Comparative spectroscopic study of the modification of cellulosic materials with different coupling agents

The reactions of two cellulosic materials (an industrial cellulosic by‐product from a Kraft pulp mill facility and a reference material) with three coupling agents, used to improve compatibility between cellulosic reinforcements and thermoplastic matrices, were studied by diffuse reflectance Fourier‐transform infrared (DRIFT) spectroscopy and diffuse reflectance ultraviolet‐visible spectroscopy. A maleated polypropylene wax (Epolene E‐43™) and two silanes (N‐2‐aminoethyl‐3‐aminopropyltrimethoxysilane and methyltrimethoxysilane) were used as coupling agents. The two cellulosic materials reacted in a similar way and the three coupling agents were covalently bonded to the cellulose. For the aminosilane, a reaction with cellulose involving a fraction of the amino groups was detected. A simple method, based on the analysis of the oxidation kinetics of treated and untreated materials, was developed to compare the degree of cellulose modification achieved by each coupling agent. The analysis revealed that a reduced fraction of the cellulose reactive groups was converted by esterification with the maleated polypropylene. However, when applied in the appropriate conditions, the two silanes converted most of such cellulose reactive groups. Finally, the reaction of cellulose with mixtures of coupling agents was studied. The aminosilane‐treated cellulose reacted with the maleated polypropylene with formation of amide links. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 256–266, 2000     

High Stiffness Natural Fiber‐Reinforced Hybrid Polypropylene Composites

Abstract

Natural fibers are potentially a high‐performance non‐abrasive reinforcing fiber source. In this study, pulp fibers [including bleached Kraft pulp (BKP) and thermomechanical pulp (TMP)], hemp, flax, and wood flour were used for reinforcing in polypropylene (PP) composite. The results show that pulp fibers, in particular, TMP‐reinforced PP has the highest tensile strength, possibly because pulp fibers were subjected to less severe shortening during compounding, compared to hemp and flax fiber bundles. Maleic‐anhydride grafted PP (MAPP) with high maleic anhydride groups and high molecular weight was more effective in improving strength properties of PP composite as a compatiblizer. Coupled with 10% glass fiber, 40% TMP reinforced PP had a tensile strength of 70 MPa and a specific tensile strength comparable to glass fiber reinforced PP. Thermomechanical pulp was more effective in reinforcing than BKP. X‐ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM) were used to aid in the analysis. Polypropylene with high impact strength was also used in compounding to improve the low‐impact strength prevalent in natural fiber‐reinforced PP from injection molding.     

Solvent‐free acetylation of lignocellulosic fibers at room temperature: Effect on fiber structure and surface properties

Acetylation is one of the most interesting chemical treatments to improve the affinity of lignocellulosic fibers with polymeric matrices for the elaboration of several types of composites. In this paper, the acetylation of flax and wood pulp (bleached softwood Kraft pulp and thermomechanical pulp) fibers was carried out at room temperature in a solvent‐free system with acetic anhydride in the presence of sulfuric acid as catalyst. The effect of acetylation on the fine structure of fibers was investigated by spectroscopic methods, while the extent of acetylation was quantified by weight percent gain. The effect of reaction time on fiber morphology was studied at macro‐ and microscale using scanning electron microscopy, optical microscopy, and fiber quality analysis. The evolution of the hydrophobic/hydrophilic character of fibers was determined by contact angle measurements. The wettability of fibers by liquid epoxy resin was also evaluated to confirm the improvement of the affinity of acetylated fibers with the epoxy matrix. It was found that the hydrophilic character of fibers decrease with increasing reaction time, whereas the trend was less pronounced beyond specific reaction times. Acetylated fibers can therefore be potential candidates for replacing nonbiodegradable reinforcing materials in composite applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42247.     

