Internal plasticization of poly(vinyl chloride) by grafting acrylate copolymers via copper-mediated atom transfer radical polymerization

Internal plasticization of poly(vinyl chloride) (PVC) was achieved in one-step using copper-mediated atom transfer radical polymerization to graft different ratios of random n-butyl acrylate and 2–2-(2-ethoxyethoxy)ethyl acrylate copolymers from defect sites on the PVC chain. Five graft polymers were made with different ratios of poly(butyl acrylate) (PBA) and poly(2–2-(2-ethoxyethoxy)ethyl acrylate) (P2EEA); the glass transition temperatures (T_g) of functionalized PVC polymers range from − 25 to − 50°C. Single T_g values were observed for all polymers, indicating good compatibility between PVC and grafted chains, with no evidence of microphase separation. Plasticization efficiency is higher for polyether P2EEA moieties compared with PBA components. The resultant PVC graft copolymers are thermally more stable compared to unmodified PVC. Increasing the reaction scale from 2 to 14 g produces consistent and reproducible results, suggesting this method could be applicable on an industrial scale.     

Quantitative study of the annealing of poly(vinyl chloride) near the glass transition

Poly(vinyl chloride) displays a normal DSC of DTA curve for the glass transition when quenched from above its T_g. However if cooled slowly or annealed near the glass transition temperature, a peak appears on the DSC or DTA curve at the T_g. In this paper quantitative studies of the time and temperature effects on the production of this endothermal peak during the annealing of PVC homopolymer and an acetate copolymer are presented. The phenomenon conforms to the Williams, Landell, and Ferry equation for the relaxation of polymer chains, the rate of the peak formation becoming negligible at more than 50°C below T_g. The energy difference between the quenched and annealed forms is small. For a PVC homopolymer annealed 2 hr at 68°C, which is T_g ?10°C, the difference is 0.25 cal/g. For a 13% acetate copolymer of PVC similarly annealed, the difference is 0.36 cal/g. The measured rates of the process give a calculated activation energy of 13–14 kcal/mole for PVC homopolymer and copolymer. This appearance of a peak on the T_g curve for a polymer when annealed near the glass temperature appears to be a general phenomenon.     

Investigation of non-isothermal crystallization,dynamic mechanical and dielectric properties of poly(ether-ketone) matrix composites

ABSTRACT

Poly(ether-ketone)/hexagonal boron nitride (h-BN) composites reinforced with micrometer-sized h-BN particles were investigated. The composites exhibited glass transition temperature (T_g) and thermal stability over 160°C and 560°C, respectively. The melting point and peak crystallization temperatures of the composites decreased up to 17°C and 12°C, respectively. The linear CTE of the composites decreased both below and above the T_g. The storage modulus increased with increasing h-BN content at all temperatures (50–250°C). The composites possessed excellent dielectric properties with insignificant dispersion with increasing frequency. Thus, resultant composites are promising candidates for the printed circuit boards/electronic substrates.     

Biocompatible shape-memory poly(vinyl chloride) with a tunable switching temperature via a plasticization effect

Biocompatible shape-memory poly(vinyl chloride) (PVC) with a tunable switching temperature (T_s) was fabricated via the incorporation of an environmentally friendly plasticizer of 1,2-cyclohexane dicarboxylic acid diisononyl (DINCH). It was revealed that both of the shape-memory effect (SME) and T_s were significantly influenced by the plasticization effect. With the addition of DINCH, the shape-fixing ratio (R_f) showed a slight reduction, whereas the shape-recovering ratio (R_r) was greatly enhanced, and T_s was decreased from 90 to 47 °C. PVC with 40 phr plasticizer realized an excellent SME with an R_f of 97.0% and a R_r of 90.1%; this resulted from the formation of an efficient shape-memory network via the physical crosslinking of the amorphous chains with crystals and rigid chain entanglements. In addition, the blood compatibility of the DINCH-plasticized PVC was evaluated, and the results indicate that it was of great potential for biomedical applications. Therefore, in this study, we successfully developed a new shape-memory polymer and provided a promising strategy for achieving SME with tunable T_s. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47992.     

