Effects of dual-crosslinking networks on shape memory performance of polynorbornene

In this article, Polynorbornene (PNB)/Zinc dimethacrylate (ZDMA)/Dicumyl peroxide (DCP) composites can form dual-crosslinking networks, which contain an ionic crosslinking network, and a part of the C─C covalent crosslinking network. DCP was used to initiate the polymerization of ZDMA to form ionic crosslinking bonds. With the increase of ZDMA, the total crosslink density (V_r) and ionic crosslink density (V_r2) increased. DCP was consumed in ZDMA polymerization, which made the PNB reduce the covalent crosslinking networks. Leading to the covalent crosslink density (V_r1) decreased. Compared with covalent crosslinking network, the dual-crosslinking networks stored more energy when deformed, provided better restoring force and a higher shape recovery ratio for materials. When ZDMA exceeded 3.9 wt%, the ZDMA aggregates hindered the movement of molecular chains leading to the shape recovery ratio slightly decreased. When ZDMA was 2.4 wt%, the composite had an optimum shape fixing and shape recovery ratio. This article provided the experimental basis for the research of PNB dual-crosslinking networks, also widened the research of PNB shape memory materials. © 2020 Wiley Periodicals Inc. J. Appl. Polym. Sci. 2020 , 137, 48955.     

Effect of C5 petroleum resin content on damping behavior,morphology, and mechanical properties of BIIR/BR vulcanizates

In this work, the white‐silica‐filled vulcanizates of brombutyl rubber (BIIR)/cis 1,4 polybutadiene rubbers (BR) with hydrogenated aromatic hydrocarbon (C5) petroleum resins were prepared by compression molding, and the effects of C5 petroleum resin content on the damping behaviors and mechanical properties of BIIR/BR vulcanizates were investigated by foam force rheometer, dynamic mechanical analysis (DMA), scanning electron microscopy, and mechanical measurements. The results of this study showed that, the C5 resins could retard the vulcanization, and reduce the crosslink density and Mooney viscosity of vulcanizates. The DMA curves exhibited two independent peaks of loss factor (tanδ) corresponding to the glass transition of BR and BIIR vulcanizates, respectively. The addition of C5 resin had a positive impact on the damping of BIIR/BR vulcanizates, with the increment content of C5 resin, the main tanδ peaks shifted significantly to higher temperature and the effective damping temperature range was broadened remarkably, especially in the range of the BIIR glass transition. The mechanical properties such as tensile strength and abrasion performance were influenced by the C5 resin and the changes in mechanical properties were mainly due to the decline of crosslink density and the improvement of filler dispersion. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effects of resin chemistry on redox polymerization of unsaturated polyester resins

Unsaturated polyester resins are the most widely used thermoset resins in the composite industry. In this study, three well‐defined unsaturated polyester resins were used. These resins have similar number‐average molecular weights, and they have different numbers of C?C bonds per molecule. The reaction kinetics of unsaturated polyester resins was studied using a differential scanning calorimeter (DSC) and a Fourier transform infrared (FTIR) spectrometer. The glass transition temperature of the isothermally cured resin was also measured. Trapped radicals were observed in the cured polyester resin from electron spin resonance (ESR) spectroscopy. Considering the diffusion‐limitation effect, a simple kinetic model was developed to simulate the reaction rate and conversion profiles of polyester vinylene and styrene vinyl groups, as well as the total reaction rate and conversion. Experimental results from DSC and FTIR measurements compare favorably with the model prediction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 211–227, 2002; DOI 10.1002/app.10317     

Toughening of epoxy novolac resin using cardanol based flexibilizers

In this work, two different cardanol based epoxies (Cardolite NC‐514 and Cardanol NC‐547) were employed as flexibilizers to toughen an epoxy novolac resin namely, poly[(phenylglycidyl ether)‐co‐formaldehyde] (PPGEF). 4,4′‐Diamino‐3,3′‐dimethyl dicyclohexyl methane (BMCHA) was used as a curing agent. Differential scanning calorimetry and dynamic mechanical thermal analysis of the composites showed a gradual decrease in glass transition temperatures (T_g) with increase in cardolite content confirming the incorporation of flexible moieties into the brittle resin matrix. Improvement in toughening of PPGEF/Cardolite composites was manifested by increase in the izod impact strength of both the composites. The tensile strength increased marginally for composites with increasing amount of Cardolite NC‐514 but decreased for the composites containing Cardolite NC‐547. This was attributed to the lack of rotational motion in the chain due to close proximity of rigid phenyl rings in NC‐547. SEM of the cryo‐fractured surfaces of composites showed good compatibility between PPGEF and cardanol based flexibilizers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43318.     

