Block copolymer mediated synthesis of amphiphilic gold nanoparticles in water and an aqueous tetrahydrofuran medium: An approach for the preparation of polymer–gold nanocomposites

The synthesis of polymer‐matrix‐compatible amphiphilic gold (Au) nanoparticles with well‐defined triblock polymer poly[2‐(N,N‐dimethylamino)ethyl methacrylate]‐b‐poly(methyl methacrylate)‐b‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate] and diblock polymers poly(methyl methacrylate)‐b‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate], polystyrene‐b‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate], and poly(t‐butyl methacrylate)‐b‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate] in water and in aqueous tetrahydrofuran (tetrahydrofuran/H₂O = 20:1 v/v) at room temperature is reported. All these amphiphilic block copolymers were synthesized with atom transfer radical polymerization. The variations of the position of the plasmon resonance band and the core diameter of such block copolymer functionalized Au particles with the variation of the surface functionality, solvent, and molecular weight of the hydrophobic and hydrophilic parts of the block copolymers were systematically studied. Different types of polymer–Au nanocomposite films [poly(methyl methacrylate)–Au, poly(t‐butyl methacrylate)–Au, polystyrene–Au, poly(vinyl alcohol)–Au, and poly(vinyl pyrrolidone)–Au] were prepared through the blending of appropriate functionalized Au nanoparticles with the respective polymer matrices {e.g., blending poly[2‐(N,N‐dimethylamino)ethyl methacrylate]‐b‐poly(methyl methacrylate)‐b‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate‐stabilized Au with the poly(methyl methacrylate)matrix only}. The compatibility of specific block copolymer modified Au nanoparticles with a specific homopolymer matrix was determined by a combination of ultraviolet–visible spectroscopy, transmission electron microscopy, and differential scanning calorimetry analyses. The facile formation of polymer–Au nanocomposites with a specific block copolymer stabilized Au particle was attributed to the good compatibility of block copolymer coated Au particles with a specific polymer matrix. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1841–1854, 2006     

Continuous reaction system to investigate the dispersion polymerization of vinyl monomers in supercritical carbon dioxide

A laboratory‐scale continuous reaction system using a stirred tank reactor was assembled in our laboratory to study the dispersion polymerization of vinyl monomers in supercritical carbon dioxide (scCO₂). The apparatus was equipped with a suitable downstream separation section to collect solid particles entrained in the effluent stream from the reactor, whose monomer concentration could be measured online with a gas chromatograph. The dispersion polymerization of methyl methacrylate in scCO₂ was selected as a model process to be investigated in the apparatus. The experiments were performed at 65 °C and 25 MPa with 2,2′‐azobisisobutyronitrile as the initiator and a reactive polysiloxane macromonomer as a surfactant to investigate the effect of the mean residence time of the reaction mixture on the monomer conversion, polymerization rate, polymer molecular weight, and particle size distribution. The results were compared with those obtained in batch polymerizations carried out under similar operative conditions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4122–4135, 2006     

Effects of the architecture and environment on polymeric molecular assemblies of novel amphiphilic diblock copolynorbornenes with narrow polydispersity via living ring‐opening metathesis polymerization

Diblock copolymers of 5‐(methylphthalimide)bicyclo[2.2.1]hept‐2‐ene (NBMPI) and 1,5‐cyclooctadiene were synthesized by living ring‐opening metathesis polymerization with a well‐defined catalyst {RuCl₂(CHPh)[P(C₆H₁₁)₃]₂}. Unhydrogenated diblock copolymers showed two glass transitions due to poly(NBMPI) and polybutadiene segments, such as two glass‐transition temperatures at ?86.5 and 115.3 °C for poly 1a and ?87.2 and 115.3 °C for poly 1b . However, only one melting temperature could be observed for hydrogenated copolymers, such as 119.8 °C for poly 2a and 121.7 °C for poly 2b . The unhydrogenated diblock copolymer with the longer poly(NBMPI) chain (poly 1a ; temperature at 10% mass loss = 400 °C) exhibited better thermal stability than the one with the shorter poly(NBMPI) chain (poly 1b ; temperature at 10% mass loss = 385 °C). Two kinds of hydrogenated diblock copolymers, poly 2a and poly 2b , exhibited relatively poor solubility but better thermal stability than unhydrogenated diblock copolymers because of the polyethylene segments. Poly[(hydrochloride quaternized 2‐norbornene‐5‐methyleneamine)‐b‐butadiene]‐1 (poly 3a ) was obtained after the hydrolysis and quaternization of poly 1a . Dynamic light scattering measurements indicated that the hydrodynamic diameters of the cationic copolymer (poly 3a ) in water (hydrodynamic diameter = 1580 nm without salt), methanol/water (4/96 v/v; hydrodynamic diameter = 1500 nm without salt), and tetrahydrofuran/water (4/96 v/v; hydrodynamic diameter = 1200 nm without salt) decreased with increasing salt (NaCl) concentration. The effect of temperature on the hydrodynamic diameter of hydrophobically modified poly 3a was also studied. The inflection point of the hydrodynamic diameter of poly 3a was observed at various polymer concentrations around 30 °C. The critical micelle concentration of hydrophobically modified poly 3a was observed at 0.018 g dL^?1. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2901–2911, 2006     

