Microwave‐assisted synthesis and characterization of polyimide/functionalized MWCNT nanocomposites containing quinolyl moiety

Polyimide‐MWCNT nanocomposites were prepared by the reaction of a heterocyclic diamine monomer of bis(4‐amino‐3,5‐dimethylphenyl)‐2‐chloro‐3‐quinolylmethane (BACQM), pyromellitic dianhydride (PMDA) with unmodified MWCNT (MWCNT), acid‐functionalized MWCNT (acid‐MWCNT) or amine‐functionalized MWCNT (amine‐MWCNT) using microwave irradiation as well as by the conventional method. The structure of the monomer was confirmed by FTIR, ¹H‐NMR, and ¹³C‐NMR spectral techniques. The glass transition temperature (T_g) of the MWCNTs/polyimide nanocomposite was found to be higher than that of the unfilled polyimide system. The T_g's of both systems were higher when prepared with the microwave method than the conventional synthesis. The T_g's of the nanocomposites using acid and amine functionalized MWCNTs are greater than 300°C, in both methods. This is attributed to the presence of hydrogen bond and strong covalent bond in both the acid‐MWCNT/polyimide and amine‐MWCNT/polyimide systems. The morphological studies of the nanocomposites synthesized using microwave irradiation show that a distinct MWCNT nanofibrillar network is formed in the matrix when MWCNT or acid‐MWCNT is used. A homogeneous morphology, without distinct nanotube domains is seen when the amine‐MWCNT is covalently linked to the polymer. POLYM. COMPOS., 37:2417–2424, 2016. © 2015 Society of Plastics Engineers     

Copolymer hydrogel microspheres consisting of modified sulfate chondroitin‐co‐poly(N‐isopropylacrylamide)

Modified chondroitin sulfate (π‐CdS) microspheres were synthesized by way of crosslinking‐copolymerization reaction with N‐isopropylacrylamide (NIPAAm), yielding CdS‐co‐PNIPAAm copolymer network. The incorporation of vinyl groups onto the CdS was processed with the use of glycidyl methacrylate (GMA) in an aqueous solution of pH 3.5 under stirring speed of 800 rpm at 50°C. ¹³C NMR and ¹H NMR spectra of CdS treated with the GMA indicated the formation of 3‐methacryloyl‐1‐glyceryl ester of π‐CdS and 3‐methacryloyl‐2‐glyceryl ester of π‐CdS that are the reaction products resultant of an epoxide ring‐opening mechanism via. The synthesis of microspheres was performed via radical reaction of the vinyl groups at the π‐CdS with vinyl groups at the NIPAAm in a water−benzyl alcohol microemulsion. The formation of spherical structures is the result of the polymerization‐crosslinking reaction of the π‐CdS with the NIPAAm monomers at the droplets of water, in view that both reactants have hydrophilic characteristics at the temperature at which the reaction was processed. The pure CdS hydrogel microspheres showed a slightly cracked structure with a lower diameter range while the CdS‐co‐PNIPAAm hydrogel microspheres showed a flat and tight structure with a more regular mass distribution. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Functional polymer from high molecular weight linear polyols and polyurethane‐based crosslinking units: Synthesis,characterization, and boron retention properties

The objective of this work was to synthesize functional polymers, with boron removal properties, from high molecular weight linear polyols based on N‐methyl‐d ‐glucamine (NMDG) and polyurethane units as crosslinking reagent. For that, (4‐vinylbenzyl)‐N‐methyl‐d ‐glucamine monomer (VbNMDG) was synthesized from vinylbenzyl chloride and NMDG, and subsequently, high molecular weight linear poly(VbNMDG) was obtained by radical free polymerization. Later, polymer dots were obtained from poly(VbNMDG) and urethanization reactions using methylene diphenyl diisocyanate at room temperature. Monomers and polymers were characterized by different techniques (FTIR, DLS, elemental analysis, H¹‐NMR). In addition, boron retention properties were studied by diafiltration technique using the azomethine‐H method. It was concluded that synthesis of polymer dots, with high boron retention capacity, can be easily synthesized by procedure described. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43895.     

