Synthesis of n‐alkyl methacrylate polymers with pendant carbazole moieties and their derivatives

New methacrylate monomers with carbazole moieties as pendant groups were synthesized by multistep syntheses starting from carbazoles with biphenyl substituents in the aromatic ring. The corresponding polymers were prepared using a free‐radical polymerization. The novel polymers contain N‐alkylated carbazoles mono‐ or bi‐substituted with biphenyl groups in the aromatic ring. N‐alkyl chains in polymers vary by length and structure. All new polymers were synthesized to evaluate the structural changes in terms of their effect on the energy profile, thermal, dielectric, and photophysical properties when compared to the parent polymer poly(2‐(9H‐carbazol‐9‐yl)ethyl methacrylate). According to the obtained results, these compounds may be well suited for memory resistor devices. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 70–76     

Study on curing reaction of 4-aminophenoxyphthalonitrile/bisphthalonitrile

<正>A series of phthalonitrile blending resins were prepared from 4-aminophenoxyphthalonitrile(APN) and 4,4'-bis(3,4- dicyanophenoxy)biphenyl(BPH) by directly powder-mixing and copolymerization.Differential scanning calorimeter(DSC) and dynamic rheology were used to study the curing reaction behaviors of APN/BPH blends,and the results indicated that the introduction of APN accelerated the curing rate of BPH,and the existence of BPH decreased the curing temperature of APN/BPH systems.The thermal stability of postcured APN/BPH resins was investigated by thermogravimetric analysis(TGA),and the TGA results indicated that the crosslinked polymers of APN/BPH systems possessed good thermal stability.     

新型含联苯结构的酚氧树脂的性能研究

摘要在催化剂和分散剂存在的条件下, 用3,3′,5,5′-四甲基-4,4′-联苯二酚和环氧氯丙烷缩聚, 合成一种新的含联苯结构的酚氧树脂. 用红外光谱, 核磁共振氢谱, 热失重分析仪, 动态力学分析仪和电子拉力机对聚合物进行了分析和性能研究. 结果表明, 这种新型酚氧树脂在热性能方面比双酚A型酚氧树脂有较大提高.     

Fire- and heat-resistant matrix resins based on ethynyl-substituted aromatic cyclotriphosphazenes

A novel class of fire- and heat-resistant matrix resins has been synthesized by thermal polymerization of ethynyl-substituted aromatic cyclotriphosphazenes. Thermal polymerization of new tris[4-(4′-ethynylbenzanilido)phenoxy]tris(phenoxy) cyclotriphosphazene ( III ) and tris[4-(4′-ethynylphthalimido)phenoxy]tris(phenoxy)cyclotriphosphazene ( VII ) at 250°C for 1–1.5 h gave tough polymers. The thermal stabilities of the polymers were evaluated in nitrogen and in air by thermogravimetric analysis (TGA). The synthesised polymers were stable to 400–410°C and showed char yield of 78–65% at 800°C in nitrogen and of 78–69% at 700°C in air. The ethynyl-substituted polymer precursor ( III ) was synthesised by the reaction of tris(4-aminophenoxy)tris(phenoxy)cyclotriphosphazene ( I ) with 4-ethynylbenzoyl chloride. The polymer precursor ( VII ) was synthesised by a solution condensation of I with 4-ethynylphthalic anhydride followed by in situ thermal cyclodehydration at 150°C. The structure of polymer precursors was characterized using proton nuclear magnetic resonance (¹H-NMR), infrared (IR) spectroscopy, and elemental analysis. The curing of polymer precursors was monitored by differential scanning calorimetery (DSC) and IR spectroscopy. The synthesised matrix resins are potential candidates for the development of heat- and fire-resistant fiber-reinforced composites. © 1993 John Wiley & Sons, Inc.     

Modification of adhesive materials based on epoxy oligomers with fluorinated organic compounds

N-Containing perfluoropentanoic acid derivatives were used as modifying additives to commercial epoxy resins. As shown by differential thermal analysis, the fluorinated organic derivatives exhibit catalytic activity in curing of epoxy resins. The following characteristics of the adhesive compounds in the cured state were determined: degree of swelling, gel fraction content, ultimate shear strength of the adhesive joint, adhesion to low-carbon St.3 steel and AMg-6 aluminum-magnesium alloy, and corrosion-protective properties with respect to these materials.     

