木质素填充LDPE、EVA对复合物性能的影响

以木质素为填充剂分别与低密度聚乙烯(LDPE)、乙烯-乙酸乙烯酯共聚物(EVA)共混,经双螺杆造粒机共混挤出造粒,再经吹塑成膜。研究了木质素/LDPE、木质素/EVA共混物薄膜的表面形貌、力学性能、热性能和红外光谱。热分析表明木质素与EVA共混物的热稳定性比木质素与LDPE的共混物热稳定性好;红外光谱分析表明木质素与EVA分子间产生了强烈的相互作用,扫描电镜分析表明木质素与EVA共混的相容性较好,力学性能分析表明低于30%的木质素与LDPE、EVA共混力学性能较好。     

Preparation of a Polyhydric Aminated Lignin and Its Use in the Preparation of Polyurethane Film

In this paper, a polyhydric aminated lignin containing both amino and hydroxyl groups was prepared by hydroxylation and amination. The temperature, the reaction time, and the composition of the reaction mixture were found to have a significant influence on the extent and rate of the hydroxylation and amination reactions. Under the optimum reaction conditions, the content of aliphatic hydroxyls in lignin increased from 1.74 to 4.73%. The amine groups, mainly primary amine groups, were also introduced into the product, which lead to the nitrogen content increased from 0.64% to 4.58%. The performances of polyurethane film containing polyhydric aminated lignin (ALPU) were significantly improved compared with those of polyurethane film using soda lignin (LPU). The polyhydric aminated lignin replaced more polyol components in polyurethane (PU) film production. The maximum tensile strength of ALPU film was about 1.7 and 4.6 times of LPU film and PU film, respectively. The thermal stability of PU was also improved because of the addition of polyhydric aminated lignin, while the thermal stabilities of ALPU film and LPU film had similar performance.     

Semi‐ and full‐interpenetrating polymer networks based on polyurethane produced from canola oil and poly(methyl methacrylate)

Semi‐ and full‐interpenetrating polymer networks (IPNs) were prepared using polyurethane (PUR) produced from a canola oil‐based polyol with primary terminal functional groups and poly(methyl methacrylate) (PMMA). The properties of the material were studied and compared using dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and tensile measurements. The morphology of the IPNs was investigated using atomic force microscopy (AFM). Semi‐IPNs demonstrated different thermal mechanical properties, mechanical properties, phase behavior, and morphology from full IPNs. Both types of IPNs studied are two‐phase systems with incomplete phase separation. However, the extent of phase separation is significantly more advanced in the semi‐IPNs compared with the full IPNs. All the semi‐IPNs exhibited higher values of elongation at break for all proportions of acrylate to polyurethane compared with the corresponding full IPNs. These differences are mainly due to the fact that in the case of semi‐IPNs, one of the constituting polymers remains linear, so that it exhibits a loosely packed network and relatively high mobility, whereas in the case of full IPNs, there is a higher degree of crosslinking, which restricts the mobility of the chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Damping Properties of Polyorganosiloxane/Poly(methyl methacrylate) Interpenetrating Networks

Interpenetrating polymer networks (IPNs) based on polyorganosiloxane/poly(methyl methacrylate) were prepared via sequential polymerization and the damping and mechanical properties of these materials were studied. The effects of crosslinking in both the first‐ and second‐formed networks were investigated. The experimental results show that the extent of damping of the IPNs was decreased and shifted to higher temperature as the content of poly(methyl methacrylate) was increased; the mechanical properties such as tensile strength and hardness (Shore A) were increased with increasing poly(methyl methacrylate) (PMMA) content. The loss factor peak becomes narrower with increasing crosslinker level in the first‐formed network (polysiloxane network), while increasing crosslinker content in the second‐formed network (PMMA network) results in a broadening of the IPN transition peak and moves the IPN transition to higher temperatures as well.     

