Influence of various reaction media on the thermal and rheological properties of poly(acrylamide‐co‐N‐hexadecylacrylamide)

A hydrophobically modified polyacrylamide (PAM) was synthesized by the copolymerization of acrylamide (Am) and N‐hexadecylacrylamide (hAm) through solution copolymerization in a polar organic solvent. Polymer synthesis was performed in three nonaqueous media, including dimethyl sulfoxide (DMSO), a mixture of DMSO and an anionic surfactant such as sodium dodecyl sulfate, and a mixture of DMSO and an acidic surfactant such as dodecyl benzene sulfonic acid. The obtained copolymer, poly(acrylamide‐co‐N‐hexadecylacrylamide) [poly(Am‐co‐hAm)], was characterized by ¹H‐NMR. The physical properties of poly(Am‐co‐hAm)s synthesized in different media were compared with those of PAM and with each other by viscosity measurement, X‐ray diffraction, thermogravimetric analysis, and differential scanning calorimetry. We investigated the ways in which the polymerization medium affected the hydrophobic distribution within the resulting copolymer structure. This aspect, in turn, should have altered the solution properties and the microstructure of the copolymer. For this purpose, we studied the viscometric behavior in diluted solutions, the thermal behavior and thermal stability of the copolymers, and finally, the crystalline structure of the copolymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39939.     

Acrylic bone cements modified with poly(ethylene glycol)‐based biocompatible phase‐change materials

The high polymerization temperature of acrylic bone cements used in hip replacement implantation may cause thermal necrosis of surrounding tissues. In order to reduce the polymerization temperature, acrylic bone cement has been modified with a biocompatible polymeric phase‐change material (PCM) based on poly(ethylene glycol) (PEG) of different molecular weights and stabilized with potato starch. Structural and morphological studies were performed, and the thermal and mechanical properties were investigated. The incorporation of PEG‐based PCM led to a decrease in the polymerization temperature of bone cement from 70 °C for unmodified cement to 58 °C for modified cement. Modified cement materials were stable in incubation tests, although acoustic analysis data revealed a decrease in propagation speed after incubation, which indicates formation of material defects (pores, cracks, voids, etc.) due to water activity. However, in the regeneration process, these defects can be filled by freshly grown bone tissue leading to better incorporation of bone cement replacements into tissue. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43898.     

Synthesis,cure kinetics,and thermal properties of the Bis(3‐allyl‐2‐cyanatophenyl)sulphoxide/BMI blends

A novel allyl functionalized dicyanate ester resin bearing sulfoxide linkage was synthesized. The monomer was characterized by Fourier Transform Infrared (FT‐IR) Spectroscopy, ¹H‐, and ¹³C Nuclear Magnetic Resonance (NMR) spectroscopy and elemental analysis. The monomer was blended with bismaleimide (BMI) at various ratios in the absence of catalyst. The cure kinetics of one of the blends was studied using differential scanning calorimetry [nonisothermal] and the kinetic parameters like activation energy (E), pre‐exponential factor (A), and the order of the reaction (n) were calculated by Coats‐Redfern method and compared with those calculated using the experimental Borchardt‐Daniels method. The thermal stability of the cured dicyanate, BMI, and the blends was studied using thermogravimetric analyzer. The initial weight loss temperature of dicyanate ester is above 380°C with char yield of about 54% at 800°C. Thermal degradation of BMI starts above 463°C with the char yield of about 68%. Inclusion of BMI in cyanate ester increases the thermal stability from 419 to 441°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and thermal properties of poly(acrylonitrile‐co‐allyl glycidyl ether)‐graft‐methoxypoly(ethylene glycol) copolymers as novel solid–solid phase‐change materials for thermal energy storage

