Near-infrared transparent high-saturation purple pigment as well as preparation method and application thereof

Abstract

The present invention relates to perylene compounds having the following general formula, a preparation method and uses thereof, wherein each symbol and index are as defined in the specification. The compound can be used as a pigment in the fields of coatings and plastics, and has the characteristics of excellent near-infrared transparency, excellent solvent resistance, excellent acid and alkali resistance and excellent heat resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic pigments, in particular to a kind of perylene compound, its preparation method and purposes. BACKGROUND

[0002] Near-infrared transparent pigments are a kind of pigments with low absorption rate in the near-infrared region (760-2000 nm). This characteristic, which is different from other organic pigments and inorganic pigments, makes near-infrared transparent pigments have wide application prospects in the industries of optical filters, architectural coatings, autonomous driving, etc. In addition, plastic products or organic coatings added with near-infrared transparent pigments also exhibit more excellent solarization resistance and weather resistance, prolonging the service life of organic coatings and plastic products.

[0003] Perylene pigments are a kind of high-performance organic pigments with near-infrared transparent characteristics. The colors of perylene pigments mainly cover the three color systems of red, purple and black, among which red pigments are the main ones. The purple perylene pigment is 3,4,9,10-perylenetetracarboxylic diimide, i.e. C.I. Pigment Violet 29. Pigment Violet 29 is obtained by reacting 3,4,9,10-perylenetetracarboxylic dianhydride with ammonia water. Although Pigment Violet 29 has near-infrared transparent characteristics, the color light is not bright, and the color is biased towards brown and black, so it is almost not used as a pigment, but only as an intermediate.

[0004] Pigment Violet 23 (Everlasting Violet RL) is the most widely used and largest amount of purple organic pigment in current application fields, with excellent resistance (weather resistance, chemical resistance, acid and alkali resistance) and very high tinting strength. However, the preparation of Pigment Violet 23 needs to go through steps such as alkylation, nitration, reduction and condensation, which not only makes the preparation process complex, but also uses a large amount of raw materials harmful to the environment and human body. At the same time, Pigment Violet 23 does not have near-infrared transparent characteristics.

[0005] US1808260A reports a synthesis method of a purple pigment, in which dichloro perylene tetracarboxylic dianhydride is prepared by reacting 3,4,9,10-perylenetetracarboxylic dianhydride with chlorosulfonic acid, and then the purple pigment is obtained by reacting dichloro perylene tetracarboxylic dianhydride with o-phenylenediamine. This preparation method needs to use chlorosulfonic acid raw material which is harmful to the environment and operators, so it limits the large-scale production of this pigment.

[0006] US1878986A reports a compound in which the perylene pigment precursor is substituted with a benzene ring. This kind of compound presents blue-black color light, and also needs to use dichloro perylene tetracarboxylic dianhydride as raw material, which has low industrial production value.

[0007] CN101688063A reported a class of perylene-based black purple pigments, which were obtained by condensation of a diamino aromatic compound (such as o-phenylenediamine, 1,8-diaminonaphthalene, etc.) with 3,4,9,10-perylenetetracarboxylic dianhydride in water. The color of this class of pigments is not bright, showing a brownish color tone, and cannot be used as a purple pigment alone.

[0008] CN116761854A reported the application of the pigments in CN101688063A, which can be used together with other perylene-based pigments to prepare perylene-based pigment solid solutions, and further used in near-infrared transparent black colorants.

[0009] Therefore, there is no report of a purple pigment with high saturation, near-infrared transparency, simple preparation process and environmental friendliness. SUMMARY

[0010] To solve the above problems, the present application provides a class of perylene-based compounds and a preparation method thereof. The compound is a class of perylene-based compounds that have not been reported before, which can be used as pigments, have excellent near-infrared transparency, good solvent resistance, good acid and alkali resistance, and good heat resistance, and provide a class of perylene-based purple pigments for the field of coatings and plastics.

[0011] In a first aspect, the present application provides a perylene-based compound having the following general formula:

[0012]

[0013] wherein:

[0014] R1groups are independently of each other at each occurrence halogen, C1-C 20 alkyl, C1-C 20 alkoxy, C1-C 20 alkylthio, -NO2, -CN, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 cycloalkylalkoxy, C4-C 20 cycloalkylalkylthio, C4-C 20 alkylcycloalkyl, or a sulfonic acid group; wherein C1-C 20 alkyl, C1-C 20 alkoxy, C1-C 20 alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 cycloalkylalkoxy, C4-C 20 cycloalkylalkylthio, or C4-C 20The alkylcycloalkyl group may optionally be substituted by one or more groups independently selected from the group consisting of: halogen, -NO2, -CN, hydroxyl, mercapto, sulfonic acid, carboxyl, or amino.