共聚结构和分子量对热塑性聚酰亚胺树脂熔融与耐热性能的影响

基于具有刚性主链结构的4,4'-(六氟亚异丙基)双邻苯二甲酸酐/对苯二胺(6FDA/p-PDA)树脂体系, 通过共聚引入间苯二胺(m-PDA)、 4,4'-二氨基-2,2'-双三氟甲基联苯(TFDB)和9,9'-双(4-氨基苯基)芴(BAFL)等主链刚性且兼具大自由体积特性的芳香二胺, 以非反应性封端剂邻苯二甲酸酐(PA)对分子量进行调控, 设计制备了系列分子量可控的热塑性聚酰亚胺(TPI)树脂. 系统研究了共聚结构和分子量对TPI树脂熔融性能和耐热性能的影响, 构建了聚合物的聚集态结构与树脂熔融性能的对应关系, 并对树脂的室温和高温力学性能进行了评价. 研究结果表明, 大自由体积的芳香二胺共聚结构的引入可有效降低分子链堆砌密度, 增大聚合物的自由体积, 从而赋予树脂良好的熔融性能. 降低设计分子量可进一步改善树脂的熔融加工性. 这类具有刚性主链结构的TPI树脂兼具优异的耐热性能和力学性能, 树脂的玻璃化转变温度在308~338 ℃之间, 以TFDB和BAFL共聚制备的TPI-C-25K和TPI-D-25K树脂表现出高强高韧的特性, 拉伸和弯曲强度分别超过120 MPa和190 MPa, 断裂伸长率大于8.2%, 并且在250 ℃高温下表现出良好的耐热稳定性.     

Phosphorus based epoxy terminated structural adhesive 2. Curing, adhesive strength and thermal stability

The curing behavior of phosphorus based epoxy terminated polymers was studied using diaminodiphenyl ether, diaminodiphenyl sulfone, benzophenone tetracarboxylic dianhydride and the commercial hardener of Ciba-Geigy's two-pack araldite, as curing agent. The adhesive strength of these adhesives was measured by various ASTM methods like lap-shear, peel, and cohesive tests on metal-metal, wood-wood and wood-metal interfaces. All these results were compared with the synthesized epoxy resins prepared from bisphenol-A and epichlorohydrin having the epoxy equivalent value of 0.519. The thermal stability of both the virgin resin and its cured form was also studied by thermogravimetric analysis.     

Molecular and nanoscale factors governing pressure‐sensitive adhesion strength of viscoelastic polymers

Pressure‐sensitive adhesives (PSAs) are finding increasing applications in various areas of industry and medicine. PSAs are a special class of viscoelastic polymers that form strong adhesive joints with substrates of varying chemical nature under application of light external bonding pressures (1–10 Pa) over short periods of time (1–5 s). To be a PSA, a polymer should possess both high fluidity under applied bonding pressure, to form good adhesive contact, and high cohesive strength and elasticity, which are necessary for resistance to debonding stresses and for dissipation of mechanical energy at the stage of adhesive bond failure under detaching force. For rational design of novel PSAs, molecular insight into mechanisms of their adhesive behavior is necessary. As shown in this review, strength of PSA adhesive joints is controlled by a combination of diffusion, viscoelastic, and relaxation mechanisms. At the molecular level, strong adhesion is the result of a narrow balance between two generally conflicting properties: high cohesive strength and large free volume. These conflicting properties are difficult to combine in a single polymer material. Individually, high cohesive interaction energy and large free volume are necessary but insufficient prerequisites for PSA strength. Evident correlations are observed between the adhesive bond strengths of different PSAs, and their relaxation behaviors are described by longer relaxation times. Innovative PSAs with tailored properties can be produced by physical mixing of nonadhesive long‐ and short‐chain linear parent polymers, with groups at the two ends of the short chains complementary to the functional groups in the recurring units of the long chains. Although chemical composition and molecular structure of such innovative adhesives are unrelated to those of conventional PSAs, their mechanical properties and adhesive behaviors obey the same general laws, such as the Dahlquist's criterion of tack. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Mechanical and Thermal Properties and Morphology of Epoxy Resins Modified by a Silicon Compound

A silicon compound (GAPSO) was synthesized to modify the diglycidyl ether of bisphenol-A (DGEBA). The chemical structure of GAPSO was confirmed using FT-IR, ²⁹Si NMR and GPC. The mechanical and thermal properties and morphologies of the cured epoxy resins were investigated by impact testing, tensile testing, differential scanning calorimetry and environmental scanning electron microscopy. The impact strength and tensile strength were both increased by introducing GAPSO, meanwhile the glass transition temperature (T_g ) was not decreased and the morphologies of the fracture surfaces show that the compatibility of GAPSO with epoxy resin was very good and the toughening follows the pinning and crack tip bifurcation mechanism. The high functional groups in GAPSO can react during the curing process, and chemically participate in the crosslinking network. GAPSO is thus expected to improve the toughness of epoxy resin, meanwhile maintain the glass transition temperature.     

