Study on degrees of mesomorphic zone of polymer.Ⅰ.Determination of degrees of crystallinity of Eucommia ulmoides gum and natural rubber by dynamic mechanical thermal analysis

According to the two-phase model theories of polymer crystallization, the degree of crystallinity of natural rubber (NR) induced to crystallize at −25 °C can be directly determined by dynamic mechanical thermal analysis (DMTA) by testing its tanδ peak areas of crystalline state and 100% amorphous state respectively. The degree of crystallinity is 86% when the induction time increases to 12 h. However, due to the tanδ peak area of 100% amorphous state cannot be measured by DMTA directly, the degree of crystallinity of Eucommia Ulmoides (EU) gum can only be determined indirectly with DMTA by using the tanδ peak areas of 100% amorphous state extrapolated from the linear equation (y = ax + b) which is derived from the relationship between tanδ peak areas and crosslink densities. The degree of crystallinity is 87%, which is very close to NR. The crystallization of NR can be prevented effectively by increasing slightly the crosslink density to the critical crystallization point, which is 6.20 × 10⁻⁵mol/cm⁻³ for vulcanized NR induced to crystallize at −25 °C for 4 h. However, it is very hard for EU gum to prevent the crystallization by crosslinking. Because, with increasing of the crosslink density, the EU gum will firstly show a percolation threshold, which is 53.34 × 10⁻⁵mol/cm⁻³, and the degree of crystallinity is 71.04%. Then, like NR, the degree of crystallinity of EU gum will decrease rapidly to zero by increasing the crosslink density to the critical crystallization point, which is 68.89 × 10⁻⁵mol/cm⁻³. In the end of the paper, the linear relationship of the equation is verified and the influence factors on slope a and intercept b of the linear equation are discussed as well.     

Determination of glass-transition temperatures of polymers: A modified computational scheme

A modified computational scheme is developed for estimation of the glass-transition temperatures of linear and network polymers. Contributions of atoms and atomic groups involved in the main chain and side chains of a polymer are separated. The suggested scheme makes it possible to avoid multiple corrections immanent to earlier advanced glass-transition temperature calculation models. The calculated and experimental values of glass-transition temperatures for polymers of the most diverse classes are in a good agreement; R ² is 0.998. This scheme makes it possible to substantially simplify calculations, and it is applicable to polymers of all chemical structures with repeating units containing elements C, H, O, N, F, Cl, Si, and S.     

Vibration damping materials based on interpenetrating polymer networks of carboxylated nitrile rubber and poly(methyl methacrylate)

Interpenetrating polymer networks (IPNs) based on carboxylated nitrile rubber (XNBR) and poly(methyl methacrylate)s were synthesized. Crosslinked XNBR was swollen in methyl methacrylate containing benzoyl peroxide as initiator and tetraethylene glycol dimethacrylate as crosslinking agent. The compositions of the IPNs were varied by changing the swelling time of the rubber in the methacrylate monomer. The dynamic mechanical properties of the IPNs were studied. The dynamic mechanical properties in the range 1–10⁵ Hz were obtained by the time‐temperature superposition of the data under multifrequency mode, which indicated high tan δ with good storage modulus in the entire frequency range. This indicates the suitability of these IPNs as vibration and acoustic dampers. Copyright © 2002 John Wiley & Sons, Ltd.     

Thermomechanical investigation of a thick film of aniline-formaldehyde copolymer and poly(methyl methacrylate)

A thick film of aniline-formaldehyde copolymer and PMMA is synthesized via dispersion of aniline-formaldehyde copolymer powder as filler particles in PMMA with two different concentrations. Variation of the complex elastic modulus and mechanical loss factor (tanδ) with temperature is studied. It is observed that the complex elastic modulus decreases with temperature owing to thermal expansion of films. On the other hand, tanδ increases up to a characteristic temperature beyond which it shows a decreasing trend toward melting. Transition temperature T _g of sample S₁ (pure PMMA) is found to be 80°C. In sample S₂ (1 wt % aniline formaldehyde copolymer), the peak of tanδ at a lower temperature (66°C) corresponds to glass transition temperature T _g of the PMMA matrix, while the peak of tanδ at a higher temperature (107.8°C) corresponds to T _g of a polymer chain restricted by filler particles of aniline-formaldehyde copolymer. A further increase (10 wt % aniline-formaldehyde copolymer) in the concentration of filler particles of aniline-formaldehyde copolymer results in a more compact structure and a shift of T _g to a higher temperature, 122.2°C. This shift in the glass transition temperature of thick films of aniline-formaldehyde copolymer and PMMA is dependent upon the concentration of filler particles in the sample.     

