N‐(2‐biphenylenyl)‐4‐[2′‐phenylethynyl] phthalimide: 2. Detailed study of the monomer cure and properties of the resulting polymer

A detailed study is presented of the high‐temperature cure of the difunctional monomer N‐(2‐biphenylenyl)‐4‐[2′‐phenylethynyl]phthalimide (BPP) and the thermal properties of the resulting homopolymer. Although the phenylethynyl groups are consumed within 1 h at 370 °C, other reactions continue well after this, leading to a cured polymer whose glass transition temperature (T_g) is highly dependent on cure time and temperature. A T_g of 450 °C is achieved after a 16 h cure at 400 °C. Use of chemometrics to analyse the infrared spectra of curing BPP provides evidence for changes in the aromatic moieties during cure, perhaps indicative of co‐reaction between the biphenylene and phenylethynyl groups; however, other processes also contribute to the overall complex cure mechanism. Despite the high T_g values, BPP homopolymer exhibits unacceptably poor thermo‐oxidative stability at 370 °C, showing a weight loss of about 50 % after 100 h ageing. This is perhaps a result of formation of degradatively unstable crosslink structures during elevated‐temperature cure. Copyright © 2004 Society of Chemical Industry     

Thermomechanical properties and shape memory effect of epoxidized natural rubber crosslinked by 3‐amino‐1,2,4‐triazole

A thermally induced shape memory polymer based on epoxidized natural rubber (ENR) was produced by curing the ENR with 3‐amino‐1,2,4‐triazole as a crosslinker in the presence of bisphenol‐A as a catalyst. Dynamic mechanical and tensile analysis was conducted to examine the variation of glass transition temperature, stiffness, and extensibility of the vulcanizates with the amount of curatives. Shape memory properties of the ENR vulcanizates were characterized by shape retention and shape recovery. It was revealed that the glass transition temperature of the ENR vulcanizates could be tuned well above room temperature by increasing the amount of curing agents. Also, ENR vulcanizates with T_g higher than ambient temperature showed good shape memory effects under 100% elongation, and the response temperatures of the recovery were well matched with T_g of the samples. Copyright © 2006 Society of Chemical Industry     

Synthesis of PS‐g‐POSS hybrid graft copolymer by click coupling via ”graft onto” strategy

Polystyrene (PS)‐incorporated polyhedral oligomeric silsesquioxanes (POSS) organic–inorganic hybrid graft copolymer could be achieved by click coupling reaction between alkyne groups in POSS and azido groups in PS via “graft onto” strategy. Alkyne‐functionalized POSS was synthesized via thiol‐ene facile click reaction and subsequent amidation reaction with very high yield. Azido‐multifunctionalized PS could be synthesized by chloromethylation and subsequent azido reaction. The chemical structures of PS‐(CH₂Cl)_m, PS‐(CH₂N₃)_m, and PS‐g‐POSS were determined by Fourier transform infrared and ¹H NMR characterization. PS‐g‐POSS presented a better hydrophobic property with contact angle of 113° than that of PS (85°). And PS‐g‐POSS with ≤5% of grafting degree had lower glass transition temperature (T_g) than that of PS and then it increased up to 112°C with grafting degree. An obvious aggregation of POSS phase with 10–80 nm in size was formed in PS‐g‐POSS matrix. In addition, 5 wt % of PS‐g‐POSS was added to general purpose polystyrene (GPPS) to remarkably improve its tensile strength from 45 to 57 MPa. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Curing kinetics and reaction‐induced homogeneity in networks of poly(4‐vinyl phenol) and diglycidylether epoxide cured with amine

