Acrylonitrile-methyl Acrylate Copolymers Research Articles

Degradation behavior of multilayer packaging films in the presence of a highly acidic sauce

Highly acidic condiments such as hot sauce can deteriorate multilayer packaging films. To date, only a multilayer polymeric film (polyethylene terephthalate/ink/polyethylene/foil/polyethylene/SiO x coated polyethylene terephthalate/adhesives/Barex®) utilizing a proprietary resin, Barex® as one of its polymeric layers can preserve hot sauce for military rations. However, the production of Barex® stopped in 2016. To identify substitutes for Barex®, an immersion study of films in hot sauce was conducted with several commercially available multilayer films (Polyethylene terephthalate/ink/adhesive/polyamide/adhesive/polypropylene and polyethylene terephthalate/waste low-density polyethylene/aluminum foil/adhesive/polyester/low-density polyethylene) and a monolayer Barex® (acrylonitrile methyl acrylate copolymer) film. All films were immersed in hot sauce, acetic acid, and sodium chloride solutions at 50 °C for 12 weeks. The mass, thickness, morphology, and chemical compositions of each film were analyzed every three weeks. Hot sauce and acetic acid solution similarly deteriorated multilayer films, causing delamination and oxidative degradation, but not sodium chloride solutions. This indicates that the failure of the multilayer packaging of hot sauce was likely caused by the low pH environment, not heat or salt ions. The two primary innovations in this study are: 1) the finding that acidic components in hot sauce deteriorate multilayer packaging by transforming aluminum foil into a soluble salt and by oxidizing polyethylene, and 2) surface erosion plays a significant role in inducing polyethylene oxidation. This is the first study to describe how a highly acidic food deteriorates multilayer packaging used for military rations. Possible deterioration mechanism of the multilayered structure (Film 2) in presence of a highly acidic hot sauce. • Acetic acid in hot sauce reacts with aluminum foil used in multilayer films. • Acids in hot sauce oxidatively degrade polyethylene (PE) layers in multilayer films. • PE in multilayer films oxidizes more in hot sauce than in acetic acid solutions. • PE in multilayer films surface erodes when immersed in hot sauce and acetic acid. • Potential multilayer film is identified for replacing Barex® for military rations.

