Synthesis of Novel Thermo‐ and pH‐Responsive Poly(L‐lysine)‐Based Copolymer and its Micellization in Water

A series of novel temperature and pH responsive block copolymers composed of poly(N‐isopropylacrylamide) (PNIPAM) and poly(L ‐lysine) (PLL) were synthesized. The effect of pH and the length of PLL on the lower critical solution temperature (LCST) of PNIPAM, and the self‐assembly of these PLL‐based copolymers induced by temperature and pH changes were investigated by the cloud point method, dynamic light scattering (DLS) and environmental scanning electron microscopy (ESEM). These PNIPAM‐b‐PLL copolymers can self‐assemble into micelle‐like aggregates with PNIPAM as the hydrophobic block at acidic pH and high temperatures; and at alkaline pH and low temperatures, they can self‐assemble into particles with PLL as the hydrophobic block. The copolymers may have potential applications in biotechnological and biomedical areas as drug release carriers.

     

Vapor‐Based Synthesis of Poly[(4‐formyl‐p‐xylylene)‐co‐(p‐xylylene)] and Its Use for Biomimetic Surface Modifications

Summary: The vapor‐based synthesis and characterization of a reactive polymer, poly[(4‐formyl‐p‐xylylene)‐co‐(p‐xylylene)] ( 1 ), have been reported. The reactive polymer coating enables the immobilization of oligosaccharides via the chemoselective aldehyde‐hydrazide coupling reaction.

     

A Multicolor Photoinitiator for Cationic Polymerization and Interpenetrated Polymer Network Synthesis: 2,7‐Di‐tert‐butyldimethyldihydropyrene

For polymer synthesis upon visible light, actual photoinitiator operates in a restricted part of the spectrum. As a consequence, several photoinitiators are necessary to harvest all of the emitted visible photons. Herein, 2,7‐di‐tert‐butyldimethyldihydropyrene is used for the first time as a multicolor photoinitiator for the cationic polymerization of epoxides. Upon addition of diphenyliodonium hexafluorophosphate and optionally N‐vinylcarbazole, the originality of this approach is to allow efficient monomer conversions under various excitation light sources in the 360–650 nm wavelength range: halogen lamps, and light‐emitting and laser diodes. The synthesis of an interpenetrated polymer network from an epoxide/acrylate blend using a red light at 635 nm is also feasible. The formed polymer material exhibits a photochromic character.

     

Carbon Nanotubes as a Ligand in Cp2ZrCl2‐Based Ethylene Polymerization

Summary: We report a simple method for tuning catalytic property of a metallocene‐based catalyst, Cp₂ZrCl₂, for ethylene polymerization by the direct adsorption of Cp₂ZrCl₂ onto multi‐walled carbon nanotubes (MWCNTs). The direct interactions between MWCNTs and the Cp rings of Cp₂ZrCl₂ controlled the polymerization behaviors, and we could generate polyethylene with an extremely high molecular weight ( = 1 000 000) at 30 °C and under 1 atm of ethylene gas.

Preparation of Cp₂ZrCl₂‐MWCNT.     

Preparation and SO2 Absorption/Desorption Properties of Crosslinked Poly(1,1,3,3‐Tetramethylguanidine Acrylate) Porous Particles

Summary: Novel crosslinked porous particles based on the ionic copolymer of 1,1,3,3‐tetramethylguanidine acrylate (TMGA) and N,N‐methylenebisacrylamide (MBA) were prepared via an inverse suspension polymerization using cyclohexane as continuous phase and Span 60 as the dispersant. The SO₂ absorption–desorption properties of the P(TMGA‐co‐MBA) particles were studied for the first time. The particles showed excellent SO₂ absorption properties: high capacity and rate. These absorption properties, as well as the particle volume, shape, and morphology, remained unchanged during the SO₂ absorption–desorption cycles. The material appeared to be a good candidate as SO₂ absorbent for fuel gas desulfurization (FGD) and purification of other SO₂‐containing gases.