Mixtures of diglycidyl ether of bisphenol‐A (DGEBA) epoxy resin with poly(4‐vinyl phenol) (PVPh) of various compositions were examined with a differential scanning calorimeter (DSC), using the curing agent 4,4′‐diaminodiphenylsulfone (DDS). The phase morphology of the cured epoxy blends and their curing mechanisms depended on the reactive additive, PVPh. Cured epoxy/PVPh blends exhibited network homogeneity based on a single glass transition temperature (T_g) over the whole composition range. Additionally, the morphology of these cured PVPh/epoxy blends exhibited a homogeneous network when observed by optical microscopy. Furthermore, the DDS‐cure of the epoxy blends with PVPh exhibited an autocatalytic mechanism. This was similar to the neat epoxy system, but the reaction rate of the epoxy/polymer blends exceeded that of neat epoxy. These results are mainly attributable to the chemical reactions between the epoxy and PVPh, and the regular reactions between DDS and epoxy. Polym. Eng. Sci. 45:1–10, 2005. © 2004 Society of Plastics Engineers.     

Effects of aromatic carboxylic dianhydrides on thermomechanical properties of polybenzoxazine‐dianhydride copolymers

Enhanced thermomechanical properties of bisphenol‐A based polybenzoxazine (PBA‐a) copolymers obtained by reacting bisphenol‐A‐aniline‐type benzoxazine (BA‐a) resin with three different aromatic carboxylic dianhydrides, i.e., pyromellitic dianhydride (PMDA), 3,3′,4,4′ biphenyltetracarboxylic dianhydride (s‐BPDA), or 3,3′,4,4′ benzophenonetetracarboxylic dianhydride (BTDA) were reported. Glass transition temperature (T_g), of the copolymers was found to be in the order of PBA‐a:PMDA>PBA‐a:s‐BPDA>PBA‐a:‐BTDA. The difference in the T_g of the copolymers is related to the rigidity of the dianhydride components. Furthermore, the T_g of PBA‐a:BTDA, PBA‐a:s‐BPDA, and PBA‐a:BTDA films was observed to be significantly higher than that of the neat PBA‐a owing to the enhanced crosslink density by the dianhydride addition. This greater crosslink density results from additional ester linkage formation between the hydroxyl group of PBA‐a and the anhydride group of dianhydrides formed by thermal curing. Moreover, the copolymers exhibit enhanced thermal stability with thermal degradation temperature (T_d) ranging from 410°C to 426°C under nitrogen atmosphere. The char yield at 800°C of the copolymers was found to be remarkably greater than that of the neat PBA‐a with a value up to 60% vs. that of about 38% of the PBA‐a. Toughness of the copolymer films was greatly improved compared to that of the neat PBA‐a. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Miscibility and crystallization behavior of biodegradable poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/phenolic blends

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV)/phenolic blends are new miscible crystalline/amorphous polymer blends prepared via solution casting method in this work, as evidenced by the single composition dependent glass transition temperature. The measured T_gs can be well fitted by the Kwei equation with a q value of 13.6 for the PHBV/phenolic blends, indicating that the interaction between the two components is strong. The negative polymer–polymer interaction parameter, obtained from the melting depression of PHBV using the Nishi‐Wang equation, indicating the thermal miscibility of PHBV and phenolic. The spherulitic morphology and crystal structure of PHBV/phenolic blends were studied with polar optical microscopy and wide angle X‐ray diffraction compared with those of neat PHBV. It is found that the growth rates of PHBV in the blends are lower than that in neat PHBV at a given crystallization temperature, and the crystal structure of PHBV is not modified by the presence of phenolic in the PHBV/phenolic blends, but the crystallinity decrease with the increasing of phenolic. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of biodegradable polymer blends from poly(3‐hydroxybutyrate)/poly(vinyl acetate)‐modified corn starch

