RU-2861364-C1 - PHOTOPOLYMERISABLE COMPOSITION BASED ON DI(METH)ACRYLATE AND FLUORINATED CARDO POLYIMIDE

RU2861364C1RU 2861364 C1RU2861364 C1RU 2861364C1RU-2861364-C1

Abstract

FIELD: chemistry. SUBSTANCE: present invention relates to a photopolymerisable composition for the manufacture of functional materials, applicable, for example, as primary coatings for quartz optical fibres, comprising a monomer, a photoinitiator 2,2’-dimethoxy-2-phenylacetophenone and a fluorinated cardo polyimide obtained from 2,2-bis-(3,4-dicarboxydiphenyl)hexafluoropropane dianhydride, 9,9-bis-(4-aminophenyl)fluorene and 2,2-bis-(4-aminophenyl)hexafluoropropane in a molar ratio of 1.00:0.75:0.25, wherein the monomer-solvent used is a di(meth)acrylate of the general formula where R 1 = H, -CH 3 ; R 2 = -(CH 2 ) 4 -O-, -(CH 2 -CH 2 -O) n -, n = 1-4, the ratio of said components in the composition being, mas.%: fluorinated cardo polyimide - 15-23; photoinitiator - 5; di(meth)acrylate - the rest. EFFECT: novel photopolymerisable compositions comprising a di(meth)acrylate, a fluorinated cardo polyimide and a photoinitiator, making it possible to obtain polymers with improved properties without additional curing. 1 cl, 1 dwg, 2 tbl, 6 ex

Inventors

SAPOZHNIKOV DMITRIJ ALEKSANDROVICH
MELNIK OLGA ALEKSANDROVNA
Chuchalov Aleksandr Vladimirovich
Bulatov Maksim Igorevich
KOVYLIN ROMAN SERGEEVICH
CHESNOKOV SERGEJ ARTUROVICH

Dates

Publication Date: 20260505
Application Date: 20241108

Claims (5)

A photopolymerizable composition for the production of functional materials applicable, for example, as primary coatings for quartz optical fibers, comprising a monomer, a photoinitiator 2,2'-dimethoxy-2-phenylacetophenone and a fluorinated carded polyimide obtained from the dianhydride 2,2-bis-(3,4-dicarboxydiphenyl)hexafluoropropane, 9,9-bis-(4-aminophenyl)fluorene and 2,2-bis-(4-aminophenyl)hexafluoropropane 1.00:0.75:0.25 mol, characterized in that di(meth)acrylate of the general formula is used as the monomer-solvent
where R 1 = H, -CH 3 ; R 2 = -(CH 2 ) 4 -O-, -(CH 2 -CH 2 -O) n -, n = 1-4, while the ratio of the specified components in the composition is, mass %:
fluorinated carded polyimide - 15-23;
photoinitiator - 5;
di(meth)acrylate - the rest.

