Polystyrene latices containing dodecanamide‐modified poly(propyleneimine) dendrimers

Polymerization of styrene in aqueous dispersions of the dodecanamide derivative of poly(propyleneimine) dendrimer DAB‐dendr‐(NH₂)₆₄ and sodium dodecyl sulfate (SDS) produced stable latices. With initial SDS concentrations of 10 mM or less, molar ratios of SDS to dendrimer end groups ranging from 2.3:1 to 9.5:1, and less than 10 wt % of SDS relative to styrene, the polystyrene latices had diameters of 30–60 nm and coefficients of variation of diameters of less than 10% when measured by transmission electron microscopy. Higher concentrations of SDS gave more polydisperse latices. The polystyrene latices formed with SDS and the dodecanamide‐modified dendrimer were almost the same size and polydispersity as those formed with SDS and the parent primary amine dendrimer DAB‐dendr‐(NH₂)₆₄. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 597–605, 2003     

Branched poly(styrene‐b‐tert‐butyl acrylate) and poly(styrene‐b‐acrylic acid) by ATRP from a dendritic poly(propylene imine)(NH2)64 core

With the aim of creating highly branched amphiphilic block copolymers, the primary amine end groups of the poly(propylene imine) dendrimers DAB‐dendr‐(NH₂)₈ and DAB‐dendr‐(NH₂)₆₄ were converted to 2‐bromoisobutyramide groups. Poly (styrene‐b‐tert‐butyl methacrylate) (PS‐b‐PtBMA) was synthesized by ATRP from the eight end group initiator, and poly(styrene‐b‐tert‐butyl acrylate) (PS‐b‐PtBA) was synthesized from the 64 end group initiator. The tert‐butyl groups were removed to produce poly(styrene‐b‐methacrylic acid) (PS‐b‐PMAA) and poly(styrene‐b‐acrylic acid) (PS‐b‐PAA). Comparison of size exclusion chromatography (SEC) absolute molecular weight analyses of the polystyrenes with calculated molecular weights showed that the eight end group initiator produced a polystyrene with about eight branches, and that the 64 end group initiator produced polystyrene with many fewer than 64 branches. The PS‐b‐PtBA materials also have many fewer than 64 branches. The PS‐b‐PAA samples dissolved molecularly in DMF but formed aggregates in water even at pH 10. AFM images of the PS‐b‐PtBAs spin coated from THF and DMF onto mica showed aggregates. AFM images of the PS‐b‐PAAs spin coated from various mixtures of DMF and water at pH 10 showed flat disks and worm‐like images similar to those observed with linear PS‐b‐PAAs. Use of a PS‐b‐PAA and a PS‐b‐PMAA as templates for emulsion polymerization of styrene produced latexes 100–200 nm in diameter. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4623–4634, 2007     

Blends of fatty‐acid‐modified dendrimers with polyolefins

Blends were made by solution and melt‐mixing fatty‐acid‐modified dendrimers with various polyolefins. Small‐angle neutron scattering (SANS) was used to determine the miscibility of the blends. Poly(propylene imine) (PPI) dendrimers G1, G3, and G5 [DAB‐dendr‐(NH₂)_y] with y = 4, 16, and 64, were reacted with stearic acid or stearic acid‐d₃₅ forming amide bonds. The modified dendrimers were then blended with high‐density polyethylene (HDPE), high‐density polyethylene‐d₄ (HDPE‐d₄), low‐density polyethylene (LDPE), amorphous polypropylene (PP), or an ethylene–butylene copolymer (E‐co‐B). Limiting power law behavior shows that all of the blends are immiscible. It is likely that the dendrimers form a second phase, being finely dispersed, but thermodynamically immiscible. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 95–100, 2000     

Study on the preparation and the self‐assembly of poly(propyleneimine)–poly(styrene) nanoparticles

