Increase In Degree Of Crosslinking Research Articles

Simulation study on the relationship between the crosslinking degree and structure, hydrophobic behavior for poly (styrene-co-divinylbenzene) copolymer

Molecular dynamics (MD) and Grand Canonical Monte Carlo (GCMC) simulation were employed to investigate the relationship between the crosslinking degree and structure, hydrophobic behavior for poly (styrene-co-divinylbenzene) （P(S-DVB)）copolymer. The structure properties of P(S-DVB) with different crosslinking degree were evaluated by density, fractional free volume (FFV) and glass transition temperature (Tg). The magnitude of the hydrophobicity of P(S-DVB) polymer was quantitatively assessed by solubility parameter, surface energy, interfacial interaction of P(S-DVB) coating-water system and adsorption isotherms. The simulation results identically showed its hydrophobicity decreased with the increase of crosslinking degree. Moreover, the free energy of interaction between the copolymer and water molecule (ΔGiwi) is −83.80 mJ/m2 (5%), −80.32 mJ/m2 (10%) and −75.60 mJ/m2 (15%), respectively, further indicating its strong hydrophobicity. Quantitative analysis of the contribution for the potential energy to the surface energy revealed that the van der Waals energy was the major contribution component.

Crosslinking induces high mineralization of apatite minerals on collagen fibers

Type I collagen, as the critical organic component of bone matrix, plays a template role in mineralization. Gamma-ray irradiation is used to prepare collagen with different crosslinking degrees without introducing foreign substances for mineralization. Significant improvement in crosslinking degree of collagen can be inferred by enzymolysis and differential scanning calorimetry analysis. Scanning electron microscopy observation reveals that, as crosslinking degree increases, the pore structure of collagen becomes more compact. Fourier transform infrared spectroscopy analysis shows the intact retention of classical triple-helical structure of collagen after crosslinking and the following mineralization. Atomic force microscopy characterization, calcium and phosphorus assay kit tests and thermogravimetry measurements indicate that the more compact the collagen structure, the more hydroxyapatite can attach on collagen fibers. These findings reveal the high crosslinking degree of collagen is favorable for the improvement of mineralization ability by providing a more stable and compact network structure. Such crosslinked collagen may provide a more potential way for the preparation of bone substitute materials.

Citric acid crosslinking of poly(vinyl alcohol)/starch/graphene nanocomposites for superior properties

Polyvinyl(alcohol)/starch/graphene nanocomposites with enhanced properties were prepared by solution mixing and casting process with the aid of glycerol as plasticizer and citric acid (CA) as crosslinker. The dispersion of graphene in water was made by sonication prior to mixing it with PVA/starch solution. The effect of varying the concentration of CA crosslinker in PVA/starch nanocomposite with 0.5 wt% of graphene was studied in detail. The structural changes, properties and morphologies were characterized by different techniques. The FTIR results revealed that the crosslinking reaction enhanced the interaction between the hydroxyl groups in PVA and/or starch and the oxygen-containing groups present on the graphene sheets. The mechanical properties were also improved by the crosslinking reaction and reinforcing with graphene. The formation of PVA crystal from solution was interrupted to a large extent by the interface at the amorphous zone of polymers and also the crosslinks between the PVA and starch polymer chains. The total crystallinity of the system was found to decrease with increase in degree of crosslinking. There was a marked increase in the thermal stability as the blend system was crosslinked with CA. CA crosslinking produced compact bulk morphology and improved the homogeneity between PVA and starch. The results of this study illustrate that citric acid can be an effective crosslinker and/or compatibilizer in PVA/starch/graphene nanocomposites for improving properties, and for this reason it is a candidate to replace non-biodegradable plastic films in food packaging sector.

