Synthesis of block copolyetherether ketones and investigations of their properties

Using oligoketones with different degrees of condensation (n = 1, 10, 20), dichlorides of isophthalic and terephthalic acids and 2,2‐bis[4‐hydroxyphenyl]‐propane block‐copolyetherether ketones (BCPEEKs) were synthesized by means of acceptor–catalytic polycondensation. Their properties were also investigated. It was shown that BCPEEK possesses good solubility, high molecular weight, and is characterized by high thermal and mechanical properties. The correlation between some properties of the polyethers and the degree of condensation of oligoketones was also investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 485–490, 2002     

Catalyzed chain extension of poly(butylene adipate) and poly(butylene succinate) with 2,2′‐(1,4‐phenylene)‐bis(2‐oxazoline)

Low‐molecular‐weight HOOC‐terminated poly(butylene adipate) prepolymer (PrePBA) and poly(butylene succinate) prepolymer (PrePBS) were synthesized through melt‐condensation polymerization from adipic acid or succinic acid with butanediol. The catalyzed chain extension of these prepolymers was carried out at 180–220°C with 2,2′‐(1,4‐phenylene)‐bis(2‐oxazoline) as a chain extender and p‐toluenesulfonic acid (p‐TSA) as a catalyst. Higher molecular weight polyesters were obtained from the catalyzed chain extension than from the noncatalyzed one. However, an improperly high amount of p‐TSA and a high temperature caused branching or a crosslinking reaction. Under optimal conditions, chain‐extended poly(butylene adipate) (PBA) with a number‐average molecular weight up to 29,600 and poly(butylene succinate) (PBS) with an intrinsic viscosity of 0.82 dL/g were synthesized. The chain‐extended polyesters were characterized by IR spectroscopy, ¹H‐NMR spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis, wide‐angle X‐ray scattering, and tensile testing. DSC, wide‐angle X‐ray scattering, and thermogravimetric analysis characterization showed that the chain‐extended PBA and PBS had lower melting temperatures and crystallinities and slower crystallization rates and were less thermally stable than PrePBA and PrePBS. This deterioration of their properties was not harmful enough to impair their thermal processing properties and should not prevent them from being used as biodegradable thermoplastics. The tensile strength of the chain‐extended PBS was about 31.05 MPa. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and investigation of the properties of poly(phenyl‐α‐naphthylsilylene)–dimethylsilylene copolymers

A Wurtz‐type reductive coupling reaction of dichlorophenyl‐α‐naphthylsilane was carried out in a mixture of toluene and o‐xylene in the presence of sodium and a catalytic amount of mercury; α,ω‐dichlorophenyl‐α‐naphthylsilylenes of various degrees of polymerization were obtained. Through the hydrolysis of α,ω‐dichlorophenyl‐α‐naphthylsilylenes, corresponding dihydroxy compounds were obtained. The heterofunctional polycondensation of α,ω‐dihydroxyphenyl‐α‐naphthylsilylenes with α,ω‐dichlorodimethylsilylenes was performed both without amines and in the presence of amines. Heterofunctional polycondensation without amines did not proceed with the formation of high molecular weight compounds because the cleavage of both ? Si? Si? and ?Si? O? Si? bonds took place during condensation. In the presence of amines, polysilylene–silylene copolymers were obtained. The synthesized copolymers were investigated with gel permeation chromatography, differential scanning calorimetry, roentgenography, and thermogravimetry. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1047–1056, 2002     

Synthesis,characterization and properties of TAP‐6FDA hyperbranched polyimides with different branching degrees