Using 2‐chloropropionamide derivative of poly(propyleneimine) dendrimer DAB‐dendr‐(NH₂)₃₂ (DAB‐32‐Cl) as the macroinitiator, atom transfer radical polymerization of styrene was successfully carried out in DMF medium. The monodisperse poly(propyleneimine)–polystyrene (dendrimer–PSt) particles with diameters smaller than 100 nm could be prepared. The morphology, size, and size distribution of the dendrimer–PSt particles were characterized by transmission electron microscopy (TEM) and photon correlation spectroscopy (PCS). The effects of reaction temperature, the ratio of St/macroinitiator, and reaction time on the size, and size distribution of the dendrimer–PSt nanoparticles were investigated. In a selective solvent (DMF/H₂O), polymers can self‐assemble into different aggregate configurations such as regular microsphere and wire‐like thread. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2658–2666, 2008     

Polyelectrolyte behavior and interpolyelectrolyte matching of AstramolTM poly(propylene imine) dendrimers

Polyelectrolyte behavior of Astramol^TM poly(propylene imine) dendrimers of five generations, G1‐G5, namely DAB‐dendr‐(NH₂)_x (where x is equal to 4, 8, 16, 32 or 64) was studied by means of potentiometric titration in salt‐free water solutions and also in the presence of a shielding low molecular electrolyte (NaCI). In addition to x outer primary amine groups the dendrimer molecule contains x‐2 inner tertiary amine groups. The repeating unit, the core molecule and the fifth generation dendrimer structure are shown in the following Scheme.     

Preparation of monodisperse nanoparticles containing poly(propylene imine)(NH2)32‐polystyrene

Polypropylenimine dendrimer (DAB‐Am‐32, generation 4.0) was converted into a macroinitiator DAB‐Am‐32‐Cl via reaction with 2‐chloropropionyl chloride. Monodisperse nanoparticles containing poly(propylene imine)(NH₂)₃₂‐polystyrene were prepared by emulsion atom transfer radical polymerization (ATRP) of styrene (St), using the DAB‐Am‐32‐Cl/CuCl/bpy as initiating system. The structure of macroinitiator was characterized by FTIR spectrum, ¹H NMR, and ¹³C NMR. The structure of poly(propylene imine)(NH₂)₃₂‐polystyrene was characterized by FT‐IR spectrum and ¹H NMR; the molecular weight and molecular weight distribution of poly(propylene imine)(NH₂)₃₂‐polystyrene were characterized by gel permeation chromatograph (GPC). The morphology, size and size distribution of the nanoparticles were characterized by photon correlation spectroscopy (PCS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The effects of monomer/macroinitiator ratio and surfactant concentration on the size and size distribution of the nanoparticles were investigated. It was found that the diameters of the nanoparticles were smaller than 100 nm (30–80 nm) and monodisperse; moreover, the particle size could be controlled by monomer/macroinitiator ratios and surfactant concentration. With the increasing of the ratio of St/DAB‐Am‐32‐Cl, the number‐average diameter (D_n), weight‐average diameter (D_w) were both increased gradually. With enhancing the surfactant concentration, the measured D_h of the nanoparticles decreased, while the polydispersity increased. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2892–2904, 2009     

Interactions and Encapsulation of Vitamins C,B3, and B6 with Dendrimers in Water

Titrations of commercial diaminobutane (DAB) and polyamidoamine (PAMAM) dendrimers by vitamins C (ascorbic acid, AA), B₃ (nicotinic acid), and B₆ (pyridoxine) were monitored by ¹H NMR spectroscopy using the chemical shifts of both dendrimer and vitamin protons and analyzed by comparison with the titration of propylamine. Quaternarizations of the terminal primary amino groups and intradendritic tertiary amino groups, which are nearly quantitative with vitamin C, were characterized by more or less sharp variations (Δδ) of the ¹H chemical shift (δ) at the equivalence points. The peripheral primary amino groups of the DAB dendrimers were quaternarized first, but not selectively, whereas a sharp chemical‐shift variation was recorded for the inner methylene protons near the tertiary amines, thereby indicating encapsulation, when all the dendritic amines were quaternarized. With DAB‐G5‐64‐NH₂, some excess acid is required to protonate the inner amino groups, presumably because of basicity decrease due to excess charge repulsion. On the other hand, this selectivity was not observed with PAMAM dendrimers. The special case of the titration of the dendrimers by vitamin B₆ indicates only dominant supramolecular hydrogen‐bonding interactions and no quaternarization, with core amino groups being privileged, which indicates the strong tendency to encapsulate vitamins. With vitamin B₃, a carboxylic acid, titration of DAB‐G3‐16‐NH₂ shows that only six peripheral amino groups are protonated on average, even with excess vitamin B₃, because protonation is all the more difficult due to increased charge repulsion, as positive charges accumulate around the dendrimer. Inner amino groups interact with this vitamin, however, thus indicating encapsulation presumably with supramolecular hydrogen bonding without much charge transfer.     

