Crystallization and melting behavior of iPP studied by DSC

This article is a part of a study of model and bulk composites, based on isotactic polypropylene (i-PP) and glass (or carbon) fibers, produced from knitted textile preforms of hybrid yarns. First, we report the results on crystallization and fusion of textile-grade i-PP, used for the processing of hybrid yarns and the corresponding knitted fabrics. The kinetics of the crystallization process, in the dynamic and isothermal regime, was followed by DSC, and the results were analyzed by Avrami, Ozawa, and Harnisch-Muschik methods. Isothermal crystallization of i-PP was carried out at 388–400 K, and values for the Avrami exponent ranging from 1.93 to 4.39 were determined. The equilibrium melting temperature was determined by the Hoffman-Weeks method, and γ = 2.54 was found. Double melting peaks were observed both when the crystallization was performed at lower temperatures (isothermal regime) and at higher cooling rates (nonisothermal regime). A single melting peak appeared upon melting following isothermal crystallization at 400 K. The nonisothermal kinetics data showed that the peak crystallization temperature changes from 377 to 386 K as the cooling rate decreases from 20 to 3 K/min. Applying the Ozawa method, a value of the exponent n = 2.33 was determined, which is in agreement with the results for isothermal crystallization at 391–400 K. The Harnisch-Muschik approach was also applied to compare the results for n, and a similar trend in the results of isothermal and nonisothermal crystallization was found, due to the predominant homogeneous mechanism of nucleation at lower cooling rates (lower isothermal T_c) in spite of being heterogeneous at higher cooling rates (higher isothermal T_c). © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 395–404, 1998     

Combination of double‐modified clay and polypropylene‐graft‐maleic anhydride for the simultaneously improved thermal and mechanical properties of polypropylene

Double‐modified montmorillonite (MMT) was first prepared by covalent modification of MMT with 3‐aminopropyltriethoxysilane and then intercalation modification by tributyl tetradecyl phosphonium ions. The obtained double‐modified MMT was melt compounded with polypropylene (PP) to obtain nanocomposites. The dispersion of the double‐modified MMT in PP was found to be greatly improved by the addition of PP‐graft‐maleic anhydride (PP‐g‐MA) as a “compatibilizer,” whose anhydride groups can react with the amino groups on the surface of the double‐modified MMT platelets and thus improve the dispersion of MMT in PP. Fourier transform infrared, X‐ray diffraction, transmission electron microscopy, thermogravimetric analysis, scanning electron microscopy, and tensile test were used to characterize the structure of the double‐modified MMT, morphology, and the thermal and mechanical properties of the nanocomposites. The results show that PP‐g‐MA promotes the formation of exfoliated/intercalated morphology and obviously increases the thermal properties, tensile strength, and Young's modulus of the PP/double‐modified MMT nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of solid‐phase graft copolymer of polypropylene with styrene and maleic anhydride

Polypropylene (PP) was modified by solid‐phase graft copolymerization with maleic anhydride (MAH) and styrene (St), using benzoyl peroxide as the initiator and xylene as the interfacial agent. Effects of various factors such as monomer concentration, monomer ratio, initiator concentration on grafting percentage, and acid value were investigated. The graft copolymer was characterized by Fourier transform infrared, pyrolysis gas chromatography—mass spectroscopy, and dynamic mechanical analysis, and the intrinsic viscosity of the extractive from the reaction product was investigated. The results showed that the grafting percentage and acid value of the graft copolymer of PP with two monomers (MAH and St) were considerably higher than those of the graft copolymer of PP with MAH alone. The graft segments were shown to be the copolymer of St and MAH with a substantial molecular weight. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2482–2487, 2000     