A series of hyperbranched polyimides were successfully synthesized by condensation polymerization of A₂‐type dianhydride monomer 2,2‐bis(3,4‐dicarboxylphenyl) hexafluoropropane dianhydride (6FDA) and B′B₂‐type triamine monomer 2,4,6‐triaminopyrimidine (TAP). Polymers with different branching degrees (DB) and terminated groups were obtained by changing the monomer addition order and the monomer molar ratio. Fourier transform infrared spectroscopy and ¹H NMR were used to verify the structure of the prepared polyimides, which indicated that the amino group still existed in all the products. The DB of the polymers indicated by ¹H NMR increased from 30% to 79% with the molar ratio of TAP:6FDA decreasing from 1:1 to 1:2. The absolute molecular weights were measured by size‐exclusion chromatography with multi‐angle laser light‐scattering detection, which suggested that the highest molecular weight would be obtained when the molar ratio of amino groups:anhydride groups of the monomers was 3:3.2. With the DB increasing, the d‐spacing values indicated by wide angle X‐ray diffraction increased from 5.15 Å to 5.68 Å and the UV ? visible spectra of the polymers exhibited decreasing cut‐off wavelengths. The 5% weight loss temperature in nitrogen increased with decreasing content of TAP monomer, and the glass transition temperatures of the obtained polyimides decreased from 282 °C to 258 °C with increasing DB. © 2013 Society of Chemical Industry     

Nanocomposites based on poly(ϵ‐caprolactone) and the montmorillonite treated with dibutylamine‐terminated ϵ‐caprolactone oligomer

Dibutylamine‐terminated ε‐caprolactone oligomers (CLOs: CLOL, CLOM, and CLOH) with number–averaged molecular weight (M_n), 500, 1300, and 2200, respectively, were synthesized by the ring‐opening polymerization of ε‐caprolactone initiated by 2‐(dibutylamino)ethanol in the presence of tin(II) 2‐ethylhexanoate. Nanocomposites based on poly(ε‐caploractone) (PCL) and the caprolactone oligomer‐treated montmorillonites (CLO‐Ms: CLOL‐M, CLOM‐M, and CLOH‐M) were prepared by melt intercalation method. The XRD and TEM analyses of the PCL composites revealed that the extent of exfoliation of the clay platelets increased with increasing molecular weight of the used CLOs. Tensile strength and modulus of the PCL/CLO‐M composites increased with increasing molecular weight of the CLO and increasing inorganic content. The tensile modulus of the PCL/CLOH‐M nanocomposite with inorganic content 5.0 wt % was three times higher than that of control PCL. Among the PCL/CLO‐M composites, the PCL/CLOM‐M composite had the highest crystallization temperature and melting temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis,thermal, and dynamic mechanical properties of 1,3‐bis(diphenylsilyl)‐2,2,4,4‐tetraphenylcyclodisilazane‐containing polydimethylsiloxanes

New and effective approaches to the synthesis of 1,3‐bis(diphenylsilyl)‐2,2,4,4‐tetraphenylcyclodisilazane‐containing polydimethylsiloxanes ( P1 and P2 ) were developed. P1 was obtained by polycondensation of cyclodisilazane lithium salt and chloroterminated polydimethylsiloxane. P2 was produced by hydrosilylation of vinyl‐terminated cyclodisilazane and hydrogen‐terminated polydimethylsiloxane. The polycondensation completed quickly at room temperature, while the hydrosilylation was facile and did not require cumbersome air‐sensitive operations. P1 and P2 were characterized by Fourier transform infrared, nuclear magnetic resonance, gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis (TGA), and isothermal gravimetric analysis (IGA). TGA revealed the outstanding thermal properties of P1 and P2 with 5% weight loss temperatures (T_d5) higher than 450°C. IGA proved their better thermal stability at 450°C for 800 min, compared to polydimethyldiphenylsiloxane. Dynamic mechanical analysis showed that silicone rubbers made from cyclodisilazane‐containing polydimethylsiloxanes could have a maximum tan δ value as high as 1.13 and had good prospects for damping material applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of polyhydroxylated polybutadiene binding 2,2′‐thiobis(4‐methyl‐6‐tert‐butylphenol) with isophorone diisocyanate

