Molecular weight dependence of phase Behavior of PEO/P(EO-b-DMS) blends: Application of Sanchez-Lacombe lattice fluid theory

Molecular weight dependence of phase separation behavior of the Poly (ethylene oxide) (PEO)/Poly(ethylene oxide-block-dimethylsiloxane) (P(EO-b-DMS)) blends was investigated by both experimental and theoretical methods. The cloud point curves of PEO/P(EO-b-DMS) blends were obtained by turbidity method. Based on Sanchez-Lacombe lattice fluid theory (SLLFT), the adjustable parameter, epsilon*(12)/k (quantifying the interaction energy between different components), was evaluated by fitting the experimental data in phase diagrams. To calculate the spinodals, binodals, and the volume changes of mixing for these blends, three modified combining rules of the scaling parameters for the block copolymer were introduced.

Well-defined higher-molecular-weight polyacrylonitrile via RAFT technique in the presence of disulfide compounds as a source of chain transfer agent

Well-defined polyacrylonitrile with a higher number-average molecular weight (R.) up to 200,000 and a lower polydispersity index (PDI, 1.7-2.0) was firstly obtained via reversible addition-fragmentation chain transfer (RAFT) process. This was achieved by selecting a stable, easy way to prepare disulfide compound intermediates including bis(thiobenzoyl) disulfide (BTBDS) and bis(thiophenylacetoyl) disulfide (BTPADS) to react with azobis(isobutyronitrile) to directly synthesize RAFT agents in situ.

Regio-regular structure high molecular weight poly(propylene carbonate) by rare earth ternary catalyst and Lewis base cocatalyst

Lewis base modification strategy on rare earth ternary catalyst was disclosed to enhance nucleophilic ability of active center during copolymerization of carbon dioxide and propylene oxide (PO), poly(propylene carbonate) (PPC) with H-T linkages over 83%, and number-average molecular weight (M-n) up to 100 kg/mol was synthesized at room temperature using Y(CCl3OO)(3)-ZnEt2-glycerine catalyst and 1,10-phenanthroline (PHEN) cocatalyst. Coordination of PHEN with active Zinc center enhanced the nucleophilic ability of the metal carbonate, which became more regio-specific in attacking carbon in PO, leading to PPC with improved H-T linkages.

Fixation of carbon dioxide into aliphatic polycarbonate, cobalt porphyrin catalyzed regio-specific poly(propylene carbonate) with high molecular weight

Cobalt porphyrin complex ((TPPCoX)-X-III) (TPP = 5, 10, 15, 20-Tetraphenylporphyrin; X = halide) in combination with ionic organic ammonium salt was used for the regio-specific copolymerization of propylene oxide and carbon dioxide. A turnover frequency of 188 h(-1) was achieved after 5 h, and the byproduct propylene carbonate was successfully controlled to below 1%, where the obtained poly(propylene carbonate) (PPC) showed number average molecular weight (M-n) of 48 kg/mol, head-to-tail content of 93%, and carbonate linkage of over 99%.

The critical lowest molecular weight for PEG to crystallize in cross-linked networks

Poly(ethylene glycol) (PEG) networks were synthesized by gamma-irradiation. The crystalline behavior of PEG was investigated by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD). It was shown that the crystallinity of PEG is dramatically lower in the cross-linked, networks than in pure PEG. When the molecular weight of PEG in the networks decreased to 1000, it could not crystallize at all. Moreover, we also found that the melting temperature of PEG is greatly affected by the presence of a cross-linked network.

