Effects of crosslinking on the mechanical properties and biodegradability of soybean protein‐based composites

A green composite with good mechanical properties and acceptable biodegradability was developed using wood flour and soybean protein that was modified by thermal‐caustic degradation and chemical crosslinking with glyoxal and polyisocyanate (PMDI). Fourier transform infrared (FTIR) spectroscopy and scanning electron microscope (SEM) in combination with the traditional evaluations were employed to investigate the structure, morphology, and properties of the crosslinked soybean protein and the crosslinking‐modified wood/soybean protein composites to understand the effects of the crosslinker species on the mechanical properties, water resistance, and microbial biodegradation of soybean protein‐wood flour composites. The results indicated that the chemical crosslinking modification could improve the mechanical properties and water resistance but decrease the biodegradability of the wood/protein composite to a certain extent. Both glyoxal and PMDI alone as crosslinkers could not perfectly modify the soybean protein because of the high reactivity of PMDI and low crosslinking reactivity of glyoxal. The incorporation of glyoxal with PMDI could result in the desired crosslinking efficiency and good interfacial adhesion by compromising the advantages and disadvantages of glyoxal or PMDI alone as crosslinkers, which balanced the performances of the wood flour/soybean protein composite. The preferable combination crosslinker was composed of 50 wt % glyoxal and 50 wt % PMDI. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41387.     

木粉疏水改性对HDPE基木塑复合材料性能的影响

采用一种操作简便且易于工业推广的方法对木粉进行疏水改性,具体过程为：将3种可热聚合的单体,即甲基丙烯酸甲酯（MMA）、甲基丙烯酸丁酯（BMA）和苯乙烯（St）均匀喷洒在木粉上,经过预热处理后,与配方中其他组分,如高密度聚乙烯（HDPE）和马来酸酐接枝聚乙烯（MAPE）等通过高速混合机混合均匀,采用双螺杆挤出机造粒后,注射制备木塑复合材料（WPC）样条,测试其力学性能。另外,考察了疏水改性对WPC接触角、维卡软化温度、洛氏硬度、吸水性能、热性能的影响规律。结果表明：疏水改性后WPC的接触角增大,木粉和HDPE的界面相容性改善,力学性能得到明显提高。其中,当MMA、BMA和St的添加量为3%时,WPC的力学性能最好,与疏水改性前相比,弯曲强度分别提高了17.3%、26.3%和27.5%,弯曲模量分别提高了24.4%、24.4%和26.0%,冲击强度分别提高了54.7%、57.7%和60.5%。 此外,疏水改性后WPC的维卡软化温度、洛氏硬度、耐水性和耐热性也得到改善。     

Synthesis of reactive soybean oils for use as a biobased thermoset resins in structural natural fiber composites

Biobased thermosets resins were synthesized by functionalizing the triglycerides of epoxidized soybean oil with methacrylic acid, acetyl anhydride, and methacrylic anhydride. The obtained resins were characterized with FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy to confirm the functionalization reactions and the extent of epoxy conversion. The viscosities of the methacrylated soybean oil resins were also measured for the purpose of being used as a matrix in composite applications. The cross‐linking capability was estimated by UV and thermally initiated curing experiments, and by DSC analysis regarding the degree of crosslinking. The modifications were successful because up to 97% conversion of epoxy group were achieved leaving only 2.2% of unreacted epoxy groups, which was confirmed by ¹H‐NMR. The ¹³C‐NMR confirms the ratio of acetate to methacrylate methyl group to be 1 : 1. The viscosities of the methacrylated soybean oil (MSO) and methacrylic anhydride modified soybean oil (MMSO) were 0.2 and 0.48 Pas, respectively, which indicates that they can be used in resin transfer molding process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Rheological and thermal properties of soybean oils with modified FA compositions

Rheological and thermal properties of five soybean oils with modified FA compositions were studied. Viscosity decreased with increasing temperature at different rates for the different oils. Oil with a high-oleic acid content had higher viscosity and a greater rate of change than did oils with typical FA compositions, oil with low-saturated FA or low-linolenic acid content, or oil from lipoxygenase-free soybeans. The melting and crystallization behaviors of the oils were examined using DSC. The high-oleic acid oil and the oil with low-saturated FA content had different DSC profiles compared with the other oils. Specific heat capacities of oils were estimated using a mathematical model; the high-oleic acid oil had a higher specific heat value, and the low-saturated FA oil had a lower value than did the other oils.     