A macromolecular hindered phenol antioxidant, polyhydroxylated polybutadiene containing thioether binding 2,2′‐thiobis(4‐methyl‐6‐tert‐butylphenol) (PHPBT‐b‐TPH), was synthesized via a two‐step nucleophilic addition reaction using isophorone diisocyanate (IPDI) as linkage. First, the ? OH groups of PHPBT reacted with secondary ? NCO groups of IPDI to form the adduct PHPBT‐NCO, then the PHPBT‐b‐TPH was obtained by one phenolic ? OH of 2,2′‐thiobis(4‐methyl‐6‐tert‐butylphenol) (TPH) reacting with the PHPBT‐NCO. The PHPBT‐b‐TPH was characterized by Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance (¹H‐NMR), ¹³C‐NMR, and thermogravimetric analysis, and its antioxidant activity in natural rubber was studied by an accelerated aging test. Influences of reaction conditions on the two nucleophilic reactions between ? OH group and ? NCO group were investigated. In addition, catalytic mechanism for the reaction between PHPBT‐NCO and TPH was discussed. The results showed that the adduct PHPBT‐NCO could be obtained by using dibutyltin dilaurate (DBTDL) as catalyst, and the suitable temperature and DBTDL amount were 35°C and 3 wt %, respectively. However, triethylamine (TEA) was more efficient than DBTDL to catalyze the reaction between PHPBT‐NCO and TPH because of steric hindrance effect. In addition, it was found that the thermal stability and antioxidant activity of PHPBT‐b‐TPH were higher than those of the low molecular weight antioxidant TPH. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40942.     

Molecular structure and properties of ethylene‐co‐styrene polymers obtained from [norbornane‐7,7‐bis(1‐indenyl)]titanium dichloride catalyst system

Ethylene‐co‐styrene polymers have been synthesized using the new catalyst system [norbornane‐7,7‐bis(1‐indenyl)]titanium dichloride, and characterized by SEC, ¹³C‐NMR, DSC, and dynamic‐mechanical analysis. The copolymers have higher average molecular weights compared with those produced in our group with other single‐site catalysts systems in the same conditions. More specifically, the homopolymers are ultra high molecular weight polyethylenes (molecular weight higher than 10⁶ g mol^?1) and with a narrow molecular weight distribution. All samples have shown an unprecedented homogeneous chemical composition with a random incorporation of the comonomer during the polymerization. The expected relationship between thermal properties and the amount of comomoner related to the exclusion of the phenyl units from the crystalline structure has been found, but the correlation is slightly different from those found in other copolymers. This is likely due to the different molecular features of the copolymers. In addition, intense and narrow mechanical relaxations have been found in the samples tested, pointing towards an extremely homogeneous microstructure. The materials obtained show a conspicuous strain hardening during tensile deformation at high strains, not only related to the constrain imposed by the bulky phenyl group in the amorphous region, but additionally to the extremely high number of entanglements in this region as a consequence of the high molecular mass of the samples. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis,characterization, and thermal properties of alternate copolymers containing N,N′‐bis(diphenylsilyl)tetraphenylcyclodisilazane

Hexamethyldisilazane was used as the starting material to synthesize N,N′‐bis(hydroxydiphenylsilanyl)tetraphenylcyclodisilazane (BHPTPC). By condensation polymerization of BHPTPC with α,ω‐bis(dialkylamino)dimethylsiloxane, a series of alternate copolymers containing N,N′‐bis(diphenylsilyl)tetraphenylcyclodisilazane was synthesized. GPC studies show that the highest molecular weight was obtained at a ratio of 1.005 : 1 (BHPTPC: α,ω‐bis(dimethyl amino)dimethylsiloxane). Data of DSC indicate that the temperature of glass transition (T_g) and temperature of melting point (T_m) decreased with the increasing of dimethylsiloxane segments units. Three stages of degradation were found in the thermogravimetric analysis curves. The activation energy of the copolymer (with m = 2, 3, and 7) was calculated by using Flynn–Wall–Ozawa method. The activation energy of the copolymer with m = 2, 3, and 7 at second stage is 214, 211, and 184 kJ/mol, respectively. Isothermal gravimetric analysis shows that for the same temperature and the same time, the weight loss of the alternate copolymer was greatly less than that of common polydimethylsiloxane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 611–617, 2007     

Poly(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane)– poly(dimethylsiloxane) block copolymers