Quantification and Effect of Residual Water in Solid Polymer Electrolytes

In the context of the urgent modern energy challenges, lithium-metal (LMB) and lithium-ion batteries (LIB) are conceivable candidates for long term electrochemical storage of renewable energies. As such, while many possible electrolytes are being investigated, solid polymer electrolytes (SPE) are potential replacements for the classic liquid electrolytes that are used in today’s commercial LIB developed and patented by Sony Energitech in 1991. Despite offering non-flammable properties, eliminating the need for heavy casings and allowing the use of higher-energy density lithium at the anode, these electrolytes still suffer from low ionic conductivities. Therefore, plenty of novel SPE systems are being developed and proposed for their captivating properties.Oftentimes, these systems seem appealing but are hardly reproducible in laboratory settings, basing oneself solely upon the published experimental conditions. An interesting inter-laboratory study was published, in which the same thiophosphate ceramic-based solid electrolyte samples were distributed across 11 different research groups. The relative standard deviation calculated from reported conductivities reached a value of 50%. (1) Recently, it has been shown that different post-drying procedures influenced the water content of electrodes which in turn affected the electrochemical properties of LIBs. (2) In SPEs, amongst different factors that could affect ionic conductivities, we believe that water plays a non-neglectable role. Knowing that relative humidity is strongly affected by the local climate, conditions can vary from laboratory to laboratory from a day to another. Being a factor that isn’t controlled effortlessly, samples’ water content can easily be overlooked. However, only a few recent papers mention that matter.(3) The issue is that on one hand, even though some authors reported enhanced ionic conductivities with an increased water content of SPEs, others claim the opposite to be true, which makes the subject ambiguous.(4) On the other hand, very few SPE systems have been studied, which makes the effect of water unclear.In this study, three different types of polymers, poly(ethylene oxide) (PEO), poly(acrylonitrile) (PAN), and acrylonitrile methyl acrylate copolymer latex (AMAC), two different lithium salts (LiTFSI and LiClO4), and two different processing methods (Wet solution casting and solvent-free dry mixing) have been used to prepare different SPE samples. Samples of PEO-LiTFSI, PAN-LiClO4, and AMAC-LiTFSI with different water contents have been prepared and analysed following a strict reproducible drying/doping protocol. Different electrochemical parameters such as the ionic conductivity, the activation barrier and the electrochemical stability window have been assessed in different samples and correlated to their respective water contents. It has been shown that water does indeed influence SPEs and that it’s a factor that needs to be taken into consideration for reproducibility purposes. 1: S.Ohno, T. Bernges, J. Buchheim, M. Duchardt, A. K. Hatz, M. A. Kraft, H. Kwak, A. L. Santhosha, Z. Liu, N. Minafra, F. Tsuji, A. Sakuda, R. Schlem, S. Xiong, Z. Zhang, P. Adelhelm, H. Chen, A. Hayashi, Y. S. Jung, B. V. Lotsch, B. Roling, N. M. Vargas-Barbosa, W. G. Zeier, ACS Energy Lett., 5, 910-915 (2020).2: F. Huttner, W. Haselrieder, A. Kwade, Energy Technol., 8, 1900245 (2020).3: B. Commarieu, A. Paolella, S. Collin-Martin, C. Gagnon, A. Vijh, A. Guerfi, K. Zaghib, J. Power Sources, 436, 226852 (2019).4: M. Z. Munshi, B. B. Owens, Appl. Phys. Commun., 8 (1987). TOTAL Classification: Restricted Distribution TOTAL - All rights reserved

Effects of copolymerization temperatures on structure and properties of melt-spinnable acrylonitrile-methyl acrylate copolymers and fibers

A series of 85/15 AN/MA copolymers (acrylonitrile-methyl acrylate copolymers with feed ratio of 85/15 mol%) were synthesized by aqueous precipitation polymerization at 20, 30, and 40 °C, and the copolymers were used to produce a series of fibers by melt spinning. The copolymers and fibers were characterized by element analysis (EA), nuclear magnetic resonance (1H NMR and 13C NMR), capillary rheometry, differential scanning calorimetry (DSC), X-ray diffraction (XRD), and scanning electronic microscopy (SEM). The average length of the contiguous AN units synthesized at 30 °C had a maximum value of 10.53. Aqueous polymerization at 30 °C resulted the lowest glass transition temperature (T g ) of 87.1 °C, the lowest melting point (T m ) of 154.5 °C, and the highest decomposition temperature (T d ) of 325.0 °C. 85/15 AN/MA prepared at 20 and 30 °C exhibited a better fluidity at 210 °C. The ideal reaction temperatures for melt processing of the AN/MA copolymers were found to be 20 and 30 °C.

2D NMR studies of acrylonitrile–methyl acrylate copolymers

The microstructure of acrylonitrile–methyl acrylate copolymers prepared by the solution polymerization using 2,2′-azobisisobutyronitrile (AIBN) as free radical initiator was investigated by two-dimensional NMR techniques. 2D-heteronuclear single quantum correlation (HSQC) and the total correlation spectroscopy (TOCSY) have been utilized to resolve the complex 1H NMR spectrum and to establish the compositional and configurational sequences of acrylonitrile–methyl acrylate copolymers. 2D HSQC and TOCSY showed compositional and configurational sensitivity of methine protons of A and M units upto the triad level. Heteronuclear multiple-bond correlation (HMBC) spectroscopy has been used to study carbon (carbonyl/nitrile)–proton coupling. The carbonyl and nitrile carbons showed compositional sensitivity upto the triad level. The values of reactivity ratios were determined by Kelen–Tudos (KT) and non-linear error in variable method (RREVM).

