Preparation and characterization of thermoplastic polyurethane–urea and carboxylated acrylonitrile butadiene rubber blend nanocomposites

This study deals with the preparation and characterization of novel thermoplastic polyurethane–urea (TPUU) and carboxylated acrylonitrile butadiene rubber (XNBR) blends. Blends of different compositions were prepared in tetrahydrofuran using a solution technique, following an ultra‐sonication. The chemical reaction between the two inherently immiscible blend phases was determined with the help of Fourier transform infrared‐attenuated total reflectance (FTIR‐ATR) spectroscopy and ¹H‐nuclear magnetic resonance (¹H‐NMR) spectroscopy. The identification of the new peaks in the FTIR‐ATR spectra corroborates the existence of chemical reaction between the carboxylic functional group of XNBR and the amide group of the TPUU. In addition, an increase in the network crosslink density of the blend investigated using ¹H‐NMR spectroscopy further supports the occurrence of the chemical reaction between the XNBR and the TPUU. The scanning and transmission electron micrographs of the blend morphology show a uniform dispersion of the minor TPUU phase in the XNBR. Furthermore, the existence of a single glass transition peak also confirms the enhancement in the interfacial miscibility. Additionally, the incorporation of 5 wt % of organomodified montmorillonite nanoclay improves the mechanical properties to a considerable extent in comparison with the unfilled blend elastomeric material. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The nature and location of SEBS–MA compatibilizer in polyethylene–wood flour composites

A maleic-anhydride-grafted styrene–ethylene—butylene–styrene (SEBS–MA) triblock copolymer has been used as a compatibilizer in low-density polyethylene–wood flour (LDPE–WF) composite system. The location of compatibilizer was studied using transmission electron microscopy (TEM). The unsaturated parts of the copolymer were stained with osmium tetraoxide (OsO₄) to enhance contrast between the different phases. TEM micrographs indicated that part of the compatibilizer was located at the interface between the wood particles and PE matrix and that wood was also stained by the OsO₄. The nature of the interface between the wood surface and the SEBS–MA was studied using Fourier transform infrared spectroscopy (FTIR). The results indicated that MA reacts with wood through esterification and hydrogen bonding and also possibly through interaction between the styrene and wood. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 201–209, 1998     

Preparation and characterization of acrylonitrile–styrene–methylmethacrylate terpolymer as a compatibilizer for rubber blends

Acrylonitrile‐co‐styrene‐co‐methylmethacrylate (AN‐S‐MMA) terpolymer was prepared by bulk and emulsifier‐free emulsion polymerization techniques. The bulk and emulsion terpolymers were characterized by means of Fourierr transform infrared spectroscopy, ¹³C nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography, thermal gravimetric analysis, and elemental analysis. The kinetics of the terpolymerization were studied. The terpolymers were then incorporated into butadiene—acrylonitrile rubber (NBR)/ethylene propylene diene monomer rubber (EPDM) blends and into chloroprene rubber (CR)/EPDM blend. The terpolymers were then tested for potential as compatibilizers by using scanning electron microscopy and differential scanning calorimetry. The terpolymers improved the compatibility of CR/EPDM and NBR/EPDM blends. The physicomechanical properties of CR/EPDM and NBR/EPDM blend vulcanizates revealed that the incorporation of terpolymers was advantageous, since they resulted in blend vulcanizates with higher 100% moduli and with more thermally stable mechanical properties than the individual rubbers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3143–3153, 2003     

Photodegradation of thermoplastic elastomeric rubber–polyethylene blends

The photodegradation of a new family of thermoplastic elastomers, based on blends of natural rubber and polyethylene, was studied with laboratory ultraviolet exposures in the unstrained state and under tensile strain (25 and 50%). Strained exposure caused reduction of the strain to failure in subsequent tensile tests. The blends were more resistant to degradation than the natural rubber homopolymer. The introduction of crosslinks (at a low concentration so that the thermoplastic nature of the blends was retained) changed the resistance to photo‐oxidation. Two different crosslinking systems were used. When dicumyl peroxide was used as the crosslinking agent, the resistance to degradation was reduced, whereas the compound containing a sulfur curing system showed improved resistance to photodegradation. Photo‐oxidation rather than ozone degradation was found to be the major cause of breakdown, even with samples held in tension. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2393–2402, 2002     

Interpenetrating polymer networks of bismaleimide and polyether polyurethane–crosslinked epoxy