We synthesized a series of poly(acrylonitrile‐co‐allyl glycidyl ether)‐graft‐methoxypoly(ethylene glycol) (PAA‐g‐MPEG) copolymers as novel polymeric solid–solid phase‐change materials by grafting methoxypoly(ethylene glycol) (MPEG) to the main chain of poly(acrylonitrile‐co‐allyl glycidyl ether) (PAA). PAA was the skeleton, and MPEG was a functional side chain, which stored and released heat during its phase‐transition process. Fourier transform infrared spectroscopy and ¹H‐NMR spectroscopy analysis were performed to investigate the chemical structures. The crystalline morphology and crystal structures were also measured with polarized optical microscopy and X‐ray diffraction. Moreover, the thermal‐energy‐storage properties, thermal stability, and thermal reliability of the PAA‐g‐MPEG copolymers were characterized by differential scanning calorimetry and thermogravimetric analysis (TGA) methods. These analysis results indicate that the MPEG chains were successfully grafted onto PAA, and we found that the PAA‐g‐MPEG copolymers had typical solid–solid phase‐transition temperatures in the range 11–54 °C and high latent heat enthalpies between 44 and 85 J/g. In addition, the as‐prepared PAA‐g‐MPEG copolymers showed reusability and thermal reliability, as shown by the thermal cycle testing and TGA curves. Therefore, the synthesized PAA‐g‐MPEG copolymers have considerable potential for thermal energy storage. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46641.     

Preparation and characterization of thermoresponsive poly(N-isopropylacrylamide-co-N-isopropylmethacrylamide) hydrogel materials for smart windows

In this study, a series of thermoresponsive cross-linked copolymer poly [N-isopropylacrylamide(NIPAm)-co-N-isopropylmethacrylamide(NIPMAm)] (P-M series samples: P-M-0, 10, 20, 30, 40, where numbers are co-monomer contents) hydrogels were prepared by free radical polymerization using the main monomer N-isopropylacrylamide (NIPAm), co-monomer N-isopropylmethacrylamide (NIPMAm), cross-linking agent N, N-methylenebisacrylamide, initiator (ammonium persulfate)/catalyst, and solvent water. In addition, a series of samples [P-G series samples: P-G-0, 10, 20, 30, 40, where numbers are co-solvent glycerol content) were prepared using P-M-40 as components and water/co-solvent glycerol as a mixed solvent. The effects of co-monomer NIPMAm and co-solvent glycerol contents on the lower critical solution temperature (LCST)/freezing temperature and light transmittance as function of temperature of the prepared copolymer gels were investigated. The resulting thermoresponsive polymer gels had LCSTs in the range of 17.9 to 38.7°C and freezing points in the range of 6.3 to −38.5°C. These gels are suitable materials for smart windows that are responsive to various environmental conditions.     

Poly(ethylene glycol)/poly(methyl methacrylate) blends as novel form‐stable phase‐change materials for thermal energy storage

In this study, we focused on the preparation and characterization of poly(ethylene glycol) (PEG)/poly(methyl methacrylate) (PMMA) blends as novel form‐stable phase‐change materials (PCMs) for latent‐heat thermal energy storage (LHTES) applications. In the blends, PEG acted as a PCM when PMMA was operated as supporting material. We subjected the prepared blends at different mass fractions of PEG (50, 60, 70, 80, and 90% w/w) to leakage tests by heating the blends over the melting temperature of the PCM to determine the maximum encapsulation ratio without leakage. The prepared 70/30 w/w % PEG/PMMA blend as a form‐stable PCM was characterized with optical microscopy and Fourier transform infrared spectroscopy. The thermal properties of the form‐stable PCM were measured with differential scanning calorimetry (DSC). DSC analysis indicated that the form‐stable PEG/PMMA blend melted at 58.07°C and crystallized at 39.28°C and that it had latent heats of 121.24 and 108.36 J/g for melting and crystallization, respectively. These thermal properties give the PCMs potential LHTES purposes, such as for solar space heating and ventilating applications in buildings. Accelerated thermal cycling tests also showed that the form‐stable PEG/PMMA blend as PCMs had good thermal reliability and chemical stability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Properties and crystallization kinetics of poly(ether ether ketone)‐co‐poly(ether ether ketone ketone) block copolymers