Piezoelectricity and crystallinity studies in thermopoled Acrylonitrile-Methylacrylate copolymer films

Molecular ordering in Acrylonitrile-Methylacrylate copolymer, P(AN-MA), films has been achieved by hot stretching. The structure, morphology of the stretched and nonstretched films, as well as the thermally stimulated depolarization current (TSDC) measurements are discussed. The piezoelectricity and charge storage in unstretched and stretched thermal poling P(AN-MA), films have been investigated at different poling fields. Quantitative analysis of the thermally stimulated depolarization current (TSDC) revealed that uniaxial stretching and subsequent poling at elevated temperatures give rise to high values of polarization and piezoelectricity in the films. The piezoelectric coefficient, d 31 was measured and the maximum value d 31 =8.6 PCN m 1 has been obtained at E p =10 MVm m 1 , T p =373 K and stretching ratio u =6. It has been concluded that the increase in crystalllnity and the polarization effects enhance the piezoelectric activity in P(AN-MA) thermoelectrets.

New organodisulfide—polyaniline composite cathode for secondary lithium battery

A new composite cathode used for high-energy density secondary lithium batteries is developed, which consists of 2,5-dimercapto-1,3,4-thiadiazole (organodisulfide), polyaniline, and gel electrolyte. Polyaniline works to promote the redox reaction of the organodisulfide in the composite electrode, providing the cyclic voltammogram showing a narrower peak-potential separation of 0.5 V between cathode and anode peaks. The lithium cell using the composite cathode and gel electrolyte based on acrylonitrile—methylacrylate copolymer has over 3.0 V cell voltage with 303 Wh kg −1 cathode energy density at a current density of 0.1 mA cm −2 at room temperature. In practice, a model cell with 80 μm thick lithium anode, 50 μm thick gel electrolyte, and 170 μm thick composite cathode is expected to deliver 220 Wh kg −1 cell energy density at 0.1 mA cm −2.

Dielectric and relaxation behaviour studies in acrylonitrile-methylacrylate copolymer

Poly(acrylonitrile-methylacrylate) copolymer is a semicrystalline material, as defined by X-ray diffraction, and is thermally stable up to 425 K as revealed by infrared investigations. The study of dielectric properties obtained from this copolymer allows us to follow the relaxation processes and showed the difference between three processes; β-, α- and ρ-relaxations. The first two processes occur in the two phases, amorphous and crystalline, and the third process is associated with the glass transition temperature. The origins of these processes were attributed to local motion of the polymer backbone segments, to a dipole orientation of the chain side groups and to an ionic space-charge relaxation, respectively.

Hygienic chemical studies of high-acrylonitrile resin.

Three kinds of high-acrylonitrile resin (acrylonitrile-methyl acrylate copolymer) were investigated for material and migration tests and pyrolysis. Material and migration tests showed that the amounts of heavy metals, acrylonitrile (AN) and methyl acrylate as volatile materials, nonvolatile residue, and KMnO4 consumption were under the regulated values for styrene-acrylonitrile copolymer and acrylonitrile-butadiene-styrene copolymer. Migration amount of AN monomer was determined to be 8-20 ng/ml in water, 5-6 ng/ml in 20% ethanol, 5-25 ng/ml in 4% acetic acid, and 22-27 ng/ml in n-heptane after treatment for 12 weeks at 37°C. Generation of AN monomer and CN-from the resins during pyrolysis at 800°C was 9.77-22.1 mg/g plastic and 53.9-134.8 mg/g plastic, respectively, and the generated AN monomer was completely trapped in n-heptane and rapidly decomposed in 1N NaOH.

