Effect of Annealing Temperature on Low-temperature Toughness of β-Nucleated Polypropylene Random Copolymer/Ethylene-Propylene-Diene Terpolymer Blends

In this study, the effect of annealing temperature on the impact toughness of β-nucleated polypropylene random copolymer(PPR) and ethylene-propylene-diene terpolymer(EPDM) blends was investigated by differential scanning calorimetry(DSC), wide-angle X-ray diffraction(WAXD), dynamic mechanical analysis(DMA) and scanning electron microscopy(SEM). Interestingly, the impact strength of β-PPR/20 EPDM blend annealed at 120 ℃ is 1.8 times as high as that of unannealed samples. In addition, the crystalline structure, the relaxation of chain segments and fracture morphology of β-PPR/EPDM blends were also investigated to explore the toughening mechanism related to annealing. The results show that annealing at moderate temperatures results in the improvement of integrity of the crystal structure and the relative content of β-phase. The work provides a possible method to toughen the semicrystalline polymer at low temperatures by annealing.     

Mechanistic Insights into the Shear Effects on Isotactic Polypropylene Crystallization Containing β-Nucleating Agent

The crystalline structures and crystallization behaviors of iPP containing β nucleation agent TMB-5(iPP/TMB-5) were investigated by synchrotron radiation wide angel X-ray diffraction(SR-WAXD), differential scanning calorimeter(DSC) and polarized light microscope(PLM). It was found that α-crystallization lagged behind β-crystallization at normal temperatures, but the discrepancy reduced with increasing temperature. TMB-5 could not induce β-iPP when the nucleation agent is wrapped up with α-crystal that crystallized at high temperatures. The polymorphic composition of iPP/TMB-5 was susceptible to the introductory moment of shear. New crystallization process of β-nucleated iPP was proposed to understand the experimental phenomena which could not be explained by those reported in the literature. It was supposed that polymer crystallization initiated from mesophase, and the formations of iPP crystals involved the organization of helical conformation ordering within mesophase. It was proposed that the iPP melt contained mesophases with stereocomplex-type ordering of right-handed and left-handed helical chains which could be disturbed by shear or TMB-5, leading to different polymorphic structures.     

A DYNAMIC MECHANICAL ANALYSIS STUDY OF THE TRANSITION BEHAVIOUR OF I-PP/EPDM BLENDS

The transition behaviour of the blends of isotactic polypropylene (i-PP) with ethylene-propylene terpolymer (EPDM) containing 42 wt% propylene was investigated by dynamic mechanical analysis technique (DMA). Owing to its high propylene content, EPDM is compatible with i-PP to some degree. The interaction between the two components was strengthened. As expected, for partially compatible system the glass transition temperature of i-PP in the blends shifted to lower temperature. It was found that there existed two transitions, αEPDM and βEPDM, for the EPDM used in this work. The former was considered to be the glass transition of the random chain segments of EPDM, while the latter the local motion of the long ethylene sequences in EPDM. The unusual transition behaviour of αEPDM in the blends was explained in terms of the greater thermal expansion of EPDM and the compatibility of the two components. On the other hand, the βEPDM changed with the composition of the blends in a regular manner.     

High damping and mechanical properties of hydrogen-bonded polyethylene materials with variable contents of hydroxyls: Effect of hydrogen bonding density

Hydrogen bonding is considered to have significant effect on the interaction between polymeric chains and on the viscoelasticity of the polymeric materials. In this paper, we attempt to discuss the relationship between hydrogen bonding density and damping behavior and mechanical properties of polyethylene-based polymeric materials. For this reason, a series of pendant chain hydrogen bonding polymers(PCHBP) with different hydrogen bonding density(HBD) were prepared by quantitatively changing the content of pendent hydroxyl groups on the main chain of polyethylene. It was found that PCHBP with low HBD showed similar properties to polyethylene, indicating that the property of the materials was dependent mainly on the structure of the main chain. However, PCHBP with high HBD exhibited two tanδ peaks and a platform of loss modulus as well as a high storage modulus(about 400 MPa) at the second tanδ peak temperature, demonstrating that a polymeric material with high strength and damping properties was obtained. More importantly, the maximum of loss modulus showed a linear increase with the HBD, indicating that a higher HBD greatly improved the damping properties of the polymeric materials.     

