Reactive blending of nylon 6 and modified poly(styrene-co-maleic anhydride); influence of poly(styrene-co-maleic anhydride) modification by fatty amine onto blend properties

Blends of PA 6 with SMA or with 12.5–100% fatty amine (C 18) modified SMA at compositions 95/5–60/40 were studied. Particle size of SMA dispersed in PA 6 matrix was around 0.1 μm due to in situ compatibilizer formation. The strength and stiffness of the blends were higher and toughness unchanged in comparison with PA 6 values. Microscopic observations confirm that improvement of mechanical properties of PA 6 by addition of brittle SMA is due to plastic deformation of SMA particles that consume significant amounts of deformational energy. This cold drawing is caused by compressive stress evolved by bulk deformation; this stress should exceed the critical brittle-to-ductile fracture mode transition. In the blends studied, cold drawing apparently occurred when the developed stress was lower than the critical one. It is concluded that a very fine phase structure with an apparently strong interface makes the plastic deformation of dispersed SMA easier. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 555–562, 1997     

Structure and properties of blends of poly(ethylene-co-vinyl alcohol) with poly(styrene-co-maleic anhydride)

In the present study, ethylene/vinyl alcohol (EVAL) copolymers with different hydroxyl contents were melt mixed with styrene/maleic anhydride (SMA) copolymers. These two copolymers have functional groups capable of reacting intermolecularly, giving stable products. All EVAL copolymers were prepared from the same ethylene/vinyl acetate (EVA) copolymer by controlled hydrolysis. The blends, prepared at constant temperature and rotation speed in the rheomixer, were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermo-gravimetric analysis, as well as mechanical properties and extraction experiments. All the above measurements lead to the conclusion that a certain part of hydroxyls of EVAL have reacted with anhydride groups of SMA, leading to the formation of branched and cross-linked products. The effect of (1) the molar ratio of hydroxyl/maleic anhydride functional groups, (2) the overall concentration of the functional groups, and (3) the mixing time on the structure and properties of the blends are discussed. Emphasis is given on the influence of these factors on the tensile strength, the elongation at break, and impact strength of the products. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 983–999, 1997     

环氧化三元乙丙胶与苯乙烯—马来酸酐共聚物的共混行为研究

利用反应共混技术实现了环氧化三元乙丙橡胶（e-EPDM）对苯乙烯－马来酸酐（SMA）共聚物的增韧改性。以EPDM／SMA共混体系为参比,考察了共混物结构、流变行为、冲击性能和断面形态。结果表明,e－EPDM与SMA反应共混可原位形成偶联接枝产物,改善共混体系的相容程度,提高SMA的韧性。     

Dielectric relaxation of monoesters based poly(styrene-co-maleic anhydride) copolymer

A series of alkyl-grafted copolymers based on styrene-maleic anhydride (SMA) copolymers were synthesized by esterification of SMA with several long chain normal aliphatic alcohols. The prepared copolymers were characterized by FT-IR and ¹H NMR and DSC. The dielectric behavior of these copolymers was investigated in the frequency 20–10⁵ Hz and temperature −40 to 180 °C ranges. Two relaxation processes were observed, α, and β-relaxation. The former is associated with the glass-rubber transition and is characterized by the Vogel–Fulcher–Tammann temperature dependence and the latter relaxation is related to the local motion of the ester side groups attached to the polymer backbone. The apparent activation energy for the β-relaxation was found to depend significantly on the alkyl chain length. The dielectric analysis of the β-relaxation process detected is discussed.     

