Synthesis and Characterization of Two-Dimensional Conjugated Polymers Incorporating Electron-Deficient Moieties for Application in Organic Photovoltaics

A series of novel p-type conjugated copolymers, PTTVBDT, PTTVBDT-TPD, and PTTVBDT-DPP, cooperating benzo[1,2-b:4,5-b′]dithiophene (BDT) and terthiophene-vinylene (TTV) units with/without thieno[3,4-c]pyrrole-4,6-dione (TPD) or pyrrolo[3,4-c]pyrrole-1,4-dione (DPP) via Stille polymerization were synthesized and characterized. Copolymer PTTVBDT shows a low-lying HOMO energy level and ordered molecular-packing behavior. Furthermore, two terpolymers, PTTVBDT-TPD and PTTVBDT-DPP, display stronger absorption ability, alower-lying HOMO energy level, and preferred molecular orientation, due to the replacement TTV-monomer units with electron-deficient groups. Furthermore, bulk-heterojunction organic solar cells were fabricated using blends of the PTTVBDT-TPD, and PC_(61)BM gave the best power conversion efficiency of 5.01% under the illumination of AM 1.5G, 100 mW·cm^(−2); the short circuit current (J_(sc)) was 11.65 mA·cm^(−2) which displayed a 43.8% improvement in comparison with the PTTVBDT/PC_(61)BM device. These results demonstrate a valid strategy combining the two-dimensional molecular structure with random copolymerization strikes promising conjugated polymers to achieve highly efficient organic photovoltaics

Modified structure of two-dimensional polythiophene derivatives by incorporating electron-deficient units into terthiophene-vinylene conjugated side chains and the polymer backbone: synthesis, optoelectronic and self-assembly properties, and photovoltaic application

Molecular engineering on the conjugated side chains of two-dimensional (2D) conjugated polymers was conducted and its effect on the optical, electronic, self-assembly and photovoltaic properties was investigated. A new monomer, M2, was prepared by capping (E)-3′-(2-(2,5-dibromothiophen-3-yl)vinyl)-4,4′′-bis(2-ethylhexyl)-2,2′:5′,2′′-terthiophene, M1, with two heptanoyl groups, and then coupled with 5,5′-bis(trimethylstannyl)-2,2′-bithiophene via microwave-assisted Stille polymerization to produce a series of polythiophene derivatives with terthiophene-vinylene conjugated side chains, TTV–PTs. Copolymer P2 shows a down-shifted HOMO energy level, enhanced solubility, and red-shifted absorption, as compared with P1; however, the bulky side chains significantly disrupt the coplanarity of thiophene rings in the polymer backbone and the ability to self-assemble into an ordered structure. The GIXRD measurements reveal that the original crystallinity of P1 can be recovered by simply inserting a few 2,1,3-benzothiadiazole units into the polythiophene main chain in P2 through a random copolymerization route to yield a terpolymer, P3, which possesses excellent crystallinity, thereby causing a three-fold increment in hole mobility. Furthermore, the P1/PC_(61)BM, P2/PC_(61)BM, and P3/PC61BM solar devices exhibit power conversion efficiencies of 3.89%, 1.52%, and 4.17%, respectively, under AM1.5G illumination with an intensity of 100 mW cm^(−2)

Modified structure of two-dimensional polythiophene derivatives by incorporating electron-deficient units into terthiophene-vinylene conjugated side chains and the polymer backbone: synthesis, optoelectronic and self-assembly properties, and photovoltaic application

Molecular engineering on the conjugated side chains of two-dimensional (2D) conjugated polymers was conducted and its effect on the optical, electronic, self-assembly and photovoltaic properties was investigated. A new monomer, M2, was prepared by capping (E)-3′-(2-(2,5-dibromothiophen-3-yl)vinyl)-4,4′′-bis(2-ethylhexyl)-2,2′:5′,2′′-terthiophene, M1, with two heptanoyl groups, and then coupled with 5,5′-bis(trimethylstannyl)-2,2′-bithiophene via microwave-assisted Stille polymerization to produce a series of polythiophene derivatives with terthiophene-vinylene conjugated side chains, TTV–PTs. Copolymer P2 shows a down-shifted HOMO energy level, enhanced solubility, and red-shifted absorption, as compared with P1; however, the bulky side chains significantly disrupt the coplanarity of thiophene rings in the polymer backbone and the ability to self-assemble into an ordered structure. The GIXRD measurements reveal that the original crystallinity of P1 can be recovered by simply inserting a few 2,1,3-benzothiadiazole units into the polythiophene main chain in P2 through a random copolymerization route to yield a terpolymer, P3, which possesses excellent crystallinity, thereby causing a three-fold increment in hole mobility. Furthermore, the P1/PC_(61)BM, P2/PC_(61)BM, and P3/PC61BM solar devices exhibit power conversion efficiencies of 3.89%, 1.52%, and 4.17%, respectively, under AM1.5G illumination with an intensity of 100 mW cm^(−2)

