Synthesis and characterization of emulsion copolymer of N‐cyclohexylmaleimide and methyl methacrylate

Copolymers of N‐cyclohexylmaleimide (ChMI) and methyl methacrylate (MMA) were synthesized by the emulsion semibatch copolymerization method. The effects of the monomer mixture composition on the average molecular weight (M_n and M_w ), glass transition temperature (T_g), degradation temperature, mechanical properties, and rheological behavior of the copolymers were investigated. The results show that M_n and M_w have maximum values when the ChMI feed content was about 20% (by wt). The degradation temperature and T_g of the copolymers increase with increasing ChMI moieties in the copolymer. The mechanical properties (tensile strength and impact strength) decrease with an increasing ChMI feed content. All copolymers in the melt show pseudoplastic behavior. The flow index n increases with an increasing ChMI feed content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1070–1075, 2002; DOI 10.1002/app.10394     

Structure and properties of heat‐resistant ABS resins innovated by NSM random copolymer

N‐phenylmaleimide(NPMI)‐styrene(St)‐maleic anhydride (MAH) copolymer was synthesized in xylene solution by one‐step free radical copolymerization, using di‐tert‐butyl diperoxyterephthalate as initiator. The resulting heat‐resistant NPMI‐St‐MAH (NSM) copolymer was characterized by Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography, differential scanning calorimetry, elemental analysis, and nuclear magnetic resonance spectroscopy (¹H‐NMR and ¹³C‐NMR). The results show that NPMI‐St‐MAH exhibits a random sequence distribution with a NPMI: St: MAH weight ratio of 47:51:2. The glass transition temperature (T_g) is about 190.0°C. Blends of acrylonitrile‐butadiene‐styrene (ABS) with various contents of NSM were prepared using a twin‐screw extruder, and the effects of NSM content on the thermal and mechanical properties of ABS blends were investigated. It was found that the Vicat softening point, tensile strength, flexural strength, flexural modulus, and Rockwell hardness of the ABS/NSM blends were all significantly enhanced with increasing NSM content, whereas the impact strength shows the opposite trend. The impact fracture surface morphology was characterized by scanning electron microscope. It was revealed that cavitation and cavity coalescence resulted in the toughening of the material, which well accounts for the decrease of impact strength with increasing NSM content. In addition, the rheological properties of the blends were examined using a capillary rheometer. The blends present excellent processing property and are suitable for injection molding, although a pseudoplastic behavior was observed in all cases. POLYM. COMPOS., 34:920–928, 2013. © 2013 Society of Plastics Engineers     

Synthesis and characterization of degradable copoly(ester–amide)s: Poly(trans‐4‐hydroxy‐L‐proline‐co‐ε‐caprolactam)

Novel copolyesteramides were synthesized by reacting trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline (N‐CBz‐Hpr) with ε‐caprolactam (CLM) in the presence of stannous octoate [Sn(II) Oct.] as a catalyst. Various techniques, including ¹H‐NMR, IR, DSC, and viscosity, were used to elucidate structural characteristics and thermal properties of the resulting copolymers. Data showed that the optimal reaction condition for the synthesis of the copolymers was obtained by using 3 wt % Sn(II) Oct. at 170°C for 24 h. The DSC analysis demonstrated amorphous structure for most of the copolymers. The glass‐transition temperature of the copolymers shifts to a higher temperature with increasing Hpr/CLM molar ratio. In vitro degradation of these poly(N‐CBz‐Hpr‐co‐CLM)s was evaluated by weight loss measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1615–1621, 2002     

Preparation and characterization of styrene/styryl–polyhedral oligomeric silsesquioxane hybrid copolymers

BACKGROUND: Organic–inorganic nanocomposites were prepared by copolymerization of various monomers and polyhedral oligomeric silsesquioxane (POSS) derivatives. Preliminary results showed that styrene/styryl–POSS copolymers could be obtained using CpTiCl₃ catalyst. In the work reported here, the copolymerization of styrene and styryl‐substituted POSS was studied in detail for a more effective catalyst, Cp*TiCl₃. RESULTS: The glass transition temperature (T_g) of the copolymers prepared increased with increasing POSS content. The degradation temperature (T_d) of the copolymers was 60 °C higher than that of syndiotactic polystyrene under nitrogen. Although the thermal properties were improved by incorporation of POSS, the catalytic activity decreased with POSS content. The racemic triad and syndiotactic index of the copolymers decreased with increasing POSS content. Gel permeation chromatograms of the copolymers exhibited multimodal distribution due to the presence of multi‐active centres, which were formed by interaction of Ti with the POSS siloxane linkage. CONCLUSION: With the incorporation of POSS, the thermal properties of polystyrene were improved. The styrene/styryl–POSS copolymers are formed through the various active sites arising from the interactions of Ti with POSS. Copyright © 2008 Society of Chemical Industry     