Flexible polyurethane foams modified with biobased polyols: Synthesis and physical‐chemical characterization

A series of flexible polyurethane foams with different polyol compositions were synthesized through the replacement of a portion of the petroleum‐based polyether polyol with biobased polyols, namely, glycerol (GLY) and hydroxylated methyl esters (HMETO). HMETO was synthesized by the alkaline transesterification of tung oil (TO; obtaining GLY as a byproduct) and the subsequent hydroxylation of the obtained methyl esters with performic acid generated in situ. FTIR spectroscopy, ¹H‐NMR, and different analytical procedures indicated that the hydroxyl content increased significantly and the molecular weight decreased with respect to those of the TO after the two reaction steps. The characterization of the obtained foams, achieved through the measurement of the characteristic reaction times, thermal and dynamic mechanical analysis, scanning electronic microscopy, and density measurements, is reported and discussed. The most important changes in the modified foams were found with the addition of GLY to the formulation; this led to an increased foam density and storage rubbery modulus, which were associated with a higher crosslinking density because of the decrease in the chain length between crosslinking points. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43831.     

Characterization of crosslinked starch materials with spectroscopic techniques

The structure, mobility, and properties of crosslinked starch materials of various compositions were investigated with FTIR and NMR spectroscopy, and relaxation time measurements were taken with cross‐polarization/magic‐angle‐spinning (CP–MAS) and magic‐angle‐spinning (MAS) spectroscopy. Characterization by Fourier transform infrared spectroscopy confirmed the crosslinking reaction. The CP–MAS and MAS spectra allowed the assignment of the principal ¹³C signals. The molecular mobility of these polysaccharides was analyzed in terms of the cross‐relaxation time between the protons and carbons, the ¹H spin–lattice relaxation time in the rotating frame, and the ¹H longitudinal spin–lattice relaxation time. Relaxation studies showed that increasing the crosslinking degree increased the amorphous content, and the material became rigid as an increasing number of covalent bonds in the polymer network reduced mobility. The values of the spin–lattice relaxation in the rotating frame reflected the homogeneous nature of the materials. The correlation between the crosslinking degree, structure, and mobility and the sorption properties of these sorbents was examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2650–2663, 2004     

Structure and mechanism of functional isotactic polypropylene via in situ chlorination graft copolymerization

This paper discusses the structure and mechanism of maleic anhydride (MAH) grafted onto isotactic polypropylene (iPP) via in situ chlorination graft copolymerization (ISCGC). The molecular structure of the grafted iPP was characterized using ¹H NMR and ¹³C NMR spectroscopy, viscosity‐average molecular weight and gel content. The structure of un‐grafted MAH present in the reaction system was investigated using Fourier transform infrared spectroscopy in order to explore the grafting of MAH on iPP. The main side‐reactions, including iPP chain scission and crosslinking, during the grafting reaction were explored. From the experimental results obtained, the reason for controlled macromolecular chain degradation and crosslinking of grafted iPP in ISCGC is proposed. Based on the structural characterization of the grafted polymer, the mechanism of grafting onto iPP obtained via ISCGC was deduced. Mechanical properties, both static and dynamic, of grafted iPP were also investigated and the results showed that the properties of the material changed due to grafted MAH. Copyright © 2011 Society of Chemical Industry     

Ethylene‐co‐vinyl acetate copolymer crosslinking through ester–alkoxysilane exchange reaction catalyzed by dibutyltin oxide: mechanistic aspects investigated through model compounds by multinuclear NMR spectroscopy

