Synthesis Of Terpolymers Research Articles

Synthesis of terpolymer from Helianthus annuus (natural oil) and evaluation as pour point depressant and viscosity reducer on Indian crude oil

Pour Point Depressant is introduced to crude oil at ppm level to overcome transportation problem of crude oil because of its complex chemical structure. Synthesized PPDs improve flow property, viscosity and also improve its numerous parameters to improve performance of crude oil. Low molecular weight and high molecular weight, copolymer having better PPD types. In present work, synthesized Terpolymer, from natural source, was formed from the reaction with Helianthus annuus oil and ester of Erucic Acid with various fatty alcohol. It was evaluated for its properties on Indian waxy crude oils, i.e., From Limbodra well. Structure and molecular weight of synthesized polymer was confirmed by Spectral data and Gel permeation chromatography (GPC). Also its effect on crude oil was evaluated by Rheological studies, SARA Analysis, Pour point depressant effect. Cross–polarizing microscopic studies were performed to study changes in morphology of wax crystals in crude oil with and without additive. A zero friction advanced Rheometer AR-500 was used to determine the viscosity by applying Bingham plastic-flow model.

Multi-objective synthesis optimization and kinetics of a sustainable terpolymer

We employed multi-objective Bayesian optimization to achieve Pareto optimal solutions for sustainable terpolymer synthesis, targeting a high glass transition temperature and increased incorporation of renewable monomers.

Controlled Synthesis of Statistical Polycarbonates Based on Epoxides and CO2

AbstractThe controlled synthesis of terpolymer structures is often limited by the intrinsic reactivities of the monomers. For the synthesis of a statistical terpolymer from cyclohexene oxide (CHO) and propylene oxide (PO) with CO2, an instrumental solution is demanded. Implementing a setup where one monomer can be added to the reaction mixture over the whole course of the reaction, the random distribution of the epoxides over the whole chain is realized. The successful terpolymerization can be determined with diffusion‐ordered nuclear magnetic resonance spectroscopy and gel permeation chromatography measurements while the statistical microstructure of the generated polymers is indicated in NMR spectroscopy and differential scanning calorimetry measurements. Furthermore, the concept is transferred to the terpolymerization of limonene oxide with PO and CO2 underlining the versatility of the setup.

Effect of Ionic Strength on the Polymerization of Acrylamide, N‐Vinylpyrrolidone and Vinylbenzyl trimethylammonium chloride

AbstractCationic polymers are promising materials for modifying the relative permeability of water in oil wells. These materials must withstand brine and temperature without losing their viscosity; one way to achieve this is by using hydrophobic groups. Some of these groups may contain a cationic part, and when polymerized, the electrostatic repulsions of the cations greatly influence the course of the reactions. In the present work, terpolymers from Acrylamide (AM), N‐vinylpyrrolidone (VP), and Vinylbenzyl trimethylammonium chloride (VBTA) were synthesized. The effect of the ionic strength exerted by the VBTA cationic monomer and NaCl added to the reaction solution over the terpolymer synthesis was studied. Interactions between VBTA and VP were found through FTIR, 1H‐, 13C‐ and 15N‐NMR, which causes inhibition of VP during the reaction. The inhibition was suppressed when using NaCl in the reaction mixture, which improved the molecular weight and the viscosity due to the suppression of the interactions between VBTA with VP. The ionic strength due to the VBTA content also influences on the properties of the terpolymers: at higher VBTA content, higher viscosity in water is obtained and present higher decomposition temperature in TGA‐DSC analysis.