Preparation and characterization of cross-linked canola protein isolate films

Cross-linked canola protein isolate (CPI) films were prepared using a bisepoxide as a chain extender by wet cast followed by heat compression. By DSC measurements, it was verified that the cross-linking reaction took place in the CPI matrix and was completed in 10min at 90°C. FTIR analysis confirmed that the chain extenders were covalently bonded with CPI chains. The reaction led to the formation of a cross-linked architecture which was revealed by an increase in molecular weight of the modified CPI films. The newly formed chain architecture increased the thermostability of CPI as evaluated by TGA; furthermore, the thermostability increased with the increase in cross-linking degree of the modified CPI films. DMA results of the unmodified CPI film showed that microcosmic phase separation occurred between two major proteins, cruciferin and napin in CPI; however, the extent of phase separation decreased with the increase of chain extenders and finally disappeared because of the increased compatibility between cruciferin and napin. Elastomeric mechanical behavior was observed with the introduction of cross-linked architecture in the modified CPI films. At low humidity of 55%, the cross-linked CPI films showed an increase in tensile strength and a decrease in elongation at break. At high humidity of 98%, the increase in hydrophobicity of cross-linked CPI matrix resisted the decreasing tensile strength seen in unmodified films.

Accelerated water tree aging of crosslinked polyethylene with different degrees of crosslinking

The effect of crosslinking degree on accelerated water tree aging in crosslinked polyethylene (XLPE) was investigated. The peroxide-crosslinking process was adopted to make XLPE specimens with different degrees of crosslinking by controlling the doping content of dicumyl peroxide (DCP) in low-density polyethylene (LDPE). The water blade electrode method was applied to accelerate water-tree aging of LDPE and XLPE specimens (hereafter referred to as the specimens), and their morphologies were observed using an optical microscope. The variation of crystalline morphology and anti-cracking performance of the amorphous region in the specimens were analyzed by differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and an electronic universal testing machine. Based on the experimental results, it was found that XLPE has great anti-water-treeing performance compared to LDPE. In addition, the higher the crosslinking degree, the better the anti-water-treeing performance. Although crystal growth is inhibited due to the crosslinking reaction, the density of tie molecular chains greatly increases in the amorphous region and exhibits significantly tighter lamellar stacking, which is the reason that water tree growth is restrained with increasing crosslinking degree.

Chitosan-functionalised poly(2-hydroxyethyl methacrylate) core-shell microgels as drug delivery carriers: salicylic acid loading and release

This work presents the evaluation of chitosan-functionalised poly(2-hydroxyethyl methacrylate) (CS/PHEMA) core-shell microgels as drug delivery carriers. CS/PHEMA microgels were prepared by emulsifier-free emulsion polymerisation with N,N ′-methylenebisacrylamide (MBA) as a crosslinker. The study on drug loading, using salicylic acid (SA) as a model drug, was performed. The results showed that the encapsulation efficiency (EE) increased as drug-to-microgel ratio was increased. Higher EE can be achieved with the increase in degree of crosslinking, by increasing the amount of MBA from 0.01 g to 0.03 g. In addition, the highest EE (61.1%) was observed at pH 3. The highest release of SA (60%) was noticed at pH 2.4, while the lowest one (49.4%) was obtained at pH 7.4. Moreover, the highest release of SA was enhanced by the presence of 0.2 M NaCl. The pH- and ionic-sensitivity of CS/PHEMA could be useful as a sustained release delivery device, especially for oral delivery.

Influence of dynamic crosslinking on the morphology, crystallization, and dynamic mechanical properties of PA6,12/EVA blends

ABSTRACTThis study investigated the effect of dynamic crosslinking of polyamide 6,12 and random copolymers of ethylene and vinyl acetate blends (PA6,12/EVA) on the morphology, crystallinity, and dynamic mechanical properties. The crosslinking agent was dicumyl peroxide (DCP), and the blends were processed in a torque rheometer. The morphology depended on the DCP content, and all blends exhibited the same crystallinity index. However, with increasing crosslinking degree, the interfacial tackiness (E) values increased from 1.8 to 2.7 nm. The lamellar structures of all blends started forming at approximately 160 °C, close to the temperature of pure polyamide. The crosslinked phase enhanced the pseudo‐elastic behavior of the blends and increased their molecular mobility activation energy. Samples with higher crosslinking degree exhibited smaller permanent deformation (0.01%) than those with low crosslinking. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44206.

