Mechanical and thermo‐mechanical studies of double networks based on thermoplastic elastomers

A new approach to prepare and characterize double network elastomeric systems was investigated. A styrene‐ethylene‐co‐butylene‐styrene (SEBS) triblock copolymer system containing physical crosslinks was used to achieve a double network by additional crosslinking using ultra‐violet (UV) light. An ethylene–propylene–diene monomer (EPDM) terpolymer system containing chemical crosslinks was used to achieve a conventional double network using UV crosslinking. Properties from conventional monotonic tensile tests, dynamic mechanical analysis, and thermomechanical properties were investigated. These double network elastomers show a transition between competitive and collaborative behavior in their mechanical properties and lower coefficients of thermal expansion arising from a competition of the networks. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 778–789, 2010     

Fracture of model polyurethane elastomeric networks

Fracture properties of model elastomeric networks of polyurethane have been investigated with a double‐edge notch geometry. The networks were synthesized from monodisperse end‐functionalized polypropylene glycol precursors and a trifunctional isocyanate. All reagents were carefully purified and nearly defect‐free ideal networks were prepared at a stoichiometry very close to the theoretical one. Three networks were prepared: an unentangled network of short chains (M_n = 4 kg mol^?1), an entangled network of longer chains (M_n = 8 kg mol^?1) and a bimodal network with 8 kg mol^?1 and 1 kg mol^?1 chains. The presence of entanglements was found to increase significantly the toughness of the rubber, in particular at room temperature, relative to the bimodal networks and to the short chains network. Fracture experiments were carried out at different strain rates and temperatures and showed for all three networks a marked decrease in fracture toughness with increasing temperature and decreasing strain rate which mirrored reasonably well the rate and temperature dependence of tan δ, the dissipative factor. However the proportionality factor between tan δ, and G_IC was very material dependent and the shift factors obtained for the master curves of the viscoelastic properties could not be used to build fracture energy master curves. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Influence of the crosslink network structure on stress‐relaxation behavior: Viscoelastic modeling of the compression set experiment

A viscoelastic approach of the compression set test is addressed in this work. This test measures the ability of rubber compounds to retain elastic properties after prolonged action of compressive stresses. Elastic properties were tested by recording the normal stress under a constant deformation of 25% with a laboratory rheometer. Considering the Boltzmann superposition principle, compression set data were modeled from the relaxation of Young's modulus, described by a Maxwell spectrum plus a constant E_∞ defining the elastic properties at the long times. This approach was developed with the copolymer of ethylene and vinyl acetate (EVA) networks crosslinked by radical chemistry and by an exchange reaction between acetate groups and silane compounds as crosslinking agents. Regarding the recovery of the elastic properties, radical chemistry provided better results than the exchange reaction for the identical crosslinking density of the network. Then, the Curro–Pincus molecular approach was developed to understand the influence of the microstructure of the EVA network on the elastic properties. The difference of the elastic properties between the two networks crosslinked by two different chemistry means was accounted for by considering the probability of having a dangling end of n units for a random crosslinking process. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1779–1790, 2003     

Partially pyrolyzed poly(dimethylsiloxane)‐based networks: Thermal characterization and evaluation of the gas permeability

In this investigation, the preparation and characterization of partially pyrolyzed membranes based on poly(dimethylsiloxane) (PDMS) are described. These membranes were obtained by the crosslinking of silanol‐terminated PDMS with multifunctional nanoclusters derived from the reaction of pentaerythritoltriacrylate with 2‐aminoethyl‐3‐aminopropyltrimethoxysilane and the in situ polycondensation of tetraethylortosilicate, followed by the thermal treatment of the resulting membranes at different temperatures. The partially pyrolyzed membranes were characterized with infrared spectroscopy, thermogravimetry, elemental analyses, dynamic mechanical analysis, small‐angle X‐ray scattering, and scanning electron microscopy. The membranes exhibited improvements in the thermal stability and mechanical strength. Even with distinct compositions with respect to the Si/O and Si/C ratios, the flexibility of these materials was maintained. The flux rates of the gases through the membranes were measured for N₂, H₂, O₂, CH₄, and CO₂, at 25 °C. The permeability of the membranes changed with increases in the pyrolysis and oxidation temperatures. These membranes could be described as PDMS chains separated by inorganic clusters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 299–309, 2007.     