聚丙烯／接枝木纤维复合材料相容性及性能的研究

为了改善木纤维与聚丙烯基体间的相容性，用马来酸酐接枝聚丙烯（ＭＡＰＰ）对木纤维进行接枝处理。通过红外光谱分析，证明了马来酸酐接枝聚丙烯和木纤维之间产生了酯化反应，提出了木纤维和聚丙烯基体的粘合性。通过扫描电镜（ＳＥＭ）的观察及示差扫描量热计（ＤＳＣ）的分析，证明了接枝木纤维比未接枝的木纤维与聚丙烯基体间的界面相容性有了明显的改善，使木纤维能均匀地分散在聚丙烯基体中，从而提高了复合材料的加工性能和力     

Crystallization of poly(hydroxybutrate-co-hydroxyvalerate) in wood fiber-reinforced composites

Wood fiber-reinforced composites were prepared from poly(hydroxybutyrate) (PHB) and poly(hydroxybutyrate-co-hydroxyvalerate) (PHB/HV) copolymers containing 9 and 24% valerate. The effects of fibers on crystallization were investigated. Thermomechanical pulp, bleached Kraft fibers, and microcrystalline cellulose filler were used as the reinforcing phase. The crystallization of PHB/HV in composite materials was examined using Modulated Differential Scanning Calorimetry (MDSC) and hot-stage microscopy. Hot-stage microscopy showed that polymer crystallites are nucleated on the fiber surface and that the density of nuclei was greater in fiber-reinforced composites than in unfilled material. Dynamic crystallization experiments showed that bleached Kraft, thermomechanical pulp, and microcrystalline cellulose increased the crystallization rate of PHB and PHB/HV both from the glass and melt. However, ultimate crystallinity determined from the heat of crystallization was the same in unreinforced and reinforced materials. The kinetics of PHB/HV crystallization were examined using nonisothermal Avrami-type analysis. Unreinforced and Kraft-reinforced PHB were characterized and compared with unreinforced PHB/9%HV. The Avrami exponent of crystallization, related to nucleation mechanism and growth morphology, is 2.0 for unreinforced PHB, 2.8 for kraft-reinforced PHB, and 3.0 for unreinforced PHB/9%HV. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1785–1796, 1997     

Preparation of microwave‐assisted polymer‐grafted softwood kraft pulp fibers. Enhanced water absorbency

A wood pulp cellulose‐based hydrogel material was prepared with poly(methyl vinyl ether‐co‐maleic acid) (PMVEMA), polyethylene glycol (PEG), and softwood ECF kraft pulp via microwave and thermal esterification and compared via hydrogel absorption and retention of water and 0.10M NaCl. The microwave initiated reaction time was optimized to 105 s at 1600 W based on maximum water absorption of 96 g/g of the 49% PMVEMA pulp hydrogels. The influence of reaction variables such as pulp fiber size and the weight ratios of PMVEMA to pulp were investigated. The maximum water absorbency of the milled pulp fibers microwave initiated products was 151 g/g, whereas the maximum water absorbency of the milled pulp fibers thermally initiated hydrogels was 198 g/g. In addition, the microwave initiated hydrogels retained a maximum of 67% of absorbed water after centrifugation at 770 rpm for 10 min, whereas the thermally initiated hydrogels retained a maximum of 49% of water absorbed. Fourier transform infrared spectroscopy (FTIR) was used to confirm the esterification of the PMVEMA with the pulp cellulose. Microwave initiated crosslinking successfully produced a pulp hydrogel with a shorter reaction time and comparable or improved water absorption and retention properties when compared with the traditional thermally crosslinked pulp hydrogel system. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of polypropylene reinforced with cellulose I and II fibers

Recently, cellulose fiber–thermoplastic composites have played an important role in some applications. Plastics reinforced with cellulose and natural fibers have been widely studied. However, composites with regenerated cellulose have rarely been investigated. In this study, the lyocell fiber of Lenzing AG (cellulose II) and its raw material a bleached hardwood pulp (cellulose I) were used as reinforcement materials. The mechanical and thermal properties of polypropylene (PP) reinforced with pulp and lyocell fibers were characterized and compared with regard to the content of the fiber and the addition of maleated polypropylene (MAPP). PPs with cellulose I or II as a reinforcement material had similar mechanical properties. However, when MAPP was used as coupling agent, the mechanical properties of the composites were different. The crystallinity of the composites were determined by differential scanning calorimetry. Cellulose I (pulp) promoted the crystallization of PP, whereas cellulose II did not. MAPP reduced this effect in cellulose I fibers, but it induced crystallization when cellulose II (lyocell) was used as a reinforcement material. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 364–369, 2006     