Biodegradable polymer blends prepared by blending poly(3‐hydroxybutyrate) (PHB) and corn starch do not form intact films due to their incompatibility and brittle behavior. For improving their compatibility and flexibility, poly(vinyl acetate) (PVAc) was grafted from the corn starch to prepare the PVAc‐modified corn starch (CSV). The resulting CSV consisted of 47.2 wt% starch‐g‐PVAc copolymer and 52.8 wt% PVAc homopolymer and its structure was verified by FT‐IR analysis. In comparison with 35°C of the neat PVAc, the glass transition temperature (T_g) of the grafted PVAc chains on starch‐g‐PVAc was higher at 44°C because of the hindered molecular mobility imposed from starch on the grafted PVAc. After blending PHB with the CSV, structure and thermal properties of the blends were investigated. Only a single T_g was found for all the PHB/CSV blends and increased with increasing the CSV content. The T_g‐composition dependence of the PHB/CSV blends was well‐fitted with the Gordon‐Taylor equation, indicating that the CSV was compatible with the PHB. In addition, the presence of the CSV could raise the thermal stability of the PHB component. It was also found that the presence of the PHB and PVAc components would not hinder the enzymatic degradation of the corn starch by α‐amylase. POLYM. ENG. SCI., 55:1321–1329, 2015. © 2015 Society of Plastics Engineers     

Hydrolytic degradation of poly(1,4‐butylene terephthalate‐co‐tetramethylene oxalate) copolymer

Experimentally synthesized poly(1,4‐butylene terephthalate‐co‐tetramethylene oxalate) (PBT–PTMO) monofilaments were evaluated for hydrolytic stability in salt water (SW) and distilled water (DW) at temperature below and above glass transition temperature (T_g), along with commercially available poly(hexamethylene adipamide) (NY), poly(ethylene terephthalate) (PET), and polypropylene (PP) monofilaments. There was no decrease in mechanical properties in case of NY, PET, and PP in either DW or SW below their T_g. The breaking strength, ultimate elongation, and thermal shrinkage of the PBT–PTMO, however, decreased as the ageing time increased. Total strength loss occurred after approximately 300 days at 25°C in either DW and SW. This can be attributed to the chain scission that occurs in the PBT–PTMO copolymer chain. The poor hydrolytic stability of the PBT–PTMO may be attributed to the higher moisture regain. The salinity of water did not have a significant effect on the breaking strength loss of the materials. The mode of hydrolytic degradation of aged PBT–PTMO polymer was confirmed by the increasing generation of the acid carbonyl and hydroxyl groups with concomitant increasing consumption of ester groups, regardless of ageing conditions. Above T_g, the hydrolytic rate constant (k^′_H, day⁻¹) of the PBT–PTMO, estimated by the rate of formation of acid carbonyl groups, is greater at a higher ageing temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 921–936, 1999     

Thermal and mechanical properties of a hydroxyl‐functional dendritic hyperbranched polymer and trifunctional epoxy resin blends

Curing characteristics of blends of a hydroxyl‐functionalized dendritic hyperbranched polymer (HBP) and a triglycidyl p‐amino phenol (TGAP) epoxy resin have been studied. THe HBP strongly enhances the curing rate owing to the catalytic effect of the hydroxyl groups. THe thermal and dynamic viscoelastic behavior of the blends of various compositions (HBP content 0–20%) have been examined and compared to the neat TGAP matrix. THe glass transition temperature (T_g) gradually decreases with increase in HBP concentration. The blends show a higher impact strength compared to neat TGAP. Scanning electron microscopy analysis indicates a single‐phase morphology.     

Direct functionalization with 3,5‐substituted benzoic acids of multiwalled carbon nanotube/epoxy composites

Directly functionalized multiwalled carbon nanotubes (MWCNTs) with benzene‐1,3,5‐tricarboxylic acid (BTC) and 3,5‐diaminobenzoic acid (DAB) were successfully accomplished with less structural damage as confirmed by XPS and FT‐Raman results. Their dispersibility and thermal stability were achieved after the functionalization. The functional groups on MWCNT surfaces can accelerate the curing reaction of epoxy composites remarkable inducing rather low exothermic peak temperature (T_p) and exothermic heat of reaction (ΔH). The values of activation energy (E_a) obtained from Kissinger and Ozawa methods obviously decreased with the introduction of MWCNTs, especially DAB‐MWCNTs. The dynamic mechanical properties notably enhanced with the incorporation of unmodified and functionalized MWCNTs. The crosslink density (ρ) increased and free volume fraction (f_g) decreased, resulting in dramatic increase of glass transition temperatures (T_g) and decrease of coefficient of thermal expansion. Additionally, epoxy composites exhibited low dielectric constant close to that of neat epoxy resin. From these remarkable properties, MWCNT/epoxy composites can be considered as a good candidate for high performance insulation materials. POLYM. ENG. SCI., 53:2194–2204, 2013. © 2013 Society of Plastics Engineers     

