Mechanical properties of SBR-networks: I. Determination of crosslink densities by stress-strain-measurements

The tube model is applied for the treatment of stress-strain measurements on SBR networks. It is shown that this theory allows the separation of crosslink and constraint contributions to the stress-strain behavior and, also, a reliable determination of crosslink densities. The consideration of dynamical contributions is discussed and a special numerical method is developed.     

羧基丙烯酸酯涂料合成及其防雾性能研究

采用种子乳液聚合法合成了一种互穿网络型羧基丙烯酸酯类聚物乳液，研究了加料方式对羧基分布的影响，结果表明丙烯酸加入到核单体中有利于羧基分布在乳胶粒表面。在体系中引入离子键交联结构提高了乳液涂料的硬度和耐水性能，离子键交联ＰＩＬＮ型涂料具有优良的防雾性能。     

On the Effect of Organic Substitution of Silicon Alkoxides in Poly(Vinyl Acetate) Organic-Inorganic Composites

Abstract

Organic-inorganic composites (OICs) were prepared via the in-situ polymerization of an organically (phenyl) substituted trialkoxysilane, phenyltriethoxysilane (PhTEOS), in the presence of poly(vinyl acetate) (PVAc). The mechanical reinforcement above T _g previously observed in OICs of unfunctionalized organic polymers such as PVAc with acid catalyzed in-situ polymerized tetraalkoxysilane was not observed when the tetraalkoxysilane was replaced with PhTEOS. Although both systems are optically transparent and both exhibit a high degree of hydrogen bonding between the carbonyl of PVAc and the residual hydroxyls of the silicate, the polymerization of the alkoxide is different. The tetra-functional alkoxide polymerizes to form a load-supporting silicate network, leading to a high plateau in the tensile modulus above T _g, whereas the trifunctional alkoxide reacts to form primarily low molecular weight oligomers. These increase the T _g of the PVAc but do not provide mechanical reinforcement.     

An Investigation into the Migration of Segments in Crosslinked Fluorinated Polyimide Adhesive

Crosslinked fluorinated polyimides (CFPI) were successfully synthesized to study and explore the effect of cross-linkage on the migration of fluorinated segments and on the adhesion strength. Characterization by dynamic thermomechanical analysis (DMA) and thermo gravimetric analysis (TGA) confirmed good thermal properties of CFPI. X-ray photoelectron spectroscopy (XPS) results showed that the ratio of fluorinated component (6FDA-ODA) concentration of the surface to the bulk decreased with the crosslink density. The water contact angle of CFPI was lower than that of non-crosslinked fluorinated polyimide, indicating that the migration of fluorinated groups to the surface was reduced by the presence of cross-linkage. Therefore, CFPI, with no fluorine segregation on the surface, exhibited excellent wetting of adherent surfaces and adhesion strength, which was proved by lap shear strength (LSS) measurements and scanning electron microscopy.     

Amplitude Modes in Mixed Polymers Trans [C2H2)y(C2D2) 1-y]x

Resonant Raman Scattering and doping induced IR absorption are explained in terms of amplitude modes of the 1-d gap. The RRS frequencies and relative intensities of the renormalized phonon lines at the various concentrations are readily obtained.     

Complex new materials from simple chemistry: Combining an amino‐substituted polysiloxane and carboxylic acids

Changes in rheological, adhesive, and swelling properties of quaternary salts, made by adding one of eight mono‐ or six α,ω‐alkanedioic acids (the latter with two to six or nine carbon atoms) to 6‐7PSil (a polysiloxane with 6%–7% of the monomer units contain a 3‐aminopropyl group) have been correlated with the salt structures. The simple acid‐base chemistry initiates drastic changes in the bulk properties of the materials that depend on the amount and type of the added acid. Thus, the quaternized forms of the 6‐7PSil have significantly enhanced viscoelastic and adhesive properties compared to those of the initial polysiloxane, and they can swell selectively liquids based on their polarity. Also, interpenetrating networks have been made in situ by photopolymerization of salts with vinylic carboxylic acids. DFT calculations on model systems consisting of dimethylammonium α,ω‐alkanedioate salts with two to six carbon atoms provide insights into the interactions responsible for the unexpected dependence of the properties of the 6‐7PSil salts on the chain lengths of the diacids. The potential for applying the methodologies described here to systems with other amino‐substituted polymers and other acid types is noted. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3851–3861     

Study of the Molecular Mobility in Polymers with the Thermally Stimulated Recovery Technique—A Review