Alder Ene functionalization of polypropylene through reactive extrusion

A commercial isotactic polypropylene was degraded to increase its terminal vinylidene group concentration, and it was subsequently functionalized with maleic anhydride through the Alder Ene reaction at temperatures above 200°C in a co‐rotating twin screw extruder. Characterization of the maleated product by Fourier transform infrared spectroscopy, ¹H NMR, differential scanning calorimetry, and gel permeation chromatography showed the anhydride group to be terminally attached, and the degree of functionalization was determined by infrared analysis. Increased temperature and maleic anhydride concentration, as well as improved mixing in the extruder, were found to improve the extent of the reaction. The catalytic contribution of Lewis acid species was evaluated, and ruthenium chloride was found to increase the extent of the reaction by 16% in comparison with stannous chloride as a catalyst in the Alder Ene reaction. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 503–516, 1999     

Surface of cellulosic materials modified with functionalized polyethylene coupling agents

The interfacial adhesion between a wood fiber and a plastic matrix strongly influences the performance of wood‐fiber‐reinforced thermoplastic composites. Fiber surface modification with coupling agents is generally needed to induce bond formation between the fiber and polymer matrix. This study investigated the chemical reactions between cellulosic materials and functionalized polyethylene coupling agents. Both wood flour and cotton cellulose powder were treated with acrylic acid‐functionalized polyethylene and maleic anhydride‐functionalized polyethylene (maleated polyethylene) for surface modifications, and chemical changes resulting from these treatments were followed by a study of the Fourier transform infrared and X‐ray photoelectron spectroscopy spectra. Variations in the band intensities, oxygen‐to‐carbon ratios, and concentrations of unoxidized carbon atoms were related to changes that occurred on the surfaces of modified cellulosic materials. The experimental results indicated that chemical bonds between the hydroxyl groups of the cellulosic materials and the functional groups of the coupling agents occurred through esterification reactions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 278–286, 2003     

Polypropylene–wood fiber composites: Effect of treatment and mixing conditions on mechanical properties

Polypropylene/wood fiber composites were prepared at three different temperatures: 170°C, 180°C, and 190°C. The surface of wood fibers was modified through the use of silane coupling agents and/or coating with polypropylene or maleated polypropylene. The fiber coating was performed by propylene polymerization in the presence of wood fibers or by immersion in an o-dichlorobenzene polypropylene (or maleated polypropylene) solution. Tensile and three-point bending tests were performed in order to evaluate the adhesion between matrix and wood fibers. Evidence shows that 180°C is the best mixing temperature, while the use of vinyl-tris (2-methoxy ethoxy) silane with or without maleated polypropylene coating is the best surface treatment. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1227–1235, 1997     

Maleated polypropylene film and wood fiber handsheet laminates

The grafting effect of maleic anhydride (MA) as an interfacial bonding agent and its influence on the tensile strength properties of thermomechanical pulp handsheet‐isotactic polypropylene (iPP) film laminates was studied. For the MA treated with benzoyl peroxide (BPO) as an initiator, tensile strength properties increased 76% with PP film over untreated laminates. The optimal strength properties were obtained with a MA and BPO ratio of 2:1. A strong correlation was observed between the number of fibers in the web and tensile strength properties for both handsheet drying conditions. The R² values were 0.95 for air‐dry conditions and 0.94 from oven‐dry conditions. Scanning electron microscopy images also showed the effectiveness of MA loading on the surface of thermomechanical pulp fibers due to increased fiber failure, which occurred without fiber being pulled out from the PP matrixes. Crystallinity and heat flow were determined using differential scanning calorimetry (DSC) and increased as expected as the ratio of MA and BPO increased from 0:0 to 2:1. These results were also in accordance with the morphological observations at the fracture surface, Fourier transform infrared spectra, and thermal analysis. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Cellulose/polypropylene composites: Influence of the molecular weight and concentration of oxidatively degraded and maleated polypropylene compatibilizers on tensile behavior