In this work, we prepared the interpenetrating polymer networks of bismaleimide and polyether-type polyurethane(polyoxypropylene)–crosslinked epoxy (BMI/PU(PPG)–EP IPNs) by employing the simultaneous bulk polymerization technique. The polyurethane (PU)–crosslinked epoxy was identified via infrared (IR) spectra analysis. Also investigated herein were the mechanical properties, including tensile strength, Izod impact strength, and fracture energy (G_IC) of the IPNs with various BMI contents in PU–crosslinked epoxy matrix. In addition, differential scanning calorimetry (DSC) analysis and the thermogravimetric analysis (TGA) were performed to examine the thermal properties of the BMI/PU(PPG)–EP IPNs. In addition, morphology and dynamic mechanical analysis (DMA) of the BMI/PU(PPG)–EP IPNs were also studied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2635–2645, 1998     

Compatibilization of poly(ethylene-co-vinyl alcohol) (EVOH) and EVOH–HDPE blends: Structure and properties

Hydrogenated and maleated S-B-S block copolymer (SEBS-g-MA) was applied as a compatibilizer in melt-mixed binary blends with poly(ethylene-co-vinyl alcohol) (EVOH) and in ternaries containing high-density polyethylene (HDPE) as the major component. The techniques applied were dynamic, mechanical, and tensile testing; differential thermal analysis; Fourier transform infrared spectroscopy; and optical and electron microscopy (SEM). Small and large deformation behavior under dynamic and static mode, coupled with other physical characterization data, as well as morphological evidence, demonstrated that SEBS-g-MA is an efficient compatibilizer in the binary and ternary blends. In the latter, its function is the coupling of EVOH with the HDPE matrix, thus reducing the moisture sensitivity of the former and the improvement of performance-to-cost ratio of the final product. After leaching out EVOH from the ternaries, morphology examination of the cross section of films, showed a laminar EVOH phase distribution, a feature desirable in barrier materials applications. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 589–596, 1998     

Thermal and dynamic mechanical characterization of polyurethane–urea–imide coatings

A series of NCO terminated polyurethane (PU)–imide copolymers were synthesized by a systematic three‐step process and were chain extended with different diol/diamine chain extenders. In the first step, isocyanate terminated PU prepolymers were prepared by reacting soft segments such as polyester (PE) polyols and polyether polyols such as polypropylene glycol (PPG‐1000) with hard segments like 2,4‐tolylene‐diisocyanate (TDI) or isophorone‐diisocyanate (IPDI) with NCO/OH ratio 2:1. In the second step, thermally stable heterocyclic imide ring was incorporated using isocyanate terminated PU prepolymers by reacting with pyromellitic dianhydride (PMDA) in a excess‐NCO:anhydride ratio of 1:0.5. The surplus NCO content after imidization was both moisture cured or partially reacted with chain extender and moisture cured. The films were characterized by thermogravimetric (TG), differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) instruments. The adhesion strength of these coatings on mild steel (MS), copper (Cu), and aluminum (Al) is dependent on the nature of the substrate. The TGA analysis show good thermal stability. The DMTA results show the microphase separation between the different hard and soft segments. Finally, a structure to property correlation was drawn based on the structure of the soft, hard, and chain extender and the observed properties are useful for understanding and design of intelligent coatings. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3158–3167, 2006     

大分子相容剂在填充聚烯烃中的应用

综述了国内外大分子相容剂在填充聚烯烃塑料中的应用，以及大分子相容剂改性填充聚烯烃塑料的物理与力学性能；指出大分子相容剂用于填充塑料，能改善高分子基体与填料间界面粘结，提高填充塑料复合材料的物理与力学性能，比传统有机偶联剂更具特点。     

Synthesis and characterization of UV-curable waterborne polyurethane–acrylate ionomers for coatings