Effect of Crosslinking on the Microtribological Behavior of Model Polymer Brushes

Polymer brushes in good solvents are known to exhibit excellent tribological properties. We have modeled polymer brushes and gels using a multibead-spring model and studied their tribological behavior via nonequilibrium molecular dynamics. Simulations of brush-against-wall systems were performed using an implicit solvent-based approach. Polymer chains were modeled as linear chains, randomly grafted on a planar surface. Quantities extracted from the simulations are the normal stress, shear stress and concentration profiles. We find that while an increase in the degree of crosslinking leads to an increase in the coefficient of friction, an increase in the length of crosslinker chains does the opposite. The effect of crosslinking can be understood in two ways: (1) There is a lower polymer concentration in the outer layer to take part in brush-assisted lubrication as the degree of crosslinking increases and (2) crosslinked polymer chains are more resistant to shear than noncrosslinked ones.

Diffusion coefficient, porosity measurement, dynamic and equilibrium swelling studies of Acrylic acid/Polyvinyl alcohol (AA/PVA) hydrogels

Objective of the present work was to synthesize hydrogels of acrylic acid/polyvinyl alcohol (AA/PVA) by free radical polymerization by using glutaradehyde (GA) as crosslinkers. The hydrogels were evaluated for swelling, diffusion coefficient and network parameters like the average molecular weight between crosslink’s, polymer volume fraction in swollen state, number of repeating units between crosslinks and crosslinking density by using Flory-Huggins theory. It was found that the degree of swelling of AA/PVA hydrogels increases greatly within the pH range 5-7. The gel fraction and porosity increased by increasing the concentration of AA or PVA. Increase in degree of crosslinking, decreased the porosity and inverse was observed in gel fraction. Selected samples were loaded with metoprolol tartrate. Drug release was studied in USP hydrochloric acid solution of pH 1.2 and phosphate buffer solutions of pH 5.5 and 7.5. Various kinetics models like zero order, first order, Higuchi and Peppas model were used for in vitro kinetic studies. The results showed that the drug release followed concentration dependent effect (First order kinetics) with non-Fickian diffusion. FTIR and SEM used to study the structure, crystallinity, compatibility, thermal stability and morphology of prepared and drug loaded hydrogels respectively.

Physicomechanical characterization of monodisperse multivesiculated polyester particles

This work describes physicomechanical properties of low-density polyester particles with multi-alveolar inner morphology, obtained via a water/oil/water double emulsion process. Monodisperse particle diameters were produced thanks to the use of a microchannel T-junction device for droplet generation. The drying conditions tested showed that rapid water evaporation at 120°C, combined with slow diffusion towards the exterior, causes internal fracture and particle deformation. Interestingly, all particles present virtually identical internal damage and external deformation features under these drying conditions, demonstrating the uniformity in internal structures. Drying at 70°C allows for efficient water removal with no damage. Thermomechanical transitions and thermal stability were analyzed by dynamic mechanical analysis (DMA in single-particle compression mode), dynamic scanning calorimetry (DSC) and thermogravimetry (TG). The effectiveness of curing conditions was evaluated by FTIR and DSC, allowing to identify the need of a thermal post-treatment for consumption of residual styrene. The consequent increase in degree of crosslinking produced a positive shift in glass transition temperature measured by DMA. Finally, mechanical reinforcement of the multivesiculated polyester particles was obtained by loading the polymer with surface-modified fumed silica, yielding 75% increase in storage modulus.

Preparation and physicochemical characteristics of cryogel based on gelatin and oxidised dextran

In this study, a novel method of preparation of cryogels based on oxidised dextran (Ox.D) and gelatin (Gel) without sodium borohydride is proposed. The physico-chemical properties of obtained hydrogels were investigated. It was found that the stability of cryogels Ox.D–Gel is significantly depended on pH, and mechanical properties were improved after the freeze drying. The schemes of the reactions between Ox.D and Gel at different steps of the treatment of the material were suggested. According to 1H-NMR data, the Amadori rearrangement occurred under the step of cryogelation. The increase of cross-linking degree through the formation of additional Schiff’s base group was observed as a result of incubation at high humidities or elevated temperature (60 °C). The obtained cryogels can be used as biocompatible and biodegradable scaffolds for proliferation of cells or other biomedical applications.