Grafting of maleic anhydride onto polypropylene by reactive extrusion

Maleic anhydride grafting onto polypropylene was conducted in a twin‐screw extruder according to an experimental design in which the maleic anhydride and peroxide concentrations were varied. The modified polypropylene was characterized by FTIR spectroscopy, melt‐flow index measurements, size‐exclusion chromatography, differential scanning calorimetry, and nuclear magnetic resonance. The results showed that only the independent variable peroxide concentration influenced the amount of reacted maleic anhydride, whereas the two variables studied influenced the molecular weight of the grafted polypropylene. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2706–2717, 2002     

Liquid crystallization of poly(styrene‐co‐maleic anhydride) induced by intermolecular hydrogen bonds

The liquid crystallization of general polymer (GP) with maleic anhydride in the main chain has been realized through molecular recognition and self‐assembly based on intermolecular hydrogen bonds. Poly[styrene‐co‐(N‐4‐carboxylphenyl)maleimide] (SMIBA) was synthesized by imidization and dehydration of Poly(styrene‐co‐maleic anhydride) (SMA) with p‐aminobenzoic acid (ABA) for use as an H‐bonded donor polymer. 4‐Methoxy‐4′‐stilbazole (MSZ) and 4‐nitro‐4′‐stilbazole (SZNO₂) were prepared as an H‐bonded acceptor. SMIBA was complexed with MSZ or SZNO₂ by slow evaporation from pyridine solution to form a self‐assembly, which exhibits the mesophase, while neither of the individual components is mesogenic. The phase diagrams of a variety of mixtures between of SMIBA and stilbazoles have been established using DSC and POM. They show complete miscibility and high thermal stability of the liquid crystalline phase over the whole composition range. The tuning of liquid crystalline properties was achieved by changing the composition of the mixture and involving it with a mixture of SZNO₂ and MSZ. IR measurements strongly support the existence of an H‐bonded complex between the carboxylic acid of SMIBA and the pyridine group of stibazoles. Unlike conventional side‐chain liquid crystalline polymer (SLCP), supramolecular SLCP with a lower molecular weigh polymeric donor has higher thermal stability of the liquid crystalline phase due to the microphase separated in the hydrogen bonding case. Liquid crystallization of GP, such as SMA, induced by hydrogen bonds, offers a new route to prepare functional material with controlled molecular architecture from readily accessible and simpler precursors. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 97–105, 1999     

Microwave radiation solid-state copolymerization in binary maleic anhydride—dibenzyl maleate systems

The microwave radiation copolymerization of maleic anhydride and dibenzyl maleate was studied in the solid state at 45°C. The composition of the monomer ratio on conversion and intrinsic viscosity and the amount of initiator on intrinsic viscosity were discussed. The copolymer can be used as a suspending agent synthesizing superabsorbent oil resin. 1997 © John Wiley & Sons, Inc. J Appl Polym Sci 66: 129–133, 1997     

Blends of polyamide1010 with unmodified and maleic‐anhydride‐grafted high‐impact polystyrene

The crystallization behaviors, dynamic mechanical properties, tensile, and morphology features of polyamide1010 (PA1010) blends with the high‐impact polystyrene (HIPS) were examined at a wide composition range. Both unmodified and maleic‐anhydride‐(MA)‐grafted HIPS (HIPS‐g‐MA) were used. It was found that the domain size of HIPS‐g‐MA was much smaller than that of HIPS at the same compositions in the blends. The mechanical performances of PA1010–HIPS‐g‐MA blends were enhanced much more than that of PA1010–HIPS blends. The crystallization temperature of PA1010 shifted towards higher temperature as HIPS‐g‐MA increased from 20 to 50% in the blends. For the blends with a dispersed PA phase (≤35 wt %), the T_c of PA1010 shifted towards lower temperature, from 178 to 83°C. An additional transition was detected at a temperature located between the T_g's of PA1010 and PS. It was associated with the interphase relaxation peak. Its intensity increased with increasing content of PA1010, and the maximum occurred at the composition of PA1010–HIPS‐g‐MA 80/20. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 857–865, 1999     