[0015] The R2 group is independently halogenated and C1-C each time it appears. 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, -NO2, -CN, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio, C4-C 20 alkyl, cycloalkyl, or sulfonic acid groups; wherein C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio or C4-C 20 The alkylcycloalkyl group may optionally be substituted by one or more groups independently selected from the group consisting of: halogen, -NO2, -CN, hydroxyl, mercapto, sulfonic acid, carboxyl, or amino.

[0016] n is 0, 1, 2, 3, or 4; and

[0017] m can be 0, 1, 2, 3, 4, 5, 6, 7 or 8. Attached Figure Description

[0018] Figure 1 The visible-near-infrared transmittance spectrum of the perylene compound according to Example 1 of the present invention is shown.

[0019] Figure 2 The visible-near-infrared transmittance spectra of the perylene compounds according to Comparative Example 1 are shown.

[0020] Figure 3 The visible-near-infrared transmittance spectra of the perylene compounds according to Comparative Example 2 are shown.

[0021] Figure 4 The mass spectrum of the perylene compound according to Example 1 of the present invention is shown.

[0022] Figure 5 The X-ray diffraction pattern of the perylene compound according to Example 1 of the present invention is shown. Detailed Implementation

[0023] As used herein, the term "halogen" refers to F, Cl, Br, I, or combinations thereof, preferably F, Cl, or combinations thereof.

[0024] The term "C1-C" used in this article 20 "Alkyl" refers to a saturated hydrocarbon group having 1-20, preferably 1-12, more preferably 1-8, particularly preferably 1-6, and especially preferably 1-4 carbon atoms, which can be branched or unbranched. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their isomers, especially methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, etc. C1-C4 alkyl groups can be methyl, ethyl, propyl, butyl and their isomers, especially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0025] The term "C1-C" used in this article 20 "Alkoxy" refers to the compound formed at C1-C2. 20 Alkyl groups correspond to open-chain C1-C 20 In alkanes, an oxygen atom is bonded to any carbon atom as a linking group in the C1-C configuration. 20 Alkyl groups, preferably C1-C 12 Alkoxy groups, more preferably C1-C8 alkoxy groups, and particularly preferably C1-C6 alkoxy groups. Examples include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and their isomers, especially methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, n-hexoxy, isohexoxy, n-heptoxy, isoheptoxy, n-octoxy, or isooctoxy. C1-C4 alkoxy groups can be methoxy, ethoxy, propoxy, butoxy, and their isomers, especially methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, etc.

[0026] The term "C1-C" used in this article 20 "Alkylthio" refers to the group formed at C1-C2. 20 Alkyl groups correspond to open-chain C1-C 20 In alkanes, a sulfur atom is bonded to any carbon atom as a linking group in the C1-C configuration. 20 Alkyl groups, preferably C1-C 12Alkylthio, more preferably C1-C8 alkylthio, and particularly preferably C1-C6 alkylthio. Examples include methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio and their isomers, especially methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio, n-pentylthio, isopentylthio, tert-pentylthio, n-hexylthio, isohexylthio, n-heptylthio, isoheptylthio, n-octylthio, or isooctylthio. C1-C4 alkylthio can be methylthio, ethylthio, propylthio, butylthio and their isomers, especially methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio, etc.

[0027] The term "C3-C" used in this article 10 "Cycloalkyl" refers to a saturated alicyclic monocyclic group having 3-10, preferably 3-8, more preferably 5-6 cyclic carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl.

[0028] The term "C4-C" used in this article 20 "Cycloalkyl" means an alkyl group substituted with a cycloalkyl group and containing a total of 4-20 carbon atoms, preferably 4-12, more preferably 4-10, and most preferably 4-8 carbon atoms, wherein alkyl and cycloalkyl are as defined herein. Examples include cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, etc.

