Showing papers on "Vinyl acetate published in 2019"

Fingerprint analysis of FTIR spectra of polymers containing vinyl acetate

Abstract: The analysis of materials using Fourier transform infrared (FTIR) spectroscopy has a unique area called the fingerprint region for each compound. However, this area is almost never discussed because of its complexity due to the large number of signals that appear in it. In this work, the fingerprint region analysis of the ethylene–vinyl acetate copolymer (EVA) with different percentages of vinyl acetate (VA) (18%, 28%, 40%) was performed. In comparison with other instrumental techniques, the crystallinity and structural arrangement of the EVA copolymers were determined simply and economically. The crystallinities for EVA18, EVA28 and EVA40 were 24.39%, 6.95% and1.03%, respectively. In terms of structural ordering, the number of linear chains of EVA copolymer decreases as the concentration of VA increases, which favors the reduction of degrees of freedom and the formation of hydrogen bonds.

Enzyme-Catalyzed Synthesis of Esters in Water

Abstract: MsAcT catalyzes the esterification of primary alcohols in water. When utilizing acid and alcohol as starting materials low yields dictated by thermodynamics were observed. However, with activated esters such as ethyl acetate and vinyl acetate very high yields of the desired ester can be achieved in combination with the appropriate alcohol. This study investigated both the intrinsic kinetic properties of MsAcT for the hydrolysis and transesterification of esters in water as well as the thermodynamics of the reaction. In comparison to the chemical or enzymatic ester synthesis using either toxic reagent, and harsh organic solvents, the MsAcT-catalyzed synthesis of esters of primary alcohols can be achieved efficiently in water without neutralization steps.

Structural investigation and enhancement of optical, electrical and thermal properties of poly (vinyl chloride-co-vinyl acetate-co-2-hydroxypropyl acrylate)/graphene oxide nanocomposites

Abstract: Different concentrations of graphene oxide (GO) were successfully embedded into poly (vinyl chloride-co-vinyl acetate-co-2-hydroxypropyl acrylate) (PVVH) copolymer. The composites obtained were characterized using XRD, FT-IR, SEM and UV/Vis techniques, in addition to investigating their electrical properties. XRD results showed the predominance of the amorphous phase inside the prepared samples. The main characteristic peaks of the used materials were observed in FT-IR spectra with changes in their intensities and/or their positions, confirming the successful complexation and strong interaction between GO and PVVH. A bathochromic shift in the main absorption sharp edge was detected in UV/Vis spectra. Additionally, the two peaks at 214 and 280 nm were ascribed to n→π* and π→π* transitions, respectively. Both optical energy gap and refractive index were calculated in terms of UV/Vis absorption spectra using Mott–Davis model and Dimitrov–Sakka equation. The thermal behavior of the current samples was carefully investigated by employing TGA. Moreover, the activation energy was studied using Coats-Redfern and Broido models. The homogeneous dispersion of GO has contributed to the significant increase in the electrical conductivity as well as improving thermal stability of the PVVH-based nanocomposites. The experimental results obtained for the current system promote these nanocomposites for use in optoelectronic applications.

Oxygen‑Triggered Switchable Polymerization for the One‑Pot Synthesis of CO 2 ‑Based Block Copolymers from Monomer Mixtures

Abstract: Switchable polymerization provides the opportunity to regulate polymer sequence and structure in a one-pot process from mixtures of monomers. Herein we report the use of O2 as an external stimulus to switch the polymerization mechanism from the radical polymerization of vinyl monomers mediated by (Salen)CoIII -R [Salen=N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine; R=alkyl] to the ring-opening copolymerization (ROCOP) of CO2 /epoxides. Critical to this process is unprecedented monooxygen insertion into the Co-C bond, as rationalized by DFT calculations, leading to the formation of (Salen)CoIII -O-R as an active species to initiate ROCOP. Diblock poly(vinyl acetate)-b-polycarbonate could be obtained by ROCOP of CO2 /epoxides with preactivation of (Salen)Co end-capped poly(vinyl acetate). Furthermore, a poly(vinyl acetate)-b-poly(methyl acrylate)-b-polycarbonate triblock copolymer was successfully synthesized by a (Salen)cobalt-mediated sequential polymerization with an O2 -triggered switch in a one-pot process.

