Forest‐based resources as fillers in biobased polyurethane foams

Six fillers from forestry wastes (wood, bark, cones and needles from young pine trees, kraft lignin, and recycled paper sludge from industry wastes) were incorporated into polyurethane (PU)‐based foams prepared via free‐rise pouring method. Variable filler contents (1, 5, and 10 wt %) and NCO/OH ratios (0.6, 0.9, and 1.2) were investigated. A simple mixture (1:3) of castor oil and crude glycerin (byproduct from biodiesel production) was used as biobased polyol. The foam composites were investigated through spectroscopy, morphological, mechanical, and hygroscopic analyses. The addition of fillers decreased water uptake and yielded rigid PU systems with more homogenous cell structure. The 1% and 5% reinforcement wood were the most effective among the studied compositions, with better mechanical and hygroscopic performance, probably due the higher compatibility of the wood with the PU system, which promote urethanic bonds between filler and isocyanate, as indicated by wet chemical results and micrographs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45684.     

A method based on the time–temperature superposition principle to predict pressurization time in compression molding

The quality of epoxy composites reinforced by glass fibers and manufactured by compression molding is affected by the pressurization time. Traditional methods, including differential scanning calorimetry and dynamic thermomechanical analysis, cannot be reliably used to predict pressurization time in the scenario of continuous production and inconstant circumstances seen in industry. In this paper, the rheological behaviors of epoxy under constant temperature were investigated and analyzed to verify if the time–temperature superposition (TTS) principle, which defines the relation between time and temperature in the deformation and relaxation response of a viscoelastic material, could be suitably applied to describe them. The results show that the TTS principle could indeed be used to predict resin viscosity by the horizontal shift factor. A new method based on the TTS principle and written into a program to forecast pressurization time in compression molding is proposed. The uniform surface color and the qualified thickness of the composite components using the program indicate that the program works well and that this method is feasible for predicting pressurization time during compression molding. The results of tensile and short‐beam shear strength tests show that pressurization time affects the mechanical properties of the final product. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45308.     

Synthesis of a novel azaphosphorine flame retardant and its application in epoxy resins

A novel P? C? N bond containing azaphosphorine, 5‐(4‐hydroxy)anilinomethyl‐1,3‐di(4‐hydroxy)phenyl‐1,3,5‐diazaphosphorinane (ADDPP‐OH), which could be used as both a cocuring agent and a flame‐retarding agent for epoxy resins (EPs), was synthesized from tetrakis(hydroxymethyl)phosphonium sulfate and characterized by FTIR, ¹H‐NMR, ¹³C‐NMR, ³¹P‐NMR, and so on. Compared with the pure EP, the ADDPP‐OH–EP composites showed increased decomposition temperatures and char yields. When the content of ADDPP‐OH was 10 wt %, the cured EP composite possessed a limiting oxygen index value of 33.7% and passed the V‐0 rating of the UL‐94 test. The mechanical properties of the ADDPP‐OH–EP composites was improved because of the increased crosslinking density. In addition, the morphology of the residual char indicated an intumescent and multiporous structure in the inner space and a compact and continual appearance in the outer layer; this was important in preventing the materials from burning further. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45721.     

Tetrafunctional epoxy as an all‐purpose modifier for homopolymerized bisphenol A diglycidyl ether

In some applications, homopolymerized epoxies, which offer better biocompatibility and lower water absorption than amine‐ and anhydride‐cured epoxy, are more preferable; however, using homopolymerized epoxy as matrix in composites still remains a challenge. Herein, homopolymerized bisphenol A diglycidyl ether curing systems with simultaneously improved tensile strength, impact strength, and glass transition temperature (T_g) were achieved by addition of small amounts of tetra‐functional epoxies (TFTEs) with different spacer lengths. Effects of spacer length in TFTE on thermal and mechanical properties were investigated. Results indicated that TFTE with the longest spacer length shows the best mechanical performance. In addition, effects of TFTE loading on thermal and mechanical properties were discussed. Compared with neat bisphenol A diglycidyl ether, addition of 5% tetraglycidyl‐1,10‐bis(triphenylmethane) decane leads to simultaneous improvements in tensile strength, impact strength, and T_g. Effects of thermal cycling on the mechanical properties were also reported. Results suggest that the modified homopolymerized epoxy shows good performances and could be used as matrix materials and possibly in some dental applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46431.     