Effect of modified phenolic resin on crosslinked network and performances of polyvinyl acetate blending emulsion

The water‐soluble phenolic resin (PF) and the poly(vinyl alcohol) (PVA) modified phenolic resin (PPF) were synthesized by alkali catalysis method. Both were used as curing agents to blend with the polyvinyl acetate (PVAc) emulsion. The obtained PF, PPF and blending emulsion were characterized by FT‐IR, DSC, DLS, TEM, and viscosity analysis. The thermal stability of latex films was enhanced after blending. When the PF and PPF content was up to 15 wt %, the peel strength of the blending emulsion increased from 17.89 N/25 mm to 21.32 N/25 mm and 23.37 N/25 mm and the shear impact strength were 1.4 and 1.6 times that of unmodified emulsion adhesive, respectively. Moreover, the modification effect of PPF was better than PF due to its tough crosslinked network. Finally, layer cohesion played an increasingly important role in bonding forces with the increment of the PPF content by the glue residue analysis. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46448.     

Studies on thermal behavior of imidazole diamine based benzoxazines

The objective of the present work is to develop a novel type of structurally modified benzoxazines with improved performance characteristics using imidazole core based diamine with formaldehyde and different types of phenolic compounds in order to utilize them for high‐performance applications. In this work, an attempt has been made to bring down the polymerization temperature of the benzoxazine monomers, which is one of the most deficient factor restrict the applications of benzoxazines, when used in the form of adhesives, sealants, encapsulants, and matrices with other substrates, though they possess numerous advantages and valuable properties than those of other available thermosets. In this context, in this study, two approaches have been adopted to bring down the polymerization temperature, viz., (i) the development of structurally modified benzoxazine monomers with imidazole core and (ii) an incorporation of varying nature of chemical compounds as catalysts, to lower the polymerization temperature and to enhance the thermal stability and char yield. Three types of benzoxazines were developed using imidazole core based diamine with monohydric phenols and formaldehyde, at appropriate conditions. The molecular structure of benzoxazines was confirmed from Fourier transform infrared spectroscopy and ¹H‐nuclear magnetic resonance analysis. From data, it was observed that the imidazole diamine based benzoxazines prepared from 1‐naphthol exhibits lower curing temperature of about 192 °C than that of other samples studied in this work. In addition, the influencing effect of catalysts viz., 4‐hydroxy acetophenone, 4‐hydroxy benzaldehyde, 4‐hydroxyphenyl maleimide, and thiodipropionic acid (TPA) on thermal properties of benzoxazines also was studied. Among the catalysts, it was found that the TPA is the most efficient catalyst. In the case of imidazole diamine based benzoxazines prepared from cyanophenol, the TPA reduces value of polymerization temperature (T_p) from 217 to 167 °C. The thermogravimetric analysis indicates that thermal stability of the benzoxazines are improved to a significant extent when 10 wt % catalysts were incorporated into the system. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46562.     

Effects of lignin as a filler on properties of soy protein plastics. I. Lignosulfonate

A series of biodegradable plastics from soy protein isolate (SPI) and lignosulfonate (LS) with a weight ratio of 0:10 to 6:4 were prepared with 40 wt % glycerol as a plasticizer by compression molding. Their properties were investigated by wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), dynamical mechanical thermal analysis (DMTA), scanning electron microscopy (SEM), and tensile tests. The results indicated that the introduction of a moderate LS content from 30 to 40 parts in the blends could simultaneously enhance the tensile strength, elongation, and Young's modulus of soy protein plastics alone. Studies of the water sensitivity of the materials suggested that the strong interaction between LS and SPI could restrict the effect of water on the swelling and the damage of the materials, resulting in lower water absorption. The improvement of the properties was attributed mainly to the existence of the beneficial microphase separation and the formation of crosslinked structures because of the introduction of LS into soy protein plastics. Therefore, a model of a crosslinked network formed from SPI molecules with an LS center was established based on the existence of strong physical interactions between LS and SPI. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3284–3290, 2003     