A new kind of ultraviolet (UV)-curable waterborne polyurethane–acrylate (PUA) ionomer, prepared from toluene diisocyanate (TDI), polyethylene glycol (PEG), dimethylolpropionic acid (DMPA), triethylamine (TEA), and 2-hydroxyethyl methacrylate (HEMA), was synthesized by the modified prepolymer mixing process in which water serves as a chain-extender and dispersant. Fourier transform infrared (FTIR) spectra demonstrated the formation of the PUA ionomers both in dispersions and in their corresponding cured films. Surface tension of the PUA dispersions decreased as the DMPA-to-PEG mole ratio increased. The investigation of rheological behavior of the PUA dispersions suggested that all the dispersions belong to pseudoplastic fluid and display the characteristic of common polymer dispersions. Differential scanning calorimetry (DSC) analysis showed that the increasing DMPA-to-PEG mole ratio may result in a higher T_g and a broader transition zone for the hard segment. The results of TGA for the PUA-cured films indicated good thermal stability with no appreciable weight loss until well above 200°C. Measurement of physical properties showed that all the PUA-cured films exhibited excellent adhesion, gloss, flexibility, and impact strength, as well as pendulum hardness, depending upon hard segment content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2869–2876, 1999     

Behavior of ionomers of sulfonated styrene–butadiene–styrene triblock copolymer in polymer blends with crystalline polyolefins and as compatibilizer

The blends of ionomers of sulfonated (styrene–butadiene–styrene) triblock copolymer with two polyolefins as well as the blends of polystyrene (PSt) with two polar, oil‐resistant elastomers, i.e., chlorohydrin rubber (CHR) and chlorosulfonated polyethylene (CSPE), using the ionomer as compatibilizer were studied. The blends of the ionomer with polypropylene or high density polyethylene showed synergistic effects with respect to tensile strength. With increasing PSt content, the blends change their behavior from thermoplastic elastomer to toughened plastics. The synergism is probably because of the thermoplastic interpenetrating polymer networks formed in the blend. The blends exhibited high resistance against diesel oil or toluene. When PSt was blended with CHR or CSPE using the ionomer as compatibilizer, only 2 or 3% ionomer was needed to enhance the mechanical properties of the blends. The effect is due to the ion–polar interaction of the ionomer with the polar polymer. The enhanced compatibility of the blends by the ionomer was demonstrated by DSC and Scanning electron micrograph. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1887–1894, 2006     

Polymer blends based on polyolefin elastomer and polypropylene

A new family of homogeneous polyolefin polymers that exhibit unique molecular and rheological properties designated polyolefin elastomers (POEs) are characterized by a narrow molecular weight and high degrees of comonomer distribution. Because these copolymers are often elastomeric in nature, one of the uses for these materials is as impact properties improver for brittle polymers such as polypropylene at low temperatures. In this work a study was carried out about the effectiveness of the polyethylene elastomer (POE) as an impact modifier for polypropylene in relation to the traditional modifier EPDM. In this study the flow properties of of the POE/PP and EPDM/PP blends were also evaluated. The blends were analyzed by solid-state ¹³C nuclear magnetic resonance (¹³C-NMR) spectroscopy, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). The results showed that PEE/PP and EPDM/PP blends present a similar crystalline behavior, which resulted in a similar mechanical performance of the blends, on the composition analyzed. It was also verified that the POE/PP blend presents lower torque values than the EPDM/PP blend, which indicates a better processability when POE is used as an impact modifier. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2005–2014, 1997     

Supramolecular semicrystalline polyolefin elastomer blends with triple‐shape memory effects

Supramolecular polyolefin elastomer blends possessing triple‐shape memory effects were prepared by melt blending of two semicrystalline maleated elastomers (maleated ethylene‐propylene‐diene rubber (mEPDM) and maleated polyethylene‐octene elastomer (mPOE)) in the presence of a small amount of 3‐amino‐1,2,4‐triazole (ATA). The amino group of ATA reacted with the maleic anhydride groups of both elastomers during melt blending to form supramolecular hydrogen‐bonded networks. Dynamic mechanical analysis of the blends showed drops in the storage modulus at two different transition temperatures (T_trans) belonging to the crystalline melting temperatures of each phase as well as a plateau above these two T_trans. This is an essential property for triple‐shape memory behavior. Dual‐shape memory properties of the blends were determined using one‐step programming under three different temperature ranges. When an individual crystalline phase is used for the fixing process, the switching temperature (T_sw) relates to the melting temperature of a particular phase during the recovery process. However, if both crystalline phases are used simultaneously for the fixing process, then the T_sw relates to the higher melting temperature. Cyclic two‐step programming revealed that two different shapes can be fixed, one by EPDM crystallization and the other by POE crystallization, and both programmed shapes can be recovered upon heating above a specific T_sw. © 2016 Society of Chemical Industry     