Living anionic polymerization of N‐methoxymethyl‐N‐isopropylacrylamide: Synthesis of well‐defined poly(N‐isopropylacrylamide) having various stereoregularity

Anionic polymerization of N‐methoxymethyl‐N‐isopropylacrylamide ( 1 ) was carried out with 1,1‐diphenyl‐3‐methylpentyllithium and diphenylmethyllithium, ‐potassium, and ‐cesium in THF at ?78 °C for 2 h in the presence of Et₂Zn. The poly( 1 )s were quantitatively obtained and possessed the predicted molecular weights based on the feed molar ratios between monomer to initiators and narrow molecular weight distributions (M_w/M_n = 1.1). The living character of propagating carbanion of poly( 1 ) either at 0 or ?78 °C was confirmed by the quantitative efficiency of the sequential block copolymerization using N,N‐diethylacrylamide as a second monomer. The methoxymethyl group of the resulting poly( 1 ) was completely removed to give a well‐defined poly(N‐isopropylacrylamide), poly(NIPAM), via the acidic hydrolysis. The racemo diad contents in the poly(NIPAM)s could be widely changed from 15 to 83% by choosing the initiator systems for 1 . The poly(NIPAM)s obtained with Li⁺/Et₂Zn initiator system possessed syndiotactic‐rich configurations (r = 75–83%), while either atactic (r = 50%) or isotactic poly(NIPAM) (r = 15–22%) was generated with K⁺/Et₂Zn or Li⁺/LiCl initiator system, respectively. Atactic and syndiotactic poly(NIPAM)s (42 < r < 83%) were water‐soluble, whereas isotactic‐rich one (r < 31%) was insoluble in water. The cloud points of the aqueous solution of poly(NIPAM)s increased from 32 to 37 °C with the r‐contents. These indicated the significant effect of stereoregularity of the poly(NIPAM) on the water‐solubility and the cloud point in water © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4832–4845, 2006     

Synthesis of poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) by the competitive single‐electron‐transfer/degenerative‐chain‐transfer‐mediated living radical polymerization in water

The synthesis of a block copolymer poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) is reported. This new material was synthesized by single‐electron‐transfer/degenerative‐chain‐transfer‐mediated living radical polymerization (SET‐DTLRP) in two steps. First, a bifunctional macroinitiator of α,ω‐di(iodo)poly (butyl acrylate) [α,ω‐di(iodo)PBA] was synthesized by SET‐DTLRP in water at 25 °C. The macroinitiator was further reinitiated by SET‐DTLRP, leading to the formation of the desired product. This ABA block copolymer was synthesized with high initiator efficiency. The kinetics of the copolymerization reaction was studied for two PBA macroinitiators with number–average molecular weight of 10 k and 20 k. The relationship between the conversion and the number–average molecular weight was found to be linear. The dynamic mechanical thermal analysis suggests just one phase, indicating that copolymer behaves as a single material with no phase separation. This methodology provides the access to several block copolymers and other complex architectures that result from combinations of thermoplastics (PVC) and elastomers (PBA). From industrial standpoint, this process is attractive, because of easy experimental setup and the environmental friendly reaction medium. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3001–3008, 2006     

Design,synthesis, and characterization of main‐chain,aromatic polyesters based on 3,4‐ethylenedioxythiophene