Self‐Healing Supramolecular Materials Constructed by Copolymerization via Molecular Recognition of Cavitand‐Based Coordination Capsules

The repeating guest units of poly‐(R)‐ 2 were selectively encapsulated by the self‐assembled capsule poly‐ 1 possessing eight polymer side chains to form the supramolecular graft polymer (poly‐ 1 )_n?poly‐(R)‐ 2 . The encapsulation of the guest units was confirmed by ¹H NMR spectroscopy and the DOSY technique. The hydrodynamic radius of the graft polymer structure was greatly increased upon the complexation of poly‐ 1 . The supramolecular graft polymer (poly‐ 1 )_n?poly‐(R)‐ 2 was stably formed in the 1:1 host–guest ratio, which increased the glass transition temperature by more than 10 °C compared to that of poly‐ 1 . AFM visualized that (poly‐ 1 )_n?poly‐(R)‐ 2 formed the networked structure on mica. The (poly‐ 1 )_n?poly‐(R)‐ 2 gelled in 1,1,2,2‐tetrachloroethane, which led to fabrication of distinct viscoelastic materials that demonstrated self‐healing behavior in a tensile test.     

Preparation of high damping elastomer with broad temperature and frequency ranges based on ternary rubber blends

Based on the blends of chlorinated butyl rubber (CIIR), nitrile butadiene rubber (NBR) and chloroprene rubber (CR), a kind of high damping elastomer with broad temperature and frequency ranges is prepared. CIIR/NBR binary blend is prepared to take advantage of the immiscibility and the large difference in cross‐link density of the different phases caused by the curatives and accelerators migration. The dynamic mechanical analysis reveals that the binary blend was immiscible and its loss factor (tanδ) versus temperature curves show two separated and expanded loss peaks when compared with those of pure cured CIIR and NBR. In order to improve its damping properties at room temperature, the third component CR with the polarity between CIIR and NBR was blended into the binary blend. The resulted CIIR/NBR/CR ternary blend has gained effective damping properties (tanδ > 0.3) in the temperature range of ?86.4 to 74.6°C and the frequency range of 10^?2 to more than 10⁹ Hz. Other effects on the damping properties of the ternary rubber were also studied. Copyright © 2013 John Wiley & Sons, Ltd.     

Hydrodynamic, electrooptical, and conformational properties of fullerene-containing poly(2-vinylpyridines) in solutions

For C₆₀ fullerene-containing poly(2-vinylpyridines) synthesized by anionic polymerization, the molecular mass and hydrodynamic size of macromolecules in solutions have been determined by molecular hydrodynamics (translational diffusion and viscometry) and electrooptics in dilute benzene and THF solutions. Under the same conditions in the molecular mass range (9.8–123) × 10³, the hydrodynamic behavior of linear poly(2-vinylpyridines) and their molecular-mass dependences have been examined and the conformational characteristics of macromolecules have been established. The branching of macromolecules has been characterized by comparing the properties of star-shaped fullerene-containing and linear poly(2-vinylpyridines). With consideration of the hydrodynamic data interpreted within the framework of regular star model, it is inferred that on average three to four linear polymer chains with a molecular mass of (8 ± 3) × 10³ for each chain are attached to a fullerene core of C₆₀ in molecules of fullerene-containing poly(2-vinylpyridines). The specific Kerr constant of fullerene-containing poly(2-vinylpyridines) in dilute benzene solution is ?(14 ± 1) × 10^?12 cm⁵/[g (300 V)²]. As evidenced by the electrooptical data, the incorporation of fullerene into the polymer weakens self-association of macromolecules in solution.     