Promoting crystallization of polylactide by the formation of crosslinking bundles

In this study, the influence of crosslinking structures on the crystallization of polylactide (PLA) samples was investigated. Chemical-induced crosslinking method was adopted and crosslinking structures were successfully achieved in the presence of dicumyl peroxide (DCP) and triallyl isocyanurate (TAIC). Originally it was commonly suggested that crosslinking would block the motion of chains, thus hindering the crystallization process. However, our results indicate that low or moderate crosslinking bundles (not complete polymer network) can promote the crystallization of PLA samples to some extent. With further increasing crosslinking degree (from 12.1% to 41.2%), although the onset crystallization temperature can be increased as well, the perfection of crystal lamellas is inferior. Based on the experimental results, a schematic model is proposed.

Influence of crosslinking and peeling rate on tack properties of polyacrylic pressure-sensitive adhesives

Tack properties and peeling behavior of crosslinked polyacrylic pressure-sensitive adhesives were investigated. The model adhesive was a crosslinked poly(n-butyl acrylate-acrylic acid) random copolymer with an acrylic acid content of 5 mol% with various crosslinking degrees. Tack was measured using a probe tack test with probe rates of 1 and 10 mm/s and various contact time. The tack increased with contact time. The degree of tack rising with contact time decreased with an increase in crosslinking degree for 10 mm/s, while the tendency was opposite for 1 mm/s. The temperature dependency of tack was measured with a contact time of 30 s. The tack peak shifted to higher temperatures with an increase in crosslinking degree and probe rate. Peeling behavior was observed using high-speed microscopy. The peeling behavior changed from A to C with the decrease of peeling rate and crosslinking degree. A: Cavitation and peeling progressed simultaneously at maximum stress at 10 mm/s independent on the crosslinking degree. B: Cavitation occurred at the edge of the probe at low stress and spread to the center of the probe at maximum stress at 1 mm/s and high crosslinking degree, then peeled out. C: After B, fibrillation occurred at 1 mm/s with low crosslinking degree. The change of peeling behavior was caused by the following: the interfacial adhesion increased, while the cohesive strength decreased as crosslinking degree and probe rate decreased.

Swelling and mechanical properties of pH‐sensitive hydrogel filled with polystyrene nanoparticles

ABSTRACTWe investigated the effect of organic filler and the degree of crosslinking on the performance of a hydrogel/filler system to control its diffusion and mechanical properties. A series of poly(acrylic acid) gels filled with polystyrene (PS) nanoparticles at well‐controlled filler loading levels was synthesized by free radical polymerization in the presence of a crosslinking agent. Three different concentrations of the crosslinking agent (methylene bis‐acrylamide), that is, 5 mg/(g of AAc), 10 mg/(g of AAc), and 20 mg/(g of AAc), were used. The hydrogel crosslinked to the least extent that included a high amount of PS showed fast swelling rates, high equilibrium swelling ratios, and the highest pH sensitivity. Three gel/filler combinations including the gel without filler, gel/filler mixture, and gel/filler copolymerization were considered. The PS particles of ∼40 nm in diameter, which were used as the fillers, were prepared by microemulsion polymerization. Copolymerization of styrene and AAc having different reactivities ratios was achieved by a seed‐microemulsion polymerization with the crosslinking agent. The gel/filler mixture showed the highest swelling rate and the gel/filler copolymer resulted in highly enforced mechanical properties and the highest pH sensitivity. The incorporation of filler by copolymerization to mechanically enforce the equilibrium swelling hydrogel was more efficient than the increase of crosslinking degree. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3574–3587, 2013

Non-isothermal crystalliztion kinetics of poly(phenylene sulfide) with low crosslinking levels