Core–shell particles to toughen epoxy resins. I. Preparation and characterization of core–shell particles

A two-stage, multistep soapless emulsion polymerization was employed to prepare various sizes of reactive core–shell particles (CSPs) with butyl acrylate (BA) as the core and methyl methacrylate (MMA) copolymerizing with various concentrations of glycidyl methacrylate (GMA) as the shell. Ethylene glycol dimethacrylate (EGDMA) was used to crosslink either the core or shell. The number of epoxy groups in a particle of the prepared CSP measured by chemical titration was close to the calculated value based on the assumption that the added GMA participated in the entire polymerization unless it was higher than 29 mol %. Similar results were also found for their solid-state ^13C-NMR spectroscopy. The MMA/GMA copolymerized and EGDMA-crosslinked shell of the CSP had a maximum glass transition temperature (T_g) of 140°C, which was decreased with the content of GMA at a rate of −1°C/mol %. However, the shell without crosslinking had a maximum T_g of 127°C, which decreased at a rate of −0.83°C/mol %. The T_g of the interphasial region between the core and shell was 65°C, which was invariant with the design variables. The T_g of the BA core was −43°C, but it could be increased to −35°C by crosslinking with EGDMA. The T_g values of the core and shell were also invariant with the size of the CSP. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2069–2078, 1998     

Interfacial interactions and properties of cellular structured polyurethane nanocomposite based on carbonaceous nano-fillers

In this article, we have studied the effect of carbonaceous nanofillers viz. fullerenol (0D), carboxylated multi-wall carbon nanotube (MWCNT, 1D), hydroxylated graphene (2D) and combination of carboxylated CNT and hydroxylated graphene as 3D in thermoplastic polyurethane on the tensile properties of the fabricated cellular structures. The concentration of nano-fillers was varied as 0.1, 1, and 5 wt%. Tensile properties of the nanocomposite cellular structures were measured as per ASTM D882 at 20°C (below glass transition temperature, T_g) and 40°C (above T_g). The results have shown that the tensile strength was found to increase by 200%–300% and the tensile modulus was found to increase by 150%–300% for 2D and 3D nano-fillers while significantly poor results were observed for 0D. However, the test data tensile strength and modulus showed marginal increase at 20°C and marginally low at 40°C for 1D filler. The interfacial adhesion was calculated by using experimental tensile data and the predictive models. The interfacial adhesion parameter (B_σ) calculated using Pukanszky equation was found significantly higher value for 2D (B_σ20 = 195.8) and 3D (B_σ20 = 192.0) fillers while poor adhesion was observed for 0D (B_σ20 = −81.6) fillers. The developed cellular structured materials were also evaluated by attenuated total reflection Fourier transform IR spectra, differential scanning calorimetry, X-ray diffraction, scanning electron microscope, and transmission electron microscope.     

Studies on glass transition temperature of chitosan with four techniques

Studies on the glass transition temperature (T_g) of chitosan are difficult to pursue because of the difficulty in sample preparation and the hydroscopicity of samples. There are a few works concerning this principal relaxation of chitosan. Among them, several quite different values (150°C, 161°C, and 203°C) have been reported. In this paper, the T_g of chitosan (140 ～ 150°C) was determined by means of four techniques, namely, dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), thermally simulated current spectroscopy (TSC), and dilatometry (DIL). DSC measurement has been assumed not to be sensitive enough to detect the relaxation temperature of polysaccharides. We propose a new method to improve the sensitivity of the DSC measurement. After a physical aging treatment of samples, the transition in DSC traces became much more distinct because of the enthalpy relaxation. This technique was also used to distinguish the T_g from other relaxations. The T_g of chitosan with different degree of deacetylation (D.D.) was examined by DSC. No influence of D.D. on T_g was found. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1553–1558, 2004     

