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Article Citation - WoS: 28Citation - Scopus: 29Functionalized Polysulfide Copolymers With 4-Vinylpyridine Via Inverse Vulcanization(Elsevier Science Bv, 2019) Berk, Hasan; Balci, Burcu; Ertan, Salih; Kaya, Murat; Cihaner, AtillaA new series of functional polysulfide copolymers called poly(sulfur-random-4-vinylpyridine) (poly(S-r-4VP)) was synthesized via inverse vulcanization technique by ring opening polymerization of elemental sulfur in the presence of 4-vinylpyridine (4VP). The corresponding copolymers can be post functionalized by using amine group in 4VP unit to get polymers bearing various properties. Elemental sulfur was heated up to 160 degrees C and 4VP was added slowly to a clear yellowish orange colored liquid at this temperature. The reaction mixture was vitrified to form a reddish-brown polymeric material at 180 degrees C in 1 h. The products were characterized by using FTIR, NMR, and Raman spectroscopic techniques. Poly(S-r-4VP) copolymers are soluble in common solvents like dichloromethane, chloroform and tetrahydrofuran. Weight-average molecular weights of poly(S-r-4VP) copolymers with different wt% 4VP were measured by using gel permeation chromatography technique. The polysulfide copolymers with different wt% 4VP have high weight-average molecular weights with polydispersity indeces (PDI) in a range from 1.88 to 4.06 measured by gel permeation chromatography. Post functionalization of the copolymer with 50 wt% 4VP as an example was performed successfully by using alkyl bromide to get N-alkyl quaternized 4VP in polymer backbone.Article Citation - WoS: 3Citation - Scopus: 2Polyhedral Oligomeric Silsesquioxane Cage Integrated Soluble and Fluorescent Poly(3,4-Propylenedioxythiophene) Dye(Elsevier Sci Ltd, 2021) Ertan, Salih; Kaya, Murat; Cihaner, AtillaA new analog of poly (3,4-propylenedioxythiophene) conjugated polymers called PProDOT-POSS, where polyhedral oligomeric silsesquioxane (POSS) nanocage with alkyl substitutions was integrated on the bridge of 3,4-propylenedioxythiophene unit and its structure was confirmed by spectroscopic techniques, was reported. The polymers were synthesized via both chemical and electrochemical polymerization techniques. While chemical polymerization was carried out in the presence of anhydrous FeCl3 as an oxidant, a solution of 0.1 M tetrabutylammonium hexafluoride electrolyte dissolved in a mixture of dichloromethane and acetonitrile (1/3: v/v) was used as an electrolyte solution for electrochemical polymerization. Electro-optical properties of the corresponding polymers were characterized by using electroanalytical techniques such as cyclic voltammetry and square wave potentiometry, and spectrophotometric methods like ultraviolet-visible and fluorescent spectrophotometry. Corresponding polymers obtained both electrochemically and chemically are soluble completely in common organic solvents such as chloroform, toluene, dichloromethane, tetrahydrofuran, etc. Polymer samples both in film and solution forms can be doped/dedoped reversibly by using a chemical oxidant or an external potential. The optical bandgap of the neutral polymer film with a maximum absorption band at 555 nm was calculated as 1.95 eV. Polymers have fluorescent property and excited polymers represented a red/orange light with an emission band centered at 605 nm in toluene. Also, PProDOT-POSS polymers have electrochromic properties under external potentials and they have an optical contrast of 55% at 555 nm between their neutral and oxidized states. Upon oxidation, they showed high transparency and they can switch between redox states in a short time (switching time = similar to 1.0 s) as well as high coloration efficiency (502 cm(2)/C for 95% switching). It can be concluded that POSS based PProDOT polymers can be good candidates for optoelectronic and bioelectronics applications. Short Abstract for Paper Submission: A new analog of poly (3,4-propylenedioxythiophene) conjugated polymers called PProDOT-POSS, was reported with the integrated of alkyl-substituted polyhedral oligomeric silsesquioxane nanocage structure. The polymers were synthesized via both chemical and electrochemical polymerization techniques. Corresponding polymers obtained both electrochemically and chemically are soluble completely in common organic solvents such as chloroform, toluene, dichloromethane, tetrahydrofuran, etc. Polymer samples both in film and solution forms can be doped/dedoped reversibly by using a chemical oxidant or an external potential. The optical bandgap of the neutral polymer film with a maximum absorption band at 555 nm was calculated as 1.95 eV. Polymers have fluorescent property and excited polymers represented a red/orange light with an emission band centered at 605 nm in toluene.
