviolet light more effectively than compound T1600.
Substituting the absorbance of the measured methyl orange into a regression equation Y=0.0676X+0.0006 of the standard curve, and respectively calculating to obtain the mass concentration of the methyl orange in different reaction containers at different time points; then substituting η= (C 0 -C t )/C 0 (wherein: C 0 Representing the initial mass concentration of the methyl orange solution; c (C) t Represents the mass concentration of the methyl orange solution at the time of photocatalysis t), the degradation rate eta of the methyl orange after 9 hours of light irradiation in each reactor is calculated and obtained by conversion into percentage, and the specific results are shown in the following table4.
TABLE 4 measurement results of methyl orange solutions in different reactors
Note that: "-" means no compound added
As can be seen from table 4, the degradation rate of methyl orange in the reactor to which the compounds of each example of the present application were added was far lower than that in the reactor corresponding to the control group, and the above results indicate that the compounds of each example of the present application were able to absorb ultraviolet rays, thereby effectively inhibiting the degradation of methyl orange. And the degradation rate of methyl orange in the reactor to which the compound T1600 of comparative example 1 was added was higher than that in the reactor to which the compound of the present example was added, indicating that the compound of the present example had a better effect of absorbing ultraviolet rays than the compound T1600.
In this specification, each embodiment is described in a related manner, and identical and similar parts of each embodiment are all referred to each other, and each embodiment mainly describes differences from other embodiments.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the present application. Any modifications, equivalent substitutions, improvements, etc. that are within the spirit and principles of the present application are intended to be included within the scope of the present application.

Claims (5)

1. A compound of formula (I):
wherein,
L 1 selected from the group consisting of
L 2 Selected from the group consisting ofHydrogen, hydrogen,
R 1 、R 2 、R 4 Selected from hydrogen; r is R 3 Selected from hydrogen,
R 5 、R 6 、R 8 Selected from hydrogen and R 7 Selected from the group consisting ofOr R is 5 、R 7 、R 8 Selected from hydrogen and R 6 Selected from the group consisting of
2. A compound, wherein the compound is selected from the group consisting of compounds represented by A1-a 64:
3. an ultraviolet absorber comprising at least one of the compounds of claim 1 or 2.
4. A composition comprising:
a) Organic substances sensitive to photodamage; and
b) At least one of the compounds of claim 1 or 2 or the ultraviolet absorber of claim 3;
wherein the mass ratio of the component A) to the component B) is 100:0.01-15;
the component A) is at least one selected from thermoplastic polymer, coating binder or photosensitive material; the thermoplastic polymer is selected from at least one of polyethylene, polypropylene, polyvinyl chloride, copolymer of vinyl chloride and vinyl acetate, polystyrene, copolymer of styrene and acrylonitrile, polyamide and polyethylene terephthalate, the coating binder is selected from at least one of polyurethane, polyacrylate, natural rubber, silicone rubber, vinyl acetate, polyvinylidene chloride and polyvinyl alcohol, and the photosensitive material is selected from at least one of color blinder sheet, positive color sheet, full color sheet, infrared sheet and color sheet.
5. Use of a compound according to claim 1 or 2 or an ultraviolet absorber according to claim 3 or a composition according to claim 4 for preventing photodamage in organic substances.
CN202210166201.3A 2022-02-23 2022-02-23 Compound and ultraviolet absorber and application thereof Active CN114605392B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210166201.3A CN114605392B (en) 2022-02-23 2022-02-23 Compound and ultraviolet absorber and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210166201.3A CN114605392B (en) 2022-02-23 2022-02-23 Compound and ultraviolet absorber and application thereof

Publications (2)

Publication Number Publication Date
CN114605392A CN114605392A (en) 2022-06-10
CN114605392B true CN114605392B (en) 2024-04-02

Family

ID=81859354

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210166201.3A Active CN114605392B (en) 2022-02-23 2022-02-23 Compound and ultraviolet absorber and application thereof

Country Status (1)

Country Link
CN (1) CN114605392B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115322161B (en) * 2022-06-27 2024-02-09 烟台京师材料基因组工程研究院 Compound, ultraviolet absorber containing compound and application of ultraviolet absorber