To improve interactions between fibrous cellulose (FC) and polypropylene (PP), oxidatively degraded polypropylene (DgPP) and maleated polypropylene (MAPP) were studied as compatibilizers. Both compatibilizers had the same mechanism, using esterification between the OH group in FC and the reactive (γ‐lactone, acid, and maleic anhydride) groups in the compatibilizers. However, the adhesion style with the ester bond was considerably different because of the arrangements of the reactive groups. DgPP had reactive groups at the polymer chain end, and the tensile behavior of the FC/PP/DgPP composite exhibited comparatively ductile behavior. However, MAPP had inner reactive groups, and the tensile behavior of the FC/PP/MAPP composite was quite brittle. Observation of these fracture surfaces suggested that the adhesion performance of the interface between FC and PP was strongly influenced by the arrangements of the reactive group. In addition, the performance was influenced by the molecular weight of DgPP and by the content of maleic anhydride groups in MAPP. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of surface morphology of the kraft pulp fibers on the growth of the transcrystalline layer of polypropylene

The objective of this study was to evaluate the influence of the wood fiber surface on the crystallization behavior of thermoplastic polymers. Unbleached and bleached kraft pulp fibers were used for this study with 100% polypropylene (PP), 95% PP/5% maleic anhydride polypropylene (MAPP), and 100% MAPP at 150°C. Nuclei were induced at the ends of the fibers and on damaged surfaces while poor crystallization behavior was observed on the fiber surfaces using 100% PP. Enhanced MAPP induced transcrystallization on the wood fiber surfaces; the nucleation density also increased with the addition of MAPP. Oxygen/carbon (O/C) ratios of smooth surfaces, damaged surfaces, and the ends of wood fibers also indicated that the oxidation process of both wood fiber and thermoplastic polymer affected the crystallization process without MAPP addition. It was observed that the MAPP played a role in increasing numbers of nuclei on the linear fiber surface to induce transcrystallization. Dynamic mechanical properties increased 52% with 100% MAPP compared to the use of 100% PP. Therefore, the increased thickness of transcrystalline layer and nucleation density on the surface of wood fiber positively correlated with the dynamic mechanical properties of wood fiber‐plastic composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Analysis of Among-Species Variability in Wood Fiber Surface Using DRIFTS and XPS: Effects on Esterification Efficiency

Abstract

Variability in the chemical composition of surface properties of various wood fibers (eastern white cedar, jack pine, black spruce, and bark) was investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and X-ray photoelectron spectroscopy (XPS). Both DRIFTS and XPS showed high variability in fiber surface composition between species and between fiber types (sapwood, heartwood, and bark). Fiber surface was modified by esterification reaction using a maleic anhydride polyethylene (MAPE) treatment. DRIFTS failed to assess surface modification, whereas XPS results showed that MAPE treatment increased the surface hydrocarbon concentration of jack pine wood fiber, indicated by a decrease in oxygen–carbon ratio and an increase in relative intensity of the C1 component in the C1s signal. Lignin concentration variability on the fiber surface was determined as the major factor that prevents esterification from taking place.     

Milling‐induced esterification between cellulose and maleated polypropylene

The ball milling of cellulose and maleic anhydride grafted polypropylene (MAPP) induced the formation of ester bonds between OH groups of cellulose and maleic anhydride groups of MAPP, in marked contrast to the melt mixing of the original cellulose and MAPP, through which the esterification was hardly observed. This esterification was hardly dependent on the chemical structure of MAPP. In agreement with the enhanced interfacial adhesion due to the formation of ester bonds, a composite prepared via ball milling revealed an improvement in the tensile strength with respect to a melt‐mixed composite. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1703–1709, 2004     

The reaction of polypropylene with maleic anhydride

An addition reaction of maleic anhydride with polypropylene takes place in the presence of radical reagents or sunlight. The initial rate of the reaction was proportional to the concentration of polypropylene and maleic anhydride, and one-half power of the concentration of the radical reagents. The increase in the temperature from 80 to 120°C increased the rate of the reaction and di-cumyl peroxide was effective as a radical reagent for this reaction. Ionic crosslinked rubber-like polymers were obtained from the reaction of maleic polypropylene with some alkali metal compounds. They showed the characteristic absorption band due to ? COO^? in their infrared spectra.     

