Synthesis,characterization, and application of a hydrolytically stable liquid phosphite

Organic alkyl and aryl phosphites are effective antioxidants and photostabilizers with applications in a wide range of polymers. The primary role of phosphites is to decompose hydroperoxide. However, aryl phosphites are also capable of reacting as antioxidants by negatively affecting the kinetics. In particular, liquid phosphites have a greater effect on polymer degradation because of their high compatibility, reactivity, and solubility with almost all polymers, but they are sensitive to hydrolysis. In order to overcome this hydrolytic sensitivity in liquid phosphites, a novel hydrolytically stable liquid phosphite incorporating a sterically hindered aromatic alcohol (2,4‐di‐tert‐butyl‐6‐methylphenol) that gives hydrolytic stability to the phosphite was synthesized and characterized, and its performance as an antioxidant for polypropylene was investigated. J. VINYL ADDIT. TECHNOL., 22:163–168, 2016. © 2014 Society of Plastics Engineers     

Synthesis,characterization, and application of oligomer‐type‐based phosphites

Organic alkyl and aryl phosphites are effective antioxidants and photostabilizers with applications in a wide range of polymers. The primary role of phosphites is to decompose hydroperoxide. However, aryl phosphites are also capable of reacting as antioxidants by affecting the kinetics. In particular, oligomer‐type phosphites have a greater effect on polymer degradation because of their high compatibility, reactivity, and solubility with almost all polymers. Generally, phosphites are sensitive to hydrolysis. In order to overcome this hydrolytic sensitivity in phosphites, a novel hydrolytically stable oligomeric phosphite incorporating a sterically hindered aromatic alcohol (2,4‐di‐tert‐butyl‐6‐methylphenol) that gives hydrolytic stability to the phosphite was synthesized and characterized, and its performance as an antioxidant for polypropylene was investigated. J. VINYL ADDIT. TECHNOL., 22:146–155, 2016. © 2014 Society of Plastics Engineers     

Effects of phenolic antioxidants on ultrahigh molecular weight polyethylene/decalin solution

The degradation of ultrahigh molecular weight polyethylene (UHMW‐PE) during its dissolution into decalin is discussed. The stabilization of the solution by three phenolic antioxidants, octadecyl β‐(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl)propionate (1076), tetrakis[methylene‐β‐(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl)propionate]methane (1010), and 1,1,3‐tris(2‐methyl‐4‐hydroxy‐5‐tert‐butylphenyl)butane (CA), and an auxiliary antioxidant, dilaurylthiodipropionate (DLTP) is also discussed. Among the three phenolic antioxidants, 1076 had the greatest effect. The auxiliary antioxidant was effective in stabilizing the solution when combined with one of the three phenolic antioxidants. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2877–2881, 2000     

Synthesis of (3‐tert‐butyl‐4‐hydroxy‐5‐methylphenyl) propionate derivatives and their thermal antioxidation behavior for POM

Polyoxymethylene (POM) has been widely utilized in industry due to its light weight properties in engineering plastics. At present, POM applications are expanding into the car industry, especially in fuel tanks. Hindered alkyl phenol derivatives have been used as antioxidants for POM; however, these compounds are easily extracted by solvents. Two antioxidants with new structures (N,N′‐triethylenedioxy‐bis(3‐tert‐butyl‐4‐hydroxy‐5‐methylhydrocinnamamide) and N,N′,N′‐tris[(3‐tert‐butyl‐4‐hydroxy‐5‐methylphenyl)propionyl‐3‐oxapentyl]melamine) were synthesized and characterized, and their performance as antioxidants for POM was investigated in the present study. The results revealed that N,N′‐triethylenedioxy‐bis(3‐tert‐butyl‐4‐hydroxy‐5‐methylhydrocinnamamide) has good heat aging resistance compared to existing antioxidants for POM, and N,N′,N′‐tris[(3‐tert‐butyl‐4‐hydroxy‐5‐methylphenyl)propionyl‐3‐oxa‐pentyl]melamine has good extraction resistance against solvents. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Analysis of the phase partitioning of additives in rubber‐modified plastics