Emulsion copolymerization of N-phenylmaleimide with styrene

Emulsion copolymerization of N-phenylmaleimide (PMI) with styrene (St) was conducted via semibatch and batch methods. The effect of monomer mixture composition and method of copolymerization on copolymer structure-property relationships was investigated. The semibatch copolymers have a homogeneous molecular structure, exhibiting a single T_g which increases linearly with increasing PMI content. The batch copolymers have a heterogeneous molecular structure, exhibiting two T_g's, assigned to the polystyrene (PSt) and poly(PMI-co-St) components. The composition drift in the batch-copolymerized product, at different conversion levels, was examined by DSC and FTIR techniques. In general, the inherent viscosity of the semibatch copolymers is lower than that of the corresponding batch ones. The Young's modulus increases for the semibatch copolymers, with increasing PMI content, while a clear trend for the batch copolymers is not found. The tensile strength tends to decrease for both types of copolymers when PMI content increases. The thermal stability increases with increasing PMI content in the copolymers. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of heat‐resistant N‐phenylmaleimide–styrene–maleic anhydride copolymers and application in acrylonitrile–butadiene–styrene resin

The heat‐resistant copolymer of N‐phenylmaleimide (NPMI)–styrene (St)–maleic anhydride (MAH) was synthesized in xylene at 125°C with di‐tert‐butyl diperoxyterephthalate as an initiator. The characteristics of the copolymer were analyzed by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy (¹H‐NMR and ¹³C‐NMR), gel permeation chromatography, and elemental analysis. The ¹³C‐NMR results show that the copolymer possessed random sequence distribution; this was also supported by the differential scanning calorimetry experiment, in which a single glass‐transition temperature (T_g) of 202.3°C was observed. The thermal stability and degradation mechanism of the copolymer were investigated by thermogravimetric analysis. Using the Kissinger equation and Ozawa equation, we proved a nucleation controlling mechanism with an apparent activation energy of 144 kJ/mol. Blends of acrylonitrile–butadiene–styrene with the NPMI–St–MAH copolymer with various contents were prepared with a twin‐screw extruder processes. The mechanical and thermal properties of the materials, such as the tensile and flexural strength, T_g's, and Vicat softening temperatures, were all enhanced with the addition of the modifier, whereas the melt flow index decreased. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal and gas permeation properties of copolymers derived from 3‐methacryloxypropyltris(trimethylsiloxy)silane and adamantyl group‐containing methacrylate derivatives

Novel copolymer membranes derived from three types of adamantyl group‐containing methacrylate derivatives and 3‐methacryloxypropyltris(trimethylsiloxy)silane (SiMA) were synthesized via free radical polymerization. The thermal and permeation properties of these copolymer membranes were investigated. Copolymer membranes with less than 11.9 mol % adamantane content exhibited good membrane forming abilities that are suitable for permeation measurement. The decomposition temperature of all copolymers increased up to approximately 40–80°C with increasing adamantane content compared with poly(SiMA). Moreover, the glass transition temperature (T_g) of all copolymers increased up to approximately 46–60°C with increasing adamantane content compared with the theoretical value, which was estimated from Fox equation. 1‐Adamantyl methacrylate copolymer had the highest fractional free volume among the three types of adamantly group‐containing methacrylate derivatives. The gas permeability coefficient of this copolymer increased by 22–45% with increasing adamantane content compared with that of poly(SiMA). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43129.     

