Search

Rod-coil block copolymers (BCPs) can self-assemble into nanostructures that are useful for the fabrication of nanodevices. However, BCPs are generally difficult to self-assemble into highly ordered nanostructures due to their low chain mobility and strong rod-rod interaction. A facile approach is developed to achieve rapid self-assembly of rod-coil BCPs by blending them with selective additive and annealing in vacuum. Poly(diethyl hexyl oxy-p-phenylene vinylene)-b-poly(methyl methacrylate) (DEHPPV-b-PMMA or PVM) was used as a model copolymer to validate this approach. By adding 30 wt% of a rod-selective additive, p-phenylene vinylene (PV), into the PVM containing 67% (v/v) PMMA, the copolymer can easily self-assemble into lamellae structure at 150 °C for 1.5hr under 0.05 torr. This is a significant improvement over the 200 °C for 60 h for the sample without additive and vacuum annealing. This energy conservation process should have broad application in the fabrication of highly ordered nanostructure using BCPs.

The auhtors report 3D biomimetic scaffolds using polymer blend of polyurethane and cellulose for cardiac tissue engineering. The biocompatible and biodegradable polyurethane is designed, synthesized and characterized. By incorporating 10 wt% of naturally ordered cellulose into the polyurethane and electrospinning them into 3D scaffold, the scaffold exhibits good biocompatibility and mechanical property to support and accommodate constant cycles of contraction/expansion of cardiac tissue. The biocompatibility is further improved using scaffold fabricated from aligned fibers due to synergistic effects between cells and ordered macromolecules. The anisotropic structured scaffold is mimicked the extracellular matrix and has therapeutic potential in reconstruction of damaged myocardium.

A facile approach is reported to process rod-coil block copolymers (BCPs) into highly ordered nanostructures in a rapid, low-energy process. By introducing a selective plasticizer into the rod-coil BCPs during annealing, both the annealing temperature and time to achieve thermodynamic equilibrium and highly ordered structures can be decreased. This process improvement is attributed to enhanced chain mobility, reduced rod-rod interaction, and decreased rod-coil interaction from the additive. The novel method is based on kinetically facilitating thermodynamic equilibrium. The process requires no modification of polymer structure, indicating that a wide variety of desired polymer functionalities can be designed into BCPs for specific applications.

Controlling the nonlamellar and bicontinuous nanostructures through changing volume fraction is a well-developed technique for coil–coil block copolymer, but it is not always effective for rod–coil block copolymer due to strong rod–rod interaction. Versatile self-assembly morphology of rod–coil copolymer can be achieved by simultaneously adjusting the rod–rod interaction, rod–coil interaction, and conformational asymmetry. This approach has been investigated by using poly(3-alkylthiophene)-b-poly(methyl methacrylate) as a model. By altering the alkyl side chain of polythiophene from linear hexyl to longer dodecyl and to branch 2-ethylhexyl, both rod–coil and rod–rod interaction are decreased with increasing spatial occupation of alkyl side chain which have been quantitatively determined for this type of rod–coil copolymer. With tunable conformational asymmetry, competition between rod–rod and rod–coil interactions, and crystallization-driven force, the presence of versatile morphology, i.e., lamellar and ...

Blending with a homopolymer is an effective approach to tailor the microphase-separated morphology of block copolymers. It has been established for the blends of coil–coil diblock copolymer (A-b-B) with the corresponding homopolymer (h-A) that h-A can be solubilized uniformly into A mcirodomain to induce structure transformation when its molecular weight is smaller than that of the A block, i.e., α = Mh-A/Mb-A < 1. Here we examine if the microdomain structure of a rod–coil diblock copolymer, poly(2,5-diethylhexyloxy-1,4-phenylenevinylene)-block-poly(methyl methacrylate) (DEH-PPV-b-PMMA), may be systematically tuned by blending with PMMA hompolymer (h-PMMA). The blends over the major composition window were found to undergo macrophase separation even when the value of α was as low as 0.3. The phase separation led to the formation of a copolymer-rich phase and a homopolymer-rich phase, in which microphase separation occurred, yielding a well-ordered lamellar structure and a sponge structure, respectively. T...