Optical microscope image of the P(TMGA‐co‐MBA) porous particles.     

A Novel Strategy for the Preparation of Reactively Compatibilized Polymer Blends with Oligomers Containing α‐Methyl Styrene Units

A novel strategy to prepare reactively compatibilized polymer blends is reported. An oligomer that consists of AMS (α‐methyl styrene) and GMA (glycidyl methacrylate) is initially synthesized. When this oligomer is melt blended with poly(propylene) (PP), the GMA units in the oligomer are successfully grafted onto the PP chain, which is proven by measuring the FT‐IR spectrum of the blended PP. When the oligomer is added to a blend of PP/Ny66, an in‐situ compatibilization occurs, which leads to an increase in torque values during blending, a decrease in crystallinity degree of Ny66, and is observed by SEM images of the resulting blends. The compatibilizing effects of the oligomer are also observed in PP/Ny6 and polyethylene/Ny6 blends. A relevant compatibilization mechanism is proposed.

     

Origin of Piezoelectricity in an Electrospun Poly(vinylidene fluoride‐trifluoroethylene) Nanofiber Web‐Based Nanogenerator and Nano‐Pressure Sensor

A single stage electrospinning process can give rise to preferentially oriented induced dipoles in poly(vinylidene fluoride‐trifluoroethylene) [P(VDF‐TrFE)] nanofibers. The piezoelectricity of as‐electrospun P(VDF‐TrFE) nanofiber webs opens up new possibilities for their use as a flexible nanogenerators and nano‐pressure sensors. In this work, the origin of the piezoelectricity has been spotlighted by randomization of the induced dipoles at the Curie temperature and analyzed by polarized FT‐IR spectroscopic techniques as well as by detecting the piezoelectric signal from a nano‐pressure sensor.

     

Aqueous RAFT Polymerization of Acrylamide and N,N‐Dimethylacrylamide at Room Temperature

Summary: The first example of a room temperature reversible addition‐fragmentation chain transfer polymerization conducted directly in aqueous media is detailed. Under these conditions acrylamide and N,N‐dimethylacrylamide may be polymerized in a controlled fashion to near quantitative conversions employing a difunctional trithiocarbonate chain transfer agent (CTA). Hydrolysis studies conducted at pH 5.5 suggest that the CTA is stable up to approximately 50 °C.

     

Modular Synthesis of Thermosensitive P(NIPAAm‐co‐HEMA)/β‐CD Based Hydrogels via Click Chemistry

Two kinds of representative polymers, poly(N‐isopropylacrylamide) (PNIPAAm) and β‐cyclodextrin (β‐CD) were selected and modified with azide and alkyne fucntional groups, respectively. When the solutions of these two modified polymers were mixed together, a cross‐linking reaction, a type of Huisgen's 1,3‐dipolar azide‐alkyne cycloaddition, occurred in the presence of Cu(I) catalyst. The strategy described here provides several advantages for the hydrogel formation including mild reaction conditions and controllable gelation rate. The resulted hydrogels were studied in terms of scanning electric microscopy (SEM), equilibrium swelling ratio and swelling/shrinking kinetics. The data obtained demonstrated the hydrogels had a porous structure as well as favorable thermosensitivity.

     

Supramolecular Assembly of Gold Nanoparticles Mediated by Polypseudorotaxane with Thiolated β‐Cyclodextrin

Summary: A water‐soluble gold nanoparticle aggregate 2 was prepared by chloroauric acid and a polypseudorotaxane 1 of mono‐6‐thio‐β‐cyclodextrin with poly(propylene glycol) bis(2‐aminopropyl ether) ( ≈ 2 000) in the presence of sodium borohydride in N,N‐dimethylformamide (DMF) solution. The investigative results indicated that the gold nanoparticle aggregate 2 might act as an efficient DNA‐cleavage reagent.

A typical TEM image of gold nanoparticle aggregate 2 .     

