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CN-121975048-A - Photopolymerizing compositions of a series of azaborol-dipyrromethene derivatives

CN121975048ACN 121975048 ACN121975048 ACN 121975048ACN-121975048-A

Abstract

A series of photopolymerisable compositions of aza-boron-fluorine dipyrrole derivatives belong to the technical field of photocuring materials. In the composition, the aza-boron fluorine dipyrrole derivative is taken as a photosensitizer, has high molar extinction coefficient, excellent light stability and wide spectral response characteristic, and can realize high-efficiency intersystem crossing and long triplet state service life. After the polymer is compounded with tri (3-chloro-4-methylphenyl) hexyl tetrabutylammonium borate (NB), the polymer can be rapidly initiated to polymerize an acrylic monomer under 365 nm ultraviolet light, the curing time is within 20 seconds, and the double bond conversion rate can reach 75 percent at most. Wherein the brominated aza-BODIPY derivative (ADP-Br) can realize high-efficiency polymerization under the irradiation of 620 nm red light, and the double bond conversion rate can reach 50 percent at most. The photopolymerization system has high initiation efficiency, high curing speed and wide application scene, and can be used in the fields of photocuring paint, adhesive, photoetching material, 3D printing and the like.

Inventors

  • Yang Huidan
  • ZHAO JIANZHANG
  • LI YANQIN

Assignees

  • 大连理工大学

Dates

Publication Date
20260505
Application Date
20260407

Claims (9)

  1. 1. A series of photopolymerisable compositions of aza-borofluoro-dipyrrole derivatives, characterized in that they comprise a polymeric monomer and a photopolymerization initiation system comprising an aza-BODIPY derivative photosensitizer and a co-initiator; The aza-BODIPY derivative is used as a photosensitizer, and after being compounded with a coinitiator, initiates a monomer to carry out polymerization reaction under ultraviolet light or visible light irradiation; The aza-BODIPY derivative has the following general structure: ; Wherein each R 1 、R 2 、R 3 is independently selected from one of hydrogen, halogen, substituted or unsubstituted C 1 –C 12 alkyl, C 2 -C 12 alkenyl, C 2 –C 12 alkynyl, C 1 –C 12 alkoxy, aryl, aldehyde, carboxyl, ester, cyano, nitro.
  2. 2. The photopolymerisable composition of a series of azaborol-dipyrromethene derivatives according to claim 1, wherein each R 1 、R 2 、R 3 is independently selected from hydrogen, halogen, C 1 -C 12 alkoxy.
  3. 3. A series of photopolymerisable compositions of azaborol-dipyrromethene derivatives according to claim 2, wherein R 1 is C 1 -C 12 alkoxy, R 2 is halogen and R 3 is hydrogen.
  4. 4. A series of photopolymerisable compositions of azaborol dipyrrole derivatives according to claim 3, characterized in that said co-initiator is selected from one or more of organic borate co-initiators selected from one or more of tetrabutylammonium tris (3-chloro-4-methylphenyl) hexyl borate, tetrabutylammonium triphenylhexyl borate, tetrabutylammonium tris (4-methylphenyl) hexyl borate, amine co-initiators selected from one or more of triethanolamine, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, thiol co-initiators selected from one or more of pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate).
  5. 5. The photopolymerisable composition of a series of azaboro-dipyrromethene derivatives according to claim 4, wherein said composition further comprises additives comprising one or more of colorants, alkali-soluble resins, adhesion promoters, surfactants, dispersants, polymerization inhibitors, leveling agents, defoamers.
  6. 6. The photopolymerisable composition of a series of azaborol dipyrrole derivatives according to claim 5 wherein the polymeric monomer is selected from one or more of isooctyl acrylate, lauryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, benzyl acrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, methyl methacrylate, hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, 1, 6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate.
  7. 7. The photopolymerisable composition of a series of azaborol-dipyrrole derivatives according to claim 6, wherein the photopolymerisable initiation system further comprises a second photoinitiator comprising one or more of benzophenone, α -hydroxy ketone, α -amino ketone, thioxanthone, triazine, acyl oxime.
  8. 8. The photopolymerizable composition of a range of azaborol-dipyrromethene derivatives according to claim 7 wherein said composition requires illumination light in the wavelength range of 320 to 700 nm.
  9. 9. Use of a series of photopolymerisable compositions of aza-borofluorodipyrromethene derivatives according to any one of claims 1 to 8 in photocurable coatings, adhesives, 3D printing materials or lithographic materials.