Characterization of PVC cable insulation materials and products obtained after removal of additives

Organic solvents cyclohexane, dichloromethane, hexane, and tetrahydrofuran were tested to separate the dioctylphthalate (DOP) as plasticizer from the poly(vinyl chloride) (PVC)‐based materials. It was found that the efficiency of ultrasound‐enhanced hexane extraction of the DOP from PVC is 70% and the efficiency of the separation of the DOP and other compounds from the PVC by dissolution in THF followed by subsequent precipitation was 98–99%. Differential scanning calorimetry (DSC) and thermogravimetry (TG) were used to characterize the thermal behavior of PVC materials before and after extraction of plasticizers. It was found that during heating in the range 20–800°C the total mass loss measured for the nontreated, extracted, and precipitated PVC samples was 71.6, 66.6, and 97%, respectively. In the temperature range 200–340°C, the release of DOP, HCl, and CO₂ was observed by simultaneous thermogravimetry (TG)/FTIR. The effect of plasticizers on thermal behavior of PVC‐based insulation material was characterized by DSC in the range ?40–140°C. It was found that, concerning the PVC cable insulation material before treatment, the value of the glass transition temperature (T_g) was 1.4°C, whereas for the PVC sample extracted by hexane, the value of T_g was 39.5°C and for the PVC dissolved in THF and subsequently precipitated, the value of T_g was 80.4°C. Moreover, the PVC samples after extraction of plasticizers, fillers, and other agents were tested to characterize their thermal degradation. The TG and FTIR results of chemically nontreated, extracted, and precipitated samples were compared. The release of DOP, HCl, CO₂, and benzene was studied during thermal degradation of the samples by FTIR. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 788–795, 2006     

Sustainable synthesis of bio‐based hyperbranched ester and its application for preparing soft polyvinyl chloride materials

In this study, bio‐based hyperbranched ester was synthesized from castor oil. The chemical structure of the bio‐based hyperbranched ester obtained was characterized with Fourier transform infrared and ¹H NMR spectra. Soft polyvinyl chloride (PVC) materials were prepared via thermoplastic blending at 160 °C using bio‐based hyperbranched ester as plasticizer. The performances including the thermal stability, glass transition temperature (T_g), crystallinity, tensile properties, solvent extraction resistance and volatility resistance of soft PVC materials incorporating bio‐based hyperbranched ester were investigated and compared with the traditional plasticizer dioctyl phthalate (DOP). The results showed that bio‐based hyperbranched ester enhanced the thermal stability of the PVC materials. The T_g of PVC incorporating bio‐based hyperbranched ester was 23 °C, lower than that of PVC/DOP materials at 28 °C. Bio‐based hyperbranched ester showed a better plasticizing effect, solvent extraction resistance and volatility resistance than DOP. The plasticizing mechanism is also discussed. © 2018 Society of Chemical Industry     

Shape-memorized crosslinked ester-type polyurethane and its mechanical viscoelastic model

A series of shape-memorized crosslinked ester-type polyurethanes (PUs), based on different compositions of 4,4′-diphenyl methane diisocyanate (MDI), poly(butylene adipate) glycol (PBAG) with different molecular weight (MW) and trimethylol propane (TMP), were synthesized. The morphology of samples was investigated by using DSC, WAXD, and dynamic mechanical analysis (DMA). It was found that the morphology of the soft segment, which was PBAG with a different MW, was in an amorphous state and no crystalline domain was found. By increasing the crosslinked density (varying the content of TMP) or decreasing the length of the soft segment (MW of PBAG), the glass transition temperature of studied samples increased. But the range of transition broadened and the modulus ratio E^′_−20°C)/E^′_+20°C) also decreased. The shape-memory behavior was studied by the bending test method adopted from the shape-memory alloy. The sample with high T_g showed not only a high recovered temperature (T_r) but also a high recovered rate (V_r) with a high modulus ratio. By introducing the chemical crosslinked structure, the deformed samples completely recovered their original shape and rendered shape-memory behavior under the complex deformation. The shape-memorized crosslinked ester-type PUs can be applied at different operating temperatures. A mechanical viscoelastic model is discussed for the shape-memory behavior of PUs, and the modified Bonart's viscoelastic model properly describes the mechanism of the shape memory of PUs. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1305–1319, 1999     