ABC-Type Periodic Terpolymer Synthesis by a One-Pot Approach Consisting of Oxirane- and Carbonyl-Derived Cyclic Acetal Generation and Subsequent Living Cationic Alternating Copolymerization with a Vinyl Monomer

ABC-Type Periodic Terpolymer Synthesis by a One-Pot Approach Consisting of Oxirane- and Carbonyl-Derived Cyclic Acetal Generation and Subsequent Living Cationic Alternating Copolymerization with a Vinyl Monomer

Synthesis of Ethylene-Propylene-Diene Terpolymers and Their Heterophase Compositions with Polypropylene in the Presence of Metallocene Catalytic Systems

Ethylene-propylene-5-ethylidene-2-norbornene terpolymerization is studied in a liquid propylene medium using catalysts based on metallocenes (MCs) of C2- and C5-symmetry, differing in the nature of bridges and ligands and activated by MAO. It is shown that the investigated MCs of C2-symmetry do not ensure the synthesis of terpolymers combining a high molecular weight (MW) and good diene incorporation. In the presence of a MC of Cs-symmetry Ph2C(CpFlu)ZrCl2, terpolymers with an MW of 120 000 to 160 000 and a diene content of 2.0 to 5.3 wt % are obtained with a high level of activity. New heterophase compositions based on isotactic PP and ethylene-propylene-diene terpolymers, which have a good balance between strength and elasticity, are synthesized.

Temperature-induced self-assembly of amphiphilic triblock terpolymers to low cytotoxic spherical and cubic structures as curcumin carriers

In this study, self-assembly of amphiphilic thermo- and UV-sensitive block terpolymers, namely poly (methyl acrylate-b-[(7-(allyloxy)-2H-chromen-2-one)-co-(2-hydroxyethyl methacrylate(]-b-N-vinylpyrrolidone) P (MA-b-[AC-co-HEMA]-b-NVP) in water at different temperatures is studied. The synthesis of terpolymers, in three various block length for hydrophobic PMA block, is carried out by atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain-transfer (RAFT)/macromolecular design by interchange of xanthate (MADIX) polymerization. Three different critical micelle temperatures (CMT) of terpolymers are calculated via UV-VIS-NIR absorptions at 600 nm. Results of self-assembly behavior of terpolymers under CMT showed spherical micelle aggregation whereas cubic-like particles with larger particle size were self-assembled at the temperatures above CMT because of second aggregation phenomena. Additionally, UV light irradiation is used to photo-crosslinking of particles owing to presence of photo-responsive coumarin derivative of AC in the middle block. The self-assembled structures are loaded with curcumin (Cur) before and after photo-crosslinking and Cur-release behavior is investigated at different temperatures of 37 and 25 °C. Drug-release behavior of samples illustrated that cumulative Cur-release above the CMT of terpolymers is higher than under CMT due to squeezing of PVP coronas and expelling of drug molecules to outside. Moreover, cumulative release of photo-crosslinked self-assembled structures was lower than before crosslinking. The cytotoxicity of terpolymers and Cur-loaded micelles was examined through culturing on the MG-63 cells which showed high cell viability after 48 h.

Advanced Thermosets from Sulfur and Renewable Benzoxazine and Ionones via Inverse Vulcanization

An unprecedented synthesis of terpolymers from bioderived monomers and elemental sulfur in one-pot is described. In this approach, biosourced compounds, namely, vanilin and furfurylamine-based benz...

Novel terpolymers containing carbazole, coumarin and Alq3 complexes

Abstract In this paper, the synthesis of terpolymers bearing carbazole, coumarin and 8-hydroxyquinoline moiety as pendant groups with content of coumarin and 8-hydroxyquinoline between 0.5 and 4 mol% was elaborated. Then the terpolymers underwent complexation reactions with aluminum bis(8-hydroxyquinoline)isopropoxylate (Alq2ispr) to form polymeric hybrid materials with aluminum tris(8-hydroxyquinoline) (Alq3) as side groups. The presence of carbazole, coumarin (MK) and 8-hydroxyquinoline (QM) as well as Alq3 in the terpolymers was confirmed by NMR, UV, photoluminescence, and size exclusion chromatography. The results indicates that these hybrid polymers have moderate molecular weights and solubility in common organic solvents. For photoluminescence spectra, an evidence for energy transfer from carbazole to coumarin and Alq3 groups was observed and highest relative fluorescence intensity was exhibited by solutions of the terpolymers containing the lowest content of MK, QM and Alq3.