Carbon black supported ultra-high loading silver nanoparticle catalyst for electro-oxidation and determination of hydrazine

Carbon black supported ultra-high loading silver nanoparticle catalyst (Ag/CB) was prepared by a modified ethylene glycol reduction method, using ethylene glycol as the reducing agent and sodium hydroxide as the pH adjusting agent. The X-ray diffraction, thermogravimetry and scanning electron microscopy characterizations showed that the Ag nanoparticles crystallized with a face-centered cubic structure and were densely stacked on the CB surface without aggregation, despite such a small average size (ca. 10 nm) and an ultra-high loading mass (392 wt.%). The electrochemical evaluation based on cyclic voltammetry, chronoamperometry and polarization tests revealed that the ultra-high loading Ag/CB catalyst possessed a superior electrocatalytic activity for the oxidation of hydrazine, via a diffusion-limited process and a 4-electron transfer pathway. Moreover, the chronoamperometry response on an electrode modified with this ultra-high loading Ag/CB catalyst exhibited a promising application for determination of hydrazine, due to a broad linear calibration ranging from 50 to 800 μM, a high sensitivity of 0.03795 A/ M and a low detection limit of 3.47 μM.     

Using an Inhibitor to Prevent Plasticizer Migration from Polyurethane Matrix to EPDM Based Substrate

The loss of adhesion between the propellant and insulator is one of the most important problems in solid propellant motors due to migration of plasticizer to interface of propellant and insulator. In this work, the polyurethane (PU) binder containing DOP plasticizer was used as a polymeric matrix and β-cyclodextrin (β-CD) was applied as inhibitor agent to prevent plasticizer migration from the PU matrix into the ethylene propylene diene monomer (EPDM) substrate. To increase the compatibility of β-CD and PU matrix, a derivative of β-CD has been synthesized using toluene diisocyanate (β-CD-TDI). The synthesized derivative was characterized by MALDI-MS and FTIR-ATR analyses. FTIR-ATR results confirmed the formation of bonding between β-CD and the polymeric network while the MALDIMS results showed that the synthesized derivative contained two β-CD and 7 TDI molecules bonded to β-CD. Investigation of the mechanical properties of PU modified by β-CD-TDI showed a decrease in tensile strength and an increase in elongation at break with increasing β-CD-TDI content. DMTA results showed a decrement in crosslinking density by increasing the β-CD-TDI content. Also, to investigate plasticizer migration, extraction of the DOP plasticizer from samples was performed using dichloromethane solvent and its concentration was measured by gas chromatography. The results of migration evaluation after four months showed that using β-CD as an inhibitor agent in the PU binder could prevent the migration of plasticizer to EPDM substrate.     

CO removal by two-stage methanation for polymer electrolyte fuel cell

In order to remove CO to achieve lower CO content of below 10 ppm in the CO removal step of reformer for polymer electrolyte fuel cell （PEFC） co-generation systems, CO preferential methanation under various conditions were studied in this paper. Results showed that, with a single kind of catalyst, it was difficult to reach both CO removal depth and CO2 conversion ratio of below 5%. Thus, a two-stage methanation process applying two kinds of catalysts is proposed in this study, that is, one kind of catalyst with relatively low activity and high selectivity for the first stage at higher temperature, and another kind of catalyst with relatively high activity and high selectivity for the second stage at lower temperature. Experimental results showed that at the first stage CO content was decreased from 1% to below 0.1% at 250-300 ℃, and at the second stage to below 10 ppm at 150-185 ℃. CO2 conversion was kept less than 5%, At the same time, influence of inlet CO content and GHSV on CO removal depth was also discussed in this paper.     

“LIVING”POLYMERIZATION OF BUTADIENE BY RARE EARTH COORDINATION CATALYST

In this paper, the kinetic method was used to study the polymerization of butadiene initiated by NdCl_3·3i-PrOH-AlEt_3 catalyst system, at-70, -30 and 0℃. Results obtained indicated that there are no both reactions of detectable transfer limiting molecular weight of polymers and irreversible termination with deactivation of propagation centers. It was found that polymers produced had narrow molecular weight distributions (MWD) and extremely high cis-1,4 content, and that the living chain had a very long lifetime. Block copolymers of butadiene and isoprene were prepared and characterized by means of GPC, ~(13)C NMR, and IR. It was fully proved that the polymerization of butadiene initiated by the rare earth catalyst under these conditions had a living polymerization nature.     