Ecofriendly modification of acetosolv lignin from oil palm biomass for improvement of PMMA thermo‐oxidative properties

The environmentally friendly esterification of acetosolv lignin (AL), obtained from pressed oil palm mesocarp fibers, is described, for the improvement of thermo‐oxidative properties of poly(methyl methacrylate) (PMMA) films. Acetylation of AL was performed in ecofriendly conditions using acetic anhydride in the absence of catalysts. Acetylated acetosolv lignin (AAL) was successfully obtained in only 12 min with a solvent‐free and catalyst‐free microwave‐assisted procedure. Lignins were characterized by Fourier transform infrared spectroscopy, size exclusion chromatography, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC), confirming the efficacy of the methodology employed. AL and AAL as fillers in different concentrations (1% and 5%) were added to PMMA films. The thermal and mechanical properties of the lignin‐incorporated films were analyzed by TGA, DSC, and dynamic mechanical analysis (DMA). The films incorporated with lignin and acetylated lignin presented initial degradation temperature (T_onset) and onset oxidative temperature (OOT) values higher than pure PMMA films, contributing thus to an enhancement of thermo‐oxidative stability of PMMA. The DMA analyses showed that incorporation of AL or AAL increased the storage modulus (E′) of PMMA films, but did not affect their glass‐transition temperatures (T_g). The results indicate the potential use of oil palm mesocarp lignin to enhance the thermo‐oxidative properties of PMMA without compromising its mechanical response. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45498.     

Recent studies on interpenetrating polymer networks

Recent investigations on interpenetrating polymer networks (IPNs) have included two component IPNs from polyurethanes and poly(methacrylates) and two component IPNs from polyurethanes and epoxies. All the IPNs were prepared by the simultaneous polymerization technique (SIN-IPNs). Two types of IPNs, polyurethane-poly(methyl methacrylate) (PU/PMMA) and polyurethane-poly(methyl methacrylate-methacrylic acid) (PU/PMMA-MAA) were prepared. Improved phase miscibility and decreasing extent of phase separation was observed in both types of IPNs with increasing the NCO/OH ratio, decreasing molecular weight of the polyol in the PU and introduction of charge groups. A comparison was made between full-IPNs, pseudo-IPNs, graft copolymers and related homopolymers from polyurethanes and epoxies. Increased compatibility in full-IPNs and graft copolymers was observed by means of DSC, SEM and was also further substantiated by a shift toward single T_gs as determined by dynamic mechanical spectroscopy. The introduction of opposite charge groups in two-component IPNs from polyurethanes and epoxies led to improved compatibility (no phase separation) and enhanced mechanical properties.     

Studies on interpentrating polymer networks of polyurethane and polybismaleimide. I. Polyurethane and bismaleimide-urethane copolymer

The interpenetrating polymer networks (IPNs) of polyurethane (PU) and the mixture of bismaleimide (BMI) and the 2-hydroxylethyl methacrylate (HEMA)-terminated PU prepolymer (HPU) were prepared by using a simultaneous polymerization technique. The effects of the PU molecular weight and the amounts of the PU on the mechanical properties, thermal stability, and dynamic mechanical properties are discussed. The IPNs exhibited superior ultimate tensile strength as the polyol of PU and HPU in the IPNs is based on poly(tetramethylene oxide) (PTMO) glycol of molecular weight 1000 (PTMO1000). Izod impact property of the IPNs indicated that the PU(PTMO1000)/BMI-HPU(PTMO1000) IPNs had much more significant improvement than that of the PU(PTM02000)/BMI-HPU(PTMO2000) IPNs. Better thermal stability was shown by the IPNs as compared with the components of the networks, i.e. PU or BMI-HPU copolymers. The dynamic mechanical analysis (DMA) indicates that these IPNs show various shifts in the loss moduli(E) at the high and low temperature transition peaks for various molecular weight of the polyol employed in the PU. Better compatibility between BMI and PU was found as the PU(PTMO1000) was employed.To whom all correspondence should be addressed.     

有机刚性粒子增韧聚苯硫醚的研究

采用有机刚性粒子聚甲基丙烯酸甲酯(PMMA)增韧改性聚苯硫醚(PPS)。考察了加工温度及PMMA用量对聚苯硫醚复合材料微观形态结构和力学性能的影响。结果表明,复合材料的力学性能随着加工温度的升高而下降。PMMA与PPS基体以“海岛”状的形式存在;少量PMMA加入时,PMMA同PPS结合较好,冲击强度显著提高;当增加PMMA的用量时,PMMA在PPS基体中的相区尺寸增大,界面变得明显,各项力学性能有小幅下降。     