Tailoring Acrylated Soybean Oil-Containing Terpolymers through Emulsion Polymerization

This work focuses on the synthesis of terpolymers using methyl methacrylate (MMA) and vinyl pivalate (VPi), along with the incorporation of methacrylate acid (MA) and acrylated fatty acids (AFA) derived from commercial soybean oil. Emulsion polymerizations were carried out using different monomeric species, along with different initiator concentrations ranging from 0.5 g∙L−1 to 2.2 g∙L−1. The thermal properties of the terpolymers were improved when acrylated fatty acid was incorporated into the polymer chains, expressing glass transition temperatures (Tg) ranging from 70 °C to 90 °C and degradation temperatures in the interval between 350 °C and 450 °C for acrylated fatty acid concentrations ranging from 5 wt% to 10 wt%. Furthermore, a change was noted in the molar mass distributions as a result of acrylated fatty oil present in the polymers. The materials with 5 and 10 wt% of acrylated fatty oil presented mass-average molar masses of 225 kg∙mol−1 and 181 kg∙mol−1, respectively. As the results in this work suggest, the molar masses of the formed polymers are significantly altered by the presence of modified fatty acids.

Polymer reaction engineering tools to design multifunctional polymer flocculants

A series of multifunctional terpolymers, poly(N-isopropyl acrylamide/2-(methacryloyloxy) ethyl trimethyl ammonium chloride/N-tert-butylacrylamide) [P(NIPAM-MATMAC-BAAM)], were designed to flocculate and dewater oil sands mature fine tailings (MFT). The hydrophobic BAAM comonomer helped in expelling water from the sediments, while the cationic MATMAC comonomer promoted the charge neutralization of negatively charged particles suspended in MFT. The chemical composition distributions of these terpolymers were designed based on the knowledge of the reactivity ratios of all comonomers, instead of by trial and error, as usually done for most polymer flocculants. The binary reactivity ratios of the comonomers were estimated by synthesizing the binary copolymers with various mole fractions of each comonomer in the feed and experimentally measuring the corresponding fraction of comonomer in the copolymers. Polymer reaction engineering tools were used to minimize compositional drift and guarantee the synthesis of terpolymers with narrow chemical composition distributions suitable for MFT dewatering. Focused beam reflectance measurement (FBRM) experiments showed that terpolymers promoted the formation of large MFT flocs (120 μm). The initial settling rate decreased with the increase in flocculant hydrophobicity, likely because the hydrophobic terpolymer segments did not take part in the bridging of the MFT particles. In contrast, the sediment dewaterability increased with the increase in terpolymer hydrophobicity. This study provides guidelines to design a polymer flocculant from first principles and demonstrates the potential of using hydrophobically modified cationic polymers to flocculate MFT effectively.

Synthesis of Terpolymers with Homogeneous Composition by Free Radical Copolymerization of Maleic Anhydride, Perfluorooctyl and Butyl or Dodecyl Methacrylates: Application of the Continuous Flow Monomer Addition Technique.

Terpolymers of homogeneous composition were prepared by free radical copolymerization of butyl or dodecyl methacrylate, 1H,1H,2H,2H-perfluorodecyl methacrylate and maleic anhydride using the continuous monomer addition technique. The copolymerization reactions were performed at 65 °C in the presence of azobisisobutyronitrile as an initiator in a mixture of methyl ethyl ketone and 1,3-bis (trifluoromethyl)benzene. The monomers and initiator are added to the reaction mixture with the same rate they are consumed in 5- and 10-fold excess compared to the initial monomer stock. The obtained terpolymers with molecular weights Mn = 50,000–70,000 are of uniform composition, close to the composition determined in low conversion experiments, proving the principle of the chosen concept. The kinetic data necessary for the design of the continuous addition experiment were obtained from binary copolymerization experiments at low monomer conversion (to avoid compositional drift). In addition, the so-called terpolymerization parameter was determined from ternary copolymerization experiments.

