Synthesis and characterization of high temperature cyanate-based shape memory polymers with functional polybutadiene/acrylonitrile

New thermosetting shape memory cyanate polymers (SMCPs) modified with polybutadiene/acrylonitrile (PBAN) were synthesized and compared with polyethylene glycol (PEG)-modified SMCPs for integration into the family of high temperature shape memory polymers with controllable glass transition temperatures (T_g) used in the aerospace industry. The materials were characterized in terms of microstructure, thermal properties, mechanical properties and shape memory properties by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, and tensile tests. Differing from the SMCP with PEG, the new cyanate-based shape memory polymer with PBAN (T_g ∼255.1.0 °C) had better shape memory properties and higher thermal stability (relatively high initial degradation temperature and high char residue value at 800 °C). Both of the SMCPs with PBAN and PEG displayed exceedingly high glass transition temperatures over 241.3 °C and higher toughness than unmodified polycyanurate. These qualities render them desirable candidates as matrices in polymer composites, particularly for space applications.     

两亲性苯乙烯嵌段共聚物的合成及结构表征

以α,α'-二甲基-α-乙酸-三硫代碳酸酯(BDATC)为链转移剂,采用可逆-加成-断裂链转移(RAFT)自由基聚合方法合成了末端带有—COOH官能团的两亲性嵌段共聚物聚苯乙烯-b-聚甲基丙烯酸聚乙二醇单甲醚-b-聚苯乙烯(PSt-b-POEOMA-b-PSt),这种含有亲水性端基的嵌段共聚物可以自组装成核-壳结构的纳米微粒,用于载药高分子的模板研究。利用FTIR、1HNMR、GPC对产物结构进行表征,用热失重(TG)和差示扫描量热(DSC)的方法研究了3种不同比例的嵌段共聚物的热性能。实验结果表明,通过RAFT聚合方法得到了所设计的嵌段共聚物,相对分子质量(简称分子量,下同)分布1.35左右;嵌段共聚物的热稳定性较好,通过玻璃化转变温度(Tg)的变化推测出嵌段共聚物中两种嵌段比例对两嵌段相容性的影响。     

丙烯腈接枝羧甲基甲壳素水溶性衍生物的制备和表征

以羧甲基甲壳素和丙烯腈为原料,制备了丙烯腈接枝羧甲基甲壳素衍生物,讨论了反应温度、反应时间、溶剂用量、引发剂用量、单体用量对接枝反应的影响。结果表明,最佳反应条件为:羧甲基甲壳素0.4 g,溶剂水40.0 mL,过硫酸铵50.0 mg,丙烯腈2.5 g,反应温度60℃,反应时间2 h。所制共聚产物具有水溶性,分析了产物具有水溶性的原因。     

NVF-DADMAC阳离子共聚物的合成与表征

以N-乙烯基甲酰胺(NVF)和二甲基二烯丙基氯化铵(DADMAC)为原料,通过水溶液聚合法合成了NVF-DADMAC阳离子共聚物。用FTIR和DSC-TG对共聚产物进行了表征,用胶体滴定法测定了共聚物的阳离子度,考察了引发剂浓度、反应温度对聚合过程中转化率以及聚合物的阳离子度和特性粘数的影响。研究结果表明:NVF与DADMAC发生了共聚,且该共聚物的热稳定性比NVF的均聚物高,DADMAC的转化率可达90%以上。     

异丁烯-对甲基苯乙烯无规共聚物的合成与表征

以二枯基氯/四氯化钛/2,6 -二叔丁基吡啶为引发体系,在-80℃条件下采用正离子聚合法合成了异丁烯-对甲基苯乙烯无规共聚物(IB -co -p - MeSt),研究了不同单体投料比(摩尔比)下聚合反应的特征,并通过示差折光指数仪/多角激光光散射仪/紫外检测器、核磁共振氢谱、差示扫描量热法和热重分析对无规共聚物进行了表...     

Optimization of synthesis and characterization of cassava starch‐graft‐poly(acrylonitrile) using response surface methodology