Regioregularity in Poly(3‐alkoxythiophene)s: Effects on the Faraday Rotation and Polymerization Mechanism

Summary: Poly(3‐alkoxythiophene)s with different degrees of regioregularity were prepared using three different methodologies. It is shown that their Faraday rotation is highly dependent on the degree of regioregularity. The origin of the differences in regiospecificity of the methodologies is discussed.

Structure of the polymer pol 3 .     

Supramolecular Gels Based on Multi‐Walled Carbon Nanotubes Bearing Covalently Attached Cyclodextrin and Water‐Soluble Guest Polymers

The preparation of associative networks containing multi‐walled carbon nanotubes (MWCNTs) with covalently attached cyclodextrin (CD) rings and poly[(isobutylene)‐co‐(maleic anhydride)‐co‐(maleic acid‐(4‐tert‐butylphenyl)amide)] in water is described in this study. The synthesis of CD containing MWCNTs is realized by an amidation reaction of oxidized MWCNTs with propargylamine followed by a 1,3‐dipolar cycloaddition with CD‐azide. Dispersion behavior indicated the high stability of these networks. An increase in viscosity compared to a solution of pure polymer as a cause of network formation is observed. The addition of a CD‐decomposing enzyme (taka‐diastase from Aspergillus oryzae) let the network collapse and results in sedimentation of the modified MWCNTs.

     

Environmentally Friendly Negative Resists Based on Acid‐Catalyzed Acetalization for 193‐nm Lithography

Novel water‐developable negative resists were designed to induce both crosslinking and polarity change upon exposure and bake. The matrix polymers were synthesized by copolymerization of glyceryl methacrylate and methacrolein. The acid‐catalyzed acetalization of the polymer induced crosslinking, polarity change, and an increase in dry‐etch resistance. The resist formulated with this polymer and cast in a water/ethanol mixture showed 0.7 μm line and space patterns using a mercury–xenon lamp in a contact printing mode and pure water as a developer.

The acid‐catalyzed acetalization of poly(GMA‐co‐MA) to form the water‐insoluble acetal.     

Low‐Density Polyethylene (LDPE) Surface With a Wettability Gradient by Tuning its Microstructures

Summary: We describe an interesting approach to the fabrication of wettability gradients from hydrophobicity to superhydrophobicity in low‐density polyethylene (LDPE) films by first forming high porosity surfaces and placing the specimens onto linear temperature gradients. While the polymer chosen for the study is non‐polar, its microporous layer provides sufficient superhydrophobicity. Lateral gradient heating of the layer results in partial melting of the polymer and correspondingly decreases porosity thus decreasing hydrophobicity.

     

Silyl‐Terminated Ethylene‐co‐Norbornene Copolymers by Organotitanium‐Based Catalysts

Ethylene (E) and norbornene (N) were copolymerized in the presence of PhSiH₃ as chain‐transfer agent with [Ti(η⁵:η¹‐C₅Me₄SiMe₂NBu^t)(η¹‐Me)₂] precatalyst combined with [Ph₃C][B(C₆F₅)₄]. The silane was introduced at chain‐ends of E‐co‐N copolymers with concomitant reinitiation of the growing polymer chain. The concentrations of the silane and polymer molecular weight are inversely correlated. The characteristic signals of  SiH₂Ph chain‐ends were observed by ¹H NMR. The Si heteroatom is predominantly adjacent to ethylene units in E‐co‐N copolymers with high N content.

     

Synthesis and Characterization of Novel Biodegradable Copolymers of 5‐Benzyloxy‐1,3‐dioxan‐2‐one and Glycolide

A series of novel biodegradable random copolymers of 5‐benzyloxy‐1,3‐dioxan‐2‐one (5‐benzyloxy‐trimethylene carbonate, BTMC) and glycolide were synthesized by ring‐opening polymerization. The copolymers were characterized by nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC). The incorporation of BTMC units into the copolymer chains results in good solubility of the polymers in common solvents. The in vitro degradation rate can be tailored by adjusting the composition of the copolymers.

The in vitro degradation of the homopolymers and poly(BTMC‐co‐GA) copolymers.