马来酸酐合成聚天冬氨酸及其分子质量对阻垢性能的影响

以马来酸酐和碳酸铵为原料合成了聚天冬氨酸(PASP),研究了反应条件对聚合物产率和分子质量的影响,考察了PASP黏均相对分子质量与其阻CaCO3垢性能的关系,并用红外光谱和核磁共振技术对反应产物进行了结构分析。结果表明聚合产物具有PASP的结构特征;当n(马来酸酐)∶n(氨)=1∶1 2、t=1 0h和T=170℃时,PASP产率最高;当t=22min时,PASP黏均相对分子质量约为1万,此时的PASP阻CaCO3垢性能最好,最大阻垢率达93 7%。     

Improved thermal stability and mechanical properties of poly(propylene carbonate) by reactive blending with maleic anhydride

To extend the application of a carbon dioxide sourced environmental friendly polymer: poly (propylene carbonate) (PPC), a small amount of maleic anhydride (MA) was melt blended to end‐cap with PPC to improve its thermal stability and mechanical properties. Thermal and mechanical properties of end‐capped PPC were investigated by TGA, GPC, mechanical test, and DMA. TGA and titration results demonstrate that PPC can be easily end‐capped with MA through simple melt blending. TGA results show that the thermal degradation temperature of PPC could be improved by around 140°C by adding MA. GPC measurement indicates that the molecular weight of PPC can be maintained after blending with MA, where pure PPC experiences a dramatic degradation in molecular weight during melt process. More importantly, the tensile strength of PPC after blending with MA was found to be nearly eight times higher than that of pure PPC. It has approached the mechanical properties of polyolefin polymers, indicating the possibility of replacing polyolefin polymers with PPC for low temperature applications. The method described here could be used to extend the applications of PPC and fight against the well known global warming problem. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dynamic mechanical properties of semi-interpenetrating networks based on poly(styrene-co-maleic anhydride)

Summary Semi-interpenetrating networks based on linear anionic polystyrene (PS) and poly(styrene-co-maleic anhydride) P(ScoMA) of low MA content are prepared by crosslinking the P(ScoMA) with 4,4-diphenylmethanediamine (DPMDA). It is demonstrated by dynamic mechanical analysis and by DSC that immiscible semi-IPN's are obtained for MA contents greater 5 wt.-%. In miscible semi-IPN's the relaxation of free PS chains is observed as a second maximum in the loss tangent at higher temperatures. The position of this maximum is shifted to higher temperatures for a polystyrene of molecular weight 500000 compared to a polystyrene of molecular weight 150000. The experimental temperature shift is in good agreement with a M ³ dependence of the terminal relaxation time. In addition the temperature of this second tan maximum is shifted to higher temperatures with increasing crosslink density. Again the shift is in good agreement with the theoretical prediction of an increased terminal relaxation time of the relaxing chains with decreasing tube diameter.     

Molar mass determination of poly(octadecene-alt-maleic anhydride) copolymers by size exclusion chromatography and dilute solution viscometry

The number average molar mass M_n of poly(octadecene-alt-maleic anhydride) (PODMA) copolymers calculated from data obtained by size exclusion chromatography (SEC) using a polystyrene (PS) calibration was found to be inaccurate. The use of SEC combined with dilute solution viscometry enabled a method to be developed using an iterative approach, which does not require knowledge of the Mark-Houwink constants for PODMA samples. A new calibration curve was constructed as a plot of molar mass M_u for PODMA. True number-average molar masses M_n (true) calculated using the new calibration are approximately twice the apparent molar mass M_n (app) based on a PS calibration for higher molar mass samples (>10?000 g mol⁻¹).     

马来酸酐接枝聚丙烯纤维的结构和性能研究

采用熔融纺丝法制备了马来酸酐(MAH)接枝聚丙烯纤维,考察了接枝纤维的力学性能和吸湿率以及马来酸酐的残留量。结果表明,马来酸酐接枝聚丙烯纤维的断裂强度比纯聚丙烯纤维的低,接枝率越高强度越低,断裂伸长率则相反;随着接枝率的增加,纤维的取向度也逐渐升高。与聚丙烯纤维相比,接枝聚丙烯纤维的吸湿率有了明显提高,在相同拉伸倍数下提高了3-5倍;MAH残留量相当于接枝率(0.73％)的3.7％,表明主要是接枝的马来酸酐改变了聚丙烯纤维的性质。     