On the mechanism of compatibilization of polyolefin/liquid crystalline polymer blends with graft copolymers

The compatibilization mechanism of some compatibilizers for blends of polyolefins with a liquid crystalline polymer (LCP) was studied. Polyethylene (PE) and polypropylene (PP) were blended with a semirigid LCP (SBH) in a batch mixer, either with and without compatibilizers. The latter were two commercially available samples of functionalized polyolefins, that is, a PE‐g‐MA (HDM) and a PP‐g‐AA (Polybond 1001) copolymer and some purposely synthesized PE‐g‐LCP and PP‐g‐LCP copolymers. Microtomed films of the binary and the ternary blends were annealed at 240°C on the hot stage of a polarizing microscope and the changes undergone by their morphology were recorded as a function of time. The results indicate that the compatibilizers lower the interfacial tension, thereby providing an improvement of the minor phase dispersion. In addition to this, the rate of the coalescence caused by the high‐temperature treatment is appreciably reduced in the systems compatibilized with the PE–SBH and PP–SBH graft copolymers. Among the commercial compatibilizers, only Polybond 1001 displayed an effect comparable to that of the above copolymers. HDM improved the morphology of the as‐prepared PE blends, but failed to grant sufficient morphological stabilization against annealing‐induced coarsening. The results are discussed with reference to the chemical structure of the different compatibilizers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3027–3034, 2000     

Unsaturated polyester as compatibilizer for styrene–butadiene (SBR)/acrylonitrile–butadiene (NBR) rubber blends

The effect of the addition of 5 and 10 phr of unsaturated polyester resin (UPE) on the compatibility and physicomechanical properties of styrene–butadiene (SBR) and acrylonitrile–butadiene (NBR) rubber blends was studied. Differential scanning calorimetry (DSC), scanning electron microscopy (SEM), electrical, and ultrasonic techniques were used to determine the degree of the compatibility (DC). The results obtained revealed that, by the addition of 10 parts per hundred parts of rubber (phr) UPE as a compatibilizer for SBR/NBR blends, the degree of compatibility was greatly enhanced. The rheological and mechanical properties of the blends were also improved. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2314–2321, 2002     

Study on synthesis and thermal properties of polyurethane–imide copolymers with multiple hard segments

Different multiple hard segment polyurethane–imide copolymers (MHPUI) were synthesized and characterized. FTIR spectroscopy confirmed the characteristic absorption of the MHPUI copolymer. The difference in the imide group FTIR absorption bands in different MH segment PUI copolymers was found in this study and was explained by the different MH segment types, hard segment contents, and hard segment rigidity with different interactions of the molecular chains. The hard segment interaction in MHPUI with an increase of the structure rigidity of the short hard segments is strengthening. The DSC analysis revealed that the glass‐transition temperature of the soft segment of PUI rose in value from ?42 to ?3.4°C with the introduction of MH and different MH segments. The DSC results suggest that the soft segment is more compatible with the hard segment rigidity increase. The TGA results showed the hard segment structure symmetry has a more important role in the MHPUI thermal stability. Every sample containing symmetrical structure short hard groups (4,4′‐diphenylmethane diisocyanate or 4,4′‐diaminodiphenylmethane) is more thermally stable than that with worse symmetry structure groups (2,4‐toluene diisocyanate or 3,3′‐dichloro‐4,4′‐diamino‐diphenylmethane). The three‐step mechanism of PUI thermal degradation was further verified by the TGA study. The thermally unstable group was confirmed as urethane or a urea–urethane segment. The TGA results showed that MHPUI copolymers with higher separation of the soft–hard phase have higher thermal stability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2206–2215, 2002     

Synthesis of polyurethane–imide (PU–imide) copolymers with different dianhydrides and their properties

