Peroxide crosslinking of linear low-density polyethylenes with homogeneous distribution of short chain branching

Extraction and swelling experiments were carried out in order to measure the crosslinkability by dicumyl peroxide (DCP) of new homogeneous linear low-density polyethylenes (LLDPEs) with different molecular weight, branch content, and length of branches. Considering that the tertiary radicals are most probable macroradicals, our results indicate that tertiary carbons in LLDPEs could be either sites for scission reaction of effective coupling, depending upon degree of branching and to a lesser extent on degree of crosslinking. In the range of branching between 16 and n CH₃/1000 C (n ? 31 for low DCP concentration and decreases with DCP content approaching the value of 23 for the range above ca. 6 DCP moles per number average PE mole), the tertiary carbons seem to be rather the sites for effective coupling. In this range of branching an increase of crosslinkability with branch concentration and molecular weight of PE is due to the increase of crosslinking efficiency, but the scission probability is very low. At branch content exceeding the value of n CH₃/1000 C, the dominant reaction on tertiary carbons is scission, leading to a small decrease of crosslinkability with increasing branch content. The possible mechanisms favoring tertiary carbons for either coupling or scission are discussed. © 1995 John Wiley & Sons, Inc.     

Short branch effects on the creep properties of the ultra-high strength polyethylene fibers

Short branch (methyl branch) effects on the creep properties of the ultra-high strength polyethylene fibers were investigated. The temperature and the stress dependence of creep rates of several high-strength polyethylene fibers having different branch contents, which were prepared by blending of two polymers of highly and less branching, was evaluated according to a model described by Ward and Wilding, and the activation energies and the activation volumes were calculated in terms of their methyl branch contents and tensile moduli. The creep rates of ultra high strength fibers are strongly influenced by their methyl branch contents. The typical branching sample with ca.6 CH₃ units per 1000 CH₂ units shows ca. 1/20 lower creep rate than that of the less branching (1.0 CH₃ per 1000 CH₂) fiber sample at the room temperature. The activation energies of creep rate obtained by those highly branching samples are higher than those of lesser branching samples; the difference is nearly proportioal to their branch contents. Wide-angle x-ray diffraction results showed that the dimension of a-axis of unit cell increases in proportion to their branch contents. These results imply that the creep mechanism of ultra-high strength polyethylene fibers is dominated by chain slippage in the crystalline part, and also imply that some amount of methyl branch sites can be incorporated in the crystalline part in proportion to the branch content and those incorporated branch sites hinder the slippage motion of molecular chains in crystalline part, which results in the extreme lower creep rate. © 1994 John Wiley & Sons, Inc.     

Effects of Branch Content and Branch Length on Polyethylene Crystallization: Molecular Dynamics Simulation

Influences of branch content (BC) and branch length (BL) on isothermal crystallization of precisely branched polyethylene are studied by molecular dynamics simulation. Branch acts as a defect both in nucleation and crystal growth process. BC affects not only crystallization kinetics but also final morphologies. Crystallization rate and crystallinity decrease as BC increases. Morphology Regimes change from lamellae crystal to bundle crystal at critical BC (20/1000 C) because of different folding pattern. 50 CH₂ is the critical methyl sequence length to form lamellae crystal. Lamellae thicknesses of final morphologies decrease in gradient corresponding to Morphologies Regimes. BL has no influence on the crystallization kinetics, and only affects the final morphologies when more branches inclusion happens with BL increasing. Trans‐rich phenomenon in pre‐crystalline state is observed. Crystallization process begins at the end of induction stage when trans state population reaches a critical value, and this value is independent of BC and BL.     

Branching degree and rheological response correlation in peroxide‐modified linear low‐density polyethylene

Correlations between rheological behavior and degree of long chain branching (LCB) of linear low‐density polyethylene (LLDPE) upon a peroxide (dicumyl peroxide [DCP]) modification process under various conditions are discussed in this paper. The gel content analysis revealed negligible insoluble crosslinked fraction implying that incorporation of DCP to LLDPE predominately leads to branching rather than crosslinking. The slight changes in average molecular weight and molecular weight distribution induced by peroxide modification under various conditions revealed that formation of low‐molecular‐weight fractions due to chain scission is also negligible. The changes in terminal, trans, and pendant double bonds concentration of the modified samples with different amounts of peroxide were well depicted by Fourier transform infrared spectroscopy. Considering insignificant changes in molecular weight and molecular weight distribution during peroxide modification, the deviation observed in zero‐shear‐rate viscosity (η₀) values of the modified LLDPE with that of power‐law equation related to the linear PEs could be reliably attributed to the presence of LCB in the peroxide modified samples. Increasing the DCP content at roughly constant molar mass led to increasing of η₀ values as a result of increased degree of LCB. The increase in η₀ values was ascribed to prolonged relaxation times of the polymer molecules due to the retarded reptation motion‐driven relaxation mechanism. Copyright © 2014 John Wiley & Sons, Ltd.     