HDPE-g-MAH改性氢氧化铝阻燃PP

在液相中用马来酸酐接枝高密度聚乙烯(HDPE-g-MAH)表面改性Al(OH)_3以改善其在高分子基相中的分散性。形态观察表明,用适量HDPE-g-MAH处理Al(OH)_3可改善Al(OH)_3在聚丙烯(PP)中的分散性,从而提高体系的力学性能;HDPE-g-MAH用量过多造成的Al(OH)_3粒子间桥联,该现象经熔融混合后依然存在,导致力学性能降低。偏光显微镜观察显示,适量HDPE-g-MAH处理Al(OH)_3可改善PP的结晶形态。     

Grafting of ethylene–ethyl acrylate–maleic anhydride terpolymer with amino‐terminated polydimethylsiloxane during reactive processing

An ethylene–ethyl acrylate–maleic anhydride copolymer (EEAMA) is grafted with aminopropyl polydimethylsiloxane (PDMS) via melt reactive mixing at 140°C. The materials produced split into two components based on their solubility in acetone. The acetone soluble material is highly enriched in PDMS, whereas the insoluble material contains levels of PDMS that are lower than the proportions added to the reaction mixture. It was found that for all reaction mixtures the PDMS content in the acetone insoluble solids increases with mixing time. Molecular weight distributions of materials become narrower as the amount of PDMS increases. Rheological testing shows that the level of PDMS in the mixtures and the presence of the acetone soluble fractions give rise to significant changes in the complex viscosity and elastic moduli for the polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4230–4237, 2006     

Impact modification of polypropylene by ethylene propylene copolymer‐grafted maleic anhydride

Blends of polypropylene (PP) and ethylene propylene rubber (EPR) were studied. The effect of the level of rubber addition and the ethylene content is described. The results show that the viscosity of the PP, rubber content, ethylene content, and grafted EPR by maleic anhydride (MA) are important factors in controlling the blend properties. The miscibility and dynamic properties of the blends were studied by DMTA. Impact and tensile properties were also studied. SEM was used for the investigation of the phase morphology and rubber particle size and particle‐size distribution. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1257–1265, 1999     

Synthesis and characterization of alkali‐modified styrene‐maleic anhydride copolymer for dispersion of TiO2

A copolymer of styrene and maleic anhydride was synthesized by free radical polymerization at 80°C using N,N‐dimethylformamide (DMF) as solvent and benzoylperoxide as initiator. The monomer feed ratio of styrene to maleic anhydride was varied in the range of 1 : 1 : to 3 : 1. The polymer yield was found to decrease with increase in styrene in the feed. The molecular weight of copolymers which were formed by taking styrene to maleic anhydride ratio of 1 : 1, 2 : 1, and 3 : 1, as determined by Ostwald Viscometery were about 1862, 2015, and 2276 respectively. The acid values of abovementioned three copolymers were found to be 480, 357, and 295, respectively. The typical viscosity values of 20% solids in ammonical solution of copolymers formed by taking feed ratios of Sty : MAn as 1 : 1 and 2 : 1 were 26 and 136 cp, respectively. For the feed ratio 3 : 1, a gel was formed. The synthesized copolymers were hydrolyzed by alkalis, namely, NaOH, KOH, and NH₄OH. The dispersing ability of hydrolyzed styrene‐maleic anhydride (SMA) copolymers for dispersion of titanium dioxide was studied. The modified SMA copolymers were found to be effective dispersants for TiO₂. Among the three alkalis studied, the Sodium salts of SMA were found to give better dispersion. The copolymer having a 1 : 1 feed ratio showed the best dispersing ability for TiO₂ particles among the three ratios studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3194–3205, 2007     

Covalent immobilization of bovine serum albumin onto (maleic anhydride–alt‐methyl vinyl ether) copolymers