Effect of the proportion of acrylonitrile-methyl acrylate copolymers on the thermomechanical properties of the fibre

Effect of the proportion of acrylonitrile-methyl acrylate copolymers on the thermomechanical properties of the fibre

Alteration of Acrylonitrile-Methylacrylate-Butadiene Terpolymer by Nocardia rhodochrous and Penicillium notatum

[C]Barex-210, a terpolymer of acrylonitrile, methylacrylate, and butadiene, was tested for bioconversion. Powdered samples of polymer, each specifically C labeled at different carbon atoms of the polymer, were incubated with either Nocardia rhodochrous or Penicillium notatum in an enriched growth medium for various periods of time. After 6 months of incubation, the C-labeled polymer was transformed from a high-molecular-weight material completely soluble in dimethyl formamide (DMF) into both a lower-molecular-weight form still soluble in DMF and a second form that was no longer soluble in DMF. The amount of C-labeled carbon atoms converted into DMF-insoluble material was 8% of the backbone carbon-carbon atoms and 12% of the side-chain nitrile and acrylate atoms from the acrylonitrile-methylacrylate copolymer and 60% of the elastomer (acrylonitrile-butadiene copolymer) atoms. Metabolism of the polymer was not established from measurements of metabolic CO(2). Evolution of CO(2) amounted to only 0.3, 0.6, 1.8, and 3.3% of these four fractions, respectively. Although the transformation of high-molecular-weight polymer into DMF-insoluble material was rapid in the early stages of microbial growth, the accompanying CO(2) evolution was much slower. Further evidence of polymer alteration was indicated by the infrared spectrum of the insoluble material, which showed a disappearance of the nitrile and methylacrylate peaks.

Study on the Distribution of Dyads in Acrylonitrile-Methyl Acrylate Copolymers by Pyrolysis Gas Chromatography

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStudy on the Distribution of Dyads in Acrylonitrile-Methyl Acrylate Copolymers by Pyrolysis Gas ChromatographyYoshiyuki Yamamoto, Shin Tsuge, and Tsugio TakeuchiCite this: Macromolecules 1972, 5, 3, 325–327Publication Date (Print):May 1, 1972Publication History Published online1 May 2002Published inissue 1 May 1972https://doi.org/10.1021/ma60027a019RIGHTS & PERMISSIONSArticle Views56Altmetric-Citations5LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (313 KB) Get e-Alerts Get e-Alerts

STUDIES ON ALKALINE DISCOLORATION OF ACRYLONITRILE POLYMER IN DIMETHYLFORMAMIDE

Alkaline discolorations of poylacrylonitrile, acrylonitrile-methyl acrylate copolymer and polyacrylonitrile-polymethyl acrylate blend in dimethylformamide were investigated in terms of conjugated double bonds formation. Viscosity and infrared spectrum of recovered polymer were also measured.The experimental results are summarized in the followings:1) Discoloration is time dependent, but the change of viscosity occurs instantaneously. Therefore, discoloration reaction and chain degradation may be considered to be two independent processes. Residual discoloration after acidification of discolored solution is also time dependent so that at least two types of mechanisms may be presumed for the discoloration.2) Alkaline discoloration of polyacylonitrile decreases remarkably with introduction of comonomer and the behavior of discoloration is reasonably explained in terms of the sequence length of acrylonitrile which relates to the conjugated double bonds formation. The large difference in discoloration behavior between copolymeric system and polymer blend provides an useful method to investigate the microstructure of acrylonitrile polymer.3) By the application of the method, it was confirmed that the fractionation of acrylonitrilemethyl acrylate copolymer had been carried out in accordance to molecular weight, but not polymer composition.4) Viscosity of alkaline degradated polymer seems to be independent of the original molecular weight and increases with increased of comonomer content. This phenomenon is discussed from the view point of abnormal linkage between acrylonitrile units in the polymer.5) Infrared spectrum of alkaline treated polymer is compared with that of heat treated polymer.6) The effects of polymerization conversion on polymer composition was investigated in terms of alkaline discoloration for different copolymeric system. The experimental result satisfies qualitatively the calculated relationship expected from monomer reactivity ratios.