The phase partitioning of additives in polymer blends has a large impact on the performance of the blend. Therefore, it is necessary to be able to quantify the level of the additives in each phase. A ¹H–NMR method is presented to determine the partitioning of additives between the rubber and rigid phases of a high‐impact polystyrene (HIPS) material. In one case, a HIPS material was modified with 2,6‐di‐tert‐butyl‐4‐methyl‐phenol (Ionol, CAS# 128‐37‐OMF) as a stabilizer for both phases. HIPS materials with varying levels of Ionol were melt‐blended by extrusion and the total level of additives was determined analytically for these standard materials. The ¹H–NMR method was used to determine the level of Ionol in the poly(butadiene) rubber phase. The Ionol was found to preferentially partition into the rubber phase with a partition coefficient of about 2. A second example of the same concept, instead utilizing ¹³C–NMR, involved the analysis of the partition coefficient for both Tinuvin P and Tinuvin 770 (CAS# 2440‐22‐4 and 52829‐07‐9), partitioning between the rigid and rubber phases of an ethylene–propylene–diene‐modified (EPDM) toughened styrene–ran–acrylonitrile (SAN) copolymer. The partition coefficient was determined to be 0.5 for Tinuvin P and 1.3 for Tinuvin 770. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1963–1970, 2001     

Photodegradation and stabilization of styrene–butadiene–styrene rubber

Photooxidative degradation and stabilization of a polystyrene–block–polybutadiene–block–polystyrene thermoplastic elastomer using a polychromatic UV light in air at 60°C has been studied by monitoring the appearance of the hydroxyl and carbonyl groups in Fourier transform infrared spectroscopy. The extent of photooxidative degradation in different samples has been compared. The rate of photooxidation was also estimated in the presence of different concentrations of 2,6‐di‐tert‐butyl‐4‐methylphenol [BHT], 2‐(2′‐hydroxy‐5′‐methylphenyl)benzotriazole [Tinuvin P] and tris(nonylphenyl) phosphite [Irgafos TNPP], and 1,2,2,6,6‐pentamethyl piperidinyl‐4‐acrylate was grafted onto the surface of the SBS film. The kinetic evolution of the oxidative reaction was determined. The morphological changes upon irradiation in the solution cast SBS films were studied by scanning electron microscopy. Based on the experimental data a suitable photooxidative degradation mechanism also has been proposed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1097–1102, 2000     

Melt free‐radical grafting of maleimides with hindered phenol groups onto polyethylene

A monomeric antioxidant, bearing carbamate groups, was synthesized from the reaction of 3,5‐di‐tert‐butyl‐4‐hydroxybenzyl alcohol and azidomaleimide. Another antioxidant was prepared from the reaction of N‐(4‐hydroxyphenyl)maleimide and 3‐(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl) propionic chloride in the presence of triethylamine. These fictional antioxidants were grafted onto polyethylene (PE) via melt processing with free‐radical initiators in a minimax molder. The IR spectra of the grafted PE showed that the monomeric antioxidants were added to PE. IR spectroscopy methods were used for the quantitative determination of the extent of grafting of the monomeric antioxidants. Also, the extent of crosslinking was determined from the gel content. To optimize the reaction conditions, we investigated the effects of the initiator concentration, monomeric antioxidant, reaction time, and temperature on the extent of grafting. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2117–2122, 2004     

Synthesis and thermal decomposition of poly(dodecamethylene terephthalamide)

A kind of semiaromatic polyamide, poly(dodecamethylene terephthalamide) (PA12T) was synthesized via a polycondensation reaction of terephthalic acid and 1,12‐dodecanediamine. The structure of prepared PA12T was characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance (¹H‐NMR), and elemental analysis. The mechanical properties of PA12T were also studied. The thermal behavior of PA12T was determined by differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis. Pyrolysis products and thermal decomposition mechanism of PA12T were analyzed by pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS). Melting temperature (T_m), glass transition temperature (T_g), and decomposition temperature (T_d) of PA12T are 310°C, 144°C, and 429°C, respectively. The Py‐GC/MS results showed that the pyrolysis products were mainly composed of 32 kinds of compounds, such as benzonitrile, 1,4‐benzenedicarbonitrile, N‐methylbenzamide, N‐hexylbenzamide, and aromatic compounds. The major pyrolysis mechanisms were β‐CH hydrogen transfer process, main‐chain random scission, and hydrolytic decomposition. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Functionalization of high‐density polyethylene in the molten state by glycidyl methacrylate grafting

