Acrylonitrile Terpolymers Research Articles

Copolymers and terpolymers of vinyl phosphonic acid, acrylonitrile, methyl acrylate, and vinyl acetate. Thermal oxidative stabilization and their nanofiber

ABSTRACT Copolymers and terpolymers of acrylonitrile (AN), methyl acrylate (MA), vinyl acetate (VA), and vinyl phosphonic acid (VPA) were synthesized. Thermal gravimetric analysis studies showed that the decomposition of PANMAVPA and PANVAVPA terpolymers started at lower temperatures than PANMA and PANVA copolymers. VPA and MA caused an increase in the ring formation of pendant nitrile groups and the total ash content of PANMAVPA terpolymer. During the thermal oxidative treatment (TOS) of PANVAVPA, the phosphonic acid moiety accelerated double bond formation via acetic acid elimination. 151–340 nm nanofibers were successfully produced from copolymers and terpolymers.

Fiber Spinning of Polyacrylonitrile Terpolymers Containing Acrylic Acid and Alkyl Acrylates

Terpolymers of acrylonitrile with acrylic acid and alkyl acrylates, including methyl-, butyl-, 2-ethylhexyl-, and lauryl acrylates, were synthesized using the reversible addition–fragmentation chain transfer method. In this study, the focus was on the investigation of the impact of different monomer addition methods (continuous and batch) on both the rheological behavior of the spinning solutions and the mechanical properties of the resulting fibers. Our findings revealed that the method of monomer addition, leading either to non-uniform copolymers or to a uniform distribution, significantly influences the rheological properties of the concentrated solutions, surpassing the influence of the alkyl-acrylate nature alone. To determine the optimal spinning regime, we examined the morphology and mechanical properties at different stages of fiber spinning, considering spin-bond and orientation drawings. The fiber properties were found to be influenced by both the nature and introducing method of the alkyl-acrylate comonomer. Remarkably, the copolymer with methyl acrylate demonstrates the maximum drawing ratios and fiber tensile strength, reaching 1 GPa. Moreover, we discovered that continuous monomer addition allows for reaching the higher drawing ratios and superior fiber strength compared to the batch method.

Изучение влияния температуры и продолжительности гидротермального воздействия на устойчивость акрилатных терполимеров

Dynamic light scattering, capillary viscometry, and IR-Fourier spectroscopy have been used to study the effect of temperature and duration of hydrothermal exposure on the chemical composition and structure of acrylate ionic terpolymers of acrylamide (AA), acrylonitrile (AN), and sodium salt 2- acrylamide-2-methylpropanesulfonic acid (AMPSNa) AA-AN- AMPSNa. It has been established that an increase in the duration and temperature of exposure increases the effect of thermo- hydrolysis on the colloidal characteristics of the terpolymer, namely, the average hydrodynamic size of the solvated macromo- lecular polymer coils decreases. A relationship has been established between the chemical composition and structure of the initial terpolymer and the chemical composition and structure of polymer fragments formed after hydrothermal exposure. It has been determined that the increase in stability during thermohydrolysis is associated with the presence of nitrile and sulfo- nate substituents in the side groups of the polymer chain. It has been shown that the AA and AN units of the acrylate terpoly- mer are primarily subjected to thermal treatment. A noticeable change in the composition of the terpolymer after thermohy- drolysis is observed for 5 hours at an exposure temperature of 180 °C, and for 3 hours at 200 °C.

Effect of the comonomer addition sequence in the synthesis of an acrylonitrile terpolymer on the solution rheology and fiber properties

Polyacrylonitrile terpolymers based on acrylonitrile, acrylic acid, and methyl acrylate were synthesized by reversible addition–fragmentation chain-transfer polymerization with varying the monomer addition sequence during the synthesis. The monomer introduction sequence in the synthesis of a ternary copolymer significantly affects both the rheological properties of solutions and the strength of obtained fibers.