Curing of Glycidyl Azide Polymer (GAP) Diol Using Isocyanate,Isocyanate‐Free,Synchronous Dual,and Sequential Dual Curing Systems

Glycidyl azide polymer (GAP) is an important energetic binder candidate for new minimum signature solid composite rocket propellants, but the mechanical properties of such GAP propellants are often limited. The mechanical characteristics of composite rocket propellants are mainly determined by the nature of the binder system and the binder‐filler interactions. In this work, we report a detailed investigation into curing systems for GAP diol with the objective of attaining the best possible mechanical characteristics as evaluated by uniaxial tensile testing of non‐plasticized polymer specimens. We started out by investigating isocyanate and isocyanate‐free curing systems, the latter by using the crystalline and easily soluble alkyne curing agent bispropargylhydroquinone (BPHQ). In the course of the presented study, we then assessed the feasibility of dual curing systems, either by using BPHQ and isophorone diisocyanate (IPDI) simultaneously (synchronous dual curing), or by applying propargyl alcohol and IPDI consecutively (sequential dual curing). The latter method, which employs propargyl alcohol as a readily available and adjustable hydroxyl‐telechelic branching agent for GAP through thermal triazole formation, gave rise to polymer specimens with mechanical characteristics that compared favorably with the best polymer specimens obtained from GAP diol and mixed isocyanate curatives. The glass transition temperature (T_g) of non‐plasticized samples was heightened when triazole‐based curing agents were included, but when plasticized with nitratoethylnitramine (NENA) plasticizer, T_g values were very similar, irrespective of the curing method.     

A high temperature polymer of phthalonitrile‐substituted phosphazene with low melting point and good thermal stability

A phthalonitrile‐substituted phosphonitrilic monomer has been synthesized from phosphonitrilic chloride trimer and then polymerized with addition of 4‐(hydroxylphenoxy)phthalonitrile (HPPN). The chemical structures of the phosphonitrilic monomer and polymer were characterized by Fourier Transform Infrared spectroscopy (FT‐IR) and proton Nuclear Magnetic Resonance spectroscopy (¹H NMR). Curing behaviors and thermal stabilities of the polymer were investigated through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Analysis showed that the monomer has large processing temperature window and good thermal stability. Apparent activation energy, initial curing temperature (T_i), curing temperature (T_p), and termination curing temperature (T_f) of the phosphonitrilic polymer were explored. Dynamic mechanical analysis (DMA), glass transition temperature (T_g) were studied, and limiting oxygen index (LOI) were estimated from the van Krevelen equation, which indicates the polymer process high modulus and good flame retardance. Micro‐scale combustion calorimetry (MCC) was also used for evaluating the flammability of the polymers. Postcuring effects were explored, showing excellent thermal and mechanical properties with postcuring. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42606.     

Azo initiator selection to control the curing order in dimethacrylate/epoxy interpenetrating polymer networks