:This study concerns the melt‐free radical grafting of glycidyl methacrylate (GMA) onto high‐density polyethylene (HDPE). We studied the effect of two initiators (tert‐butyl cumyl peroxide and di‐tert‐butyl peroxide) onto HDPE. Crosslinking of polymer was observed in the presence of 0.3 wt % tert‐butyl cumyl peroxide but not with 0.3 wt % di‐tert‐butyl peroxide. The grafting was carried out in a Brabender batch mixer at 190 °C. The grafting yield of GMA onto HDPE (determined by infrared spectrometry) is weak (<1 wt % for an initial concentration in monomer of 6 wt %). Moreover, it was noted that the degree of grafting did not vary with the concentration and the nature of peroxide used. To increase the grafting yield of GMA, we added to the HDPE/peroxide/GMA system an electron‐donating monomer, such as styrene. Adding this comonomer multiplied the rate of grafted GMA 3‐ or 4‐fold, resulting in a ratio [styrene]_i/[GMA]_i = 1 mol/mol with [GMA]_i = 6 wt %. So, the copolymerization is favored compared with the homopolymerization. This kind of copolymer presenting reactive functions is very attractive in the field of compatibilizing immiscible polymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 581–590, 2001     

Poly(silyl ester)s: A new route of synthesis via the condensation of Di‐tert‐butyl ester of dicarboxylic acid with dichlorosilane

Poly(silyl ester)s were synthesized by a new route via the condensation of di‐tert‐butyl ester of dicarboxylic acid with dichlorosilane by the elimination of tert‐butyl chloride as a driving force. Three new poly(silyl ester)s with molecular weights typically ranging from 2000 to 5000 amu were produced by the condensation of di‐tert‐butyl adipate with 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl trisiloxane and di‐tert‐butyl fumarate with 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl trisiloxane or 1,3‐dichlorotetramethyl disiloxane. Each polymer was characterized with infrared, ¹H‐NMR, and ¹³C‐NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis. This new approach showed several advantages. First, it did not require a catalyst or solvent. Second, the tert‐butyl chloride byproduct was volatile and was easily eliminated. Third, there was no reaction between the growing poly(silyl ester)s and the condensation byproduct, tert‐butyl chloride. Fourth, the monomers could be readily purified. Finally, the polymerization could be performed at relatively low temperatures and in a short time. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1378–1384, 2006     

Synthesis,characterization, and optoelectronic properties of two new polyfluorenes/poly(p‐phenylenevinylene)s copolymers

Two novel copolymers of polyfluorenes/poly(p‐phenylenevinylene)s copolymers with p‐tert‐butyl‐phenylenemethylene groups in the C‐9 position of alternating fluorene unit, poly[1,4‐(2,5‐dibutyloxyl)‐phenyleneviny lene‐alt‐9‐(p‐tert‐butyl‐phenylenemethylene)fluorene] and poly[1,4‐(2,5‐dioctyloxyl)‐phenylenevinylene‐alt‐9‐(p‐tert‐butyl‐phenylenemethylene)fluorine], have been synthesized via the Heck polycondensation reaction. The synthesized polymers were characterized by FTIR, NMR, DSC, TGA, UV–vis, and PL spectra. The polymers showed high glass transition temperatures and good thermal stability. A polymer light‐emitting diode with the configuration ITO/PEDOT:PSS/P2/Ca/Al has been fabricated. The device emitted a yellow light with a peak wavelength of 578 nm similar to the PL spectra of the copolymer film. A maximal luminance of 534 cd/m² was obtained at a driving voltage of 24.5 V. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3955–3962, 2006     