Dilute solution properties of acrylonitrile-methyl acrylate copolymers in dimethylformamide

Viscosities and osmotic pressures of dilute solutions of fractions of polyacrylonitrile and of copolymers of acrylonitrile and methyl acrylate, and of polymethyl acrylate in dimethylformamide have been measured at different temperatures. Temperature coefficients of intrinsic viscosity [η] are negative and those for polyacrylonitrile and the copolymers are relatively large. A maximum value of —d[ η]/d T is obtained at a copolymer composition approximating to 85 per cent by weight of acrylonitrile. Values of the polymer-solvent interaction parameter χ 1 are a minimum at this composition and increase with increasing temperature. These results are considered in terms of chain flexibility and polymer—solvent interaction. It is concluded that the negative temperature coefficients of [η] and their variation with copolymer composition are consequences of polymer—solvent interaction rather than chain stiffness.

STUDIES ON THE PRODUCTION OF ACRYLIC FIBER BY WET SPINNING

The properties of the dope solution of acrylonitrile-methyl acrylate copolymer of 0.95 to 0.05 which was prepared by 50% aqueous solution of NaCNS were studied.(1) The specific gravity of the dope was measured at 30°C in the concentration range from 0.63% to 11.93%.(2) Hygroscopic behaviours of the 50% aqueous solution of NaCNS and the dope sulution with the polymer concentration of 9.5% were measured and compared at the relative humidity of 60% and at 25°C.(3) Microscopic measurement was utilized to evaluate the dissolving rate of acrylonitrile fiber and polymer particle. The minimum concentration of NaCNS to dissolve the polymer is presumed to be around 46%.(4) The viscosity of the dope solution was measured by the ball fall method in the polymer concentration range from 7% to 13%, and in the temperature range from 0.8°C to 65°C. At 30°C, the modified Baker equation obtained is as follows.where η is the viscosity (sec.), M: molecular weight obtained by using the Staudinger equation, ηBP/C=1.5×10-4M (C: 0.5 mole/l), C: the polymer concentration of the dope (%).(5) A linear relationship was observed between the logarithm of the viscosity and the recipr ocal of the absolute temperature in the temperature range from 30°C to 65°C. This relationship did not hold at the temperature below 10°C.(6) The Copolymers of different molecular weights were mixed in various ratios to prepare six dope solutions of the copolymer mixture and the viscosity of the solutions were measured.The relationship of the viscosity of each of the original polymer solution to those of the mixed polymer solutions may be expresed as: where η: the viscosity of the mixed polymer solution (sec.), η1: the viscosities of the original polymer solutions (sec.), W1: the weight fractions of the original polymer solutions (%).

ULTIMATE TENSILE PROPERTIES OF ACRYLONITRILE-METHYLACRYLATE COPOLYMERIC FIBERS

The ultimate tensile properties for an after-heat stretched and a heat-relaxed fiber of acrylonitrile-methylacrylate copolymer have been measured under a condition of constant load and the results obtained are summarized as follows:(1) The tensile strength and the ultimate elongation vary with the after-treatments, but the shape of the composite curve of the logarithmic tensile strength plotted against the logarithmic time to break is unchanged and independent of the after-treatments. Therefore it may be assumed that the after-treatments have no effects on a critical condition for rupture. The temperature dependence of the shift factor along the axis of the time to break can be also assumed to be independent of the after-treatments.(2) From the previous result that the location on the logarithmic axis of the time to break for the composite curve of the tensile strength is linearly related to the reciprocal of a characteristic temperature Tc, it is deduced that Tc for the heat-relaxed fiber is nearly the same as the value for the untreated and that of Tc for the heat-stretched fiber is lower than that of the untreated.(3) Assuming that the shift factor along the logarithmic axis of the ultimate elongation represents a relative concentration of active chain, the free energy difference ΔF_??_ between active and inactive chains is calculated. From the maximum values of ΔF_??_ it is concluded that the active chains in the heat-stretched fiber are in restricted state and those of the heat-relaxed fiber are in relaxed and stable state.(4) The effective stretch ratios for the untreated and the heat-relaxed fibers calculated from the maximum value of the ultimate elongation (εb)max coinside with those values calculated from the shrinkage in a I2-KI aqueous solution of high I2 concentration, and for the after-heat stretched fiber the value calculated from (εb)max coinsides with that obtained in a low I2 concentration ofthe solution, The tensile strength of the after-stretched fiber depends on a lower order region of the fiber structure, and this consideration associates with the decrease in Tc observed for the after-heat stretched fiber.

