Effect of vinylacetate content on crystallinity and second-order transitions in ethylene—vinylacetate copolymers

Thermal characteristics of ethylene—vinylacetate (EVA) copolymers having vinylacetate contents ranging from 5 to 40 w/w % are studied by differential scanning calorimetry. It is first shown that EVA copolymers having a vinylacetate content lower than 30 w/w % obey the Flory and Burfield theories of copolymer crystallisation. The minimum sequence length of CH₂ ethylenic entities required to participate in a crystalline lamella is also deduced. One can conclude that EVA copolymers represent cases of “total exclusion” of the noncrystallizable comonomer. Moreover, it is observed that when the vinylacetate content is increased, the relative quantity of polyethylene amorphous phase increases and the degree of crystallinity decreases; whereas the β transition temperature of a characteristic-oriented amorphous phase is kept constant. A phase model of ethylene-vinylacetate copolymers, based on an enrichment process of the interlamellar amorphous phase by polyethylene segments originating from the crystalline phase, at increasing vinylacetate content, is proposed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1903–1912, 1997     

Studies of crosslinked styrene–alkyl acrylate copolymers for oil absorbency application. I. Synthesis and characterization

The prepolymers for a novel oil absorbent were synthesized by copolymerizing styrene with 2‐ethylhexyl acrylate (EHA), lauryl acrylate (LA), lauryl methacrylate (LMA), and stearyl acrylate (SA). Suspension polymerization was carried out using benzoyl peroxide (BPO) as an initiator with a varying monomer feed ratio, and the copolymers were characterized by FTIR, ¹H‐NMR, DSC, and a solubility test. The copolymers were random copolymers with a single phase, and their compositions were similar to those in the monomer feed. The T_g of the copolymer could be controlled by varying the styrene/acrylate ratio. Acrylates introduced the crosslinking to linear polymers as a side reaction. Crosslinked copolymers were synthesized by adding divinylbenzene (DVB) as a crosslinking agent. At a low degree of crosslinking (0.5 wt % DVB), the T_g of the crosslinked copolymers was lower than or similar to that of the uncrosslinked ones. At a high degree of crosslinking, the T_g increased with increasing crosslinking density. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 903–913, 2000     

Physical properties of high-pressure ethylene vinylacetate copolymers and their saponified derivatives

The physical properties of high-pressure ethylene vinylacetate (EVA) copolymers having an average melt index of 8.5 g/10 min and a mol% of VA less than 20 are studied. A comparison is made with the properties of their saponified derivatives, the ethylene vinylalcohol (EVAl) co- and ethylene vinylalcohol vinylacetate (EVAlVA) terpolymers. A melt-index effect is noted. Density, thermal, and mechanical properties of EVA copolymers are determined by the degree of crystallinity, which depends on the mol% VA and on the degree of alkyl shortchain branches. EVAlVA terpolymer properties depend on the residual mol% VA. EVAl copolymers proved to have some properties similar to low-density polyethylene. The hydrogen-bonding effect via hydroxyl groups was negligible for this level of vinylalcohol incorporation.     

Adsorption of Zn(II) by crosslinked acrylic copolymers with amine functional groups

Adsorption of Zn(II) ions from diluted aqueous solutions by the acrylic copolymer based on ethylacrylate : acrylonitrile : divinylbenzene matrix with different crosslinking degrees and ethylenediamine and triethylenetetramine functional groups was investigated. Adsorption experiments were carried out by batch method. The effects of the pH, initial concentration of zinc, time of contact, and the crosslinking degree of the copolymers were studied. On the basis of Langmuir and Freundlich isotherms, the parameters that characterize the adsorption were determined. The maximum Zn(II) retention capacity value (500 mg g^?1) was obtained for the acrylic copolymer with 2% crosslinking degree and ethylenediamine, as functional groups. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 803–808, 2004     

Manipulating the microstructure and rheology in polymer‐organoclay composites

A series of nanocomposites prepared by melt‐blending of cloisite‐based organoclays with poly(ethylene‐vinylacetate) (EVA) and neutralized poly (ethylene‐methacrylic acid) (EMA) copolymers were investigated via DSC, small‐angle X‐ray scattering (SAXS), and rheological techniques. SAXS results indicated partial clay exfoliation in all samples. In both EMA and EVA systems, the nominal melting temperature T_m and bulk crystallinity are not significantly affected by the presence of organoclays, suggesting that clay particles are predominantly confined in the amorphous phase. In rheological measurements (above T_m), the EVA‐clay system demonstrated a solid‐like rheological behavior under the small‐strain oscillatory shear, yet it was able to yield and flow under a steady shear, which is the characteristic of physical crosslinking. In contrast, the EMA‐clay system exhibited a melt‐like rheological behavior, where the influence of organoclay on the thermorheological behavior of the EMA composite was quite minimal. We propose that the carbonyl groups of vinylacetate in EVA interact with the clay surface, resulting in a strong physically crosslinking like interaction in the melt. On the other hand, the interaction between EMA and clay is weak because of repulsion between carboxyl anions and negatively charged clay surface.     