Effect of Al2O3 addition on thermo‐electrical properties of polymer composites: An experimental investigation

To develop a new class of composites with adequately high thermal conductivity and suitably controlled dielectric constant for electronic packages and printed circuit board applications, polymer composites are prepared with microsized Al₂O₃ particle as filler having an average particle size of 80–100 μm. Epoxy and polypropylene (PP) are chosen as matrix materials for this study. Fabrication of epoxy‐based composite is done by hand lay‐up technique and its counterpart PP‐based composite are fabricated by compression molding technique with filler content ranging from 2.5–25 vol%. Effects of filler loading on various thermal properties like effective thermal conductivity (k_eff), glass transition temperature (T_g), coefficient of thermal expansion (CTE) and electrical property like dielectric constant (ε_c) of composites are investigated experimentally. In addition, physical properties like density and void fraction of the composites along with there morphological features are also studied. The experimental findings obtained under controlled laboratory conditions are interpreted using appropriate theoretical models. Results show that with addition of 25 vol% of Al₂O₃, k_eff of epoxy and PP improve by 482% and 498% respectively, T_g of epoxy increases from 98°C to 116°C and that of PP increases from −14.9°C to 3.4°C. For maximum filler loading of 25 vol% the CTE decreases by 14.8% and 26.4% for epoxy and PP respectively whereas the dielectric constants of the composites get suitably controlled simultaneously. POLYM. COMPOS., 36:102–112, 2015. © 2014 Society of Plastics Engineers     

Properties of poly(vinyl chloride) fibers crosslinked by 2-dibutylamino-4,6-dimercapto-1,3,5-triazine

PVC fibers, fastened to a needle frame, were crosslinked by 2-dibutylamino-4, 6-dimercapto-1,3,5-trizine in the presence of tetra-n-butylammonium bromide and alkali in water at 96°C. Solvent resistance, characterized by the gel fraction of THF, improves markedly. Mechanical properties of the fibers investigated by tensile tests at 20°C show that both the modulus and tensile strength at break increase, while elongation at break decreases over 40% gel content. Creep tests indicate that the resistance to heat deformation improves by crosslinking. The heat distortion temperature increases by 12°C at 75% gel content. Results of dynamic tests show that the T_g of PVC fibers determined by a peak in the loss modulus (E'') increases from 40% gel content. Dynamic modulus (E') increases by 74% at 23°C and the T_g by 37°C in the case of crosslinked PVC fibers having a 92% gel content. The shrinkage of PVC fibers in hot water at 94°C for 30 min decreases more than 50% over 75–80% gel content indicating the improved resistance to heat deformation.     

The effect molecular weight of polyol components on shape memory effect of epoxy-polyurethane composites

This paper describes the experimental findings of the study of a series of PU/epoxy composites, which formed interpenetrating networks and have shape-memory properties. The morphological variation for different chemical compositions and the influences of morphology on mechanical performance and shape-memory behavior are discussed. Length and mass fraction of polyethylene glycol (PEG) units are chosen as the key parameters in this study. The molecular weight of PEG was varied from 400 (as such PEG units are unable to crystallize) to 1500, 4000, and 6000, which are crystallizable. It was shown that the crystallization of PEG units is the key parameter, which determines the mechanical performance and shape-memory behavior of PU/epoxy composites in this study. DMTA results show the linear dependence of glass transition temperature and tensile strength, elongation, and other mechanical parameters on the amount of PEG in PU/epoxy composites independently of the amount of PEG unit lengths. The maximal value of shape fixation rate was achieved for 30–40 mass percentage of PEG 4000 (4.5 × 10⁻² s⁻¹ at T_g + 20°C) or PEG 6000(4.1 × 10⁻² s⁻¹ at T_g + 20°C) in PU/epoxy composites.     