Thermooxidative stabilization of acrylonitrile terpolymers obtained under reversible chain-transfer conditions: Effects of synthesis temperature and initiation method

The terpolymerization of acrylonitrile, methyl acrylate, and itaconic acid mediated by a reversible addition-fragmentation chain transfer agent, dibenzyl trithiocarbonate, and initiated by AIBN at 80°C, potassium persulfate at 45–55°C, and radiolysis at 20°C is studied. In all the cases, polymerization proceeds via the pseudoliving mechanism, which is preserved up to ultimately high monomer conversions (80–90%). According to FTIR ATR and NMR spectroscopy, all the synthesized terpolymers are characterized by close monomer compositions and their degree of branching is too low to be detected spectroscopically. However, the thermal behaviors of terpolymers obtained by polymerizations at various temperatures are different, namely, the lower the temperature of terpolymer synthesis, the slower the thermooxidative stabilization processes occurring in it.

Gradient terpolymers with long ε-caprolactone rich sequence derived from propylene oxide, CO2, and ε-caprolactone catalyzed by zinc glutarate

We report here an efficient one-pot synthesis of terpolymers from propylene oxide (PO), carbon dioxide (CO2), and ε-caprolactone (CL) with long CL rich sequence using zinc glutarate as catalyst. The terpolymer yields increase significantly from 50 to 103 (g polymer per g catalyst) with the introduction of CL as a third monomer. The propylene oxide conversion increases by nearly 44% at relatively low polymerization temperature (60 °C). Moreover, the differences in reaction rates of polycarbonate and polyester moieties were examined by in situ infrared monitoring. 1H NMR, GPC and DOSY NMR results show the as-prepared polymer being a gradient terpolymer. As confirmed by XRD and DSC methods, the synthesized terpolymers are a kind of semicrystalline polymer in which the crystalline domains consist mainly of PCL rich segment. Consequently, the semicrystalline terpolymers exhibit much better thermal properties and superior mechanical strength compared with amorphous polycarbonate PPC.

Биосинтез и свойства ПГА, содержащих мономеры 3-гидрокси-4-метилвалерата

The ability of wild-type strain Cupriavidus eutrophus B10646 to synthesize copolymers containing 3-hydroxy-4-methylvalerate (3H4MV) (P(3HB/3HV/3H4MV)) was studied. The possibility of synthesis of terpolymers containing 3HB, 3HV and 3H4MV monomers using glucose, or butyric acid and co-substrate was shown. A family of copolymers with different content of 3H4MV monomer was synthesized. The highest content of 3H4MV was 7.7 mol. %. Increase of 3HV and 3H4MV content in copolymers caused the reduction of crystallinity degree and of molecular weight, and changes of thermal characteristics of copolymers.

One-pot synthesis of terpolymers with long l -lactide rich sequence derived from propylene oxide, CO2 , and l -lactide catalyzed by zinc adipate

One-pot synthesis of terpolymers with long <scp>l</scp> -lactide rich sequence derived from propylene oxide, CO₂ , and <scp>l</scp> -lactide catalyzed by zinc adipate

Development of new multifunctional terpolymer sorbent for proteomics applications.