Converting water absorbent polymer to alcohol absorbent polymer

In this paper, a commercial water absorbent polymer based on poly (sodium acrylate) (PAANa) was converted to an alcohol absorbent polymer. PAANa collapses in alcoholic swelling media such as ethanol and methanol. In the present paper, first, a full interpenetrating polymer network (IPN) gel was prepared through immersing PAANa hydrogel in a solution containing 2‐acrylamido2‐methyl propane sulfonic acid (AMPS), polyethylene glycol dimetahcrylate and ammonium persulfate. The second network was formed in hydrated PAANa through heating. It was synthesized in two conditions by chemical crosslinker and crosslinker‐free. The IPN was acid treated to investigate the effect of removing Na⁺ on alcohol absorbency. The synthesized IPN gels have the ability of absorbing up to 21 and 39 g/g ethanol and methanol, respectively. The samples which were synthesized using the chemical crosslinker in the second stage had more alcohol absorbency in comparison with the crosslinker‐free samples. Unexpectedly, acid treatment caused a decrease in alcohol absorbency. The IPN gels were characterized through thermogravimetric analyses (TGA) and dynamic mechanical thermal analysis (DMTA). The DMTA results confirmed the IPN structure of the gels, two distinctive peaks, which can be attributed to PAANa, and poly (AMPS) was observed in tan delta figures. TGA thermograms demonstrated that IPN had lower thermal stability in comparison with the initial PAANa, which can be attributed to higher vulnerability of SO₃H group for degradation that reduced initial decomposition temperature. Copyright © 2012 John Wiley & Sons, Ltd.     

Birefringence in solutions and films of poly[4,4'-bis(4'-<Emphasis Type="Italic">N</Emphasis>-phenoxy)diphenylsulfon]imide of 1,3 bis(3',4-dicarboxyphenoxy)benzene

Birefringence in solutions and films of poly[4,4'-bis(4''-N-phenoxy)diphenylsulfon]imide of 1,3-bis(3',4-dicarboxyphenoxy)benzene macromolecules is studied. The method of birefringence in the flow of polymer solutions in DMF allows one to determine the proper specific optical anisotropy of the repeating unit of chain β_M = +15 × 10^–27 cm³ mol/g. Spontaneous birefringence in polymer films of different thickness is studied under various incidence angles of a polarized beam. The total data analysis allows one to estimate the orientation order parameter of polymer chain fragments in the vicinity of surface S ₀ =–0.01, which is typical of flexible-chain polymers.     

Synthesis and characterization of new semifluorinated linear and hyperbranched poly(arylene ether phosphine oxide)s through B2 + A2 and AB2 approaches

A new phosphorus containing trifluoromethyl-activated bisfluoro B₂ monomer has been synthesized successfully by coupling reaction of 4-methoxyphenylphosphonic dichloride and the Grignard salt of 5-bromo-2-fluorobenzotrifluoride. This monomer was converted to linear poly(arylene ether phosphine oxide)s by nucleophilic displacement of the fluorine atom on the benzene ring with several diphenols. The B₂ monomer was further demethylated to form an AB₂ monomer which on self condensation yielded hyperbranched poly(arylene ether phosphine oxide) with identical phosphorous containing moiety. The products obtained exhibit weight-average molecular weights as high as 600,000 g mol⁻¹ in SEC. These linear and hyperbranched poly(arylene ether phosphine oxide)s showed thermal stability as high as 516 °C for 10% weight loss in TGA in nitrogen and showed glass transition temperatures up to 253 °C in DSC. All the polymers were soluble in a wide range of organic solvents, e.g., CHCl₃, THF, NMP and DMF, however, the hb sample showed a significant lower solution viscosity compared to linear samples of similar molar mass. Transparent thin films of linear poly(arylene ether phosphine oxide)s casted from dichloromethane exhibited tensile strengths up to 50 MPa, a modulus of elasticity up to 0.95 GPa and elongation at break up to 36% depending on their exact repeating unit structures. No free standing films could be prepared from the hb analogue due to the missing entanglements, but stable thin polymer films on silicon wafers with high hydrophobicity were formed which showed water contact angles as high as 91°.     