The hydrolytic condensation of 1,3‐dichloro‐1,3‐disila‐1,3‐diphenyl‐2‐oxaindane under neutral conditions produced α'ω‐dihydroxy‐1,3‐disila‐1,3‐diphenyl‐2‐oxaindane (polymerization degree ≈ 4). The homofunctional condensation of α'ω‐dihydroxy‐1,3‐disila‐1,3‐diphenyl‐2‐oxaindane in a toluene solution and in the presence of activated carbon was performed, and dihydroxy‐containing oligomers with various degrees of condensation were obtained. Through the heterofunctional condensation of dihydroxy‐containing oligomers with α'ω‐dichlorodimethylsiloxanes in the presence of amines, corresponding block copolymers were obtained. Gel permeation chromatography, differential scanning calorimetry, thermomechanical analysis, thermogravimetry, and wide‐angle roentgenography investigations were carried out. Differential scanning calorimetry and roentgenography studies of the block copolymers showed that their properties were determined by the ratio of the lengths of the flexible and linear poly(dimethylsiloxane) and rigid poly(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane) fragments in the macromolecular chain. At definite values of the lengths of the flexible and rigid fragments, a microheterogeneous structure was observed in the synthesized block copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1409–1417, 2002; DOI 10.1002/app.10335     

Atom transfer radical polymerization of (R)‐2‐methacryloyloxy‐2′‐methoxy‐1,1′‐binaphthalene

Atom transfer radical polymerization (ATRP) of (R)‐2‐methacryloyloxy‐2′‐methoxy‐1,1′‐binaphthalene ((R)‐MAMBN) mediated by different amine ligands, copper(I) chloride and ethyl 2‐bromopropionate in different solvents, and reverse ATRP of (R)‐MAMBN were studied. It was shown that optically active polymers were obtained, with poor control of the molecular weights, and low polydispersities. Specific rotation of the polymers increased with increasing molecular weights. By comparison with (R)‐MAMBN, poly((R)‐MAMBN)s exhibits higher specific rotation and a positive Cotton effect. Copyright © 2003 Society of Chemical Industry     

Synthesis,characterization, rheological and thermal behavior of metallocene ethylene − norbornene copolymers with low norbornene content using pentafluorophenol modified methylaluminoxane

Ethylene ? norbornene copolymers were synthesized using rac‐ethylene bis(indenyl) zirconium dichloride/pentafluorophenol modified methylaluminoxane. First, the effect of using a modifier in combination with a low ratio of Al/Zr on the catalyst activity and co‐monomer incorporation was studied. The results of copolymerization reveal a 20% co‐monomer incorporation improvement and a rise of activity by 2‐fold in the presence of the modifier. Rheological measurements show a higher molecular weight in copolymers synthesized using modified methylaluminoxane. The alternative and dyad block microstructures of copolymers become possible in the case of a norbornene content of more than 14 mol%. Second, the effect of co‐monomer content on the rheological and thermal behavior of the synthesized copolymers was investigated. The results of the rheological study indicate a lower molecular weight in samples containing a higher norbornene content. Dynamic mechanical thermal analysis confirms the influence of different microstructures on the glass transition temperature. The crystal structure of copolymers having a higher molecular weight is emphasized using wide angle X‐ray scattering and DSC even with a greater incorporation of norbornene. © 2015 Society of Chemical Industry     

Optical and electrochemical properties of oligo(1,5‐dialkoxynaphthalene‐2,6‐diyl)s with self‐assembled ordered structures in solid state

Oligo(1,5‐dialkoxynaphthalene‐2,6‐diyl)s were synthesized by Ni(cod)₂ (cod = 1,5‐cyclooctadiene)‐promoted condensation reactions of 1,5‐dialkoxy‐2,6‐dibromonaphthalenes. The UV–Vis, photoluminescence (PL), and powder X‐ray diffraction (XRD) measurements suggested that the oligomers have a self‐assembling ordered structure in the solid state. The oligomers underwent electrochemical oxidation (p‐doping), which occurred at lower potentials for films than for acetonitrile solutions containing [Et₄N]BF₄. This effect is caused by the longer π‐conjugation lengths of the oligomers in films, which was attributed to molecular self‐assembly leading to ordered structures in the solid state. The electrochemical reaction of the oligomers was accompanied by electrochromism. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41840.     