Hydrophobically modified polyelectrolytes Ⅲ. Reactivity ratio determination of FX14/AA, LA/AA and SA/AA

The reactivity ratios of three hydrophobia monomers, FX14, LA and SA, to a hydrophilic monomer, acrylic acid (AA), were determined. For the fluorocarbon containing hydropho-bic monomer FX14, elemental analysis was adopted to obtain the relative content of FX14 to AA. For two hydrocarbon monomers, 13C NMR was used. FR, KT linear method and EVM nonlinear method were applied in calculating reactivity ratios. It is found that the reactivity of LA and SA is lower than that of AA, for solution polymerization in cyclohexane. Whereas FX14 is more reactive than AA in benzene. Finally, the distribution of small amounts of these hydrophobic monomers along the polymeric chain is discussed and a random sequence is confirmed.     

A convenient,highly-efficient method for preparation of hydroxyl-terminated isotactic poly(propylene) and functional di-block copolymer

Both terminated functional isotactic polypropylene （iPP） and block copolymers containing iPP segment are desirable for commercial applications. This paper provides a convenient, highly-efficient method to prepare hydroxyl-terminated isotactic polypropylene （iPP-t-OH） and functional di-block copolymer containing the iPP segment through a combination of coordination polymerization and coupling reaction. The coordination polymerization was catalyzed by TiCI4/MgCI2/AIEt3 catalyst system using ZnEt2 as chain transfer agent. Further, the Zn-terminated iPP was oxidized and subsequently hydrolyzed to provide iPP-t-OH. Soxhlet extraction and 13C NMR were used to calculate the isotacticity of iPP-t-OH. The degree of polymerization and the number of hydroxyl groups at the chain end of iPP-t-OH were measured by GPC and 1H NMR. Despite the high molecular weight and heterogeneous reaction, iPP-t-OH is effectively linked with PEG-t-NCO to produce di-block copolymers. DSC analysis of the di-block copolymer shows an obvious decrease in Tm and To, which indicated that PEG was successfully linked to the terminal end of iPP.     

Multi-walled carbon nanotube as a solid phase extraction adsorbent for analysis of indole-3-butyric acid and 1-naphthylacetic acid in plant samples

In this work,a new sample pretreatment method prior to HPLC separations was developed for the determination of auxins in plant samples.Owing to its large surface area and high adsorption capacity, multi-walled carbon nanotube(MWCNT) was chosen as the adsorbent for the extraction of auxins from plant samples.In this study,two important auxins were selected as model analytes,namely indole-3-butyric acid(IRA) and 1-naphthylacetic acid(NAA).They could be extracted and concentrated due to theirπ-πstacking interactions with MWCNT.Then HPLC-UV was introduced to detect IBA and NAA after sample pretreatment.Factors that may affect the enrichment efficiency were investigated and optimized.Comparative studies showed that MWCNT was superior to C18 for the extraction of the two analytes.Validation experiments showed that the optimized method had good linearity(0.9998 and 0.9960),high recovery(81.4%-85.4%),and low detection limits(0.0030 mg/L and 0.0012 mg/L).The results indicated that the novel method had advantages of convenience,good sensitivity,high efficiency, and it was feasible for the determination of auxins in plant samples.     

Vibration-dependent Crystal Form of Isotactic Polypropylene under Nonisothermal Crystallization

A study concerning the effect of vibration on the crystal structure and morphology for isotactic polypropylene(iPP) was conducted. The crystallite size. crystal structure and crystallinity of iPP under or without vibration treatment were investigated by means of differential scanning calorimetry(DSC) and wideangle X-ray diffraction(WAXD). The results reveal that the crystallinity of the vibrated samples decreases at a high cooling rate, but it remains constant at a low cooling rate because of the chain relaxation of iPP. It has been found that vibration obviously increases the content of β-form of crystal phase and the amount of β-crystal mainly depends on the vibration amplitude.     