Cationic grafting of norbornadiene, indene, and 1,3-cyclohexadiene from PVC

Summary The synthesis of three novel graft copolymers consisting of a PVC backbone fitted with polynorbornadiene (PNbd), polyindene (PInd), polycyclohexadiene (PCHD) branches, i.e., PVC-g-PNbd, PVC-g-PInd, and PVC-g-PCHD, is described. The synthesis strategy was to initiate the grafting of norbornadiene (Nbd), indene (Ind), and 1,3-cyclohexadiene (CHD) by a PVC containing ∼ 1.6 active (tertary and allylic) chlorines in conjunction with Et₂AlCl. The products were characterized by solvent fractionation, molecular weight determination, T_g, and NMR spectroscopy. The effect of temperature on the grafting was investigated in the 20 to −50 °C range. Received: 8 October 2001/ Revised version: 22 April 2002/ Accepted: 23 April 2002     

Silane cross-linking of PVC. II. Influence of silane type and conditions on cross-linking by water

The cross-linking of plasticized and unplasticized poly(vinyl chloride) (PVC) grafted with amino- and mercaptoalkyltrialkoxysilanes has been studied in water and in air at 20–140°C. In both media, the cross-linking occurs faster for plasticized PVC grafted with aminosilanes; however, at temperatures above 100°C, the effect of degradation cross-linking is apparent. For mercaptosilanes, a marked dependence of the cross-linking rate on the silane structure was found; plasticized PVC with grafted 3-mercaptopropyltrimethoxysilane was cross-linked in water at 100°C after 6 h, whereas this process took 12 h for 5-mercaptopentyltriethoxysilane. Practically no cross-linking occurred in unplasticized PVC below T_g, whereas the rate at 100°C was comparable with that for plasticized PVC. The cross-linking rate is affected by the chain mobility, water content, and diffusion of water into the material; a very slight dependence on the thickness of the material was found for plasticized PVC. © 1993 John Wiley & Sons, Inc.     

Block copolyetheresters. V. Low-temperature properties of thermotropic block copolyetheresters

The low-temperature properties of block copolyetheresters with hard segments of poly(alkylene p,p′-bibenzoate) and soft segments of poly(tetramethylene ether) were investigated by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). In the temperature range of −100 to 60°C, two transition temperatures, a glass transition temperature (T_g) and a melting temperature (T_m), were found by DSC and are attributed to the polyether segments. The T_g monitored by DSC of the polyether segments of the block copolyetheresters is around −68°C and independent of the composition and the type of polyester segment. Thus, the amorphous parts of the polyether segments should be immiscible with the amorphous parts of the polyester segments. The polyether segments of the block copolyetheresters exhibit a lower T_m and a lower crystallinity than those of the poly(tetramethylene ether)glycol due to the presence of the polyester segments. The crystallizability of the polyether segments is dependent on the composition to some extent. The DMA data show that the dynamic modulus drops more abruptly around −10 to 15°C, indicating that the mechanical properties may change significantly due to the melting of the polyether segments. © 1996 John Wiley & Sons, Inc.     