Influence of the additive type and modification on the properties of blends of polyamide-6 with poly(styrene-co-maleic anhydride)

Addition of rigid poly(styrene-co-maleic anhydride) (SMA) to a polyamide-6 (PA-6) matrix leads to a system with increased stiffness and unchanged toughness as a consequence of absorption of deformational energy by the plastic deformation of brittle inclusions together with the matrix. The range of properties of both components, where this effect occurs, was studied. In addition to the use of various PA-6 and SMA types, PA-6 was also modified with epoxy resin, as well as SMA with liquid rubber bearing amino groups. Owing to the crosslinking ability of both modifiers, the influence of the changed deformability of blend components was demonstrated. Simultaneous influencing of rheological properties and reduction of the amount of reactive groups usable for the in situ compatibilizer formation make it possible to vary the size of dispersed SMA particles and the interfacial adhesion. Thus, a more comprehensive insight into the behavior of ductile-brittle blends is gained. As SMA and modifiers have negative effect on the PA-6 crystallinity, comparison of the obtained data with model calculations is difficult.     

聚(苯乙烯/马来酸酐/丙烯酸丁酯)的合成

以过氧化苯甲酰为引发剂,在甲苯介质中引发聚合制备苯乙烯(St),马来酸酐(MAH)/丙烯酸丁酯(BA)三元聚合物[P(St/MAH/BA)].探讨了反应时间、温度和单体配比等对P(St/MAH,BA)产量的影响,并对P(St,MAH,BA)的结构和性能进行了表征.结果表明,共聚单体质量比对三元聚合物的产率有决定性的作用.当m(St)/m(MAH)/m(BA)为1.00:1.00:0.78时,聚合物的产率最高,达到70%,相对分子质量为3.5×105,且热稳定性良好.     

Synthesis of ultrafine poly(styrene‐maleic anhydride) and polystyrene fibers by electrospinning

Fiber formation from atactic polystyrene (aPS) and alternating poly(styrene‐maleic anhydride) (PSMA) synthesized by free radical polymerization (AIBN, 90°C, 4 h) were investigated by electrospinning from various solutions. aPS was soluble in dimethylformamide (DMF), tetrahydrofuran (THF), toluene, styrene, and benzene, whereas PSMA was soluble in acetone, DMF, THF, dimethylsulfoxide (DMSO), ethyl acetate, and methanol. aPS fibers could be electrospun from 15 to 20% DMF and 20% THF solutions, but not from styrene nor toluene. PSMA, on the other hand, could be efficiently electrospun into fibers from DMF and DMSO at 20 and 25%, respectively. Few PSMA fibers were, however, produced from acetone, THF, or ethyl acetate solutions. Results showed that solvent properties and polymer–solvent miscibility strongly influenced the fiber formation from electrospinning. The addition of solvents, such as THF, generally improved the fiber uniformity and reduced fiber sizes for both polymers. The nonsolvents, however, had opposing effects on the two polymers, i.e., significantly reducing PSMA fiber diameters to 200 to 300 nm, creating larger and irregularly shaped aPS fibers. The ability to incorporate the styrene monomer and divinylbenzene crosslinker in aPS fibers as well as to hydrolyze PSMA fibers with diluted NaOH solutions demonstrated potential for post‐electrospinning reactions and modification of these ultrafine fibers for reactive support materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Enhanced dynamic mechanical and shape‐memory properties of a poly(ethylene terephthalate)–poly(ethylene glycol) copolymer crosslinked by maleic anhydride