[0029] The term "C4-C" used in this article 20 "Cycloalkylalkoxy" refers to an alkoxy group substituted with a cycloalkyl group and containing a total of 4-20, preferably 4-12, and more preferably 4-10 carbon atoms, wherein the cycloalkyl and alkoxy groups are as defined herein. Examples include cyclopropylmethoxy, cyclopropylethoxy, cyclopropylpropoxy, cyclopropylbutoxy, cyclobutylmethoxy, cyclobutylethoxy, cyclobutylpropoxy, cyclobutylbutoxy, cyclopentylmethoxy, cyclopentylethoxy, cyclopentylpropoxy, cyclopentylbutoxy, cyclohexylmethoxy, cyclohexylethoxy, cyclohexylpropoxy, cyclohexylbutoxy, etc.

[0030] The term "C4-C" used in this article 20"Cycloalkyl alkylthio" refers to an alkylthio group substituted with a cycloalkyl group and containing a total of 4-20, preferably 4-12, and more preferably 4-10 carbon atoms, wherein the cycloalkyl and alkylthio groups are as defined herein. Examples include cyclopropylmethylthio, cyclopropylethylthio, cyclopropylpropylthio, cyclopropylbutylthio, cyclobutylmethylthio, cyclobutylethylthio, cyclobutylpropylthio, cyclobutylbutylthio, cyclopentylmethylthio, cyclopentylethylthio, cyclopentylpropylthio, cyclopentylbutylthio, cyclohexylmethylthio, cyclohexylethylthio, cyclohexylpropylthio, cyclohexylbutylthio, etc.

[0031] The term "C4-C" used in this article 20 "alkylcycloalkyl" means a cycloalkyl group substituted with an alkyl group and containing a total of 4-20 carbon atoms, preferably 4-12, more preferably 4-10, and most preferably 4-8 carbon atoms. Alkyl and cycloalkyl are used as defined herein. Examples include methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethylcyclobutyl, propylcyclobutyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, etc.

[0032] In this paper, "R1" refers to a substituent on the perylene ring of a perylene compound, which can be at any possible position on the perylene ring.

[0033] In this paper, "R2" refers to a substituent on the benzene ring of a perylene compound, which can be at any of the possible substitution positions on the benzene ring.

[0034] In a preferred embodiment of the invention, the R1 group is independently halogenated and C1-C each time it appears. 20 Alkyl, C1-C 20 Alkoxy, -NO2, -CN, C3-C 10 cycloalkyl or sulfonic acid groups; wherein C1-C 20 Alkyl, C1-C 20 Alkoxy or C3-C 10 The cycloalkyl group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, -NO2, or -CN;

[0035] Preferably, the R1 groups are halogenated and C1-C each time they appear. 20 Alkyl, C1-C 20 alkoxy or sulfonic acid groups; wherein C1-C 20 Alkyl or C1-C 20 The alkoxy group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, -NO2, or -CN;

[0036] Most preferably, the R1 group is independently F, Cl, Br, I or a sulfonic acid group each time it appears.

[0037] In a preferred embodiment of the invention, the R2 group is independently halogenated and C1-C each time it appears. 20 Alkyl, C1-C 20 Alkoxy, -NO2, -CN, C3-C 10 cycloalkyl or sulfonic acid groups; wherein C1-C 20 Alkyl, C1-C 20 Alkoxy or C3-C 10 The cycloalkyl group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, -NO2, or -CN;

[0038] Preferably, the R2 groups are halogenated and C1-C each time they appear. 20 Alkyl, C1-C 20 Alkoxy, C3-C 10 cycloalkyl or sulfonic acid groups; wherein C1-C 20 Alkyl, C1-C 20 Alkoxy or C3-C 10 The cycloalkyl group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, -NO2, or -CN;

[0039] Most preferably, the R2 group is independently methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine, iodine, sulfonic acid, or methoxy each time it appears.

[0040] In embodiments of the present invention, n is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and more preferably 0 or 1.

[0041] In embodiments of the present invention, m is 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3 or 4, and more preferably 0 or 1.

[0042] In a preferred embodiment of the present invention

[0043] The R1 group is independently halogenated and C1-C each time it appears. 20 Alkyl, C1-C 20 Alkoxy, -NO2,

[0044] -CN、C3-C 10 cycloalkyl or sulfonic acid groups; wherein C1-C 20 Alkyl, C1-C 20 Alkoxy or C3-C 10 The cycloalkyl group may optionally be substituted by one or more groups independently selected from the group consisting of halogens,

[0045] -NO2 or -CN;

[0046] The R2 group is independently halogenated and C1-C each time it appears. 20 Alkyl, C1-C 20 Alkoxy, -NO2,

[0047] -CN、C3-C 10 cycloalkyl or sulfonic acid groups; wherein C1-C 20 Alkyl, C1-C 20 Alkoxy or C3-C 10 The cycloalkyl group may optionally be substituted by one or more groups independently selected from the group consisting of halogens,

[0048] -NO2 or -CN;

[0049] n is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1; and m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1.