ULTIMATE TENSILE PROPERTIES OF ACRYLONITRILE-METHYLACRYLATE COPOLYMERIC FIBERS

The ultimate tensile properties for an after-heat stretched and a heat-relaxed fiber of acrylonitrile-methylacrylate copolymer have been measured under a condition of constant load and the results obtained are summarized as follows:(1) The tensile strength and the ultimate elongation vary with the after-treatments, but the shape of the composite curve of the logarithmic tensile strength plotted against the logarithmic time to break is unchanged and independent of the after-treatments. Therefore it may be assumed that the after-treatments have no effects on a critical condition for rupture. The temperature dependence of the shift factor along the axis of the time to break can be also assumed to be independent of the after-treatments.(2) From the previous result that the location on the logarithmic axis of the time to break for the composite curve of the tensile strength is linearly related to the reciprocal of a characteristic temperature Tc, it is deduced that Tc for the heat-relaxed fiber is nearly the same as the value for the untreated and that of Tc for the heat-stretched fiber is lower than that of the untreated.(3) Assuming that the shift factor along the logarithmic axis of the ultimate elongation represents a relative concentration of active chain, the free energy difference ΔF_??_ between active and inactive chains is calculated. From the maximum values of ΔF_??_ it is concluded that the active chains in the heat-stretched fiber are in restricted state and those of the heat-relaxed fiber are in relaxed and stable state.(4) The effective stretch ratios for the untreated and the heat-relaxed fibers calculated from the maximum value of the ultimate elongation (eb)max coinside with those values calculated from the shrinkage in a I2-KI aqueous solution of high I2 concentration, and for the after-heat stretched fiber the value calculated from (eb)max coinsides with that obtained in a low I2 concentration ofthe solution, The tensile strength of the after-stretched fiber depends on a lower order region of the fiber structure, and this consideration associates with the decrease in Tc observed for the after-heat stretched fiber.

STUDIES ON ACRYLIC FIBER

The acrylonitrile-methyl acrylate copolymer (content of methyl-acrylate 3_??_5 mol%) was dissolved in those solvents which are shown below and these polymer-solvent systems did not gel at room temperature for remarkably long period.β-Propiolactone γ-Butyrolactone Dimethylsulfoxide (DMSO) Tetramethylene sulfoxide Tetramethylene sulfone DMF DMA N-Formylmorphorine N-Acetylmorphorine N-Acetylpyrrolidine GlyconitrileThe viscosities and viscosity stabilities of the AN polymer concentrated solutions in Y-butyrollactone, DMSO, DMF and DMA, whose prices are relatively low, may be used for spinning solution.

アクリル繊維の研究

Viscosities of concentrated solutions of acrylonitrile-methyl acrylate copolymers (methyl acrylate contents in copolymers were 3-5%) in dimethyl formamide were measured by a rotational viscometer (so-called B-type viscometer).The stability of the solution was examined viscometrically under various conditions of dissolution.The stable and molecular-dispersed solutions of this polymer does not show much increase in viscosity with time.The effect of rate of shear upon the viscosity of solution can be written as follows:is the rpm of viscometer and k and n are constants. It has been found that the different values of viscosity were obtained for various types of polymers of the same Mn. The relationship between viscosity and concentration of the solution, temperature and molecular weight of polymer can be expressed respectively as follows:1.(The influence of the concentration of the solution)2.(The influence of molecular weight of polymer)3.(The influence of temperature)The apparent activation energy of flow is not constant but varies with the concentration of the solution and with the molecular weight of the polymer.