A series of block copolymers composed of poly(ether ether ketone) (PEEK) and poly(ether ether ketone ketone) (PEEKK) components were prepared from their corresponding oligomers via a nucleophlilic aromatic substitution reaction. Various properties of the copolymers were investigated with differential scanning calorimetry (DSC) and a tensile testing machine. The results show that the copolymers exhibited no phase separation and that the relationship between the glass‐transition temperature (T_g) and the compositions of the copolymers approximately followed the formula T_g = T_g1X₁ + T_g2X₂, where T_g1 and T_g2 are the glass‐transition‐temperature values of PEEK and PEEKK, respectively, and X₁ and X₂ are the corresponding molar fractions of the PEEK and PEEKK segments in the copolymers, respectively. These copolymers showed good tensile properties. The crystallization kinetics of the copolymers were studied. The Avrami equation was used to describe the isothermal crystallization process. The nonisothermal crystallization was described by modified Avrami analysis by Jeziorny and by a combination of the Avrami and Ozawa equations. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1652–1658, 2005     

Non‐isothermal crystallization kinetics of poly(L‐lactide)

The non‐isothermal crystallization kinetics of poly( L ‐lactide) (PLLA) in comparison with a polylactide stereocopolymer (PLA₉₈) containing 98% L ‐lactyl and 2% D ‐lactyl units were investigated using differential scanning calorimetry to examine the effect of the configurational structure. Avrami, Ozawa and Liu models were applied to describe the crystallization process. The Avrami analysis exhibited two stages in non‐isothermal crystallization, while the Ozawa and Liu models did not successfully describe the crystallization behaviour. The activation energy was calculated with Kissinger's method. The energy barrier was found to be the same for PLLA and PLA₉₈ with a value of 126 kJ mol^?1. Copyright © 2010 Society of Chemical Industry     

Cross-linked poly(benzoxazole-co-siloxane) networks with high thermal stability and low dielectric constant based on a new ortho-amide functional benzoxazine

In this study, an amide functionalized bis-benzoxazine (AI-al) has been synthesized using allylamine, ortho-amide functional bis-phenol and paraformaldehyde as raw materials via Mannich condensation. This newly obtained benzoxazine has been used to react with polydimethylsiloxane (PDMS) through hydrosilylation to form poly(benzoxazine-co-amide-co-siloxane) (AI-al-PDMS) featuring siloxane, amide and benzoxazine as repeating units. The chemical structures of both oxazine ring-containing monomer and copolymer are confirmed by NMR and FT-IR spectroscopies. Besides, the thermally activated polymerization behaviors of AI-al and AI-al-PDMS are investigated by DSC, and the subsequent conversion of benzoxazole formation is studied by in situ FT-IR. Moreover, dynamic mechanical analysis and thermogravimetric analysis are used to determine the thermal properties of the cross-linked polymers. The resulting cross-linked poly(benzoxazole-co-siloxane) derived from AI-al-PDMS shows excellent thermal stability (no T_g can be observed before 400°C; Td5 of 393°C) and low dielectric constants (2.52–2.13 in the frequency range of 1 Hz to 1 MHz), evidencing its great potential applications in electronic packing, aerospace, and other high-performance fields.     