Preparation of AgBiVMoO/γ-Al_2O_3 Catalysts for the Partial Oxidation of Propane to Acrylic Acid by the Mixed Sol Method

A novel mixed sol method was developed for the preparation of supported catalysts. Analyses by means of XRD and BET show that a 40%AgBiVMoO/γ-Al2O3 catalyst prepared by this method possessed high specific surface area and high dispersion of the active phase. As a result, high acrylic acid selectivity of 8.5% was obtained when the catalyst was used in the reaction of propane partial oxidation to acrylic acid in a fixed-bed reactor.     

Nickel and potassium co-modified β-Mo2C catalyst for CO conversion

Nickel and potassium co-medified β-Mo2C catalysts were prepared and used for CO hydrogenation reaction. The major products over β-Mo2C were C1-C4 hydrocarbons, only few alcohols were obtained. Addition of potassium resulted in remarkable selectivity shift from hydrocarbons to alcohols at the expense of CO conversion over β-Mo2C. Moreover, it was found that potassium enhanced the ability of chain propagation with a higher C2+OH production. Modified by nickel, β-Mo-2C showed a relatively high CO conversion, however, the products were similar to those of pure β-Mo2C. When co-modified by nickel and potassium,β-Mo2C exhibited high activity and selectivity towards mixed alcohols synthesis, and also the whole chain propagation to produce alcohols especially for the stage of C1OH to C2OH was remarkably enhanced. It was concluded that the Ni and K had, to some extent, synergistic effect on CO conversion.     

Establishment of Constitutive Model of Silicone Rubber Foams Based on Statistical Theory of Rubber Elasticity

In this study, a constitutive model based on microscopic physical mechanism of silicone rubber foams was established. A theoretical statistical model of rubber elasticity considering the effect of dangling chains was modified to build this model. When a strain amplification factor(X) was introduced, the theoretical model could fit the tensile stress-strain data of mono-and bi-modal foam matrix well(Adj. R-Square = 0.9989, 0.9983). Parameters related to the polymer network, namely, average molecular weight(Mc) and volume fraction(ф) of chain segments between adjacent cross-linking points(network strands), were calculated by probabilistic method from the number-average molecular weight(Mn), vinyl content(w Vi) of the primary polysiloxanes and percent conversion(q) of vinyl groups. The primary and infinite strain amplification factors(X0, X∞) and decay exponent(z), introduced by X and related to the nanoparticles, were obtained by fitting. Inspired by the fact that the actual strain of matrix was lower than that of the foams', we introduced another item, strain hysteresis item(H, related with the foam porosity and cell structure), into the statistical model as well. With the same above values of Mc,ф, X0 and X∞, the model could also fit the compressive stress-strain data of mono-and bi-modal foams well(Adj. R-Square = 0.9948,0.9985). Interestingly, the strain hysteresis items of the mono-and bi-modal foams almost completely coincided under all experimental strains, which may be attributed to the almost equal porosity and similar cell structure of the two foams. This constitutive model may connect the macroscopic stress-strain behaviour to the parameters of microscopic molecular structures, promisingly providing a basis for the performance improvement and optimization of silicone rubber foams.     

Effects of crystallization temperature and blend ratio on the crystal structure of poly(butylene adipate) in the poly(butylene adipate)/poly(butylene succinate) blends

The effects of crystallization temperature and blend ratio on the polymorphic crystal structures of poly(butylene adipate)(PBA) in poly(butylene succinate)(PBS)/poly(butylene adipate)(PBS/PBA) blends were studied by means of differential scanning calorimetry(DSC), wide-angle X-ray diffraction(XRD) and atomic force microscopy(AFM). It was revealed that the polymorphism of PBA can be regulated by the blend ratio even in a non-isothermal crystallization process. The results demonstrate that high temperature favors flat-on α crystals, while low temperature contributes to edge-on β crystals. It was also found that the effect of blend ratio on the crystallization mechanism of PBA is well coincident with that of the crystallization temperature. The increment of PBS content in the PBS/PBA blend gives rise to more β-form crystals of PBA. For those PBS/PBA blends with low PBA content, the interlamellar phase segregation of PBA makes its molecular chains so difficult to diffuse from one isolated microdomain to another that high crystallization temperature and sufficiently long crystallization time will be required if the PBA α-type crystals are targeted.     