Graft copolymerization of poly(acrylonitrile) onto cassava starch was carried out with potassium persulphate (PPS) as the free radical initiator using a response surface Box–Behnken design. Different levels of monomer concentration, initiator concentration, and temperature were used, and regression models were generated in terms of these factors, which can be used to predict the grafting level and efficiency at a given level of the factors. The grafted starches were characterized by FTIR, XRD, and SEM analyses and determination of %grafting (%G), N‐content, thermal properties, water and saline solution retention, and rheological properties. Under the conditions used, %G was found to depend only on the temperature used for the reaction. The maximum %G of 120.1 was obtained for the sample synthesized under the following conditions: weight of AN = 0.753 mol/10 g starch, weight of PPS = 0.284 g and temperature = 55°C, and the grafting efficiency was 30.03%. The absorption bands at 2243 cm^?1 for the nitrile group (? CN) in the FTIR spectra of the products confirmed the grafting reaction. There was a decrease in crystallinity and disappearance of the granular structure after grafting of the starch. The melting temperatures of the graft copolymers determined by differential scanning calorimetry analysis were higher than that of the native starch. The grafted starches exhibited very high thermal stability as observed from the thermogravimetric analysis. The superabsorbent polymer prepared from the grafted starch by alkali saponification exhibited a maximum water absorbency of 636 g/g. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of wood/styrene‐acrylonitrile copolymer/MMT nanocomposite

Wood polymer nanocomposite (WPNC) was prepared by impregnating Simul (Salmalia malabarica) wood with styrene‐acrylonitrile copolymer (SAN), glycidyl methacrylate(GMA), and a reactive polymerizable surfactant modified montmorillonite (MMT). The physical and mechanical properties of WPNC were investigated by using XRD, tensile tester, SEM, and FTIR. The polymer loading, dimensional stability, water uptake, mechanical property, and thermal stability were found to improve due to inclusion of MMT. SEM micrographs showed the presence of polymer and MMT into cell wall and cell lumen. FTIR analysis confirmed the presence of MMT and SAN in WPNC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis,characterization and kinetics of terpolymerization of acrylonitrile,N-vinyl pyrrolidone and styrene

Synthesis of a series of novel terpolymers, consisting of two electron-donating monomers, viz. N-vinyl pyrrolidone (N-VP) (heterocyclic polar monomer) and styrene (Sty) (non-polar monomer), with one electron-accepting polar monomer, i.e. acrylonitrile (AN), using α,α'-azobisisobutyronitrile as radical initiator and benzene as diluent at 60°C, has been extensively surveyed. Besides the synthesis, an attempt has been made to study the kinetics and various properties of the terpolymers, such as softening temperature and chemical resistance. The system follows non-ideal kinetics and the kinetic equation for the present system can be written as This non-ideality can be explained on the basis of significant initiator-dependent termination through primary radicals and degradative chain transfer to acrylonitrile monomer. The overall energy of activation is 72.4 kJ mol^?1 and k_p²/k_t is 0.26 × 10^?3 litre mol^?1 s^?1. The effects of various additives such as imidazolium-p-chlorophenacylide (ICPY) and ZnCl₂ were also studied. ICPY functions as a chain transfer agent (C^tr = 0.43 × 10^?4), whereas ZnCl₂ accelerates the rate of reaction. IR spectroscopy was used to confirm the structure of the terpolymers.     

Synthesis and characterization of novel polyesterimides

A series of soluble novel polyesterimides was synthesized from diamines [a mixture of 2,2‐bis(4‐(4‐aminophenoxy)phenyl)propane (BAPP) with amine‐terminated polysiloxane (ATPS) in various mole ratios] and the ester‐group‐containing dianhydrides. The ester group containing dianhydrides in turn was synthesized by the transesterification reaction of trimellitic anhydride (TMA) with diacetate ester of hydroquinone (HQ), 4,4′‐dihydrophenyl (BP), 1,6‐hexanediol, or ethylene glycol. The resulted polyesterimides were characterized by using Fourier‐transform infrared spectroscopy, inherent viscosity, solubility, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The polyesterimides of BP and HQ had relatively high glass transition temperatures in the range of 214.7–227.2 and 195.7–210.5°C, respectively. The glass transitions decreased rather slowly with the increase in polysiloxane content. Thermal stability and the weight‐loss behavior of polyesterimides were studied by TGA. All polyesterimides of BP and HQ (BPI and HQI) showed no significant weight loss below 500°C in a N₂ environment, and the decomposition temperatures (T_d5%) of BPI and HQI were >520°C. Most polyesterimides were soluble in polar aprotic solvents and m‐cresol. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 730–738, 2004     

Functional copolymers of p‐cumyl phenyl methacrylate and glycidyl methacrylate: Synthesis,characterization, and reactivity ratios

Free‐radical polymerization of p‐cumyl phenyl methacrylate (CPMA) was performed in benzene using bezoyl peroxide as an initiator at 80°C. The effect of time on the molecular weight was studied. Functional copolymers of CPMA and glycidyl methacrylate (GMA) with different feed ratios were synthesized by free‐radical polymerization in methyl ethyl ketone at 70°C, and they were characterized by FTIR and ¹H‐NMR spectroscopy. The molecular weights and polydispersity indexes of the polymers and copolymers were determined by gel permeation chromatography. The copolymer composition was determined by ¹H‐NMR. The glass‐transition temperature of the polymer and the copolymers was determined by differential scanning calorimetry. The reactivity ratios of the monomers were determined by the Fineman–Ross and Kelen–Tudos methods. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 336–347, 2005     