It was shown that the crosslinking of ethylene‐co‐vinyl acetate (EVA) copolymer by a tetraalkoxysilane in molten state, in the temperature range 100–250 °C, was obtained only in the presence of dibutyltin oxide. At this temperature EVA pendant ester groups readily react with dibutyltin oxide to give a dimeric 1‐alkoxy‐3‐acetoxytetrabutyldistannoxane distributed along the polymer chains. The exact role of this tin compound in the ester–alkoxysilane reaction was elucidated through reactions of the tetraalkoxysilane with parent tin compounds: tributylethoxytin, dimeric diacyloxydistannoxane and finally a dimeric 1‐alkoxy‐3‐acyloxydistannoxane, obtained by reaction of the dibutyltin oxide with a model ester instead of the EVA‐ester pendant group. Ligand exchanges on tin atoms characterized by multinuclear NMR spectroscopy (¹H, ¹³C and ¹¹⁹Sn) showed that substitutions were selective and concern only the exo‐cyclic tin ligand (OR or OCOR′) without alteration of the dimeric distannoxane structure. Furthermore, these ligand exchanges occurred at room temperature. This approach with model compounds gave evidence that the crosslinking occurred via an alkoxy‐Sn/alkoxy‐Si exchange on the exo‐cyclic sites of the distannoxane structure formed in situ. This distannoxane was shown to be an efficient catalyst of this transesterification. The temperature of formation of this catalytic species governed the temperature of the beginning of the crosslinking reaction. Copyright © 2004 Society of Chemical Industry     

Synthesis and thermomechanical properties of allyl‐functionalized polycaprolactone urethane‐co‐2‐hydroxylethyl methacrylate networks

PCL‐segmented multiallyl‐functionalized poly (ester urethane) prepolymers (PEUs) were prepared in a two‐step process. First, hydroxyl‐terminated PCL and glycerol simultaneously reacted with an excess of a diisocyanate, the obtained isocyanate functionalized prepolymers then reacts with allyl amine. PEUs structure choice mainly focused on two aspects: the PCL segments concentration and the allyl functionality that, respectively, affects the biodegradability and the density of the issued networks. The concentrations of the different reactants were fixed, taking into account the desired mean structure and also to prevent crosslinking during the synthesis of the prepolymers. FTIR was principally used to monitor the synthesis of allyl functionalized PEUs. The carbonyl absorption of PCL, initially located at 1720 cm^?1, reaction of the PCL and shifted toward 1730 cm^?1, due to a decrease in crystallinity as confirmed by DSC. The structure of allyl‐functionalized PCL‐segmented PEU analyzed by ¹H NMR, double bond content was between 0.2 and 1.2 mmol g^?1. Networks were obtained by UV‐initiated radical copolymerization of allyl‐functionalized PEUs and HEMA. The effects of PCL concentration and molar mass on their thermomechanical and thermal properties were analyzed. Particular damping properties were obtained. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41295.     

Synthesis of a glycosaminoglycan polymer mimetic using an N‐alkyl‐N,N‐linked urea oligomer containing glucose pendant groups

The synthesis of a glycosaminoglycan polymer mimetic is reported. An isopropylidene protected glucose methacrylate monomer was copolymerized under reversible addition fragmentation chain transfer polymerization control with an azido‐containing comonomer to a molecular weight of 29 000 g mol^?1 with polydispersity of 1.21. The comonomer ratio was determined to be 15:1 based on ¹H NMR spectroscopy. This copolymer was coupled to sugar‐functionalized N‐alkyl‐N,N‐linked urea oligomers using a copper catalyzed alkyne/azide cycloaddition reaction. The reaction efficiency was 100% as monitored by ¹H NMR spectroscopy. The isopropylidene protecting groups on the polymer and N‐alkyl‐N,N‐linked urea oligomers were removed using acid hydrolysis to give the final polysaccharide mimetic. It is expected that these polymers will have applications in a variety of future therapeutic applications. © 2013 Society of Chemical Industry     

Crystallization and photo‐curing kinetics of biodegradable poly(butylene succinate‐co‐butylene fumarate) short‐segmented block copolyester