[0050] In a preferred embodiment of the present invention

[0051] The R1 group is independently halogenated and C1-C each time it appears. 20 Alkyl, C1-C 20 alkoxy or sulfonic acid groups; wherein C1-C 20 Alkyl or C1-C 20 The alkoxy group may optionally be substituted with one or more groups independently selected from halogens;

[0052] The R2 group is independently halogenated and C1-C each time it appears. 20 Alkyl, C1-C 20 alkoxy or sulfonic acid groups; wherein C1-C 20 Alkyl or C1-C 20 The alkoxy group may optionally be substituted with one or more groups independently selected from halogens;

[0053] n is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1; and m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1.

[0054] In one embodiment of the present invention, the perylene compound may be a mixture of compounds of the above general formula.

[0055] In a preferred embodiment of the present invention, n is 0 and m is 0.

[0056] In a preferred embodiment of the invention, the R2 groups are halogens that are independent of each other, n is 1 and m is 0.

[0057] In a preferred embodiment of the invention, the R2 groups are chlorine groups that are independent of each other, n is 1 and m is 0.

[0058] In a preferred embodiment of the invention, the perylene compound has formula (I), (II), (III), or (IV):

[0059]

[0060]

[0061] In a more preferred embodiment of the invention, the perylene compound has formula (I) and / or (II):

[0062]

[0063]

[0064] In a second aspect, the present invention provides a method for preparing perylene compounds, comprising a compound of formula (V):

[0065]

[0066] Reaction with compounds of formula (VI) in water:

[0067]

[0068] R1, R2, m, and n are defined as above.

[0069] The molar ratio of compound (V) to compound (VI) can be 1:2 to 1:10, preferably 1:2 to 1:5, and more preferably 1:2 to 1:3.

[0070] The reaction is carried out in the presence of a catalyst. A suitable catalyst may be a soluble zinc salt, such as zinc acetate, zinc chloride, zinc sulfate, zinc benzoate, zinc stearate, etc., which may be in hydrated or non-hydrated form. The amount of catalyst used may be 0.5-15% by weight, preferably 2-5% by weight, based on the total weight of the reactants used. The reaction is carried out in water. The amount of water used is preferably 30-50 times the weight of the compound of formula (VI).

[0071] A pH adjuster can be added to the reaction system to adjust the pH to 6-9. Suitable pH adjusters are soluble organic or inorganic bases, such as triethylamine, diethylamine, pyridine, quinoline, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, or cesium carbonate.

[0072] The reaction can be carried out at a temperature of 100-250°C, preferably 120-220°C.

[0073] The reaction can be carried out under an inert atmosphere. Suitable inert atmospheres include, for example, nitrogen or other inert gases such as helium, with nitrogen being preferred.

[0074] The reaction can be carried out in a pressure vessel, and those skilled in the art can adjust the pressure of the pressure vessel.

[0075] The reaction time can be 1-24 hours, preferably 2-12 hours, and more preferably 4-8 hours.

[0076] After the reaction, the reaction mixture can be filtered, and the filter cake can be washed once or several times with an aqueous solution of alkali (e.g., potassium hydroxide, sodium hydroxide, sodium carbonate, or potassium carbonate), and finally washed once or several times with water. The resulting reaction product can then be dried, for example in a forced-air oven at 50-120°C, preferably 60-100°C, for 1-10 hours, preferably 2-8 hours.

[0077] The perylene compounds of this invention are a class of previously unreported perylene compounds that can be used as pigments. They possess excellent near-infrared transparency, good solvent resistance, good acid and alkali resistance, and good heat resistance, providing a class of perylene purple pigments for the coatings and plastics industries.

[0078] Therefore, in a third aspect, the present invention provides the use of the perylene compounds as pigments (such as purple pigments).

[0079] The perylene compounds of the present invention can be used as pigments (such as purple pigments) in coatings and plastics.

[0080] Suitable coatings can be water-based coatings, solvent-based coatings, or powder coatings, etc.