Curing behavior and properties of benzoxazine‐co‐self‐promoted phthalonitrile polymers

A new high‐performance copolymer was successfully obtained via concerted catalysis polymerization of mono‐functional benzoxazine (P‐a) and self‐promoted 4‐aminophenoxy phthalonitrile (4‐APN) monomers. The FTIR and DSC curves of the P‐a/4‐APN in different blend ratios suggested that the monomer blends can be completely cured without the addition of curing additive. The P‐a/4‐APN copolymers were cured at relatively lower curing temperatures and time. The TGA curves revealed that the P‐a/4‐APN copolymers have good thermal stability in terms of T₅, T₁₀, and char yield. A gradual increase in the glass transition temperature (T_g) values and decline were seen in the storage modulus as the loading of 4‐APN was increased from 10 to 30 wt % in the copolymer. The SEM analyses showed that copolymer's fracture surface is dendritic, showing the stress has been dispersed to a certain extent. The study revealed that the poly(P‐a/4‐APN) copolymer have much better thermal stabilities than the poly(P‐a), and the prepared copolymer can be used as a high‐performance thermosetting resin. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46578.     

Molecular and thermal studies of carbon fiber precursor polymers with low thermal‐oxidative stabilization characteristics

In this investigation, terpolymers, copolymers, and homopolymer of acrylonitrile with dimethylaminopropyl acrylamide (DMAPA), itaconic acid (IA) viz., poly(acrylonitrile‐ran‐3‐dimethylaminopropyl acrylamide‐ran‐itaconic acid) [P(AN‐DMAPP‐IA)], poly(acrylonitrile‐co‐3, dimethylaminopropyl acrylamide) [P(AN‐DMAPP)] were synthesized with varying amounts of comonomers using solution polymerization process. The chemical structure, composition, bonding network were determined employing infrared, 1H and, 13‐carbon nuclear magnetic resonance spectroscopic techniques. Molecular characteristics of as‐synthesized polymers such as different kinds of average molecular weights, molecular weight distribution were estimated applying solution viscometry and size exclusion chromatography. The influence of comonomers (DMPAA, IA) on the thermal stabilization characteristics of acrylonitrile terpolymers in comparison with copolymers and homopolymers of acrylonitrile were studied using differential scanning calorimetry (DSC), hyphenated thermal techniques (thermal gravimetry coupled with differential thermal analyzer).The DSC curves of P(AN‐DMAPP‐IA) exhibit a distinct broader bimodal peaks with thermal exotherm initiating at as low as 165 °C, and followed by two peaks with temperature difference of 42 °C, releasing the evolved heat at a release rate of 0.7–0.11 J g^?1s^?1over 10 min as compared to 1.2, 7.5 J g^?1s^?1 in 4.5, 2 min as observed in P(AN‐DMAPP), polyacrylonitrile, respectively. The thermal stability of P(AN‐DMAPP‐IA) and P(AN‐DMAPP), as evidenced by TGA‐DTA was found to be higher than PAN homopolymers. Specific heat capacity measurements confirmed the DSC results. Bulk densities of P(AN‐DMAPP‐IA) were in the range 0.31–0.35 g/cc. These results confirm the low‐temperature stabilization characteristics and suitability of P(AN‐DMAPP‐IA) as low cost carbon fiber precursor polymers. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46381.     