Study of Petroleum Resins Modification by Ethanolamins

Possibilities of synthesis and properties of the products of the ozonated petroleum resins modification by ethanolamines was considered. It is founded that ethanolamines interact both with decomposition products of the ozonized groups obtained from ozonated resins, and directly with the ozonized groups themselves. The obtained modified petroleum resins can be used as adhesive and film-forming components in paint materials.     

Copolymers of 4-thieno[3,2-b]thiophen-3-ylbenzonitrile with anthracene and biphenyl; synthesis,characterization, electronic,optical, and thermal properties

Two novel copolymers of 4-thieno[3,2-b]thiophen-3-ylbenzonitrile (TT-CN), possessing electron withdrawing cyano moiety, with anthracene (P1) and biphenyl (P2) were prepared via Suzuki coupling. Optic, electronic, and thermal properties of the copolymers were investigated through UV–Vis spectroscopy, cyclic voltammetry, gel permeation chromatography, and thermal gravimetric analysis. The polymers with anthracene and biphenyl had electronic band gaps of 2.01 and 1.90 eV, respectively. Both polymers demonstrated excellent large Stokes shifts of 101 (anthracene) and 105 nm (biphenyl) as well as very good thermal properties. As they had good optical, electronic, and thermal properties, they are promising candidates for electronic applications.     

Thermoplastic modification of monomeric and partially polymerized Bisphenol A dicyanate ester

Bisphenol A dicyanate ester (BADCy) was modified with different amounts of an engineering thermoplastic, polysulfone (PS) to improve impact strength of the parent resin. Differential scanning calorimetry of the blends suggested that addition of PS widens the curing exotherm of the BADCy considerably. FTIR of cured neat resins indicated total conversion of cyanate functional groups into triazine rings by cyclotrimerization. The cured neat resins showed phase separated morphology with cyanate ester as the continuous phase. The modified resins were shown to have better thermal, hygrothermal and impact strength properties. However, when glass fiber reinforced composites were made using partially polymerized BADCy and PS, very little or no phase separation in the resin was noticed. Flexural and impact strength measurement of composites showed that PS modification has compromised the flexural properties and only retained the impact strength of the parent resin containing composite. This study thus suggests that improvements realized in thermoplastic modification of monomeric BADCy are not directly transferable to composites using a partially prepolymerized BADCy.     

Comparison between thermal crosslinkers based on melamine-formaldehyde and benzoguanamine resin and their influence on main performance of acrylic pressure-sensitive adhesives as tack,peel adhesion,shear strength and pot-life

An acrylic pressure-sensitive adhesive (PSA) was synthesized in ethyl acetate at about 80 °C by the use of 2-ethylhexyl acrylate, ethyl acrylate, methyl acrylate and acrylic acid at presence of thermal radical initiator AIBN. The synthesized acrylic PSA was crosslinked at relatively low temperatures at about 110–125 °C using thermal crosslinkers selected from melamine-formaldehyde resins and benzoguanamine resins. The crosslinking process runs between carboxylic groups of acrylic PSA and reactive groups from investigated amine resins. The choice of suitable thermal reactive crosslinkers has significant and relevant influence at presence of organic acid catalysts on main performance of crosslinked PSA such as tack, peel adhesion and shear strength.     

Preparation of thermal-enhanced epoxy resin adhesive with organic PCM for applying wood flooring

Epoxy resins are well-known materials that show beneficial properties, such as high tensile strength and modulus, good adhesive properties, low cost, and ease of processing and environmental advantages. However, epoxy resin adhesive has no characteristic of thermal storage. Latent heat storage is one of the favorable kinds of thermal energy storage methods considered for energy saving and thermal efficiency in various fields, such as solar air conditioning systems and buildings. So we prepared thermal-enhanced epoxy resin adhesive by using PCM. This paper addresses the effects of n-hexadecane and sodium lauryl sulfate on the thermal properties and chemical properties of epoxy resin adhesive and HEAC, using differential scanning calorimetry, thermal gravimetric analysis, and Fourier transform-infrared spectroscopy. Also, we evaluated the applicability of composite epoxy resin adhesive to wood-based flooring using n-hexadecane, through measurement of bonding strength from universal testing machine analysis.     

Effect of aromatic substitution on the cure reaction and network properties of anhydride cured triphenyl ether tetraglycidyl epoxy resins

A systemic study of the impact of aromatic substitution on the reaction rate and network properties of the isomers of a tetraglycidylaniline triphenyl ether epoxy resin cured with anhydride hardeners is presented here. The epoxy resins synthesized in this work were based upon N,N,N,N‐tetraglycidyl bis(aminophenoxy)benzene (TGAPB), where the glycidyl aniline and ether groups change from being all meta (133 TGAPB), to meta and para (134 TGAPB), and finally to an all para substituted epoxy resin (144 TGAPB). Increasing para substitution increased reaction rate, promoted the onset of vitrification and increased epoxide conversion. Thermal properties such as glass transition temperatures (T_g) and coefficients of thermal expansion (CTE) both increased consistently with increasing para substitution, although thermal stability as measured via thermogravimetric analysis decreased. Mechanical properties also varied systematically with flexural strength and ductility increasing with increased para substitution, while the modulus decreased. Indeed, the ductility almost doubled, as measured by the work of fracture and displacement at failure highlighting the importance of substitution on properties.     

