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.     

Novel heat resistant methyl‐tri(phenylethynyl)silane resin: Synthesis,characterization and thermal properties

Methyl‐tri(phenylethynyl)silane (MTPES) was successfully synthesized by the reaction of lithium phenylacetylide with methyltrichlorosilane. The structure was characterized by HRMS, FTIR, ¹H‐NMR, ¹³C‐NMR, ²⁹Si‐NMR, and elementary analysis. Thermal cure process was monitored by DSC, DMA, and FTIR. MTPES was heated to free flowing liquid around 130°C and thermally polymerized at 327–377°C to form thermoset. Thermal and oxidative properties were evaluated by TGA analysis. Thermoset exhibits extremely high heat‐resistance and TGA curve in nitrogen shows the temperature of 5% weight loss (Td₅) of 695°C and total weight loss at 800°C of 7.1%. TGA shows a high Td₅ of 565°C even in air, although the total weight loss at 800°C was 56.1% of the initial weight, much higher than that in nitrogen. The high heat resistance of MTPES was ascribed to crosslinking reaction concerning ethynyl groups. Aging studies performed at elevated temperatures in air on a thermoset showed that MTPES is oxidatively stable to 300°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2488–2492, 2006     

Water states and thermal processability of boric acid modified poly(vinyl alcohol)

To further improve the processability of water plasticized poly(vinyl alcohol) (PVA), boric acid (BA), which can rapidly form reversible crosslinked structure with the hydroxyl groups of PVA, was adopted as a modifier, and the water states, thermal performance, and rheological properties of modified PVA were investigated. The results showed that ascribing to the formation of the crosslinked structure between PVA and BA, the content of nonfreezing water in system increased, indicating that the bondage of PVA matrix on water enhanced, thus retarding the tempestuous evaporation of water in system during melt process and making more water remained in system to play the role of plasticizer. Meanwhile, this crosslinked structure shielded part hydroxyl groups in PVA chains, leading to the further weakening of the self‐hydrogen bonding of PVA, and guaranteeing a lower melting point and higher decomposition temperature, thus obtaining a quite wide thermal processing window, i.e., ≥179°C. The melt viscosity of BA modified PVA slightly increased, but still satisfied the requirements for thermal processing, thus reinforcing the flow stability of the melt at high shearing rate. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43246.     

Characterization of polyacrylonitrile,poly(acrylonitrile‐co‐vinyl acetate), and poly(acrylonitrile‐co‐itaconic acid) based activated carbon nanofibers

In this study, three different acrylonitrile (AN)‐based polymers, including polyacrylonitrile (PAN), poly(acrylonitrile‐co‐vinyl acetate) [P(AN‐co‐VAc)], and poly(acrylonitrile‐co‐itaconic acid) [P(AN‐co‐IA)], were used as precursors to synthesize activated carbon nanofibers (ACNFs). An electrospinning method was used to produce nanofibers. Oxidative stabilization, carbonization, and finally, activation through a specific heating regimen were applied to the electrospun fibers to produce ACNFs. Stabilization, carbonization, and activation were carried out at 230, 600, and 750 °C, respectively. Scanning electron microscopy, thermogravimetric analysis (TGA), and porosimetry were used to characterize the fibers in each step. According to the fiber diameter variation measurements, the pore extension procedure overcame the shrinkage of the fibers with copolymer precursors. However, the shrinkage process dominated the scene for the PAN homopolymer, and this led to an increase in the fiber diameter. The 328 m²/g Brunauer–Emmett–Teller surface area for ACNFs with PAN precursor were augmented to 614 and 564 m²/g for P(AN‐co‐VAc) and P(AN‐co‐IA), respectively. The TGA results show that the P(AN‐co‐IA)‐based ACNFs exhibited a higher thermal durability in comparison to the fibers of PAN and P(AN‐co‐VAc). The application of these copolymers instead of AN homopolymer enhanced the thermal stability and increased the surface area of the ACNFs even in low‐temperature carbonization and activation processes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44381.     