Die Darstellung von Gelen als stationäre Phase für die Gelchromatographie

The influence of the mode of synthesis on the characteristics of crosslinked polymers is examined for crosslinked copolymers of ethylvinylbenzol/divinylbenzol and vinylacetate/divinyladipate. Homogeneously crosslinked gels are mostly suited for separation of oligomers; polymers are able to be separated by use of heterogeneously crosslinked gels. It is demonstrated that in case of a heterogeneously crosslinking polymerization the heterogenity of the copolymers with decreasing solvatizing ability of the inert component is increasing; this leads simultaneously to an increase of the excluded molecular weight.     

Quantitative valuation of composition in vinylformal,vinylacetate and vinylalcohol ter-copolymers by1H- and13C-n.m.r. spectroscopy

The¹³C-n.m.r. signals were assigned to the composing structural groups of the copolymers. The composition of the copolymers was determined by¹³C n.m.r. using the NOE extinction technique. The analyzed samples were synthesized under normal and relatively mild reaction conditions. Despite this and purification methods that avoided elevated temperatures, it was not possible to find hemiformal groups in any amount. Therefore it is possible to analyze these copolymers composed of formal, vinylacetate and vinylalcohol structural groups in a relatively easy way by means¹H n.m.r.     

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

This 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.     

Crystallization and photo‐curing kinetics of biodegradable poly(butylene succinate‐co‐butylene fumarate) short‐segmented block copolyester

Short‐segmented block copolymers of poly(butylene succinate‐co‐butylene fumarate) were synthesized and their crystallinity and crosslinking behavior were investigated. ¹H NMR was used to characterize the microstructure and composition of the copolyesters. Molecular weight determination was performed using gel permeation chromatography. Based on the DSC results all copolyesters were crystalline and the degree of crystallinity of the copolymers did not change with butylene fumarate mole fraction due to co‐crystallization of the butylene succinate and butylene fumarate groups. Crosslinked copolyesters showed a lower crystallization rate and degree of crystallinity while the crystallization temperature shifted to higher temperatures compared with uncrosslinked copolyesters due to the formation of nucleating agents by crosslinkages. Photo‐DSC was used to investigate the crosslinking kinetics for UV‐initiated photo‐curing. Three kinetics parameters including the rate constant (k) and the orders of the initiation and propagation reactions (m and n, respectively) were determined for the quenched and unquenched copolymers. © 2016 Society of Chemical Industry     

Kinetics of silane grafting and moisture crosslinking of polyethylene and ethylene propylene rubber

Peroxide initiated graft copolymerization of vinyl trimethoxy silane (VTMO) and vinyl triethoxy silane (VTEO) onto polyethylene (PE) and ethylene propylene copolymer (EPR) was studied. The kinetics of grafting, studied by differential scanning calorimetry, are the same for all the systems and the activation energy for VTMO is 170 ± 4 KJ/mol. Activation energy for VTEO is 185 ± 5 KJ/mol. The VTMO and VTEO graft copolymers of PE and EPR were prepared by reactive processing in a Brabender extruder in the temperature range of 150–200°C. Moisture catalyzed crosslinking of the silane grafted copolymer was also studied. The influence of the structure of the catalyst, its concentration, moisture concentration, temperature, and time on degree and rate of crosslinking has been evaluated. Crosslinking reactions follow first order kinetics with respect to both catalyst and moisture concentration. Activation energy (E_a) of the crosslinking reaction has been determined as 65 KJ mol^?1. The mechanism of grafting and crosslinking is discussed.     

Synthesis and swelling properties of grafting‐type and crosslinking‐type water‐swellable elastomers

A grafting water‐swellable elastomer (WSE) that is, chlorinated polyethylene (CPE)‐graft‐poly(ethylene glycol) (PEG), was synthesized by a grafting reaction. The synthesis was based on the reaction between chlorine in CPE and sodium salt of PEG. PEG with molecular weights of 600 and 1000 were used. The maximum grafting percentage of the resulted copolymers after purification was 9.79%. The structure of the copolymer was confirmed by an IR spectrum. The grafting degree and PEG content increased with increasing reaction time and reaction temperature. The equilibrium swelling degree of the grafting copolymer was very small, only 16.94%. However, for the crosslinking WSE, the swelling degree was influenced by the absorbency temperature and absorbency time. The absorbency rate was faster than that of the grafting WSE, and the swelling degree in the equilibrium state was higher than that of the grafting WSE, too. The maximum swelling degree of the crosslinking WSE was 70%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2637–2642, 2007     