Copolymerization of N‐(4‐carboxyphenyl) itaconimide or N‐(4‐carboxyphenyl) itaconamic acid with methyl methacrylate

This paper describes the synthesis and characterization of N‐(4‐carboxyphenyl) itaconamic acid (CPA) and N‐(4‐carboxyphenyl) itaconimide (CPI) obtained by reacting itaconic anhydride with p‐aminobenzoic acid. Structural and thermal characterization of CPA and CPI was done using ¹H‐NMR, FTIR, and differential scanning calorimetry (DSC). Copolymerization of CPA or CPI with methyl methacrylate (MMA) in solution was carried out at 60 °C using azobisisobutyronitrile as an initiator and dimethyl acetamide or THF as solvent. Feed compositions having varying mole fractions of CPA or CPI ranging from 0.05–0.20 or 0.1–0.5 were taken to prepare copolymers. Copolymerizations were terminated at low percentage conversion. Structural characterization of copolymers was done by ¹H‐NMR and elemental analysis. Copolymer composition was determined using percentage nitrogen content. The reactivity ratios were r₁ (MMA) = 0.68 ± 0.06 and r₂ (CPI) = 0.46 ± 0.06. The intrinsic viscosity [η] was determined using an Ubbelohde suspension level viscometer. [η] decreased with increasing mole fraction of N‐(p‐carboxyphenyl) itaconimide or N‐(p‐carboxyphenyl) itaconamic acid in copolymers. Glass transition temperature and thermal stability of the copolymers were determined using DSC and thermogravimetric analysis, respectively. The glass transition temperature (T_g) as determined from DSC scans increased with increasing amounts of CPA or CPI in copolymers. A significant improvement in the char yield was observed upon copolymerization. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1909–1915, 2005     

Preparation of heat‐resistant branched poly(styrene‐alt‐NPMI) by ATRP with divinylbenzene as the branching agent

Heat‐resistant branched poly(styrene‐alt‐NPMI) has been prepared via atom transfer radical polymerization (ATRP) of styrene (St) and N‐phenyl maleimide (NPMI) with divinylbenzene (DVB) as the branching agent in anisole at 80°C. Gas chromatography (GC) was used to determine the conversion of the reactants. Triple detection gel permeation chromatography (TD‐GPC) was used to analyze the copolymers. The results show that the polymerization yields primary chains predominately in the early stages and the formation of branched molecules occurs mainly when conversion is higher than 50%. As expected, higher dosage of DVB in our investigation range favors the formation of polymers with higher degree of branching. All the resulting branched poly(styrene‐alt‐NPMI)s have glass transition temperature (T_g) above 175°C, extrapolated initial weight loss temperature (T_i) above 410°C and statistic heat‐resistant index above 200°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal characterization and thermal degradation of copolyimides containing fluorine and phosphine oxide

A series of copolyimides containing different ratios of fluorine and phosphine oxide were synthesized. The copolymers were characterized with Fourier transform infrared, differential scanning calorimetry, and thermogravimetric analysis measurements. The copolymers were thermally stable up to 700 K and exhibited glass‐transition temperatures in the range of 495–562 K. The glass‐transition temperatures of the copolymers decreased with an increase in the phosphine oxide content. The thermal decomposition behavior of the copolymers was investigated. The copolymers with higher phosphine oxide contents displayed lower onset decomposition temperatures and char yields. A new method involving the multiple‐rate isotemperature was used to define the most possible mechanism [G(α)] for the reactions. The overall kinetic model function of the thermal decomposition of these copolymers obeyed the Avrami–Erofeev model equation, G(α) = [?ln(1 ? α)]^1/m, where α is the conversion degree. The apparent kinetic parameters of the degradation processes were also obtained. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2139–2143, 2005     

Synthesis and properties of gradient copolymers of butyl methacrylate and fluorinated acrylate via RAFT miniemulsion copolymerizations

A series of gradient fluorinated copolymers with a broad variation of the monomer units in the polymer chain were synthesized via semibatch CPDB‐mediated RAFT miniemulsion polymerization technique. In the presence of RAFT agent 2‐cyanoprop‐2‐yl dithiobenzoate (CPDB), the copolymerization of BMA and FMA in miniemulsion exhibited typical features of a controlled molecular weights and narrow polydispersities. The macromolecular structure and thermal behavior of the synthesized fluorinated copolymers were investigated in detail. The DSC analyses show that the gradient copolymers showed a unique thermal behavior with broad range of transition temperature. It was also confirmed that the fluorinated gradient copolymer exhibited obvious surface segregation structure and ultra‐low surface energy between 16.8 and 20.3 mN/m. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42936.     