顺丁橡胶/生物基酚醛树脂复合材料的研究

利用生物基材料木质素代替部分苯酚合成生物基酚醛树脂,并将其应用到顺丁橡胶中;采用同步法制备顺丁橡胶/生物基酚醛树脂复合材料(BR/LPF),并对其形态结构、机械性能及热稳定性等进行了研究。SEM及DSC结果表明,BR/LPF形成了互穿网络结构,两相出现相分离,相畴尺寸较大。机械性能实验结果表明,BR与LPF的比例对复合材料的拉伸强度、撕裂强度、硬度、拉断伸长率等影响较大,其中以BR/LPF(80/20)复合材料综合性能最佳;LPF的构成组分对机械性能也有较大影响。TGA实验表明,BR/LPF复合材料具有较好的热稳定性,加入LPF可提高复合材料的降解温度(T50%)。     

Interpenetrating polymer networks based on carboxylated nitrile rubber and poly(alkyl methacrylate)s

A series of interpenetrating polymer networks (IPNs) based on carboxylated nitrile rubber (XNBR) and poly(alkyl methacrylate)s such as poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA) and poly(butyl methacrylate) (PBuMA) were synthesized. The compositions of the IPNs were also varied by changing the swelling time of the rubber in the methacrylate monomer. The tensile and dynamic mechanical properties of the IPNs were studied. The dynamic mechanical properties in the range of 1–10⁵ Hz were obtained by the time‐temperature superposition of the data under multifrequency mode, which indicated high tanδ with good storage modulus in the entire frequency range. This indicates the suitability of these IPNs as vibration and acoustic dampers.     

A comparison between lignin modified by ionic liquids and glyoxalated lignin as modifiers of urea-formaldehyde resin

The aim of this research was to compare the influence of modified lignin by ionic liquid (IL) on the physical and mechanical properties of wood-based panels bonded with urea-formaldehyde (UF) resin with the effect of glyoxalated lignin (GL) on UF properties. For this purpose, soda bagasse lignin was respectively modified by 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) IL and glyoxal and then the various content of modified lignins (10, 15, and 20%) were added at pH=7 during the UF resin synthesis instead of the second urea . The changes in the structure and thermal properties of lignin, after and before modification with glyoxal and IL, were analyzed by Fourier transform infrared spectrometry (FTIR) and differential scanning calorimetry (DSC). The physicochemical properties of the prepared resins as well as the water absorption, shear strength, and formaldehyde emission of the plywood panels made with these adhesives were measured according to standard methods. According to the FTIR spectra, the content of C=O bond increased in GL while in the IL-treated lignin the content of C–N bond markedly increased. DSC analysis indicated that lignin modified by IL had lower glass transition temperature (T_g) value compared to those modified with glyoxal and unmodified lignin, respectively. The UF resins containing IL-treated lignin exhibit a faster gel time compared to those prepared with GL. Equally, the plywood panels prepared with an IL had lower formaldehyde emission and higher mechanical strength compared to those made from UF resin containing GL. There were no significant differences in dimensional stability of the panels bonded with UFs modified with GL and those with IL-modified lignin.     

Polyurethane–poly(methyl methacrylate) interpenetrating polymer networks. I. Synthesis,characterization, and preliminary blood compatibility studies

Simultaneous polyurethane–poly(methyl methacrylate) (PU–PMMA) interpenetrating polymer networks (IPNs) were synthesized with the PMMA polymerization initiated at room temperature. Transparent IPNs with better miscibility and synergism of mechanical properties were obtained. Dynamic mechanical analysis data indicated that up to 30% PMMA can be incorporated into PU networks without substantial phase separation. The PU–PMMA 90/10 IPNs elicit less than 2% hemolysis, suggesting that these materials could be used as blood contacting materials. © 1996 John Wiley & Sons, Inc.     

HDPE/木质素复合材料的制备及性能

采用甲酸法制备了木质素,将木质素和羟甲基化木质素分别与高密度聚乙烯(HDPE)熔融共混制备了 HDPE／木质素复合材料,研究了其力学性能和相态结构。结果表明:随术质素或羟甲基化木质素加入量的增加,复合材料的断裂伸长率逐渐提高;弯曲模量和弯曲强度随羟甲基化木质素含量的增加分别提高了17.3％和12．2％;与木质素共混时,弯曲强度在木质素质量分数为2．5％处达到最高值(16．1 MPa),随后叉呈下降趋势;HDPE／木质素和 HDPE／羟甲基化木质素的断裂拉伸强度分别提高了8．0％和16．2％;但材料的抗冲击性能有所降低;总体上,木质素的羟甲基化使复合材料的性能优于木质素复合材料。     