Shape memory effect of ethylene–vinyl acetate copolymers

Crosslinked ethylene–vinyl acetate (EVA) copolymers with VA content of 28% by weight were prepared by a two‐step method by evenly dispersing the crosslinking agent (dicumyl peroxide) into the EVA matrix and then crosslinking at elevated temperatures. The crosslinking features of the samples were analyzed by Soxhlet extraction with xylene and dynamic mechanical measurements. All the samples were crystalline at room temperature, and the chemical crosslinks seemed to have little effect on the melting behavior of polyethylene segment crystals in the EVA copolymers. The shape recovery results indicated that only those specimens that had a sufficiently high crosslinking degree (gel content higher than about 30%) were able to show the typical shape memory effect, a large recoverable strain, and a high final recovery rate. The degree of crosslinking can be influenced by the amount of the peroxide and the time and temperature of the reaction. The response temperature of the recovery effect (about 61°C) was related to the melting point of the samples. The EVA shape memory polymer was characterized by its low recovery speed that resulted from the wide melting range of the polyethylene segment crystals. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1063–1070, 1999     

Methacrylic acid microcellular highly porous monoliths: Preparation and functionalisation

By polymerisation of high internal phase emulsions (HIPEs), containing styrene (STY), divinylbenzene (DVB) and methacrylic acid (MAA) in the continuous phase, highly porous polymers including carboxylic functional groups were prepared. The ratio of methacrylic acid to divinylbenzene was varied in order to obtain polyHIPEs with a different degree of crosslinking which influenced a surface area of the polymers, being substantially higher (185 m²/g) with a higher degree of crosslinking (51% DVB) than with a lower degree of crosslinking (24% DVB, 46 m²/g). Up to 90% porous samples were prepared and the optimum hidrophilicity-lipophilicity balance (HLB) of the surfactant was found to be around 4.8–4.9. Both thermal and photo initiation were used to induce polymerisation. The resulting polymers had an open cellular morphology with cavity diameters between 21.8 μm and 44.2 μm and with interconnecting pores between 2.2 μm and 5.0 μm. Monolithic supports were used for further functionalisation with thionyl chloride and multifunctional amines, namely 1,4-diaminobutane and 1,12-diaminododecane. The functionalisation degree with thionyl chloride was 76%.     

Swelling of High Oil-Absorptive Network Based on 1-Octene and Isodecyl Acrylate Copolymers

Crosslinked 1-octene-isodecyl acrylate copolymers were synthesized and evaluated for oil-absorbency application. The copolymer was crosslinked at different concentrations of ethylene glycol diacrylate (EGDA) and ethylene glycol dimethacrylate (EGDMA) crosslinkers via catalytic initiation or by electron-beam irradiation at dose rate 80 kGy. The concentration of both crosslinkers was varied from 0.5% to 2%. The effect of crosslinking conditions, such as crosslinker concentration, method of polymerization and monomers concentration on conversion and gel fraction was examined through an oil-absorption test using petroleum crude oil. It was found that, the oil absorbency was influenced mainly by the degree of crosslinking and the hydrophobicity of the copolymer units. The final equilibrium oil content, volume fraction of polymer and swelling capacity were determined at 298 K. The effective crosslinking density V_e, the average molecular weight between the crosslinks M_c and the polymer-toluene interaction parameter were determined from stress–strain measurements. The crosslinking efficiencies of EGDA and EGDMA towards copolymers were determined.     

Synthesis and characterization of biodegradable copolymers based on 6-aminocaproic acid and α-L-alanine

Random copolymers based on 6-aminocaproic acid and α-L-alanine were prepared by melt phase polycondensation method and characterized by FTIR, ¹H NMR, DSC and WAXD. The density, water absorptivity and enzymatic degradation of copolymers were measured. The results show that with increasing of alanine content in comonomers, the density, water absorptivity and rate of enzymatic degradation of copolymers increase, but the intrinsic viscosity and the degree of crystallization decrease. When the molar percentage of alanine increases to 40% in comonomers, copolymer is amorphous.     