The covalent immobilization of bovin serum albumin (BSA) onto maleic anhydride‐alt‐methyl vinyl ether copolymers (MAMVE) was successfully achieved under aqueous conditions. The grafting reaction was shown to be controlled by attractive electrostatic interactions and so took place at a low salt concentration. Under these conditions, the covalent binding reaction was quite efficient, reproducible, and complete within 20 min. The maximum loading capacity of the polymer was of 20 BSA molecules per polymer chain. This preliminary study demonstrated that the immobilization of proteins in an aqueous medium could be an efficient process, despite the existing hydrolysis of the functional polymer by water molecules. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1565–1572, 1999     

Fracture toughness of modified polypropylene/poly(styrene‐ran‐butadiene) blends

Fracture toughness of polypropylene (PP)/poly(styrene‐ran‐butadiene) rubber (SBR) blends as a function of concentration of maleic anhydride (MA) in the maleated polypropylene (MAPP) compatibilizer was investigated under uniaxial static and impact loading conditions. The addition of MAPP to the unmodified PP/rubber blend enhanced the tensile modulus and yield stress as well as the Charpy impact strength. The maximum values were recorded at 1.0 wt% grafted MA in the compatibilizer. V‐shaped blunt‐notched specimens exhibited typical ductile behavior and no breakage of the specimens occurred during the impact fracture tests. Sharp‐notched specimens of uncompatibilized and low‐content MA blends broke in a semibrittle manner, supported by a rapid crack propagation process. Increasing MA content in the blends led to semibrittle‐to‐ductile transition characterized by stable crack propagation. Fracture mechanics experiments, supplemented by scanning electron microscopy (SEM), were also employed to obtain a better understanding of the fracture and deformation behavior. Copyright © 2005 Society of Chemical Industry     

Thermal properties of poly(maleic anhydride‐alt‐acrylic acid) in the presence of certain metal chlorides

Polychelates were synthesized by the addition of aqueous solutions of copper(II), cadmium(II), and nickel(II) chlorides to aqueous solutions of poly(maleic anhydride‐alt‐acrylic acid) [poly(MA‐alt‐AA)] in different pH media. The thermal properties of poly(MA‐alt‐AA) and its metal complexes were investigated with thermogravimetry and differential scanning calorimetry (DSC) measurements. The polychelates showed higher thermal stability than poly(MA‐alt‐AA). The thermogravimetry of the polymer–metal complexes revealed variations of the thermal stability by complexation with metal ions. The relative thermal stabilities of the systems under investigation were as follows: poly(MA‐alt‐AA)–Cd(II) > poly(MA‐alt‐AA)–Cu(II) > poly(MA‐alt‐AA)–Ni(II) > poly(MA‐alt‐AA). The effects of pH on the complexation and gravimetric analysis of the polychelates were also studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3926–3930, 2006     

Copolymerization of the pair maleic anhydride–dicyclopentadiene: I. Copolymerization and post‐copolymerization at high conversion

The present study describes the kinetic investigation of the complex binary copolymerization system maleic anhydride (MA)—dicyclopentadiene (DCPD). All syntheses were carried out in homogeneous solution; high conversions in soluble and linear copolymer are achievable when starting from an equimolecular monomer feed. Excess of DCPD would limit the attainable conversions, while surplus of MA would induce crosslinking of the copolymers. The findings of the thorough kinetic study were sustained by structural assessment from IR and NMR spectra recorded for various copolymers, both soluble and gels. Copyright © 2004 Society of Chemical Industry     

PP/PP-g-MAH/HGB复合材料非等温结晶行为研究

采用熔融法制备了聚丙烯/马来酸酐接枝聚丙烯/空心玻璃微珠（PP/PP-g-MAH/HGB）复合材料,采用差示扫描量热仪研究了PP、PP/HGB、PP/PP-g-MAH/HGB复合材料的非等温结晶过程,并通过Jeziorny法和Mo法研究了3种材料的非等温结晶动力学。结果表明,随着降温速率的增大,3种材料的结晶峰温、结晶起始温度和结晶度均减小,结晶速率增大;HGB抑制了PP的结晶行为,降低了结晶速率;PP-g-MAH对PP结晶速率的影响较小,HGB和PP-g-MAH都会改变PP的结晶成核和生长机理。     