Grafted stock synthesis of ABS at the ultimate high ratio of polybutadiene to poly(styrene‐co‐acrylonitrile)

This study describes the emulsion grafting of styrene and acrylonitrile onto 60–70% polybutadiene (PB), in the presence or absence of tert‐dodecanetiol as a chain transfer reagent with a radical initiator, and the properties of the obtained grafted stock. There was no significant difference in terms of effect of the initiation mode on the grafting efficiency resulting from the high grafting reactivity of PB. However, the grafted stock with 70% PB prepared in the presence of tert‐dodecanetiol and the adequate selection of an initiation system gave a homogeneous dispersion of the PB particles into poly(styrene‐co‐acrylonitrile) (SAN) matrix. The initiation system involves tert‐butyl peroxylaurate, tert‐butyl peroxyacetate, and tert‐butyl peroxyisopropylcarbonate coupled with ferrous sulfate. The efficient coverage of the SAN grafted layer around 70% PB particles was observed by TEM to eventually give excellent impact resistance, high surface gloss, and good thermal resistance. The absence of tert‐dodecanetiol resulted in a toughness reduction of ABS. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3462–3470, 2001     

Electron beam sterilization of cyclo olefin polymer leads to polymer degradation and production of alkyl radicals

We investigated the effects of electron‐beam (EB) sterilization on syringe barrels manufactured from cyclo olefin polymer (COP). The chemical structure of the polymer was determined by interpreting the ¹³C NMR and DEPT‐135 spectra of the COP resin. The antioxidants in the resin were identified by analyzing the liquid chromatography‐photo diode array‐mass spectrometry (LC‐PDA‐MS) data for the methanol extract of the resin and the gas chromatography‐mass spectrometry (GC‐MS) data for the supercritical methanol degradation products of the extract. NMR and LC‐PDA‐MS analyses revealed that EB sterilization produces degradation products in the COP main chain and reduces the quantity of the antioxidants in the COP resin. ESR spectra of the EB‐sterilized syringe barrels indicated the presence and location of alkyl radicals, which were generated in the COP main chain by EB sterilization. ESR analyses also indicated that the quantity of alkyl radicals decreased over time. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43498.     

Thermal degradation of liquid polysulfide polymers: Pyrolysis–GC–MS and thermogravimetric studies

The thermal decomposition of Thioped, a liquid polysulfide polymer based on dichloroethyl formal, was studied using pyrolysis–GC–MS. The nature and composition of the products of pyrolysis at 358 and 485°C are given. A striking feature of the product analysis is the presence of several disulfide compounds only at the higher decomposition temperature. The pyrolysis-GC of other liquid polysulfide polymers (LP-2, LP-32, LP-3, and LP-33) showed that molecular weight had only marginal effect on the product composition. Ionic and radical mechanisms were considered to account for the product formation. Isothermal and dynamic thermogravimetric studies were carried out to differentiate between the two mechanisms. The results were found to be in agreement with a free radical mechanism, with cleavage of the formal C? O linkage as the preferred mode of initiation. The overall activation energy for the decomposition was found to be 190 kJ mol^?1.     

ZnS as fire retardant in plasticised PVC

The flame retardant effect of zinc sulphide (ZnS) in plasticised poly(vinyl chloride) (PVC‐P) materials was investigated. PVC‐P containing different combinations of additives such as 5% ZnS, 5% of antimony oxide (Sb₂O₃) and 5% of mixtures based on Sb₂O₃ and ZnS were compared. The thermal degradation and the combustion behaviour were studied using thermogravimetry (TG), coupled with FTIR (TG–FTIR) or with mass spectroscopy (TG–MS), and a cone calorimeter, respectively. A detailed and unambiguous understanding of the decomposition and release of the pyrolysis products was obtained using both TG–MS and TG–FTIR. The influence of ZnS, Sb₂O₃ and the corresponding mixtures on the thermal decomposition of PVC‐P was demonstrated. Synergism was observed for the combination of the two additives. The combustion behaviour (time to ignition, heat release, smoke production, mass loss, CO production) was monitored versus external heat fluxes between 30 and 75 kW m^?2 with the cone calorimeter. Adding 5% of ZnS has no significant influence on the fire behaviour of PVC‐P materials beyond a dilution effect, whereas Sb₂O₃ works as an effective fire retardant. Synergism of ZnS and Sb₂O₃ allows the possibility of replacing half of Sb₂O₃ by ZnS to reach equivalent fire retardancy. © 2002 Society of Chemical Industry     