Effect of the composition and degree of crosslinking on the properties of poly(l‐lactic acid)/crosslinked polyurethane blends

Poly(l ‐lactic acid)/crosslinked polyurethane (PLLA/CPU) blends which were prepared via reactive blending of PLLA with poly(?‐caprolactone) (PCL), glycerol and 4,4′‐methylenediphenyl diisocyanate showed excellent toughness. The effects of the composition of the mixture and degree of crosslinking of CPU on the toughness of the PLLA/CPU blends (80/20 w/w) were studied in detail. Dynamic mechanical analysis and rheological measurements were used to characterize the structure of the in situ formed CPU in the PLLA matrix. A novel netlike phase structure was observed when the average molecular weight of PCL and degree of crosslinking were 1 kDa and 10%, respectively. The impact strength of the blend was enhanced from 2.2 kJ m^?2 for pure PLLA to 62.4 kJ m^?2; meanwhile, the elongation at break was increased to 489.8%. Therefore, the mechanical properties of PLLA/CPU blends can be easily tailored by tuning the composition of the mixture and the degree of crosslinking of CPU. © 2018 Society of Chemical Industry     

Structure of some styrene–divinylbenzene copolymers

Structures of copolymers of styrene and divinylbenzene (50% crosslinking degree) prepared in suspension polymerization in the presence of mixtures of nonsol (heptane or decane) and sol (toluene or tetralin) diluents were investigated. The studies showed that the diluents enriched with nonsol solvents resulted in an increase of pore volumes and posities for the prepared copolymers. The sol diluents affected mainly the gel regions of the polymer matrices. Isotropic swelling of the matrices prepared in the presence of toluene is the opposite of the effect observed for tetralin family copolymers. The virtual difference of both kind of matrices was demonstrated in the sorption of phenol. The tetralin family copolymers were characterized by a prolonged time for column breakthrough. © 1995 John Wiley & Sons, Inc.     

Glutaraldehyde‐crosslinked chitosan/hydroxyapatite bone repair scaffold and its application as drug carrier for icariin

Chitosan/hydroxyapatite (CS/HA) bone repair scaffolds crosslinked by glutaraldehyde (GA) were prepared. Characterization of morphology, structure, mechanical property, and porosity of scaffolds were evaluated. The influences of CS viscosity, HA content, and crosslinking degree on properties of scaffolds were discussed. SEM images showed that CS/HA scaffolds were porous with short rod‐like HA particles dispersing evenly in CS substrate. When [η]_CS = 5.75 × 10^?4, HA content = 65%, and crosslinking degree = 10%, the resulting CS/HA scaffolds had a flexural strength of 20 MPa and porosity of 60%, which could meet the requirements of bone repair materials. The scaffolds were used as drug carriers for icariin, and the impacts of loading time and crosslinking degree of scaffolds on drug‐loading dose were discussed. The suitable loading time was 24 h and it would be better to keep crosslinking degree no more than 10%. The drug release behavior demonstrated that the icariin‐loading CS/HA scaffolds could achieve basic drug sustained release effect. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1539–1547, 2013     

Morphology and thermal properties of liquid crystal p‐PAEB/n‐propyl methacrylate copolymers

The copolymers of p‐phenylene di{4‐[2‐(allyloxy) ethoxy]benzoate} (p‐PAEB) with n‐propyl methacrylate (PMA) were synthesized. The liquid crystalline behavior and thermal properties of copolymers were studied by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), X‐ray diffractometer (XRD), and torsional braid analysis (TBA). The results of XRD, POM, and DSC demonstrate that the phase texture of copolymers is affected by the composition of liquid crystal units in copolymers. The POM and XRD reveal that liquid crystal monomer (p‐PAEB) and copolymers of p‐PAEB with PMA are all smectic phase texture. The dynamic mechanical properties of copolymers are investigated with TBA. The results indicate that the phase transition temperatures and dynamic mechanical loss peak temperature T_p of copolymers are affected by the composition of copolymers and liquid crystal cross networks. The maximal mechanical loss T_p is 114°C and is decreased with added PMA. The behaviors of phase transition are affected by the crosslinking density, and it is revisable for lightly crosslinking LC polymer networks, but it is nonreversible for the densely crosslinking of LC polymer networks. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Using conjugated system from natural sources for the synthesis of sulfur copolymers by bi-function catalysts at mild temperatures

Sulfur-rich polymers are promising materials to cover several applications including mercury capture adsorbents. Tung oil, a natural conjugated triene triglyceride oil, were selected to prepare sulfur-rich copolymers. The unique second monomer made reaching the gel point possible at a mild temperature of 130°C in 2.5 h. The reaction accomplishment was confirmed by the depletion of double bonds in tung-oil-sulfur copolymers measured by ¹H NMR, FTIR, XRD, and DSC. A bi-function catalyst calcium hydroxide accelerates the reactions between triglyceride and sulfur before it is removed to increase the surface area and achieve the aims of preparing adsorbents, which has zero free sulfur, high crosslinking degree, and efficient mercury capture. Newly developed tung-oil-sulfur copolymers catalyzed by calcium hydroxide offer the possibility to synthesize sulfur-rich copolymers that combine the advantages of the high performance and the utility of greener and more environmental friendly raw materials.