Structure and mechanical properties of novel composites based on glycidyl azide polymer and propargyl‐terminated polybutadiene as potential binder of solid propellant

Instead of the traditional isocyanate curing system as the binder of solid propellant, a triazole curing system has been developed by the reaction of azide group and alkynyl group due to a predominant advantage of avoiding to the interference of humidity. In this work, the propargyl‐terminated polybutadiene (PTPB) was blended with glycidyl azide polymers (GAPs) to produce new composites under the catalysis of cuprous chloride at ambient temperature. The triazole‐crosslinked network structure was regulated by changing the molar ratio of azide group in GAP versus alkynyl group in PTPB, and hence various crosslinked densities together with the composition changes of GAP versus PTPB cooperatively determined the mechanical properties of the resultant composites. Furthermore, the formed triazole‐crosslinked network derived from the azide group in GAP and alkynyl group in PTPB resulted in the slight increase of glass transition temperatures and a‐transition temperatures, and improved the miscibility between GAP and PTPB. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40007.     

Wood–polymer composites prepared by the in situ polymerization of monomers within wood

Wood–polymer composites (WPCs) were prepared from poplar wood (P. ussuriensis Komarov) in a two‐step procedure. Maleic anhydride (MAN) was first dissolved in acetone and impregnated into wood; this was followed by a heat process; and then, glycidyl methacrylate (GMA) and styrene (St) were further impregnated into the MAN‐treated wood, followed by a second thermal treatment. Finally, the novel WPC was fabricated. The reactions occurring in the WPC, the aggregation of the resulting polymers, and their interaction with the wood substrate were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, and dynamic mechanical analysis. The performance of WPC was also evaluated in terms of the mechanical properties and durability, which were then correlated with the structural analysis of the WPC. The test results show that MAN and GMA/St chemically reacted with the wood cell walls in sequence, and the quantity of hydroxyl groups in the wood cell walls was evidently reduced. Meanwhile, St copolymerized with GMA or MAN, and the resulting polymers mainly filled in the wood cell lumen in an amorphous form, tightly contacting the wood cell walls without noticeable gaps. As a result, the mechanical properties, decay resistance, and dimensional stability of the WPC were remarkably improved over those of the untreated wood, and its glass‐transition temperature also increased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Triacylglycerol composition and structure in genetically modified sunflower and soybean oils

Changes in composition were examined in oils extracted from genetically modified sunflower and soybean seeds. Improvements were made to the analytical methods to accomplish these analyses successfully. Triacylglycerols (TAG) were separated on two 300 mm × 3.9 mm 4μ Novapak C18 high-performance liquid chromatography (HPLC) columns and detected with a Varex MKIII evaporative light-scattering detector. Peaks were identified by coelution with known standards or by determining fatty acid composition of eluted TAG by capillary gas chromatography (GC). Stereospecific analysis (fatty acid position) was accomplished by partially hydrolyzing TAG with ethyl magnesium bromide and immediately derivatizing the resulting diacylglycerols (DAG) with (S)-(+)-1-(1-naphthyl)ethyl isocyanate. The derivatized sn-1,2-DAG were completely resolved from the sn-2,3-DAG on two 25 mm × 4.6 mm 3 μ silica HPLC columns. The columns were chilled to −20°C to obtain baseline resolution of collected peaks. The distribution of fatty acids on each position of the glycerol backbone was derived from the fatty acid compositions of the two DAG groups and the unhydrolyzed oil. Results for the sn-2 position were verified by hydrolyzing oils with porcine pancreatic lipase, isolating the resulting sn-2 monoacylglycerols by TLC, and determining the fatty acid compositions by GC. Results demonstrated that alterations in the total fatty acid composition of these seed oils are determined by the concentration of TAG species that contain at least one of the modified acyl groups. As expected, no differences were found in TAG with fatty acid quantities unaffected by the specific mutation. In lieu of direct metabolic or enzymatic assay evidence, the authors’ positional data are nevertheless consistent with TAG biosynthesis in these lines being driven by the mass action of available acyl groups and not by altered specificity of the acyltransferases, the compounds responsible for incorporating fatty acids into TAG.     