Lightly crosslinked,mesomorphic networks obtained through the reaction of dimeric,liquid‐crystalline epoxy–imine monomers and heptanedioic acid

We reacted various dimeric, liquid‐crystalline epoxy–imine monomers, differing in the length of the central aliphatic spacer or the dipolar moments, with heptanedioic acid. The resulting systems showed a liquid‐crystalline phase in some cases, depending on the dimer and on the reaction conditions. The systems were characterized with respect to their mesomorphic properties and then were submitted to dynamic mechanical thermal analysis in both fixed‐frequency and frequency‐sweep modes in the shear sandwich configuration. The arrangement in the liquid‐crystalline phase seemed to be mainly affected both by the polarization of the mesogen and by the reaction temperature, which favored the liquid‐crystalline arrangement when it was lying in the range of stability of the dimer mesophase. In agreement with other recent literature data, dynamic mechanical thermal analysis results suggested that the presence of the mesogen directly incorporated into the main chain increased the lifetimes of the elastic modes both in the isotropic phase and in the liquid‐crystalline phase with respect to side‐chain liquid‐crystalline elastomers and that the time–temperature superposition principle did not hold through the liquid‐crystalline‐to‐isotropic transition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44:6270–6286, 2006     

The influence of vinyl activating groups on β‐allyl sulfone‐based chain transfer agents for tough methacrylate networks

In radical polymerization of monofunctional monomers, addition fragmentation chain transfer (AFCT) agents are well known to regulate polymerization and yield polymers with lower molecular weights and narrower molecular weight distributions. Papers concerning bulk photopolymerization of monomer mixtures with AFCT agents are rarely found in literature. In this article, AFCT reagents based on β‐allyl sulfones with different vinyl activating groups were synthesized and compared. The compounds were tested in mono‐ and difunctional monomer systems providing information about the influence on photoreactivity, molecular weight, as well as thermal and mechanical properties of the resultant polymers. Where more potent activating groups (‐Ph, ‐CN) markedly influenced polymerization at lower concentrations, the AFCT reagent with an ester activating group reacted at a similar rate to the methacrylate monomer (C_T ≈ 1) and provided the best overall performance. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1417‐1427     

Synthesis and characterization of poly(isobutylene‐co‐isoprene)‐derived macro‐monomers

Allylic halide displacement from brominated poly(isobutylene‐co‐isoprene) (BIIR) by carboxylate nucleophiles is used to prepare elastomer derivatives containing pendant polymerizable functionality. These solvent‐borne substitutions are conducted under homogeneous and phase‐transfer catalyzed reaction conditions to synthesize acrylate and vinylbenzoate esters in high yield. The resulting macro‐monomer derivatives are shown to crosslink efficiently with peroxide initiation to give high modulus, thermoset products that cannot otherwise be accessed from isobutylene‐rich elastomers. The extent of cure, as measured by the storage modulus of the vulcanizate, scales with RCH=CH₂ content, and can be extended by co‐oligomerization of pendant unsaturation with that contained within multifunctional coagents. An alternate approach involving the introduction of pendant sulfonyl azide functionality is described, wherein thermal decomposition to nitrene intermediates supports an efficient crosslinking process. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

A novel shape memory poly(ε‐caprolactone) network via UV‐triggered thiol‐ene reaction

A facile method to prepare shape memory polymers crosslinked by SiO₂ is described. A series of biodegradable shape memory networks were obtained through thiol‐ene reaction triggered by UV irradiation between surface‐thiol‐modified SiO₂ nanoparticles and end‐acrylate poly (ε‐caprolactone) (PCL). The highly selective thiol‐ene reaction ensured a uniform distribution of PCL chains between crosslinkers, contributing well‐defined network architecture with enhanced mechanical and shape‐memory properties. Thiol‐functionalized silica nanoparticle was characterized by using FTIR and XPS analysis, and ¹H NMR spectra was used to confirm the successful modification of terminal hydroxyl group of PCL diol. Surface‐modified silica particles were found well dispersible in acrylate‐capped PCL supported by SEM. Thermal and crystalline behaviors of the obtained polymers were analyzed by DSC and XRD, and DMA measurement proved good mechanical property. The shape memory behavior and tensile strength was somewhat tunable by the length of PCL. Acceptably, sample SiO₂‐SMP2k presented 99% recovery ratio and 97% shape fixity, and its relatively high tensile strength showed an attractive potential for biomedical application. Finally, a possible molecular mechanism accounting for the shape memory property was illustrated. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 692–701     

Comparing the mechanical response of di‐, tri‐, and tetra‐functional resin epoxies with reactive molecular dynamics

The influence of monomer functionality on the mechanical properties of epoxies is studied using molecular dynamics (MD) with the Reax Force Field (ReaxFF). From deformation simulations, the Young's modulus, yield point, and Poisson's ratio are calculated and analyzed. Comparison between the network structures of distinct epoxies is further advanced by the monomeric degree index (MDI). Experimental validation demonstrates the MD results correctly predict the relationship in Young's moduli. Therefore, ReaxFF is confirmed to be a useful tool for studying the mechanical behavior of epoxies. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 255–264     