微纤形态结构对PP/PA66原位微纤复合材料流变性能的影响

利用三角形排列三螺杆挤出机(triangle arrayed triple-screw extruder,TTSE)低温原位拉伸直接挤出制备了聚丙烯/聚己二酰己二胺(PP/PA66)原位微纤复合材料.通过三螺杆挤出机内部高强度的剪切-拉伸流场,研究了不同工艺参数如PA66含量、加工温度和螺杆转速下原位微纤复合材料中纤维的直径和长径比,并分析微纤长径比对复合材料动态流变性能的影响,且着重探究微纤长径比对凝胶点形成的影响.形貌分析结果显示,工艺条件极大地影响了微纤形貌,且PA66微纤长径比随分散相含量和螺杆转速的提高逐渐增加;动态流变数据说明,随着微纤长径比的增加,复合材料低频下的储能模量明显提高且比纯PP要高,同时,低频下的损耗角正切值降低且变化趋于平缓,而Cole-Cole圆半径显著增大,此时微纤复合材料表现出类凝胶的流变行为;原位微纤自缠结形成凝胶网络,微纤长径比越大,形成临界凝胶网络所需的PA66微纤含量越低,当长径比为210时,形成凝胶点时微纤含量仅3.80 wt%.     

Direct Electrochemistry and Electrocatalysis of Hemoglobin Immobilized in a Polymeric Ionic Liquid Film

A polymer film based on polymeric ionic liquid, which was poly(1‐vinyl‐3‐butylimidazolium chloride) (poly(ViBuIm⁺Cl^?)for short), was firstly used as matrix to immobilize hemoglobin (Hb). FTIR and UV‐vis spectra demonstrated that the native structure of Hb was well preserved after entrapped into the polymer film. The Hb immobilized in the poly(ViBuIm⁺Cl^?) film showed a fast direct electron transfer for the Hb‐Fe^III/Fe^II redox couple. Based on the direct electron transfer of the immobilized Hb, polyvinyl alcohol (PVA)/Hb/poly(ViBuIm⁺Cl^?)/GC electrode displayed good sensitivity and wide linear range for the detection of H₂O₂. The linear range of the PVA/Hb/poly(ViBuIm⁺Cl^?)/GC electrode to H₂O₂ is from 3.5 to 224 μM with a limit of detection of 1.17 μM. Such an avenue, which integrated polymeric ionic liquid and redox protein via a simple method, may provide a novel and efficient platform for the fabrication of biosensors, biofuel cells and other bioelectrochemical devices.     

Multicomponent latex IPN materials: 2. Damping and mechanical behavior

The integrals of the linear loss shear modulus vs. temperature (loss area, LA) and linear tan δ vs. temperature (tan δ area, TA) were characterized for various core/shell latex particles with synthetic rubber, poly(butadiene-stat-styrene) [P (Bd/S), 90/10], and interpenetrating polymer networks (IPN) as the cores. The IPN cores were composed of P(Bd/S) (T_g ≃ − 70°C) and an acrylate based copolymer (T_g around 10°C) for potential impact and damping improvement in thermoplastics. Poly(styrene-stat-acrylonitrile) (SAN, 72/28) was the shell polymer for all these polymers. Under the same loading, for both toughening and damping controls, among the IPN core/shell, blend of separate core/shell, and multilayered core/shell polymers, the IPN core/shell polymers were the best dampers. However, the other core/shell polymers also showed higher LA values than P(Bd/S)/SAN core/shell polymer. A comparison of LA values via a group contribution analysis method was made, the effect of particle morphology and phase continuity on damping being studied. Inverted core/shell latex particles (glassy polymer SAN was synthesized first) showed much higher LA and TA values than normal core/shell ones (rubbery polymer was synthesized first). Models for maximum LA and TA behavior are proposed. The damping property was essentially controlled by the phase miscibility and morphology of the core/shell latex particles. The LA values for each peak in these multiphase materials provided some indication of the several fractional phase volumes. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1501–1514, 1997     

Volumetric properties of random copolymers. An experimental and theoretical study