UV curable micro-structured shape memory epoxy with tunable performance

Micro-structured shape memory polymer (SMP) surfaces are indispensable in various applications. Epoxy polymer emerged as an ideal candidate for SMP surfaces due to its low curing shrinkage and superior thermo-mechanical properties. In this study, we develop a UV curable epoxy system with tunable glass transition temperature and superior shape memory performance. The glass transition temperatures can widely range from 49 to 164°C by simply tuning the ratio of two comonomers. All samples possess excellent shape fixity, shape recovery ratios, and cycling stability. The synergy of the moldable liquid epoxy precursors and the spatiotemporal UV light allows shape memory epoxy with both surface microstructures and complex macro-geometries. We anticipate this UV curable epoxy will expand the scopes of surface shape memory applications.     

Short glass fiber reinforced radiation crosslinked shape memory SBS/LLDPE blends

The poly(styrene‐b‐butadiene‐b‐styrene) triblock copolymer (SBS) and linear low density polyethylene(LLDPE) were blended and irradiated by γ‐rays to prepare shape memory polymer(SMP). Various amounts of short glass fiber (SGF) were filled into SMP to form a novel shape memory SGF/SBS/LLDPE composite. The effect of SGF on the shape memory SGF/SBS/LLDPE composite was studied in terms of mechanical, dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC) and shape memory effects. It is found that the SGF act as reinforcing fillers and significantly augment the glassy and rubbery stated moduli, tensile strength and shape memory properties. When SGF content is <2.0 wt %, full recovery can be observed after only several minutes at different temperatures and shape recovery speed reduces as the SGF content increases. The shape recovery time decreases as the temperature of the shape memory test increases and the shape recovery rate decreases with increment of cycle times. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40691.     

GAP/PTPET弹性体的交联与热性能研究

采用点击化学反应制备了GAP(叠氮缩水甘油聚醚)/PTPET(端炔基环氧乙烷–四氢呋喃共聚醚)弹性体,通过平衡溶胀法和DSC-TG(差热–热重)表征了弹性体的交联与热性能。在不同增塑比条件下,研究了不同配比的GAP/PTPET弹性体的交联密度、玻璃化转变温度(T_g)和热分解表观活化能。结果表明:在相同增塑比条件下,GAP/PTPET弹性体的交联密度随反应物中PTPET含量的增大而呈增大的趋势;增塑比为2.6时,弹性体有较高的交联密度;GAP/PTPET弹性体中软段的T_g偏高于原材料PTPET中软段的T_g;在相同增塑比条件下,随PTPET质量分数的增大,弹性体中软段的T_g减小。GAP/PTPET弹性体的热分解分为3个阶段,第一阶段和第二阶段的热分解表观活化能分别为122.2kJ/mol和137.4kJ/mol,均低于GAP均聚物的热分解表观活化能。     

Synergistic toughening effect of chlorinated polyethylene and acrylic resin on SAN/ASA blends at low temperature

Styrene–acrylonitrile copolymer (SAN)/acrylonitrile–styrene–acrylate terpolymer (ASA) blends (75/25, w/w) were toughened by blending with chlorinated polyethylene (CPE) and acrylic resin (ACR) at three different temperatures (?30, 0, and 25 °C). When the testing temperature was 0 and 25 °C, CPE played a key role in improving the impact strength of blends instead of ACR. However, an obvious synergistic toughening effect of CPE and ACR was observed at ?30 °C: when both 10 phr CPE and 15 phr ACR were added, the impact strength of the blends reached a peak at 7.50 kJ/m², which was about two to three times higher than when 25 phr CPE or 25 phr ACR was introduced into the blends individually. Scanning electron microscopy, dynamic mechanical analysis, and surface energy measurements were used to investigate the toughening mechanism. Furthermore, other mechanical properties and the heat distortion temperatures were evaluated. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43958.     

