Adhesive and composite evaluation of acetylene-terminated phenylquinoxaline resins

A series of acetylene-terminated phenylquinoxaline (ATPQ) oligomers of various molecular weights were prepared and subsequently chain extended by the thermally induced reaction of the ethynyl groups. The processability and thermal properties of these oligomers and their cured resins were compared with that of a relatively high molecular weight linear polyphenylquinoxaline (PPQ) with the same chemical backbone. The ATPQ oligomers exhibited significantly better processability than the linear PPQ but, the PPQ displayed substantially better thermooxidative stability. Adhesive (Ti/Ti) and composite (graphite filament reinforcement) work was performed to evaluate the potential of these materials for structural applications. The PPQ exhibited better retention of adhesive and laminate properties than the ATPQ resins at 260°C after aging for 500 h at 260°C in circulating air.     

Adhesive Properties of Cured Phenylethynyl-Terminated Imide Oligomers

As part of a program to develop structural adhesives for high performance aerospace applications, phenylethynyl-terminated imide oligomers are under evaluation. Imide oligomers with different molecular weights and compositions endcapped with either 4-(3-aminophenoxy)-4'-phenylethynylbenzophenone (3-APEB) or 4-phenylethynylphthalic anhydride (PEPA) have been prepared and characterized. These oligomers exhibit excellent processability. After heating to 350°C for 1 hour, the terminal phenylethynyl groups have reacted to provide chain extension, branching and crosslinking. The cured polymers exhibit excellent solvent resistance and high mechanical properties as neat resins and in various adhesive forms (tensile shear, sandwich flatwise tension and climbing drum peel specimens). The chemistry and properties of these phenylethynyl-terminated imide oligomers are discussed.     

15N CP/MAS NMR Study of the Isocyanate/Wood Adhesive Bondline. Effects of Structural Isomerism

Structurally isomeric ¹⁵N-labeled polymeric methylenebis(phenylisocyanate), pMDI, adhesives were synthesized. One resin had a high content of 4,4'-MDI, and another was prepared with a high content of 2,4'-MDI. Both resins were cured with wood (Liriodendron tulipifera) for various times and temperatures and then analyzed using ¹⁵N CP/MAS NMR. It was found that resin polymerization occurs via the reaction of isocyanate with wood moisture to form polyurea. Biuret formation and isocyanate dimerization were detected. Urethane formation probably also occurs; however, signal overlap of urea and urethane signals prevents a definitive conclusion. These findings are similar to previous ones; however, subtle differences are noted. The structurally isomeric resins displayed similar chemistries. Of the two resins, the resin prepared with a high content of 2,4'-MDI cured more slowly, and resulted in a network that was more mobile in the midkilohertz frequency range. This leads to the prediction that resins high in 2,4'-MDI may have a superior performance in impact loading.     

Properties of compression‐molded plates made from wood powders impregnated with liquefied wood‐based novolak‐type phenol‐formaldehyde resins

Novolak‐type phenol‐formaldehyde (PF) resins with solution form were prepared by reacting phenol‐liquefied Cryptomeria japonica (Japanese cedar) wood with formalin in the presence of methanol. Wood powders of Albizzia falcate (Malacca albizzia) impregnated with these resins were air dried followed by an oven‐dried at 60°C. DSC analysis showed the PF resin existing in wood powders could be melted, and could be cured if hexamine was mixed and heated at high temperature. Compression‐molded plates made with PF resin impregnated woods had a high degree of curing reaction. However, compression‐molded plates hot‐pressed at 180°C for 8 min or 200°C for 5 min had better internal bonding strength and dimensional stability than others. Premixing hexamine with PF resin and impregnating into wood powders simultaneously could enhance the reactivity of PF resin, but it was not useful for improving the properties of compression‐molded plates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dependence of microstructure and properties of polypropylene/bromo-isobutylene-isoprene rubber thermoplastic vulcanizates on the molding process