Synthesis and thermal stability properties of boron‐doped silicone resin

In this article, a novel boron‐doped silicone resin (BSR) was synthesized by hydrolysis‐polycondensation method, with propyl‐triethoxysilane (PTES), dimethyl‐diethoxysilane (DMDES), and boric acid (BA) as starting materials, using absolute ethyl alcohol as solvent and hydrochloric acid as catalyst. The structures of the BSR were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), X‐ray photoelectron spectroscopy (XPS), and gel permeation chromatography (GPC). FTIR spectra showed characteristic B? O? Si and Si? O? Si stretching modes. XPS and NMR results confirmed further that boron element was doped successfully into the main chains of the silicone resin as Si? O? B bond motifs, and hydroxyl groups from BA were condensed properly with Si? OH or Si? OR to form cross‐linked structure of BSR with narrowed molecular weight distributions in optimum experimental condition. The thermal stability of the BSR was studied by thermogravimetry analysis and derivative thermogravimetry. The thermal degradation temperature of the silicone resin improved greatly after doping element boron into the main chain, and the thermal stability of the BSR was influenced by the content of boron. The thermal degradation mechanism of this BSR was also discussed. The degradation process can be divided into two stages, the weight loss in the first stages may be corresponding to the loss of the small groups and weaker bonds in the chains, such as ? CH₃, and ? C₃H₇, the weight loss in the second stage may be corresponding to the loss of the group as ? OC₂H₅. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40934.     

Mechanical properties and thermal stability of poly(L‐lactide)/calcium carbonate composites

Poly(L ‐lactide) (PLA) was melt‐mixed with micrometer‐sized and nanosized calcium carbonate (CaCO₃) particles before and after modification with calcium stearate. Adhesion between the CaCO₃ particles and the PLA matrix was assessed qualitatively by scanning electron microscopy observation of the fractured surface morphology of the composites. The effect of the incorporation of the CaCO₃ particles on the thermal stability of the PLA‐based composites was quantified by the temperatures corresponding to 5 and 50% of weight loss and the activation energy determined through thermogravimetric analyses of the composites. The tensile strength and modulus values of the composite were improved greatly without a significant loss in the elongation at break when the nanosized CaCO₃ was incorporated up to 30 wt %. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis,characterization, and thermal degradation kinetics of poly(decamethylene 2‐oxoglutarate)

Poly(decamethylene 2‐oxoglutarate) [poly (DMOG)] was synthesized by a melt polycondensation reaction. The structure of poly(DMOG) was confirmed by means of Fourier transform infrared, ¹H‐NMR, and ¹³C NMR spectroscopies. The molecular weight distribution values of poly(DMOG) were determined with size exclusion chromatography. The number‐average molecular weight, weight‐average molecular weight, and polydispersity index values of poly(DMOG) were found to be 13,200, 19,000, and 1.439, respectively. Also, characterization was made by thermogravimetry (TG)–dynamic thermal analysis. The kinetics of the thermal degradation of poly (DMOG) was investigated by thermogravimetric analysis at different heating rates. TG curves showed that the thermal decomposition of poly(DMOG) occurred in one stage. The apparent activation energies of thermal decomposition for poly(DMOG), as determined by the Tang method, the Flynn–Wall–Ozawa method, the Kissinger–Akahira–Sunose method, and the Coats–Redfern method were 122.5, 126.8, 121.4, and 122.9 kJ/mol, respectively. The mechanism function and pre‐exponential factor were also determined by the master plots method. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and physicochemical study of polyester polyols of epoxy resin of 2,4,6‐tris(4‐hydroxyphenyl)‐1,3,5‐triazine and their polyurethanes

Polyester polyols of ricinoleic acid (ETPRA), oleic acid, linoleic acid (ETPLA), and rosin (ETPR) and epoxy resin of 2,4,6‐tris(4‐hydroxyphenyl)‐1‐3‐5‐triazine (ETP) and their polyurethanes (PUs) were synthesized and characterized by Fourier transform infrared spectroscopy, NMR, differential scanning calorimetry, and thermogravimetric analysis techniques. The PU films showed the following density order: ETPRPU600 > ETPRAPU600 > ETPLAPU600. ETPLAPU600 showed good tensile strength and volume resistivity values compared to ETPRAPU600 and ETPRPU600. All three PUs showed good electric strength. ETPLAPU600 showed almost double the electric strength of ETPRAPU600 and ETPRPU600. The incorporation of soft‐segment poly(ethylene glycol) 600 into PU chains resulted in the flexibility of the films. The PU films showed a high water absorption tendency in water, acidic, and saline environments, and they degraded in an alkaline environment. The weight gain tendency of the films was due to surface solvolysis and was also probably due to microcrack formation. The polyester polyols and PUs were thermally stable up to about 167–221 and 184–214°C, respectively, and followed multistep degradation reactions with either fractional or integral order (0.43–2.71) degradation kinetics. Thus, the structure of the PUs affected the studied physicochemical properties of the films. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40203.     