Nonmigratory Poly(vinyl chloride)- block-polycaprolactone Plasticizers and Compatibilizers Prepared by Sequential RAFT and Ring-Opening Polymerization (RAFT-T-ROP)

Abstract: Well-defined nonmigrating polymeric plasticizers, poly(vinyl chloride)-block-polycaprolactone (PVC-b-PCL), were synthesized by sequential reversible addition–fragmentation chain transfer (RAFT) polymerization and ring-opening polymerization (ROP) with 2-hydroxyethyl 2-(ethoxycarbonothioylthio)propanoate (HECP) as RAFT agent and incipient initiator for ROP of e-caprolactone (CL, oxepan-2-one). Kinetic experiments demonstrated that HECP provided good control in RAFT polymerization of vinyl chloride (VC) with dispersity (Đ) ∼ 1.2 for 3400 < Mn < 11000. Chain extension experiments with VC and vinyl acetate proved the high end-group fidelity of the macroRAFT agent formed. The hydroxy end-group of the PVC macroRAFT agent allowed its use as a ROP initiator in forming a series of PVC-b-PCL with different PCL block lengths by RAFT-T-ROP. Characterization by wide-angle X-ray diffraction (WAXD), polarized light microscopy (PLM), and differential scanning calorimetry (DSC) indicates that there is enhanced chain enta...

The Thermal and Mechanical Properties of Poly(ethylene-co-vinyl acetate) Random Copolymers (PEVA) and its Covalently Crosslinked Analogues (cPEVA).

Abstract: The thermal and mechanical properties of poly(ethylene-co-vinyl acetate) random copolymers (PEVA) and its covalently crosslinked analogues (cPEVA) were controlled by the overall crystallinity of the polymer networks. The cPEVAs with different VA-content were synthesized by thermally-induced crosslinking of linear PEVA with dicumyl peroxide (DCP). This work was mainly concerned with the effect of vinyl acetate (VA) content on the crosslinking density, thermal and mechanical properties of PEVAs and cPEVAs, respectively. The chemical composition was analyzed by thermogravimetric analysis and 1H-NMR. The thermal and mechanical properties of PEVAs and cPEVAs have been studied through a series of conventional analytical methods, including gel content determination, different scanning calorimetry, thermogravimetric analysis, dynamic mechanical thermal analysis and traditional mechanical measurements. The experimental results show that the thermal and mechanical properties of PEVAs and cPEVAs increase with decreasing the VA-content. A broad melting transition with a ΔTm in the range from 78 °C to 95 °C was observed for all polymer networks.

Effect of flow rate on wetting and optical properties of electrospun poly(vinyl acetate) micro-fibers

Abstract: In this work, extremely hydrophobic micro-fibers from polyvinyl acetate (PVAc) were obtained by changing the flow rate of the solution in electrospinning process. Surface morphologies and wettability of the fiber surfaces were strongly affected from the flow rate of the electrospinning solutions; it was found that with the increase of flow rates from 2 to 5 mL/h, the diameters of the fibers have shown an increase from 3.22 to 4.75 μm, and also water contact angle (CA) values were increased up to 146°. Equilibrium (θe) and advancing (θa) CA results showed us that fiber surfaces become extremely hydrophobic in the case of 4 mL/h and 5 mL/h solution flow rates and CA values were measured 148° and 161°, respectively. Increase in flow rates has changed the optical transmittance values; PVAc fibers have shown lower light transmittance and poor transparency at higher flow rates. When flow rates were increased from 2 to 5 mL/h, the transmittance values have shown a decrease from 3 to 0.25% and 2.5 to 0.25%, at 400 nm and 700 nm, respectively.