EFFECT OF IRRADIATION TEMPERATURE ON GENERAL EQUATION OF SOL FRACTION-DOSE RELATIONSHIP FOR FLUOROPOLYMERS

In this paper, the effect of irradiation temperature on sol fraction-dose relationship of tluoropolymers was studied. It was found that the increasing of irradiation temperature can result in the decreasing of βvalue of fluoropolymer, which increases the crosslinking probability of fluoropolymer. The relationship between crosslinking parameter βand irradiation temperature (T_i)of fluoropolymer is established as follows:β=2.2×10~(-3) T_g+4×10~(-4)(T_g-T_i)+0.206.values of some tluoropolymers calculated from the above expression are in agreement with the experimental values.     

Studies on diphenylguanidine–accelerated sulfur vulcanization of styrene butadiene rubber in the presence and absence of dicumylperoxide

Diphenylguanidine (DPG) raises the rate of decomposition of dicumylperoxide (DCP) and the crosslinking maxima due to DCP is lowered to some extent by DPG. When the molar proportion of DPG–S is approximately 1:1, no additive results of crosslink formation (as reported for NR) are observed. Zinc oxide and stearic acid increase the rate of crosslinking as well as the crosslinking maxima. In the present study it appears most probable that DPG-accelerated sulfuration of SBR is an ionic process. At a constant level of DCP and sulfur crosslink density increases when the amount of DPG is increased; a constant level of DCP and DPG crosslinking increases with rising sulfur concentration. An increase in the concentration of DPG or sulfur leads to greater formation of the complex as well as a change in its composition. The effect of DPG is more pronounced, for by reducing the number of sulfur atoms more sulfur is available for crosslinking. Sulfur absorbs little SO₂ or H₂S; if it is already saturated, there is no perceptible effect. DPG does absorb H₂S or SO₂ and the rate and maxima of crosslinks is increased. The effect of SO₂ is higher because of the higher K_a values of H₂SO₃ and consequently higher concentration of HSO₃^?. Reversion is a free-radical process inhibited by free DPG present in the system. In the presence of zinc oxide and stearic acid the reaction follows a polar mechanism as well as a radical mechanism.     

Studies of accelerated sulfur vulcanization of styrene–butadiene rubber by N-cyclohexylbenzothiazol-2-sulfenamide in the presence and absence of dicumyl peroxide

This study embodies the results and discussion of a comprehensive and systematic investigation of the mechanism of sulfuration of styrene–butadiene rubber accelerated by N-cyclohexylbenzothiazole-2-sulfenamide (CBS) with and without activators. Dicumyl peroxide (DCP) has been taken as a chemical aid to distinguish between free-radical and polar mechanisms of sulfuration. The rate constant for DCP decomposition in presence of CBS and the reduction in crosslink density by CBS have also been studied. With a constant amount of DCP and sulfur the crosslink density increases with increasing CBS concentration. In the presence of ZnO and stearic acid, crosslinking proceeds faster than in a similar system without these ingredients, and with DCP the crosslinks are found to be formed nearly additively as confirmed by methyl iodide treatment of the vulcanizates. In the absence of DCP, the crosslinking is characterized by an induction period, even in presence of ZnO and stearic acid. In the presence of sulfur, the 2-mercaptobenzothiazole (MSH) or amine or amine salt form crosslinkins by ionic reaction.     

Temperature-sensitive poly(vinyl methyl ether) hydrogel beads

Temperature-sensitive hydrogel beads were prepared by radiation crosslinking of poly(vinyl methyl ether) PVME spheres wrapped in Ca-alginate. The obtained gel beads have diameters in the sub-millimeter or millimeter range (depending on the PVME concentration). They were characterized by sol-gel analysis, swelling measurements, and differential scanning calorimetry. The gel content g increases with increasing radiation dose D. The swelling degree Q_v decreases with increasing PVME concentration c_p and increasing D. In comparison to PVME bulkgels the phase-transition temperature of the synthesized PVME gel beads is a little decreased.     

