The dynamic rheological measurements have been a preferred approach to the characterization of the structure and properties for multi-component or multi-phase polymer systems, due to its sensitive response to changes of structure for these heterogeneous polymers. In the present article, recent progresses in the studies on dynamic rheology for heterogeneous polymer systems including polymeric composites filled with inorganic particles, thermo-oxidized polyolefins, phase- separated polymeric blends and functional polymers with the scaling and percolation behavior are reviewed, mainly depending on the results by the authors’ group. By means of rheological measurements, not only some new fingerprints responsible for the evolution of morphology and structure concerning these polymer systems are obtained, the corresponding results are also significant for the design and preparation of novel polymer-based composites and functional materials.

A novel ordered reactive oligomeric ladderlike copolymethyl-aminopropylsilsesquioxane (Me-AP-T), was successfully synthesized by an efficient hydrosilylation graft reaction of 1,1,1-trimethyl-N-2-propenyl-silanamine with a reactive oligomeric ladderlike copolymethyl-hydrosilsesquioxane (Me-H-T), which was prepared by “supramolecular chemistry-dictated stepwise coupling polymerization” process. FT-IR, 1H- and 29Si-NMR spectra show that hydrosilylation reaction proceeds completely. Moreover, 1H-NMR spectra also indicate that both the molar ratios of ≡SiMe group to Si―H and ≡SiMe group to ≡SiPrNH2 are approximately 1:1 respectively based on the ratio of integrated resonance areas of the different groups. XRD analysis and 29Si-NMR spectra are used for investigating the ladderlike structure of the polymers. A high Tg (128.38℃) of Me-AP-T shown in DSC measurement implies that the ordered reactive Me-AP-T macromolecules have much stiff chains.

The aging property of radiation vulcanized natural rubber was studied using various kinds of antioxidants. Aging test was done at 100℃ for various lengths of time. It was found that some antioxidants are excellent in preventing the oxidative degradation of the irradiated rubber. DAH (2,5-di-tert-amylhydroquinone) + CBP (2,2-dihydroxy-3,3-di(-methyl-cyclohexyl)-5,5-dimethyl diphenyl methane) + P16 (tris(2,4-di-tert-butylphenyl)phosphate) in a proportion of (1:0.5:0.5) was found to be the best combination to achieve 100% retention of tensile strength.

The viscosity behavior of polyvinylpyrrolidone (PVP) has been determined at 25℃ in mixed solvents comprising of water/dimethylformamide (DMF) and water /methanol (MeOH). Analysis of the data has considered the PVP as being both host and guest polymer in solution. The intrinsic viscosity of PVP in DMF is higher than in water and in MeOH, but also increases in a mixed solvent with high water content because of the effect of polymer-solvent interactions. It was also found that the intrinsic viscosity of PVP at finite concentration, decreases with an increase in the concentration of PVP in solution. The viscosity behavior of PVP in a mixed solvent is affected by the concentration-dependent intermolecular excluded volume effect, which can be quantitatively expressed by the parameter, bY, which reflects the shrinkage of PVP chain coils, resulting in a decrease of . The effect of temperature on the viscosity behavior of PVP in MeOH shows that the interaction parameter increases up to a maximum value, and then decreases after a certain temperature.

Single and binary adsorption behaviors of salicylic acid and 5-sulfosalicylic acid onto hypercrosslinked polymeric adsorbents, i.e. NDA-101 and NDA-99 were investigated. The Freundlich model can successfully describe all the adsorption isotherms tested, which indicates a favorable and exothermic adsorption process. The adsorption of salicylic acid relies on p-p interaction, while the electrostatic interaction further influences the adsorption of 5-sulfosalicylic acid onto NDA-99. The adsorptive capacity of salicylic acid on NDA-99 decreases but increases on NDA-101 with 5-sulfosalicylic acid as the background component in a binary solute system. The amount of 5-sulfosalicylic acid adsorbed was decreased with the increase in initial concentration of salicylic acid on both adsorbents. The competition for the adsorption sites is considered to be predominant in the solid-to-liquid interaction process. The adsorption selectivity of salicylic acid onto NDA-101 is higher than onto NDA-99 by more than an order of magnitude. Thus, combination technique involving NDA-101 followed by NDA-99 can be effectively applied to separate and recover salicylic acid and 5-sulfosalicylic acid from wastewater.

