Search

CN-121991526-A - High-stability near-infrared dichroism dye, liquid crystal composition and application thereof

CN121991526ACN 121991526 ACN121991526 ACN 121991526ACN-121991526-A

Abstract

The invention discloses a dichroic dye, a liquid crystal composition and application thereof. The structural general formula of the disclosed dichroic dye compound is shown as I. The liquid crystal composition comprises the dichroic dye of the present invention and at least one liquid crystal compound. The light-adjusting glass device prepared by the dichroic dye or the liquid crystal composition has the advantages of high photo-thermal stability, high order parameter and wide working temperature area.

Inventors

  • LI JIAN
  • WU YIN
  • SHI FENGJIAO
  • HU ZHIGANG
  • Bai pujiang
  • ZHANG LU
  • YANG CHENG
  • Liang Lexuan
  • HU MINGGANG
  • LI JUANLI
  • MO LINGCHAO
  • CHE ZHAOYI
  • Wan danyang

Assignees

  • 西安近代化学研究所

Dates

Publication Date
20260508
Application Date
20241108

Claims (15)

  1. 1. A dichroic dye characterized by having the structural formula I: In formula I: W is an oxygen atom, a sulfur atom or a selenium atom; L 1 、L 2 is independently selected from hydrogen atom, fluorine atom, chlorine atom, cyano carbon or alkyl with 1-6 carbon atoms; y is selected from 0,1,2; Each of a 1 and a 2 is independently selected from the group shown in the following structure: Wherein L 3 and L 4 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 7 carbon atoms; A 3 and A 4 are an aromatic ring, a hydrogenated quinoline ring, a hydrogenated benzopyran ring, a hydrogenated naphthalene ring, a hydrogenated benzoxazine ring, a hydrogenated benzothiazine ring or a hydrogenated quinoxaline ring represented by the following structures: and at least one of A 3 and A 4 is selected from a hydrogenated benzoxazine ring, a hydrogenated benzothiazine ring or a hydrogenated quinoxaline ring; Wherein R 1 ,R 2 ,R 3 ,R 4 ,R 6 ,R 7 ,R 9 is independently a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, R 5 is a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or an ethyl group, R 8 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, -NHR 9 or-N (R 9 ) 2 ).
  2. 2. The dichroic dye according to claim 1, wherein W is a sulfur atom, and the rings a 1 and a 2 are each independently selected from benzene rings, thiophene rings, or benzothiophene rings.
  3. 3. The dichroic dye according to claim 2, characterized by being selected from the structural general formula I-1~I-8:
  4. 4. a black dye composition comprising a dichroic dye represented by the general structural formula I and a dichroic dye represented by the general structural formula D; in formula D: W is an oxygen atom, a sulfur atom or a selenium atom; X is C-L 2 or a nitrogen atom; L 1 and L 2 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 6 carbon atoms; y is selected from 0,1,2; a 1 and a 2 are represented by the groups shown in the following structures: Wherein L 3 and L 4 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group having 1 to 7 carbon atoms or a cyano group; A 3 and a 4 are an aromatic ring, a hydrogenated quinoline ring, a hydrogenated benzopyran ring, a hydrogenated naphthalene ring, and at least one of a 3 and a 4 is selected from the group consisting of a hydrogenated quinoline ring, a hydrogenated benzopyran ring, and a hydrogenated naphthalene ring, which are represented by the following structures: Wherein R 1 ,R 2 ,R 3 ,R 4 ,R 6 ,R 7 ,R 9 is independently a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, R 5 is a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or an ethyl group, and R 8 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, -NHR 9 or-N (R 9 ) 2 ).
  5. 5. A liquid crystal composition comprising a dichroic dye of the general structural formula I and one or more liquid crystal compounds.
  6. 6. The liquid crystal composition according to claim 5, comprising the black dye composition according to claim 4 and one or more liquid crystal compounds.
  7. 7. The liquid crystal composition according to claim 5 or 6, wherein the liquid crystal compound is selected from the group consisting of liquid crystal compounds represented by structural formula II: In formula II: r is alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms or cycloalkyl with 3-6 carbon atoms; Ring a, ring B and ring C are each independently selected from cyclohexane, cyclohexene, a benzene ring, a tetrahydropyran ring or a benzene ring substituted by a hydrogen atom fluorine; X 0 is hydrogen, fluorine, chlorine, cyano, trifluoromethoxy, trifluoromethyl, alkyl of 1 to 10 carbon atoms, alkoxy of 1 to 10 carbon atoms, alkenyl of 2 to 10 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; X 1 、X 2 、X 3 is hydrogen or fluorine, X 4 is a single bond, -COO-, -CH 2 CH 2 -or-CF 2 O-; k. p and q are 0,1,2, and k+p+q is not less than 1.
  8. 8. The liquid crystal composition according to claim 5 or 6, wherein the liquid crystal compound is selected from the group consisting of liquid crystal compounds of the general structural formula III: In formula III: r is alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms or cycloalkyl with 3-6 carbon atoms; ring A is cyclohexane, cyclohexene, benzene ring, tetrahydropyran ring or benzene ring with hydrogen atom replaced by fluorine; X 0 is hydrogen, fluorine, chlorine, cyano, trifluoromethoxy, trifluoromethyl, alkyl of 1 to 10 carbon atoms, alkoxy of 1 to 10 carbon atoms, alkenyl of 2 to 10 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; X 4 is a single bond, -COO-, -CH 2 CH 2 -、-CF 2 O-、-CH 2 O-;X 5 is an oxygen atom or a sulfur atom, and k is 0,1,2.
  9. 9. The liquid crystal composition according to claim 5 or 6, wherein the dichroic dye composition comprises 0.1 to 10% by mass of the liquid crystal compound represented by the general structural formula II, 80 to 99.9% by mass of the liquid crystal compound represented by the general structural formula III, and 0 to 19.9% by mass of the liquid crystal compound represented by the general structural formula III, and the dichroic dye composition is selected from the dichroic dyes represented by the general structural formula I, or from the dichroic dyes represented by the general structural formula I and the dichroic dyes represented by the general structural formula D.
  10. 10. The liquid crystal composition according to claim 5 or 6, further comprising one or more chiral compounds.
  11. 11. The liquid crystal composition according to claim 11, wherein the chiral compound is added in an amount of 0.01% to 5% of the sum of the mass of the dichroic dye composition and the mass of the liquid crystal compound.
  12. 12. The liquid crystal composition according to claim 5 or 6, further comprising one or more heat stabilizers or light stabilizers.
  13. 13. The liquid crystal composition according to claim 7, wherein the addition mass of the heat stabilizer or the light stabilizer is 0.001% to 1% of the sum of the mass of the dichroic dye composition and the mass of the liquid crystal compound.
  14. 14. Use of a liquid crystal composition according to claim 4, 5 or 6 for the preparation of a light-modulating glass device.
  15. 15. A light-adjusting glass device characterized in that the raw material for preparation comprises the liquid crystal composition according to claim 4, 5 or 6.