Description

Photopolymerizing compositions of a series of azaborol-dipyrromethene derivatives Technical Field The invention relates to a series of photopolymerisable compositions of aza-boron fluorine dipyrrole derivatives, which belongs to the technical field of photocuring materials. Background Triplet photosensitizers refer to molecules that, upon excitation by light, can undergo intersystem crossing to produce a triplet excited state. The spin multiple of the molecule changes in the process of relaxation from the triplet excited state to the ground state, and the process is a spin forbidden process, so that the service life (microsecond level) of the triplet excited state is longer than that of the singlet excited state (nanosecond level), and the subsequent energy transfer and charge transfer processes are facilitated. The triplet state generated after the molecule is excited by light can directly generate active species or induce the decomposition of a coinitiator to generate active free radicals so as to initiate the polymerization of monomers. How to realize efficient photopolymerization under mild illumination has become a research hotspot in the field in recent years. The current commercial ultraviolet photosensitizer has wide application, but generally has the problems of insufficient photoinitiation efficiency, short triplet state service life, poor compatibility with monomers and the like, and is difficult to meet the actual requirements of high-speed and high-precision photopolymerization scenes such as 3D printing, fine photoetching and the like, and meanwhile, the traditional ultraviolet photosensitizer depends on a small-molecule dye skeleton, has limited structure modification space and cannot achieve both light stability and initiation activity. Disclosure of Invention The invention mainly solves the problems of weak long-wave response and insufficient initiation efficiency of the existing photopolymerization initiation system, and provides a series of photopolymerization compositions of aza-boron-fluorine dipyrrole derivatives aiming at the defects of narrow absorption wave band, low activity of partial long-wave absorption molecules, poor compatibility with monomers and the like of a visible light photosensitizer. The aza-BODIPY derivative photosensitizer has high molar extinction coefficient, excellent light stability and wide spectral absorption range (ultraviolet to near infrared), can realize long triplet state service life and high-efficiency intersystem crossing through structural modification, has good performance in photopolymerization, and can be used for various directions such as photo-curing coating, adhesive, photoetching material, 3D printing and the like. The technical scheme adopted by the invention is that the composition comprises a series of photopolymerizing compositions of aza-boron fluorine dipyrrole derivatives, a photopolymerization initiation system, a polymerization initiator system and a polymerization initiator system, wherein the photopolymerization initiation system comprises an aza-BODIPY derivative photosensitizer and a co-initiator; The aza-BODIPY derivative is used as a photosensitizer, and is compounded with a coinitiator to initiate a polymer monomer to carry out polymerization reaction under ultraviolet light or visible light irradiation; The aza-BODIPY derivative has the following general structure: Wherein each R 1、R2、R3 is independently selected from one of hydrogen, halogen, substituted or unsubstituted C 1–C12 alkyl, C 2–C12 alkenyl, C 2–C12 alkynyl, C 1–C12 alkoxy, aryl, aldehyde, carboxyl, ester, cyano, nitro. Preferably, each R 1、R2、R3 is independently selected from hydrogen, halogen, C 1–C12 alkoxy. More preferably, R 1 is C 1–C12 alkoxy, R 2 is halogen and R 3 is hydrogen. Further, the co-initiator is selected from one or more of organic borate co-initiator, amine co-initiator and mercaptan co-initiator, wherein the organic borate co-initiator is selected from one or more of tri (3-chloro-4-methylphenyl) hexyl tetrabutylammonium borate, triphenyl hexyl tetrabutylammonium borate and tri (4-methylphenyl) hexyl tetrabutylammonium borate, the amine co-initiator is selected from one or more of triethanolamine, 4-dimethyl amino ethyl benzoate and 4-dimethyl amino 2-ethylhexyl benzoate, and the mercaptan co-initiator is selected from one or more of pentaerythritol tetra (3-mercaptopropionate) and trimethylolpropane tri (3-mercaptopropionate). Further, the composition also comprises an additive, wherein the additive comprises one or more of a colorant, alkali-soluble resin, an adhesion promoter, a surfactant, a dispersing agent, a polymerization inhibitor, a leveling agent and a defoaming agent, and the colorant is one or more of carbon black, titanium dioxide and an organic pigment; The alkali-soluble resin is selected from one or more than two of acrylic resin, styrene-acrylic copolymer and phenolic modified acrylic resin, the adhesion promoter is selected f