Fourier transform infrared studies of poly(vinyl chloride) blends with ethylene Co- and terpolymers

The miscibility of poly(vinyl chloride) (PVC) with various ethylene copolymers and terpolymers were investigated using FT-IR spectroscopy. All blends reported were 50/50 by weight. In blends of PVC with ethylene/dimethyl acrylamide copolymer (E/DMA), frequency shifts were observed in the amide carbonyl (proton acceptor) and the α-hydrogen of PVC (proton donor) characteristic bands. In blends of PVC with ethylene/ethyl acrylate/carbon monoxide terpolymer (E/EA/CO), both the ester carbonyl and the ketone carbonyl characteristic frequencies showed mutual shifts and appeared as if they merged together. Small frequency shifts were also observed in the α-hydrogen of PVC characteristic bands. In blends of PVC with ethylene/vinyl acetate/carbon monoxide terpolymer (E/VA/CO), the ester carbonyl frequency showed a shift while that of the ketone carbonyl was essentially unchanged. On the other hand, in PVC blends with ethylene/vinyl acetate copolymer (E/VA), the ester CO frequency did not show any shift, which is consistent with their observed immiscibility. Thus, it is clear that incorporating a ketone ? C?O in ethylene/ester copolymers to form the corresponding terpolymers enhances their miscibility with PVC as earlier proposed on the basis of dynamic mechanical studies. Similar results were shown for blends of PVC with ethylene/2 ethyl hexyl acrylate/carbon monoxide terpolymer (E/2EHA/CO). Frequency shifts imply specific interactions which suggest polymer-polyer miscibility on a molecular scale.     

Preparation and characterization of a methyl methacrylate/ethyl acrylate/acrylic acid terpolymer to improve the homogeneity of ethylene–propylene–diene monomer rubber/poly(vinyl chloride) blends

The emulsion terpolymerization of methyl methacrylate (MMA), ethyl acrylate (EA), and acrylic acid (AA) was carried out under a nitrogen atmosphere at 70°C. The final terpolymer conversion was determined gravimetrically. The synthesized MMA–EA–AA terpolymer was characterized with ¹H‐NMR spectroscopy, thermal analysis, and gel permeation chromatography. Glass‐transition temperatures of the MMA–EA–AA terpolymer were determined with a differential scanning calorimeter. Ethylene–propylene–diene monomer rubber (EPDM)/poly(vinyl chloride) (PVC) blends were prepared with different blend ratios (10/90, 20/80, 30/70, 40/60, and 50/50) in the presence and absence of MMA–EA–AA as a compatibilizer. The morphology of those blends was examined with the aid of a scanning electron microscope. The scanning electron micrographs in the presence of the MMA–EA–AA terpolymer illustrated the disappearance of the macroscale phase separation of EPDM/PVC blends as a result of the incorporation of MMA–EA–AA into that blend, indicating an improvement of the homogeneity. The mechanical properties of the EPDM/PVC blend films and the dielectric properties of the melt blends were investigated. The swelling behavior of the cured blends in the brake fluid was also discussed. The results illustrated that the mechanical properties, the weight swelling values, and the dielectric constant values showed linear behavior versus the blend ratios after the incorporation of the terpolymer. However, those values showed deviations from linearity in the absence of the terpolymer. That, in turn, ensured the results obtained with the scanning electron microscope. The results reveal that the MMA–EA–AA terpolymer prepared can be used successfully to improve the homogeneity of EPDM/PVC blends used in hose and oil seal applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Blends containing polymers of epichlorohydrin and ethylene oxide. II. Polyacrylates