Terpolymers of Acrylonitrile, Acrylic Acid, and Alkyl Acrylates: Effect of Alkyl Acrylate on the Thermal Properties of Copolymers

Terpolymers of Acrylonitrile, Acrylic Acid, and Alkyl Acrylates: Effect of Alkyl Acrylate on the Thermal Properties of Copolymers

Challenges in electroplating of additive manufactured ABS plastics

Additive manufacturing of plastics as modern technology introduces new perspectives towards exceptional structures and allows realization of contemporary designs. For those purposes a post-treatment of the components, e.g. surface coating with metals, is crucial. Electroplating on polymers, like ABS (terpolymer of acrylonitrile, butadiene and styrene), is an established industrial process applied on components manufactured by standard technologies, like injection molding. It consists of various steps – from cleaning over creating electric conductivity on the non-conducting polymer surface towards galvanic coating with metals. In this publication, the challenges in transferring this process to additive manufactured ABS components are analyzed by focusing on the surface quality. Surface quality is evaluated by macroscopic imaging and different microscopic technologies (transmission light microscopy, laser scanning microscopy and scanning electron microscopy). The success of electroplating processes on plastics strongly depends on the nature of the plastic surfaces and therefore on the additive manufacturing parameters applied. The used additive technology of fused deposition modelling is characterized by the deposition of single plastic strands. Adjustments of selected manufacturing parameters, such as the layer thickness and the overlap of the stored plastic strands, create the conditions of homogenous and well adhering metal coatings. According to the surface topology from this additive manufacturing process, pre-treatment with levelling and sealing the surface is identified as important challenge towards success and reproducibility of electroplating process.

Green synthesis of biodegradable terpolymer modified starch nanocomposite with carbon nanoparticles for food packaging application

AbstractAs to control the increased rate of environmental pollution there is an urgent need to develop improved biodegradable materials regarding the old polymeric packaging materials. It has been done by the incorporation of carbon nanomaterials to the biodegradable starch terpolymers of acrylic acid, methyl methacrylate (MMA), acrylonitrile (AN), 2‐Ethylhexyl acrylate (2‐EHA), and Ethyl acrylate (EA). The starch‐terpolymers were prepared through the free radical polymerization technique using AA, MMA, AN, 2‐EHA, EA as monomers. Two different starch‐terpolymers were further mixed with carbon nanoparticles (NPs) to form a biodegradable nanocomposite. The biodegradable starch‐grafted terpolymers‐carbon nanocomposites (STPC NCs) were characterized through scanning electron microscopy, Fourier‐transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimeter, and UV–Visible spectrophotometry. Further, resistivity, electrical conductivity, and biodegradability tests were performed to check its properties for packing materials. The biodegradation of SGCP‐composites recorded using the soil burial method was up to 78%. Starch‐terpolymers were prepared via free‐radical polymerization The biodegradation capability of starch‐grafted terpolymers was found to be 78% The decrease in water vapor permeability and solubility proves their utilization as food packaging material

An efficient chitosan-based adsorption material containing phosphoric acid and amidoxime groups for the enrichment of Cu(II) and Ni(II) from water

A novel modified chitosan (CS) material, CS-g-AOPAM, was prepared by the amidoximation of the crosslinking compound of CS and a terpolymer of acrylamide, acrylonitrile and 3-dimethylaminoallyl phosphonic acid, which was applied to adsorb Cu(II) and Ni(II). The material CS-g-AOPAM was characterized by SEM, FTIR, XPS and TG, indicating porous structure and excellent thermal stability. In order to investigate the effects of coexisting ions, pH, initial concentration, adsorption time, and temperature on adsorption capacity of CS-g-AOPAM, batch adsorption experiments were carried out to obtain the corresponding adsorption behavior. According to the linear fitting of Langmuir model, the results proved that CS-g-AOPAM had excellent adsorption performance, exhibiting the maximum adsorption capacities of 215.5 mg·g−1 and 213.4 mg·g−1 for Cu(II) and Ni(II), respectively, which was higher than that of most similar CS adsorbents. The adsorption isotherms were in good agreement with Langmuir model, indicating a monolayer adsorption. Moreover, various adsorption kinetic and thermodynamic models were employed for analyzing adsorption behavior of CS-g-AOPAM, suggesting that the adsorption was a chemisorption as well as spontaneous endothermic process. Further, based on the analysis of FTIR and XPS, the adsorption sites and potential bonding modes of Cu(II) and Ni(II) were proposed. Overall, CS-g-AOPAM is a pretty promising novel adsorption material for the removal of heavy metal ions from wastewater.