Synthesis and characterization of novel polyimides starting from 1,2‐bis(p‐dimethylaminobenzylideneimino)alkane homologues and various dianhydrides

The objective of this research was the preparation of polyimides from 1,2‐bis(p‐dimethylaminophenylimino)alkane homologues and various dianhydrides in N‐methylpyrrolidone by one‐stage polycondensation. The monomers were prepared via condensation of p‐dimethylaminobenzaldehyde and the corresponding diamines, 1,4‐diaminobutane, 1,3‐diaminopropane and 1,2‐diaminoethane. The influence of the incorporation of this moiety into the polymer backbone on the properties of the polyimides has been evaluated. The thermogram of the polyimides indicated that PI‐10 to PI‐32 had T_g values ranging from 181 to 290 °C. The inherent viscosities of the polymers ranged from 0.99 to 2.05 dl g^?1, and the highest solubility was obtained without significant loss of the thermal properties. Copyright © 2004 Society of Chemical Industry     

Syntheses,characterization, and hydrolytic degradation of P(ε‐caprolactone‐co‐δ‐valerolactone) copolymers: Influence of molecular weight

Biodegradable poly(ε‐caprolactone‐co‐δ‐valerolactone) copolymers were synthesized and investigated to study their behavior in aqueous medium. The copolyesters were produced by ring opening polymerization between ε‐caprolactone (CL) and δ‐valerolactone (VL) in bulk at 140°C using tin(II) octoate as catalyst. They were characterized by using ¹H NMR, size exclusion chromatography, differential scanning calorimetry, and MALDI TOF mass spectrometry. Reactivity ratio determination gave an insight on their microstructure. Hydration, hydrolytic degradation, and biocide release of P(CL‐VL) films with different molecular weights values were studied. A one‐order kinetic whose rate constant decreases with copolymer macromolecular weight was observed. Although the molecular weight decrease remained relatively weak after 8 months of immersion, a correlation between molecular weight and hydrolysis rate was shown by high performance liquid chromatography‐mass spectrometry. The ability of the P(CL‐VL) films to release active compounds dispersed in the films was studied by atomic absorption spectroscopy. The release behavior of all copolymers was identical with a zero‐order kinetic. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43007.     

Synthesis and characterization of novel lipid functionalized poly(ε‐caprolactone)s

A series of novel lipid functionalized poly(ε‐caprolactone)s (PCLs) were synthesized through ROP of ε‐caprolactone in the presence of threo‐9,10‐dihydroxyoctadecanoic acid, synthesized from oleic acid. PCLs with different molecular weights were obtained by controlling the molar ratio of the initiator to the monomer. DSC and XRD analysis indicate that the crystallinity of PCLs decreased when compared to unfunctionalized PCL. The enzymatic degradation study shows that for samples with lower lipid derivatives content, a higher enzymatic degradation rate was observed because the lipase enzymes attack the ester bonds of the polymer; increased lipid content therefore inhibits the action of the lipase enzymes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of biodegradable poly(ester‐urethanes) based on bacterial poly(R‐3‐hydroxybutyrate)

A series of poly(R‐3‐hydroxybutyrate)/poly(ε‐caprolactone)/1,6‐hexamethylene diisocyanate‐segmented poly(ester‐urethanes), having different compositions and different block lengths, were synthesized by one‐step solution polymerization. The molecular weight of poly(R‐3‐hydroxybutyrate)‐diol, PHB‐diol, hard segments was in the range of 2100–4400 and poly(ε‐caprolactone)‐diol, PCL‐diol, soft segments in the range of 1080–5800. The materials obtained were investigated by using differential scanning calorimetry, wide angle X‐ray diffraction and mechanical measurements. All poly(ester‐urethanes) investigated were semicrystalline with T_m varying within 126–148°C. DSC results showed that T_g are shifted to higher temperature with increasing content of PHB hard segments and decreasing molecular weight of PCL soft segments. This indicates partial compatibility of the two phases. In poly(ester‐urethanes) made from PCL soft segments of molecular weight (M_n ≥ 2200), a PCL crystalline phase, in addition to the PHB crystalline phase, was observed. As for the mechanical tensile properties of poly(ester‐urethane) cast films, it was found that the ultimate strength and the elongation at the breakpoint decrease with increasing PHB hard segment content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 703–718, 2002     