The phase behavior of blends of various polyacrylate homopolymers and two commercial ethyl acrylate (EA) and n-butyl acrylate (nBA) copolymers with polyepichlorohydrin (PECH), poly(ethylene oxide) (PEO), and a copolymer of epichlorohydrin and ethylene oxide [P(ECH/EO)] was examined using differential scanning calorimetry and optical indications of phase separation on heating, i.e., lower critical solution temperature (LCST) behavior. Poly(methylacrylate) (PMA) was shown to be miscible with PECH, PEO, and P(ECH/EO) while only PECH was found to be miscible with the higher polyacrylates: poly(ethyl acrylate), EA copolymer, poly(n-propyl acrylate), and nBA copolymer. However, even PECH was found to be only partially miscible with poly(n-butyl acrylate). In general, glass transitions observed by DSC for blends were not as broad as those found in corresponding polymethacrylate blends. All mixtures showed LCST behavior, and, based on this and excess volume measurements, to the extent possible, qualitative conclusions were made concerning the relative strength of the interactions among the various blend pairs. For PECH it appears that the interaction with polyacrylates decreases with increasing size of the alkyl group. The commercial copolymers seem to interact more exothermically with PECH than the corresponding homopolymers. The interaction with PMA is apparently larger for PECH than for PEO or for P(ECH/EO). Interactions for the latter two are about the same. The apparently exothermic interactions between ECH and EO units are not sufficiently strong to preclude miscibility of P(ECH/EO) with PMA. As for the polymethacrylates, it is clear that the chlorine moeity of PECH is needed for miscibility with higher polyacrylates.     

Miscibility of poly(vinyl acetate) and vinyl acetate-ethylene copolymers with styrene-acrylic acid and acrylate-acrylic acid copolymers

Poly(vinyl acetate) and vinyl acetate-ethylene (VAE) copolymers compose one of the more important polymeric materials, widely employed in coating and adhesive applications. A new class of miscible polymer blends involving poly(vinyl acetate) and VAE with styrene-acrylic acid and acrylate-acrylic acid copolymers has been found. Experimental windows of miscibility as a function of the ethylene content for VAE copolymers and the acrylic acid content of the acrylate-acrylic acid copolymers are observed (acrylate = methyl acrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate). Employing well-established analog heat of mixing measurements, predicted windows of miscibility were compared with experimental results. Fair qualitative agreement was observed and supported the hypothesis that specific rejection arguments can be employed to explain the observed miscibility. Failure to quantitatively predict miscibility based on the analog heat of mixing measurements may be due to the higher association tendencies of the model compounds relative to acrylic acid units in the high molecular weight polymers. No miscible combinations were found for methyl methacrylate-acrylic acid copolymers or acrylate-methacrylic acid copolymers in admixture with poly(vinyl acetate) or the VAE copolymers, thus indicating the sensitivity of phase behavior to minor structural changes. VAE (30 wt % ethylene) copolymers were also noted to be miscible with several polymers previously noted to be miscible with poly(vinyl acetate), namely, poly(vinylidene fluoride), poly(ethylene oxide), and nitrocellulose. © 1995 John Wiley & Sons, Inc.     

聚氯乙烯/氯乙烯-丙烯酸乙酯共聚物/高密度聚乙烯合金的制备及其性能研究

以氯乙烯-丙烯酸乙酯共聚物(VC/EA)作为聚氯乙烯(PVC)和高密度聚乙烯(HDPE)的增容剂,研究了共混物的相容性和加工性能,在此基础上研制了聚氯乙烯/氯乙烯-丙烯酸乙酯共聚物/高密度聚乙烯合金,进而研究了合金的力学性能。结果表明,合适配比的共混体系具有一定程度的相容性和良好的流动性能,明显改善了PVC的加工性能,并在保持PVC材料拉伸强度、弯曲强度等具有较高保持率的前提下,显著提高了材料抗冲性能。     

Effect of dehydrochlorination of PVC on miscibility and phase separation of binary and ternary blends of poly(vinyl chloride), poly(ethylene-co-vinyl acetate) and poly(styrene-co-acrylonitrile)