Laser‐Induced Crosslinking of Ultra‐Low‐ and High‐Density Polyethylene

The use of laser radiation to initiate the crosslinking process in ultra low‐density polyethylene (ULDPE) and high‐density polyethylene (HDPE) was evaluated. The process was found to be most effective for pulsed laser irradiation when the polymer was traced with a photoinitiator: 4‐chlorobenzophenone (CBP). The gel content measurements proved that crosslinking took place in all the irradiated samples. The degree of crosslinking was measured for different values of irradiation energy, temperature, photoinitiator concentration and the nature and type of crosslinking agents. The effects of all these parameters on the degree of crosslinking and the consequent effects on mechanical properties of the polymers were analyzed. Also found in the present study is the fact that a better efficiency of crosslinking was achieved at longer laser irradiation wavelength. The ultimate tensile stress and elongation at fracture were measured for all cross‐linked samples and compared with those of the controlled ones.

     

Synthesis and crosslinking of biphenyl and naphthalene liquid‐crystalline polyethers with pendant full‐saturated and vinyl‐terminated aliphatic chains

Two series of vinyl‐terminated, side‐chain liquid‐crystalline polyethers containing 4,4′‐biphenyl and 2,6‐naphthalene moieties as mesogenic cores with several contents of vinyl crosslinkable groups were synthesized by chemically modifying poly(epichlorohydrin) with mixtures of saturated and vinyl‐terminated mesogenic acids. In most cases the degree of modification was over 90%. The polymers were characterized by chlorine analysis, IR and ¹H and ¹³C NMR spectroscopies, viscometry, size exclusion chromatography/multi‐angle laser light scattering, and thermogravimetric analysis. The liquid‐crystal behavior of all the synthesized polymers was examined by differential scanning calorimetry, polarized optical microscopy (POM), and X‐ray diffraction on mechanically oriented samples. The crosslinking of most polymers was done by peroxide‐type initiators, which generally led to liquid‐crystal elastomers. The mesophase organization was maintained on the crosslinked materials, as confirmed by POM and X‐ray diffraction. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3384–3399, 2003     

Synthesis and photopolymerization of new dental monomers from o‐hydroxyaryl phosphonates

Novel aromatic mono‐ and diphosphonate monomers based on t‐butyl α‐bromomethacrylate were prepared for use in dental composites. The synthesis of the two monomers involved three steps: the reaction of diethyl phosphite with phenol or hydroquinone, the rearrangement of the resulting phosphate derivatives into o‐hydroxyaryl phosphonates with lithium diisopropylamide, and the reaction of o‐hydroxyaryl phosphonates with t‐butyl α‐bromomethacrylate. Then, the selective hydrolysis of the t‐butyl ester groups of the monomers with trifluoroacetic acid gave the other carboxylic acid containing monomers. The photopolymerization behaviors of the synthesized monomers with glycerol dimethacrylate and triethylene glycol dimethacrylate were investigated with photodifferential scanning calorimetry at 40 °C with 2,2′‐dimethoxy‐2‐phenyl acetophenone as the photoinitiator. The hydrolysis of the t‐butyl groups of the monomers increased the reactivity and the rates of polymerization of the monomers. The mixtures of the acid monomers showed rates of polymerizations similar to those of homopolymerizations of triethylene glycol dimethacrylate and glycerol dimethacrylate. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6775–6781, 2006     

Morphology and orientation during the deformation of segmented elastomers studied with small‐angle X‐ray scattering and atomic force microscopy

Small‐angle X‐ray scattering (SAXS), atomic force microscopy (AFM), and other techniques were combined in a study of segmented thermoplastic elastomers (Pebax) containing poly(tetramethylene oxide) soft segments and hard blocks of nylon‐12. AFM was used to provide real‐space resolution of the morphology during tensile elongation and after subsequent relaxation. Nanofibril formation, starting at strains of about 1.5×, was characterized in detail, showing the evolution of the number, orientation, and size of these highly stressed load‐bearing fibrils that dominated the mechanical properties. AFM results were combined with two‐dimensional SAXS data to develop a model considering the breakup of the original ribbonlike nylon‐12 lamellae in combination with progressive reformation and orientation of highly stressed fibrils. The complex changes in the two‐dimensional SAXS images included a distorted arc pattern due to increased spacing of the lamellae in the stretch direction at low strains, with an evolution to completely different patterns dominated mainly by intrafibrillar and interfibrillar scattering contributions. Between stretch ratios of 1.5 and 2.3× original lamellae were progressively broken up, and by 3.2×, all lamellae independent of the initial orientation were broken into smaller crystals with low aspect ratios. The results were combined with differential scanning calorimetry and birefringence data taken on films under strain to obtain insight into the microscopic basis for strain softening and plastic deformation in Pebax and related segmented polymers. Birefringence cycling with strain provided a consistent picture with the other techniques for understanding the redistribution of stress on a nanoscopic scale during deformation and relaxation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1727–1740, 2002     