Influence of branching on the thermal behavior of poly(butylene isophthalate)

The thermal behavior of linear and randomly branched poly(butylene isophthalate) samples was investigated by thermogravimetric analysis and differential scanning calorimetry. As to the thermal stability, it was found to be good and similar for all the samples. The thermal analysis carried out using DSC technique showed that the melting temperature of the polymers decreased with increasing branching unit content, although the glass‐transition temperature was practically not affected by ramifications. The multiple endotherms typical of linear PBI were also observed in branched samples and were found to be influenced both by temperature and degree of branching. By applying the Hoffman‐Weeks' method, the equilibrium melting temperatures of the polymers were obtained. The presence of a crystal‐amorphous interphase was evidenced only for the branched samples and the interphase amount was found to increase as the branching unit content was increased. Isothermal melt crystallization kinetics was analyzed according to Avrami's treatment. The introduction of branching points was found to decrease the overall crystallization rate of poly(butylene isophthalate). Values of Avrami's exponent n close to 3 were obtained for all the samples, in agreement with a crystallization process originating from predetermined nuclei and characterized by three dimensional spherulitic growth. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2001–2010, 2002; DOI 10.1002/app.10517     

Crystallization and melting behavior of trans‐1,2‐syndiotactic polypentadiene

(E)‐1,3‐pentadiene was polymerized at ?30°C by using the catalyst system CoCl₂(PⁱPrPh₂)²–MAO. A trans‐1,2‐syndiotactic structure was attributed to the semicrystalline polymer obtained on the basis of the characterization carried out by FTIR, NMR, and WAXD techniques. The thermal behavior of the polypentadiene was investigated by thermogravimetry and differential scanning calorimetry. Isothermal melt crystallization kinetics were analyzed according to the Avrami equation. Nonisothermal crystallization kinetics were elaborated by using Ziabicki and Avrami methods modified by Jeziorny. The equilibrium melting temperature was calculated. The thermal behavior of trans‐1,2‐syndiotactic polypentadiene was compared with that of 1,2‐syndiotactic polybutadiene. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1970–1976, 2005     

Influence of titanium dioxide on crystallization behavior of an ethylene–propylene copolymer

Crystallization of an ethylene–propylene copolymer (E/P) filled with diverse weight percentages of titanium dioxide (TiO₂) was performed under isothermal and nonisothermal conditions to investigate the influence of the inorganic substance on the nucleation and growth mechanisms of the matrix. The overall and radial crystallization rates of the composite materials were measured using, respectively, differential scanning calorimetry (DSC) and optical microscopy. The nucleation density of E/P spherulites as a function of composition was investigated by scanning electron microscopy (SEM), revealing a nucleating effect of TiO₂. A comparison between the spherulitic texture of specimens showed a higher fineness of the composites relative to the neat matrix, whereas no changes of surface nucleation density were appreciable among composites within the explored compositional range. The thermal behavior is discussed in the light of the enhanced thermal conductivity of polymer composites, which conciliates the crystallization kinetics of the matrix, analyzed using the Avrami equation, to optical and SEM observations. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3409–3416, 2003     

Polyester-based phase change materials with flexible poly(ethylene glycol) chains for thermal energy storage

Phase change materials are capable of storing renewable energy in an economical, feasible, and green way. Here, novel polyester-based solid–solid phase change materials (PPCMs) are synthesized through solvent-free crosslinking polymerization. Poly(ethylene glycol) (PEG) is used as the phase change ingredient, while crosslinked polyester acts as the supporting material. One chain end of PEG reliably bonds with the rigid skeleton, while another chain end is movable. The combination of reliable crosslinked structures with flexible PEG chains endows the PPCMs with good thermal storage capacity and outstanding thermal reliability simultaneously. Fourier transform infrared spectroscopy is adopted to confirm the chemical structures of PPCMs. Their excellent crystalline properties are confirmed by wide-angle X-ray diffraction and polarizing optical microscopy (POM). Phase change properties are investigated using differential scanning calorimetry (DSC) and POM images. It is obvious in the DSC results that PPCMs have good thermal storage capacity in the range 18–63 °C with phase change enthalpy reaching 139.0 J/g. POM images vividly reveal the crystallization process of PPCMs. Additionally, thermal stability is studied using thermogravimetric analysis, and the results show that PPCMs are thermally stable up to 300 °C. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47108.     