PU／EP／PBA三元IPN弹性体的合成与表征

合成了以ＰＵ为第一网络的ＰＵ／ＥＰ／ＰＢＡ三元同步ＩＰＮ弹性体,并通过密度测试、红外光谱分析、玻璃化转变行为、溶剂萃取以及电镜分析等手段对体系进行了表征。实验证明,通过改变多种合成条件,在不引入电荷的情况下仍仍可得到宏观的一透明的体系,同时体系的红外光谱谱图的单一玻璃化转变温度以及试样良好的耐溶剂性都充分证帝了体系具有互穿特征。     

Synthesis and characterization of phthalonitrile resins from ortho‐linked aromatic and heterocyclic monomers

This article describes the synthesis and properties of phthalonitrile polymers prepared from three different ortho‐linked monomers, namely 2,2′‐bis(3,4‐dicyanophenoxy)biphenyl, 1,2‐bis(3,4‐dicyanophenoxy)benzene and 2,2′‐bis(3,4‐dicyanophenoxy)‐1,3,4‐oxadiazole. The resins exhibited a low complex viscosity, with a varying range of processing temperatures for all three systems. Thermogravimetric analysis showed that the synthesized polymers exhibited high thermal and thermo‐oxidative stability. The high char yields, which ranged from 64 to 69% at 900 °C under nitrogen atmosphere, and the high glass transition temperatures of the polymers indicated a high crosslinking density in the network structure. Dynamic mechanical measurements demonstrated that the fully cured monomer 2,2′‐bis(3,4‐dicyanophenoxy)‐1,3,4‐oxadiazole exhibited no change in glass transition temperature or in storage modulus up to 500 °C. © 2013 Society of Chemical Industry     

Synthesis and characterization of some aromatic polyimides

The diamine 2‐methyl‐1,3‐bis(4‐aminophenyloxy)benzene was prepared via a nucleophilic substitution reaction and was characterized with Fourier transform infrared, elemental analysis, and ¹H‐ and ¹³C‐NMR spectroscopy. The prepared diamine was also characterized with single‐crystal analysis. The geometric parameters of C₁₉H₁₈N₂O₂ were in the usual ranges. The dihedral angles between the central phenyl ring and the two terminal aromatic rings were 88.9 and 91.6°. The crystal structure was stabilized by N? H···N hydrogen bonds. The diamine was then polymerized with 3,3′,4,4′‐benzophenone tetracarboxylic acid dianhydride, 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 3,4,9,10‐perylenetetracarboxylic acid dianhydride, and pyromellitic dianhydride by either a one‐step solution polymerization reaction or a two‐step procedure. These polymers had inherent viscosities ranging from 0.61 to 0.85 dL/gm. Some of the polymers were soluble in most common organic solvents even at room temperature, and some were soluble on heating. The degradation temperatures of the resultant polymers fell in the range of 260–500°C in nitrogen (with only 10% weight loss). The specific heat capacity at 200°C ranged from 1.0 to 2.21 J g^?1 K^?1. The temperatures at which the maximum degradation of the polymer occurred ranged from 510 to 610°C. The glass‐transition temperatures of the polyimides ranged from 182 to 191°C. The activation energy and enthalpy of the polyimides ranged from 44.44 to 73.91 kJ/mol and from 42.58 to 72.08 kJ/mol K, respectively. The moisture absorption was found in the range of 0.23–0.71%. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of terpolymer of N‐cyclohexylmaleimide,methyl methacrylate,and acrylonitrile

Terpolymers of N‐cyclohexylmaleimide, methylmethacrylate, and acrylonitrile (AN) at different AN feed content were synthesized by suspension polymerization. The thermal properties of the terpolymers such as glass transition temperature (T_g) and Vicat softening temperature (T_Vicat) were determined by torsion braid analysis and Vicat softening temperature tester, respectively. The value of T_g and T_Vicat decreased with increasing AN feed content. Thermogravimetric analyses were carried out with the results that the incorporated AN units enhanced the thermal stability of the resulting polymers and a second degradation step appeared with the addition of AN. The mechanical properties (tensile strength and impact strength) of the terpolymers were also detected and the results show that the tensile strength and impact strength of terpolymers increase with increasing AN feed content. The rheological results illustrated that the terpolymers showed rheological behavior similar to that of pseudoplastic liquid. The apparent shear viscosity decreased with the increasing of AN feed content. The flow power index n increased with increasing AN feed content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 792–796, 2007     

