Lastingly Colored Polylactide Synthesized by Dye-Initiated Polymerization (original) (raw)
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End functionalized polylactides are prepared by ring opening polymerization of L-lactide in the presence of stannous octoate (Sn(Oct)2). Three chromophores, 9H-carbazol-ethanol (CA), 9-fluorenyl-methanol (FM), and 2-(4-(2-chloro-4-nitrophenylazo)-N-ethylphenylamino)ethanol (Disperse Red 13, DR), are for the first time used as co-initiators in the polymerization process. The polymerization reaction is initiated by conventional thermal treatment, but in the case of FM, microwave-assisted polymerization is also carried out. CA and FM absorb and emit in the UV portion of the electromagnetic spectrum, whereas DR absorbs in the visible part. The obtained end-capped polylactides derivatives show the same photophysical properties as the initiator, so they are “macromolecular dyes” (MDs) that can be used “as synthesized” or can be blended with commercial poly(lactic acid) (PLA). The blends of PLA with MDs have ultraviolet-visible (UV-Vis) absorption and fluorescence emission features similar...
Acta Polymerica, 1999
Formation of the polycation/dye complexes by the interaction between polycations with (N,N-dimethyl-2-hydroxypropylene ammonium chloride) units in the main chain and three anionic dyes with two, three and six sulfonic groups (Crystal Ponceau 6R, Ponceau 4R and Direct Red 80) confirmed the chromotropic properties of these polycations and gave information on the influence of the polycation and the dye structure on the stability of the polycation/dye complex. The interaction between polycations and dyes and the stoichiometry of the polycation/dye complexes were followed by UV-VIS spectrophotometry and viscometry. The presence of the nonpolar side chains in polycation structure did not increase the ability to bind these dyes. The stability of the polycation/dye complexes increased with the increase of the content of quaternary ammonium salt groups in the main chain and with the increase of the sulfonic group number of the dye.
Chemical Communications, 2008
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New two- and three-cationic polymethine dyes. Synthesis, properties and application
Dyes and Pigments, 2015
Three new two-and three-cationic monochromophoric polymethine dyes based on the 2methylbenzothiazole were synthesized and applied as visible light initiators for acrylic monomer polymerization. In the photoinitiating system, the polymethine dye cation acts as an electron acceptor whereas borate anion is an electron donor. The actual photoinitiators can only operate in a restricted part of the visible light region; as a consequence, a several photoinitiators are usually necessary to harvest all the emitted visible photons. In the present paper, new dyes based on a donor-p-acceptor structure (2-methylbenzothiazole derivatives) are incorporated into visible light sensitive photoinitiating systems of triacrylate polymerization. They exhibit an unusual and remarkable broad absorption lying from the blue to the red. When employed in the presence of organoborate salts, these dyes can efficiently initiate the radical photopolymerization of acrylates under exposure at 514 nm.
Polyhedron, 2008
The reaction between ZnCl 2 and (S)-N-ethyl-N-phenyl-2-pyrrolidinemethanamine (S-EPP) as a chiral ligand affords [ZnCl 2 (S-EPP)], whose structure has been determined by X-ray crystallography. [ZnEt 2 (S-EPP)] has demonstrated high activity toward the polymerization of rac-lactide with a maximum turnover frequency (TOF) of 121. Despite the intended stereocontrol by employing a chiral ligand, however, the observed heterotacticity was limited to under 0.6. The MWDs of the PLAs were found to be modulated by changing the solvent or controlling the concentration of the monomer in the solution. The glass transition temperature (T g ) was critically dependent on the MW within the narrow MWD regime, but the dependence became significantly shallow when the MWD was broadened.
We describe the synthesis of an end-functionalized copolymer of N-(2-hydroxypropyl)methacrylamide (HPMA) and N-hydroxysuccinimide methacrylate (NMS) by reversible addition-fragmentation chain transfer (RAFT) polymerization. To control the polymer composition, the faster reacting monomer (NMS) was added slowly to the reaction mixture beginning 30 min after initating the polymerization (ca. 16% HPMA conversion). One RAFT agent, based on azocyanopentanoic acid, introduced a -COOH group to the chain at one end. Use of a different RAFT agent containing a 4-amino-1,8-naphthalimide dye introduced a UV-vis absorbing and fluorescent group at this chain end. The polymers obtained had molecular weights of 30 000 and 20 000, respectively, and contained about 30 mol% NMS active ester groups.