Laboratory and Field Experiments on the Effect of Vinyl Acetate Polymer-Reinforced Soil

Abstract: Soil stabilizer can enhance the soil properties, which can improve ecological environmental problems such as soil erosion and slope instability. This study investigates the water-related and mechanical properties of soil stabilization using a polymer soil stabilizer solution synthesized from vinyl acetate polymer. The water properties test, mechanical properties test, durability test and seed growth test were carried out in the laboratory. Also, the effect of vinyl acetate polymer was verified by field tests. The results revealed that vinyl acetate polymer can enhance the water-retaining property, anti-erosion resistance, strength property and durability of soil, all of which increase with the increase of polymer concentration. At the same time, the polymer also has a certain promoting effect on vegetation growth. In addition, field tests proved that vinyl acetate polymer has good effects on soil engineering. These results could be applied as a reference for vinyl acetate polymer-improved soil engineering.

Sustainable Approach for the Direct Functionalization of Cellulose Nanocrystals Dispersed in Water by Transesterification of Vinyl Acetate

Abstract: Herein we report a novel method for a high-yield surface esterification of cellulose nanocrystals (CNCs) in water, by transesterification of vinyl esters. The esterified nanoparticles were simply p...

Two-dimensional liquid chromatography with active solvent modulation for studying monomer incorporation in copolymer dispersants.

Abstract: A pseudo-comprehensive two-dimensional liquid chromatography approach with size exclusion chromatography in the first dimension and gradient reversed-phase liquid chromatography in the second dimension was successfully developed for the characterization of vinyl acetate/acrylic acid copolymers and vinyl acetate/itaconic acid/acrylic acid terpolymers. Active solvent modulation was exploited to prevent the polymer breakthrough in the second dimension separation caused by the strong solvent used in the first dimension. The conditions of the active solvent modulation valve were optimized to achieve sufficient on-line dilution and to completely prevent polymer breakthrough without adding excessive time to the modulation cycle. Using this approach, copolymers made with different monomer ratios and processes were studied. Heterogeneous composition distribution due to insufficient monomer incorporation was detected in some of the copolymer samples. We demonstrated that with active solvent modulation, the two-dimensional liquid chromatography approach is no longer limited to water-soluble polymers and can be used for a broader range of polymers and copolymers.

Interplay of Head, Tail, and Mid-Chain Radicals in Bulk Free-Radical and Reversible Degenerative Addition Fragmentation Chain-Transfer Polymerizations of Vinyl Acetate

Abstract: A detailed kinetic model for isothermal bulk free-radical and degenerative reversible addition–fragmentation chain-transfer (RAFT) polymerizations of vinyl acetate is presented up to monomer conversions of ca. 0.95, considering a distinction between head and tail end-chain radicals and primary and tertiary mid-chain radicals (MCRs). Diffusional limitations are taken into account for conventional initiation and termination, with a reduction of the gel-effect as chain transfer to the monomer lowers the apparent termination reactivities. The tail radicals are essential for the accurate description of backbiting and RAFT deactivation and the primary MCRs for chain transfer to the polymer. The model is based on the application of the method of moments with over 100 macrospecies types and thousands of reactions to obtain the temporal evolution of the monomer conversion, the number and mass average chain length, the number fraction of short- and long-chain branches, the number fraction of unsaturated chains, and the number fraction of chains with head-to-head defects. After a successful model validation of the experimental literature data, the model is applied to understand the complex interplay of the radical types involved and to highlight the control of the branching and unsaturation amounts under RAFT polymerization conditions. Head-to-head defects can however not be avoided for realistic average chain lengths.

Solvent-Free Acetylation of Cellulose by 1-Ethyl-3-methylimidazolium Acetate-Catalyzed Transesterification

Abstract: Cellulose acetate is one of the oldest synthetic thermoplastic polymers and has various applications including usage as films, fibers, and membrane products. Traditionally, cellulose acetate is pre...