[0081] Suitable plastics include polyolefins such as polyethylene, polypropylene, polybutene, polyisobutylene, and poly-4-methyl-1-pentene; polyolefin copolymers; cyclic olefin copolymers; polytetrafluoroethylene (PTFE); ethylene / tetrafluoroethylene copolymers; polyvinylidene fluoride (PVDF); polyvinyl chloride; polyvinyl alcohol; polyvinyl esters such as polyvinyl acetate; vinyl ester copolymers such as ethylene / vinyl acetate copolymers; polyvinyl alcohol acetals such as polyvinyl alcohol acetal and polyvinyl alcohol butyral; polyvinyl alcohol ketal; polyamides such as nylon 6, nylon 12, and nylon 6,6; polyimides; polycarbonates; polycarbonate copolymers and physical blends of polycarbonates with acrylic acid-butadiene-styrene copolymers; acrylonitrile-styrene-acrylate copolymers; polymethyl methacrylate; polybutyl acrylate; polybutyl methacrylate; polybutylene terephthalate; and polyethylene terephthalate. Polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, copolymers, transesterification products, and physical mixtures (blends) of the above-mentioned alkylene terephthalates, poly(meth)acrylates, polyacrylamide, polyacrylonitrile, poly(meth)acrylate / polyvinylidene fluoride blends, polyurethanes, polystyrene, styrene copolymers such as styrene / butadiene copolymers, styrene / acrylonitrile copolymers (SAN), styrene / ethyl methacrylate copolymers, styrene / butadiene / ethyl acrylate copolymers, styrene / acrylonitrile / methacrylate copolymers, acrylonitrile / butadiene / styrene copolymers (ABS), and methacrylate / butadiene / styrene copolymers, polyethers such as polyphenylene ether, polyetherketone, polysulfone, polyethersulfone, polyoxymethylene, polysiloxanes, ionomers, thermoplastic and thermosetting polyurethanes, and mixtures thereof.

[0082] The specific embodiments described below will help those skilled in the art to understand the present invention, but are not intended to limit the scope of the invention.

[0083] Implementation Scheme 1. Perylene compounds having the following general formula:

[0084]

[0085] in:

[0086] The R1 group is independently halogenated and C1-C each time it appears. 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, -NO2, -CN, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio, C4-C 20 alkyl, cycloalkyl, or sulfonic acid groups; wherein C1-C20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio or C4-C 20 The alkylcycloalkyl group may optionally be substituted by one or more groups independently selected from the group consisting of: halogen, -NO2, -CN, hydroxyl, mercapto, sulfonic acid, carboxyl, or amino.

[0087] The R2 group is independently halogenated and C1-C each time it appears. 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, -NO2, -CN, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio, C4-C 20 alkyl, cycloalkyl, or sulfonic acid groups; wherein C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio or C4-C 20 The alkylcycloalkyl group may optionally be substituted by one or more groups independently selected from the group consisting of: halogen, -NO2, -CN, hydroxyl, mercapto, sulfonic acid, carboxyl, or amino.

[0088] n is 0, 1, 2, 3, or 4; and

[0089] m can be 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0090] Implementation Scheme 2. The compound according to Implementation Scheme 1, wherein the R1 group is independently halogenated and C1-C each time it appears. 20 Alkyl, C1-C 20 alkoxy or sulfonic acid groups; wherein C1-C 20 Alkyl or C1-C 20 The alkoxy group may optionally be substituted with one or more groups independently selected from halogens;

[0091] Preferably, the R1 group is independently a fluorine, chlorine, bromine, iodine, or sulfonic acid group each time it appears.

[0092] Implementation Scheme 3. The compound according to Implementation Scheme 1 or 2, wherein the R2 group is independently halogenated and C1-C each time it appears. 20 Alkyl, C1-C 20 alkoxy or sulfonic acid groups; wherein C1-C 20 Alkyl or C1-C 20 The alkoxy group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, -NO2, or -CN;

[0093] Preferably, the R2 group is independently methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine, iodine, sulfonic acid, or methoxy each time it appears.

[0094] More preferably, the R2 groups are halogens each time they appear.

[0095] Implementation Scheme 4. The compound according to any one of Implementation Schemes 1-3, wherein n is 0 and m is 0.

[0096] Implementation Scheme 5. The compound according to any one of Implementation Schemes 1-3, wherein n is 1 and m is 0.

[0097] Implementation Scheme 6. The compound according to Implementation Scheme 5, wherein the R2 group is a halogen, preferably chlorine.