不同聚合物基体对复合材料性能的影响

研究了以不同类型聚合物为基体的高分子夏合材料的导电性和力学强度的变化规律，并从聚合物的结晶性，对填料的粘结性及其表面张力等方面进行了分析。若基体的结晶性和极性较强，则在导电性提高的同时，冲击强度下降；若基体本身比较柔软且对填料有足够的亲和力，则在一定的填料含量范围内，导电性和冲击强度可同时提高。     

Mechanical and thermal flow properties of wood flour–biodegradable polymer composites

Wood flour (WF)–polycaprolactone (PCL) and polybutylenesuccinate–butylenecarbonate (PBSC) composites were prepared by knead processing. The effects of a compatibilizer on the tensile and thermal flow properties of the composites were investigated. PCL‐graft‐maleic anhydride (PCL‐g‐MA) was used as a compatibilizer. Tensile properties were improved by adding PCL‐g‐MA to both composites. The tensile strength and Young's modulus were increased from 13 to 27 MPa and 581 to 1011 MPa in WF–PCL (50/50, w/w) composites, respectively, and from 17 to 28 MPa and 814 to 1007 Mpa in WF–PBSC (50/50, w/w) composites, respectively, with the addition of 5% PCL‐g‐MA. Elongation at break increased from 4 to 7% and from 3 to 6% in the WF–PCL and the WF–PBSC composites, respectively. Tensile strength was further increased with increasing WF content in the presence of PCL‐g‐MA. Thermal flow temperature and melt viscosity of the composites were increased, and water absorption and thickness swelling were improved with the addition of PCL‐g‐MA. It was found from the burial test that all composites were more than 40% degraded within 6 weeks, and there was no considerable difference in degradation between composites with PCL‐g‐MA and those without. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1900–1905, 2003     

有机硅改性苯丙乳液的合成及其性能研究

采用半连续乳液聚合反应的方法合成有机硅改性苯丙乳液,系统考察了乙烯基硅油、乳化剂、引发剂等因素对乳液聚合反应及乳胶粒尺寸和涂膜性能的影响。以乙烯基质量分数为0.30%的羟基硅油与苯乙烯、丙烯酸丁酯、甲基丙烯酸乳液共聚,以过硫酸铵(APS)为引发剂,采用m(十二烷基苯磺酸钠)∶m(聚乙二醇辛苯基醚)=1∶2的复合型乳化剂,70℃下共聚5～6h。所得的乳液带蓝色荧光,乳胶粒粒径为70～100nm,粒径分布窄,乳液具有良好的钙离子稳定性、贮存稳定性和耐温性,涂膜耐水性较好。     

Dielectric properties of polymer/ceramic composites based on thermosetting polymers

Summary A series of thermosetting polymer/ceramic composites were prepared. Three kinds of thermosetting polymers, i.e. cyanate resin, bismaleimide resin, and epoxy resin, were used as matrixes, and BaTiO₃ particles were as fillers. The dielectric properties of these composites were investigated. Experimental data of the dielectric constants were fitted to several theoretical equations in order to obtain the best-fitting equations of the dielectric constants of these composites. The result indicates that the dielectric constants of composites all increase with the increase of BaTiO₃ content. Using bismaleimide resin and epoxy resin as matrixes, the dielectric losses both increase obviously as the amount of BaTiO₃ particles is increased, but the dielectric loss of cyanate/BaTiO₃ composite decreases. With the increase of the frequency, the variation ranges of the dielectric constant and dielectric loss of cyanate/BaTiO₃ composite are both the smallest. The predications of the effective dielectric constants by Lichterecker mixing rule are in good agreement with experiment data.     