Influence of thermal reactive crosslinking agents on the tack,peel adhesion,and shear strength of acrylic pressure-sensitive adhesives

In recent decades, the basic technology of pressure-sensitive adhesive (PSA) acrylics has developed into a sophisticated science. The main properties of acrylic PSAs such as tack, peel adhesion, and shear strength are determined to a large extent by the kind and quantity of crosslinking agents added to the synthesized PSAs. In order to improve their adhesive (tack, peel adhesion) and cohesive (shear strength) properties, a wide range of amino resin thermal crosslinkers are tested. An acrylic PSA based on 2-ethylhexylacrylate, n-butyl acrylate, and acrylic acid was synthesized by performing a radical polymerization in ethyl acetate. After the addition of amino resins to the acrylic PSA and carrying out thermally initiated crosslinking processes to prepare one-sided self-adhesive tapes, their properties were assessed.     

New processable polyaromatic amides curable by intramolecular cyclization. XVI

New Processable Polyaromatic amides were prepared from 2,2′-diiododiphenyl-4,4′-dicarbonyl dichloride (I) and several aromatic diamines. Phenylethynyl groups were introduced in these polymides by replacing the iodine groups with copper phenyl acetylide. On thermal curing, 2,2′-di(phenylethynyl)biphenyl group undergoes intramolecular cyclization to form 9-phenyl dibenzanthracene derivative. The cured polymers showed increased heat and chemical stabilities. No melting points were observed for all the polymers below 500°C. The viscosity of the polymers was decreased on substitution of the iodine by phenylethynyl groups.     

Influence of liquefied wood polyol on the physical-mechanical and thermal properties of epoxy based polymer

Epoxy resins are mostly produced from petroleum-based bisphenol A and epicholorhydrin. Bisphenol A is synthesized from non-renewable petroleum-based phenol and acetone. Biomass derived epoxy-based polymers (EBPs) are becoming the most promising alternative for petroleum-based counterparts, but still these biomass-based EBPs have inferior properties. In the present work, two types of epoxy resins were prepared with different weight percentages of resin (bisphenol A) and hardener. They were then modified with different weight percentages of liquefied wood from spruce sawdust. The derived EBPs were analysed in terms of tensile strength and tensile modulus, fractured surface morphology, thermal stability, long-term water adsorption and resistance to brown-rot fungus decay. The results revealed that the percentages of hardener and liquefied wood significantly influenced the overall properties of the EBPs.     

Effect of the melt flow index of an HDPE matrix on the properties of composites with wood particles

Composites of wood waste and high-density polyethylene (HDPE) resins and different melt flow index (MFIs) was development in this work. Therefore, it was possible to assess their effect on the mechanical, thermal, and morphologic properties of these composites. The formulations were prepared using a twin-screw extruder, and the MFI, tensile strength, flexural strength, and impact strength of the composites were analyzed. Additionally, the thermal properties were evaluated by differential scanning calorimetry (DSC). Finally, structural analyses using optical microscopy (OM) and scanning electron microscopy (SEM) were performed to assess the particles’ dispersion, distribution, and adhesion to the polymer matrix. The results indicated that composites from HDPE resins with a lower MFI yielded a better dispersion of the wood waste. During processing was observed, reduce the MFI and better dispersion of the polymer matrix, which positively influenced some of the mechanical properties analyzed in the study.     

化学结构变化对刚棒状环氧树脂相行为和热力学性能的影响

用线性酚醛树脂(PN)和4-氨基苯基氨基砜(SAA)作为固化剂, 与刚性棒状环氧树脂联苯环氧(DGEBP)、四甲基联苯环氧(DGETMBP)和传统双酚A环氧树脂(DGEBA)分别进行固化. 研究了固化剂和环氧树脂化学结构的改变对热固网络相行为和热力学性能的影响. 结果表明, 刚性环氧网络比传统的DGEBA具有更好的热力学性能. DGEBP可形成不同类型的取向网络, 而取向态的类型也直接影响了热固网络的热力学性能. 用扫描电镜(SEM)观察不同网络体系的断裂面结构, 发现取向的刚性棒状环氧网络的断裂面呈韧性断裂, 而其它无定形环氧网络则呈典型的脆性断裂.