Properties of aminosilane grafted moisture curable poly(vinyl chloride) formulations

The reaction of plasticized PVC with [N-(2-amino ethyl)-3aminopropyl trimethoxy silane] yielded silane-grafted PVC that was crosslinked by a hydrolytic mechanism. It was found that crosslinking resulted in improvement of mechanical properties (tensile strength and elongation at break) specially at temperatures higher than 80°C. Properties at 130°C were substantially enhanced, showing a fourfold increase in ultimate tensile strength (UTS), and a twofold increase in elongation at break. There was a unique relationship between UTS at 130°C and gel content irrespective of processing conditions, with UTS starting to increase sharply around 30% gel content, and reaching a plateau at about 60%. Also, the softening temperature was improved. The crosslinked material had a higher softening temperature (up to 165°C, compared with 95°C for the compound without crosslinking agent), indicating that the hydrolytic crosslinking of PVC yielded a material with improved properties.     

Cell coalescence suppressed by crosslinking structure in polypropylene microcellular foaming

A series of crosslinked polypropylene samples with increased melt strengths were prepared via a copolymerization reaction, followed by melt processing. These crosslinked PP samples (PP‐Cs) were foamed by a temperature rising process using supercritical CO₂ as the physical blowing agent. The introduction of crosslinking structure resulted in PP‐Cs foams with well‐defined closed cell structure, decreased cell size, and increased cell density in comparison with a linear PP, which were attributed to the suppressed cell coalescence due to the significant increase in melt strength of PP‐Cs. Further increasing the crosslinking degree tended to enhance the suppression effect on the cell coalescence, and hence increase the cell density of PP foams under the same foaming conditions, especially at the longer foaming times. The well‐defined closed cell structure was observed at the foaming temperature of 170–250°C and saturation pressure of 12–20 MPa. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Biocomposites composed of epoxidized soybean oil cured with terpene‐based acid anhydride and cellulose fibers

Epoxidized soybean oil (ESO) was cured with a terpene‐based acid anhydride (TPAn) at 150°C, and the thermal and mechanical properties of the cured product were compared with ESO cured with hexahydrophthalic anhydride (HPAn), maleinated linseed oil (LOAn), or thermally latent cationic polymerization catalyst (CPI). The ESO‐TPAn showed a higher glass transition temperature (67.2°C) measured by dynamic mechanical analysis than ESO‐HPAn (59.0°C), ESO‐LOAn (?41.0°C), and ESO‐CPI (10.0°C). The storage modulus at 20°C of ESO‐TPAn was higher than those of ESO‐LOAn and ESO‐CPI. Also, ESO‐TPAn showed higher tensile strength and modulus than the other cured ESOs. Regarding the biodegradability measured by biochemical oxygen demand in an activated sludge, ESO‐TPAn possessed some biodegradability, which was lower than that of ESO‐LOAn. Next, biocomposites composed of ESO‐TPAn and regenerated cellulose (lyocell) fabric were prepared by compression molding method. The tensile strength of ESO‐TPAn/lyocell composites increased with increasing fiber content. The tensile strength and modulus of ESO‐TPAn/lyocell composite with fiber content 75 wt % were 65 MPa and 2.3 GPa, which were three times higher than those of ESO‐TPAn. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Studies on blends of ethylene vinyl acetate and polyacrylic rubber with reference to their shrinkability

Preferential crosslinking was introduced in the rubber phase of a blend of ethylene vinyl acetate (EVA) and polyacrylic rubber (AR‐801). The heat shrinkability of the polymer blends was measured at room temperature (RT) and at a high temperature (HT) of 150°C. Various parameters were tried for a correlation with shrinkability. Shrinkability goes up with the increase in rubber content and is increased with increasing cure time in blends of a fixed ratio. The crystallinity of an HT (at 150°C) stretched sample was higher than that of a RT stretched sample, which was higher than that of the shrunk and original sample. The continuous cure characteristics, showed that the torque was increased with the rubber content. High temperature DSC demonstrated that the increase in AR‐801 content decreased the stability and further HT processing increased the stability. SEM showed that the rubber phase was more elongated in the HT stretched sample compared to the RT stretched sample. In the shrunk sample the rubber phase was more globular. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2088–2095, 2000     

Effect of crosslinking on the positive temperature coefficient stability of carbon black‐filled HDPE/ethylene‐ethylacrylate copolymer blend system

