In this work, four kinds of cellulose aliphatate esters, cellulose acetate (CA), cellulose propionate (CP), cellulose butyrate (CB) and cellulose acetate butyrate (CAB) are synthesized by the homogeneous acylation reactions in cellulose/AmimCl solutions. These cellulose aliphatate esters are used to prepare gas separation membranes and the effects of molecular structure, such as substituent type, degree of substitution (DS) and distribution of substituents, on the gas permeability are studied. For CAs, as the DS increases, their gas permeabilities for all five gases (O2, N2, CH4, CO and CO2) increase, and the ideal permselectivity significantly increases first and then slightly decreases. At similar DS value, the homogenously synthesized CA (distribution order of acetate substituent: C6 C3 C2) is superior to the heterogeneously synthesized CA (distribution order of acetate substituent: C3 C2 C6) in gas separation. With the increase of chain length of aliphatate substituents from acetate to propionate, and to butyrate, the gas permeability of cellulose aliphatate esters gradually increases. The cellulose mixed ester CAB with short acetate groups and relatively long butyrate groups exhibits higher gas permeability or better permselectivity than individual CA or CB via the alteration of the DS of two substituents.

In this work, polypropylene (PP)/octene-ethylene copolymer (POE) blends were injection-molded using the so-called dynamic packing injection technique, which imposed oscillatory shear on the gradually cooling melt during the packing solidification stage. In this way, the effect of shear on the size distribution and anisotropy of the minor phase droplets could be investigated. Besides, by using two kinds of POE with different octene contents, the effect of component miscibility was also studied. The results show that the droplet size is mainly determined by composition and miscibility, and droplet anisotropy is mainly determined by droplet size and shear. Most importantly, under the same processing condition, droplet anisotropy increases with droplet size, and there seems a linear fit between them, disregarding the miscibility factor. These results may provide guidance for preparing polymer blends with desired properties by tailoring their phase morphologies.

In order to prepare hollow latex particles with optimum morphology based on osmotic swelling principle, three-layer core/shell latex particles with 40 wt% MAA in the core were first prepared via multistep seeded emulsion copolymerization, in which monomers were added by a semi-continuous process with monomer addition under two different forms: pure monomers' mixture (monomer addition), and pre-emulsified monomers (pre-emulsion addition). Then, the hollow latex particles with different morphologies were obtained after alkali post-treatment. Influences of the monomer feeding mode on the emulsion polymerization and the particle morphology were investigated. Results showed that the pre-emulsion addition could significantly improve the polymerization stability in each step, and greatly enhance the uniformity of shell encapsulation. The sizes of the core and core/shell latex particles obtained by the pre-emulsion addition were smaller and more uniform than those synthesized by the monomer addition, and the hollow latex particles with intact morphology were generated by alkali post-treating of the core/shell latexes prepared from the pre-emulsion addition. As the core size increased, the morphology of the post-treated particles underwent evolution from hollow to collapse. Moreover, the mechanism of the particle morphological evolution was proposed.

Ca(Ⅱ) ions are added in the spinning dope to adjust the solidification rate of regenerated silk fibroin (RSF) solution during the wet-spinning process since Ca(Ⅱ) ions are proved to be favorable to maintain the stable silk fibroin network in our previous work. The results show that when Ca(Ⅱ)/RSF ratios are 1/50 and 1/20, the resulted RSF fibers exhibit good performance with the breaking energy more than 70 kJ/kg. However, higher Ca(Ⅱ)/RSF ratio (for example, 1/10) hinders the solidification of spinning dope and results in poor RSF fibers. These observations together with earlier papers from this laboratory confirm that to produce tough silk fibers the spinning conditions must allow sufficient time for the adjustment of silk fibroin molecular chains.

The polyaniline/partially phosphorylated poly(vinyl alcohol)(PANI/P-PVA) nanoparticles were prepared by the chemical oxidative dispersion polymerization of aniline monomer in 0.5 mol/L HCl aqueous media with the partially phosphorylated poly(vinyl alcohol) (P-PVA) as the stabilizer and co-dopant. The PANI/P-PVA nanoparticles were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), X-ray diffraction (XRD), electrical conductivity measurements and re-dispersion stability testing. All the results were compared with the properties of the conventional polyaniline in the emeraldine salt form (PANI ES). It was found that the feeding ratio of P-PVA obviously affected the morphology, re-dispersion stability and electrical conductivity of the PANI/P-PVA nanoparticles. When the feeding ratio of P-PVA ranged from 40 wt% to 50 wt%, the PANI/P-PVA nanoparticles showed spherical shape with good uniformity, significant re-dispersion stability in aqueous media and good electrical conductivity.