The enhancement of miscibility at the lower critical solution temperature (LCST) of the blends poly(vinyl chloride)/poly(ethylene-co-vinyl acetate) (PVC/EVA), poly(vinyl chloride)/poly(styrene-co-acrylonitrile) (PVC/SAN) and poly(vinyl chloride)/poly(ethylene-co-vinyl acetate)/poly(styrene-co-acrylonitrile) (PVC/EVA/SAN) was observed at the micron level. Such miscibility is attributed to the dehydrochlorination and formation of hydrogen bonds between blend components. However, macrolevel immiscibility of these blends heated to the LCST was observed. Such microdomain compatibility of these blends gives a synergistic character. Brittle-type failure observed for LCST samples testifies to the synergism in treated blends. ©1997 SCI     

Synthesis of poly(2-oxo-1,3-dioxolane-4-yl) methyl methacrylate by polymer reaction of carbon dioxide and miscibility of its blends with copolymers of methyl methacrylate and ethyl acrylate

Polymeric epoxides were converted to corresponding five-membered cyclic carbonates in an effective manner. Poly(glycidyl methacrylate) (PGMA) was converted to a poly(2-oxo-1,3-dioxolane-4-yl) methyl methacrylate (PDOMMA) by the polymer reaction with carbon dioxide using tetraoctylammonium chloride (TOAC) as a catalyst. The miscibility of blends of PGMA or PDOMMA with copolymers of MMA and ethyl acrylate (MMA-EA) of two different EA compositions (2 and 5 wt %) was investigated by differential scanning calorimetry (DSC). The films of PGMA or PDOMMA and MMA-EA (2 and 5 wt %) blends were cast from N,N-dimethylformamide solution. An optical clarity test and DSC analysis showed that PDOMMA blends were miscible over the entire composition range, but PGMA was immiscible with the MMA-EA copolymers. It was also found that the miscibility of PDOMMA with 2 wt % MMA-EA copolymer was better than that of DOMMA with 5 wt % MMA-EA copolymer. The different miscibility behaviors were investigated in terms of Fourier transform IR spectra and interaction parameters based on the binary interaction model. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2161–2169, 2001     

Properties and morphologies of PVC/nylon terpolymer blends

A new kind of blends of polyvinyl chloride (PVC)/nylon terpolymer was reported in this article. Two compatibilizers were used in this study: one is a terpolymer of ethylene–n‐butyl acrylate–monoxide (EnBACO); the other is terpolymer of EnBACO grafted with maleic anhydride (EnBACO‐g‐MAH). The observation of scanning electron microscope (SEM) reveals that the PVC/nylon terpolymer blends have a two‐phase structure; and the nylon terpolymer phase is the continuous phase, and PVC domains in the PVC/nylon terpolymer/EnBACO‐g‐MAH blends have fine dispersion over a broad range of the PVC/nylon terpolymer ratio. EnBACO‐g‐MAH is more compatible with the nylon terpolymer than EnBACO. EnBACO and EnBACO‐g‐MAH have different effects on the glass transition temperatures of the PVC phase and nylon terpolymer phase in the blends. The notched Izod impact strength, tensile strength, elongation at break, Vicat softening temperature (VST), and melt flow index (MFI) critically depend on PVC/nylon terpolymer ratio, the kinds and concentration of the compatibilizers. The PVC/nylon terpolymer/EnBACO‐g‐MAH blends display a good combination of high toughness, high flowability, and high VST under low load. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2823–2832, 2001     

Cellulose nanocrystals as a compatibilizer for improved miscibility of water-soluble polymer binary blends

Cellulose nanocrystals (CNCs) have been studied as compatibilizers for improving the interfacial miscibility of polymer binary blends. Binary blends of water-soluble polymers–poly(vinyl alcohol), poly(ethylene oxide), and polyvinylpyrrolidone—containing different amounts of CNC (16 and 25 wt %) were prepared by a solution casting method. For the first time, a systematic side-by-side comparison between the morphological, thermal, and mechanical properties of the polymer blends reinforced by CNC has been conducted. It has been determined that in the presence of CNC, the degree of crystallinity of the blend components decreased and the miscibility of the blends increased. The blends possess enhanced thermal and mechanical properties as a result of improved miscibility of the blend components. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48662.     