[0098] Implementation Scheme 7. The compound according to any one of Implementation Schemes 1-3, wherein the perylene compound has formula (I) or (II):

[0099]

[0100] Implementation Scheme 8. The compound according to any one of Implementation Schemes 1-7, wherein the perylene compound is near-infrared transparent.

[0101] Implementation Scheme 9. A method for preparing a perylene compound according to any one of Implementation Schemes 1-8, comprising making a compound of formula (V):

[0102]

[0103] Reaction with compounds of formula (VI) in water:

[0104]

[0105] R1, R2, m, and n are defined as in any of the implementation schemes 1-8.

[0106] Implementation Scheme 10. The method according to Implementation Scheme 9, wherein the molar ratio of compound (V) to compound (VI) is 1:2 to 1:10, preferably 1:2 to 1:5, more preferably 1:2 to 1:3.

[0107] Implementation Scheme 11. The method according to Implementation Scheme 9 or 10, wherein the reaction is carried out in the presence of a catalyst selected from soluble zinc salts, such as zinc acetate, zinc chloride, zinc sulfate, zinc benzoate, and zinc stearate.

[0108] Implementation Scheme 12. The method according to any one of Implementation Schemes 9-11, wherein the method is carried out at a temperature of 100-250°C for 1-24 hours.

[0109] Implementation Scheme 13. Use of the perylene compounds according to any one of Implementation Schemes 1-8 as pigments.

[0110] Implementation Scheme 14. According to the use of Implementation Scheme 13, the perylene compound is used as a purple pigment.

[0111] The present invention will be further described below with reference to specific embodiments, but should not be construed as limiting the scope of protection of the present invention.

[0112] Analytical tests

[0113] Mass spectrometry analysis was performed on a Mass Tech brand AP / MALDI(ng)UHR.

[0114] The X-ray diffraction pattern was obtained using a Bruker D8 Advance X-ray diffractometer.

[0115] Example 1

[0116] Add 130 g of 3,4,9,10-perylenetetracarboxylic dianhydride (0.33 mol), 100 g of 2-aminobenzylamine (0.82 mol), and 5 g of zinc acetate dihydrate (0.023 mol) to 3500 g of water.

[0117] The reaction system was transferred to a pressure vessel (1.25 MPa), and the temperature was gradually increased to 190°C. After holding the reaction at this temperature for 6 hours, the reaction system was cooled to room temperature, filtered, and the filter cake was washed twice with 1000 g of 1% potassium hydroxide aqueous solution. Finally, the filter cake was washed once with 500 g of water.

[0118] The filter cake was dried in an 80℃ forced-air oven for 5 hours to obtain purple pigment with a yield of 97%.

[0119] Mass spectrometry analysis: Molecular ion peak [M+H] = 565.16.

[0120] The X-ray diffraction pattern obtained by the Bruker D8 Advance X-ray diffractometer is as follows: Figure 5 As shown.

[0121] Comparative Example 1

[0122] According to Example 1 of CN101688063A, 200 g of 3,4,9,10-perylenetetracarboxylic dianhydride (50 wt% water-wetted filter cake) (corresponding to 0.255 mol), 1100 g of water, and 22 g of piperazine (corresponding to 0.255 mol) were first added to an autoclave and stirred at 70°C to homogenize the mixture. After adding 69 g of 1,2-diaminobenzene (corresponding to 0.637 mol), the reaction suspension was heated to 210°C over 4 hours and stirred at this temperature for 18 hours.

[0123] After cooling to 70°C, 20g of potassium alkali dissolved in 1000ml of water was added, and the mixture was stirred at 70°C. The suspension was filtered and washed successively with water, 10% acetic acid, and water. Drying at 80°C yielded 133g of perylene pigment in black powder form, with a yield of 97.5%.

[0124] Mass spectrometry analysis: Molecular ion peak [M+H] = 537.1.

[0125] Comparative Example 2

[0126] According to Example 7 of CN101688063A, 116 g of 3,4,9,10-perylenetetracarboxylic dianhydride (corresponding to 0.290 mol), 1200 g of water, and 24 g of piperazine (corresponding to 0.287 mol) were first added to an autoclave and stirred at 90 °C to homogenize the mixture. After adding 92 g of 1,8-diaminonaphthalene (corresponding to 0.573 mol), the reaction suspension was heated to 210 °C and stirred at this temperature for 14 hours.