To explore the dependence of the microstructure and properties of thermoplastic vulcanizates (TPVs) on the molding process. The polypropylene/bromo-isobutylene-isoprene rubber thermoplastic vulcanizates (PP/BIIR-TPVs) are molded by high rate shear injection and compression molding, and the phase morphology and physical-mechanical properties of PP/BIIR-TPVs specimens are investigated. Detailed small-angle X-ray scattering, scanning electron microscopy and atomic force microscopy investigations demonstrate that the high rate shear of injection molding not only decreases the size of BIIR particles but also induces the orientation of the PP matrix and further increases its crystallinity. Subsequently, the PP/BIIR-TPVs molded by injection molding have higher tensile strength and Young's modulus, while the compression molding benefits to higher elongation at break. The mechanism regarding the effects of high rate shear during injection molding on phase morphology development of PP/BIIR-TPVs is discussed. This study guides the preparation of TPVs products with desired properties.     

Polyphenylquinoxalines containing alkylenedioxy groups

A series of new polyphenylquinoxalines (PPQ) containing alkylenedioxy units within the backbone were prepared in high molecular weight forms (η_inh = 0.82–1.5 dL/g). The glass transition temperatures ranged between 203 and 241°C, decreasing with increasing length of the alkylenedioxy groups. Solution-cast films gave tensile strength, tensile modulus, and elongation at room temperature as high as 14,400 psi, 378,000 psi, and 8.1%, respectively. The PPQ were readily compression molded to provide compact tension specimens that gave fracture energy (G_Ic) as high as 10.5 in. lb/in.² Titanium to titanium tensile shear specimens provided average strengths of 4400 psi at 26°C, 3100 psi at 177°C, and 2010 psi at 203°C. The PPQ were resistant to normal aircraft fluids but were soluble in chlorinated solvents.     

Synthesis of imide-aryl ether benzoxazole block copolymers

Summary Imide-aryl ether benzoxazole multiblock copolymers were investigated. A key feature of these copolymers was the preparation of bis(amino) terminated aryl ether benzoxazole oligomers (PBO) via a novel nucleophilic aromatic displacement polymerization. Oligomers with number average molecular weights of 10,500 and 26,000 g/mol were prepared, which displayed T_g's of 210 and 227°C, respectively. The oligomers were co-reacted with 4,4-oxydianaline (ODA) and pyromellitic dianhydride (PMDA) diethyl ester diacyl chloride in a NMP/ cyclohexanone solvent mixture in the presence of N-methylmorpholine. The resulting amic ester-aryl ether benzoxazole copolymers were isolated and washed to remove homopolymer contamination. Copolymer compositions were analyzed by ¹³C NMR. Solutions of the copolymers were cast and cured to effect the imidization, affording tough films with high elongations. Multiphase morphologies were obtained for both of the PBO block lengths used in the copolymerization.     

Performance of protein-based wood bioadhesives and development of small-scale test method for characterizing properties of adhesive-bonded wood specimens

A small-scale test method to measure the tensile strength of adhesive-bonded wood strip specimens was developed by simple modification of commercially available binder clips. As bioadhesives, soy protein concentrate (SPC) and gelatin resins were prepared and were evaluated for shear and tensile bond strengths of bamboo and maple wood-bonded specimens. Titebond-II (TB-II), a commercially available wood glue was also tested to compare its bonding property to SPC and gelatin-based bioadhesives. TB-II glue showed the highest shear and tensile bond strengths with both bamboo and maple wood strips. Hot-pressing increased the shear and tensile bond strengths of SPC resin with wood specimens by 500% while the increase for gelatin resins was up to 200%. Roughness profile and surface properties were also characterized with an optical interferometric profiler and a scanning electron microscope. The results indicated that rougher surface significantly increased the bond strengths in both shear and tensile modes.     

New acetylene-terminated phenylquinoxaline oligomers

A series of new acetylene-terminated phenylquinoxaline oligomers and diacetylene compounds have been prepared utilizing 4-(3-ethynylphenoxy)benzil. The amorphous materials with molecular weights from 500 to 1460 exhibited softening in the 25–160°C range with a strong polymerization exotherm reaching a maximum at 270–290°C. The addition nonvolatile cure provides materials which show excellent thermoxidative stability and processability for high-temperature matrix and adhesive resins.     