Journal of Polymer Science Part A: Polymer Chemistry, 2018
Seven (half-)titanocene alkoxide complexes, [Cp 2 TiCl (OEt)], [Cp 2 TiCl(O-2-Bu)], [Cp 2 TiCl(OCH 2 CF 2 CF 2 H)], [CpTiCl 2 (OEt)], [CpTiCl 2 (O-(S)-2-Bu)], [CpTiCl 2 (OCH 2 CF 3)], and [Cp 2 TiCl(OCH 2 CF 3)], were synthesized and employed in lactide coordination polymerization. These organotitanium (IV) compounds proved to be very efficient initiators for the ring-opening polymerization of enantiomeric L-lactide and racemic mixture of rac-lactide, leading to end-functionalized polymers. Kinetic studies illustrated that these compounds produce well-defined polymers in a controlled manner. This was further demonstrated by synthesizing poly(L-lactide-b-hexyl isocyanate) diblock copolymer. The effect of the alkoxy end groups on the thermal behavior of the polymers was also studied by thermogravimetric analysis and differential scanning calorimetry. The polymers were characterized using size exclusion chromatography and proton nuclear magnetic resonance spectroscopy. The optical properties of the diblock copolymer were also investigated.
Turkish Journal of Chemistry
Introduction Polymeric dyes are a novel form of dyes in which organic dyes are chemically incorporated into the main or side chains of polymer [1]. Polymeric colorants have acquired popularity, applicability, and acceptance as a viable alternative to traditional colorants (dyes and pigments) [2]. The marriage of polymer and dye chemistry enables the chemist to design unique materials that exploit the best characteristics of both pigments and dyes [3]. The synthetic dyes play the major role in textile fiber fashioning [4], specialty materials having several advantages over their monomeric dyes counterparts, consequently in the last few decades; they have been documented well by many research scientists [4]. They have been widely applied on fiber because of certain essential dye properties such as fast leveling, fastness to light and wet treatment, low sublimation rate, and very good thermal and chemical resistance [5]. Habibu et al. studied the synthesis, characterization, and application of some polymeric dyes derived from monoazo disperse dyes [6]. The dyes generally have a good exhaustion in both fabrics, while nylon exhausts better than polyester. Their fastness ratings on nylon and polyester were satisfactory, with the polymeric dyes having more brilliant colors in general. Polymerization of prospective monomeric dyes on nylon and polyester results in increased shade brilliancy as well as improved fastness capabilities [6]. Polymeric dyes have excellent brightness and extremely fadeless [7]. Colorants, which include chromophores of dyes usually consisting of C=C, N=N, C=N, attached to aromatic or heterocyclic rings, containing oxygen, nitrogen or sulfur, have been widely used as dyes owing to their versatility in various fields and high technology, including textiles, paper, leather, plastics, biological staining, lasers, liquid crystalline displays, ink-jet printers, and in specialized applications, such as food, drug,
Polymer, 2007
Poly(butyl methacrylate) (PBMA) latex particles have been copolymerized with new fluorescent naphthalimide dyes by miniemulsion polymerization. A new pair of naphthalimide dye monomers was synthesized and copolymerized with butyl methacrylate (BMA) via miniemulsion polymerization, producing approximately 80 nm diameter particles with a narrow size distribution. We were able to prepare polymers with molecular weights in excess of 100,000 g/mol. We also prepared 30,000 g/mol polymers using 1-dodecanethiol as a chain transfer agent. GPC and UV characterization suggest that nearly all of the dye monomers were incorporated into the PBMA polymer chains. The polymerized naphthalimide dyes can be used as a donoreacceptor pair for fluorescence resonance energy transfer (FRET) experiments. The analysis of FRET experiments is complicated by the slightly non-exponential decay of the donor naphthalimide dye. We propose a simple method to deal with this non-exponential behavior in the data analysis. Using our approach, we find that the Förster radius (R o) between the donor and the acceptor dyes incorporated in the PBMA latex is 3.8 nm. This value is similar to the 3.6 nm Förster radius of a comparable model dye pair in ethyl acetate obtained by a different method.