Short‐segmented block copolymers of poly(butylene succinate‐co‐butylene fumarate) were synthesized and their crystallinity and crosslinking behavior were investigated. ¹H NMR was used to characterize the microstructure and composition of the copolyesters. Molecular weight determination was performed using gel permeation chromatography. Based on the DSC results all copolyesters were crystalline and the degree of crystallinity of the copolymers did not change with butylene fumarate mole fraction due to co‐crystallization of the butylene succinate and butylene fumarate groups. Crosslinked copolyesters showed a lower crystallization rate and degree of crystallinity while the crystallization temperature shifted to higher temperatures compared with uncrosslinked copolyesters due to the formation of nucleating agents by crosslinkages. Photo‐DSC was used to investigate the crosslinking kinetics for UV‐initiated photo‐curing. Three kinetics parameters including the rate constant (k) and the orders of the initiation and propagation reactions (m and n, respectively) were determined for the quenched and unquenched copolymers. © 2016 Society of Chemical Industry     

Amide pectin: A carrier material for colon‐targeted controlled drug release

In order to deliver bioactive components to the colon, an oral colon‐targeted bioadhesive microparticle delivery system based on pectin was developed. Unmodified pectin exhibited a poor hydrophobicity and weak tablet‐crushing strength. Pectin was modified by an amide reaction, which results in a dramatic decrease in water solubility and viscosity, as well as favorable controlled release properties. Amide pectin (AP) were characterized by Fourier transform infrared spectroscopy (FTIR), Nuclear magnetic resonance (¹H‐NMR), and Differential scanning calorimetry (DSC). Results of FTIR and ¹H‐NMR revealed that amide groups were introduced into the pectin molecules; DSC analysis exhibited that the thermal stability of pectin was decreased. An in vitro release assay demonstrated that matrix tablets prepared by AP could deliver bioactive components to the colon when the pectin content and hydrophobicity were properly controlled. The relationship between the structure and in vitro release properties of amide pectin suggests that an optimal tablet structure and composition can be responsible for a suitable BSA release rate. The optimal tablets making conditions were using methylcellulose (MC) as tablet adhesive, amidation reaction time of 60 min, drug loading of 0.008 g and tableting pressure of 8 kg/mm. The results indicated that matrix tablets made by AP exhibited good colon‐targeted drug release. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43697.     

Synthesis and phase behavior of nematic liquid‐crystalline elastomers derived from smectic crosslinking agent

A mesogenic crosslinking agent M‐1 was synthesized to minimize the perturbations of nonmesogenic crosslinking agent for liquid‐crystalline elastomers. The synthesis of side‐chain liquid‐crystalline elastomers containing a rigid mesogenic crosslinking agent M‐1 and a nematic monomer M‐2 was described by a one‐step hydrosilylation reaction. The chemical structures of the obtained monomers and network polymers were confirmed by Fourier transform infrared and ¹H‐NMR spectroscopy. The mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, polarizing optical microscopy, and X‐ray diffraction measurements. The influence of the crosslinking units on the phase behavior was discussed. The liquid‐crystalline elastomers containing less than 15 mol % of the crosslinking units showed elasticity, reversible phase transition, and threaded texture. The experimental results demonstrated that isotropic temperature and liquid‐crystalline range of polymers P‐1–P‐7 decreased a little as the concentration of crosslinking agent M‐1 increased, and the use of mesomorphic crosslinking agent M‐1 promotes the arrangement of liquid‐crystalline units from P‐1 to P‐5. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1712–1719, 2005     

Morphology and molecular mobility of plasticized polylactic acid studied using solid‐state 13C‐ and 1H‐NMR spectroscopy

MAS ¹³C‐NMR measurements were used for the study of morphology and molecular mobility in amorphous quenched and triacetine‐plasticized PLA samples and PLA samples which underwent cold crystallization during annealing at 80 and 100 °C. The single pulse MAS ¹³C‐NMR spectra indicate that plasticizer promotes cold crystallization which results in the decrease of the temperature of crystallization and formation of more perfect crystalline domains. The T₁(¹³C) spin‐lattice relaxation times show that the presence of plasticizer molecules leads to an increase of local mobility in PLA chains but plasticized PLA after annealing at 100 °C shows more rigid structure. The series of broad line ¹H‐NMR spectra performed at temperatures up to 100 °C provided information on the changes in relaxation processes and morphology of the studied samples. The interpretation of the results obtained using the techniques of NMR spectroscopy were supported by WAXD and DSC measurements. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43517.     