The drawing behavior of polyethylene copolymers

The tensile drawing behavior of a range of selected polyethylene copolymers has been studied. Sheets were prepared by quenching molten polymer into cold water. Two-centimeter-gauge-length samples were then drawn in air at 75 or 115°C in an Instron tensile testing machine at a crosshead speed of 10 cm/min. It was found that even at the very low concentration of one side branch per 1000 carbon atoms there was a very marked effect on the strain hardening behavior and the maximum draw ratio that could be achieved. The reduction in draw ratio increased with increasing branch concentration, and long branches were more effective than short branches in limiting the draw ratios achieved. The similarity between these effects and the effects of increasing M?_w or radiation crosslinking is noteworthy. This suggests that even a very small concentration of branches can significantly reduces the moleculer motions required for the process of plastic deformation. The Young's modulus/draw ratio relationship follows a pattern virtually identical to that observed in the case of homopolymers.     

Effect of the length of branches on hydrodynamic and conformational properties of hyperbranched polycarbosilanes

The hydrodynamic and conformational properties of hyperbranched polycarbosilanes with different lengths of branches, namely, poly(methyl(allyl)carbosilane) containing three CH₂ groups between branching centers and poly(methyl(undecenyl)carbosilane) whose branches are composed of 11 CH₂ groups, have been studied in dilute solutions in hexane using the methods of molecular hydrodynamics and optics. Fractions with M < 17.5 × 10⁴ have been used in experiments. The hydrodynamic properties of the above polycarbosilanes differ significantly from those of linear polymers since hyperbranched macromolecules are compact and their shape differs only slightly from spherical. The lengthening of chains between branching centers causes a change in the hydrodynamic characteristics, and the difference between hyperbranched polymers and dendrimers becomes more pronounced. As the length of branches increases, their conformation changes from an extended trans chain to a more or less bent rod.     

A pulsed field gradient NMR study of diffusion in semicrystalline polymers: self-diffusion of alkanes in polyethylenes

By means of the pulsed field gradient NMR technique the self-diffusion of six alkanes (from n-butane to n-pentadecane) in three low density polyethylenes and one high density polyethylene differently thermally treated was examined. The concentration dependence could be described very satisfactorily with the free volume theory in the form of Fujita (Adv. Polymer Sci. 3(1961) 1). The parameter B of the diffusants and the fractional free volumef ₂ of the polyethylenes were determined from the experimental data. The fractional free volumesf ₂ show a strong dependence on the type of polyethylene, the main influence results from the different content of CH₃ groups or short chain branches. The diffusion coefficient extrapolated to zero diffusant concentration is proportional to the eighth power of the amorphous content. This strong dependence shows that the free volumes of the amorphous parts of the polyethylenes are intimately connected with crystallinity, both determined by the different degrees of short chain branching. The pre-exponential factor in the free volume expression decreases with increasing amorphous content of the polyethylenes and increases with increasing length of the diffusants. It was found that the spherulite boundaries in the polyethylenes do not act as diffusion barriers.     

Preparation and Characterization of trans‐1,4‐Polybutadiene Nanocomposites Containing in situ Generated Silica

Abstract

trans‐1,4‐Polybutadiene (tPBD) networks crosslinked free radically with dicumyl peroxide (DCP) were reinforced by in situ silica formed in a two‐step sol–gel technique. Changing the degree of crosslinking by changing the amount of DCP, or changing the amounts of the sol–gel components [tetraethoxysilane (TEOS) and dibutyltin diacetate (DBTDA)], changed the silica generated with regard to the amount precipitated, particle size, and degree of dispersion. Stress–strain measurements in continuous extension indicated good reinforcement, even at relatively low amounts of silica. Differential scanning calorimetry (DSC) indicated decreases in heat of crystallization with increases in the amounts of silica, but thermogravimetric analysis showed initial decomposition temperatures (IDT) remained relatively constant. Suggestions are made regarding interpretation of these properties in terms of the composite morphologies.     

Unit cell dimensions in model ethylene-butene-1 copolymers

The lattice parameters of a series of hydrogenated polybutadiene (HPB) model copolymers is measured as a function of branch content between 0 and 73 ethyl branches per 1000 C atoms. Expansion of the a and b axes nearly ceases for branch contents greater than 20 per 1000 C atoms. The c axis is seen to contract by a small amount with increased branching. The major cause of lattice expansion is limitation of crystal thickness by exclusion of branch points from the lamellar crystals coupled with surface stress on thin lamellae. A small fraction of ethyl branches are incorporated in the crystal; these expand the lattice by an additional amount.     