Thermally stimulated recovery (TSR) is a non‐conventional mechanical spectroscopy technique that allows to analyse in detail the relaxation processes of polymeric systems in the low frequency region. This work reviews the main aspects and potentialities of this technique. The different kinds of TSR experiments that can be performed, global and thermal sampling (TS) experiments, are described and illustrated with several examples. Also, the different methods for the determination of the thermokinetic parameters (activation energy and pre‐exponential factor) of the thermal sampling (TS) procedure are explained and compared. In this context, the compensation phenomenon, which always appears in TSR results when the studies are performed in the glass transition region of a given system, is discussed. Examples of the application of this technique to different polymeric systems during the last 20 years are provided. An emphasis will be made on the analysis of the effect of crystallinity degree and crosslink density on the TSR response. A comparison between the results (characteristic times and activation energies) obtained by different techniques, namely TSR, dynamic mechanical analysis (DMA), and differential scanning calorimetry (DSC), is made.     

Effects of the type of crosslink on viscoelastic properties of natural rubber

The viscoelastic properties of various crosslinked natural rubbers, NR, were investigated by mechanical spectroscopy. The glass transition temperature, T_g, was found to be dependent on both the crosslink density and the crosslink type. Higher values of T_g were obtained for sulfur-crosslinked NR than for peroxide-crosslinked NR at the same crosslink density. The greater influence of the sulfur content on T_g may be attributed to polysulfidic crosslinks and cyclic sulfide structures favored at high sulfur contents. Sulfur-vulcanized NRs with monosulfidic crosslinks, favored at relatively high accelerator/sulfur ratios, have properties more similar to the peroxide-cured NR with simple carbon(SINGLE BOND)carbon crosslinks covalent bonds, resulting in only small shifts in T_g. A qualitative analysis of monosulfidic crosslinks and polysulfidic structures was performed with ¹³C solid-state NMR spectroscopy. The storage modulus, E′, in the rubbery plateau region increased with increasing crosslink density. However, the crosslink type did not influence the moduli values as much as it influenced the T_g values. Different methods of detecting the crosslink density were also discussed. © 1996 John Wiley & Sons, Inc.     

Alkaline Stable Anion Exchange Membranes Based on Cross-Linked Poly(arylene ether sulfone) Bearing Dual Quaternary Piperidines for Enhanced Anion Conductivity at Low Water Uptake

Alkaline stable anion exchange membranes based on the cross-linked poly(arylene ether sulfone) grafted with dual quaternary piperidine (XPAES-DP) units were synthesized. The chemical structure of the synthesized PAES-DP was validated using ¹H-NMR and FT-IR spectroscopy. The physicochemical, thermal, and mechanical properties of XPAES-DP membranes were compared with those of two linear PAES based membranes grafted with single piperidine (PAES-P) unit and conventional trimethyl amine (PAES-TM). XPAES-DP membrane showed the ionic conductivity of 0.021 S cm⁻¹ at 40 °C which was much higher than that of PAES-P and PAES-TM because of the possession of more quaternary ammonium groups in the cross-linked structure. This cross-linked structure of the XPAES-DP membrane resulted in a higher tensile strength of 18.11 MPa than that of PAES-P, 17.09 MPa. In addition, as the XPAES-DP membrane shows consistency in the ionic conductivity even after 96 h in 3 M KOH solution with a minor change, its chemical stability was assured for the application of anion exchange membrane fuel cell. The single-cell assembled with XPAES-DP membrane displayed a power density of 109 mWcm⁻² at 80 °C under 100% relative humidity.     

A novel approach to the determination of the crosslink density in rubber materials with the dipolar correlation effect in low magnetic fields

We present a novel NMR approach to the determination of crosslink densities in rubber materials. The method is based on the dipolar correlation effect (DCE) on the stimulated echo examined in a series of rubber samples and linear polyisoprene. The parameter evaluated from the echo attenuation curves is the mean‐squared dipolar fluctuation associated with anisotropic reorientations of macromolecular backbones. The contributions to the DCE of the constraints due to excluded volume effects and chemical crosslinks are estimated. A strong dependence of the mean‐squared dipolar fluctuation on the crosslink density of rubber combined with the simplicity of performing the measurements with inexpensive low‐field instruments suggests that the DCE is a useful tool for routine applications. The potential and problems of performing DCE measurements in low‐magnetic‐field conditions are discussed in detail. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2207–2216, 2001