Experimental assessment of the thermodynamic theory of the compositional variation of Tg: PVC systems

The glass-transition temperatures (T_g's) and specific heats (C_p) of poly(vinyl chloride) (PVC) and PVC plasticized with 5–120 phr di(2-ethylhexyl) adipate (DOA) and tri(2-ethylhexyl) trimellitate (TOTM) have been determined by differential scanning calorimetry (DSC). Measured T_g's were compared to predictions by the Couchman and Karasz (C–K) thermodynamic theory, three related empirical equations, and a new equation obtained from the C–K relation by assuming the product T_gΔC_p to be constant. It was found that the T_g's of the PVC/TOTM mixtures are adequately predicted only by the C–K and the derivative relation. The T_g's of the PVC/DOA mixtures follow a sigmoidal or cusp-like dependence on plasticizer composition as has been observed for some other PVC/plasticizer mixtures. In this case, the approximation afforded by the C–K or derivative equations is still superior to the empirical models over a wide composition range. Dynamic mechanical analysis of the PVC/DOA mixtures suggests that the DSC transitions may consist of two overlapping phase transitions. The reported sigmoidal composition dependence of the DSC T_g's may therefore result from the measured T_g's being weighted towards the temperature corresponding to the predominant dynamic mechanical transition (i.e., the high T_g phase at low plasticizer concentrations and the low T_g phase at high plasticizer concentrations). In such cases of partial phase separation, the C–K or the derivative equation may be used to estimate the composition of the two phases at each overall plasticizer concentration.     

Experimental investigation and optimization of printing parameters of 3D printed polyphenylene sulfide through response surface methodology

Today fused filament fabrication is one of the most widely used additive manufacturing techniques to manufacture high performance materials. This method entails a complexity associated with the selection of their appropriate manufacturing parameters. Due to the potential to replace poly-ether-ether-ketone in many engineering components, polyphenylene sulfide (PPS) was selected in this study as a base material for 3D printing. Using central composite design and response surface methodology (RSM), nozzle temperature (T), printing speed (S), and layer thickness (L) were systematically studied to optimize the output responses namely Young's modulus, tensile strength, and degree of crystallinity. The results showed that the layer thickness was the most influential printing parameter on Young's modulus and degree of crystallinity. According to RSM, the optimum factor levels were achieved at 338°C nozzle temperature, 30 mm/s printing speed, and 0.17 mm layer thickness. The optimized post printed PPS parts were then annealed at various temperatures to erase thermal residual stress generated during the printing process and to improve the degree of crystallinity of printed PPS's parts. Results showed that annealing parts at 200°C for 1 hr improved significantly the thermal, structural, and tensile properties of printed PPS's parts.     

(AB)n Segmented Copolyetherimides for 4D Printing

The fourth dimension in 4D printing comprises the ability of materials to recover their shape with time by utilizing 3D printing in combination with shape memory polymers. The focus of this work is on 3D printing of physically crosslinked thermoplastic polymers, which allow a reversible transformation from a temporary to an original shape by an external stimulus temperature, thus realize 4D printing. In this context, (AB)_n segmented copolyetherimides consisting of perylene and poly(ethylene glycol) (PEG) segments are synthesized and characterized regarding their thermal and rheological properties in view of 3D printing. The perylene imide segments act as reversible physical crosslinks which disassemble between 100 and 200 °C. The PEG segments exhibit a low melting temperature around 40 to 60 °C and are semi-crystalline at room temperature. The results show that this type of (AB)_n segmented copolyetherimide combines reliable 3D printing performance, which is indicated by low warp deformation and excellent interlayer bonding. With a blend of two copolymers, it is able to realize 4D printing.     

Facile control of high temperature shape memory polymers

Glass transition temperature (T_g) is crucial in determining application areas of high temperature shape memory polymers (SMPs), but some T_gs are difficult or uneconomic to be obtained. Here we introduce a facile way to prepare high temperature SMPs with controllable T_gs from 183 to 230 °C by copolymerization of polyimides, and relationships between T_gs and diamine components of the shape memory copolyimides agree with Fox Equation. These copolyimides can fix temporary shape and return to original shape nicely, and the possible mechanisms of their high shape fixity and shape recovery are analyzed on the basis of thermomechanical properties and molecular structures. The copolymerization of shape memory polyimides has offered an effective way to obtain high temperature SMPs with desired properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44902.