Rheological Properties of Acrylonitrile Terpolymer Solutions Synthesized by Different Methods

Series of polyacrylonitrile terpolymers with molecular weights of (7–20) × 104 have been synthesized in dimethylsulfoxide using classical radical polymerization and reversible addition-fragmentation chain transfer (RAFT) polymerization. The effect of the synthesis method on the rheological behavior of dilute and concentrated solutions of the resulting copolymers has been analyzed. No differences have been found in the viscous properties and viscoelastic behavior of the concentrated solutions in the temperature range of 20–80°C. However, viscometry of the dilute solutions made it possible to detect a difference in the interaction between the solvent and macromolecules of the copolymers obtained by these methods. The copolymers differ in the values of the second virial coefficient, which indicates that the interaction of the solvent and polymer is specific to the synthesis method. This phenomenon seems to be caused by different branching of chains in the copolymer and/or its compositional heterogeneity. For dilute solutions, it was possible to construct a single generalized concentration dependence of reduced viscosity in the coordinates of the Martin equation. Transition to the region of concentrated solutions required an introduction of yet another parameter that describes the effective density of the mesh network, namely, the ratio of the current solution concentration to the crossover concentration. This approach made it possible to construct a generalized dependence of viscosity in the entire concentration range of solutions of polyacrylonitrile copolymers.

Molecular and thermal studies of carbon fiber precursor polymers with low thermal‐oxidative stabilization characteristics

ABSTRACTIn this investigation, terpolymers, copolymers, and homopolymer of acrylonitrile with dimethylaminopropyl acrylamide (DMAPA), itaconic acid (IA) viz., poly(acrylonitrile‐ran‐3‐dimethylaminopropyl acrylamide‐ran‐itaconic acid) [P(AN‐DMAPP‐IA)], poly(acrylonitrile‐co‐3, dimethylaminopropyl acrylamide) [P(AN‐DMAPP)] were synthesized with varying amounts of comonomers using solution polymerization process. The chemical structure, composition, bonding network were determined employing infrared, 1H and, 13‐carbon nuclear magnetic resonance spectroscopic techniques. Molecular characteristics of as‐synthesized polymers such as different kinds of average molecular weights, molecular weight distribution were estimated applying solution viscometry and size exclusion chromatography. The influence of comonomers (DMPAA, IA) on the thermal stabilization characteristics of acrylonitrile terpolymers in comparison with copolymers and homopolymers of acrylonitrile were studied using differential scanning calorimetry (DSC), hyphenated thermal techniques (thermal gravimetry coupled with differential thermal analyzer).The DSC curves of P(AN‐DMAPP‐IA) exhibit a distinct broader bimodal peaks with thermal exotherm initiating at as low as 165 °C, and followed by two peaks with temperature difference of 42 °C, releasing the evolved heat at a release rate of 0.7–0.11 J g−1s−1over 10 min as compared to 1.2, 7.5 J g−1s−1 in 4.5, 2 min as observed in P(AN‐DMAPP), polyacrylonitrile, respectively. The thermal stability of P(AN‐DMAPP‐IA) and P(AN‐DMAPP), as evidenced by TGA‐DTA was found to be higher than PAN homopolymers. Specific heat capacity measurements confirmed the DSC results. Bulk densities of P(AN‐DMAPP‐IA) were in the range 0.31–0.35 g/cc. These results confirm the low‐temperature stabilization characteristics and suitability of P(AN‐DMAPP‐IA) as low cost carbon fiber precursor polymers. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46381.