Synthesis and characterization of poly(ethylene isophthalate‐co‐ethylene terephthalate) copolyesters

Poly(ethylene isophthalate‐co‐ethylene terephthalate) (PEIPET) copolymers of various compositions and molecular weights were synthesized by melt polycondensation and characterized in terms of chemical structure and thermal and rheological properties. At room temperature, all copolymers were amorphous and thermally stable up to about 400°C. The main effect of copolymerization was a monotonic increase of glass transition temperature (T_g) as the content of ethylene terephthalate units increased. The Fox equation accurately describes the T_g–composition data. The presence of ethylene terephthalate units was found to influence rheological behavior in the melt, with the Newtonian viscosity increasing as the content of ethylene terephthalate units increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 186–193, 2004     

Effects of the o‐aromatic ring in the molecular chain on the properties of polyester polyols

A series of liquid polyester polyols from adipic acid (AA), phthalic anhydride (PA), ethylene glycol, propanediol‐1,2, and trihydroxymethylpropane, varying in the molar ratio of PA to AA, were prepared. The effects of the o‐aromatic ring in the molecular chain, which came from PA, on the viscosity, glass‐transition temperature, and thermal degradation temperature of the polyester polyols were studied with viscometry, differential scanning calorimetry, and thermogravimetry. The intrinsic viscosity and glass‐transition temperature increased with the concentration of the o‐aromatic ring increasing. The temperature of the maximum thermal degradation rate for aliphatic polyester polyols was 434.20°C. Two steps of thermal degradation were found when there were o‐aromatic rings in the molecular chain. One thermal degradation temperature was 358.36–360.48°C, and the other was 412.85–427.18°C. Polyester polyols with o‐aromatic rings had higher stability at lower temperatures (<240.00°C). However, aliphatic polyester polyols had higher stability at higher temperatures (300.00–480.00°C). The activation energy and order of degradation were calculated from thermogravimetric curves. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1617–1624, 2002     

Nitroxide‐terminated poly(styrene‐co‐diethyl fumarates) and derived block copolymers

Copolymerization of styrene (S) and diethyl fumarate (DEF) at 125°C in the presence of 2,2,6,6‐ tetramethylpiperidin‐1‐yloxyl radical (TEMPO) and initiated with a thermal initiator, 2,2′‐azobisisobutyronitrile (AIBN), was studied. The molar fraction of DEF in the feed, F_DEF, varied within 0.1–0.9. An azeotropic composition, (F_DEF)_A = 0.38, was found for the copolymerization under study. At F_DEF = 0.1–0.4, a quasi‐living process was observed, transforming to a retarded conventional radical copolymerization at a higher content of DEF in the initial mixtures. The obtained TEMPO‐terminated S‐DEF copolymers were used to initiate polymerization of styrene. Poly(styrene‐ co‐diethyl fumarate)‐block‐polystyrene copolymers were prepared with molecular weight distributions depending on the amount of inactive polymer chains in macroinitiators, as indicated by size‐exclusion chromatography. A limited miscibility of the blocks in the synthesized block copolymers was revealed by using differential scanning calorimetry. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2432–2439, 2002     

Synthesis and characterization of poly(ethylene terephthalate‐co‐isophthalate)s with low content of isophthalate units

The objective of this work was to study the effect of the introduction of low amounts of isophthalate units on the mechanical properties, crystallization rates, and thermal parameters of poly(ethylene terephthalate). For this reason a series of five random poly(ethylene terephthalate‐co‐isophthalate) copolymers, containing 0.5, 1, 1.5, 2, and 4 mol % isophthalic acid, were prepared by the melt polycondensation process. The intrinsic viscosity of copolymers ranged between 0.7 and 0.8 dL/g. The increase of isophthalate content resulted in a significant decrease of the crystallization rates, but in a small decline of tensile strength, Young's modulus, and elongation at break, whereas tensile strength at yield point remained almost unaffected. Also, a decrease in the melting point was recorded, whereas the glass‐transition temperature was only very slightly affected. The higher decrease for the aforementioned parameters was noted for the copolymer with 4 mol % isophthalate units content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1931–1941, 2002     

Synthesis and characterization of degradable triarm low unsaturated poly(propylene oxide)‐block‐polylactide copolymers