Synthesis and properties of cationic ionomers from poly(ester‐urethane)s based on polylactide

l ‐Lactide (l ‐LA) was polymerized in the presence of N‐methyldiethanolamine as an initiator and Sn(Oct)₂ as a catalyst to give hydroxy‐telechelic poly(l ‐lactide) (PLLA‐diol) bearing a tertiary amine group at the center of the polymer chain. Successive chain extension of the PLLA‐diol with hexamethylene diisocyanate afforded PLLA‐based poly(ester‐urethane)s (PEU) with equally spaced tertiary amine groups. Treatment of the PEU with iodomethane converted tertiary amine groups to quaternary ammonium groups to give cationic ionomers (PEU‐MeI). The thermal, mechanical, hydrophilic, and biodegradation properties of the obtained polymers were investigated. The thermal properties of the PEUs and the PEU‐MeIs were similar each other. The PEU‐MeIs exhibited higher tensile modulus than those of the starting PEUs. The contact angles of water on the PEU‐MeIs were lower than those of the PEUs with similar NMDA content indicating their higher hydrophilicity. In compost degradation tests, the PEU‐MeIs showed slower degradation than those of the PEUs. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4423–4428     

Synthesis of poly(L‐lactide)‐grafted pullulan through coupling reaction between amino group end‐capped poly(L‐lactide) and carboxymethyl pullulan and its aggregation behavior in water

Poly(L ‐lactide) (PLLA) with terminal primary amino groups (PLLA‐NH₂) was synthesized and used to construct PLLA‐grafted pullulan (Pul‐g‐PLLA). It consisted of a hydrophilic carboxymethyl Pul (CM‐Pul) main chain and hydrophobic PLLA graft chains that were created through a direct coupling reaction between PLLA‐NH₂ and CM‐Pul using 2‐ethoxy‐1‐(ethoxycarbonyl)‐1,2‐dihydroquinoline as a condensation reagent. Pul‐g‐PLLAs with over 78 wt % sugar unit content were found to form nanometer‐sized aggregates in water. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5482–5487, 2004     

Efficient energy transfer between amphiphilic dendrimers with oligo(p‐phenylenevinylene) core branches and oligo(ethylene oxide) termini in micelles

The efficient fluorescence resonance energy transfer (FRET) between amphiphilic dendrimers with oligo(p‐phenylenevinylene) core branches and oligo(ethylene oxide) termini have been observed in micelles. All dendrimers show the critical micelle concentration and lower critical solution temperature as well as fluorescent emission. Tailoring electronic structures of the conjugated amphiphiles for FRET have been conveniently achieved by varying the branch number and/or the conjugated core structure. The Stern‐Volmer constants (K_SV) for FRET were found to be 4.51 × 10^?5 and 8.78 × 10^?5 M for Den 30–40 and Den 50–40, respectively. The effects external stimuli such as solvent and temperature on FRET have been also investigated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Minute amounts of organically modified montmorillonite improve the properties of polyisobutylene‐based polyurethanes

We discovered that polyisobutylene (PIB)‐based polyurethanes (PIB‐PUs) containing minute amounts (0.5%) of chemically bound organically modified montmorillonite (OmMMT) surprisingly produce films exhibiting improved properties. The OmMMT was prepared by reacting sodium montmorillonite (Na⁺MMT^?) with quaternary ammonium salts of a tertiary amine carrying a ? NH₂ functionality. The positively charged quaternary amine group becomes electrostatically attached to negatively charged MMT layers and defoliates it, whereas the free ? NH₂ group reacts with diisocyanates and acts as an additional chain extender. Thus, when OmMMT is added to a mixture of ingredients assembled for the synthesis of PIB‐PUs, this modified clay becomes an integral part of the PU. Specifically, we found that the integration of 0.5% OmMMT to PIB‐based PUs produces films with significantly enhanced tensile strength, elongation, toughness, creep, and stress relaxation relative to that of PIB‐PUs. The findings were discussed and explained in terms of a proposed morphology for the nanocomposite. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4076–4087     