Applied analysis and identification of ancient lacquer based on pyrolysis‐gas chromatography/mass spectrometry

Three lacquer samples taken from a “four‐eared” pottery container, which was designated an important National Cultural Property of Japan excavated in 16–17th century ruins of Kyoto City, were analyzed by pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS) and infrared (IR) spectroscopy to determine the source of the lacquer. It is an unexpected result that the lacquer in this pottery container is actually used by Melanorrhoea usitata. Alkylbenzene and alkenylbenzene as cleavage pieces of undecylbenzene (MW = 232 g/mol) and undecenylbenzene (MW = 230 g/mol), which are products of the pyrolysis of thitsiol, were detected in all three samples. Moreover, ω‐phenylalkylcatechols and ω‐phenylalkylphenols, which are the specific components of M. usitata, were also detected by Py‐GC/MS, suggesting that lacquer sap of M. usitata was used by the Japanese people in the 16–17th centuries. In addition, Japanese lacquer culture and the advantages of the Py‐GC/MS method for lacquer analysis are discussed in detail. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Radical-Initiated Reaction of Methyl Linoleate with Dialkyl Phosphites

The addition of dialkyl phosphite (methyl, ethyl and n‐butyl) to methyl linoleate (MeLin) double bonds was investigated. The reaction proved to be more challenging than the analogous reaction with methyl oleate (MeOl), due to inhibition of the radical reaction by the bis‐allylic hydrogens of MeLin and the lower reactivity of MeLin double bonds. However, we demonstrated that this self‐inhibition problem can be solved by simply keeping the MeLin reagent at low concentrations, while keeping the dialkyl phosphite at high concentrations. For optimization of the reaction, four different radical initiators were investigated: dilauroyl peroxide (LP), 2,2′‐azobis(2‐methylpropionitrile) (AIBN), tert‐butyl perbenzoate (t‐BP), and tert‐butyl peroxide (TOOT). The initiators were used at temperatures that provided a half‐life of 10 h: 64, 64, 104, and 125 °C respectively for LP, AIBN, t‐BP, and TOOT. The tests showed the reaction to be faster at higher temperatures, but transesterification of the ester groups was also observed at elevated temperatures. t‐BP was chosen as an optimal initiator for carrying the reaction. The apparent order of reactivity of the dimethyl, diethyl and di‐n‐butyl phosphites (Me >Et >n‐Bu) towards MeLin was due to differences in their molar volumes. When the concentrations of dialkyl phosphite were kept the same, the order reversed (n‐Bu > Et~Me). GC–MS spectra of the resulting phosphonates are reported and the main fragments assigned.     

PY‐GC/MS an effective technique to characterizing of degradation mechanism of poly (L‐lactide) in the different environment

The biotic and abiotic degradation of poly (L‐lactide) (PLLA) has been studied with pyrolysis gas chromatography mass spectrometry (Py‐GC‐MS). A mixed culture of compost micro‐organisms was used as the biotic medium. Size‐exclusion chromatography (SEC), gas chromatography‐mass spectrometry (GC‐MS), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) were utilized to monitor the degradation and degradation mechanism. Differences in pH, molecular weight, surface structure, and degradation mechanisms were noted between sample aged in biotic and abiotic medium. Using fractionated Py‐GC‐MS at 400 and 500°C, acetaldehyde, acrylic acid, lactoyl acrylic acid, two lactide isomers, and cyclic oligomers up to the pentamer were identified as thermal decomposition products of PLA as well as some other not completely identified products. The ratio of meso‐lactide to L‐lactide was lower in the sample aged in the biotic media than the abiotic media. This is a result of the preference of the micro‐organisms for L‐form of lactic acid and lactoyl lactic acid rather than the D‐form that in turn influences the formation and the amounts of meso and D,L‐lactide during the pyrolysis. Based on SEM micrographs, it was shown that degradation in the biotic medium proceeded mainly via a surface erosion mechanism, whereas bulk erosion was the predominant degradation mechanism in the abiotic medium. The SEC and Py‐GC‐MS data indicate that degradation was faster in the biotic than in the abiotic sample. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2369–2378, 2000     