The volumetric properties of five random copolymers have been studied, both experimentally and theoretically, over extended ranges of external conditions of temperature (up to 500 K) and pressure (up to 200 MPa). The experimental measurements have been conducted on a high pressure densitometer (SWO, model PVT100). In copolymers of the type vinyl chloride-co-vinyl acetate, simple linear combining rules are sufficient to describe properly the PVT behavior by using an equation of state appropriate for copolymers. This, however, is not true in copolymers of the styrene-co-acrylonitrile type where the repeating units are significantly different in size and shape. The combination of our theoretical and experimental approach permitted the assignment of equation of state scaling constants to the fictitious polymer poly(maleic anhydride). This is of importance since maleic anhydride is one of the most widely used repeating units in polymer alloying and blending. The proposed equation of state model also permits the study of systems of the type styrene-co-vinyl phenol, in which a highly complex network of hydrogen bonding is involved.     

Interpenetrating networks of conjugated ionic polyacetylenes

An interpenetrating polymer network (IPN) based on poly(N-butyl 2-ethynylpyridinum bromide) (PB2EPB) and polycarbonate-urethane (PCU) has been prepared and characterized. The simultaneous full IPNs of PCU and PB2EPB have two glass transition temperatures corresponding to those of the linear chain blends measured by DSC. This suggests immiscibility of the two networks in the IPNs. The IPNs display a multiphase morphology which is confirmed by SEM observation. The full IPNs exhibit excellent solvent resistance, good thermal stability and good mechanical properties. High UV absorption of these materials extending to the visible range and beyond indicates that the polyacetylene network is extensively conjugated. The electrical conductivity of the IPNs increases linearly with increasing polyacetylene content reaching 10^-4 S/cm. © 1996 John Wiley & Sons, Inc.     

EFFECT OF INCORPORATING STARCH/SILICA COMPOUND FILLERS INTO UNCURED SSBR ON ITS DYNAMIC RHEOLOGICAL PROPERTIES

The dynamic rheological properties of a composite composed of solution-polymerized styrene butadiene rubber (SSBR) filled with starch/silica (SiO_2) compound fillers were studied by means of temperature,frequency and strain sweeps, respectively,and the influence of the starch content in the compound fillers (SCCF) on the rheological behaviors was discussed.It is found from frequency sweeps that a maximum of loss tangent (tanδ) appears at 20 rad/s,which is independent of SCCF.G' of the composites decrease...     

Conducting polymer membranes for low activity potentiometric ion sensing

Conducting polymer (CP) films, used as ion-sensing membranes under open circuit potentiometric conditions, are usually characterised with rather high detection limit, in the range of 10⁻⁴-10⁻⁵ mol dm⁻³. This effect is unfavourable, not only from the point of view of CP applications in potentiometry as ion sensitive membranes, but also when these materials are used as ion-to-electron transducers (solid contacts) for ion-selective electrodes. The theoretical considerations presented underline the crucial role of spontaneous processes of polymer charging/discharging—the source of observed high detection limit of sensors comprising CP layer under zero current conditions. Although the mechanism of occurring process is different from that observed for plastic, solvent polymeric based ion-selective electrodes, the ultimate result—alteration of activity of electrolyte at the membrane/solution interface leading to elevation of the detection limit—is the same.The method of estimation of parameters characterising spontaneous charge transfer processes is presented. The values obtained can be used to calculate the resulting polymer/solution interface activity of electrolyte ions, thus the detection limit of CP membrane can be theoretically predicted.A method of lowering of the detection limit of conducting polymer membranes, applying galvanostatic polarisation to compensate the spontaneous process of polymer charging/discharging, is presented.The experimental results obtained for poly(pyrrole), poly(N-methylpyrrole) and poly(3,4-ethylenedioxythiophene) are in good accordance with predictions of the presented model.     