Syntheses and nickel coordination properties of cyclen substituted with mixed stilbene/poly(ethylene glycol) dendritic arms

We synthesized a series of cyclens substituted with mixed stilbene and poly(ethylene glycol) dendritic arms. All dendrimers terminated with different peripheral groups had good solubility in common organic solvents, and dendrimers terminated with ? CO₂H groups (CO₂H‐dendrimers) were also soluble in alkaline solutions. The nickel coordination properties of these dendrimers were investigated in organic solvents. Dendrimers terminated with ? CN groups (CN‐dendrimers) and the second‐generation CO₂H‐dendrimer [(CO₂H)₈L2] could produce pentacoordinated nickel complexes; the third‐generation CO₂H‐dendrimer [(CO₂H)₁₆L3] could form tetra‐ and pentacoordinated nickel complexes, and the nickel complex of the fourth‐generation CO₂H‐dendrimer [(CO₂H)₃₂L4] could not be obtained. This result was due to the fact that the globular surface of (CO₂H)₁₆L3 formed a hydrogen‐bond network that selectively penetrated cations and inhibited the access of anions to the core. The formation of the hydrogen‐bond network was confirmed by Fourier transform infrared, ¹H NMR, and fluorescence data. The CN‐dendrimers could not form hydrogen bonds on the surface, and the first‐ and second‐generation CO₂H‐dendrimers could not form intramolecular hydrogen‐bond networks. Therefore, they had no selectivity for positive nickel ions and negative chloride ions. (CO₂H)₃₂L4 could not produce a nickel complex because it had a crammed backbone structure that could not penetrate nickel and chloride ions. Therefore, it was possible to control the ion access of cations and anions with the hydrogen‐bond network of (CO₂H)₁₆L3. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5414–5428, 2005     

Synthesis,characterization, and aqueous self‐assembly of amphiphilic poly(ethylene oxide)‐functionalized hyperbranched fluoropolymers

Complex amphiphilic polymers were synthesized via core‐first polymerization followed by alkylation‐based grafting of poly(ethylene oxide) (PEO). Inimer 1‐(4′‐(bromomethyl)benzyloxy)‐2,3,5,6‐tetrafluoro‐4‐vinylbenzene was synthesized and subjected to atom transfer radical self‐condensing vinyl polymerization to afford hyperbranched fluoropolymer (HBFP) as the hydrophobic core component with a number‐averaged molecular weight of 29 kDa and polydispersity index of 2.1. The alkyl halide chain ends on the HBFP were allowed to undergo reaction with monomethoxy‐terminated poly(ethylene oxide) amine (PEO_x‐NH₂) at different grafting numbers and PEO chain lengths to afford PEO‐functionalized HBFPs [(PEO_x)_y‐HBFPs], with x = 15 while y = 16, 22, or 29, x = 44 while y = 16, and x = 112 while y = 16. The amphiphilic, grafted block copolymers were found to aggregate in aqueous solution to give micelles with number‐averaged diameters (D_av) of 12–28 nm, as measured by transmission electron microscopy (TEM). An increase of the PEO:HBFP ratio, by increase in either the grafting densities (y values) or the chain lengths (x values), led to decreased TEM‐measured diameters. These complex, amphiphilic (PEO_x)_y‐HBFPs, with tunable sizes, might find potential applications as nanoscopic biomedical devices, such as drug delivery vehicles and ¹⁹F magnetic resonance imaging agents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3487–3496, 2010     

Calcite Microneedle Arrays Produced by Inorganic Ion‐Assisted Anisotropic Dissolution of Bulk Calcite Crystal