Loss and transformation products of the aromatic antioxidants in MDPE film under long‐term exposure to biotic and abiotic conditions

The loss of a primary phenolic antioxidant Irganox 1010 and of a secondary phosphite antioxidant Irgafos 168 from a medium density polyethylene film (MDPE) was investigated after exposure of the film for 4 years to different environments such as aqueous media at pH5 and 7, open air, and compost, with an exposure of exposition of 25°C. An ultrasonic extraction technique using chloroform as extraction solvent was applied to recover the residual antioxidants from the polymeric matrix, and this was followed by High‐Performance Liquid Chromatography (HPLC) with acetonitrile as mobile phase and a quantitative analysis at a wavelength of 280 nm of the extracted antioxidants. The amount of antioxidant lost varied remarkably depending on the testing medium. The fastest loss of antioxidant was found on exposure to open air and sunlight while the slowest loss was observed in compost. Thermo‐analytical measurements were made to characterize the residual thermo‐oxidative stability of MDPE film in terms of oxidation temperature and oxidation induction time, to provide a greater insight into the underlying mechanisms of ageing in the different environments. Analysis by Gas chromatography–Mass Spectrometry (GC‐MS) revealed that degradation of the polymeric matrix resulted in the formation of hydrocarbons and oxygen‐containing compounds such as alcohols, carboxylic acids, aldehydes, and esters. The transformation products of the antioxidants formed as result of processing or exposure to the tested media were also identified. The transformation of the phenoxy radical of the Irganox 1010 produced the ester, acid, dealkylated cinnamate, and quinone products, whereas Irgafos 168 yielded oxidation products and the phenolic hydrolysis byproduct 2,4‐di‐tert‐butylphenol. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 974–988, 2002     

A methacrylate monomer bearing nitro,aryl, and hydroxyl side groups: Homopolymerization,characterization, dielectric,and thermal degradation behaviors

2‐Hydroxy‐3‐(4‐nitrophenoxy)propyl methacrylate (HNPPMA) monomer was synthesized. The poly(HNPPMA) was prepared by free radical polymerization (FRP) method. The characterization of poly(HNPPMA) was carried out using FT‐IR, NMR, differential scanning calorimetry, and GPC techniques. The thermal stability and degradation behavior of this polymer have been studied by using thermogravimetry (TG), GC‐MS, NMR, and FT‐IR. The results were in comparison to poly[2‐hydroxy‐3‐(1‐naphtyloxy)propyl methacrylate] sample with α‐naphtyloxy side group prepared by the same method in the our previous study. The effect of thermal activation on non‐isothermal decomposition kinetics of poly(HNPPMA) was investigated using thermogravimetric analysis according to Flynn‐Wall‐Ozawa method. The dielectric measurements of poly(HNPPMA) and doped with europium(III)chloride (EuCI₃) were investigated by impedance analyzer technique in range of 10–4000 Hz frequency by depending on the alternating current conductivities. The mode of thermal degradation including formation of the main products of poly(HNPPMA) degraded from ambient temperature to 500 °C was identified. S°, the cold ring fraction (CRF) was collected from room temperature to 500 °C. The structure of the degradation products has also been studied depending on the GC‐MS analysis. The thermal degradation mechanism for poly(HNPPMA) with radical degradation processes thought to dominate at high temperature was proposed based on GC/MS, NMR, FT‐IR, and taking into account the new products and differences in stability. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43925.