Grafting polymer glycols onto nano-silica surface through one-step procedure was investigated. The major characteristic of this procedure is that all the materials and reagents (silica, PEG, TDI, DBTDL, solvent) required for grafting were added simultaneously into the reaction vessel. TDI and DBTDL were used as coupling agent and catalyst, respectively. The products were characterized by FTIR, TGA, elemental analyses and TEM, giving evidence for successful grafting of PEG. Possible mechanism of this grafting was studied and two grafting processes were proposed. The process through which the grafting proceeds depends on the reaction temperature. Effect of molecular weight of PEG on grafting was also investigated.

In protein molecules each residue has a different ability to form contacts. In this paper, we calculated the number of contacts per residue and investigated the distribution of residue-residue contacts from 495 globular protein molecules using Contacts of Structural Units (CSU) software. It was found that the probability P(n) of amino acid residues having n pairs of contacts in all contacts fits Gaussian distribution very well. The distribution function of residue-residue contacts can be expressed as: P(n) = P0 + aexp[-b(n - nc)2]. In our calculation, P0 = -0.06, a = 11.4, b = -0.04 and nc = 9.0. According to distribution function, we found that those hydrophobic (H) residues including Leu, Val, Ile, Met, Phe, Tyr, Cys, and Trp residues have large values of the most probable number of contact nc, and hydrophilic (P) residues including Ala, Gly, Thr, His, Glu, Gln, Asp, Asn, Lys, Ser, Arg, and Pro residues have the small ones. We also compare with Fauchere-Pliska hydrophobicity scale (FPH) and the most probable number of contact nc for 20 amino acid residues, and find that there exists a linear relationship between Fauchere-Pliska hydrophobicity scale (FPH) and the most probable number of contact nc, and it is expressed as: nc = a + b × FPH, here a=8.87, and b=1.15. It is important to further explain protein folding and its stability from residue-residue contacts.

Modification of transition metal cations to polymer-stabilized Pt colloidal clusters modified with cinchonidine was studied in enantioselective hydrogenation of methyl pyruvate. Compared to the enantiomeric excess (e.e.) value (71.4%) obtained without the presence of metal cations, obvious e.e. enhancement (up to 82.5%) was resulted from the addition of Zn2+ but with a certain decrease in activity. The reaction parameters in the presence of Zn2+ were also studied. It was found that the Pt colloidal catalysts in the presence of metal cations performed very differently from that in the absence of metal cations.

Although a number of investigations have been devoted to the analysis of silica or carbon black filled elastomer networks, little work has been done on the reinforcement of CaCO3 filled elastomer network. In this work, the reinforcement of polydimethylsiloxane (PDMS) network by using CaCO3 nano-particles was investigated. We have found a simultaneous increase of tensile strength, modulus and elongation with the increase in nano-CaCO3 content, which suggests that nano-CaCO3 particles can indeed be used as a reinforcing agent, just like silica or carbon black. Interestingly, the tensile strength, modulus and elongation were seen to leave off for the first time when the content of nano-CaCO3 particles reaches to 80%. PDMS also showed an enhanced elastic modulus and storage modulus with the increase in nano-CaCO3 content, particularly for samples with high nano-CaCO3 content. SEM was used to investigate the dispersion of the filler in PDMS matrix. A better dispersion was found for samples with high nano-CaCO3 content. A great increase of viscosity was found for samples with higher filler content, which is considered to be the reason for the good dispersion thus the reinforcement, because high viscosity will be helpful for breaking the agglomerates of fillers into small size particles under effect of shear. Our work provides a new way for the reinforcement of elastomer by using an adequate amount of nano-CaCO3 particles instead of a small quantity of silica, which is not only economically cheap but also very effective.