Differential Scanning calorimetry (DSC) and Fourier‐transform infrared (FT‐IR) spectroscopic studies have been undertaken of the cure of interpenetrating polymer networks (IPNs) formed with imidazole‐cured diglycidyl ether bisphenol‐A (DGEBA) and with either diethoxylated bisphenol‐A dimethacrylate (DEBPADM) or bisphenol‐A diglycidyl dimethacrylate (bisGMA), polymerized by a range of azo initiators (AIBN64, VAZ088, VR110 and AZO168). Due to the differing decomposition rates of the azo initiators, the neat dimethacrylate resin either cured faster than (with AIBN64 and VAZO88), or similar to (VR110), or slower than (AZO168), the neat epoxy resin. In the neat DGEBA/1‐methyl imidazole (1‐MeI), DEBPADM/AIBN64, DEBPADM/VAZO88 and DEBPADM/VR110 resins, close to full cure was achieved. For the neat, high‐temperature DEBPADM/AZO168 resin, full cure was not attained, possibly due to the compromise between using a high enough temperature for azo decomposition while avoiding depolymerization or decomposition of the methacrylate polymer. IPN cure studies showed that, by appropriate initiator selection, it was possible to interchange the order of cure of the components within the IPN so that either the dimethacrylate or epoxy cured first. In the isothermal cure of the 50:50 DEBPADM/AIBN64:DGEBA/1‐Mel IPN system, the cure rate of both species was less than in the parent resins, due to a dilution effect. For this system, the dimethacrylate cured first and to high conversion, due to plasticization by the unreacted epoxy, but the subsequent cure of the more slowly polymerizing epoxy component was restricted by the high crosslink density developed in the IPN. After post‐curing, however, high conversion of both reactive groups was observed and the fully cured IPN exhibited a single high‐temperature T_g, close to the T_g values of the parent resins. In the higher‐temperature, isothermal cure of the 50:50 DEBPADM/VR110:DGEBA/1‐Mel IPN system, the reactive groups cured at a similar rate and so the final conversions of both groups were restricted, while in the 50:50 DEBPADM/AZO168:DGEBA/1‐Mel system it was the epoxy which cured first. Both of these higher‐temperature azo‐initiated IPN systems exhibited single T_gs, indicating a single‐phase structure; however, the T_gs are significantly lower than expected, due to plasticization by residual methacrylate monomer and/or degradation products resulting from the high cure temperature. Copyright © 2004 Society of Chemical Industry     

Carbazole‐based poly(aryl ether ketone) containing crosslinkable allyl groups on the side chains: synthesis,characterization and properties

This paper presents a feasible method for introducing crosslinkable groups into a polymer to achieve excellent chemical resistance and improved thermal stability. Here, 3,6‐bi(4‐fluorobenzenzoyl)‐N‐allylcarbazole, a novel allyl‐containing difluoroketone monomer, is synthesized and characterized. The resulting monomer is polymerized with phenolphthalein through the aromatic nucleophilic substitution reaction at 160 °C to provide the soluble poly(aryl ether ketone) (PAEK) with a pendant allyl group. The obtained PAEK is characterized using Fourier transform infrared spectroscopy, NMR and gel permeation chromatography. The crosslinking reaction of the polymer occurs at 270 °C, and it imparts excellent solvent resistance. DSC analysis shows that the glass transition temperature (T_g) of the cured polymer increases to 262–306 °C when the curing temperature is elevated or when the curing time is extended within certain limits. The rate of increase of T_g and the rate of the crosslinking reaction decrease as the curing time is extended under all of the investigated curing temperatures. The cured PAEKs possess good thermal stability with 5% weight loss temperatures up to 450 °C. The tensile strength and Young's modulus of the polymer film cured at 300 °C for 2 h are 65 MPa and 1.4 GPa, respectively. In addition, the polymer films before and after curing exhibit similar UV?visible absorption and blue light emission. © 2014 Society of Chemical Industry     