Influence of fillers on the properties of a phenolic resin cured in acidic medium

The curing behavior of a phenolic resol resin in the presence of p‐toluensulphonic acid is reported herein. The gel time of different systems has been determined by thermal scanning rheometry. Thermal and mechanical properties of the resin have been modified by the addition of varying amounts of fillers, talc, and kaolin. dynamic mechanical thermal analysis is used to determine the mechanical properties of the systems and the influence of the fillers and the postcuring. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of polycaprolactone molecular weights on thermal and mechanical properties of polybenzoxazine

Polymer blends of polybenzoxazine (PBA‐a) and polycaprolactone (PCL) of different molecular weights (M_n = 10,000, 45,000, and 80,000 Da) were prepared at various PBA‐a/PCL mass ratios and their properties were characterized. The results from dynamic mechanical analyzer (DMA) revealed two glass transition temperatures implying phase separation of the two polymers in the studied range of the PCL contents. Moreover, a synergistic behavior in glass transition temperature (T_g) was evidently observed in these blends with a maximum T_g value of 281°C compared with the T_g value of 169°C of the PBA‐a and about ?50°C of the PCL used. The blends with higher M_n of PCL tended to provide greater T_g value than those with lower M_n of PCL. The modulus and hardness values of PBA‐a were decreased while the elongation at break and area under the stress?strain curve were increased with an increase of the content and M_n of PCL, suggesting an enhancement of toughness of the PBA‐a. Scanning electron micrographs (SEM) of the sample fracture surface are also used to confirm the improvement in toughness of the blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41915.     

Amino‐capped aniline trimer/epoxy resin intercrosslinked networks

An amino‐capped aniline trimer (ACAT) in emeraldine base form was reacted with an epoxy resin to produce intercrosslinked networks. The quinoid structure of the ACAT was able to crosslink on curing and, thus, led to a very high glass‐transition temperature of the cured resin. The epoxy resin cured with the ACAT showed superior thermal properties over the resins cured with p‐phenylenediamine and 4,4′‐diamino diphenylamine. These findings were based on differential scanning calorimetry, IR, dynamic mechanical analysis, and thermogravimetric analysis data. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 222–226, 2006     

Shape memory CTBN/epoxy resin/cyanate ester ternary resin and their carbon fiber reinforced composites

Carboxylated-terminated liquid acrylonitrile rubber (CTBN) and epoxy resin (JEF-0211) were coreacted with cyanate ester (CE) to form CTBN/EP/CE ternary resin systems. Further, the ternary resin system was applied as prepreg for carbon fiber composites with vacuum bag degassing molding process. CTBN/EP/CE ternary shape memory polymer (SMP) exhibited relatively high tensile strength, Young's modulus, impact strength, and excellent shape memory properties. Compared with CTBN/EP/CE ternary SMP, CTBN/EP/CE carbon fiber composites showed much higher mechanical properties, such as their tensile strength and Young's modulus were high to 570 MPa and 36.7 GPa, respectively. Furthermore, CTBN/EP/CE carbon fiber composites exhibited good shape memory properties, their shape fixity ratio and shape recovery ratio were more than 95% after 30 times repeating shape memory tests. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48756.     

Thermally and light-triggered reconfigurable shape memory polydopamine/epoxy composite with self-healing and recyclable ability

Shape memory epoxy with self-healing ability has received much more academia and industry attention. In this work, 4-aminophenyl disulfide containing disulfide bonds was used to replace the traditional epoxy resin-curing agent, and the waterborne epoxy resin (sWEP) was composited with the polydopamine (PDA) nanoparticles with photothermal conversion effect through the melt mixing and hot-press molding. As revealed, the addition of 1 wt% PDA increases the tensile strength of sWEP from 36.1 to 50.3 MPa. Specifically, the shape memory properties of the PDA/sWEP composite as manifested by a ca. 97.4% shape memory fixing ratio and ca. 67.8% shape memory recovery ratio. Moreover, the PDA/sWEP composite had the temperature-dependent thermosetting and thermoplastic conversion capabilities, which can be programmed to a new permanent shape via a photothermal-induced plasticity process.     