Miscibility of poly(tetrahydrofurfuryl methacrylate) and poly(tetrahydropyranyl-2-methacrylate) with some chlorine-containing polymers

The miscibility of poly(tetrahydrofurfuryl methacrylate) (PTHFMA) and poly(tetrahydropyranyl-2-methacrylate) (PTHPMA) with some chlorine-containing polymers was studied by differential scanning calorimetry (DSC). PTHPMA was found to be miscible with poly(vinyl chloride) (PVC), polyepichlorohydrin (PECH), and a vinylidene chloride/vinyl chloride copolymer [P (VDC/VC)] and only partially miscible with an epichlorohydrin/ethylene oxide copolymer [P (ECH/EO)]. PTHFMA was shown to be miscible with PECH and P(VDC/VC), but its miscibility with P(ECH/EO) is composition-dependent. Information about interactions between components in PTHFMA/P (VDC/VC) and PTHPMA/P(VDC/VC) blends was estimated from melting-point depression. The interaction parameters B were found to be ?1.7 and ?3.6 J/cm³ for PTHFMA/P(VDC/VC) and PTHPMA/P(VDC/VC) blend systems, respectively. The miscibility behavior of PTHFMA and PTHPMA is compared to that of poly(cyclohexyl methacrylate).     

The miscibility of polyacrylates and polymethacrylates with PVC: In situ polymerization and the miscibility of poly(methyl acrylate) and poly(ethyl acrylate) with PVC

The in situ polymerization of vinyl chloride with various polyacrylates and polymethacrylates has been studied. The products were examined by dynamic mechanical analysis. Poly(methyl acrylate) and poly(ethyl acrylate) had previously produced two-phase blends with poly(vinyl chloride) (PVC) by solvent casting, but poly(ethyl acrylate) was shown to be miscible with PVC when blends were produced by in situ polymerization. Poly(methyl acrylate) and poly(octyl acrylate) were found to be immiscible with PVC whereas other polyacrylates and polymethacrylates with intermediate ester group concentrations were found to be miscible, confirming previous studies. The glass transition temperatures of the blends were measured and the deviations from the expected mean of the two base polymers were calculated as an indication of the strength of interaction between the polymers. The polymers having intermediate ester group concentrations showed the strongest interactions and the results correlated well with previously measured interaction parameters.     

Effect of dynamic vulcanization on the microstructure and performance of polyethylene terephthalate/elastomer blends

Blends of polyethylene terephthalate (PET) and ethylene‐ethyl acrylate‐maleic anhydride terpolymer (E‐EA‐MAH) were dynamically crosslinked in a one‐step extrusion process. An amine‐terminated glycol reacting with MAH moieties was used as the crosslinking agent. The effect of blend composition and dynamic crosslinking on the microstructure and mechanical properties were investigated. Blend ratios ranging from 80:20 to 20:80 PET/E‐EA‐MAH were studied. The region of phase inversion was located for uncrosslinked and dynamically crosslinked blends. The rheological characterization was also carried out for these blends in comparison with the neat materials. After dynamic crosslinking, the phase inversion is shifted from the 30–40% range to the 70–80% range of elastomer content. This shift is induced by the increase of viscosity and elasticity of the network formed. Dynamically crosslinked blends show significant improvements in impact strength but also exhibit a decrease in elongation at break.     

Miscibility and interaction studies on some aqueous polymer blend solutions by ultrasonic and rheological techniques

The aqueous solutions of poly(ethylene oxide)–polyacrylic acid, poly(vinyl pyrrolidone)–poly(vinyl alcohol), and poly(ethylene oxide)–poly(vinyl alcohol) blends have been studied by ultrasonic, rheological, and viscometric techniques. Extensive investigation over a wide range of concentrations, temperatures, compositions, pH, and shear rates indicate the degree of miscibility, extent of interaction between the polymers, and stoichiometry of the polymer complexes formed by the strong interaction between the polymers in solutions. These investigations indicate the miscibility of poly(ethylene oxide)–polyacrylic acid and poly(ethylene oxide)–poly(vinyl pyrrolidone) blends and the immiscibility of poly(ethylene oxide)–poly(vinyl alcohol) blends in conformity with other reported investigations. © 1994 John Wiley & Sons, Inc.     