[0127] After cooling to 70°C, 30g of potassium alkali dissolved in 1300ml of water was added, and the suspension was stirred at 85°C. The suspension was filtered and washed successively with water, 10% acetic acid, and water. Drying at 100°C and 100 mbar yielded 184g of perylene pigment in black powder form, with a yield >99%.

[0128] Mass spectrometry analysis: Molecular ion peak [M+H] = 637.2.

[0129] Performance measurements

[0130] Determination of hue value

[0131] The hue values ​​of pigments in Example 1 and Comparative Examples 1-2, as well as pigment violet 29, in the AM system (alkyd resin system) were measured using a CM-26d spectrophotometer obtained from Metan Corporation of Japan. The results are shown in Tables 1 to 4.

[0132] Table 1. Hue values ​​of the pigments in Example 1 in the AM system (alkyd resin system)

[0133]

[0134]

[0135] Table 2. Hue values ​​of the pigments in Comparative Example 1 in the AM system (alkyd resin system)

[0136]

[0137] Table 3. Hue values ​​of the pigments in Comparative Example 2 in the AM system (alkyd resin system)

[0138]

[0139] Table 4. Hue values ​​of pigment violet 29** in AM system (alkyd resin system)

[0140]

[0141] *AM Test Method: In the alkyd resin system (Xinhua Resin 3150) coating system, the full color test method is to add 5% pigment by weight of the total coating formulation, apply a wet film thickness of 100 micrometers, and use LEADER black and white cardstock as the substrate for application; the AM dilution test system is the same as the AM full color test system, except that TiO2 (Kronos 2310) based on 10% pigment weight is added.

[0142] Pigment Violet 29 was purchased from Anhui Zesheng Technology Co., Ltd.

[0143] As can be seen from Tables 1 to 4, compared with Comparative Example 1, Comparative Example 2 and Pigment Purple 29, the purple pigment prepared in Example 1 of the present invention has significantly higher saturation (i.e., higher C value), and exhibits high saturation purple in both AM full color and diluted color (i.e., higher C value, and a greater than 0 and b less than 0).

[0144] Solvent resistance

[0145] Take 0.8g of pigment, wrap it in filter paper, and immerse it in the corresponding solvent at room temperature for 24 hours. Then, remove the pigment and compare the solvent color with the color chart to visually determine the solvent resistance level. Level 5 is the best, and level 1 is the worst.

[0146] The results of the pigment's solvent resistance are shown in Table 5.

[0147] Table 5

[0148] Solvent resistance test Ethanol 2-butanone Butyl acetate Xylene Example 1 5 4 5 4

[0149] As can be seen from Table 5, the pigments of the present invention have excellent solvent resistance.

[0150] Resistance to acids and bases

[0151] The acid and alkali resistance test method is the same as the solvent resistance test method, except that the solvent in the solvent resistance test method is replaced with a 2% hydrochloric acid aqueous solution or a 2% NaOH aqueous solution.

[0152] The acid and alkali resistance of the pigments is shown in Table 6, with grade 5 being the best and grade 1 being the worst.

[0153] Table 6

[0154] Resistance to acids and bases test 2% HCI 2% NaOH Example 1 5 4

[0155] As can be seen from Table 6, the pigments of the present invention have excellent acid and alkali resistance.

[0156] Heat resistance

[0157] The test pigment was formulated into an alkyd resin (Xinhua Resin 3150) coating, sprayed onto a metal plate, and dried (drying temperature 130℃, time 30min). The hue value was then measured. The metal plate was placed in a forced-air drying oven at 150℃ and 200℃ for 30min, and then removed and the hue value was measured again to obtain the color difference value ΔE before and after drying.

[0158] The results of the heat resistance of the pigments are shown in Table 7.

[0159] Table 7

[0160]

[0161] As can be seen from Table 7, the pigments of the present invention have excellent heat resistance.

[0162] Near infrared transparency

[0163] Near-infrared transmittance test sample preparation method: 5% pigment by weight of the total coating formulation was added to the alkyd resin system (Xinhua Resin 3150). The wet film thickness of the coating was 100 micrometers, and the substrate was a transparent PET film with a thickness of 0.2 mm. The test results are listed in Table 8.

[0164] Near-infrared transmittance testing instrument: PerkinElmer LAMBDA 950 UV-Vis-NIR spectrophotometer.