Studies on the curing behavior,thermal, and mechanical properties of epoxy resin-co-amine-functionalized lead phthalocyanine

A high performance copolymer was prepared by using epoxy (EP) resin as matrix and 3,10,17,24-tetra-aminoethoxy lead phthalocyanine (APbPc) as additive with dicyandiamide as curing agent. Fourier-transform infrared spectroscopy, dynamic mechanical analysis (DMA), differential scanning calorimetric analysis (DSC), and thermogravimetric analysis (TGA) were used to study the curing behavior, curing kinetics, dynamic mechanical properties, impact and tensile strength, and thermal stability of EP/APbPc blends. The experimental results show that APbPc, as a synergistic curing agent, can effectively reduce the curing temperature of epoxy resin. The curing kinetics of the copolymer was investigated by non-isothermal DSC to determine kinetic data and measurement of the activation energy. DMA, impact, and tensile strength tests proved that phthalocyanine can significantly improve the toughness and stiffness of epoxy resin. Highest values were seen on the 20 wt% loading of APbPc in the copolymers, energy storage modulus, and impact strength increased respectively 388.46 MPa and 3.6 kJ/m², T_g decreased 19.46°C. TGA curves indicated that the cured copolymers also exhibit excellent thermal properties.     

Thermal stability of modified end‐capped poly(lactic acid)

The influence of functional end groups on the thermal stability of poly(lactic acid) (PLA) in nitrogen‐ and oxygen‐enriched atmospheres has been investigated in this article using differential scanning calorimetry, thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). Functional end groups of PLA were modified by succinic anhydride and l ‐cysteine by the addition–elimination reaction. PLA was synthesized by azeotropic condensation of l ‐lactic acid in xylene and characterized by nuclear magnetic resonance. The values of the activation energies determined by TGA in nitrogen and oxygen atmospheres revealed that the character of functional end groups has remarkable influence on the thermal stability of PLA. Moreover, DMA confirmed the strong influence of functional end groups of PLA on polymer chains motion. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41105.     

Investigation of thermal behavior of poly(2‐hydroxyethyl methacrylate‐co‐itaconic acid) networks

The thermal behavior of poly(2‐hydroxyethyl methacrylate) [PHEMA] homopolymer and poly(2‐hydroxyethyl methacrylate‐co‐itaconic acid) [P(HEMA/IA)] copolymeric networks synthesized using a radiation‐induced polymerization technique was investigated by differential scanning calorimetry, thermogravimetric analysis, and Fourier transform infrared spectroscopy. The glass‐transition temperature (T_g) of the PHEMA homopolymer was found to be 87°C. On the other hand, the T_g of the P(HEMA/IA) networks increased from 88°C to 117°C with an increasing amount of IA in the network system. The thermal degradation reaction mechanism of the P(HEMA/IA) networks was determined to be different from the PHEMA homopolymer, as confirmed by thermogravimetric analysis. It was observed that the initial thermal degradation temperature of these copolymeric networks increased from 271°C to 300°C with IA content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1602–1607, 2007     

Characterization of the mechanical and thermal properties and morphological behavior of biodegradable poly(L‐lactide)/poly(ε‐caprolactone) and poly(L‐lactide)/poly(butylene succinate‐co‐L‐lactate) polymeric blends

Two series of biodegradable polymer blends were prepared from combinations of poly(L ‐lactide) (PLLA) with poly(?‐caprolactone) (PCL) and poly(butylene succinate‐co‐L ‐lactate) (PBSL) in proportions of 100/0, 90/10, 80/20, and 70/30 (based on the weight percentage). Their mechanical properties were investigated and related to their morphologies. The thermal properties, Fourier transform infrared spectroscopy, and melt flow index analysis of the binary blends and virgin polymers were then evaluated. The addition of PCL and PBSL to PLLA reduced the tensile strength and Young's modulus, whereas the elongation at break and melt flow index increased. The stress–strain curve showed that the blending of PLLA with ductile PCL and PBSL improved the toughness and increased the thermal stability of the blended polymers. A morphological analysis of the PLLA and the PLLA blends revealed that all the PLLA/PCL and PLLA/PBSL blends were immiscible with the PCL and PBSL phases finely dispersed in the PLLA‐rich phase. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(l‐lactic acid) with the organic nucleating agent N,N,N′‐tris(1H‐benzotriazole) trimesinic acid acethydrazide: Crystallization and melting behavior