Synthesis and Characterization of Two-Dimensional Conjugated Polymers Incorporating Electron-Deficient Moieties for Application in Organic Photovoltaics

A series of novel p-type conjugated copolymers, PTTVBDT, PTTVBDT-TPD, and PTTVBDT-DPP, cooperating benzo[1,2-b:4,5-b′]dithiophene (BDT) and terthiophene-vinylene (TTV) units with/without thieno[3,4-c]pyrrole-4,6-dione (TPD) or pyrrolo[3,4-c]pyrrole-1,4-dione (DPP) via Stille polymerization were synthesized and characterized. Copolymer PTTVBDT shows a low-lying HOMO energy level and ordered molecular-packing behavior. Furthermore, two terpolymers, PTTVBDT-TPD and PTTVBDT-DPP, display stronger absorption ability, alower-lying HOMO energy level, and preferred molecular orientation, due to the replacement TTV-monomer units with electron-deficient groups. Furthermore, bulk-heterojunction organic solar cells were fabricated using blends of the PTTVBDT-TPD, and PC_(61)BM gave the best power conversion efficiency of 5.01% under the illumination of AM 1.5G, 100 mW·cm^(−2); the short circuit current (J_(sc)) was 11.65 mA·cm^(−2) which displayed a 43.8% improvement in comparison with the PTTVBDT/PC_(61)BM device. These results demonstrate a valid strategy combining the two-dimensional molecular structure with random copolymerization strikes promising conjugated polymers to achieve highly efficient organic photovoltaics

A Study of the Curing and Flammability Properties of Bisphenol A Epoxy Diacrylate Resin Utilizing a Novel Flame Retardant Monomer, bis[di-acryloyloxyethyl]-p-tert-butyl-phenyl Phosphate

A UV-curable, flame-retardant monomer, DAPP (bis[di-acryloyloxyethyl]-p-tert-butyl-phenyl-phosphate), was synthesized based on BPDCP (4-tert-butylphenyl-dichloro phosphate) and HEA (2-hydroxy ethyl acrylate). DAPP was blended with regular bisphenol A epoxy acrylate (BAEA) in various ratios to yield various phosphorus contents. The TGA-IR (thermogravimetric analyzer interface with an infrared spectrometer) results demonstrate that compounding 30 mol % DAPP with BAEA significantly reduced the amount of released CO gas. In contrast, the peak intensity of CO2 is independent of phosphorus content. The limiting oxygen index (LOI), reaching the saturated value of 26, and the heat release rate (HRR) measured using a cone-calorimeter, 156.43 KW/m2, confirm the saturation point when 30 mol % DAPP was compounded into BAEA. A study of the kinetics of pyrolysis reveals that Ea decreases as the phosphorus content increases. Both the TGA-IR and pyrolysis results reveal that the phosphorus compound DAPP is easily decomposed during the initial stage of burning to form an insulating layer, which inhibits further burning of the resin and the consequent release of other flammable gases

Synthesis and Rheological Characterization of Water-Soluble Glycidyltrimethylammonium-Chitosan

In this study, chitosan (CS) grafted by glycidyltrimethylammonium chloride (GTMAC) to form GTMAC-CS was synthesized, chemically identified, and rheologically characterized. The Maxwell Model can be applied to closely simulate the dynamic rheological performance of the chitosan and the GTMAC-CS solutions, revealing a single relaxation time pertains to both systems. The crossover point of G′ and Gʺ shifted toward lower frequencies as the CS concentration increased but remained almost constant frequencies as the GTMAC-CS concentration increased, indicating the solubility of GTMAC-CS in water is good enough to diminish influence from the interaction among polymer chains so as to ensure the relaxation time is independent of the concentration. A frequency–concentration superposition master curve of the CS and GTMAC-CS solutions was subsequently proposed and well fitted with the experimental results. Finally, the sol-gel transition of CS is 8.5 weight % (wt %), while that of GTMAC-CS is 20 wt %, reconfirming the excellent water solubility of the latter