Noise and vibration damping with latex interpenetrating polymer networks

Damping systems based on interpenetrating polymer networks (IPN's) provide noise and vibration attenuation over broad temperature and frequency ranges. Semicompatible latex IPN's are employed in both extensional and constrained layer configurations. The damping behavior of IPN's of compositions poly(ethyl methacrylate)/poly(n-butyl acrylate) [PEMA/PnBA], poly(ethyl methacrylate–co–ethyl acrylate)/poly(n-butyl acrylate–co–ethyl acrylate) [P(EMA–co–EA)/P(nBA–co–EA)], and poly(vinyl chloride)/poly(butadiene–co–acrylonitrile) [PVC/P(B–co–AN)] were investigated and compared to both commercially available materials and to theory. The damping of both the PEMA/PnBA and the P(EMA–co–EA)/P(nBA–co–EA) IPN's in a constrained layer configuration was significantly better, over a broad temperature range of ?10° to 60°C, than the commercial materials. In addition, the P(EMA–co–EA)/P(nBA–co–EA) IPN was found to be effective in damping phenolic-impregnated Kevlar cloth laminates. A reduction of 10 dB in impact noise resulted with a 6–8% by weight layer inserted between the Kevlar-phenolic panels. The relationship between the peak damping temperature of a constrained layer system to maximum tan δ along with that of an extensional damping system to maximum E″ was also demonstrated. Although the amount of damping predicted by the theory approached that found experimentally, sufficient differences existed such that the exact detail of the damping curve was not described.     

EA-MA共聚乳液处理木质素与PVC的共混

用丙烯酸乙酯（EA）-马来酸酐（MA）共聚乳液对木质素进行处理后与聚氯乙烯进行共混,并考察了共混物的流变性能、热稳定性和力学性能,同时用扫描电子显微镜观察了共混试样的低温脆断表面形貌。在聚氯乙烯中添加木质素后,其流变性能的变化表现为最小扭矩和塑化峰扭矩大幅升高,同时塑化时间大幅缩短;对热稳定性的影响为后期分解速率降低,达到最大分解速率时的温度升高,最大分解速率变小。EA-MA共聚物对共混试样的作用主要体现在力学性能方面,用固重相对于木质素为1%的共聚乳液处理的木质素,共混后具有最佳的力学性能。共混试样低温脆断表面的扫描电子显微图片表明,用EA-MA共聚乳液对木质素进行处理,可以大大改善其与聚氯乙烯之间的相容性。     

Development and assessment of the advanced graft copolymers obtained from Hibiscus sabdariffa biomass

In this article, the morphological transformation in Hibiscus sabdariffa stem fiber through graft copolymerization with effective ethyl acrylate (EA) and its binary vinyl monomeric mixtures using ceric ammonium nitrate—nitric acid initiator system has been reported. Different reaction parameters such as temperature, time, initiator concentration, monomer concentration, and pH were optimized to obtain the maximum graft yield (117.3%). The optimized reaction parameters were then used to screen the additive effect of EA with n‐butyl acrylate (BA), acrylic acid (AA), and 4‐vinyl pyridine (4‐VP) in binary vinyl monomer mixtures on percentage grafting, properties, and the behavior of the fiber. The graft copolymers were characterized by FTIR, SEM, XRD, TGA, and DTA techniques and evaluated for physico‐chemical changes. With increase in the P_g a significant physico‐chemico‐thermal resistance, miscibility in organic solvents, hydrophobicity were found to increase, whereas crystallinity, crystallinity index, dye‐uptake, and hydrophylicity decreased, however, the cellulose form I remained unchanged. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The in situ polymerization of vinyl chloride in poly(butyl acrylate)