Engineering plastics from lignin. VI. Structure–property relationships of PEG-containing polyurethane networks

Hydroxypropyl lignin-based thermosetting polyurethanes were synthesized with excess hexamethylene diisocyanate (HDI) and tolylene diisocyanate (TDI) by solution casting. Four polyethylene glycols (PEG) of molecular weight 400, 600, 1000, and 4000 were mixed with lignin polyol to incorporate different proportions of soft segment into the network prior to crosslinking. Neither thermal nor mechanical and limited small angle x-ray scattering (SAXS) analysis provided distinct evidence for phase separation and microstructure formation. The study examines the effect of the soft segment in relation to chain length and weight contribution on the thermal and mechanical properties of the final networks. A significant sensitivity of glass transition temperature (T_g), of swelling in DMF, and of the mechanical properties to soft segment content was observed. Some of this sensitivity must, however, be attributed to differences in crosslink density since the polyol to diisocyanate weight ratio was kept constant throughout the synthesis series. The magnitude of the change of the different properties was found to be influenced by both glycol content and glycol molecular weight. The T_g of the network decreased from 105°C to as low as 38°C (HDI), and from 158°C to 70°C (TDI), with incorporation of up to 17.8% glycol, and it was greater with lower molecular weight glycols than with higher ones at any weight fraction. Swelling in DMF increased as expected with soft segment content. Mechanical properties were affected most if HDI and lower molecular weight glycols were used. The uniformity in structure, reduction in brittleness, and considerable improvement in mechanical properties with inclusion of minor PEG contents indicates that lignin-based network polyurethanes can be synthesized with controllable performance characteristics.     

Engineering plastics from lignin

Summary Low density polyurethane foams (ca. 2 lbs./cu. ft.) with acceptable strength and excellent flammability resistance properties were formulated with a commercial furan polyol containing 20% hydroxypropyl lignin derivative. Propylene oxide-modified lignin from two sources, kraft and organosolv lignin, were employed. The organosolv lignin derivative exhibited better foaming characteristics than the corresponding kraft lignin, which collapsed when the rising foam was touched for testing. The weight contribution of lignin derivative was limited to 20% by compatibility with the fluorocarbon blowing agent, and solubility in polyol. Preliminary tests encourage further research on structural materials containing hydroxypropyl lignin derivatives.     

制备工艺对木质素基弹性体力学性能的影响

利用聚醚多元醇在硫酸存在下直接与木质素反应制备木质素基弹性体并研究了制备工艺对弹性体力学性能的影响。结果表明：通过提高聚醚多元醇和木质素质量比、聚醚多元醇中聚丙二醇（PPG）比例、浓硫酸用量、提高液化温度和延长固化时间可以有效提升弹性体的拉伸强度,但扯断伸长率会降低;适当加入增塑剂丙三醇可同时提高其拉伸强度和扯断伸长率,但加入过多会使力学性能降低。通过平衡弹性体的拉伸强度和扯断伸长率,较优的工艺条件为液固比（多元醇和木质素质量比）1.8∶1,多元醇中PEG和PPG质量比1∶1.2,催化剂用量2%,增塑剂用量10%,液化温度120℃,固化时间10 h,此时制得的木质素基弹性体的拉伸强度3.64 MPa,扯断伸长率173%。FT-IR分析表明将木质素、多元醇PEG和PPG以及浓硫酸直接混合而未高温液化情况下,并不会让它们之间的活性基团发生化学反应,而仅仅是物理性的混合;在高温液化时,体系开始发生酯化反应,并在高温固化阶段反应程度进一步提高,同时固化阶段还发生烷基化反应和缩合反应。     

Damping analysis of polyurethane/polyacrylate interpenetrating polymer network composites filled with graphite particles