Isothermal Crystallization Kinetics Study of Fully Aliphatic PA6 Copolyamides: Effect of Novel Long-Chain Polyamide Salt as a Comonomer

N1, N6-bis (4-aminobutyl) adipamide (BABA) diamine and sebacic acid (SA), also called BABA/SA polyamide salt, were used in a typical melt polymerization processes of polyamide 6 (PA6) to form a series of PA6-BABA/SA copolyamides. The effects of BABA/SA on the isothermal crystallization kinetics of PA6-BABA/SA were studied for the first time. An isothermal crystallization analysis demonstrates that the PA6-BABA/SA matrix provided a higher crystallization rate and shorter half-crystallization time than virgin PA6 did. The degree of crystallization of the PA6-BABA/SA30 matrix was also the lowest among all of the samples considered herein. This result is attributed to the high nucleation efficacy of a small amount of BABA/SA in the crystallization of PA6. Values of the Avrami exponent (n) from 1.84 to 3.91 were observed for all of the polyamide samples, suggesting that the crystallization was involved via a two- to three-dimensional growth mechanism. These findings deepen our understanding of the structure–property relationship of PA6-BABA/SA copolyamides, favoring their practical application

Highly Stretchable Fully Biomass Autonomic Self-Healing Polyamide Elastomers and Their Foam for Selective Oil Absorption

Renewable polymers with self-healing ability, excellent elongation, hydrophobicity, and selective oil absorption attributes are of interest for an extensive range of applications, such as e-skin, soft robots, wearable devices, and cleaning up oil spills. Herein, two fully renewable eco-friendly polyamide (PA)-based self-healing elastomers (namely, PA36,IA, and PA36,36) were prepared by a facile and green one-pot melt polycondensation of itaconic acid (IA), PripolTM 1009, and PriamineTM 1075 monomers. The molecular structures of these PAs were analyzed by FITR, 1H NMR, and 13C NMR. The distinct structure of these PAs shows superior strain values (above 2300%) and high ambient temperature autonomous self-healing ability. Interestingly, the synthesized renewable PA36,36 showed zero water absorption values and hydrophobic properties with a contact angle of θ = 91° compared to the synthesized PA36,IA and other previously reported PAs. These excellent attributes are due to the low concentration of amide groups, the highly entangled main chains, the intermolecular diffusion, the manifold dangling chains, and the numerous reversible physical bonds within the renewable PAs. Furthermore, the hydrophobic properties may aid in the selective oil absorption of the PA36,36-based foam, for which PA36,36 foam is produced by the green supercritical carbon dioxide (scCO2) batch foaming process. The PA36,36 foam with a microporous cellular structure showed better absorption capacity and high stability in repeated use. Due to these advantages, these bio-based PAs have potential for the production of eco-friendly self-healing materials, superabsorbent foams, and other polymeric materials

Synthesis and Magnetorheology Study of Iron Oxide and Iron Cobalt Oxide Suspensions

This study investigates the magnetorheology (MR) of polydimethylsiloxane (PDMS) that contains magnetic powders of various compositions, shapes, and concentrations. Two magnetic powders, Fe3O4 and CoFe2O4, were synthesized. TEM images reveal that a powder of spherical particles was obtained at high temperature. A powder with nonspherical star shape was synthesized at low temperature. A rheological test confirmed a typical Bingham behavior for all the MR fluids prepared in this study. Experimental results demonstrated that the cobalt ferrite exhibited a more superior yield stress than the ferrite compound. A magnetic powder of larger particles was found to have higher yield stress. Moreover, the spherical particles yielded a higher yield stress than the star-shaped particles. The “saturated magnetic strength” increased with the loading of the magnetic powder. Finally, the results demonstrate that 12 wt% CoFe2O4 nanopowder (10 nm) dispersed in the PDMS liquid exhibited a large range of yield stresses (0 to 644 Pa)