Carbon black‐filled high‐density polyethylene (HDPE)/ethylene ethylacrylate copolymer (EEA) blends were prepared and the effect of crosslinking of the blends on the positive temperature coefficient (PTC) stability was investigated. By irradiation and silane‐crosslinking methods, crosslinked composites with various degrees of crosslinking were obtained. Crosslinking of the matrix polymer led to the disappearance of the negative temperature coefficient (NTC) phenomenon. Also, the PTC intensity increased with an increasing degree of crosslinking. The PTC stability of silane‐crosslinked samples was notably improved at heat cycles of 140°C. This was sufficiently improved by both the silane‐ and radiation‐crosslinking methods when they were treated at 85°C. Therefore, the limiting temperature of self‐regulating heat is about 85°C. Both radiation‐ and silane‐crosslinked samples are thought to be of use to the industry.     

Peroxide crosslinking of rigid poly(vinyl chloride)

The optimum conditions for crosslinking rigid poly(vinyl chloride) with trimethylolpropane trimethacrylate (TMPTMA) and peroxide have been examined. The extent of crosslinking was measured by determining gel content by Soxhlet extraction in tetrahydrofuran. Mechanical properties were measured at 130°C and dynamic viscoelastic measurements were carried out to detect changes in the glass transition temperature (T_g). It was found that 15 phr of TMPTMA and 0.3 phr of peroxide were optimum concentrations for maximizing the extent of crosslinking, tensile strength, and T_g. The lower molding temperature of 170°C was preferred to minimize thermal degradation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2904–2909, 2007     

Fast responsive poly(acrylic acid‐co‐N‐isopropyl acrylamide) hydrogels based on new crosslinker

Novel dual temperature‐ and pH‐sensitive poly(acrylic acid‐co‐N‐isopropylacrylamide), AA/NIPAAm, hydrogels were successfully prepared by chemical crosslinking with crosslinkers. Copolymers of AA/NIPAAm were crosslinked in the presence of different mol % of N,N‐methylene bisacrylamide (MBA) and melamine triacrylamide (MAAm) as crosslinkers by bulk radical polymerization. The resultant xerogels were characterized by extracting the soluble fractions and measuring the equilibrium water content. Lower critical solution transition temperatures (LCST) were measured by DSC. The properties of crosslinked AA/NIPAAm series are evaluated in terms of compositional drift of polymerization, heterogeneous crosslinking, and chemical structure of the relevant components. Soluble fractions of the crosslinked networks were reduced by varying the MAAm and MBA concentrations. The influence of environmental conditions such as temperature and pH on the swelling behavior of these polymeric gels was investigated. The swelling behaviors of the resulting gels show pH sensitivity. The prepared MAAm type AA/NIPAAm hydrogels exhibited a more rapid deswelling rate than MBA type AA/NIPAAm hydrogels in ultra pure water in response to abrupt changes from 20°C to 50°C. The results of this study provide valuable information regarding the development of dual stimuli‐sensitive hydrogels with fast responsiveness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Proton‐conducting blend membranes of crosslinked poly(vinyl alcohol)–sulfosuccinic acid ester and poly(1‐vinyl‐1,2,4‐triazole) for high temperature fuel cells

New type of composite membranes were synthesized by crosslinking of poly(vinyl alcohol) (PVA) with sulfosuccinic acid (SSA) and intercalating poly(1‐vinyl‐1,2,4‐triazole) (PVTri) into the resulting matrix. The complexed structure of the membranes was confirmed by Fourier transform infrared (FTIR) spectroscopy. The resulting hybrid membranes were transparent, flexible, and showed good thermal stability up to ～200°C. The proton conductivities of the membranes were investigated as a function of PVTri and SSA and operating temperature. The water/methanol uptake was measured and the results showed that solvent absorption of the materials increased with increasing PVTri content in the matrix. The proton conductivity of the membranes continuously increased with increasing SO₃H content, PVTri content, and the temperature. In the anhydrous state, the maximum proton conductivity is 7.7 × 10^?5 S/cm for PVA–SSA–PVTri‐1 and for PVA–SSA–PVTri‐3 is 1.6 × 10^?5 S/cm at 150°C. After humidification (RH = 100%), PVA–SSA–PVTri‐4 showed a maximum proton conductivity of 0.0028 S/cm at 60°C. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Preparation of microgel composite hydrogels by heating natural drying microgel composite polymers