Microstructure and ultimate properties of injection molded amorphous engineering plastics: Poly(ether imide) and poly(2,6-dimethyl-1,4-phenylene ether)

Specimens of two engineerig plastics i.e., poly(ether imide), PEI, and poly(2,6-dimethyl- 1,4-phenylene ether), PPE, were injection molded employing a 40t Van Dorn injection molding machine and industrial practices. The mold and melt temperatures and the injection speed were varied in a limited range which furnished acceptable samples. The density, birefringence, residual stress distributions, flexure and tensile properties, and crack development of the injection molded specimens were studied. Vacuum compression molded samples were also prepared to investigate the role played by the cooling rate in shaping microstructural distributions. The results revealed significant differences in the development of microstructure of the molded specimens of the two resins, which was related to rheology and molding conditions on one hand and to development of cracks and ultimate properties on the other hand.     

Influence of processing conditions on the mechanical properties of SEBS/PP/oil blends

A common type of thermoplastic elastomer is a blend of styrene-ethylene-butylene-styrene copolymer (SEBS) with polypropylene and mineral oil. The knowledge about the processing parameters that influence the blend of these components is important to achieve the best material properties. In this study, were evaluated the influence of screw configuration (low and high shear) and speed (200, 300, and 400 rpm), molding form (compression and injection) and SEBS type (high and low molecular weight). The specimens were characterized according to their morphology, crystallinity, thermomechanical and mechanical properties. Samples processed in a screw with more kneading zones had a lower modulus value. Compression molded specimens had lower mechanical performance than injected samples. Samples prepared with low molecular weight SEBS presented a loss of mechanical properties. It was possible to correlate processing form with all the properties evaluated. The analyzed variables influenced the morphology, crystallinity and thermomechanical properties, but had low influence on the tensile properties.     

Improving mechanical properties of poly(vinyl chloride) by doping with organically functionalized reactive nanosilica

Nanosilica particles are functionalized by in situ surface‐modification with trimethyl silane and vinyl silane. Resultant reactive nanosilica (coded as RNS) contains double bonds and possesses good compatibility with vinyl chloride (VC) and polyvinyl chloride (PVC). This makes it feasible for RNS to copolymerize with VC generating RNS/PVC composites via in situ suspension polymerization. As‐prepared RNS/PVC composite resins are analyzed by means of FTIR. The tensile strength and impact strength of compression‐molded RNS/PVC composites are measured and compared with that of compression‐molded PVC composites doped with dispersible nano‐SiO₂ particles (abridged as DNS) surface‐modified with trimethyl silane alone. Moreover, the thermal stability of compression‐molded RNS/PVC and DNS/PVC composites is evaluated by thermogravimetric analysis. It has been found that RNS/PVC composites possess greatly increased impact strength and tensile strength than PVC matrix, while DNS/PVC composites possess higher impact strength than PVC matrix but almost the same tensile strength as the PVC matrix. This implies that DNS is less effective than RNS in improving the mechanical strength of PVC matrix. Particularly, RNS/PVC composites prepared by in situ suspension polymerization have much higher mechanical strength than RNS/PVC composites prepared by melt‐blending, even when their nanosilica content is only 1/10 of that of the melt‐blended ones. Besides, in situ polymerized RNS/PVC and DNS/PVC composites have better thermal stability than melt‐blended nanosilica/PVC composites. Hopefully, this strategy, may be extended to fabricating various novel high‐performance polymer‐matrix composites doped with organically functionalized nanoparticles like RNS. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