Poly(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane)‐diphenylsiloxane‐poly(dimethylsiloxane) block copolymers

The heterofunctional condensation of 1,3‐dichloro‐1,3‐disila‐1,3‐diphenyl‐2‐oxaindane with dihydroxydiphenylsilane at various ratios of initial compounds in the presence of amines was carried out, and α,ω‐dihydroxy(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane)‐diphenylsiloxane oligomers with various degrees of condensation were obtained. Corresponding block copolymers were obtained by heterofunctional polycondensation of synthesized α,ω‐dihydroxy(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane)‐diphenylsiloxane oligomers with α,ω‐dichlorodimethylsiloxanes in the presence of amines. Thermogravimetry, gel permeation chromatography, differential scanning calorimetry, and wide‐angle X‐ray analysis were carried out on the synthesized block coplymers. Differential scanning calorimetry and wide‐angle X‐ray studies of these copolymers showed that their properties were determined by the ratio of the lengths of the flexible linear poly(dimethylsiloxane) and rigid poly(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane)‐diphenylsiloxane fragments in the main macromolecular chain. Two‐phase systems were obtained with specific flexible and rigid fragment length values in synthesized block copolymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3462–3467, 2006     

Dynamic mechanical analysis of ethylene/1‐hexene copolymers: The effect of the catalyst type on the short‐chain branching distribution and properties of the amorphous and crystalline phases

Dynamic mechanical analysis was used to study ethylene/1‐hexene copolymers with different compositions, molecular weight distributions, and profiles of short‐chain branching (SCB) versus molecular weight. These copolymers were produced over a highly active supported titanium–magnesium catalyst (TMC), a highly active supported vanadium–magnesium catalysts (VMC), and a supported zirconocene catalyst. A higher fraction of the crystalline phase in the copolymers prepared with VMC was shown to result in higher elastic modulus values. β relaxation was found to be sensitive to the SCB distribution versus the molecular weight. The copolymers prepared with the zirconocene catalyst and VMC were characterized by more uniform SCB distributions and higher temperatures of β relaxation compared to the copolymers prepared with TMC. The mobility of the polymer chains at room temperature in the amorphous phase obtained by the spin‐probe method rose with increasing branch content in the copolymers and was not sensitive to different SCB distribution profiles. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44638.     

Synthesis,characterization, thermal stability,and compatibility properties of poly(vinyl p‐nitrobenzal acetal)‐g‐polyglycidylazides

A series of energetic polymers, poly(vinyl p‐nitrobenzal acetal)‐g‐polyglycidylazides (PVPNB‐g‐GAPs), are obtained via cross‐linking reactions of poly(vinyl p‐nitrobenzal acetal) (PVPNB) with four different molecular weights polyglycidylazides (GAPs) using toluene diisocyanate as cross‐linking agent. The structures of the energetic polymers are characterized by ultraviolet visible spectra (UV‐Vis), attenuated total reflectance‐Fourier transform‐infrared spectroscopy (ATR‐FT‐IR), ¹H nuclear magnetic resonance spectrometry (¹H NMR), and ¹³C nuclear magnetic resonance spectrometry (¹³C NMR). Differential scanning calorimetry (DSC) is applied to evaluate the glass‐transition temperature of the polymers. DSC traces illustrate that PVPNB‐g?2^#GAP, PVPNB‐g?3^#GAP, and PVPNB‐g?4^#GAP have two distinct glass‐transition temperatures, whereas PVPNB‐g?1^#GAP has one. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) are used to evaluate the thermal decomposition behavior of the four polymers and their compatibility with the main energetic components of TNT‐based melt‐cast explosives, such as cyclotetramethylene tetranitramine (HMX), cyclotrimethylene‐trinitramine (RDX), triaminotrinitrobenzene (TATB), and 2,4,6‐trinitrotoluene (TNT). The DTA and TGA curves obtained indicate that the polymers have excellent resistance to thermal decomposition up to 200°C. PVPNB‐g?4^#GAP also exhibits good compatibility and could be safely used with TNT, HMX, and TATB but not with RDX. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42126.