A series of new thermoplastic polyesters based on 3,4‐ethylenedioxythiophene (EDOT) with flexible aliphatic spacers have been synthesized and characterized for the first time. The thermal properties of these polyesters based on EDOT are comparable to those of conventional polyesters based on the 1,4‐phenyl unit, indicating that EDOT is a viable replacement for the phenyl units. The glass‐transition and melting‐transition temperatures decrease monotonically with an increase in the spacer length. Theoretical calculations have revealed that the core angle for EDOT is comparable to that of unsubstituted thiophene and hence should be compatible with the formation of the mesophase. This has been confirmed experimentally by the synthesis of a main‐chain, thermotropic, liquid‐crystalline polyester based on EDOT that exhibits fluid birefringence. In fact, this is the first report in which a main‐chain, liquid‐crystalline polymer based on 3,4‐disubstituted thiophene has been successfully designed and synthesized. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3479–3486, 2006     

Random multiblock poly(ester amide)s containing poly(L‐lactide) and cycloaliphatic amide segments: Synthesis and biodegradation studies

Novel multiblock poly(ester amide)s containing poly(L ‐lactide) and cycloaliphatic amide segments were synthesized from telechelic oligomer of α,ω‐hydroxyl terminated poly(L ‐lactide), 1,3‐cyclohexylbis(methylamine), and sebacoylchloride by the “two‐step” interfacial polycondensation method. The blocky nature of PEAs was established by FTIR and ¹H NMR spectroscopies. The effect of relative content of ester and amide segments on the crystallization nature of PEAs was investigated by WAXD and DSC analyses. PEAs having lower content of PLLA, PEA 1 and PEA 2, showed a crystallization pattern analogous to polyamides, whereas PEA 3, having higher content of PLLA, showed two crystalline phases characterized by polyester and polyamide segments. Random nature of PEAs was observed from single T_g values. Biodegradation studies using the enzyme lipase from Candida Cylindracea showed higher degradation rate for PEA 3 than that for PEA 1 and PEA 2. FTIR, ¹H NMR, and DSC analyses of the degraded products indicated the involvement of ester linkages in the degradation process. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3250–3260, 2006     

Lithographic design of photosensitive polyarylates based on reaction development patterning

The factors affecting pattern‐forming properties in reaction development patterning were examined with polyarylates with various bisphenol moieties. The developability of the photosensitive polyarylates was dependent on the properties of the subtituent (R) in the bisphenol moieties. The development time decreased in the following order: R?C(CH₃)₂ > fluorenyl unit ? phenolphthalein unit > C(CF₃)₂ > SO₂. This order agreed with that of the reactivity between the polyarylates and ethanolamine, and these orders can be explained by pK_a of the bisphenol used to prepare the polyarylates. The development with NH₂? R′? OH resulted in successful positive‐tone pattern formation. However, pattern formation with the developers containing NH₂? R′? OCH₃ was unsuccessful. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2694–2706, 2006     

Investigation of sulfonated poly(ether ether ketone sulfone)/heteropolyacid composite membranes for high temperature fuel cell applications

The sulfonated poly(ether ether ketone sulfone) (SPEEKS)/heteropolyacid (HPA) composite membranes with different HPA content in SPEEKS copolymers matrix with different degree of sulfonation (DS) were investigated for high temperature proton exchange membrane fuel cells. Composite membranes were characterized by Fourier transfer infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). FTIR band shifts suggested that the sulfonic acid groups on the copolymer backbone strongly interact with HPA particles. SEM pictures showed that the HPA particles were uniformly distributed throughout the SPEEKS membranes matrix and particle sizes decreased with the increment of copolymers' DS. The holes were not found in SPEEKS‐4/HPA30 (consisting of 70% SPEEKS copolymers with DS = 0.8 and 30% HPA) composite membrane after composite membranes were treated with boiling water for 24 h. Thermal stabilities of the composite membranes were better than those of pure sulfonated copolymers membranes. Although the composite membranes possessed lower water uptake, it exhibited higher proton conductivity for SPEEKS‐4/HPA30 especially at high temperature (above 100 °C). Its proton conductivity linearly increased from 0.068 S/cm at 25 °C to 0.095 S/cm at 120 °C, which was higher than 0.06 S/cm of Nafion 117. In contrast, proton conductivity of pure SPEEKS‐4 membrane only increased from 0.062 S/cm at 25 °C to 0.078 S/cm at 80 °C. At 120 °C, proton conductivity decreased to poor 0.073 S/cm. The result indicated that composite membranes exhibited high proton conductivity at high temperature. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1967–1978, 2006