Flame‐retardancy properties of tris(2‐hydroxyethyl) isocyanurate based charring agents on polypropylene

Tris(2‐hydroxyethyl) isocyanurate based charring agent (TBCA) was synthesized by melt polycondensation with tris(2‐hydroxyethyl) isocyanurate (THEIC) and terephthalic acid as raw materials. It was characterized by Fourier transform infrared spectroscopy, elemental analysis, ¹H‐NMR, and thermogravimetric analysis (TGA). TBCA was blended with ammonium polyphosphate (APP) to form an intumescent flame retardant (IFR) for polypropylene (PP). The charring properties of TBCA was tested by flame retardancy in the PP/APP/TBCA (PP/IFR₂) composite and compared with that of the PP/APP/THEIC (PP/IFR₁) composite. The results show that PP/IFR₂ had lower flame‐retardant properties but better water resistance than that of the PP/IFR₁ composite because PP/IFR₂ could still obtain a V‐0 rating after it had been soaked in water at 70°C for 96 h, whereas PP/IFR₁ could not achieve any rating after 36 h. Their combustion performance was further evaluated by a cone calorimeter test, their thermal degradation processes were studied by TGA, and the morphology of the char residue was observed by scanning electron microscopy. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41810.     

Synthesis and characterization of new polyureas derived from 4‐(4′‐Methoxyphenyl)urazole

4‐(4′‐Methoxyphenyl)urazole (MPU) was prepared from 4‐methoxybenzoic acid in five steps. The reaction of monomer MPU with n‐isopropylisocyanate was performed at room temperature in N,N‐dimethylformamide solution, and the resulting bis‐urea derivative was obtained in high yield and was finally used as a model for polymerization reaction. The step‐growth polymerization reactions of monomer MPU with hexamethylene diioscyanate, isophorone diioscyanate, and toluene‐2,4‐diioscyanate were performed in N,N‐dimethylacetamide solution in the presence of pyridine as a catalyst. The resulting novel polyureas have an inherent viscosity (η_inh) in a range of 0.07–0.21 dL/g in DMF and sulfuric acid at 25°C. These polyureas were characterized by IR, ¹H‐NMR, elemental analysis, and TGA. Some physical properties and structural characterization of these novel polyureas are reported. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1141–1146, 2002     

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.     

Aqueous‐solution and solid‐film properties of poly(vinyl alcohol), poly(vinyl pyrrolidone), gelatin,starch, and carboxymethylcellulose polymers

With the density and viscosity results for five polymers—poly(vinyl alcohol) (PVA), poly(vinyl pyrrolidone) (PVP), gelatin (Ge), starch (St), and carboxymethylcellulose (CMC)—measured in aqueous solutions at different temperatures, we have computed the excess molar volumes and activities. Smaller excess molar volumes for PVA solutions are attributed to specific types of interactions, whereas for other polymers, these data are quite large, indicating dispersion‐type interactions. The activity data of the polymer solutions vary widely, depending on the nature of the polymers and their intermolecular interactions. The freestanding film properties of the polymers indicate that Ge and PVA produce stable films, whereas brittle films can be obtained for PVP and St. The mechanical strength properties of PVA and CMC have been found to be suitable for membrane fabrication. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Reinforcement of graphene nanoplatelets on plasticized poly(lactic acid) nanocomposites: Mechanical,thermal, morphology,and antibacterial properties

Plasticized poly(lactic acid) (PLA)‐based nanocomposites filled with graphene nanoplatelets (xGnP) and containing poly(ethylene glycol) (PEG) and epoxidized palm oil (EPO) with ratio 2 : 1 (2P : 1E) as hybrid plasticizer were prepared by melt blending method. The key objective is to take advantage of plasticization to increase the material ductility while preserving valuable stiffness, strength, and toughness via addition of xGnP. The tensile modulus of PLA/2P : 1E/0.1 wt % xGnP was substantially improved (30%) with strength and elasticity maintained, as compared to plasticized PLA. TGA analysis revealed that the xGnP was capable of acting as barrier to reduce thermal diffusion across the plasticized PLA matrix, and thus enhanced thermal stability of the plasticized PLA. Incorporation of xGnP also enhanced antimicrobial activity of nanocomposites toward Escherichia coli, Salmonella typhimurium, Staphylococcus aureus, and Listeria monocytogenes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41652.     