Description

Field of technology to which the invention relates The invention relates to polymer chemistry, namely to a liquid photopolymerizable composition (LPC) based on di(meth)acrylate of the general formula where R 1 =H, CH 3 ; R 2 =(CH 2 ) 4 -O, (CH 2 -CH 2 -O) n , n=1-4, including the photoinitiator 2,2'-dimethoxy-2-phenylacetophenone and dissolved fluorinated carded polyimide (FCPI) obtained from 2,2-bis-(3,4-dicarboxydiphenyl)hexafluoropropane dianhydride, 9,9-bis-(4-aminophenyl)fluorene and 2,2-bis-(4-aminophenyl)hexafluoropropane (1.00:0.75:0.25 mol), with the following ratio of the said components in the composition (wt.%): fluorinated carded polyimide - 15-23; photoinitiator - 5; di(meth)acrylate - the rest. The invention can be most effectively used in the production of functional materials for electronics, optics, medicine, and energy, for example as primary coatings for quartz optical fibers (light guides). State of the art Radical photopolymerization is a well-known method for converting liquid compositions into a solid polymer under the influence of visible light, UV, or IR irradiation [Fouassier J.-P. Photoinitiation, Photopolymerization, and Photocuring: Fundamentals and Applications; Hanser Publishers: Munich, Germany, 1995; 275p; Kaur M., Srivastava A. Photopolymerization: A review. J. Macromol. Sci. Part C Polym. Rev. 2002, 42, 481–512; Yagci Y., Jockusch S., Turro N.J. Photoinitiated polymerization: Advances, challenges, and opportunities. Macromolecules 2010, 43, 6245–6260]. The main advantage of photopolymerization is the ability to cure compositions that do not contain inert solvents in a matter of seconds under normal conditions. This process occurs much faster than thermal radical polymerization. The existence and possibility of obtaining various photopolymerizable compositions (PPC), the obvious advantages of their transformation and rapidly developing technologies make it possible to obtain a variety of functional materials from them [Pagac M., Hajnys J., Ma Q.-P. et al. Polymers, 2021, 13, 598; Shaukat U., Rossegger E., Schlogl S. Polymers, 2022, 14, 2449]. PPCs differ both in composition and in characteristics: RU 2244335 (2005), RU 2395827 (2010), US 2004131975 A1 (2004), JP 2016084478 A (2016), RU 2685211 (2019). Photopolymerizable compositions are known that are used to obtain photocurable coatings applicable in the production of electronic and medical devices, optical fibers, etc. [Khudyakov I.V. Progress in Organic Coatings, 2018, 121, 151-159; Kra'skiewicz A., Kowalczyk A., Kowalczyk K., Schmidt B. Progress in Organic Coatings, 2023, 175, 107-365]. Most of the curable compositions contain multifunctional (meth)acrylates - di- and tri(meth)acrylates. Such compounds, unlike monofunctional unsaturated monomers, do not require thermal post-curing [Ligon-Auer S.C., Schwentenwein M., Gorsche C. et al. Polymer Chemistry, 2016, 7, 257-286]. Polyurethanes/polysiloxanes/polyether acrylates or expensive fluoroacrylates are used to improve the thermal stability of photocurable coatings of optical fibers made of silica [Janani R., Majumder D., Scrimshire A. et al. Progress in Organic Coatings, 2023, 180, 107557]. The use of such starting systems has its own characteristics and limitations; their disadvantages are, as a rule, low thermal stability and mechanical strength of the resulting materials. It has been shown that the introduction of polyheteroarylenes into the monomer(s) and subsequent radical polymerization in situ leads to an improvement in the thermal and mechanical properties of the resulting copolymers compared to unmodified carbon-chain homopolymers, opening up wide possibilities for obtaining various materials and products [Zabegaeva O.N., Sapozhnikov D.A., Vygotsky Ya.S. High-molecular Compounds, Series C, 2020, 62(2), 186-199]. Photopolymerizable compositions are known consisting of polyimide oligomers with terminal maleimide groups and side methacrylate groups as a base; N-vinyl-2-pyrrolidone, lauryl methacrylate and polyethylene glycol diacrylate as active solvents, and the photoinitiator Irgacure 819 [Guo Y., Ji Z., Zhang Y., Wang X., Zhou F. J. of Materials Chemistry A, 2017, 5(31), 16307-16314]. Good solubility of these oligomers in unsaturated diluents made it possible to form photocurable inks without an inert solvent for 3D printing. A disadvantage of the composition is the complex multi-stage synthesis of the functionalized oligoimide, including reactions of the terminal amino groups of the oligoimide with maleic anhydride and then the side phenolic hydroxyl groups with glycidyl methacrylate. The closest analogue of the declared FPCs, taken as a prototype, are the previously developed compositions based on monofunctional (meth)acrylates, including fluorinated carded polyimides (FCPI) [Sapozhnikov D.A., Volkova T.V., Sakharova A.A. et al. High-Molecular Compounds, Series B, 2009, 51(2), 286-297]. There is no information in the literature on similar compositions based on