Dimethyl terephthalate (DMT) and ethylene glycol (EG) were used for the preparation of poly(ethylene terephthalate) (PET), and poly(ethylene glycol) (PEG) was added as a soft segment to prepare a PET–PEG copolymer with a shape‐memory function. MWs of the PEG used were 200, 400, 600, and 1000 g/mol, and various molar ratios of EG and PEG were tried. Their tensile and shape‐memory properties were compared at various points. The glass‐transition and melting temperatures of PET–PEG copolymers decreased with increasing PEG molecular weight and content. A tensile test showed that the most ideal mechanical properties were obtained when the molar ratio of EG and PEG was set to 80:20 with 200 g/mol of PEG. The shape memory of the copolymer with maleic anhydride (MAH) as a crosslinking agent was also tested in terms of shape retention and shape recovery rate. The amount of MAH added was between 0.5 and 2.5 mol % with respect to DMT, and tensile properties and shape retention and recovery rate generally improved with increasing MAH. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 27–37, 2002     

壳聚糖交联聚丙烯酸/马来酸酐吸水树脂的制备

以马来酸酐(MA)、丙烯酸(AA)为原料,过硫酸铵(APS)和亚硫酸氢钠为引发剂,N-马来酰化壳聚糖(N-MACH)为交联剂,采用水溶液自由基聚合反应合成了高吸水树脂,并用正交实验法对合成条件进行了优化,得到最佳合成条件。结果表明,当单体浓度为20%,交联剂的用量为0.03 g,AA中和度为50%,m(MA)/m(AA)为5%时,可以合成具有较好吸水性的高吸水树脂,在蒸馏水中的吸水倍率为1 560.42 g/g;合成的吸水树脂具有较好的吸水速度;不同种类盐溶液浓度的变化对吸水树脂吸水率的影响较大。     

Hole structure and its formation in thin films of hydrolyzed poly(styrene maleic anhydride) alternating copolymers

Maleic anhydride moieties on the backbone chains of poly(styrene maleic anhydride) alternating copolymer (SMA) hydrolyzed in a THF solution containing water and hydrochloric acid. Well‐arrayed holes were obtained in spin‐cast thin hydrolyzed SMA films on a single crystal silicon wafer, and the hole diameter and its distribution were measured with AFM data. Results showed that the hole size was almost uniform, and was influenced by water content when spin speed was kept unchanged. The THF solution with a SMA concentration of about 1 g/mL and weight ratio H₂O/SMA of 1/3 produced holes having an average diameter of 0.60 μm and depth of 206.12 nm, when cast at a spin speed of 1400 rpm. It was noted that the formation of the holes in thin hydrolyzed SMA film was different from the dewetting process in thin homopolymer films, but was associated with the intrinsic properties of the copolymer forming the films. The surfactant effect of hydrolyzed SMA was suggested to interpret the formation of the holes. The holes were described to be the traces of water droplets that were emulsified by the hydrolyzed SMA during casting. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 267–274, 2000     

The influence of the interphase on composite properties: Poly(ethylene-co-acrylic acid) and poly(methyl vinyl ether-co-maleic anhydride) electrodeposited on graphite fibers

The electrodeposition of saturated copolymers onto carbon fibers is investigated, focusing particular attention on improvement of shear and impact properties of the corresponding composites. Carbon fibers are electrocoated with poly(ethylene-co-acrylic acid) and poly(methyl vinyl ether-co-maleic anhydride) from aqueous media, and fabricated into epoxy composites. The results of interlaminar shear strength (ILSS) tests, initially employed to assess fibermatrix adhesion, are vitiated by the occurrence of mixed-mode failure. Interfacial shear strength (IFSS) is hence evaluated by stressing single-fiber composite specimens to obtain ultimate aspect ratios of the fiber fragments. The data are combined with fiber strengths by a recently developed statistical theory (1) to yield a distribution for IFSS. Both copolymer interphases improve fiber-matrix bonding to an extent greater even than that obtained with commercial fiber surface treatment. Good fiber-matrix adhesion is further apparent from SEM studies of fractured ILSS test specimens. A key to this improved adhesion is the interpenetration of matrix resin and interphase polymer, revealed by electron microprobe analysis (2). Notched Izod impact strength is also increased over uncoated-fiber composites. These copolymer interphases behave as deformable interlayers, absorbing impact energy and blunting the growing crack tip. Further energy is absorbed in deflecting the crack through a more tortuous path. Simultaneous improvements in impact and shear strengths are thus obtained, which may be further enhanced by optimizing the electrodeposition parameters and the coating thickness. The influence of the interphase on composite properties is better understood from this study, paving the way for refinement in interphase design.     