Synthesis and characteristics of poly(3,4-azopyridylene) (PAP), conductivity and oxygen-binding affinity of its complex with meso-a,a,a,a-tetrakis(o-pivalamidophenyl) porphyrinatocobalt(II) (CoP) were studied. PAP was prepared by oxidative polymerization of 3,4-diaminopyridine (DAP) in DMF solution using CuCl/pyridine as the catalyst. IR and NMR results showed that the peak of amido group in DAP was converted to the azo group in PAP and a p conjugated polymer was synthesized. The average molecular weight of PAP was determined to be 5.0 103. The PAP-CoP complex was prepared by complexing the pyridyl group of PAP with the fifth coordination site of CoP in DMF solution. In comparison with the CoP complex with a non-p conjugated polymer, the PAP-CoP complex shows good electroconductivity of 5.8 10-6 S cm-1. The PAP-CoP complex displays a reversible change in the UV-Visible absorption spectrum from the deoxy form to the oxy or oxygen-binding one with an isosbestic point, in response to the partial oxygen pressure of the atmosphere. The oxygen-response behavior was monitored at the absorbance ascribed to the oxy form at 548 nm to give the oxygen-binding affinity. The oxygen-binding equilibrium curves of PAP-CoP complex obey a Langmuir isotherm. DMF has great effects on the oxygen-binding properties of the PAP-CoP complex. The oxygen-binding affinity of PAP-CoP complex in the solid state is higher than that in DMF solution. With decreasing temperature, the oxygen-binding affinity of the PAP-CoP complex increases.

The isothermal crystallizations of three kinds of commercial isotactic polypropylene have been studied by DSC and rheometric experiments, in a range of temperatures where the rate of crystallization is moderate. As the crystallization proceeds, volume contraction induces tensile force upon the parallel plates. The tensile force relaxed quickly in liquid states, but after a critical amount of the relative crystallinity, it starts to accumulate in the static test, that is, with the motionless parallel plates. A new method to determine the liquid-solid transition by the static tensile force is proposed and compared with two dynamic methods of detecting liquid-solid transition, that is, the power-law modulus theory and the yield modulus model. The tensile force method predicted considerably earlier transition than the dynamic methods, and the corresponding DSC data indicate relative crystallinity of larger than 0.2 at the transition times. The limitation of dynamic methods and other possible errors have been analyzed. While the dynamic methods are suitable for slow crystallization, the tensile force method is more appropriate for the crystallization of moderate rates. Moreover, it has the advantage of almost not disturbing the crystallizing materials before the transition.

The adsorption behavior of pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution has been investigated using a hypercrosslinked polystyrene adsorbent (NDA-99) modified by dimethylamine group as well as a nonionic macroporous adsorbent (XAD-4). The Langmuir and Freundlich isotherm models were employed to fit the experimental data to describe adsorption mechanism. It shows that NDA-99 resin exhibits an adsorption affinity for 2,4-D higher than XAD-4 resin owing to its exceptional micropore structure and the amine group of the hypercrosslinked matrix. Further studies indicate that hydrogen bonding interaction and the stronger π-π conjugation play a significant role in the course of the adsorption of 2,4-D on NDA-99 resin, which is in agreement with the IR spectroscopic results and the ΔE values of HOMO (the highest occupied molecular orbit) of adsorbent and LUMO (the lowest unoccupied molecular orbit) of adsorbate calculated from the MINDO/3 model.

In this paper, the adsorption behaviors of phenol on polymeric adsorbents (Amberlite XAD4, NDA101, and D301) were investigated in batch system at 293, 303, and 313 K, respectively. As the results shown, the adsorption isotherms of phenol on all adsorbents can be well fitted by Langmuir and Freundlich equations, which indicate a favorable and exothermic process. The adsorption capacity on a newly developed aminated adsorbent, NDA101, on which adsorption could be achieved by both hydrogen bonding interaction and π-π interaction, are higher than that on a weak base adsorbent, D301, on which adsorption could be achieved by hydrogen bonding interaction only, and on a nonpolar adsorbent, XAD4, on which adsorption could be achieved by π-π interaction only. The results of this paper indicate that the synergistic effect of some weak interactions, which occur simultaneously would contribute more to the adsorption than that occur individually.

In order to improve the nonthrombogenicity of chitin, a new monomer, N, N-dimethyl(b-hydroxyethyloxyethyl) ammonium propanesulfonate (DHAPS) was designed, synthesized and grafted onto the chitin membrane by using hexamethylene diisocyanate (HDI) as a coupling agent. Surface analysis of the grafted membranes by ATR-FTIR and XPS confirms that DHAPS has been successfully grafted onto the membrane surface. The platelet resistant property of the grafted membranes was evaluated by a platelet-rich plasma adhesion method. The results showed that platelet-adhesive resistance of the modified membrane has been greatly improved.