Chitosan-graft-poly(lactic acid) (CS-g-PLA) copolymer was synthesized through emulsion self-assembly in a water-in-oil (W/O) microemulsion. The water phase was composed of CS aqueous solution, while the oil phase was made up of PLA in chloroform. The W/O microemulsion was fabricated in the presence of surfactant span-80 and the self-assembly was performed between PLA and CS under the effect of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDCHCl). FTIR and 1H-NMR analysis indicated PLA was grafted onto the backbone of CS via the reaction between the carboxyl groups in PLA and the amino groups in CS. 1H-NMR characterization further revealed the grafting content of PLA was 16%. The obtained CS-g-PLA could self-assemble to form micelles, their size distributed in the range of 125-375 nm with average diameter of 142 nm. The present design integrates the favorable biological properties of CS and the excellent mechanical properties of PLA, which makes CS-g-PLA copolymer a promising candidate as a carrier for targeted bioactive molecules delivery.

A variety of linear and 3-arm star polyethylene (PE) model polymers covering a wide range of molecular weight are synthesized by the living polymerization of butadiene and the subsequent hydrogenation. Several rheological parameters of these model linear and 3-arm star PE samples are analyzed for detecting the long chain branching (LCB) structure. It is found that the analyses based on zero shear viscosity, vGP plot and flow activation energy are very sensitive to the 3-arm star PEs. The information on the presence of LCB can be obtained with these methods even for low molecular weight samples, which can not be determined by GPC-MALLS. However the information about the LCB structure can not be obtained by the rheological methods alone.

An aromatic azo-polymer, poly(thiourea-azo-sulfone) (PTAS), has been prepared using 4-(4-aminophenylsulfonyl)benzenamine and diazonium salt solution of 2,6-diaminopyridine. PTAS was easily processable using polar solvents and had high molar mass 63103 gmol-1 according to GPC. Mechanically and thermally stable and electrically conducting polymer/CNTs nano-composites were obtained via melt processing technique. Fine distribution of CNTs in a polymer matrix performed an essential role in the preparation of polymer/CNTs nano-composites based on interfacial interaction between CNTs and polymer matrix. Scanning electron micrographs showed good dispersion of filler and adhesion of matrix on the surface of nanotubes. Accordingly, increasing the amount of CNTs from 0.1 wt% to 5 wt% increased the electrical conductivity from 2.99 Scm-1 to 3.56 Scm-1. Mechanical strength of functional nanotubes-based hybrids was enhanced from 43.22 MPa to 65.02 MPa compared with that of hybrids with non-functional filler in matrix 37.21 MPa. A rapport between nanotube loading and thermal stability of the materials was also observed. 10% gravimetric loss temperature was increased from 528 ℃ to 578 ℃, while glass transition was improved from 241 ℃ to 271 ℃. Adding up of small quantity of functional CNTs strongly affected the tensile, electrical and thermal properties of materials. Improvement of the physical properties of CNT-reinforced polymer nano-composites was ascribed to the melt processing technique.

Novel functional hyperbranched poly(aryl ether ketone)s (HPAEKs) bonded with nonlinear optical chromophores (meso-tetrakis(4-hydroxyphenyl) porphyrin, THPP and its metal derivatives) were synthesized and characterized by 1H-NMR and UV-Vis absorption spectra. The incorporation of chromophores into HPAEKs endowed HPAEKs novel NLO and OL properties. Indeed, dendritic architecture allowed for maximum dispersion of the chromophores, avoided aggregation, more optical limiting property was obtained. Simultaneously, they retained the excellent properties of the materials, particularly in thermal stability. Their optical properties were evaluated by nonlinear optical analyses and optical limiting. The results showed that these polymers possessed good optical limiting (OL) property and large nonlinear optical (NLO) susceptibilities (ca. 10-12 esu). All polymers containing chromophores presented excellent thermal stability (DT5 524.17 ℃).