Formation,structure, and elasticity of loosely crosslinked epoxy-amine networks. II. Mechanical and optical properties

The mechanical and optical behavior in the dry and swollen states of loosely crosslinked epoxy networks prepared from the diglycidyl ether of bisphenol A, phenylglycidyl ether, and 4,4′-diaminodiphenylmethane was investigated, and the weight fraction of sol in the networks was determined. The crosslinking density was controlled by an excess of diamine and by the fraction of monoepoxide. The reaction proceeded to almost full conversion of epoxy groups. With increasing content of monoepoxide or with increasing excess of diamine, the main transition region is shifted to lower temperatures. The dependence of the viscoelastic modulus on temperature and the optical behavior indicate that the networks are homogeneous. In all cases, the sol fraction is adequately described by the theory of branching processes (cf. Part I). The equilibrium modulus related to the dry state is the same irrespective of whether it is obtained by measurements in the dry or swollen state. The mechanical behavior in the rubbery state can be described by the theory of phantom networks with fully suppressed fluctuations of crosslinking (front factor A = 1) or by the theory of phantom networks with fully released fluctuations of crosslinks (front factor) A = f_e?2/f_e] and contribution of trapped entanglements of the Langley-Graessley type (cf. Part I). In the analysis of the equilibrium behavior, it is advantegeous to use the plot of superimposed dependences of G_e on the gel fraction, which considerably reduces the effect of experimental inaccuracy in determination of composition and degree of conversion.     

Dynamic mechanical behavior of acrylonitrile butadiene rubber/poly(ethylene‐co‐vinyl acetate) blends

The dynamic mechanical behavior of uncrosslinked (thermoplastic) and crosslinked (thermosetting) acrylonitrile butadiene rubber/poly(ethylene‐co‐vinyl acetate) (NBR/EVA) blends was studied with reference to the effect of blend ratio, crosslinking systems, frequency, and temperature. Different crosslinked systems were prepared using peroxide (DCP), sulfur, and mixed crosslink systems. The glass‐transition behavior of the blends was affected by the blend ratio, the nature of crosslinking, and frequency. sThe damping properties of the blends increased with NBR content. The variations in tan δ_max were in accordance with morphology changes in the blends. From tan δ values of peroxide‐cured NBR, EVA, and blends the crosslinking effect of DCP was more predominant in NBR. The morphology of the uncrosslinked blends was examined using scanning electron and optical microscopes. Cocontinuous morphology was observed between 40 and 60 wt % of NBR. The particle size distribution curve of the blends was also drawn. The Arrhenius relationship was used to calculate the activation energy for the glass transition of the blends, and it decreased with an increase in the NBR content. Various theoretical models were used to predict the modulus of the blends. From wide‐angle X‐ray scattering studies, the degree of crystallinity of the blends decreased with an increasing NBR content. The thermal behavior of the uncrosslinked and crosslinked systems of NBR/EVA blends was analyzed using a differential scanning calorimeter. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1556–1570, 2002     

Postgel properties in the statistical crosslinking of heterochains. I. Systems with N types of chains

The heterochain crosslinking model describes nonrandom crosslinking of polymer chains and is an extension of the classical Flory/Stockmayer gelation theory. We consider the postgelation relationship for the system consisting of N types of polymer chains, in which the probability that a crosslink point on an i‐type chain is connected to a j‐type chain is explicitly given by p_ij. The analytical solutions for the weight fraction of the sol, the number‐average and weight‐average molecular weights within the sol fraction, and the crosslinking density within the sol and gel fractions are derived for the systems, with each type of chain conforming to the Schulz–Zimm distribution. Illustrative calculations are shown for the systems consisting of two and three types of chains, and the obtained results agree with those from the Monte Carlo method. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2333–2341, 2000     

Crosslinking kinetics of polyethylene with small amount of peroxide and its influence on the subsequent crystallization behaviors

Crosslinking reactions of high density polyethylene with low peroxide concentrations ranging from 0.1 wt% to 1.0 wt% at temperatures of 170, 180 and 190 ° C were monitored by rheological measurements. A critical gel forms at the peroxide concentration of 0.2 wt%, where the transition from long chain branching generation to crosslinking network formation could occur. Rheokinetics of crosslinking can be fitted well by Ding-Leonov's model. The curing rate k_2 at the earlier stage exhibits about 3 times acceleration per 10 °C with increasing temperature, while the equilibrium modulus G′ at the fully cured stage is almost independent of temperature. Influences of crosslinking on the subsequent crystallization behaviors were detected by DSC measurements. Above the critical gel concentration, crystallization is largely retarded as evidenced by the lower crystallization temperature Tc and crystallinity X_c due to the network formation. The secondary crystallization valley located at the temperature near 80 °C can be observed above the critical concentration, which becomes more evident with the increasing peroxide concentration and curing temperature. This phenomenon provides another evidence of crystallization retardation by the crosslinking network.     