Steam-exploded wheat straw fibers as reinforcing material for polypropylene-based composites. Characterization and properties

Composites of wheat straw fibers with polypropylene (iPP) and maleic anhydride modified polypropylene (iPPMA) were prepared. Before being mixed with polypropylene matrices, the wheat straw fibers were subjected to a steam explosion process that induces morphological and structural changes in lignocellulosic materials. Such changes are able to enhance the interactions with the thermoplastic matrix. Compared with iPP, the modified matrix (iPPMA) has shown higher mechanical performances (tensile and impact behavior) and a remarkable decrease of water absorption, that is one of the main drawbacks of natural fiber composites. Finally, the presence of covalent bonds between maleic anhydride and steam-exploded (STEX) fibers, by means of an esterification reaction, produced during the melt-mixing process, can explain the resulting good interfacial adhesion found in iPPMA-based composities.     

Influence of processing conditions and material compositions on the performance of formaldehyde‐free wood‐based composites

This study examined the differences between formaldehyde‐free wood composite panels made with maleated polyethylene (MAPE) and maleated polypropylene (MAPP) binding agents. Specifically, the study investigated the contrasts of (a) base resin type, PE vs. PP, (b) molecular weight/maleic anhydride content in MAPP binding agents, and (c) the manufacturing methods (reactive extrusion vs. hot press) on the physicomechanical properties of the composites. FTIR and XPS analyses of unmodified and modified wood particles after reactive extrusion with maleated polyolefins provided evidence of chemical bonding between the hydroxyl groups of wood particles and maleated polyolefins. Although extruding the particles before panel pressing gave better internal bond (IB) strength, superior bending properties were obtained through compression molding alone. MAPP‐based panels outperformed MAPE‐based panels in stiffness. Conversely, MAPE increased the IB strength of the panels compared with MAPP. Polymer base resin had no effect on modulus of rupture or screw holding capacity. Differences between the two maleated polypropylene compounds were not significant for any of the mechanical properties tested. Formaldehyde‐free wood composites manufactured in this study often outperformed standard requirements for conventional particleboard, regardless of material composition or manufacturing method used. POLYM. COMPOS., 27:599–607, 2006. © 2006 Society of Plastics Engineers     

Influence of functionalized polyolefin on interfacial adhesion of glass fiber‐reinforced polypropylene

Several types of functionalized polyolefins, grafted with maleic anhydride, were synthesized and used to modify the surface of fiberglass in reinforced polypropylene composites. The influence of maleated polyolefin, matrix, and compounding conditions on the interfacial bonding strength of composite were studied by measuring interfacial shear strength. The results showed that strong interactions, e.g., chemical bonding, were formed between maleated polyolefin and fiber surface. When the modified fibers were compounded with polypropylene, firm entanglements of molecular chain were formed due to the segmental interdiffusion between maleated polyolefin and matrix polypropylene. As a result, the degree of fiber‐matrix adhesion was improved. The extent of such improvement depended on the grafting degree, chain length of maleated polyolefin, and the compatibility between maleated polyolefin and matrix resin. At the same time, the compounding temperature and the cooling procedure affected the interfacial adhesion too. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1359–1365, 2000     

二氢月桂烯醇与马来酸酐酯化反应的研究

利用一端含双键、一端含羟基的二氢月桂烯醇与马来酸酐进行酯化反应得到一种新型的两亲性单体。实验中考察了催化剂用量、反应温度、酸醇比对酯化反应的影响,得到了最佳的单酯化反应条件。实验表明：催化剂的加入利于双酯化;不加催化剂,n（马来酸酐）：n（二氢月桂烯醇）=1．05：1．0,温度为110℃下只发生单酯化反应,反应6h后,二氢月桂烯醇马来酸单酯的产率可以达到80％以上。利用红外光谱分析表征了产物的结构,证明合成产物为目标产物。