Besides studies on the mineralization process, research on the demineralization of minerals provides another way to understand the crystallization mechanism of biominerals and fabricate crystals with complicated morphologies. The formation of ordered arrays of c‐axis‐oriented calcite microneedles with a tri‐symmetric structure and lengths of more than 20 μm was realized on a large scale for the first time through anisotropic dissolution of calcite substrates in undersaturated aqueous solution in the presence of ammonium salts. The lengths and the aspect ratios of the calcite microneedles can be tuned by simply changing the concentrations of the ammonium salts and the dissolution time. The shape of the transverse cross sections of the calcite microneedles obtained in the presence of NH₄Cl and NH₄Ac is almost regularly triangular. The tri‐symmetric transverse cross‐section geometry of the calcite microneedles could be attributed to the tri‐symmetric feature of rhombohedral calcite atomic structures, the synergetic interactions between electrostatic interaction of ammonium ions and dangling surface carbonate groups, and the ion incorporation of halide ions.     

Highly active polymeric organocatalyst: Chiral ionic polymers prepared from 10,11‐didehydrogenated cinchonidinium salt

Since few examples of 10,11‐didehydrogenated (3‐ethynyl) cinchona alkaloids have been utilized as organocatalysts in asymmetric reaction, we synthesized 10,11‐didehydrogenated cinchonidine. The 3‐vinyl group of cinchonidine was transformed into a 3‐ethynyl functionality. Based on the resulting 10,11‐didehydrogenated cinchonidine, the corresponding quaternary ammonium salt and its dimers were prepared. The ion‐exchange reaction between the quaternary ammonium salt and sodium sulfonate produced the quaternary ammonium sulfonate as a stable ionic compound. Chiral ionic polymers were then synthesized by the ion‐exchange polymerization of the 10,11‐didehydrogenated cinchonidinium salt dimer and a disulfonate. The chiral ionic polymers were found to be capable of efficiently catalyzing the asymmetric alkylation of N‐(diphenylmethylene)glycine tert‐butyl ester. The enantioselectivities obtained with the polymeric catalysts were higher than those obtained with the corresponding monomeric catalyst. Dimers of 10,11‐didehydrogenated cinchonidinium salts were prepared. Treatment of the dimer with disodium disulfonate gave the chiral ionic polymers, which showed high catalytic activity in asymmetric benzylation of N‐(diphenylmethylen)glycine tert‐butyl ester. The polymeric catalysts were reused several times without the loss of catalytic activity. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 621–627     

Synthesis of poly[(2‐oxo‐1,3‐dioxolane‐4‐yl) methyl methacrylate‐co‐ethyl acrylate] by incorporation of carbon dioxide into epoxide polymer and the miscibility behavior of its blends with poly(methyl methacrylate) or poly(vinyl chloride)

This study was related to the investigation of the chemical fixation of carbon dioxide to a copolymer bearing epoxide and the application of the cyclic carbonate group containing copolymer‐to‐polymer blends. In the synthesis of poly[(2‐oxo‐1,3‐dioxolane‐4‐yl) methyl methacrylate‐co‐ethyl acrylate] [poly(DOMA‐co‐EA)] from poly(glycidyl methacrylate‐co‐ethyl acrylate) [poly(GMA‐co‐EA)] and CO₂, quaternary ammonium salts showed good catalytic activity. The films of poly(DOMA‐co‐EA) with poly(methyl methacrylate) (PMMA) or poly(vinyl chloride) (PVC) blends were cast from N,N′‐dimethylformamide solution. The miscibility of the blends of poly(DOMA‐co‐EA) with PMMA or PVC have been investigated both by DSC and visual inspection of the blends. The optical clarity test and DSC analysis showed that poly(DOMA‐co‐EA) containing blends were miscible over the whole composition range. The miscibility behaviors were discussed in terms of Fourier transform infrared spectra and interaction parameters based on the binary interaction model. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1472–1480, 2001     

Hyperbranched polyethyleneimine architecture onto poly(allylamine) by simple synthetic approach and the chelating characters