Synthesis and characterization of diamide–diimide–diamines based on p‐amino benzoic acid and their curing and thermal behavior with epoxy blends containing phosphorus/silicon in the main chain

Diimide–diacid ( I ) having an imide group in its rigid structure was synthesized by the refluxing of 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride [4,4′‐carbonyldiphthalic anhydride (BTDA)] and p‐amino benzoic acid in a mixture of acetic acid and pyridine (3 : 2 v/v). The chloroderivative of the diacid ( I ) was synthesized by its reaction with thionyl chloride, this was followed by condensation with different diamines with phenyl, naphthyl, ether, sulfide, and cardo groups to generate a series of diamide–diimide–diamines (DADIDAs). The resultant DADIDAs were characterized by elemental analysis and spectroscopic techniques, namely, Fourier transform infrared spectroscopy and NMR spectroscopy, and were used as epoxy curing agents to impart flame retardancy to the epoxy system. Two epoxy blends (designated as ES and EP) were prepared by the homogeneous mixing of diglycidyl ether of bisphenol A (DGEBA) with 1,3‐bis(3‐glycidyloxypropyl)tetramethyl disiloxane and DGEBA with tris(glycidyloxy)phosphine oxide: each in a ratio of 3 : 2 respectively. The synergistic effect of phosphorus/silicon with nitrogen on the thermal properties of the modified epoxy system was studied. The curing behavior of the epoxy resins formulated by the reaction of stoichiometric amounts of ES/EP with the synthesized DADIDAs were determined by differential scanning calorimetry, and the thermal stabilities of the cured epoxies were evaluated by thermogravimetric analyses (TGAs) under nitrogen and air. TGA indicated that the residual weight percentage of polymers at 800°C was in the range 36.4–60.0 in nitrogen, and in air, it was up to 6.5. However, the major loss in weight in air occurred at elevated temperature; this demonstrated their potential use as flame‐retardant epoxy systems for electronic/electrical encapsulants. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Sb‐intercalated layered double hydroxides–poly(vinyl chloride) nanocomposites: Preparation,characterization, and thermal stability

In this study, a novel ‐intercalated layered double hydroxide (Sb‐LDH) was prepared by simultaneous recovering of LDH structures and intercalation of into LDH layers. The prepared Sb‐LDH composites remain the hydrotalcite structure with layered geometry and show higher thermal property than that of LDH. When applied to poly(vinyl chloride) (PVC) composites, Sb‐LDH showed limited thermal stability for PVC at the early stage of thermal and thermooxidative degradation processes. However, Sb‐LDH could retard the thermal cracking of the carbonaceous conjugated polyene of PVC which may hinder further degradation, and the moderate amount of Sb‐LDH (1, 2, and 5 wt %) in PVC resin can retard the process of decarbonation and enhance char formation. Sb‐LDH also promoted the transparency of PVC but darkened the color. With the advantages of transparency promotion, high temperature resistance, and long‐term stability, the prepared Sb‐LDH is a potential thermal stabilizer for PVC resins. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42524.     

Synthesis,characterization, and thermal degradation kinetics of the copolymer poly(4‐methoxybenzyl methacrylate‐co‐isobornyl methacrylate)

A copolymer of 4‐methoxybenzyl methacrylate and isobornyl methacrylate was synthesized by atom transfer radical polymerization. The structure of poly(4‐methoxybenzyl methacrylate‐co‐isobornyl methacrylate) was confirmed by means of Fourier transform infrared, ¹H‐NMR, and ¹³C‐NMR techniques. The molecular weight distribution values of the copolymer were determined with gel permeation chromatography. The number‐average molecular weight and polydispersity index values of poly(4‐methoxybenzyl methacrylate‐co‐isobornyl methacrylate) were found to be 12,500 and 1.5, respectively. The kinetics of the thermal degradation of the copolymer was investigated with thermogravimetric analysis at different heating rates. The activation energy values obtained with the Kissinger, Flynn–Wall–Ozawa, and Tang methods were determined to be 166.38, 167.54, and 167.47 kJ/mol, respectively. Different integral and differential methods were used, and the results were compared with these values. Doyle approximation was also used for comparing the experimental results to master plots. An analysis of the experimental results suggested that the reaction mechanism was an R₁ deceleration type in the conversion range studied. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermal decomposition kinetics of poly(nButMA‐b‐St) diblock copolymer synthesized by ATRP