Acrylamide‐co‐2‐acrylamido‐2‐methylpropane sulfonic acid‐based microgel composite (MC) hydrogels were prepared by heating natural drying MC polymers. It can reduce the influence of water content on the hydrogel properties. The natural drying MC polymer was swelling when the microgel content exceeded 0.5. It was soluble when the microgel content was 0.25, which was used to investigate the heating conditions. Under 50°C, MC hydrogels was obtained and hydrogen bonding was the reason for their formation. The tensile strength increased and the tensile elongation decreased as the heating time increased. When the heating time was 3 h, the tensile elongation decreased, as the heating temperature increased from 50°C to 80°C. However, the tensile strength increased first and then decreased. Under 60°C, the MC hydrogel had a high tensile strength of 155.3 kPa and a high tensile elongation of 313.3%. The more crosslinking density and the formation of covalent crosslinking bonds between the microgel particles and hydrogel matrix led to an increase in the tensile strength. However, the excess crosslinking of the polymer chains under high temperature could reduce the tensile strength. The tensile strength increased as the microgel content increased to 0.75 and then decreased as microgel content further increased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40841.     

Preparation and evaluation of two kinds of solid polymer electrolytes made from crosslinked poly(ether urethane) elastomers consisting of a comb‐like and a hyperbranched polyether

Two novel polyethers, one comb‐like and another hyperbranched, were synthesized by the cationic ring‐opening polymerization of 3‐(methoxy(triethylenoxy))methyl‐ and 3‐(hydroxy‐(triethylenoxy))methyl‐3′‐methyloxetane, respectively. The former reacted with a multifunctional isocyanate and the latter with a difunctional isocyanate to give rise to the corresponding crosslinked poly(ether urethane) elastomers, PCEU and PHEU. Accordingly, two kinds of solid polymer electrolytes (SPEs) were prepared from these two elastomers in situ in the presence of lithium salt trifluoromethanesulfonimide. It was found that the PCEU‐based SPEs shows a higher ionic conductivity than that PHEU‐based ones due to its more mobile pendent chains and appropriate crosslinking density in the polymeric network. The maximum ionic conductivities of 1.4 × 10^?5 S/cm at 30°C and 3.5 × 10^?4 S/cm at 80°C were attained at the molar ratio of O/Li = 7.5. The DSC measurements clearly demonstrated that PCEU indeed possesses the more flexible chain motion ability than PHEU. The electrochemical stability window of PCEU, which is 1.7–4.0 V was measured by cyclic voltammogram. Additionally, the significantly high decomposition temperature as evidenced by TGA analyses endowed these SPEs a good safe performance. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Physical properties of ethylene vinyl acetate copolymer (EVA)/natural rubber (NR) blend based foam

In this study an attempt was made to improve the rebound resilience and to decrease the density of ethylene‐vinyl acetate copolymer (EVA) foam. For this purpose, EVA was blended with natural rubber (NR), and EVA/NR blends were foamed at 155°C, 160°C, and 165°C. To investigate the correlation between crosslinking behavior and physical properties of foams, crosslinking behavior of EVA/NR blends was monitored. The physical properties of the foams were then measured as a function of foaming temperatures and blend compositions: 165°C was found to be the optimal temperature for a crosslinking of EVA/NR foam. As a result, the density of EVA/NR blend foamed at 165°C was found to be the lowest. EVA/NR (90/10) blend, foamed at 165°C, showed lower density, better rebound resilience, and greater tear strength than EVA foam. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2212–2216, 2004     

Study on the long‐term thermal‐oxidative aging behavior of polyamide 6

The long‐term thermal‐oxidative aging behavior of polyamide 6 (PA6) was studied by comparison with the stabilized sample in this work. The variation of mechanical properties of the pure and the stabilized samples of PA6 with aging time at 110°C, 130°C, and 150°C were investigated, respectively. The aging mechanism of PA6 under heat and oxygen was studied in terms of the reduced viscosity, crystallization behavior, dynamic mechanical behavior, and chemical composition through the methods of polarized light microscopy (PLM), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X‐ray photoelectron energy spectrum (XPS), and so on. The results indicated that at the initial stage of aging, the molecular crosslinking reaction of PA6 dominated resulting in the increase of the mechanical strength, reduced viscosity, and the glass transition temperature of the sample. And the molecular degradation dominated in the subsequent aging process resulting in the decrease of the melting temperature, the increase of the crystallinity, and the formation of the oxides and peroxides products. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Rheology and extrusion of medical‐grade thermoplastic polyurethane