Mechanism analysis of Eucommia ulmoides gum reducing the rolling resistance and the application study in green tires

Eucommia ulmoides (EU) gum is a natural polymer material extracted from Eucommia ulmoides (EU) oliver, which can be applied in the tire industry to reduce the rolling resistance of the tread compound and save the energy. However, the mechanism is not explicit, which limits EU gum to be applied widely. Therefore, the crystallization characteristics and mechanical properties of EU gum with different cross-linking densities are studied systematically to reveal the mechanism. It is found that the “forced crystallization”, namely the crystallization of EU gum is hindered by the internal stress caused by numerous cross-linking points, is the main reason to reduce the rolling resistance. When the temperature reaches the melting point (about 60 °C), the EU gum converts into the random elastic network state immediately under the internal stress without the viscous sliding existed in the traditional molten polymer material, which greatly decreases the tanδ value at 60 °C, an index can evaluate the rolling resistance of tread material. Compared with the pure EU gum, the tanδ value at 60 °C decreases with a maximum drop of 45.2% under the forced crystallization caused by vulcanizing. However, EU gum cannot be made into tire directly for its crystallization at ambient temperature, which damages the high elastic property of tire. So EU gum is blended into natural rubber (NR) and reinforced by the carbon black. As a result, the comprehensive properties are improved when the content of EU gum is controlled lower than 30phr. Compared with NR nanocomposite, the NR/EU gum nanocomposite with 10phr EU gum can reduce the rolling resistance by 25.6% and improve the abrasion resistance by 9.5%.     

Silver and lead all-plastic sensors—polyaniline vs. poly(3,4-ethyledioxythiophene) solid contact

Silver and lead selective all-plastic ion-selective electrodes were obtained using poly(vinyl chloride)-based membranes and either poly(3,4-ethylenedioxythiophene) or polyaniline dispersion cast on an insulating plastic support as transducer and electrical lead. The effect of interactions of applied conducting polymer with analyte ions on potentiometric responses was evaluated and correlated with changes in elemental composition and element distribution within the ion-selective membrane and the conducting polymer transducer revealed in course of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) experiments. In the case of silver selective electrodes, potentiometric responses obtained are much dependent on the oxidation state of the polymer placed beneath the ion-selective membrane. For semi-oxidized polymer (poly(3,4-ethylenedioxythiophene)-based electrodes, linear responses with detection limit equal to 10^−5.4 M were obtained. For a more oxidized polyaniline (of higher conductivity), although the electrodes were pretreated exactly in the same way and tested in parallel, super Nernstian potential slope was recorded within the AgNO₃ activities range form 10⁻⁶ to 10⁻⁷ M. These responses were consistent with results of LA-ICP-MS, revealing profoundly higher silver signals intensities for poly(3,4-ethylenedioxythiophene) underlying silver selective membrane. It seems highly probable that silver is accumulated in this polymer layer as Ag⁰ due to spontaneous redox reaction leading to oxidation of the polymer; however, this process requires also the presence of silver ions at the interface. In fact, when reduced (deprotonated) polyaniline was used as transducer, the potentiometric responses of the sensor were, within the range of experimental error, the same as obtained for poly(3,4-ethylenedioxythiophene)-based sensor. On the other hand, for lead(II) selective sensors, the difference in responses of electrodes prepared using poly(3,4-ethylenedioxythiophene) or polyaniline was less pronounced, which is in accordance with the elemental composition of these sensors.     

One‐pot synthesis of polyrotaxane by clipping and cyclopolymerization of α,ω‐diethynyl isophthalamide with pyridiniumdicarboxamide chloride

The one‐pot synthesis of a main chain‐type polyrotaxane composed of axle molecules threaded through the macrocyclic units on the polymer main chain was achieved via the combination of cyclopolymerization and clipping procedures. The cyclopolymerization of an α,ω‐diethynyl monomer bearing an isophthalamide moiety ( 1 ), which clips onto an axle component bearing a pyridiniumdicarboxamide moiety ( 2·Cl ) through a chloride anion was carried out in chloroform with the monomer concentration of 0.06 mol L^?1 at 40 °C using [Rh(nbd)Cl]₂/Et₃N as a catalyst to afford a gel‐free polymer. The resulting polymer was assigned to the main chain‐type polyrotaxane with a poly(phenylacetylene) backbone (poly‐ 3·Cl ) based on size exclusion chromatography and ¹H NMR measurements. The diffusion‐order two‐dimensional NMR and circular dichroism spectra provided definitive proof of the rotaxaned architecture in the polymer. The mole fraction of the rotaxane unit in the total cyclic repeating unit was determined to be 26.3%. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011