An environmental friendly approach for recycling of post‐vulcanized fluoroelastomer scraps through high‐shear mechanical milling

An environmental friendly approach for partial de‐crosslinking of post‐vulcanized fluoroelastomer (FKM) scraps through high‐shear mechanical milling has been developed for recycling of the FKM. The method not only overcomes the expensive use and recovery of organic solvents but also gives rise to reclaimed rubbers with superior mechanical properties. After 32 cycles of milling, the gel fraction of FKM decreased from its original 97.8% to 79.7%. The appearance of the –CF₂‐associated peaks C1s spectra after mechanical milling confirmed the partial de‐crosslinking of FKM. The structure change of FKM sol part before and after mechanical milling was also investigated by Fourier transform infrared (FTIR) analysis and gel permeation chromatography (GPC) measurements. The reclaimed FKM exhibited excellent mechanical and thermal properties, indicating a strong potential for future applications. The tensile strength of FKM re‐vulcanizates is 6.6 MPa, retaining about 84% properties of virgin FKM vulcanizates (7.9 MPa), and the elongation at break was increased from 337.1% to 368.7%. Copyright © 2010 John Wiley & Sons, Ltd.     

Biodegradable network elastomeric polyesters from multifunctional aromatic carboxylic acids and poly(ϵ‐caprolactone) diols

Novel biodegradable network polyesters were prepared from multifunctional aromatic carboxylic acids [trimesic acid (Y), pyromellic acid (X), and mellic acid (Y_M)] and poly(?‐caprolactone) (PCL) diols with molecular weights of 530, 1250, and 2000. Prepolymers prepared by a melt polycondensation method were cast from dimethylformamide solutions and postpolymerized at 220 °C for various times to form a network. The resultant films were transparent, flexible, and insoluble in organic solvents. The network polyesters obtained were characterized by infrared absorption spectra, wide‐angle X‐ray diffraction analysis, density measurements, differential scanning calorimetry, thermomechanical analysis, and tensile testing. Some network polyester films, including YPCL_1250, XPCL₁₂₅₀, and Y_MPCL₂₀₀₀, showed elastomeric properties with high ultimate elongation and low tensile modulus. The enzymatic degradation was measured by the weight loss of the network polyester films in a buffer solution with Rhizopus delemar lipase at 37 °C. The degree and rate of degradation increased with the increasing molecular weight of the PCL diols, but they decreased in the order of YPCL > XPCL > Y_MPCL because of the increase in the crosslinking densities of the network films. The degraded products after enzymatic degradation showed that the ester linkage of the PCL component and the aromatic ester linkage between Y and PCL diols were hydrolyzed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4523–4529, 2002     

Synthesis and dielectric properties of photoreactive polystyrene containing [1‐(3‐isopropenyl‐phenyl)‐1‐methyl‐ethyl]‐carbamate in the side chain

Novel polystyrene derivatives comprising [1‐(3‐isopropenyl‐phenyl)‐1‐methyl‐ethyl]‐carbamate in the side chain were synthesized as photoreactive copolymers. Poly(4‐vinylphenol) was made to react with 1‐(1‐isocyanato‐1‐methyl‐ethyl)‐3‐isopropenyl‐benzene (m‐TMI) and the unreacted hydroxyl groups were protected with acetyl chloride. The copolymers are highly sensitive to the radical photoinitiators that can be activated by irradiation of UV light (λ = 300–365 nm). FTIR spectroscopy was employed to monitor the structural changes in the copolymers exposed to UV irradiation. The dielectric properties of the copolymers were investigated by measuring the capacitance and calculating the permittivity as a function of frequency, along with the I–V characteristics. Their properties were compared with those of thermally crosslinkable poly(4‐vinylphenol) blended with poly(melamine‐co‐formaldehyde), which is frequently used as a dielectric layer in organic field‐effect transistors (OFETs). No significant dielectric dispersion was observed in the frequency range of 1 kHz–1 MHz. The dielectric constant was determined to be in the range of 4.2–6.0, which offers a potential for the application of these copolymers to OFET gate insulators. These soluble dielectrics exhibit good film uniformity and can also be patterned using a standard photolithographic technique. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1710–1718, 2008     