The selection of operating conditions and geometry for the processing of thermoplastic polyurethane, TPU, is a complicated task. This complication arises from the relatively high melting temperature of the crystalline hard blocks and the oxidative and thermal degradation and crosslinking that occur at temperatures that are relatively close to the melting temperature of the TPU. This article documents the rheology, extrusion, and structure development of a medical‐grade TPU. The medical application requires that the additives commonly utilized in the development of polymeric resins, i.e., stabilizers, antioxidants, and lubricant, should be minimized; the TPU of this study contains no additives. At temperatures 10–20°C lower than the melting temperature of the TPU, the morphology of the hard blocks continues to evolve to generate a reversible increase in elasticity and shear viscosity of the TPU with increasing time. At temperatures greater than the melting temperature, the TPU undergoes degradation and crosslinking reactions, which give rise to a permanent increase in the elasticity and the shear viscosity of the TPU. The ramifications of the degradation and crosslinking at temperatures greater than 200°C and morphology modification upon the continuing evolution of the hard blocks at temperatures less than 200°C on the rheology and processing were investigated.     

Poly(vinyl alcohol) films crosslinked by glutaraldehyde under mild conditions

The use of mild conditions to perform the entrapment of biomolecules in polymeric matrices is a crucial step in a broad range of applications as biosensors, biocarrier‐mediated facilitated transport membranes, and drug‐controlled release devices. In this study, we investigated the crosslinking of poly(vinyl alcohol) (PVA) by glutaraldehyde in the absence of an acid catalyst and organic solvents to improve the water resistance of the hydrophilic biocompatible polymer. Glutaraldehyde was chosen as the crosslinking agent because it favors the intermolecular reaction with PVA and is able to bind nonspecifically to proteins. The effects of the temperature and glutaraldehyde content on the thermal and structural properties of the PVA films were examined. Membranes prepared at 40°C showed a maximum crosslinking density for low glutaraldehyde content namely, 0.04 wt % in the spreading solution. Higher amounts of the crosslinker led to the branching of PVA. The increase in membrane thermal properties and reduction in crystallinity were ascribed to the crosslinking treatment, which was confirmed by Fourier transform infrared analysis. The oxygen permeability of the films was reduced up to 2.7 times, which indicated that the crosslinking of the polymer was successfully accomplished. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of rubber‐seed‐oil‐based polyurethanes

Novel biobased polyurethanes were synthesized from rubber seed oil (RSO), a renewable resource. The RSO monoglyceride, together with xylene and hexamethylene diisocyanate (HMDI), was employed to synthesize the desired urethane‐based prepolymer with isocyanate (NCO)‐terminated end groups followed by curing. The degrees of crosslinking of the polyurethane after curing were assessed with their swelling behavior. The properties of the resulting polyurethanes were found to be dependent on the type of diisocyanate and their molar ratios to the RSO monoglyceride. The network structures, which were assessed through swelling studies, showed that networks based on HMDI with an NCO/OH ratio of 1.50 were better crosslinked than with those toluene diisocyanate. The thermal properties of the samples analyzed by thermogravimetric analysis showed two and three decomposition stages in aliphatic‐ and aromatic‐based RSO polyurethanes, respectively. The highest stability with initial decomposition temperature (253°C) and percentage residual at 500°C (11.4%) was achieved with an aliphatic‐based RSO polyurethane. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal and dynamic mechanical properties of organic–inorganic hybrid composites of itaconate‐containing poly(butylene succinate) and methacrylate‐substituted polysilsesquioxane

Itaconate‐unit‐containing poly(butylene succinate) (PBSI) was synthesized by the reaction of 1,4‐butanediol, succinic acid, and itaconic acid in a molar ratio of 2.0 : 1.0 : 1.0, and the obtained PBSI was reacted with methacryl‐group‐substituted polysilsesquioxane (ME‐PSQ) in the presence of benzoyl peroxide (BPO) at 130°C to produce PBSI/ME‐PSQ hybrid composites. The thermal and dynamic mechanical properties of the PBSI/ME‐PSQ hybrid composites were investigated in comparison with those of PBSI cured at 130°C in the presence of BPO. As a result, the hybrid composites showed a much higher thermal degradation temperature and storage modulus in the rubbery state than the cured PBSI (C‐PBSI). The thermal degradation temperature and storage modulus of the hybrid composites increased with increasing ME‐PSQ content. The glass‐transition temperature, measured by dynamic mechanical analysis of the hybrid composites, somewhat increased with increasing ME‐PSQ content. However, the glass‐transition temperatures of all the hybrid composites were lower than that of C‐PBSI. Although the IR absorption peak related to C?C groups was not detected for C‐PBSI, some olefinic absorption peaks remained for all the hybrid composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Intercrystalline crosslinking of polyethylene