Description

High-stability near-infrared dichroism dye, liquid crystal composition and application thereof Technical Field The invention belongs to the technical field of liquid crystal materials, and particularly relates to a dichroic dye with high stability, high solubility and high order parameters, a synthesis method thereof, a liquid crystal composition containing the dichroic dye, a dimming glass device, a polaroid and application. Background The dimming glass can realize controllable adjustment of ultraviolet light, visible light and even infrared light waves, and has wide application prospects in building daylighting glass, automobile windows and the like. The energy consumption of an air conditioner and the like can be reduced by regulating and controlling the input light and heat energy through the dimming glass, and energy conservation and emission reduction are realized. The current dimming glass scheme comprises dye liquid crystal, PDLC (polymer dispersed liquid crystal), EC (electrochromic), SPD (suspended particles) and other technical schemes. The EC (electrochromic) principle is that the redox reaction realizes color-changing dimming, but the response speed is slower (5 min/m 2), and the larger the glass size is, the slower the color change is, and the phenomenon of uneven color change is easy to occur. The PDLC (polymer dispersed liquid crystal) dimming glass is powered on and transparent, and is powered off to be in a fog state, so that the application scene of the PDLC is limited due to larger fog degree, and the PDLC is suitable for meeting room partitions and the like, and is limited in application scenes such as window glass and the like. SPD (suspended particle) dimming glasses have an operating voltage of up to 110V, which presents a safety risk, and thus are of great limitation in application to vehicle glazing. The dimming glass based on dye liquid crystal has the advantages of electrodeless dimming and second-level response, is low in driving voltage and power consumption, is beneficial to energy conservation and consumption reduction, and has the problems of high permeability, small haze and no viewing angle. Thus, dye liquid crystal based dimming glasses have significant technical advantages over other dimming glass technologies. The working principle of the dye liquid crystal dimming glass is a guest-host mode, which is favorable for the difference of light absorption of the long axis and the short axis of the dichroic dye molecules and realizes the absorption and adjustment of light. The properties of dichroic dyes, in particular the light stability, solubility, absorption spectrum range, anisotropy of absorption spectrum, order parameters, etc., play a decisive role in the properties and long-term use reliability of the dye liquid crystal light-adjusting glass device. For dimming glass applications, there is not only a need for visible light regulation, but also a need for thermal regulation that includes the near infrared band. Currently, the absorption spectrum band of dichroic dyes for use in dimming glass is mostly located in the visible light band, while the absorption spectrum contains less dye in the near infrared band. Patent CN107580622a discloses a dichroic dye based on a thiadiazoloquinoxaline receptor unit, the absorption band is located in the near infrared band, and the maximum absorption peak is located at 700 to 800nm. The dichroic dye disclosed in patent CN107580622a also has the problem of low order parameters, which needs to be further addressed. Disclosure of Invention In order to overcome the defects or shortcomings in the background art, the invention provides a near infrared dichromatic dye with high light stability, high solubility, high order parameter and high light modulation capability. In order to achieve the task, the structure of the dichroic dye compound provided by the invention is shown as a general formula I: In formula I: W is an oxygen atom, a sulfur atom or a selenium atom; L 1、L2 is independently selected from hydrogen atom, fluorine atom, chlorine atom, cyano carbon or alkyl with 1-6 carbon atoms; y is selected from 0,1,2; Each of a 1 and a 2 is independently selected from the group shown in the following structure: Wherein L 3 and L 4 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 7 carbon atoms; A 3 and A 4 are an aromatic ring, a hydrogenated quinoline ring, a hydrogenated benzopyran ring, a hydrogenated naphthalene ring, a hydrogenated benzoxazine ring, a hydrogenated benzothiazine ring or a hydrogenated quinoxaline ring represented by the following structures: and at least one of A 3 and A 4 is selected from a hydrogenated benzoxazine ring, a hydrogenated benzothiazine ring or a hydrogenated quinoxaline ring; Wherein R 1,R2,R3,R4,R6,R7,R9 is independently a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, R 5 is a hydrogen atom, a fluorine atom, a ch