Synthesis by radical polymerization and structure of drag reducing terpolymers based on acrylamide, acrylonitrile, and 2-acrylamido-2-methylpropanesulfonic acid

Terpolymers of acrylamide, acrylonitrile, and sodium 2-acrylamido-2-methylpropanesulfonate were prepared by radical copolymerization in aqueous solution. The terpolymers obtained are enriched in acrylamide units and depleted of acrylonitrile units relative to the initial monomer ratio. The acrylamide–acrylonitrile–sodium 2-acrylamido-2-methylpropanesulfonic acid terpolymers show high performance as drag reduction agents. Under the conditions of thermal, salt, and acid aggressions, the terpolymer containing 71.6 mol % acrylamide, 10.5 mol % acrylonitrile, and 17.9 mol % sodium 2-acrylamido-2-methylpropanesulfonate ensures drag reduction no less than 70%.

Controlled synthesis of random, block-random and gradient styrene, methyl methacrylate and acrylonitrile Terpolymers via Nitroxide-mediated free radical polymerization

Different types of the styrene − methyl methacrylate −acrylonitrile terpolymers were synthesized according to the recently proposed concept of the living nitroxide-mediated terpolymerization. Random azeotropic and gradient terpolymers were prepared using the living TEMPO-mediated polymerization. Block random terpolymer was obtained via the living terpolymerization initiated by macro-alkoxyamine polystyrene-SG1. In all systems, terpolymerization proceeds in the living manner even in the presence of TEMPO. Upon complete polymerization at high conversions of monomers, the molecular weight of terpolymers linearly increases with the monomer conversion. The resultant terpolymers were characterized by the methods of turbidimetric titration, GPC, DSC, and TGA, and their characteristics were compared with their non-living analogs synthesized by the conventional radical polymerization. The effect of the macromolecular structure on the thermal stability of the terpolymers was studied.

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.

A high molecular weight acrylonitrile copolymer prepared by mixed solvents polymerization: II. effect of DMSO/water ratios on polymerization and stabilization

A bifunctional comonomer β-methylhydrogen itaconate was synthesized to prepare high molecular weight poly [acrylonitrile-co-(β-methylhydrogen itaconate)] [P (AN-co-MHI)] by mixed solvents polymerization, which was used as carbon fiber precursor instead of acrylonitrile terpolymers. The effect of dimethyl sulfoxide (DMSO)/deionized water ratios on the polymerization, structure and stabilization of P (AN-co-MHI) was studied by elemental analysis, UV-Visible Spectroscopy, fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The highest viscosity-average molecular weight (76.72 × 104 g/mol) of P(AN-co-MHI) was obtained in the mixed solvents of DMSO/deionized water = 10/90 (wt/wt) due to the zero chain transfer constant of deionized water for radical ~ ~ ~AN·, which is 10 times larger than that of P(AN-co-MHI) copolymers prepared in DMSO solution polymerization under the same conditions and is beneficial to improving the tensile strength of resulting carbon fiber. The composition of P(AN-co-MHI) was controlled by the ratio of DMSO/deionized water in the mixed solvents, it is attributed to the changes of AN/MHI ratio taking part in the polymerization reactions, which is caused by the different solubility of AN in the mixed solvents. From elemental analysis and FTIR studies, it can be found out that the content of MHI in P(AN-co-MHI) copolymer becomes larger with the increase of DMSO content in the mixed solvents. The FTIR, XRD and DSC results show that the stabilization of P(AN-co-MHI) copolymer was significantly improved by MHI compared with PAN homopolymer and poly (acrlonitrile-methyl acrylate-acrylic acid) terpolymer, such as larger extent of stabilization, lower initiation temperature and smaller Ea of cyclization, which is beneficial to preparing high performance carbon fiber.