[0165] Near-infrared transmittance test method: GB / T 9721-2006

[0166] Table 8. Comparison of Near-Infrared Transmittance Data

[0167] Near infrared wavelength Example 1 Comparative Example 1 Comparative Example 2 800 nm 79.2％ 52.3％ 43.9％ 1000 nm 85.6％ 76.0％ 83.7％ 1200 nm 86.7％ 80.1％ 87.4％ 1400 nm 86.4％ 81.8％ 87.0％ 1600 nm 87.5％ 84.6％ 88.2％ 1800 nm 84.8％ 82.2％ 85.9％ 2000 nm 85.6％ 83.7％ 86.2％

[0168] As shown in Table 8, the pigment of Example 1 exhibits excellent infrared transmittance in the near-infrared region of 760–2000 nm. Compared to Comparative Example 1, the pigment of Example 1 shows 6.6–26.9% higher transmittance in the 800–1200 nm range. Compared to Comparative Example 2, the pigment of Example 1 shows 1.9–35.3% higher transmittance in the 800–1000 nm range. Furthermore, from… Figures 1-3 The visible-near-infrared transmittance spectrum also shows that the pigment of the present invention has significantly better infrared transmittance in the near-infrared region of 760-2000 nm than that of comparative examples 1-2.

Claims

1. Perylene compounds having the following general formula: in: The R1 group is independently halogenated and C1-C each time it appears. 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, -NO2, -CN, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio, C4-C 20 alkyl, cycloalkyl, or sulfonic acid groups; wherein C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio or C4-C 20 The alkylcycloalkyl group may optionally be substituted by one or more groups independently selected from the group consisting of: halogen, -NO2, -CN, hydroxyl, mercapto, sulfonic acid, carboxyl, or amino. The R2 group is independently halogenated and C1-C each time it appears. 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, -NO2, -CN, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio, C4-C 20 alkyl, cycloalkyl, or sulfonic acid groups; wherein C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio or C4-C 20 The alkylcycloalkyl group may optionally be substituted by one or more groups independently selected from the group consisting of: halogen, -NO2, -CN, hydroxyl, mercapto, sulfonic acid, carboxyl, or amino. n is 0, 1, 2, 3, or 4; and m can be 0, 1, 2, 3, 4, 5, 6, 7 or 8.

2. The compound according to claim 1, wherein the R1 group is independently halogenated and C1-C each time it appears. 20 Alkyl, C1-C 20 alkoxy or sulfonic acid groups; wherein C1-C 20 Alkyl or C1-C 20 The alkoxy group may optionally be substituted with one or more groups independently selected from halogens; Preferably, the R1 group is independently a fluorine, chlorine, bromine, iodine, or sulfonic acid group each time it appears.

3. The compound according to claim 1 or 2, wherein the R2 group is independently halogenated and C1-C each time it appears. 20 Alkyl, C1-C 20 alkoxy or sulfonic acid groups; wherein C1-C 20 Alkyl or C1-C 20 The alkoxy group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, -NO2, or -CN; Preferably, the R2 group is independently methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine, iodine, sulfonic acid, or methoxy each time it appears. More preferably, the R2 groups are halogens each time they appear.

4. The compound according to any one of claims 1-3, wherein n is 0 and m is 0.

5. The compound according to any one of claims 1-3, wherein n is 1 and m is 0.

6. The compound according to claim 5, wherein the R2 group is a halogen, preferably chlorine.

7. The compound according to any one of claims 1-3, wherein the perylene compound has formula (I) or (II):

8. The compound according to any one of claims 1-7, wherein the perylene compound is near-infrared transparent.

9. A method for preparing a perylene compound according to any one of claims 1-8, comprising making a compound of formula (V): Reaction with compounds of formula (VI) in water: Wherein R1, R2, m, and n are defined as in any one of claims 1-8.

10. The method according to claim 9, wherein the molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:2 to 1:10, preferably 1:2 to 1:5, more preferably 1:2 to 1:

3.

11. The method according to claim 9 or 10, wherein the reaction is carried out in the presence of a catalyst selected from soluble zinc salts, such as zinc acetate, zinc chloride, zinc sulfate, zinc benzoate, and zinc stearate.

12. The method according to any one of claims 9-11, wherein the method is carried out at a temperature of 100-250°C for 1-24 hours.

13. Use of the perylene compound according to any one of claims 1-8 as a pigment.

14. The use according to claim 13, wherein the perylene compound is used as a purple pigment.

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