This study reports the synthesis of polyurethane–imide (PU–imide) copolymers using 4,4′-diphenylmethane diisocyanate (MDI) polytetramethylene glycols (PTMGs) and different aromatic dianhydrides. Differential scanning calorimetry (DSC) results indicate that PU–imide copolymers had two phase structures containing four transition temperatures (T_gs, T_ms, T_gh and T_mh). However, only PU–imide copolymers were formed by soft PTMG(2000) segments possessing a T_ms (melting point of soft segment). When different aromatic dianhydrides were introduced into the backbone chain of the polyurethane, although the T_gs (glass transition temperature of the soft segment) of some of PU–imide copolymers did not change, the copolymers with long soft segments had low T_gs values. The T_gh (glass transition temperature of hard segment) values of PU–imide copolymers were higher than that of polyurethane (PU). In addition, the high hard segment content of PU–imide copolymer series also had an obvious T_mh (melting point of hard segment). According to thermogravimetric analysis (TGA) and differential thermogravimetric analysis (DTGA), the PU–imide copolymers had at least two stages of degradation. Although the T_di (initial temperature of degradation) depended on the hard segment content and the composition of hard segment, the different soft segment lengths did not obviously influence the T_di. However, PU–imide copolymers with a longer soft segment had a higher thermal stability in the degradation temperature range of middle weight loss (about T_d 5%–50%). However, beyond T_d 50% (50% weight loss at temperature of degradation), the temperature of degradation of PU–imide copolymers increased with increasing hard segment content. Mechanical properties revealed that the modulus and tensile strength of PU–imide copolymers surpassed those of PU. Wide angle X-ray diffraction patterns demonstrated that PU–imide copolymers are crystallizable. © 1999 Society of Chemical Industry     

In situ compatibilization of polystyrene/polyolefin elastomer blends by the Friedel–Crafts alkylation reaction

Blends of polystyrene (PS) with polyolefin elastomer (POE) were prepared by a reactive extrusion method. In order to increase the compatibility of the two blending components, a Lewis acid catalyst, aluminium chloride (AlCl₃), was adopted to initiate the Friedel–Crafts alkylation reaction. Fourier‐transform infrared (FTIR) spectra of the PS/POE/AlCl₃ blends extracted with butanone verified the graft structure between the PS and POE. Because the in situ generated PS‐graft‐POE copolymers acted as compatibilizers, the mechanical properties of PS/POE blends were greatly improved. For example, after compatibilization, the Charpy impact strength of an 80/20 (wt%) PS/POE blend was increased from 6.29 to 8.50 kJ m^?2. Scanning electron microscopy (SEM) showed that the size of the droplets decreased from 9–10 µm to less than 2 µm with the addition of AlCl₃. Gel permeation chromatography (GPC) showed competition between the grafting reaction and the degradation of blending components in the presence of AlCl₃. Copyright © 2005 Society of Chemical Industry     

Adsorption of color dyestuffs on polyurethane–chitosan blends

This study made use of poly(ethylene glycol) (PEG) samples of different molecular weights, which were reacted with a diisocyanate ester, and an anion center for the synthesis of polyurethane (PU), which was then mixed with chitosan to form a polymer adsorbent. It was tested for the determination of its adsorption toward acidic dyestuffs under various conditions. Our results showed that under all the tested conditions, the blended polymer adsorbent possessed a better adsorbing ability than chitosan by itself, and the degree of adsorption varied positively as the adsorbent concentration, ambient temperature, and contact time increased. Furthermore, the addition of PU remarkably increased the adsorption efficiency, whereas PEG with a greater molecular weight yielded a better adsorption performance. As for the dyestuffs, the red one surpassed the others in adsorption efficiency. Finally, a 5 mg/mL concentration of the adsorbent solution, a temperature of 45°C, and a contact time of 15 min gave fairly good adsorption results. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3991–3998, 2004     

Modifications of the rigid polyurethane–polyisocyanurate foams

The method of boroorganic compounds preparation by esterification of boric acid and glycols has been presented. The obtained compounds tri(2‐hydroxybutyl)borate, tri(hydroxythiodiethylene)borate, tri[(3‐chloro‐2‐hydroxy‐1‐propoxy)‐1‐methylpropyl]borate, and tri[3‐chloro‐2‐hydroxy‐1‐propoxy)thiodiethyl]borate were used to produce the rigid polyurethane–polyisocyanurate (PUR‐PIR) foams. The foams were prepared by one‐stage method and the amount of borates added varied, within the range from 0.0 to 0.4 of chemical equivalent. The method of preparation, determination of foaming parameters, and methods of testing of the physicochemical properties of PUR‐PIR foams as well as their results have been presented. A special emphasis was put on reduction of the foam flammability. It was found that application of the obtained compounds as polyolic components has a favorable effect on the properties of the produced rigid PUR‐PIR foams. The obtained rigid PUR‐PIR foams were characterized by a higher compressive strength, lower brittleness, considerably reduced flammability, and higher content of the closed cells. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2020–2029, 2006