The in situ polymerization of vinyl chloride with poly(butyl acrylate) has been studied. Vinyl chloride was polymerized using a peroxydicarbonate initiator in sealed ampoules in the presence of various weights of poly(butyl acrylate). The products were examined by dynamic mechanical analysis and electron microscopy. It was found that if about 50% or less vinyl chloride was present in the mixture homogeneous blends were formed. If more than 50% vinyl chloride was present the polymerization passed through a two phase region in the three component phase diagram and inhomogeneous blends were formed. If homogeneous blends prepared as above were reswollen with vinyl chloride and the latter polymerized, then homogeneous blends containing more poly(vinyl chloride) could be prepared, avoiding the two phase region. The interaction parameters between vinyl chloride and both poly(vinyl chloride) and poly(butyl acrylate) were estimated using inverse gas chromatography. Using these and an estimate of the polymer/polymer interaction parameter the three component phase diagram could be qualitatively explained.     

A study of aromatic polyester/chlorinated polymer blends

A large number of studies have been devoted in recent years to the miscibility behavior of linear polyesters with chlorinated polymers, including poly(vinyl chloride) (PVC), chlorinated PVC, chlorinated poly(ethylenes), and copolymers of vinylidene chloride (Saran). However, similar studies with aromatic polyesters are lacking. It is the purpose of this paper to compare the properties of blends made of poly(ethylene terephthalate), poly(butylene terephthalate) or poly(hexamethylene terephthalate) and of various chlorinated polymers. It is shown that a high concentration of chlorine atoms is required to achieve miscibility. Moreover, there is a “miscibility window” in terms of the carbonyl concentration of polyesters, immiscibility being found for carbonyl concentrations outside this window, A similar behavior was observed before for linear polyester/chlorinated polymer blends and for polyester/polycarbonate blends. Solid state small-angle light scattering experiments were also conducted to follow the morphology of the blends as a function of composition. Spherulites were found but their size vary with composition.     

Organotin polymers—XVII. Azeotropy in terpolymerization reactions of tri-n-butyltin 4-acryloyloxybenzoate wit alkyl acrylates or styrene and acrylonitrile

Ternary copolymerizations of tri-n-butyltin 4-acryloyloxybenzoate (ABTB) with acrylonitrile (AN) and alkyl acrylates [methyl (MA), ethyl (EA) or butyl acrylate (BA)], methyl methacrylate (MMA) or styrene (ST) were carried out in solution at 70°C in the presence of free radical initiator. Experimental terpolymerization data agreed well with calculations based on the Alfrey-Goldfinger equation. The determination of unitary, binary and ternary azeotropies of various systems studied was easily handled by a computer program. The results obtained show that there is no ternary azeotropic composition for any terpolymer, system studied. Selective unitary and binary azeotropic compositions were polymerized and the results obtained show good agreement between the theoretical and experimental terpolymer composition for each case.     

Study of poly(vinyl chloride) blends with solid‐state chlorinated polyethylene

The influence of solid‐state chlorinated polyethylene of various chlorine content and residual crystallinity on the mechanical properties of rigid poly(vinyl chloride) has been studied. The impact strength of poly(vinyl chloride) was found to increase significantly as 10–20 mass% chlorinated polyethylene, containing from 10.2 to 27.3% chlorine content (preferably 21.8% Cl) were added. This dependence corresponded to the higher elasticity and impact strength of the solid‐state chlorinated polyethylene with chlorine content below 30% as well as the microstructure of its chlorinated block fragments. Multicomponent system of high impact strength and good flowability, consisting of poly(vinyl chloride), chlorinated polyethylene, hydroxyl‐terminated polybutadiene, and ethylene–propylene–ethylidenenorbornene terpolymer was also obtained. Regardless of the incompatibility between the polymer components of this blend, the similarity in the chemical nature of poly(vinyl chloride) and chlorinated polyethylene blocks on one hand, and the methylene sequences in the chlorinated polyethylene and elastomers on the other, resulted in the formation of an efficient interfacial layer. The changes in the structure of the blends were established by both calorimetric and microscopic studies. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2602–2613, 2006