Fluorocarbon- containing hydrophobically modified poly(N-isopropylacrylamide)

A fluorocarbon-modified poly(N-isopropylacrylamide) has been synthesized by copolymerization of N-isopropyl acrylamide with a small amount of acrylate or methacrylate containing a perfluoroalkyl group. It was found that the hydrophilicity of macromolecular backbone is an important factor to the solution properties of the copolymers and that hydrophobic association between fluorocarbon groups is stronger than that between the corresponding hydrocarbon analogies. The viscosity of some of the copolymer solutions was very sensitive to temperature. It was dilatant at higher fluorocarbon comonomer content ( > 0.20-1.0 mol%) and was Newtonian at very low fluorocarbon comonomer content (0.03-0.2 mol% ) . Evidence for hydrophobic association of the fluorocarbon groups was obtained from the effects of adding Nad and surfactants on the solution viscosity. The LC-ST properties of these copolymers were studied by DSC method and this was also found to be consistent with hydrophobic association between the fluorocarbo     

Synthesis and characterization of yellow water-borne polyurethane using a diol colorant as extender

<正>A novel and facile method toward a series of yellow water-borne polyurethane was developed by using an intrinsically colored diol in this paper.The yellow aqueous dispersion PCLD-HENA-PU was synthesized based on isophorone diisocyanate(IPDI), polycaprolactonediol(PCLD) and 2,2-dimethylol propionic acid(DMPA) using a yellow diol N,N-bis(2-hydroxyethyl)-4-nitroaniline (HENA) as a chain extender.Due to the complete reaction of OH group in colorant HENA with NCO group in diisocyanate,a series of stable yellow polyurethanes could be obtained conveniently and easily.The structure of PCLD-HENA-PUs was confirmed by means of Fourier transform infrared spectroscopy.The UV-visible absorption analysis showed a blue shift effect of about 7 nm when HENA was blocked into polyurethane chain.The absorption intensity of PCLD-HENA-PUs increased with increasing HENA content.It was found that the tensile strength enhanced from 8.6 to 19.6 MPa with HENA content increased from 0 to 18.0%,while the extensibility decreased from 449 to 300%.The thermal gravimetric analysis presented that the initial decompose temperature began from about 250℃,and had a little increase with increasing the HENA content.     

Synthesis of polybutadienes with controllable microstructure by a novel binary Nd(3-NBSO3)3/alkylaluminum catalyst system

The polymerization of 1,3-butadiene was examined by using a novel halogen-free neodymium m-nitrobenzenesulfonate(Nd(3-NBSO3)3·donors)/alkylaluminum binary catalyst system. The catalyst showed fairly high activity and controllable selectivity. The microstructure of the resultant polymer was adjustable by variation of electron donor and/or the alkylaluminum. 13C-NMR and thermal analysis demonstrate that the produced polybutadienes have stereo-block chain structures of cis-1,4 and trans-1,4 segments with adjustable Tm and Tc. The neodymium sulfonate-based catalyst is believed to be significant in regulating the chain structure of polydienes and in exploring 1,3-diene polymerization mechanism.     

THE STUDY OF HUMAN TRANSFER FACTOR

In this paper, the study of human transfer factor is reported. We established a negative pressure dialysis method instead of ordinary dialysis for treatment of the crude leukocyte extract. Dialysate is rapidly obtained in only 5h so that a large volume of preparation is easier to handle and the chance of contamination avoided. When humau TF was incubated With human cord blood T-lymphocytes and pig lymphocytes, a very high biological activity on SRBC rosette enhancement and an increase in electrophoresis rate appeared. It suggests that these assays may be used as in vitro method of evaluation of TF activity. In our clinic, TF has been in clinical trials for 5 years and has now been administered to a large number of patients with a variety of diseases, in which cell-mediated immune responses have been compromised. We observe that TF has served an efficient immunopotentiating or immunemodulation agent.