N,N,N′‐Tris(1H‐benzotriazole) trimesinic acid acethydrazide (BD) was synthesized from 1H‐benzotriazole acetohydrazide and trischloride to serve as an organic nucleating agent for the crystallization of poly(l ‐lactic acid) (PLLA). First, the thermogravimetric analysis of BD exhibited a high thermal decomposition temperature; this indicated that BD maybe used as a heterogeneous nucleating agent of PLLA. Then, the effect of BD on the crystallization and melting behavior of PLLA was investigated through differential scanning calorimetry, depolarized light intensity measurements, and wide‐angle X‐ray diffraction. The appearance of a nonisothermal crystallization peak and increases in the glass‐transition temperature and the intensity of the diffraction peak suggested that the presence of BD accelerated the overall PLLA crystallization. Upon cooling at a rate of 1°C/min, the addition of just 0.5 wt % BD to PLLA increased the onset crystallization temperature from 101.4 to 111.3°C, and the nonisothermal crystallization enthalpy increased from 0.1 to 38.6 J/g. The isothermal crystallization behavior showed that the crystallization half‐time of PLLA with 0.5 wt % BD (PLLA/0.5% BD) decreased from 49.9 to 1.1 min at 105°C. However, the equilibrium melting point of PLLA/0.5% BD was lower than that of the pristine PLLA; this resulted from the increasing nucleating density of PLLA. The melting behavior of PLLA/0.5% BD further confirmed that BD improved the crystallization of PLLA, and the double‐melting peaks of PLLA/0.5% BD were assigned to melting–recrystallization. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42402.     

Synthesis,structure, and physical properties of poly(trimethylene terephthalate)-block-poly(caprolactone) copolymers

The series of poly(trimethylene terephthalate)-block-PCLT (PTT-block-PCLT) copolymers with different contents of PTT as rigid, and poly(caprolactone) (PCL) as flexible segments have been synthesized from dimethyl terephthalate (DMT), 1,3-bio-propanediol, and PCL diol) in a two-step process involving transesterification and polycondensation in the melt. The weight amount of flexible PCLT segments varied from 0 (homopolymer PTT), 25, 35 to 45%. The molecular structure of the synthesized copolymers was confirmed by nuclear magnetic resonance and Fourier transform infrared spectroscopy analyses. According to Hoy's method, one confirmed that PTT and PCL are likely miscible, as the difference of the solubility parameters of PTT and PCL block pairs, equals to 3.15 MPa^1/2. Moreover, the phase structure and mutual miscibility for the series of PTT-block-PCLT copolymers was characterized by differential scanning calorimetry, dynamic mechanical thermal analysis, and wide-angle X-ray scattering measurements. In copolymers with 35 and 45 wt % of flexible segments, the crystalline phase is formed during annealing above glass-transition temperature of copolymer. These copolymers during cooling at the standard rate do not crystallize. It was also found that incorporation of PCLT flexible segments, due to the macrophase separated structure, cause the decrease of the melting point and glass-transition temperature, along with the tensile modulus and tensile strength of PTT-block-PCLT copolymers, and at the same time cause an increase in the value of the elongation at break. As a result of copolymerization of PTT with PCLT, one obtained multiblock copolymers with a heterophase structure. By changing the PTT/PCLT ratio, one obtained copolymers that differ in hardness and tensile strength. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47341.