Effects of molecular weight, solvent and substrate on the dewetting morphology of polystyrene films

Surface morphology of polystyrene (PS) films on different substrates by spin-coating before and after annealing was observed using atomic force microscopy (AFM). The effects of polymer molecular weight, substrates, solvents, and annealing conditions on the morphology of the films were investigated. Before annealing, the grain height decreases, and simultaneously the grain diameter increases with molecular weight (M-w) within the measured molecular weight. After annealing. the situation is opposite, i.e., the grain height increases while the grain diameter decreases with M-w. Furthermore, after annealing the smaller surface roughness (Ra) was obtained. It was also found that film surface roughness (Ra) depends on the vapor pressure and dipole moment of different used solvents as well as the substrates. The experimental results show that when the used solvents have similar dipole moment but different vapor pressure, the Ra of PS film decreased with the decreasing vapor pressure of solvents whether on silicon or on mica. And when the used solvents have close vapor pressure but different dipole moment, the Ra decreased with the increasing of solvent dipole moments on both substrates.

Microwave-assisted synthesis of high-molecular-weight poly(ether imide)s by phase-transfer catalysis

A facile and rapid polycondensation reaction of disodium bisphenol A with bis(chlorophthalimide)s was preformed with a domestic microwave oven in o-dichlorobenzene by phase-transfer catalysis. The polymerization reactions, in comparison with conventional heating polycondensation, proceeded rapidly and were completed within 25 min. The polymerizations gave the corresponding poly(ether imide)s with inherent viscosities of 0.55-0.92 dL g(-1). The effects of various factors on the polymerization, such as the amount of the catalyst, the reaction time, and the microwave power were studied. The properties of the polymers were briefly characterized.

Molecular weight effects on the phase morphology of PS/P4VP blend films on homogeneous SAM and heterogeneous SAM/Au substrates

The effects of the molecular weight of polystyrene (PS) component on the phase separation of PS/poly(4-vinylpyridine) (PS/P4VP) blend films on homogeneous alkanethiol self-assembled monolayer (SAM) and heterogeneous SAM/Au substrates have been investigated by means of atomic force microscopy (AFM). For the PS (22.4k)/P4VP (60k) system, owing to the molecular weight of PS component is relatively small, the well-aligned PS and P4VP stripes with good thermal stability are directed by the patterned SAM/Au surfaces. With the increase of the molecular weight of PS component (for the PS (582k)/P4VP (60k) system), the diffusion of P4VP is hindered by the high viscosity of PS during the fast spin-coating process. The phase separation behavior of PS/P4VP on the SAM/Au patterned substrates is similar to that on the homoueneous SAM and cannot be easily directed by the patterned SAM surfaces even though the characteristic length of the lateral domain morphology is commensurate with the stripe width.

A modified Wittig polycondensation - to high-trans- and high-molecular weight PPVs

A modified Wittig polycondensation was developed by replacing the bulky -PPh3 with -PBu3 ylide. Our studies suggested that the modified polymerization dramatically enhances trans-selectivity due to the decreased 1.3-steric interaction between butyl chain and triphenylamine group, together with the 1,2-steric interaction between the phenyl ring of the ylide and the triphenylamine group of the aldehyde. Moreover, the method also enhances high-molecular weight products by increasing the activity and solubility of the ylide.

Preparation of linear alpha-olefins to high-molecular weight polyethylenes using cationic alpha-diimine nickel(II) complexes containing chloro-substituted ligands

A series of alpha-diimine nickel(II) complexes containing chloro-substituted ligands, [(Ar)N=C(C10H6)C=N(Ar)]NiBr2 (4a, Ar = 2,3-C6H3Cl2; 4b, Ar = 2,4-C6H3Cl2; 4c, Ar = 2,5-C6H3Cl2; 4d, Ar = 2,6-C6H3Cl2; 4e, Ar = 2,4,6-C6H2Cl3) and [(Ar)N=C(C10H6)C=N(Ar)](2)NiBr2 (5a, Ar = 2,3-C6H3Cl2; 5b, Ar = 2,4-C6H3Cl2; 5c, Ar = 2,5-C6H3Cl2), have been synthesized and investigated as precatalysts for ethylene polymerization. In the presence of modified methylaluminoxane (MMAO) as a cocatalyst, these complexes are highly effective catalysts for the oligomerization or polymerization of ethylene under mild conditions. The catalyst activity and the properties of the products were strongly affected by the aryl-substituents of the ligands used. Depending on the catalyst structure, it is possible to obtain the products ranging from linear alpha-olefins to high-molecular weight polyethylenes.