The copolymerizations of ethylene with 1-hexene or 1-octene by using TiCl4/MgCl2/THF catalysts modified with different metal halide additives (ZnCl2, SiCl4, and the combined ZnCl2-SiCl4) were investigated based on catalytic activity and copolymer properties. It was found that the catalyst modified with mixed ZnCl2-SiCl4 revealed the highest activities for both ethylene/1-hexene and ethylene/1-octene copolymerization. The increase in activities was due to the formation of acidic sites by modifying the catalysts with Lewis acids. Based on the FTIR measurements, the characteristic C―O―C peaks of the catalysts modified with metal halide additives were slightly shifted to lower wavenumber when compared to the unmodified catalyst. This showed that the modified catalysts could generate more acid sites in the TiCl4/MgCl2/THF catalytic system leading to an increase in activities as well as comonomer insertion (as proven by 13C-NMR). However, Lewis acid-modifications did not affect the microstructure of the copolymers obtained. By comparison on the properties of copolymers prepared with the unmodified catalyst, it was found that polymers with ZnCl2 and/or SiCl4 modification exhibited a slight decrease in melting temperature, crystallinity and density. It is suggested that these results were obtained based on the different amount of a-olefins insertion, regardless of the types of Lewis acids and comonomer.

pH-sensitive wettability of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) self assembled films, exhibiting superoleophobicity under water and hydrophilicity at low pH value, and oleophobicity under water and hydrophobicity at neutral condition, has been realized. The wettability properties resulted from the surface topological and chemical transition, which were confirmed by in situ AFM measurements under water at different pH. At low pH, P4VP chains, which were confined in the hexagonal-packed nanodomains, got protonated into a swollen state, while at high pH, P4VP chains were deprotonated into a collapsed state. The reversible protonation/deprotonation procedure on the molecular scale leads to surface topological and chemical transition, thereby pH-sensitive wettability.

Aluminum hypophosphite (AP) was used to prepare flame-retarded thermoplastic polyurethane (FR-TPU) composites, and their flame retardancy, thermal degradation and mechanical properties were investigated by limiting oxygen index (LOI), vertical burning test (UL-94), thermogravimetric analysis (TGA), cone calorimeter (CC) test, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and tensile test. TPU containing 30 wt% of AP could reach a V-0 rating in the UL-94 test, and its LOI value was 30.2. TGA tests revealed that AP enhanced the formation of residual chars at high temperatures, and slightly affected the thermal stability of TPU at high temperatures. The combustion tests indicated that AP affected the burning behavior of TPU. The peak of heat release rate (PHRR), total heat release (THR) and mass loss rate (MLR) greatly reduced due to the incorporation of AP. The tensile test results showed that both the tensile strength and the elongation at break slightly decreased with the addition of AP. The digital photos and SEM micrographs vitrified that AP facilitated the formation of more compact intumescent char layer. Based on these results mentioned above, the flame-retarding mechanism of AP was discussed. Both the self-charring during the decomposing process of AP and its facilitation to the charring of TPU led to the great improvement in the flame retardancy of TPU.

Morphology and phase compositions of different starch-gelatin blends were investigated by various microscopes: optical, SEM and synchrotron FTIR microscopy. A high amylose (80%) corn starch, grafted with hydroxypropyl to enhance flexibilty and hydrophilicity, and plasticized by poly(ethylene glycol) (PEG), was used in this work. SEM revealed that the surface became smoother after adding PEG. Optical microscopy observation revealed that compatibility between gelatin and starch was improved by adding PEG. An FTIR beam focused on a 5 m5 m detection area by the micro-spectroscope was used to map chemical composition. The ratio of areas of the saccharide bands (1180-953 cm-1) and the amide I and Ⅱ bands (1750-1483 cm-1) was used to monitor the relative distributions of the two components in the blends. The FTIR maps indicated that gelatin constituted the continuous phase up to 80% of starch content. All of the FTIR spectra showed contributions from both starch and gelatin absorptions, therefore indicating that complete demixing with pure starch and gelatin domains did not occur. The PEG improved the compatibility of the gelatin-starch blends.

Polyamide 11 (PA11) and its nanocomposites with different organoclay loadings were prepared by melt-compounding and subsequent pelletizing. The crystal phase transitions of PA11 and its clay nanocomposites were investigated by variable-temperature X-ray diffraction. It was found that the Brill transition of the nanocomposite was 20 K higher than that of the neat PA11 for both heating and cooling processes. The PA11 d-spacings of the nanocomposites were observed to be smaller than those of the neat PA11 for melt crystallization. The constraints imposed by the addition of layered clay, restricting the thermal expansion of the polymer chains, are probably responsible for such a reduction of the d-spacing.