Crosslinking of poly(silyl ester)s containing fumaryloxyl units in the main chain and characteristics of the crosslinked products

Two unsaturated poly(silyl ester)s that contained innoxious fumaryloxyl units in the main chain were prepared by the polycondensation reaction of 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyltrisiloxane or 1,3‐dichlorotetramethyldisiloxane with di‐tert‐butyl fumarate under nitrogen at 100°C for 1–3 days. To investigate the crosslinking reaction of the unsaturated poly(silyl ester)s, the two unsaturated poly(silyl ester)s were crosslinked in the presence of 2,2′‐azobisisobutyronitrile as a radical initiator. After the crosslinking, the unsaturated poly(silyl ester)s, which were viscous liquids, turned into solid products. The characterization of the two poly(silyl ester)s and the crosslinked products included infrared spectroscopy, ¹H‐NMR spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. Comparisons were made between the linear poly(silyl ester)s and the crosslinked poly(silyl ester)s. After the crosslinking, the important resonance signal for ethenylene (C?C) disappeared, and this showed that the crosslinking reaction was carried out progressively. The glass‐transition temperatures of the crosslinked poly(silyl ester)s were higher than those of the uncross‐ linked poly(silyl ester)s, and the thermal stability of the crosslinked poly(silyl ester)s was better than that of uncrosslinked poly(silyl ester)s. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1221–1225, 2007     

Thermoreversible crosslinked thermoplastic starch

A novel furan‐modified thermoreversible crosslinked thermoplastic starch was synthesized. The crosslinking mechanism was based on a thermoreversible furan/maleimide adduct formed by the Diels ? Alder reaction. Thermoplastic starch (TPS) was first modified by forming a urethane linkage between the product of the reaction of furfuryl alcohol with 4,4‐methylene diphenyldiisocyanate and a starch hydroxyl group. Crosslinking was then achieved by the addition of 1,1′‐(methylene‐di‐4,1‐phenylene) bismaleimide to the furan‐grafted starch in solution (dimethylsulfoxide) and in the molten state during conventional extrusion. The materials were characterized by Fourier transform infrared and ¹H NMR spectroscopy. The thermoreversible reaction was assessed by viscosity measurement and ¹H NMR, for the system in dimethylsulfoxide, and by solubility tests, hot‐pressing experiments and dynamic mechanical analysis measurements for the extruded product. The crosslinked product showed a higher storage modulus and water resistance than its non‐crosslinked counterpart, opening novel opportunities to widen the range of TPS applications. © 2015 Society of Chemical Industry     

A novel polybenzoxazine containing styrylpyridine structure via the Knoevenagel reaction

In this article, a kind of styrylpyridine‐containing polybenzoxazine was obtained via the Knoevenagel reaction between benzaldehyde and methylpyridine groups. The benzoxazine monomer (MPBC) containing the benzaldehyde and methylpyridine groups was synthesized firstly and its structure was characterized by Fourier transform infrared (FTIR) spectra, ¹H NMR and ¹³C NMR. With the aid of differential scanning calorimetry, FTIR, and photoluminescent tests, the interesting curing behaviors were probed. The results showed that the ring‐opening polymerization occurred at lower temperature, and the Knoevenagel reaction further took place at elevated temperature. The amine and phenol moieties were bonded together to form the styrylpyridine structure. Due to these special crosslinking structures, the corresponding polybenzoxazine exhibited excellent thermal stability, and had a special high char yield of 74.5%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40823.     