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103896924A (en) * 2012-12-27 2014-07-02 海洋王照明科技股份有限公司 Organic semiconductor material and preparation method thereof, and electroluminescent device
KR20160082067A (en) * 2014-12-30 2016-07-08 희성소재 (주) Compound and organic light emitting device using the same
CN110041268A (en) * 2019-05-17 2019-07-23 西安瑞联新材料股份有限公司 A kind of miazines bipolarity compound and its application in OLED device
CN111205272A (en) * 2020-02-20 2020-05-29 长春海谱润斯科技有限公司 Material for organic electroluminescent device and organic electroluminescent device thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103896924A (en) * 2012-12-27 2014-07-02 海洋王照明科技股份有限公司 Organic semiconductor material and preparation method thereof, and electroluminescent device
KR20160082067A (en) * 2014-12-30 2016-07-08 희성소재 (주) Compound and organic light emitting device using the same
CN110041268A (en) * 2019-05-17 2019-07-23 西安瑞联新材料股份有限公司 A kind of miazines bipolarity compound and its application in OLED device
CN111205272A (en) * 2020-02-20 2020-05-29 长春海谱润斯科技有限公司 Material for organic electroluminescent device and organic electroluminescent device thereof

Also Published As

Publication number Publication date
CN114605392A (en) 2022-06-10

Similar Documents

Publication Publication Date Title
Qu et al. Dendronized perylenetetracarboxdiimides with peripheral triphenylamines for intramolecular energy and electron transfer
CN114605392B (en) Compound and ultraviolet absorber and application thereof
KR20150135346A (en) Wavelength conversion films with multiple photostable organic chromophores
Geervliet et al. Luminescent solar concentrators based on renewable polyester matrices
CN103339221A (en) Wavelength conversion material as encapsulate for solar module systems to enhance solar harvesting efficiency
Li et al. A structurally modified perylene dye for efficient luminescent solar concentrators
Doroshenko et al. Fluorescence quenching of the ketocyanine dyes in polar solvents: anti-TICT behavior
WO2015023574A1 (en) Luminescent solar concentrator utilizing organic photostable chromophore compounds
CN111440193B (en) Indene-thick naphtho-spirooxazine photochromic compound and preparation method thereof
Sousa et al. Joining High Coloration and Fast Color Fading with Photochromic Fused‐Naphthopyrans
CN1046284C (en) Spiro (indolino) oxazine photochromic compounds
CN101239976A (en) Dithienylethene compounds containing naphthalimide unit
JP2013084872A (en) Wavelength conversion film having pressure sensitive adhesive layer for increasing photovoltaic light collection efficiency
CN101709054B (en) Preparation and application of pyrazolone methyl thiosemicarbazone photochromic compound
CN115322161B (en) Compound, ultraviolet absorber containing compound and application of ultraviolet absorber
Lee et al. Multiple switching behaviors of poly (N-isopropylacrylamide) hydrogel with spironaphthoxazine and D-π-A type dye
Cavazzini et al. Intimately bound coumarin and bis (alkylaminostyryl) benzene fragments: synthesis and energy transfer
CN116854639A (en) Compound, ultraviolet absorber containing compound, composition and application of ultraviolet absorber
Zhao A highly sensitive sensor for ethyl acetate by changing fluorescent colour of lanthanide complex
CN102307910B (en) The polymer of imidizate comprising luminophore and the method for obtaining them
CN108250790B (en) Organic dye with near-infrared absorption based on alkynyl triphenylamine and perylene diimide, and preparation method and application thereof
CN101624519A (en) Preparation and application of pyrazolone-shrinking phenyl semicarbazide photochromic compounds
Mattiello et al. First Demonstration of the Applicability of the Latent Pigment Approach to Plastic Luminescent Solar Concentrators
CN117510421B (en) Fluorine-containing benzotriazolyl fluorescent compound for optical transfer film and synthesis method thereof
CN115181056B (en) Fluorescent organic CNS and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant