Characterization of crosslinked ethylene—Vinylacetate copolymers

Two types of ethylene-vinylacetate copolymers, containing 16% and 9% of vinylacetate, respectively, were crosslinked with dicumyl peroxide in a Brabender plastograf. The time of the torque maximum was proportional to the degree of crosslinking. The degree of crosslinking was determined by extraction and depended on the concentration of the crosslinking agent and of vinylacetate in the copolymer, and on the crosslinking temperature and time. It was found by DSC and by solid-state CP-MAS ¹³C NMR that with the progress of crosslinking the crystalline phase of the copolymers changed to the amorphous phase. Crosslinking took place mostly on the acetate groups.     

Thermoreversible crosslinked thermoplastic starch

A novel furan‐modified thermoreversible crosslinked thermoplastic starch was synthesized. The crosslinking mechanism was based on a thermoreversible furan/maleimide adduct formed by the Diels ? Alder reaction. Thermoplastic starch (TPS) was first modified by forming a urethane linkage between the product of the reaction of furfuryl alcohol with 4,4‐methylene diphenyldiisocyanate and a starch hydroxyl group. Crosslinking was then achieved by the addition of 1,1′‐(methylene‐di‐4,1‐phenylene) bismaleimide to the furan‐grafted starch in solution (dimethylsulfoxide) and in the molten state during conventional extrusion. The materials were characterized by Fourier transform infrared and ¹H NMR spectroscopy. The thermoreversible reaction was assessed by viscosity measurement and ¹H NMR, for the system in dimethylsulfoxide, and by solubility tests, hot‐pressing experiments and dynamic mechanical analysis measurements for the extruded product. The crosslinked product showed a higher storage modulus and water resistance than its non‐crosslinked counterpart, opening novel opportunities to widen the range of TPS applications. © 2015 Society of Chemical Industry     

低场核磁表征交联橡胶性能的研究

研究低场核磁法测定的天然橡胶(NR)硫化胶的交联密度、核磁参数T2随测试温度的变化趋势,确定测试的温度区间;改变硫黄用量,测定NR硫化胶的交联密度并与平衡溶胀法的测定值进行比较。结果表明:低场核磁法与平衡溶胀法测定结果有很强的相关性;将核磁参数与力学性能进行比较,指出了交联密度增大时力学性能的变化趋势。     

Thermal and surface characterization of plasticized starch polyvinyl alcohol blends crosslinked with epichlorohydrin

Starch‐polyvinyl alcohol (PVA) blends in 2:8 wt % were prepared with various plasticizers such as polyethylene glycol (PEG‐200, PEG‐400) and glycerol. The crosslinking of starch‐PVA blends by epichlorohydrin was carried out in the presence of a plasticizer in situ. The obtained films were analyzed by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), dynamic mechanical and thermal analysis (DMTA), and X‐ray photoelectron spectroscopy (XPS), and remarkable changes in thermal stability and glass‐transition temperature have been observed on plasticizing and crosslinking in different concentrations. Different kinetic models such as Coats–Redfern, Broido, Friedman, and Chang were used to calculate the kinetic parameters of thermal decomposition. The results suggest that the thermal stability and activation energy of thermal decomposition passes through maxima at a critical concentration of plasticizer and increases with increasing crosslinker concentration. High‐resolution C 1s XPS analysis was used to provide a method of differentiating the presence of various carbons associated with different environment in the films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 25–34, 2006     

用淀粉制备高吸水材料的工艺研究

研究了以淀粉经环氧氯丙烷为交联剂制备吸水材料的工艺方法及产品性能,了醚化剂及交联睡量对产品吸水性能的影响。研究结果表明本方法可得到水吸附保持值可达到１１０￣１３５ｍｌ／ｇ、盐水吸附保持值为３５￣４５ｍｌ／ｇ的产品。     

Properties of supercritical fluid extrusion‐based crosslinked starch extrudates

Starch microcellular foam was produced by supercritical fluid extrusion (SCFX) using native and pregelatinized starch mixtures. The starch solution was reacted with epichlorohydrin (EPI) under alkaline conditions in a continuous twin‐screw extruder in the presence of supercritical carbon dioxide. The relationship between crosslinking density and cell size and their distribution in the foamed extrudates was studied. An increase in the EPI concentration from 0 to 0.5% was accompanied by an increase in the degree of crosslinking as measured by differential scanning calorimetry and confirmed by diffusion coefficient measured by nuclear magnetic resonance. The diffusion coefficient of crosslinked sample was observed to be 12.5 times lower than that of non crosslinked control. The average cell size of the microporous structure, observed by scanning electron microscopy, showed a decrease from 147 to 61 μm as the concentration of EPI was increased. The cell size distribution of the crosslinked samples was significantly improved but the total expansion was lowered. The results obtained to date indicate, for the first time, that reactive extrusion of starch with EPI with supercritical carbon dioxide as a blowing agent offers a promising new technique to generate microporous foams for use in various applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

硅烷交联LDPE的微观分析

用扫描电子显微镜、凝胶渗透色谱、差示扫描量热法等分析了低密度聚乙烯(LDPE)接枝及交联前后微观结构的变化。结果表明,LDPE被接枝后交联,形成了明显的网状结构;LDPE2102TN00被硅烷A15l接枝后,交联形成的网状结构比采用2种硅烷A151／A171接枝具有更好的规整性。A151／A171接枝LDPE每11个分子中有1个硅原子。     

Characterization of sodium alginate membrane crosslinked with glutaraldehyde in pervaporation separation

Dense sodium alginate (SA) membranes crosslinked with glutaraldehyde (GA) have been prepared by the solution method, wherein a nonsolvent of SA (acetone) was used in a reaction solution instead of an aqueous salt solution. Through infrared radation, X-ray diffractometry, and the swelling measurement, the crosslinking reaction between the hydroxyl groups of SA and the aldehyde groups of GA was characterized. To investigate the selective sorption behavior of the crosslinked SA membranes, swelling measurements of the membranes in ethanol-water mixtures of 70–90 wt % ethanol contents were conducted by equipment that was able to measure precisely the concentration and amount of the liquid absorbed in the membranes. It was observed that the crosslinking could reduce both the solubility of water in the resulting membrane and the permselectivity of the membrane toward water at the expense of membrane stability against water. The pervaporation separation of a ethanol-water mixture was conducted with the membranes prepared at different GA contents in the reaction solution. When the membrane was prepared at a higher GA content, both flux and separation factor to water were found to be reduced, thus resulting from the more crosslinking structure in it. The pervaporation separations of ethanol-water mixtures were also performed at different feed compositions and temperatures ranging from 40 to 80°C. A decline in the pervaporative performance was observed due to the relaxation of polymeric chains taking place during pervaporation, depending on operating temperature and feed composition. The relaxational phenomena were also elucidated through an analysis on experimental data of the membrane performance measured by repeating the operation in the given temperature range. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 209–219, 1998     

均匀设计在交联淀粉微球合成中的应用

以N,N′-亚甲基双丙烯酰胺为交联剂,用反相悬浮法合成了新型交联淀粉微球CSM。采用均匀设计实验法,考察了影响产率、溶胀度、平均粒径的因素,对实验结果进行了回归分析和多目标综合寻优。结果表明,影响产率和溶胀度的主要因素是交联剂质量分数、反应温度和引发剂浓度,而平均粒径则更多地取决于搅拌速度和分散剂质量分数。调节这些因素,可以在一定程度上实现微球结构与形态的控制。在最佳工艺条件下合成CSM的产率是77.5%,溶胀度是246%,平均粒径是16.5μm。     

Study on adsorption behavior between Cr(VI) and crosslinked amphoteric starch

Crosslinked amphoteric starches (CASs) with quaternary ammonium cationic and carboxymethyl anionic groups were prepared by a hemidry reaction. Their adsorption behavior for Cr(VI) was investigated, and was found to follow the Langmuir isotherm. The adsorption process was found to be dependent on initial pH, concentration of Cr(VI), dose of CAS, and temperature. The adsorption capacity decreased with increasing degree of substitution of anionic groups. The thermodynamic study indicated that the adsorption process was exothermic, and the enthalpy changes (ΔH^θ), the entropy changes (ΔS^θ), and free energy changes (ΔG^θ) for CASs were determined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 263–267, 2003     

Chemical sensing materials II: Electrically conductive peroxide crosslinked SEBS copolymers systems

Chemical sensing materials based on electrically conductive styrene–ethylene butylene–styrene (SEBS) triblock‐copolymers systems were investigated. Systems based on crosslinked rather than thermoplastic SEBS systems can be exposed to a wide range of chemical environments. Composites of SEBS containing various amounts of CB and Varox DBPH (peroxide crosslinking agent) were prepared by blending at relative low temperatures, limiting the peroxide activation, and then compression molding at elevated temperatures. Samples containing CB at a level near the corresponding percolation threshold were used for the sensing experiments. Structure characterization included crosslink level and density, dynamic mechanical analysis (DMA), and calorimetry (DSC). The crosslinked SEBS composites exhibit large reversible changes in conductivity on exposure to various solvents and air drying cycles The observed electrical conductivity changes on solvent sorption/desorption is based on the polymer reversible swelling, resulting in breakdown and reconstruction of conductive CB networks, respectively. Sensing performance depends mainly on the solvents solubility parameter and volatility. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

交联聚乙烯的应用及技术进展

对交联聚乙烯(CLPE)的应用情况及生产技术的发展概况进行了综述，并从交联原理和生产工艺等方面对辐射交联、紫外光交联、过氧化物交联和硅烷交联等CLPE生产方法进行了对比介绍。由于硅烷交联和过氧化物交联比较容易实现且投资相对较少而被广泛应用，而辐射交联和紫外光交联对厚制品很难实现均匀交联，仅限于薄制品领域。建议国内相关单位加大专用料的研制开发力度，在提高塑料加工设备的精度和水平上多做工作。     

Adsorption characterization of lead(II) and cadmium(II) on crosslinked carboxymethyl starch

The adsorption of Pb(II) and Cd(II) ions with crosslinked carboxymethyl starch (CCS) was investigated as function of the solution pH, contact time, initial metal‐ion concentration, and temperature. Isotherm studies revealed that the adsorption of metal ions onto CCS better followed the Langmuir isotherm and the Dubinin–Radushkevich isotherm with adsorption maximum capacities of about 80.0 and 47.0 mg/g for Pb(II) and Cd(II) ions, respectively. The mean free energies of adsorption were found to be between 8 and 16 kJ/mol for Pb(II) and Cd(II) ions; this suggested that the adsorption of Pb(II) and Cd(II) ions onto CCS occurred with an ion‐exchange process. For two‐target heavy‐metal ion adsorption, a pseudo‐second‐order model and intraparticle diffusion seem significant in the rate‐controlling step, but the pseudo‐second‐order chemical reaction kinetics provide the best correlation for the experimental data. The enthalpy change for the process was found to be exothermic, and the ΔS^θ values were calculated to be negative for the adsorption of Pb(II) and Cd(II) ions onto CCS. Negative free enthalpy change values indicated that the adsorption process was feasible. The studies of the kinetics, isotherm, and thermodynamics indicated that the adsorption of CCS was more effective for Pb(II) ions than for Cd(II) ions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and property of starch nanoparticles reinforced aldehyde–hydrazide covalently crosslinked PNIPAM hydrogels

Injectable, de‐crosslinkable, and thermosensitive hydrogels are obtained by hydrazide‐functionalized poly(N‐isopropylacrylamide) and aldehyde‐functionalized dextrin through in situ crosslinked method. Natural based and degradable starch nanoparticles (SNPs) are used as fillers in order to improve mechanical property of hydrogels. Internal morphology, dynamic modulus, thermosensitivity property, de‐crosslinking performance, drug release, and in vitro cytotoxicity of hydrogels are investigated. Results show that SNPs disperse well throughout hydrogel and have no significant influence on gelation time and de‐crosslinking performance. Elasticity property of composite hydrogel prepared from 9.0 wt % precursors with 1.5 wt % fillers is improved significantly by SNPs and maximum storage modulus reaches 399.2 kPa, but 89.6 kPa of unreinforced hydrogels. Hydrogels exhibit good thermosensitive performance at alternating cyclic temperature of 25 and 37 °C. Doxorubicin hydrochloride‐loaded hydrogels can release more than 25 days. No significant cytotoxicity to L929 fibroblast cells is observed through a CCK‐8 assay for hydrogels, precursors, and SNPs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45761.     

Probing molecular mobility during crosslinking process of commercial resins by NMR multiexponential relaxation data analysis

In this study, we present the experimental results for the crosslinking process of a commercial polyester resin based on measurements of the spin lattice relaxation time T₁ of protons, as function of the crosslinking time evolution. Multiexponential decomposition of the evolution of magnetization measured in inversion‐recovery experiments is performed. The population of “rigid” and “mobile” nuclear spin sites was estimated as function of time evolution. In analogy to the usual monomer conversion u, site conversion from “mobile” to “rigid” sites u_M were also estimated as a function of time evolution and initial concentrations of the reagents. The multiexponential decomposition approach of T₁ relaxation data allows one to follow crosslinking processes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Double crosslinked polyetheretherketone-based polymer electrolyte membranes prepared by radiation and thermal crosslinking techniques

Novel one-step preparation of polymer electrolyte membranes without a membrane casting process is achieved by radiation crosslinking of a polyetheretherketone (PEEK) film to prevent dissolution and deformation of the original film in sulfonating solutions. The films crosslinked with doses more than 33 MGy can be effectively sulfonated in a chlorosulfonic solution, resulting in a crosslinked sulfonated PEEK (sPEEK) electrolyte membrane with high proton conductivity comparable to Nafion. Nevertheless, its water uptake was high for application in fuel cells. The thermal treatment was effective for further crosslinking of the membrane; as a result, the water uptake and methanol permeability of the double crosslinked sPEEK membranes drastically decreased, compensating for a slight decrease of proton conductivity. In addition, unlike the traditional cast sPEEK membrane showing the irreversible swelling in hot water, the double crosslinked sPEEK membranes exhibited excellent stability toward 100 °C hot water for more than 200 h without any decrease in proton conductivity, and had the mechanical and thermal properties superior to those of Nafion.     

Analysis of the foaming mechanisms of materials based on high‐density polyethylene (HDPE) crosslinked with different irradiation doses

Different crosslinked high‐density polyethylene based cellular polymers have been produced by a free foaming process using a chemical blowing agent. The polymer matrix was crosslinked by electron beam irradiation using different doses ranging from 25 to 175 kGy. The main aim of this work is to study the effect of the different irradiation doses on the density, cellular structure, and foaming mechanisms. Results show that irradiation doses as high as 175 kGy have to be used to obtain cellular materials with a low relative density (0.06), cell sizes of around 50 μm, and cell densities of 1.6 × 10⁷ cells cm^?3. The strain hardening of the polymer matrix increases with the irradiation dose leading to an increase of the polymer resistance to be stretched, which helps to avoid undesirable cellular degeneration processes. Irradiation doses lower than 175 kGy are not able to stabilize the cellular structure leading to foams with relative densities higher than 0.1 and degenerated cellular structures. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46276.     

Thermally recoverable crosslinked polyethylene

The thermal recovery of the stored stress in crosslinked polyethylene has been commercially exploited in the preparation of heat shrinkable materials. The study on thermally recoverable crosslinked polyethylene compositions is reported in this paper. Thermally recoverable compositions were prepared by cross-linking of four grades of polyethylenes in air using γ-rays from a Co-60 source. The effect of the irradiation dose on the gel fraction and radiation dose to gelation is studied. The effect of the melt index (MI) and the density of the polyethylene on the gel fraction, radiation dose to gelation, and recovery percentage of the stored stress is also studied. It is observed that the gel fraction is higher in case of the lower MI material and that rate of recovery is higher at higher temperatures. The rate of recovery of the stored stress is higher in case of the 100 kGy irradiated sample. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 823–829, 1997.     

Characterization of unsaturated polyester and alkyd resins using one‐ and two‐dimensional NMR spectroscopy

One‐ (1D) and two‐dimensional (2D) ¹H‐ and ¹³C‐NMR spectroscopy was used to characterize polyester and alkyd resins used in the coatings industry. The wealth of chemical composition information of the ¹H‐ and ¹³C‐NMR 1D spectra of the resins is revealed through 2D NMR experiments that spread chemical shifts in two dimensions, thus facilitating the peak assignment of the various components of the resins. It is shown that the types of polyols, acids, and vegetable oils used to modify the resins can be efficiently traced by NMR spectroscopic techniques. Information on the quantitative composition of the resins and especially the abundance of unsaturated fatty acid double bonds, which influences resin dryability and hardness, can be easily extracted from the ¹H‐NMR spectra upon successful assignment. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1881–1888, 2003     

Gallic acid crosslinked peanut protein-corn starch composite edible films produced at alkaline pH with ultrasound application

Corn starch and peanut protein blend films were prepared with and without gallic acid addition (0.25%, w/v) at pH 7, 9, and 11 by casting. The ultrasound (160 W, 20 kHz, 10 min) treatment was applied to the film-forming solutions. This study aimed to develop biopolymer-based films with gallic acid and to determine the interactions of components at different pHs and with ultrasound. The barrier, optical, mechanical, and thermal properties of films were examined. Moreover, structural characterization of films was conducted by Fourier transform infrared (FTIR), x-ray diffraction, and trinitro benzenesulfonic acid assay to enlighten the crosslinking interactions of gallic acid with biopolymers at different pHs. At neutral pH, gallic acid behaved as plasticizer. By acting as a crosslinker at pH 9, gallic acid provided the lowest moisture content, darker and more opaque appearance, enhanced barrier performance and thermal stability. The crosslinking degrees of gallic acid-enriched films were 49.1% (pH 7), 77% (pH 9), and 67.4% (pH 11). Additionally, gallic acid increased antioxidant capacity. The ultrasonication adversely affected the film properties by breaking bonds in the film structure. Peanut protein-corn starch-gallic acid films under mild alkaline conditions exhibited outstanding thermal stability, mechanical durability, light, and water barrier characteristics, making them appropriate for sustainable food packaging applications.