New aromatic poly(ether-ketone)s containing hexafluoroisopropylidene groups

Summary New aromatic poly(ether-ketone)s containing hexafluoroisopropylidene groups have been prepared by aromatic nucleophylic displacement reaction of the potassium salts of aromatic dihydroxy compounds containing fluoren, 1,3,4-oxadiazole or phenylquinoxaline rings with 2,2-bis[4-(4-fluorobenzoylphenyl)hexafluoropropane. These polymers were readily soluble in various organic solvents such as N,N-dimethylformamide, pyridine, tetrahydrofuran and chloroform and gave flexible films by casting such solutions. Their glass transition temperatures (T_g) were in the range of 189–222°C and they were thermally stable up to 480°C. The polymer films displayed low dielectric constants, in the range of 2.8 – 3.2, and good mecanical properties, with tensile strength in the range of 46 – 61 MPa and elastic modulus of 1.4 – 1.6 GPa. Received: 6 April 2001/Revised version: 31 July 2001/Accepted: 31 July 2001     

Molecular weight distribution and environmental stress cracking of linear polyethylene

Molecular weight distributions of both Phillips and Zieglertype high density polyethylenes were determined following fractionation of the polymer samples using a column elution technique. The Wesslau log normal distribution function was used to describe the distributions of the resins investigated. Resistance to environmental stress rupture of speciments cut from compression molded plaques of these samples was measured by the constant tensile loading procedure. Data are presented showing annealed resins with “broad” molecular weight distributions, characterized particularly by a quantity of low molecular weigt material and a high molecular weight “tail,” to have poorer stress crack resistance than samples having a “narrow” molecular weight distribution. Stress crack resistance of specimens quenched from the melt, however, tends to improve for “broad” distribution resins, while decrasing for those polyethylenes having a “narrow” molecualar weigt distribution. Differences in crystal structure are used to explain the physical bassis for these effects.     

Preparation of cardanol–formaldehyde resins from cashew nut shell liquid for the reinforcement of natural rubber

Natural rubber was reinforced with a high loading of a cardanol–formaldehyde resin prepared from cashew nut shell liquid. Cardanol–formaldehyde resins, both resoles and novolaks, were synthesized from cardanol, which was extracted from cashew nut shells. This was done by the condensation polymerization of cardanol and formaldehyde in the presence of base and acid catalysts. The cardanol–formaldehyde resole with the highest yield (ca. 75%) was prepared with a formaldehyde/cardanol molar ratio of 2.0 at pH 8.0 and 90°C for 8 h. The cardanol–formaldehyde novolak with the highest yield (ca. 80%) was prepared with a formaldehyde/cardanol molar ratio of 0.8 at pH 2.2 and 100°C for 7 h. Fourier transform infrared and ¹³C‐NMR were employed to characterize the chemical structures of the obtained cardanol–formaldehyde resins. The resins were compatible with natural rubber in various formulations. The cured behaviors of natural rubber blended with the cardanol–formaldehyde resole and novolak resins were investigated. The cured behaviors of cardanol–formaldehyde resole and cardanol–formaldehyde novolak samples were different, reflecting differences in their chemical reactivities. Furthermore, the incorporation of cardanol–formaldehyde resins into natural rubber provided significant improvements in mechanical properties such as the hardness, tensile strength, modulus at 100 and 300% elongation, and abrasion resistance. However, the elongation at break and compression set of the blends decreased as expected. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1997–2002, 2007     

Synthesis and characterization of phenylquinoxaline-arylene ester block copolymers

Summary Phenylquinoxaline-arylene ester block copolymers were prepared from phenolic hydroxyl terminated oligomers of defined molecular weight using an oligomer/monomer(s) approach, in which generation of the ester linkage coupling the blocks occurred concomitantly with the growth of the polyester block. The molecular weight of the phenylquinoxaline block was held constant at 12,900, while the stoichiometry of the arylene ester monomers were adjusted to afford copolymers containing 15, 30, and 50 wt% poly(arylene ester). These copolymers represent the first example of PPQ-based block copolymers derived from well defined phenylquinoxaline oligomers.     