Properties of a reactive‐graphitic‐carbon‐nanofibers‐reinforced epoxy

Our previous studies showed that herringbone graphitic GNFs surface‐derivatized with reactive linker molecules bearing pendant primary amino functional groups capable of binding covalently to epoxy resins. Of special importance, herringbone GNFs derivatized with 3,4′‐oxydianiline (GNF‐ODA) were found to react with neat butyl glycidyl ether to form mono‐, di‐, tri‐, and tetra‐glycidyl oligomers covalently coupled to the ODA pendant amino group. The resulting reactive GNF‐ODA (butyl glycidyl)_n nanofibers, r‐GNF‐ODA, are especially well suited for reactive, covalent incorporation into epoxy resins during thermal curing. Based on these studies, nanocomposites reinforced by the r‐GNF‐ODA nanofibers at nanofiber loadings of 0.15–1.3 wt% were prepared. Flexural property of cured r‐GNF‐ODA/epoxy nanocomposites were measured through three‐point‐bending tests. Thermal properties, including glass transition temperature (T_g) and coefficient of thermal expansion (CTE) for the nanocomposites, were investigated using thermal mechanical analysis. The nanocomposites containing 0.3 wt% of the nanofibers gives the highest mechanical properties. At this 0.3‐wt% fiber loading, the flexural strength, modulus and breaking strain of the particular nanocomposite are increased by about 26, 20, and 30%, respectively, compared to that of pure epoxy matrix. Moreover, the T_g value is the highest for this nanocomposite, 14°C higher than that of pure epoxy. The almost constant change in CTEs before and after T_g, and very close to the change of pure epoxy, is in agreement with our previous study results on a chemical bond existing between the r‐GNF‐ODA nanofibers and epoxy resin in the resulting nanocomposites. POLYM. COMPOS., 28:605–611, 2007. © 2007 Society of Plastics Engineers     

Monitoring the reaction progress of a high‐performance phenylethynyl‐terminated poly(etherlmide). Part II: Advancement of glass transition temperature

The cure schedule for carbon fiber‐reinforced, phenylethynyl‐terminated Ultem™ (GE Plastics) composites was studied in an attempt to optimize the resultant glass transition temperature, T_g. Reaction progress and possible matrix degradation were monitored via the T_g. On the basis of previous research, matrix degradation induced T_g reduction was expected for increases in cure time or temperature beyond approximately 70 minutes at 350°C. Using the central composite design (CCD) of experiment technique, composite panels, neat resin, and polymer powder‐coated tow (towpreg) were cured following various cure schedules to allow for the measurement of the glass transition temperatures resulting fronm cure time and temperature variations. The towpreg and neat resin specimens were cured in a differential scanning calorimeter. The glass transition temperatures of all specimens were measured via differential scanning calorimetry; the composite glass transition temperatures were also measured with dynamic mechanical thermal analysis. The composite panels and towpreg specimens showed similar trends in T_g response to cure schedule variations. Composite and towpreg glass transition temperatures increased to a plateau with increasing cure time and temperature, whereas, the neat resin showed an optimal T_g followed by T_g reduction with increasing cure time and temperature. The optimal neat resin T_g occurred within a cure time and temperature significantly below that required to maximize the composite and towpreg glass transition temperatures.     

Functionalization of lignin: Synthesis of lignophenol‐graft‐poly(2‐ethyl‐2‐oxazoline) and its application to polymer blends with commodity polymers

Lignophenol (LP)‐graft‐poly(2‐ethyl‐2‐oxazoline) (POZO) was prepared to reuse lignin, an industrial waste material, and to produce novel LP‐based polymer blends with poly(vinyl chloride) (PVC), poly(bisphenol A carbonate) (PC), polyvinylpyrrolidone (PVP), and polystyrene (PSt) as commodity polymers. The resulting graft polymer was soluble in various types of organic solvents such as chloroform, THF, acetone, and methanol, unlike LP. The miscibility of LP‐graft‐POZO with commodity polymers was measured by differential scanning calorimetry (DSC) to determine the glass transition temperatures (T_g). In the cases of the blends of LP‐graft‐POZO with PVC, PC, and PVP, the T_g values decreased during the second scan. Moreover, in the cases of the blends with PVC and PVP, the T_g values were not detected during the third scan. Therefore, it was inferred that LP‐graft‐POZO was miscible with PVC, PC, and PVP while forming single phases; in particular, the blends of LP‐graft‐POZO with PVC and PVP exhibited a secondary miscibility because the T_g values were not detected. Furthermore, the blend of LP‐graft‐POZO with PC exhibited better thermostability than LP and LP‐graft‐POZO. These results indicated that LP blended with POZO could be used as a polymer additive and as an adhesive to combine different polymers, organic–inorganic polymers, etc. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and dynamic mechanical properties of poly(styrene‐b‐butadiene)‐modified clay nanocomposites