The reaction mechanism of decomposition process and the kinetic parameters of the poly(n‐butyl methacrylate‐b‐styrene), poly(nButMA‐b‐St), diblock copolymer synthesized by atom transfer radical polymerization (ATRP) were investigated by thermogravimetric analysis (TGA) at different heating rates. TGA curves showed that the thermal decomposition occurred in one stage. The apparent activation energies of thermal decomposition for copolymer, as determined by the Kissinger's, Flynn–Wall–Ozawa and Tang methods, which does not require knowledge of the reaction mechanism (RM), were 112.52, 116.54, and 113.41 kJ/mol, respectively. The experimental results were compared with master plots, in the range of the Doyle approximation. Analysis of experimental results suggests that in the conversion range studied, 3–18%, the actual RM is an A₂ sigmoidal type. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Comparison of the effects of phenyl dichlorophosphate modified and unmodified β‐iron(III) oxide hydroxide on the thermal,combustion, and mechanical properties of ethylene–vinyl acetate/magnesium hydroxide composites

The objective of this study was to compare the impact of β‐iron(III) oxide hydroxide [β‐Fe(O)OH] and iron hydroxide modified with phenyl dichlorophosphate [β‐Fe(O)OPDCP] on the thermal, combustion, and mechanical properties of ethylene–vinyl acetate (EVA)/magnesium hydroxide (MH) composites. For the EVA/MH composites in combination with these iron‐containing co‐additives, β‐Fe(O)OH and β‐Fe(O)OPDCP both led to an increase in the thermal stability at higher temperatures. The results of microscale combustion calorimetry indicate that the peak heat‐release rate, total heat release, and heat‐release capacity, which are indicators of a material fire hazard, all decreased. Moreover, significant improvements were obtained in the limiting oxygen index (LOI) and Underwriters Laboratories 94 ratings. However, the EVA4 system reached a V‐0 rating, whereas the EVA3 system reached a V‐2 rating. The LOI values for the EVA3 and EVA4 systems were 35 and 39, respectively. A homogeneous and solid structure of char residue caused by β‐Fe(O)OPDCP was observed by scanning electron microscopy. Furthermore, because of the good interfacial compatibility between the fillers and the EVA matrix, the EVA4 system presented better mechanical properties than the EVA3 system. Thermogravimetric analysis/IR spectrometry showed that β‐Fe(O)OPDCP reduced the combustible volatilized products of EVA/MH. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40112.     

Siloxane‐based segmented poly(urethane‐urea) elastomer: Synthesis and characterization

A series of segmented poly(urethane‐urea) block copolymers were synthesized with varying proportions of polydimethylsiloxane diols in combination with polytetramethylene ether glycol (PTMG) using 4,4'‐methylenediphenyl diisocyanate followed by chain extension with a (50:50 mol %) mixture of 4,4'‐methylene‐bis(3‐chloro‐2,6‐diethylaniline) (M‐CDEA) and 1,4‐butanediol (BD). The molecular structures of polydimethylsiloxane urethane‐ureas were characterized by ATR‐FTIR and ¹H‐NMR spectroscopic techniques. Distribution of siloxane domain and its influence on surface roughness were investigated by scanning electron microscopy (SEM) and atomic forced microscopy (AFM), respectively. The mechanical and thermal properties of the elastomers were studied by thermogravimetric analysis, dynamical mechanical thermal analysis, and tensile measurement. The results showed that by incorporation of polydimethylsiloxane diol and M‐CDEA chain extender in polyurethane formulation, some improvements in thermal stability, fire resistance and surface hydrophilicity were achieved. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1743–1751, 2013     

Synthesis and thermal properties of poly(urethane‐imide)

The synthesis and thermal properties of thermoplastic poly(urethane‐imide) (PUI) resins were studied. Model reaction studies on the reactions of 4,4′‐diphenylcarbamatodiphenylmethane and 4,4′‐diisocyanatodiphenylmethane with phthalic anhydride were performed. We found that the reaction of anhydrides with urethane groups could take place under certain reaction conditions. According to the model reaction studies, N‐2‐methyl‐pyrrolidone was employed as a solvent, and no catalyst was used in the polymerization. To restrain the side reaction of anhydrides with urethane groups, we adopted a two‐step chain‐extending procedure in a chain‐extending reaction. The inherent viscosity of PUI was 0.83–0.99 dL/g. The prepared polymers not only exhibited improved solubility in organic solvents but also formed flexible films. Thermogravimetric analysis showed that PUI exhibited a two‐step thermal weight‐loss pattern. The first step of the thermal degradation of PUI was attributed to the thermooxidizing cleavage of weak and labile linkage, such as urethane groups, isopropylidene, and methylene, except for imide rings. The polymer inherent viscosity decreased sharply during the first step of thermal degradation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 773–781, 2001