A high molecular weight acrylonitrile copolymer prepared by mixed solvent polymerization: I. effect of monomer feed ratios on polymerization and stabilization

A bifunctional comonomer β-methylhydrogen itaconate (MHI) was employed to prepare high molecular weight poly[acrylonitrile-co-(β-methylhydrogen itaconate)] [P(AN-co-MHI)] copolymers by radical polymerization in a mixed solvent of dimethyl sulfoxide/deionized water = 60/40 (wt/wt), which was used as a carbon fiber precursor instead of acrylonitrile terpolymers for improving the stabilization and spinnability simultaneously. The structure and stabilization of P(AN-co-MHI) copolymers with different monomer feed ratios were characterized by elemental analysis (EA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The results show that both the polymerization conversion and molecular weight reduce with the increase of MHI content in the feed due to the larger molecular volume of MHI. The monomer reactivity ratios were calculated by Fineman–Ross and Kelen–Tüdõs methods and the reactivity of MHI is higher than that of AN. Two parameters Es = A1618 cm−1/A2244 cm−1 and SI = (I0 − Is)/I0 were defined to evaluate the extent of stabilization and the activation energy (Ea) of the cyclization. The FTIR, XRD and DSC results show that P(AN-co-MHI) copolymers exhibit significantly improved stabilization characteristics than the PAN homopolymer and poly(acrlonitrile–methyl acrylate–acrylic acid) terpolymer, such as a larger extent of stabilization, lower initiation temperature and smaller Ea of cyclization, which is attributed to the ionic initiation of the MHI comonomer and is beneficial for preparing high performance carbon fiber.

Molecular design and pre-oxidation mechanism of acrylonitrile copolymer used as carbon fiber precursor

In order to improve the pre-oxidation and spinnability of polyacrylonitrile (PAN) at the same time, a bifunctional comonomer 3-ammoniumcarboxylate-butenoic acid-methyl ester (ACBM) was designed and synthesized to prepare poly(acrylonitrile-co-3-ammoniumcarboxylate-butenoic acid-methyl ester) [P(AN-co-ACBM)] copolymers used as carbon fiber precursor instead of acrylonitrile terpolymers. The P(AN-co-ACBM) copolymers with different compositions were characterized by elemental analysis, Fourier transform infrared spectroscopy, X-ray diffraction and differential scanning calorimetry. Both the conversion of polymerization and molecular weight decease with the increasing of ACBM content in P(AN-co-ACBM) due to the larger molecular volume of ACBM than AN, and the monomer reactivity ratios study shows that ACBM possesses higher reactivity than AN. Two parameters $$ {E}_s={A}_{1619c{m}^{-1}}/{A}_{2244c{m}^{-1}} $$ and SI = (I 0 − I S )/I 0 were defined to evaluate the extent of pre-oxidation, and the activation energy (E a) of the cyclization was calculated by Kissinger and Ozawa methods. The results show that P(AN-co-ACBM) copolymers exhibit significantly improved pre-oxidation characteristics than PAN homopolymer, such as lower initiation temperature, larger extent of pre-oxidation and smaller E a of cyclization, which is attributed to the initiation of ACBM through ionic mechanism. In addition, the rheological analysis shows that the spinnability of P(AN-co-ACBM) copolymer is better that that of PAN, which is beneficial to preparing high performance carbon fiber.