Determination of the availability of phases for specific separations is an important task achieved by a separation chemist. This becomes vital when the complex samples like biofluids are dealt with in proteome science. The work presented here involves the synthesis and application of terpolymeric sorbent with different functionalizations adopted for the selective enrichment of biomolecules of interest from biological fluids. Synthesis of terpolymer was carried out by the radical polymerization of monomers: methyl acrylate, acrylic acid and vinyl acetate with diethylene glycol dimethacrylate as cross-linking agent, benzoyl peroxide as initiator and chloroform as a porogenic solvent. Characterization was done through Fourier transform infrared spectroscopy, scanning electron microscopy and nitrogen adsorption porosimetry. The polymer was further modified to immobilized metal ion affinity chromatographic material, with immobilized Fe(3+)/La(3+) ions that allowed phosphopeptide enrichment from tryptic digests of standard proteins as well as milk, egg yolk and human serum. Sensitivity of enrichment down to 50 fmol was achieved in the presence of complex protein background as bovine serum albumin. Hydrophobicity was introduced through octadecyl amine, which provides comparable results to ZipTip C18/C4 for desalting of complex mixtures of all caseins. Analysis of the enriched content was performed by Matrix Assisted Laser Desorption Ionization Mass Spectrometry (MALDI-MS).

Hyperbranched fluoropolymer-polydimethylsiloxane-poly(ethylene glycol) cross-linked terpolymer networks designed for marine and biomedical applications: heterogeneous nontoxic antibiofouling surfaces.

Synthesis of terpolymer coatings composed of hyperbranched fluoropolymers cross-linked with bisamino-propyl poly(ethylene glycol) and bisamino-propyl polydimethylsiloxane (PDMS) was performed to generate antibiofouling surfaces. Nanoscale imaging and surface spectroscopy confirmed that this system possessed complex surface topographies and chemical compositions. Surface complexity was determined to be due to molecular interactions, phase segregation, and compositional gradients arising between the three components. A clear difference in surface behavior was observable before and after exposure to water. Antibiofouling characteristics were investigated by bovine serum albumin (BSA) adsorption studies; the terpolymer coating displayed a 60% greater resistance to protein adsorption in comparison to the fouling of a commercial antibiofouling silicone coating. The unique surface topography, topology, and chemical heterogeneity expressed at a variety of scales provide a robust regime for the generation of hardy, complex surfaces known to incorporate characteristics appropriate for antibiofouling applications. Thorough assessment of thermal responses and mechanical properties in relevant environments demonstrated a formulation platform immediately appropriate for consideration in marine and in vivo applications.

Terpolymers as precursors for CuO nanoparticles synthesis

ABSTRACTThis work describes the synthesis of terpolymers of aniline, diphenylamine, and o‐anthranilic acid (PANIDPAA) by 1 : 1 : 1 molar ratio of the respective monomers doped by different concentration of copper ions via in situ chemical terpolymerization. The results are justified by measuring spectral characteristics namely, UV‐vis absorption spectra, FTIR, and TGA. Calcining these PANIDPAA terpolymers doped by copper at temperatures in the range of 700°C led to the formation of CuO nanoparticles in the nanoscale by thermal decomposition in air directly. The stages of decompositions and the calcination temperature of the precursors have been determined from thermal analysis data sheet. The obtained CuO nanoparticles have been characterized by X‐ray diffraction and transmission electron microscope (TEM). TEM showed a particle size less than 40 nm. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41150.

Biosynthesis of P(3HB-co-3HV-co-3HHp) terpolymer by Cupriavidus necator PHB-4 transformant harboring the highly active PHA synthase gene of Chromobacterium sp. USM2

Aims: This study evaluates potentials of Cupriavidus necator PHB  4 transformant harboring the highly active polyhydroxyalkanoate synthase gene (phaC) of a locally isolated Chromobacterium sp. USM2 for its ability to incorporate 3-hydroxyheptanoate (3HHp) monomer. Methodology and results: A mixture of fructose and sodium heptanoate fed to the culture gave rise to poly(3hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyheptanoate), [P(3HB-co-3HV-co-3HHp)] terpolymer synthesis, with traces of 3HHp monomers confirmed through gas chromatography (GC), proton ( 1 H) and carbon ( 13 C) NMR spectra. Conclusion, significance and impact of study: This study has revealed that the PHA synthase of Chromobacterium sp. USM2 has a broad range of substrate specificity. The synthase is able to polymerize 3-hydroxyalkanoate monomers having 4–7 carbon atoms.