In resemblance to the ethoxylation of alkylamine or polymeric amines to introduce the nonionic hydrophiles by incorporation of ethylene oxide groups to make surfactants, ethyleneimine (EI) groups were introduced into poly(allylamine) by a simple in situ reaction of this polymer with 2‐chloroethylamine hydrochloride. The resultant polymers were allylic and chain‐pendant with hyperbranched polyethyleneimine. The EI number (n) of the polymers was determined by ¹H NMR. The percentages of primary, secondary, and tertiary amine present were estimated by potentiometric titration. The chelating abilities of the polymers that were applied growth conditions once (G₁, n ≈ 2) and twice (G₂, n ≈ 6) were also examined by potentiometric titration and ultraviolet–visible spectoscopy in the presence of metal ions (Cu⁺²). Continuous‐variation analysis revealed that each repeat unit of G₁ and G₂ behaves as a multident chelate and forms a stable complex with Cu⁺² ions utilizing an average of three EI dents per ion. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3018–3023, 2001     

Biodegradation of copolymers composed of optically active L‐lactide and (R)‐ or (S)‐1‐methyltrimethylene carbonate

Random copolymerizations of L ‐lactide with (R)‐, (S)‐, or rac‐1‐methyltrimethylene carbonate with bis(pentamethylcyclopentadienyl) samarium‐methyl tetrahydrofuranate [(C₅Me₅)₂SmMe(THF)] as a novel initiator provided high molecular weight polymers with low polydispersities. Biodegradation of the resulting polymers with tricine and {N‐[tris(hydroxymethyl)methyl]‐2‐aminoethane sulfonic acid (TES) buffers as well as activated sludge showed only a small weight loss, whereas the polymer with proteinase K revealed high biodegradability independent of the optical activity of 1‐methyltrimethylene carbonate. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3916–3927, 2001     

Binding of uranyl ion by 2,2′-dihydroxyazobenzene attached to crosslinked polystyrenes covered with highly populated quaternary ammonium cations

2,2′-Dihydroxyazobenzene (DHAB) derivatives were attached to poly(chloromethylstyrene-co-divinylbenzene) (PCD) because of the high affinity of DHAB for uranyl ion. Chloromethyl groups of PCD were converted to quaternary ammonium ions by treating them with tertiary amines. Two strategies were adopted to improve the uranyl-binding ability of the immobilized DHAB: (1) the creation of a highly cationic microenvironment around the DHAB moieties and (2) the introduction of electron-withdrawing groups to DHAB. Capacity of the resins for uranyl uptake was measured, revealing that about 10 to 46 mg of uranium could be complexed to 1 g of the resins. Formation constants (K_f) for the uranyl complexes of the resins were determined. In the presence of ≥0.02 M bicarbonate ion at pH 8.02, log K_f values of 14.3 to 15.8 were obtained. Uranium extraction from seawater with two kinds of resins prepared in this study was carried out on the east coast of the Korean peninsula. The amount of uranium extracted from seawater was up to 150 μg/g resin. Thus, the uranium-extracting capability of the DHAB-containing polystyrene resins was improved significantly by the structural modifications. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4117–4125, 1999     

Optimization of preparation of thermally stable cellulose nanofibrils via heat‐induced conversion of ionic bonds to amide bonds

Improving the thermal stability of nanocelluloses is important for practical applications such as melt compounded nanocellulose‐reinforced polymer composites and flexible substrates for nanocellulose‐containing electronic devices. Here, we report optimum conditions for a straightforward surface modification strategy for improving the thermal stability of 2,2,6,6‐tetramethypiperidine‐1‐oxyl (TEMPO)‐oxidized cellulose nanofibrils (TOCNs); the heat‐induced conversion of TOCN alkyl ammonium carboxylates to amides. Different amine‐terminated compounds (R‐NH₂) were grafted onto the surface of TOCNs under aqueous conditions. The influences of R‐NH₂ molecular weight, R‐NH₂/TOCN‐COOH molar ratio, and thermal stability of R‐NH₂ on the properties of the grafted TOCN films were investigated through infrared spectroscopy and thermogravimetric analysis. For maximum thermal improvement of up to 90 °C, complete ionic bonding of TOCN carboxy groups with R‐NH₂ was required, as well as proper selection of the R‐NH₂ compound. A controlled heating process was also needed to achieve effective ionic‐to‐amide bond conversion. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1750–1756