Synthesis of highly branched polyethylene using para‐phenyl‐substituted α‐diimine nickel catalysts

A series of para‐phenyl‐substituted α‐diimine nickel complexes, [(2,6‐R₂‐4‐PhC₆H₂N═C(Me))₂]NiBr₂ (R = ⁱPr ( 1 ); R = Et ( 2 ); R = Me ( 3 ); R = H ( 4 )), were synthesized and characterized. These complexes with systematically varied ligand sterics were used as precatalysts for ethylene polymerization in combination with methylaluminoxane. The results indicated the possibility of catalytic activity, molecular weight and polymer microstructure control through catalyst structures and polymerization temperature. Interestingly, it is possible to tune the catalytic activities ((0.30–2.56) × 10⁶ g (mol Ni·h)^?1), polymer molecular weights (M_n = (2.1–28.6) × 10⁴ g mol^?1) and branching densities (71–143/1000 C) over a very wide range. The polyethylene branching densities decreased with increasing bulkiness of ligand and decreasing polymerization temperature. Specifically, methyl‐substituted complex 3 showed high activities and produced highly branched amorphous polyethylene (up to 143 branches per 1000 C).     

Kinetics of the CH3O2 + HO2 reaction: A temperature and pressure dependence study using chemical ionization mass spectrometry

A temperature and pressure kinetic study for the CH₃O₂ + HO₂ reaction has been performed using the turbulent flow technique with a chemical ionization mass spectrometry detection system. An Arrhenius expression was obtained for the overall rate coefficient of CH₃O₂ + HO₂ reaction: k(T) = (3.82^+2.79_?1.61) × 10^?13 exp[(?781 ± 127)/T] cm^?3 molecule^?1 s^?1. A direct quantification of the branching ratios for the O₃ and OH product channels, at pressures between 75 and 200 Torr and temperatures between 298 and 205 K, was also investigated. The atmospheric implications of considering the upper limit rate coefficients for the O₃ and OH branching channels are observed with a significant reduction of the concentration of CH₃OOH, which leads to a lower amount of methyl peroxy radical. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 571–579, 2007     

On the evidence of crosslinking in methyl pendent PBZT fiber

In order to influence the compressive strength of the rigid rod polymeric fibers, methyl pendent poly(p-phenylene benzobisthiazole) fibers have been heat treated in the 400 to 550°C temperature range in air and in nitrogen for varying times to achieve intermolecular crosslinking. These fibers have been examined using Fourier transform infrared (FTIR) spectroscopy, ¹³C solid-state nuclear magnetic resonance (NMR) swelling behavior, and scanning electron microscopy. ¹³C NMR has also been carried out on solutions of as-spun fibers. Fibers heat-treated at 400°C, both in nitrogen and in air, up to heat-treatment times of 60 min are insoluble in 99% chlorosulfonic acid, however no direct evidence of crosslinking has been obtained for these fibers using spectroscopic techniques, suggesting that in these fibers the degree of crosslinking must be very low. Evidence that methyl groups are precursors to certain crosslinks was first seen via a weak methylene resonance in ¹³C solid-state NMR, corresponding to about 2% of the original methyl intensity, in a sample heat-treated at 450°C in air. Fibers heat-treated in nitrogen at 550°C for 10 minutes do not exhibit any swelling in chlorosulfonic acid, are brittle, have lost most methyl groups; however, some CH₂ groups form. In this fiber, the carbon intensity for the CH₂ group in the ¹³C solid-state NMR is 18% of the intensity for the CH₃ group in the as-spun fiber. The fibers heat-treated at 400 and 450°C show a fibrillar morphology, while the fibrillar morphology is not observed in the fibers heat-treated at 550°C in nitrogen for 10 min. Based on this work, it is our judgment that if heat treatment of this material is to improve compressive strength, the heat treatment protocol of time and temperature will probably be critical and the highest temperatures of exposure will probably lie in the 450 to 550°C range. © 1996 John Wiley & Sons, Inc.