Properties of poly(ethylene terephthalate) and maleic anhydride-grafted polypropylene blends by reactive processing

The properties of poly(ethylene terephthalate) (PET) and polypropylene (PP) blends and PET/maleic anhydride-grafted PP (MAgPP) reactive blends were investigated. Two blend systems were immiscible based on tan δ measured by dynamic mechanical analyzer (DMA). In case of PET/MAgPP blends, the reaction of ester groups of PET and MA sites on MAgPP occurred during melt mixing at 280°C for 30 min. The reaction was confirmed by a new peak between the glass transition temperatures of PET-rich and MAgPP-rich phase on tan δ curves, as well as from the rheological properties. From the morphology, the improvement of the dispersibility in PET/MAgPP reactive blends was observed. The modulus of PET/MAgPP blends was higher than that of PET/PP blends, and the strength of PET/MAgPP blends showed the good adhesion compared with the PET/PP blends. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 389–395, 1998     

The effect of maleic anhydride modified polypropylene on the mechanical properties of feather fiber,kraft pulp,polypropylene composites

Composites made of feather fiber (Ff), kraft pulp fiber (Pf), polypropylene (PP), and maleic anhydride modified polypropylene (MaPP) were tested in tension and three‐point bend tests. Composite panels were compression molded from multiple plies of nonwoven, fabric‐like prepreg manufactured with wetlay papermaking equipment. Composites containing all four materials were manufactured with MaPP substitutions for PP of 0–10 wt % at 2 wt % increments. The best mechanical properties were observed with a substitution of 8 wt % MaPP. Composites containing either Pf or Ff were manufactured with MaPP substitutions for PP of 0, 4, and 8 wt %; mechanical properties improved with increases in MaPP content. The improvements in mechanical properties were attributed to fiber/matrix interface improvement by the addition of MaPP. Scanning electron microscopy revealed evidence of improved interfacial bonding on the tensile fracture surfaces. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3771–3783, 2004     

Synthesis,characterization and cytotoxicity of novel modified poly[(maleic anhydride)‐ co‐(vinyl acetate)]/noradrenaline conjugate

Poly[(maleic anhydride)‐co‐(vinyl acetate)] (MAVA) copolymer was synthesized by free radical polymerization reaction, in methyl ethyl ketone at 80 °C, using benzoyl peroxide as the initiator. The copolymer was then modified with a biomolecule, noradrenaline (NA). The modification reaction was performed at 70 °C in dimethylformamide containing triethylamine as the catalyst. The modified polymer was named MAVA/NA. Structural characterization of the copolymer and the modified product was carried out by Fourier transform infrared (FTIR) and ¹H NMR and ¹³C NMR spectroscopy. The FTIR, ¹H NMR and ¹³C NMR spectra confirmed that NA was successfully covalently bound to the MAVA copolymer backbone. Surface morphology was visualized by atomic force microscopy. The cumulative release of NA from MAVA/NA was determined in phosphate buffered saline solution for 7 days at 37 °C and compared with MAVA. Cytotoxicity of the MAVA/NA was evaluated by using a mouse fibroblast cell line (L929). Results obtained indicated that MAVA/NA had almost no toxicity and no negative effect on cell viability at 250 µg mL^?1 concentration. © 2012 Society of Chemical Industry     

马来酸酐接枝聚丙烯的方法及其发展

介绍了马来酸酐(MAH)接枝聚丙烯(PP)的方法,主要有熔融接枝、溶液接枝、固相接枝、悬浮接枝等。指出了每种接枝方法的优缺点及研究进展。提出了工业放大、接枝机理的研究以及接枝过程中应考虑经济环保等是接枝技术的发展方向。