A series of novel degradable triarm poly(propylene oxide)‐block‐polylactide (PPO‐b‐PLA) copolymers was synthesized by ring‐opening polymerization of L ‐lactide (LLA) or D ,L ‐lactide (DLLA) using low unsaturated PPO triols as macromolecular initiator. The chemical structures of the resulting copolymers were characterized by Fourier transform infrared (FTIR), gel permeation chromatography (GPC), and proton nuclear magnetic resonance (¹H‐NMR) spectroscopy. Combination of FTIR, GPC, and NMR results confirmed the formation of PPO‐b‐PLA copolymers. One glass transition was observed by differential scanning calorimetry (DSC), suggesting good miscibility between PPO and PLA segments in the copolymers. DSC and wide‐angle X‐ray diffraction demonstrated that PPO‐b‐PLLA copolymers were semicrystalline materials, and the crystallinity increased with increasing the PLLA content. In contrast, PPO‐b‐PDLLA copolymers were totally amorphous. The PPO‐b‐PLA copolymers exhibited improved thermal stability when compared with PPO polyols according to thermogravimetric analysis. The thermal degradation behavior of the copolymers depended on the composition. Polyurethane foams were prepared by crosslinking PPO and PPO‐b‐PLA copolymers using isocyanate. Alkaline degradation of the foams was investigated in 10 wt/vol % NaOH at 80°C. The results show that the novel PPO‐b‐PLA copolymers could be promising as degradable polymeric materials. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Copolymerization of N‐aryl substituted itaconimide with methyl methacrylate: Effect of substituents on monomer reactivity ratio and thermal behavior

The article describes the synthesis and characterization of N‐(4‐methoxy‐3‐chlorophenyl) itaconimide (MCPI) and N‐(2‐methoxy‐5‐chlorophenyl) itaconimide (OMCPI) obtained by reacting itaconic anhydride with 4‐methoxy‐3‐chloroanisidine and 2‐methoxy‐5‐chloroanisidine, respectively. Structural and thermal characterization of MCPI and OMCPI monomers was done by using ¹H NMR, FTIR, and differential scanning calorimetry (DSC). Copolymerization of MCPI or OMCPI with methyl methacrylate (MMA) in solution was carried out at 60°C using AIBN as an initiator and THF as solvent. Feed compositions having varying mole fractions of MCPI and OMCPI ranging from 0.1 to 0.5 were taken to prepare copolymers. Copolymerizations were terminated at low percentage conversion. Structural characterization of copolymers was done by FTIR, ¹H NMR, and elemental analysis and percent nitrogen content was used to calculate the copolymer composition. The monomer reactivity ratios for MMA–MCPI copolymers were found to be r₁ (MMA) = 0.32 ± 0.03 and r₂ (MCPI) = 1.54 ± 0.05 and that for MMA–OMCPI copolymers were r₁ (MMA) = 0.15 ± 0.02 and r₂ (OMCPI) = 1.23 ± 0.18. The intrinsic viscosity [η] of the copolymers decreased with increasing mole fraction of MCPI/or OMCPI. The glass transition temperature as determined from DSC scans was found to increase with increasing amounts of OMPCI in copolymers. A significant improvement in the char yield as determined by thermogravimetry was observed upon copolymerization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2391–2398, 2006     

Thermal characteristics of IPNs composed of polyallylamine and chitosan

Interpenetrating polymer network (IPN) hydrogels composed of polyallylamine and chitosan were synthesized by radical polymerization using 2,2‐dimethyl‐2‐ phenylacetophenone (DMPAP) and methylene bisacrylicamide (MBAAm) as initiator and crosslinker, respectively. The IPNs thus obtained were characterized by using Fourier transform infrared (FT‐IR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). The melting temperatures of IPNs were observed with increasing chitosan content by DSC. DEA was employed to ascertain the glass transition temperature (T_g) of IPNs. From the result of DEA, IPNs exhibited two T_gs indicating the presence of phase separation in the IPN. The thermal decomposition of IPNs was investigated by TGA and appeared at near 270 °C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1956–1960, 2002     

Thermal characteristics of poly(vinyl alcohol) and poly(vinylpyrrolidone) IPNs

Interpenetrating polymer network (IPN) hydrogels based on poly(vinyl alcohol) (PVA) and 1‐vinyl‐2‐pyrrolidone (VP) were prepared by radical polymerization using 2,2‐dimethyl‐2‐phenylacetophenone (DMPAP) and methylene bisacrylicamide (MBAAm) as initiator and crosslinker, respectively. The thermal characterization of the IPNs was investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). Depressions of the melting temperatures of PVA segments in IPNs were observed with increasing VP content via the DSC. The DEA was employed to ascertain the glass transition temperature (T_g) of IPNs. From the result of DEA, IPNs exhibited two T_gs indicating the presence of phase separation in the IPN. The thermal decomposition of IPNs was investigated using TGA and appeared at near 270°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1844–1847, 2002