Poly(phenylene sulfide) (PPS) with different crosslinking levels was successfully fabricated by means of high-temperature isothermal treatment (IT). The crosslinking degree of PPS was increased with IT time as revealed by Fourier-transform infrared spectroscopy and dynamic viscosity measurements. Its influence on the non-isothermal crystallization behaviors of PPS was studied by differential scanning calorimeter (DSC). The crystallization peak temperature of PPS with 6 h IT was 15 K higher than that of the one with 2 h IT at 30 K/min cooling rate. The non-isothermal crystallization data were also analyzed based on the Ozawa model. The Ozawa exponent m decreased from 3.5 to 2.2 at 232°C with the increase of the IT time, suggestive of intensive thermal oxidative crosslinking reducing the crystallite dimension as PPS crystal grew. The reduced cooling crystallization function K(T) was indicative of the larger activation energy of crosslinked PPS chain diffusion into crystal lattice, resulting in a slow crystal growth rate. Additionally, the overall crystallization rate of PPS was also accelerated with the increase of crosslinking degree from the observation of polarized optical micrograph. These results indicated that the chemical crosslinked points and network structures formed during the high-temperature isothermal treatment acted as the effective nucleating sites, which greatly promoted the crystallization process of PPS and changed the type of nucleation and the geometry of crystal growth accordingly.

Synthesis, self-assembly, and pH-responsive behavior of (photo-crosslinked) star amphiphilic triblock copolymer

Conventional polymeric micelles employed as drug carriers suffer from the drawback of disaggregation when diluted into body fluids, giving rise to premature release of drugs. In this work, cinnamate was chosen as a crosslinker to overcome this issue and regulate pH response. A series of photo-crosslinkable star amphiphilic triblock copolymers, star poly(ε-caprolactone)-b-poly(2-cinnamoyloxyethyl methacrylate)-b-poly(2-(dimethylamino)ethyl methacrylate) (SPCL-b-PCEMA-b-PDMAEMA), were prepared by combination of stepwise reversible addition-fragment chain transfer (RAFT) polymerization and carbodiimide-mediated coupling reaction. These star amphiphilic copolymers could self-assemble into core–shell-corona micelles. Facile photo crosslinking of the micelles was carried out via UV irradiation. The crosslinked micelles showed an improved stability determined by critical micelle concentration (CMC). The degree of photo crosslinking was easily regulated by tuning UV irradiation time, and the hydrodynamic diameters (Dh) decreased with increasing degree of photo crosslinking. The pH responses of micelles were investigated by dynamic light scattering (DLS), indicating pH-induced swelling-shrinking behavior. For photo-crosslinked micelle, its capability of swelling-shrinking weakened with increasing crosslinking degree, suggesting that pH response was controlled by crosslinking density. This novel photo-crosslinked micelle system with adjustable pH response was expected to have potential as drug carriers for controlled release.

Synthesis and characteristics of poly(methyl methacrylate-methacrylic acid-3,3-(trimethoxysilyl) propyl methacrylate) hollow latex particles and their application to drug carriers

In this study, the hollow latex particle was synthesized by three processes. The first process was to synthesize the poly(methyl methacrylate-co-methacrylic acid) (poly(MMA-MAA)) copolymer latex particles by the method of soapless emulsion polymerization. Following the first process, the second process was to polymerize MMA, MAA, 3,3-(trimethoxysilyl) propyl methacrylate (MPS), and ethylene glycol dimethacrylate in the presence of poly(MMA-MAA) latex particles to form the linear poly(MMA-MAA)/crosslinking poly(MMA-MAA-MPS) core–shell latex particles. In the third process, the core–shell latex particles were heated in the presence of ammonia to form the poly(MMA-MAA-MPS) hollow latex particles. A sufficient heating time and high-heating temperature were necessary for the ammonia to dissolve the linear poly(MMA-MAA) core to form a perfect hollow structure. The crosslinking poly(MMA-MAA-MPS) shell was a barrier for the ammonia to diffuse into the latex particles so that the latex particle with the high-crosslinking shell showed an imperfect hollow structure. Besides, the hollow poly(MMA-MAA-MPS) latex particles reacted with ZnO nanoparticles, which were synthesized by a traditional sol-gel method, to form the polymer/inorganic poly(MMA-MAA-MPS)/ZnO composite hollow latex particles. With the increase of crosslinking degree would increase the amount of ZnO bonding. Moreover, the poly(MMA-MAA-MPS) hollow latex particles were used as carriers to load with the model drug, caffeine. The release of caffeine from poly(MMA-MAA-MPS) hollow latex particles was investigated.