The heat distortion temperature (British Standards Method 102C) and DTA nominal melting point of high density polyethylene have been raised to 140°C by nonrandom crosslinking in which the crosslinks are superimposed on the existing semicrystalline structure. The crosslinking agent was a mixture of dicumyl peroxide and allyl methacrylate, and the crosslinking temperature was 120°C, just below the crystal melting range. In contrast, random crosslinking by the same system above the melting range at 160°C lowered the HDT (heat distortion temperature). Conventional peroxide crosslinking also lowered the HDT. The gel swelling of randomly crosslinked polyethylene was higher than that of nonrandomly crosslinked polyethylene having the same gel content. This dependence of the gel swelling on the crosslink distribution can be correlated with the HDT. The effect of γ-radiation and carbon black loading on the HDT has also been studied.     

Thermal and morphological studies of chemically prepared emeraldine‐base‐form polyaniline powder

In this study, emeraldine base (EB)‐form polyaniline (PANI) powder was chemically prepared in 1M HNO₃ aqueous solution. The thermal characteristics and chemical structures of this powder were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), and X‐ray diffraction (XRD). A polarizing optical microscope was also used to examine the crystalline morphology of this sample. The results indicated that the EB‐form PANI powder had a discernible moisture content. Moreover, in the first run of DSC thermal analysis, the exothermic peak at 170–340°C was due to the crosslinking reaction occurring among the EB‐form PANI molecular chains. FTIR and XRD examinations further confirmed the chemical crosslinking reaction during thermal treatment. TGA results illustrated that there were two major stages for weight loss of the EB‐form PANI powder sample. The first weight loss, at the lower temperature, resulted from the evaporation of moisture. The second weight loss, at the higher temperature, was due to the chemical structure degradation of the sample. The degradation temperature of the EB‐form PANI powder was around 420–450°C. The degradation temperature of emeraldine salt (ES)‐form PANI powder was lower (around 360–410°C) than that of the EB form (around 420–450°C). From the TGA results, I roughly estimated that 2.74 aniline repeat units, on average, were doped with 1 HNO₃ molecule in the ES‐form PANI. I found a single crystalline morphology of EB‐form PANI, mostly like a conifer leaf. More complex, multilayered dendritic structures were also found. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2142–2148, 2003     

Effects of the composition ratio,eosin addition,and γ irradiation on the dielectric properties of poly(vinyl alcohol)/glycogen blends

The dielectric relaxation spectra of various poly(vinyl alcohol) (PVA)/glycogen blends and irradiated blend samples with 70 wt % PVA content that were undoped and doped with eosin were measured in extended temperature (30–160°C) and frequency (1 kHz to 1 MHz) ranges. Dielectric relaxation spectroscopy separates different molecular groups of a repeating unit of a polymer with respect to the rate of its orientation dynamics. In the high‐temperature range (>100°C), the σ relaxation, which is associated with the hopping motion of ions in the disordered structure of the biopolymeric material, can be measured. The electric dipole moment and the activation energy of the glass‐transition temperature relaxation process were calculated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Construction of efficient desalting layer on a cellulose acetate membrane by acetalized surface crosslinking treatment

For the purpose of enhancing the desalination performance, a desalting layer was successfully constructed on a cellulose acetate (CA) virgin membrane via acetalized surface crosslinking treatment. The acetalization crosslinking reaction consists of two hydroxyl groups reacting with one aldehyde group to remove one molecule of water. Results showed that the reaction occurred on the surface of the CA membrane, as measured by Fourier‐transform infrared (FTIR), differential scanning calorimeter (DSC), X‐ray photoelectron spectroscopy (XPS), and scanning electron microscope (SEM). The water flux and desalination performance were compared before and after crosslinking, and the formation of the desalting layer greatly improved the desalination performance of the membrane. In addition, the crosslinking temperature, crosslinking time, and formaldehyde solution mass fraction of the CA membrane structure and performance were explored. It was observed that the CA flat membrane showed better desalination performance, with a salt rejection rate of 98.55% and a water flux of 9.88 L/(m²·h), under a processing temperature of 100 °C 11% formaldehyde solution mass fraction and a crosslinking time of 60 min. POLYM. ENG. SCI., 59:913–918, 2019. © 2018 Society of Plastics Engineers