Biocomposites composed of epoxidized soybean oil cured with terpene‐based acid anhydride and cellulose fibers

Epoxidized soybean oil (ESO) was cured with a terpene‐based acid anhydride (TPAn) at 150°C, and the thermal and mechanical properties of the cured product were compared with ESO cured with hexahydrophthalic anhydride (HPAn), maleinated linseed oil (LOAn), or thermally latent cationic polymerization catalyst (CPI). The ESO‐TPAn showed a higher glass transition temperature (67.2°C) measured by dynamic mechanical analysis than ESO‐HPAn (59.0°C), ESO‐LOAn (?41.0°C), and ESO‐CPI (10.0°C). The storage modulus at 20°C of ESO‐TPAn was higher than those of ESO‐LOAn and ESO‐CPI. Also, ESO‐TPAn showed higher tensile strength and modulus than the other cured ESOs. Regarding the biodegradability measured by biochemical oxygen demand in an activated sludge, ESO‐TPAn possessed some biodegradability, which was lower than that of ESO‐LOAn. Next, biocomposites composed of ESO‐TPAn and regenerated cellulose (lyocell) fabric were prepared by compression molding method. The tensile strength of ESO‐TPAn/lyocell composites increased with increasing fiber content. The tensile strength and modulus of ESO‐TPAn/lyocell composite with fiber content 75 wt % were 65 MPa and 2.3 GPa, which were three times higher than those of ESO‐TPAn. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

改性空心玻璃微珠/环氧树脂复合材料力学性能研究

采用偶联剂对玻璃微珠表面进行改性处理,借助超声波振动,使改性空心玻璃微珠在环氧树脂中均匀、稳定分散,增强了玻璃微珠与环氧树脂之间的相容并探讨了改性空心玻璃微珠对环氧树脂力学性能的影响。结果表明,复合材料中改性空心玻璃微珠添加质量分数为3%时,其拉伸强度达到最大值68.54 MPa,与空白样相比提高了20.3%;冲击强度达到最大值24.42 kJ/m2,比纯环氧树脂提高了166%;KIC(断裂韧性)达到最大值2.338 MPa/m2,是空白试样的2.27倍,增韧效果较为明显。     

Mechanical properties and morphology of impact modified polypropylene–wood flour composites

The mechanical properties and morphology of polypropylene/wood flour (PP/WF) composites with different impact modifiers and maleated polypropylene (MAPP) as a compatibilizer have been studied. Two different ethylene/propylene/diene terpolymers (EPDM) and one maleated styrene–ethylene/butylene–styrene triblock copolymer (SEBS–MA) have been used as impact modifiers in the PP/WF systems. All three elastomers increased the impact strength of the PP/WF composites but the addition of maleated EPDM and SEBS gave the greatest improvements in impact strength. Addition of MAPP did not affect the impact properties of the composites but had a positive effect on the composite unnotched impact strength when used together with elastomers. Tensile tests showed that MAPP had a negative effect on the elongation at break and a positive effect on tensile strength. The impact modifiers were found to decrease the stiffness of the composites. Scanning electron microscopy showed that maleated EPDM and SEBS had a stronger affinity for the wood surfaces than did the unmodified EPDM. The maleated elastomers are, therefore, expected to form a flexible interphase around the wood particles giving the composites better impact strength. MAPP further enhanced adhesion between WF and impact-modified PP systems. EPDM and EPDM–MA rubber domains were homogeneously dispersed in the PP matrix, the diameter of domains being between 0.1–1 μm. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1503–1513, 1998     

The rheology and extrusion processing performance of wood/melamine composites

A modified melamine resin that exhibits both thermoplastic and thermoset behaviors was used as a matrix for wood plastic composites (WPCs). The thermoplastic melamine (TPM) resin exhibits a glass transition at approximately 34°C and continues to be thermally malleable until a crosslinking reaction develops with additional heating and an acid catalyst. Varying blends of TPM and wood flour were evaluated for their rheology and curing behavior using torque rheometry. WPC composites were manufactured with extrusion methods and final product properties determined. The torque rheometry results showed a highly dependent relationship of the curing behavior to the amount of wood flour utilized and temperature. Based upon the torque rheometry results, two extrusion platforms were developed to initiate the curing process; (1) cure within the die land and (2) post‐cure of the extrudate. The post‐cure procedure provided composites with higher mechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39858.     