Permeation of Chlorinated Hydrocarbon Vapors through High Density Polyethylene/Ethylene Propylene Diene Terpolymer Rubber Blends

Polymer membranes were prepared by blending high density polyethylene (HDPE) with ethylene propylene diene terpolymer rubber (EPDM) and were tested for vapor permeation characteristics. The variation in sorption, diffusion, and permeation coefficients with blend composition has been studied and it was found that in these blends the permeability coefficient and sorption coefficients increased with increase in EPDM concentration. The permeation rate decreased with the increase in molecular mass of the penetrants. The permeability of the HDPE/EPDM blends vulcanized with three different vulcanizing systems has been studied and found that as the degree of crosslinking increases, the permeability decreases. The permeability measurements provide useful information on the morphology changes with composition of the blends and on the composition corresponding to the maximum level of co-continuity of the two phases.

Effect of Glycerin and Starch Crosslinking on Molecular Compatibility of Biodegradable Poly(lactic acid)-Starch Composites

Poly(lactic acid) (PLA) is a biodegradable material. However, PLA is relatively cost effective. Blending starch with PLA is one of the promising efforts because starch is a widely distributed and inexpensive product. PLA and starch were blended using a rheometer to form composites in this report. Glycerin was added into the blends to make the mixture molecular compatible and more homogeneous. The starch was crosslinked using epichlorohydrin to improve the compatibility of starch with PLA. Two series of composite were fabricated. One was PLA and the crosslinked starch containing 32 wt% glycerin. In this group, the crosslinking degree of the modified starch was varied. The second group was PLA and non-crosslinked starch with varied amount of glycerin added. Micro-structure of the blending composites was observed using a SEM to view the homogeneity of the mixture. The SEM pictures indicated that the compatibility of PLA and starch molecules was poor. The addition of glycerin can change the compatibility of PLA and starch. The higher the glycerin content in the composites, the better the compatibility between PLA and starch. Furthermore, when the starch was crosslinked by epichlorohydrin, the compatibility of PLA and starch can be greatly improved. The compatibility increases with the increase of crosslinking degree. This is due to the change of hydrophilicity of starch because the hydroxyl groups on the starch molecules were crosslinked into ether groups by the epichlorohydrin molecules.

Kinetics and molecular orbital calculations of desulfonation of strong acid cation-exchange resin

This paper deals with the desulfonation properties of some strong acid cation-exchange resins. The sulfate concentration in solution is continuously increased when a strong acid cation-exchange resin is mixed with water. The leaching of sulfate results from the desulfonation of the fixed group, and the amount of leached sulfate depends on the counter ion charge, the crosslinking degree and the exchanger matrix. The effects of the counter ion charge on the desulfonation rate suggested that the counter ion induces the nucleophilic attack of a water molecule on the sulfo group. This interpretation was supported by semiempirical molecular orbital calculations for the C 6H 5SO 3 −M m+ (M m+ = Na +, Mg 2+ and Al 3+) systems, and the transition state of the Na + system was successfully predicted by DFT calculations. The crosslinking degree influenced the desulfonation rate, which can be related to the decreasing hydration number of each counter ion in the resin phase with the increasing crosslinking degree. Furthermore, different exchanger matrices produced the differences in the rates, which may be derived from the electron-density donation from the exchanger matrix to the sulfo group. The desulfonation is governed by the electron-density of the sulfur atom and the water activity in the solid phase.