Thermo‐/moisture‐responsive shape‐memory effect of poly(2‐ethyl‐2‐oxazoline) networks

In this work, poly(2‐ethyl‐2‐oxazoline) (PEtOx) is crosslinked to realize a moisture‐ and thermo‐responsive shape‐memory polymer. The obtained PEtOx networks exhibit excellent shape‐memory properties with storable strains of up to 650% and recovery values of 100% over at least 10 shape‐memory cycles. The trigger temperature (T_trig) of 68 °C of a PEtOx network at a relative humidity (RH) of 0% decreases with increasing moisture and equals room temperature at an RH of 40%. Thus, programmed PEtOx networks trigger sensitively on a certain temperature/moisture combination and, further, can be programmed as well as triggered at room temperature exclusively by varying humidity. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1053–1061     

On the Effects of UV‐C and pH on the Mechanical Behavior,Molecular Conformation and Cell Viability of Collagen‐Based Scaffold for Vascular Tissue Engineering

Collagen‐based vascular substitutes represent in VTE a valid alternative for the replacement of diseased small‐calibre blood vessels. In this study, collagen gel‐based scaffolds were crosslinked combining modulation of pH and UV‐C radiation. The effects on the mechanical properties, on the molecular structure and on cell viability and morphology were investigated. The mechanical response increased as a function of pH or UV‐C dose and strongly depended on the test speed. Collagen molecular conformation resulted only slightly modified. While cell adhesion was not significantly altered, cell proliferation partially decreased in function of pH and UV‐C. These findings suggest that UV‐C treated collagen gels can represent an adequate substrate for VTE applications.

     

Crosslinking polymerization leading to interpenetrating polymer network formation. I. Polyaddition crosslinking reactions of poly(methyl methacrylate‐co‐2‐methacryloyloxyethyl isocyanate)s with ethylene glycol resulting in polyurethane networks

At the start of our research program concerned with the elucidation of the crosslinking polymerization mechanism leading to interpenetrating polymer network (IPN) formation, in which IPNs consist of both polymethacrylates and polyurethane (PU) networks, this article deals with the polyaddition crosslinking reaction leading to PU network formation. Therefore, 2‐methacryloyloxyethyl isocyanate (MOI) was radically copolymerized with methyl methacrylate (MMA) in the presence of CBr₄ as a chain‐transfer agent. The resulting poly(MMA‐co‐MOI)s, having pendant isocyanate (NCO) groups as novel multifunctional polyisocyanates, were used for polyaddition crosslinking reactions with ethylene glycol as a typical diol. The second‐order rate constants depended on both the functionality of poly(MMA‐co‐MOI) and the NCO group concentration. The actual gel points were compared with the theoretical ones calculated according to Macosko's equation; the deviation of the actual gel point from the theoretical value became more remarkable for a greater functionality of poly(MMA‐co‐MOI) and at a lower NCO group concentration or at a lower poly(MMA‐co‐MOI) concentration. These are discussed mechanistically, with consideration given to the significance of intramolecular cyclization and intramolecular crosslinking reactions leading to the shrinkage of the molecular size of the prepolymer, along with the data of the intrinsic viscosities of resulting prepolymers and the swelling ratios of resulting gels. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 606–615, 2003     

Influence of varying hard segments on the properties of chemically crosslinked moisture‐cured polyurethane‐urea

Polyurethane prepolymers are widely used in the reactive hot melt adhesives and moisture‐cured coatings. The chemically crosslinked moisture‐cured formulation based on PEG‐1000 and isophorone diisocyanate was prepared with NCO/OH ratio of 1.6:1.0. Trimethylol propane was used as a crosslinking agent. The excess isocyanate of the prepolymer was chain extended in the ratio of 2:1 (NCO/OH) with different aliphatic diols, and 4:1 with different aromatic diamines. The polymer network maturation during moisture cure was followed by dynamic mechanical thermal analyzer (DMTA) instrument. The thermal and dynamic mechanical properties of the crosslinked polymers were evaluated using thermogravimetric analysis, differential scanning calorimetric analysis and DMTA. Surface properties were evaluated through angle‐resolved X‐ray photoelectron spectroscopy. The present article discusses the physical properties of moisture‐cured polyurethane‐urea (MCPU) containing chemical crosslinks in the hard segment. The complete moisture‐cured polymers showed amorous results toward room temperature modulus, tensile strength, hardness, thermal stability, and transparency. The surface properties showed the enrichment of soft segments. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 102–118, 2006