Antibacterial polymer composites based on low‐density polyethylene and essential oils immobilized on various solid carriers

In this study, we investigated the antibacterial modification of polymers with biologically active substances in essential oils [EOs; linalool, 4‐allylanisole (ALY), and trans‐anethole]. These compounds were thermoplastically incorporated into a low‐density polyethylene matrix via solid inert carriers [wood flour (WF) and talc and molecular sieves] with physically immobilized EOs. The concentrations of the antibacterial modifiers on the carriers and in the resulting composites were determined with three chromatographic techniques (gas chromatography with mass spectrometry, pyrolysis and gas chromatography with mass spectrometry, and high‐performance liquid chromatography). The effects of such modifications to the mechanical properties of the prepared composites were studied by stress–strain analysis. Interactions on the polymer matrix carriers were observed by scanning electron microscopy. The prepared composites were also tested for antibacterial activity against both Gram‐negative and Gram‐positive bacterial strains. The highest efficiency of isothermal immobilization was found for systems consisting of ALY and WF. This finding was in accordance with microbiological studies. The phase of immobilizing the EOs did not influence the mechanical properties of the studied composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42816.     

尼龙6改性研究

采用经化学改性的芳纶纤维增强尼龙6,并通过红外光谱和电镜分析其界面层,结果表明芳纶纤维经异氰酸酯化及封端稳定处理后,其表面所接技的不稳定基团-NCO转化成稳定的-NHCO-,封端结果较为明显;改性后纤维表面附有接枝物,从而使表面粗糙程度大大增加。用挤出和注塑的方法加工了PA6／Kevlar纤维（KF）复合材料,研究了它的拉伸、弯曲和冲击性能破坏形态。力学性能测试表明了改性尼龙6复合材料的拉伸和弯曲强度得到了改善,但冲击性能略为下降。     

Soybean and linseed oil‐based composites reinforced with wood flour and wood fibers

Composites consisting of a conjugated linseed or soybean oil‐based thermoset reinforced with wood flour and wood fibers have been prepared by free radical polymerization. The thermoset resin consists of a copolymer of conjugated linseed oil (CLO) or conjugated soybean oil (CSO), n‐butyl methacrylate (BMA), divinylbenzene (DVB), and maleic anhydride (MA). The composites were cured at 180°C and 600 psi and postcured for 2 h at 200°C under atmospheric pressure. The effect of varying filler load, time of cure, filler particle size, origin of the fillers, and resin composition has been assessed by means of tensile tests, DMA, TGA, Soxhlet extraction followed by ¹H‐NMR spectroscopic analysis of the extracts, and DSC. The best processing conditions have been established for the pine wood flour composites. It has been observed that the addition of MA to the resin composition improves the filler‐resin interaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of nanoclay on properties of HDPE/wood composites

Composites based on high density polyethylene (HDPE), pine flour, and organic clay were made by melt compounding and then injection molding. The influence of clay on crystallization behavior, mechanical properties, water absorption, and thermal stability of HDPE/pine composites was investigated. The HDPE/pine composites containing exfoliated clay were made by a two‐step melt compounding procedure with the aid of a maleated polyethylene (MAPE). The use of 2% clay decreased the crystallization temperature (T_c), crystallization rate, and the crystallinity level of the HDPE/pine composites, but did not change the crystalline thickness. When 2% MAPE was added, the crystallization rate increased, but the crystallinity level was further lowered. The flexural and tensile strength of HDPE/pine composites increased about 20 and 24%, respectively, with addition of 1% clay, but then decreased slightly as the clay content increased to 3%. The tensile modulus and tensile elongation were also increased with the addition of 1% clay. The impact strength was lowered about 7% by 1% clay, but did not decrease further as more clay was added. The MAPE improved the state of dispersion in the composites. Moisture content and thickness swelling of the HDPE/pine composites was reduced by the clay, but the clay did not improve the composite thermal stability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007