Acrylonitrile copolymers containing guanidine oligomer: Synthesis and use for the preparation of nonleaching antimicrobial acrylic fibers

AbstractNonleaching acrylic fibers with permanent antibacterial activity were prepared via a combination of copolymerization and a wet‐blend‐spinning method. Specifically, poly[acrylonitrile‐co‐modified poly(hexamethylene guanidine hydrochloride)] [poly(AN‐co‐M‐PHMG)] copolymers containing a covalently connected antibacterial guanidine oligomer were first synthesized via the precipitation copolymerization of acrylonitrile (AN) with a modified poly(hexamethylene guanidine hydrochloride) (M‐PHMG) macromonomer in water. Then, modified acrylic fibers were prepared from a mixture of the copolymer and commercial fiber‐grade AN terpolymer via a wet‐spinning process with dimethyl sulfoxide as the solvent. The influences of the reaction time, temperature, pH value of the medium, and amount of initiator on the copolymerization and the effect of the copolymer content on the mechanical properties and antibacterial activity of the modified acrylic fibers were investigated in detail. The results show that the M‐PHMG macromonomer exhibited a lower reactivity than AN. The poly(AN‐co‐M‐PHMG) copolymer with a PHMG content of 5.49% and an intrinsic viscosity of 11.2 dL/g could be synthesized under optimized conditions. With increasing copolymer content, the tensile strength of the modified acrylic fibers decreased slightly, and the antibacterial activity increased. The modified acrylic fibers with a copolymer content of 50% (i.e., a PHMG content of 2.75%) exhibited both good mechanical properties and excellent antibacterial activity. The additional antibacterial function would surely enlarge the applications of the fiber. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Investigation of the relaxation behavior of novel terpolymers of acrylonitrile, methyl methacylate and indene

AbstractTerpolymer samples were prepared by free radical polymerization of methyl methacrylate (MMA), indene (In) and acrylonitrile (AN) in bulk. The samples were chosen so that the molar ratio of AN to MMA varied from 1.00:4.39 to 1.00:0.83, while the molar ratio of In was kept almost unchanged. The glass transition temperatures (Tg) of the samples were determined using differential scanning calorimetry. Moreover, isochronal dynamic mechanical measurements of the complex bending modulus as well as the complex dielectric permittivity were carried out over wide temperature ranges, namely from 50 to 190 °C, depending on the material investigated. All samples exhibited a single common Tg value, which increased to higher temperature upon increasing the content of AN. In addition, the results were investigated quantitatively in the framework of a molecular model. Copyright © 2006 Society of Chemical Industry

Separation of Styrene - Methyl Methacrylate - Acrylonitrile Terpolymers by Composition Using High-Performance Liquid Chromatography

Separation of styrene - methyl methacrylate - acrylonitrile terpolymers by chemical composition was studied using high-performance liquid chromatography (HPLC). Cross-linked polyacrylamide (PAA) gel or polyacrylonitrile (PAN) gel was used as a stationary phase for normal-phase HPLC and cross-linked polystyrene (PS) gel for reversed-phase HPLC. Each system was based on a solvent gradient, and the separation was governed by an adsorption mechanism. Terpolymers were successfully separated by the cross-fractionation, i.e., the combination of two types of HPLC systems with PAN and PAA columns or PAN and PS columns. The chemical composition distribution (CCD) of a high-conversion terpolymer was analyzed by this cross-fractionation technique with the combination of PAA and PAN columns. The CCD obtained experimentally was reasonably consistent with that of theoretical calculation.

Synthesis and thermoanalysis of emulsion terpolymers ofN-phenylmaleimide, styrene, and acrylonitrile

Terpolymers of N-phenylmaleimide (PMI), styrene, and acrylonitrile (AN) were synthesized by emulsion polymerization. The thermal properties of terpolymers at different PMI and AN feed contents were investigated by differential scanning calorimetry, torsional braid analysis, thermogravimetric analysis, and a Vicat softening point test. The results showed the glass-transition temperature and decomposition temperature of the terpolymers increased with increasing PMI feed content. Furthermore, the Vicat softening point of the terpolymers rose with PMI feed content. The weight- and number-average molecular weights (M w and M n ) of the terpolymers were also determined by gel permeation chromatography. The results showed that the M w and M n of the terpolymers decreased with increasing PMI feed content and increased with increasing AN feed content. The mechanical properties (tensile strength and impact strength) of the terpolymers decreased with increasing PMI feed content and increased with increasing AN feed content.