Polybutyl acrylate (PBA) was intercalated into clay by the method of multistep exchange reactions and diffusion polymerization. The clay interlayer surface is modified, and obtaining the modified clay. The structures of the clay‐PBA, clay‐GA (glutamic acid), and the clay‐DMSO (dimethyl sulfoxide) were characterized using X‐ray diffraction (XRD). The new hybrid nanocomposite thermoplastic elastomers were prepared by the clay‐PBA with poly(styrene‐b‐butadiene) block copolymer (SBS) through direct melt intercalation. The dynamic mechanical analysis (DMA) curves of the SBS/modified clay nanocomposites show that partial polystyrene segments of the SBS have intercalated into the modified clay interlayer and exhibited a new glass transition at about 157°C (T_g3). The glass transition temperature of polybutadiene segments (T_g1) and polystyrene segments out of the modified clay interlayer (T_g2) are about ?76 and 94°C, respectively, comparied with about ?79 and 100°C of the neat SBS, and they are basically unchanged. The T_g2 intensity of the SBS‐modified clay decreases with increasing the amounts of the modified clay, and the T_g3 intensity of the SBS‐modified clay decreases with increasing the amounts of the modified clay up to about 8.0 wt %. When the contents of the modified clay are less than about 8.0 wt %, the SBS‐modified clay nanocomposites are homogeneous and transparent. The T_gb and T_gs of the SBS‐clay (mass ratio = 98.0/2.0) are ?78.39 and 98.29°C, respectively. This result shows that the unmodified clay does not essentially affect the T_gb and T_gs of the SBS, and no interactions occur between the SBS and the unmodified clay. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1499–1503, 2002; DOI 10.1002/app.10353     

Relation of swelling and Tg depression to the apparent free volume of a particle‐filled,epoxy‐based adhesive

The effect of hygrothermal aging on a particle‐filled, epoxy‐based adhesive was studied using a gravimetric sorption technique. This study has explored moisture sorption characteristics as well as the associated behaviors of swelling and the depression of the glass transition temperature (T_g). We observed that the diffusion of water in this adhesive has a non‐Fickian behavior, and the depression of T_g proceeds to a definite value that is independent of the final equilibrium water content of the system. Our observations suggest that water diffuses into the polymer in a dual‐sorption mode, in which water resides in two populations. In one population, water is considered to occupy apparent free volume of the adhesive, and the second population water infiltrates polymer structure and forms hydrogen‐bonded clusters. Our results show that hygrothermal aging temperature and swelling do not alter the apparent free volume of this adhesive. We conclude that the constant value of T_g depression at saturation implies that only water in the apparent free volume is responsible for the T_g depression, whereas the swelling proceeds through the formation of hydrogen bonds in the adhesive. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1436–1444, 2003     

Synthesis and characterization of homo‐ and copolymers of 3‐(2‐cyano ethoxy)methyl‐ and 3‐[methoxy(triethylenoxy)]methyl‐3′‐methyl‐oxetane

Two oxetane‐derived monomers 3‐(2‐cyanoethoxy)methyl‐ and 3‐(methoxy(triethylenoxy)) methyl‐3′‐methyloxetane were prepared from the reaction of 3‐methyl‐3′‐hydroxymethyloxetane with acrylonitrile and triethylene glycol monomethyl ether, respectively. Their homo‐ and copolyethers were synthesized with BF₃· Et₂O/1,4‐butanediol and trifluoromethane sulfonic acid as initiator through cationic ring‐opening polymerization. The structure of the polymers was characterized by FTIR and¹H NMR. The ratio of two repeating units incorporated into the copolymers is well consistent with the feed ratio. Regarding glass transition temperature (T_g), the DSC data imply that the resulting copolymers have a lower T_g than pure poly(ethylene oxide). Moreover, the TGA measurements reveal that they possess in general a high heat decomposition temperature. The ion conductivity of a sample (P‐AN 20) is 1.07 × 10^?5 S cm^?1 at room temperature and 2.79 × 10^?4 S cm^?1 at 80 °C, thus presenting the potential to meet the practical requirement of lithium ion batteries for polymer electrolytes. Copyright © 2005 Society of Chemical Industry