Kinetic and thermomechanical analysis of hydrophobic–hydrophilic copolymer thermosets synthesized via free‐radical polymerization

The synthesis of a crosslinked copolymer of hydrophobic and hydrophilic monomers, diglycidyl ether of bisphenol A vinyl ester (VE), and 2‐acrylamido 2‐methyl 1‐propane sulfonic acid (AMPS) respectively, is discussed. A methodology for real‐time monitoring of the copolymerization reaction using transmission mode near infrared (NIR) spectroscopy was employed that resolves overlapping peaks associated with the reactive double bonds. The influence of solvent, monomer ratio, and initiator concentration on the kinetic behavior of the system was investigated. The method of Mayo and Lewis was used to provide a qualitative understanding of the microstructure being formed. At low conversions (<15%) and within the compositions of interest, greater VE homopolymerization as compared with AMPS homopolymerization was observed and the product of the reactivity ratios (r_AMPS.r_VE) was close to 0.5, suggesting the formation of a moderately random copolymer structure. Thermo‐mechanical analysis shows large concentrations of AMPS had a plasticizing effect on the network structure. Solvent removal using supercritical carbon dioxide and thermal drying were compared, and the drying technique were shown to have an effect on the glass transition temperature (T_g), with the lowest T_g being 146°C for supercritically dried samples and 121°C for thermally dried systems. Gel permeation chromatography shows that there is a significant fraction of an unbound mobile phase within the network structure that might be acting as a plasticizing agent for the copolymer structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of magnetorheological polyimide gels

Magnetorheological polymer gels (MRPGs) are composite fluids containing ferrous particles suspended in a polymer gel. In addition to modification of the carrier fluid, the polymer gel, which includes crosslinked copolyimide (CCPI) and solvent N‐octylpyrrolidone, also changes the surface properties of the ferrous particles, thus reducing the particle settling and improving particle redispersion. The viscosity of MRPGs can be easily adjusted by controlling the concentration of CCPI in the carrier medium. High thermally resistant CCPI is synthesized from dianhydride, diamine, diaminobenzonic acid, and crosslinker and has a high glass transition temperature because the crosslinking ratio can be controlled by the molar ratio of diamine to diaminobenzonic acid. The redispersion and rheological properties are also investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2402–2413, 2005     

Synthesis and characterization of novel dihydrobenzoxazine resins

Three dihydrobenzoxazines are synthesized from bisphenol A (BPA), 4,4′‐biphenol (BIP), and dicyclopentadiene phenol adduct (DCPD). Polydihydrobenzoxazine containing 4,4′‐biphenol (BIPDB) had the most rigid structure of the three and was found to possess the best mechanical and thermal properties. The glass transition temperature of BIPDB was 206°C, and that of BPA‐type polydihydrobenzoxazine (BPADB) and dicyclopentadiene type polydihydrobenzoxazine (DCPDDB) were 184 and 183°C, respectively. DCPDDB, with a rigid hydrophobic cycloaliphatic structure, was found to possess excellent properties such as low moisture absorption, low dielectric constant, low polarization. The resulted polymer from DCPDDB had a dielectric constant of 2.94U, which was better than that of polymers derived from BPA (3.31U), BIP (3.45U), and traditional phenolic resin (3.9–4.0U). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 342–347, 2006     

丙烯腈催化剂用硅溶胶的制备及其性能研究

采用常压粒子增长工艺合成丙烯腈催化剂载体专用硅溶胶,研究了硅溶胶的粒径、pH、稳定剂对丙烯腈催化剂性能的影响。结果表明:当硅溶胶粒径分布集中、平均粒径23～25nm、pH9.0～9.5、适量加入氢氧化钠和氨水混合溶液作为稳定剂和加入少量助剂时,丙烯腈单程收率接近80%。     

Synthesis and characterization of gelatin‐polydimethylsiloxane graft copolymers

Gelatin‐polydimethylsiloxane (PDMS) graft copolymers were prepared through the reaction between gelatin and α‐[3‐(2,3‐epoxypropoxy)propyl]‐ω‐butyl‐PDMSs. The copolymers were characterized by FTIR and ¹H‐NMR spectra. As proved by wide angle X‐ray analysis, a new characteristic crystalline peak appeared after the bonding of PDMS to gelatin chains. The microstructure and the elemental identification of gelatin and copolymers were followed through scanning electron microscope with energy dispersive spectrometer. The glass transition temperature of gelatin and copolymers were obtained by differential scanning calorimetry analysis. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011