A study about the structure of vulcanized natural rubber/styrene butadiene rubber blends and the glass transition behavior

A study of the thermal behavior of cured elastomeric blends of natural rubber (NR) and styrene butadiene rubber (SBR) prepared by solution blending in toluene is presented. Binary blends with different compositions of NR/SBR were produced using a conventional cure system based on sulfur and TBBS (n-t-butyl-2-benzothiazole sulfonamide as accelerator. The compounds were vulcanized at 433 K up to an optimum time of cure determined by rheometric tests. From swelling tests, the crosslink densities of the compounds were obtained and compared with those obtained in similar blends prepared by mechanical mixing. The results were analyzed in terms of the disentangling of the chain structures of the SBR and NR phases and the achieved cure state of the blend. Using differential scanning calorimetry, the glass transition temperature T_g of each blend was measured. In most compounds, the value of T_g corresponding to each phase of the blend was determined, but in some blends a single value of T_g was obtained. The variation of T_g with the composition and cure level in each phase was analyzed. On the other hand, a physical mixture of two equal parts of NR and SBR vulcanized was measured and the results were compared to those of the NR50/SBR50 cured blend. Besides, to analyze the influence of the network structure, pure NR and SBR unvulcanized samples were measured. On the basis of all the obtained results, the influence of the interphase formed in the blend between SBR and NR phases is discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

磺甲基酚醛树脂抗温性能研究

利用环镜扫描电镜研究了220℃老化16 h前后SMP-2与SMC水溶液的自组装形态的变化,以及粘土在该混合液中的吸附状态。根据交联机理分析,找了一种温度保护剂,并测定加入前后的钻井液性能。高温促进分子间交联,从而使自组装形态由线性构形成稀疏的膜状结构,形成了致密的大片膜状结构;粘土颗粒主要分散在SMP-2与SMC所形成的膜状结构内部,且复配后单位空间内吸附基团增加,增加了粘土颗粒在处理剂上的吸附量,老化后,颗粒被包裹在大片膜状结构内,形成更致密的自组装结构;温度保护剂有效的减少了老化后的API、HTHP滤失量,且温度保护剂加量应控制在一定范围内,维持处理剂的交联程度与护胶作用的动态平衡,确定温度保护剂的最优加量为2%。     

Studies on polyethylene oxide and phenolic resin blends

Blends of poly(ethylene oxide) (PEO) and novolac type phenolic resin were prepared by a solution cast method using acetonitrile as a solvent. In this work, we have investigated the PEO/phenolic blends having low phenolic content (0 to 30 wt %) with the objective in mind to design a crystallizable component for a shape memory polymer system having adjustable switching temperature. The blends were characterized by Fourier transform infrared (FTIR) spectroscopy, polarized optical microscopy (POM), and differential scanning calorimetry (DSC). The rate of crystallization and crystallinity (calculated from heat of crystallization value) decrease with increase in novolac content. FTIR analysis indicates the existence of H‐bonding between hydroxyl groups of novolac and ether groups of PEO. POM studies indicate that size of Maltese cross section decreases with increase in novolac content and in the blends containing higher novolac content less regular leaf like texture was obtained. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

环保型酚醛环氧树脂乳液的制备及性能研究

以对氨基苯甲酸改性双酚A甲醛酚醛环氧树脂(bis-ANER),使其具有亲水性。通过红外光谱和核磁共振谱对改性前后的水性酚醛环氧树脂进行了表征,研究了反应温度、时间和乳化剂对改性水性双酚A甲醛酚醛环氧乳液的影响。结果发现,当反应体系处于105°C、反应时间15~40 h时,水溶性较佳;加了乳化剂SDS的乳液,其颗粒粒径为194 nm;采用4,4′–二氨基二苯基甲烷作固化剂,改性后的bis-ANER涂膜保留了原来酚醛环氧树脂的高硬度、附着力好的特性,并具有更优的耐水性、耐盐水性和耐化学介质性。