Adhesive and Thermo-Mechanical Behavior of Phosphorus-Containing Thermoplastic Polyimides

Thermally stable, soluble and amorphous bis(m-aminophenoxy) triphenylphosphine oxide (m-BAPPO) based polyimides were synthesized in controlled high molecular weight via solution imidization. Several dianhydrides were used to establish chemical-structure-physical property behavior. The m-BAPPO based polyimides were characterized by several techniques, including intrinsic viscosity, thermal analysis, single lap shear adhesive bond strength and thermo-mechanical behavior. The resulting phosphorus-containing polyimides were demonstrated to be thermally stable via dynamic TGA in air up to 500°C and showed 10 ∼ 20% char yield at 750°C, suggesting improved fire resistance. In addition, these polyimides showed good tensile modulus, ductile stress-strain behavior and excellent adhesion to a Ti-6A1-4V substrate, as determined by single lap shear tests. The rheological behavior was investigated by using a parallel plate type viscometer which confirmed that the materials were true thermoplastics. Tailoring the polyimides with the non-reactive phthalimide end group inhibited crosslinking and chain extension and, hence, was essential for the observed good processibility.     

Compressive Properties and Curing Behaviour of Unsaturated Polyester Resins in the Presence of Vinyl Ester Resins Derived from Recycled Poly(ethylene terephthalate)

Poly(ethylene terephthalate) waste was depolymerised in the presence of tetraethylene glycol and manganese acetate as a catalyst, so as to produce oligomers. An epoxy resin was then prepared by the reaction of these oligomers with epichlorohydrin in presence of NaOH as a catalyst. New diacrylate and dimethacrylate vinylester resins were then synthesized by reaction of the terminal epoxy groups with acrylic and methacrylic acid in the presence of triphenyl phosphite as a catalyst. The chemical structures of the resulting vinyl ester resins were confirmed by ¹HNMR. The vinyl ester resins were used as crosslinking agents for unsaturated polyester resin diluted with styrene, using free radical initiator and accelerator. The curing behaviour of the unsaturated polyester resin, vinyl ester resins and styrene was evaluated at temperatures from 25 to 55 ^○C. The compression properties of the cured resins, having different vinyl ester contents and different cure temperatures, were evaluated. Increasing the cure temperature and the vinyl ester content led to a pronounced improvement in the compression strength and Young’s modulus.     

脆性材料哑铃形拉伸试样的应力分布及断裂位置研究

应用大型有限元分析软件ANSYS模拟分析了哑铃形拉伸试样在拉伸过程中的应力分布及应力集中的位置和应力集中系数,分析结果显示过渡圆弧处出现应力集中,应力集中系数达到了1.123。分别采用聚苯乙烯（PS）的压制和注射成型的两种哑铃形试样,研究了试样的拉伸断裂过程及断裂位置,并验证了模拟分析结果正确性。结果表明压制哑铃形试样是均质各向同性,其断裂发生在应力集中系数最大的圆弧过渡位置;对于各向异性的注塑哑铃形试样,断裂发生在表层和剪切层较薄的浇口远端平直段,应力集中对其影响较弱。     

Dual‐curable unsaturated polyester inorganic/organic hybrid films

An unsaturated polyester, based on maleic anhydride, 1,6‐hexanediol, and trimethylol propane, was formulated with tetraethylorthosilicate (TEOS) oligomers and a coupling agent to prepare inorganic/organic hybrid films. TEOS oligomers were prepared through the hydrolysis and condensation of TEOS with water, and 3‐(triethoxysilyl)propylisocyanate was used as the coupling agent between the organic and inorganic phases. The hybrid materials were cured by moisture via sol–gel chemistry and by the UV curing of unsaturated polyesters. To compare the properties of the moisture‐cured inorganic/organic hybrid films, a conventional 2K polyurethane system was also prepared. The tensile, adhesion, abrasion, and fracture toughness properties were investigated as functions of the coupling agent and relative amount of UV cure versus thermal cure. Although no difference could be observed in the tensile properties, the abrasion resistance, fracture toughness, and adhesion were enhanced by the incorporation of TEOS oligomers into polyurethane films. Also, the abrasion resistance, fracture toughness, and tensile properties were increased with both moisture and UV exposure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 115–126, 2006