Double propagation based on diepoxide, a facile route to high molecular weight poly(propylene carbonate)

Poly(propylene carbonate) (PPC) with number average molecular weight (M-n) higher than 200 kg/mol was prepared via the terpolymerization of carbon dioxide, propylene oxide and diepoxide using Y(CCl3OO)(3)-ZnEt2-glycerine coordination catalyst. When equimolar ZnEt2 and diepoxide were used, double propagation active species were generated in situ by nucleophilic attack of metal alkoxide on diepoxide, leading to PPC of doubled M-n value. The molecular weight of PPC has dramatic influence on its thermal and mechanical performances. PPC with M of 227 kg/mol showed modulus of 6900 MPa, while the modulus of PPC with M-n of 109 kg/mol was only 4300 MPa. Moreover, when M-n increased from 109 to 227 kg/mol, a 37 degrees C increase of the onset degradation temperature was observed.

Syntheses of biphenyl polyimides via nickel-catalyzed coupling polymerization of bis(chlorophthalimide)s

A facile method for the synthesis of biphenyl polyimides, which involves the nickel-catalyzed coupling of aromatic dichlorides containing imide structure in the presence of zinc and triphenylphosphine, has been developed. The polymerizations proceeded smoothly under mild conditions and produced biphenyl polyimides with inherent viscosities of 0.13-0.98 dL/g. The polymerizations of bis(4-chlorophthalimide)s with bulky side substituents gave high molecular weight polymers. Low molecular weight polymers from bis(4-chlorophthalimide)s containing rigid diamine moieties and bis(3-chlorophthalimide)s were obtained because of the formations of polymer precipitate and cyclic oligoimides, respectively. The effects of various factors, such as amount of catalyst, solvent volume, ligand, reaction temperature, and time, on the polymerization were studied. The random copolymerization of two bis(chlorophthalimide)s in varying proportions produced medium molecular weight material. The TgS of prepared polyimides were observed at 245-311 degreesC, and the thermogravimetry of polymers showed 10% weight loss in nitrogen at 470-530 degreesC.

Determination of molecular weight and molecular sizes of polymers by high temperature gel permeation chromatography with a static and dynamic laser light scattering detector

Flow-mode static and dynamic laser light scattering (SLS/DLS) studies of polymers, including polystyrene, polyethylene, polypropylene and poly(dimethylsiloxane) (PDMS), in 1,2,4-trichlorobenzene (TCB) at 150 degreesC were performed on a high temperature gel permeation chromatography (GPC) coupled with a SLS/DLS detector. Both absolute molecular weight (M) and molecular sizes (radius of gyration, R-g and hydrodynamic radius, R-h) of polymers eluting from the GPC columns were obtained simultaneously. The conformation of different polymers in TCB at 150 degreesC were discussed according to the scaling relationships between R-g, R-h and M and the rho-ratio (p = R-g/R-h). Flow-mode DLS results of PDMS were verified by batch-mode DLS study of the same sample. The presented technique was proved to be a convenient and quick method to study the shape and conformation of polymers in solution at high temperature. However, the flow-mode DLS was only applicable for high molecular weight polymers with a higher refractive index increment such as PDMS.

Liquid crystal alignment generated by linearly polarized UV light on photoactive low molecular mass compounds

Alignment films prepared from low molar mass photo-crosslinkable materials containing the cinnamate group can be used for aligning LCs after irradiating the films with linearly polarized UV light. The high contrast observed in the polarizing optical microscope between dark and bright images indicates that the alignment is quite uniform. As the photoreaction progresses. the average roughness of the films is increased. All the aggregate structures, 'lamellar crystals'. produced by the photo-crosslinking reaction are of a square shape.