Electrospinning of Ethylene Vinyl Acetate/Carbon Nanotube Nanocomposite Fibers.

Abstract: Nanocomposites, based on an ethylene vinyl acetate (EVA) copolymer with a vinyl acetate content of 34 wt % and varying amounts of multiwall carbon nanotubes (MWCNTs), were prepared by an electrospinning method. The dispersibility of the MWCNTs in the solution was improved by using cholesteryl 1-pyrenecarboxylate (PyChol) as a compatibilizer. The transmission electron microscopy images showed that the MWCNTs were aligned inside of the elastomeric matrix by the electrospinning process. The morphologies of the fibers were evaluated by scanning electron microscopy. When the amount of MWCNTs in the polymer solution reached 3 wt %, fibers with a diameter of 846 ± 447 nm were prepared. The chemical composition of the prepared fibers was investigated by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). FTIR results confirmed the presence of a carboxyl group, originating from the presence of PyChol. XPS results showed that the EVA fibers produced by electrospinning were oxidized in ethylene units, when comparing the spectra of the original EVA granules, but the presence of MWCNTs enhanced the stability of the EVA. The thermal stabilities of the fibers were tested with thermogravimetric analysis. The results confirmed that the presence of MWCNTs inside the fibers enhanced the thermal stabilities of the prepared nanocomposites.

Fabrication, Characterization, and Properties of Poly (Ethylene-Co-Vinyl Acetate) Composite Thin Films Doped with Piezoelectric Nanofillers

Abstract: Ethylene vinyl acetate (EVA) is a copolymer comprehending the semi-crystalline polyethylene and amorphous vinyl acetate phases, which potentially allow the fabrication of tunable materials. This paper aims at describing the fabrication and characterization of nanocomposite thin films made of polyethylene vinyl acetate, at different polymer concentration and vinyl acetate content, doped with piezoelectric nanomaterials, namely zinc oxide and barium titanate. These membranes are prepared by solvent casting, achieving a thickness in the order of 100–200 µm. The nanocomposites are characterized in terms of morphological, mechanical, and chemical properties. Analysis of the nanocomposites shows the nanofillers to be homogeneously dispersed in EVA matrix at different vinyl acetate content. Their influence is also noted in the mechanical behavior of thin films, which elastic modulus ranged from about 2 to 25 MPa, while keeping an elongation break from 600% to 1500% and tensile strength from 2 up to 13 MPa. At the same time, doped nanocomposite materials increase their crystallinity degree than the bare ones. The radiopacity provided by the addition of the dopant agents is proven. Finally, the direct piezoelectricity of nanocomposites membranes is demonstrated, showing higher voltage outputs (up to 2.5 V) for stiffer doped matrices. These results show the potentialities provided by the addition of piezoelectric nanomaterials towards mechanical reinforcement of EVA-based matrices while introducing radiopaque properties and responsiveness to mechanical stimuli.

ADMET polymerization of $\alpha$,$\omega$-unsaturated glycolipids: synthesis and physico-chemical properties of the resulting polymers

Abstract: Trehalose diesters exhibiting $\alpha$,$\omega$-unsaturation are glycolipids which can be easily polymerized by ADMET (acyclic diene metathesis) polymerization. In this paper, enzymatic esterification was performed to selectively esterify primary hydroxyl groups of trehalose (6 and 6'-positions) with vinyl undecenoate. The vinyl ester was beforehand obtained by palladium-catalyzed transesterification of undecenoic acid with vinyl acetate. The resulting trehalose diundecenoate was homopolymerized and copolymerized with undecenyl undecenoate in order to obtain random copolymers with different compositions. The synthesis of such copolymers was confirmed by 1 H NMR spectroscopy and size exclusion chromatography (SEC). Their solid-state phase separation were investigated by DSC and X-ray scattering as function of temperature and their solution self-assembly was investigated by dynamic light scattering (DLS) in water.