Effect of poly(styrene-co-maleic anhydride) compatibilizer on properties of polystyrene/zinc oxide composites

The effects of polystyrene-co-maleic anhydride (SMA) compatibilizer on mechanical, thermal and morphological properties of polystyrene (PS)/zinc oxide (ZnO) composites were investigated for the first time in this study. PS/ZnO composites were prepared using a twin screw extruder and were then molded by compression method. In order to improve adhesion between filler and matrix, SMA compatibilizer is used in the composites. Tensile strength and Young??s modulus were increased with increasing ZnO and SMA at low concentration, but they were decreased with increasing high concentrations of ZnO and SMA content. Thus, mechanical properties can be enhanced in the composites with SMA compatibilizer. Moreover due to the effect of particle size, 250?nm ZnO particles (ZnO250) improved the mechanical properties of PS more than 71?nm ZnO particles (ZnO71) due to the increased aggregation of latter particles. Glass transition temperatures were not significantly changed when both ZnO and SMA were incorporated. Degradation temperatures of the composites increased with the addition of ZnO particles compared with neat PS and slightly decreased with the incorporation of SMA compared with the nascent composite. Scanning electron microscopy (SEM) analysis showed the better dispersion and compatibility of ZnO particles in PS/ZnO composites with the addition of SMA especially at the content of 3?wt%.     

Synthesis and characterization of maleated poly(3‐hydroxybutyrate)

Graft copolymerization of maleic anhydride (MA) onto poly(3‐hydroxybutyrate) (PHB) was carried out by use of benzoyl peroxide as initiator. The effects of various polymerization conditions on graft degree were investigated, including solvents, monomer and initiator concentrations, reaction temperature, and time. The monomer and initiator concentrations played an important role in graft copolymerization, and graft degree could be controlled in the range from 0.2 to 0.85% by changing the reaction conditions. The crystallization behavior and the thermal stability of PHB and maleated PHB were studied by DSC, WAXD, optical microscopy, and TGA. The results showed that, after grafting MA, the crystallization behavior of PHB was obviously changed. The cold crystallization temperature from the glass state increased, the crystallization temperature from the melted state decreased, and the growth rate of spherulite decreased. With the increase in graft degree, the banding texture of spherulites became more distinct and orderly. Moreover, the thermal stability of maleated PHB was obviously improved, compared with that of pure PHB. Its thermal decomposition temperature was enhanced by about 20°C. In addition, the introduction of the MA group promoted the biodegradability of PHB. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 659–668, 2003     

Solid‐state grafting of succinic anhydride onto poly(vinyl alcohol)

The graft reaction of succinic anhydride onto poly(vinyl alcohol) (PVA) was catalyzed by p‐toluenesulfonic acid monohydrate in solid state. The infrared spectra and ¹H‐NMR spectra confirmed that succinic anhydride was successfully grafted onto PVA backbone. The influences of reaction temperature, reaction time, the amount of succinic anhydride, and the amount of catalyst on the graft reaction were studied. Uncrosslinked PVA graft copolymer with grafting degree up to about 6.5% could be obtained under low reaction temperature, short reaction time, and low amount of catalyst, whereas crosslinked PVA with high gel content could be obtained under high reaction temperature, long reaction time, and high amount of catalyst. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 848–852, 2007     

马来酸酐改性氯化聚乙烯的合成及粘接性能研究

研究了马来酸酐改性ＣＰＥ的合成反应条件,比较了纯ＣＰＥ和改性ＣＰＥ的粘接强度,用ＩＲ对 产物进行了表征。实验表明：马来酸酐能改善ＣＰＥ表面的粘接性;并探讨了己内酰胺作为电子给体添加剂对 接枝反应的影响。