Mechanical enhancement of amine‐functionalized TiO2 reinforced polyimine composites

Polyimine vitrimers are known for their malleability, which endows these materials with properties such as self‐healing, recycling, and reshaping. To enhance the mechanical properties of the polyimine vitrimers, composites were fabricated by incorporating amine‐functionalized TiO₂ microspheres (amTiO₂MS) into polyimine matrix. The pure polyimine matrix and polyimine composites hybridized with TiO₂ microspheres (TiO₂MS) without surface modification were also obtained and examined as the controls in characterization. X‐ray powder diffraction, scanning electron microscopy, and energy dispersive X‐ray spectroscopy were employed to demonstrate the presence and distribution of amTiO₂MS and TiO₂MS in the polyimine matrices. The investigation of mechanical properties of the amTiO₂MS enhanced polyimine composites and control samples indicated that incorporation of amTiO₂MS and TiO₂MS exhibited different characteristic distribution, which strongly affected the performance of the composites. The optimal filling concentration of amTiO₂MS was found to be 3%, with which the microspheres were uniformly distributed in the polyimine matrix. The self‐healing behavior of the polyimine‐amTiO₂‐X was also studied. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46446.     

Multifunctional epoxy resin/polyacrylonitrile‐lithium trifluoromethanesulfonate composites films with very high transparency,high dielectric permittivity,breakdown strength and mechanical properties

Multifunctional transparent composite films with high dielectric permittivity (high‐k), breakdown strength, and mechanical properties are urgently required by cutting‐edge fields. Herein, novel multifunctional films were facilely prepared through building unique cross‐linked structure based on epoxy resin (EP) and polyacrylonitrile (PAN)‐lithium trifluoromethane sulfonate (LiTf) complex. Compared with high‐k materials reported previously, EP/(PAN‐LiTf) films simultaneously show very high transparency, good flexibility, high tensile, and breakdown strengths. For 0.22EP/(PAN‐LiTf) film with 22 wt % EP, its average transmittance and elongation at break are as high as 91% (600–800 nm) and 12.7%, respectively; moreover, its dielectric permittivity, AC breakdown strength and the maximum energy density are severally about 4.9, 1.8, and 15.2 times of those of EP resin, completely overcoming the sticky problems in conductor/polymer composites. The origin behind these attractive properties is intensively discussed, and believed to be attributed to the unique structure of EP/(PAN‐LiTf) films. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45218.     

Six‐arm star‐shaped polymer with cyclophosphazene core and poly(ε‐caprolactone) arms as modifier of epoxy thermosets

A six‐arm star‐shaped poly(ε‐caprolactone) (s‐PCL) based on cyclophosphazene core was obtained by presynthesis of a hydroxy‐teminated cyclophosphazene derivative and subsequent initiation of the ring‐opening polymerization of ε‐caprolactone, and its use in different proportions as toughening modifier of diglycidylether of bisphenol A/anhydride thermosets was studied. The star‐shaped polymer was characterized to have approximately 30 caprolactone units per arm. Differential scanning calorimetry revealed a nonsignificant influence on the curing process of the epoxy‐anhydride formulation by the addition of s‐PCL. The s‐PCL‐modified epoxy thermosets exhibited a great improvement in both toughness and strength compared with the neat resin, as the result of a joint effort by the internal rigid core and the external ductile polyester chains of s‐PCL. When the addition of the modifier was 3 wt %, an optimal mechanical and thermomechanical performance was achieved. The impact resistance and tensile strength of the cured epoxy resin were enhanced by 150% and 30%, respectively. The glass transition temperature was also increased slightly. Moreover, the addition of the star‐shaped modifier had little harmful effect on the thermal stability of the material. Thus s‐PCL was proved to be a superior toughening agent without sacrificing thermal and mechanical properties of the thermosets. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44384.     

Curing kinetics and curing process of phenolic impregnated carbon ablator

Phenolic impregnated carbon ablator (PICA), which is composed of the phenolic resin (PR) and carbon fiber, is of particular interest to researchers in the aerospace field. In this work, PICA was prepared by the double‐stage isothermal heating curing. Then, the curing kinetics of boron‐modified phenolic resin (BPR) was investigated by non‐isothermal differential scanning calorimetry method in order to optimize the curing temperature of BPR. Further, the effect of the heating rate during curing process on the compressive strength of PICA was discussed in detail. The experimental data show that the curing of BPR needs more energy so that the curing temperature of BPR under different condition is higher than that of virgin PR. Notably, with the increasing heating rate during the curing process, the micro‐cracks increase and the compressive strength of PICA decreases. Once the heating rate exceeds a critical value, the micro‐cracks no longer increase and the heating rate has insignificant effect on the compressive strength. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45434.