A series of all-conjugated diblock copolythiophenes of poly(3-hexylthiophene)-b-poly(3-thiophene hexylacetate) (P3HT-b-P3THA) were synthesized via modified sequential Grignard metathesis polymerization. The living P3HT was formed first, then reacting with the monomer of P3THA. By using 2-bromo-3-hexyloxycarbonylmethylene-5-iodothiophene instead of dibromo monomer in metal exchange reaction and by controlling the polymerization temperature relatively low at 16–20 °C, the reaction between carboxylate group and Grignard reagent can be minimized and the polymerization can be controlled; low PDI ( 95%), and well-controlled block ratios of block copolymer were obtained. The introduction of carboxylate group in the side chain of one of the monomers, and controlling the side-chain length difference by only three atoms between two monomers, there are profound effects on the optical and electrochemical properties and morphologies of the block copolymers. The electron-withdrawing carboxy...

A series of poly(diethylhexyloxy-p-phenylenevinylene-b-methyl methacrylate) (DEH-PPV-b-PMMA) polymers with narrow polydispersity (PDI < 1.1) were synthesized using Siegrist polycondensation and anionic polymerizations followed by “click” chemistry. Alkyne-terminated DEH-PPV and azido-terminated PMMA were synthesized first, and then the two functionalized polymers underwent 1,3-cycloaddition reaction to obtain copolymers. Both the conversion of the end-functionalization of the homopolymers and the yield of the “click” reaction were higher than 98% as determined by 1H nuclear magnetic resonance (1H NMR) and gel permeation chromatography (GPC). Transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies reveal the details of copolymer morphology. The DEH-PPV-b-PMMA system presented here has higher block segregation strength than many previously studied rod−coil block copolymers yet still shows experimentally accessible phase transitions with respect to temperature. As a result, thi...

Well-defined poly(methyl methacrylate) (Mn ¼ 3630 g mol � 1 , PDI ¼ 1.06) with a primary benzylic bromide prepared using anionic polymerization was suc- cessfully transformed into diverse end-functionalities (x- carboxyl, x-hydroxy, x-methyl-vinyl, x-trimethylsilane, and x-glycidyl-ether) via ''click'' reaction. The bromine end-terminated poly(methyl methacrylate) was first sub- stituted by an azide function and sequentially was reacted with various functional alkynes (propiolic acid, propargyl alcohol, 2-methyl-1-buten-3-yne, propargyl tri- methylsilane, and propargyl glycidylether). In all the cases, 1 H-NMR, 13 C NMR, FT-IR, and GPC measure- ments show qualitative and quantitative transformation of the chain-end poly(methyl methacrylate) into the desired functionalities with high conversion (above 99%). V C 2008 Wiley Periodicals, Inc. J Appl Polym Sci 111: 1571-1580, 2009

Isoindigo based conducting polymers have attracted extensive interest for polymer solar cell application since isoindigo is a green material and renewable from plants. We have synthesized four soluble low band gap isoindigo based polymers (PCI) with cyclopentadithiophene (CPDT) as the donor unit and isoindigo (I) as the acceptor unit, decorated with two kinds of alkyl side chains, octyl (8) and 2-ethylhexyl (e), via the Stille cross-coupling reaction denoted as PC8I8, PC8Ie, PCeI8 and PCeIe. By changing the side chain of copolymers from linear (PC8I8) to branched (PCeIe), the λmax of absorption is blue shifted from 1.37 to 1.48 eV and the HOMO level is lowered from −5.24 to −5.45 eV. The changes are due to the twist coplanarity of the polymer backbone. The density functional theory calculation revealed that the dihedral angle of copolymers has been increased from 14° to 20°. The properties of PC8Ie and PCeI8 lie between those of PC8I8 and PCeIe. The type of the side chain plays a major role in determining the photovoltaic performance of copolymers. The branched side chain improves the solubility of the polymer and increases the effective phase separation between the copolymer and PCBM. This results in favorable nanomorphology of the active layer. Thus, PCeIe with branched side chains on both donor and acceptor units exhibits the best photovoltaic properties with a Voc of 0.80 eV, Jsc of 11.6 mA cm−2 and fill factor of 43.0% and power conversion efficiency of 4.0%. The power conversion efficiency of this type of polymer could be further improved by optimizing the fabrication conditions and interlayer modification. This study offers a useful guideline for the molecular design of high efficiency isoindigo-based polymer solar cells.