Linear segmented polyurethanes: I. A kinetics study

This work investigates the two‐step polymerization between methylene diphenyl diisocyanate (MDI), two different poly(tetramethylene oxide) macrodiols, and 1,4‐butanediol (BD) as chain extender. At the end of the prepolymerization, the reaction mixture contains MDI in excess and a prepolymer with isocyanate end group. Then, BD and a solvent (tetrahydrofuran) were added to start the finishing stage under nominal stoichiometric equilibrium. The reaction was analyzed by Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance (¹H‐NMR), and size exclusion chromatography. ¹H‐NMR was employed to follow global concentrations of unreacted isocyanate end groups and internal urethane groups. This information enabled to estimate the following “effective” rate constants: k₁ = 1.07 × 10^?3 L mol^?1 s^?1 for the prepolymerization; and k₂ = 1.94 × 10^?4 L mol^?1 s^?1 for the finishing stage. These values are subject to errors caused by biases introduced in the recipe, in the measurements, in the reaction conditions, in the quality of reagents, and in the reaction mechanism assumptions. Such errors also explain the dispersion of the published rate constants values. The ¹H‐NMR measurements also enabled to estimate the evolution (with extent of reaction) of the number‐average number of structural units along the prepolymerization and finishing stages; and such estimates reasonably verify Flory's classical expressions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45747.     

Chain transfer of vegetable oil macromonomers in acrylic solution copolymerization

The use of vegetable oil macromonomers (VOMMs) as comonomers in emulsion polymerization enables good film coalescence without the use of solvents that constitute volatile organic compounds (VOCs). VOMMs are derived from renewable resources and offer the potential of post‐application crosslinking via auto‐oxidation. However, chain transfer reactions of VOMMs with initiator and/or polymer radicals during emulsion polymerization reduce the amount of allylic hydrogen atoms available for primary auto‐oxidation during drying. Vegetable oils and derivatives were reacted with butyl acrylate and methyl methacrylate via solution polymerization, and the polymerization was monitored using in situ infrared spectroscopy to determine the extent of chain transfer. ¹H NMR spectroscopy was used to determine the loci of chain transfer and the molecular weight characteristics of the polymers were characterized by SEC. Solution polymerization was utilized because this limited temperature fluctuations and insolubility of the polymer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Slightly crosslinked polyurethane with Diels–Alder adducts from trimethylolpropane

Diels–Alder (DA) reactions between furan and maleimide have been widely applied in thermally remendable polymeric materials. Crosslinked polyurethane with DA adducts exhibited much better mechanical properties than linear polyurethane with DA adducts. However, the highly crosslinked polyurethane needs a higher temperature and a longer healing time. This will increase the possibility of side reactions proceeding during the healing procedure. In this paper, slightly crosslinked polyurethane with DA adducts was synthesized by incorporating trimethylolpropane into linear polyurethane with DA adducts. The structure of the intermediate and final products was characterized by Fourier transform infrared spectroscopy, ¹H‐NMR, and differential scanning calorimetry, confirming that the synthesizing process proceeded successfully. The images from the polarizing optical microscope demonstrated that the final product with slight crosslinking needed less time and a lower healing temperature to complete the healing procedure. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43971.     

Gamma radiation effect of polymethylvinylphenylsiloxane rubbers under different temperatures

The gamma radiation effect on polymethylvinylphenylsiloxane (PMVPS) rubbers is investigated by irradiation exposure of PMVPS rubbers to a maximum dose of 200 kGy in the temperature range 28–110 °C. Compared with unirradiated PMVPS rubber, the elongation at break of irradiated PMVPS rubber decreases while its elastic modulus increases with the increase of absorbed dose or radiation temperature. DSC, ATR‐FTIR, XPS, and ¹H‐NMR indicate that slight degradation and oxidation reaction occur during the irradiation of PMVPS. Solvent swelling and gel fraction study confirms that the crosslinking density of PMVPS rubbers increases gradually with increasing absorbed dose or radiation temperature. Therefore, radiation‐induced crosslinking of PMVPS is dominant reactions for the chosen dose or temperature range. Furthermore, synergistic effect exists in the high‐temperature radiation process for PMVPS rubbers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45404.