The graphite‐filled polyurethane/poly(methyl methacrylate‐butyl methacrylate) (PU/P(MMA‐BMA)) semi‐interpenetrating polymer networks (IPNs) were synthesized by sequential method. The influences of graphite particle content and size on the 60/40 PU/P(MMA‐BMA) IPNs were studied. The damping properties of IPN composites were evaluated by dynamic mechanical thermal analysis (DMA) and cantilever beam resonance methods. The mechanical performances were investigated using tensile and hardness devices. DMA results revealed that the incorporation of graphite particles improved damping properties of IPNs significantly. The 5% graphite‐filled IPN composite exhibited the widest temperature range and the highest loss factor (tan δ) when the test frequency was 1 Hz. As to the damping properties covering a wide frequency range from 1 to 3,000 Hz, the addition of graphite particles broadened the damping frequency range (Δf, where tan δ is above 0.3) and increased the tan δ value of IPNs. Among them, the composite with 7.5% graphite showed the best damping capacity. And the hardness and the tensile strength of IPN composites were also improved significantly. POLYM. COMPOS., 2013 © 2013 Society of Plastics Engineers     

Engineering plastics from lignin. VII. Structure property relationships of poly(butadiene glycol)-containing polyurethane networks

Hydroxypropyl lignin-based thermosetting polyurethanes containing polybutadiene (PBD) glycol soft segments (M_n of 2800 g M^?1) were synthesized with excess hexamethylene diisocyanate (HDI) and tolylene diisocyanate (TDI) by solution casting. Miscibility of the glycol with the lignin derivative was found to be poor as expected, and phase separation between the two polyol components in polyurethanes was detected by thermal and mechanical analysis, and by electron microscopy. This study examines the effect of concentration of polybutadiene glycol on the thermal and mechanical properties of the polyurethanes. The two-phase network system displayed significantly different properties than either the poly(ethylene glycol)-containing polyurethanes or their soft segment-free counterparts described previously. Macrophase separation was observed at nearly all degrees of mixing and was found to affect thermal and mechanical properties. The glass transition temperature (T_g) of the lignin phase in the TDI-based networks increased with poly(butadiene glycol) content rising from 3.6 to 71.4% of polyurethane, and this was attributed to the employment of a constant diisocyanate weight fraction which gave rise to a variable NCO/OH ratio and crosslink density. Distinct phase separation was evidenced by scanning electron microscopy (SEM) at above 3.6 and 7.1% glycol content for HDI- and TDI-based films, respectively. The polyurethane films behaved like rubber-toughened lignin networks when PBD was the discrete phase, and like lignin-reinforced rubber when the lignin derivative was discrete. This behavior was evidenced by the Young's modulus decreasing from 2000 to 50 MPa and ultimate strain rising from 6 to greater than 150%, with soft segment content increasing from 0 to 71.4%.     

Temperature dependence of the tensile properties of lignin/paper composites

The mechanical properties of dioxane lignin (DL)/paper and kraft lignin (KL)/paper composites were investigated as functions of temperature and strain rate. The tensile properties of the lignin/paper composites were governed by the viscoelastic properties of lignins used as a matrix. In the temperature dependence of the tensile properties, the strength of DL/paper composite decreased at 70° and 130°C at which the elongation had maxima. This behaviour was caused by the viscoelastic properties of DL having two relaxations in the primary dispersion region at 120° and 160°C. In the case of KL/paper composite, a drastic decrease in the strength and maximum of elongation were observed at the glass transition of KL (140°C). The strain rate dependence of the strength of DL/paper composite showed behaviour typical of viscoelastic materials. The strength increased with increase of the strain rate and then decreased after reaching a maximum, which showed a transition from a brittle to a ductile type of fracture.     

Novel transparent lignin/epoxy resin nanocomposite film development with enhanced UV resistance performance

The increased importance of nanostructured lignin exhibits a plethora of multifunctional groups, making it a highly adaptable material basis with significant potential for use in the rapidly expanding composite sector. Initially, lignin nanoparticles (NPs) were incorporated into epoxy networks via an in situ polymerization process where isophorone diamine functioned as a hardener to produce lignin/epoxy resin nanocomposites (lignin@TN). These lignin@TN exhibit promising characteristics, enhancing UV-blocking efficiency (35.69% at 404 nm with 3.72 wt% lignin) in transparent nanocomposite films while simultaneously improving mechanical properties compared with neat epoxy resin. Adding lignin nanoparticles to epoxy nanocomposites boost up tensile strength by an impressive 24% compared with the pristine epoxy but it affected the glass transition temperature (T_g). After all, this study has opened new possibilities for utilizing renewable, sustainable, and economic lignin feedstocks as a potential ingredient for reinforcing with thermoset polymers like epoxy.