纳米纤维素协同聚氨酯增强增韧聚乳酸的研究

以聚乳酸（PLA）为基体、聚氨酯（PU）为增韧相、纳米纤维素（NCF）为增强相,通过溶液法与熔融共混制得PLA/PU/NCF复合材料,研究了PU和NCF的含量对PLA力学性能与热稳定性的影响。采用傅里叶变换红外光谱仪、热失重分析仪、扫描电子显微镜和力学性能测试手段对PLA/PU/NCF复合材料的结构和性能进行了表征和分析。结果表明,柔顺的PU分子限制了PLA的结晶,提升了PLA基体的韧性;刚性的NCF通过氢键作用提升了PLA基体的强度;当NCF含量为3 %、PU含量为17 %时,PLA/PU/NCF复合材料的拉伸强度和断裂伸长率比纯PLA提升了12.10 %和694.91 %;高温热稳定性有了显著改善,复合材料的600 ℃残炭率为19.36 %。     

Enhanced adhesion force based on microphase separation induced by complexation of ferric ions and polyurethane matrix

Waterborne polyurethane elastomer (WPU) has been widely used as a glue, but it still has some drawbacks, including a long cure time and weak adhesive force. In order to overcome these drawbacks, a new composite [PU/ferric ion complexation (Fe/PU)] with high adhesive strength was successfully prepared using ferric ion (Fe³⁺) as a complexing agent. Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, and tensile testing were used to characterize the chemical structure and mechanical properties of the as‐obtained composites. Introduction of the ferric ion induces a certain degree of microphase separation, resulting in better mechanical strength and interfacial adhesion. The mechanical properties of the PU composite with ferric ions are higher than that of pure PU. The adhesive strength of the 25%‐Fe/PU composite is 32.46 ± 3.1 MPa, exhibiting superior adhesive strength. The tensile strength was enhanced 34%, and the elongation was enhanced 23.6% compared to pure PU. Furthermore, the Fe/PU composite, coordinated with ferric ions, exhibits an enhanced storage modulus and reduced loss coefficient compared to PU. We can foresee that Fe/PU composites will play an important role in the building and engineering areas. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46069.     

挤出-注塑制备黄麻增强PLA复合材料及其性能

通过挤出共混、造粒、注射成型的方式制备了黄麻纤维填充聚乳酸(PLA)复合材料,研究了复合材料的力学性能以及黄麻与PLA之间的微观界面形貌。结果表明:黄麻的加入,并没有很好地改善黄麻/PLA复合材料的拉伸强度和弯曲强度;碱处理后的黄麻与PLA之间的界面性能有所改善;碱处理黄麻的加入,改善了黄麻/PLA复合材料的断裂伸长率与冲击韧性。     

Influence of interfacial adhesion on stress-strain properties of highly filled polyethylene

This paper studied the structure and properties of highly filled polyethylene/magnesium hydroxide composite. A third additive component was introduced to alter interfacial adhesion. Scanning electronic microscopy proved that the filler particles were totally surrounded by additive material. Interfacial adhesion played an essential role in determining the fracture mechanism and, consequently, the mechanical properties of the composites. The composites with good interfacial adhesion had high tensile strength and relatively low elongation at break. Conversely, a poor interfacial adhesion led to a composite with low tensile strength and high elongation.     

聚乙二醇对聚乳酸/淀粉纳米晶复合材料性能的影响

以聚乳酸（PLA）和淀粉纳米晶（SNC）为主要原料,聚乙二醇（PEG）为增塑剂,采用溶剂蒸发法制备PLA/SNC和PLA/SNC/PEG复合材料,通过差示扫描量热仪（DSC）、热台偏光显微镜（PLM）、X射线衍射仪（XRD）、扫描电子显微镜（SEM）等研究了PEG对复合材料结晶行为、力学性能及界面相容性的影响。结果表明,PEG能够与SNC协同促进PLA结晶,使PLA/SNC/PEG复合材料的结晶速率明显提高;PEG的添加未改变PLA/SNC复合材料的结晶结构;随着PEG含量的增加,PLA/4%（质量分数,下同）SNC复合材料的拉伸强度先升高后下降,断裂伸长率不断提高;当PEG含量为2%时,PLA/4%SNC/2%PEG复合材料的力学性能最佳,拉伸强度为47.86 MPa,断裂伸长率为10.20%,PLA与SNC间界面相容性得到改善。     

Underwater polyurethane adhesive with enhanced cohesion by postcrosslinking of glycerol monomethacrylate

Polyurethane (PU) has been widely used as a glue in various areas. However, adhesion in the presence of water is greatly impeded and results in most synthetic adhesive failure. In this study, we designed and synthesized a novel PU construction; underwater PU adhesives were created by the incorporation of synthetic glycerol monomethacrylate (GMA). Furthermore, the urethane structure helped the adhesive eliminate the interfacial water barrier through interactions that were stronger than hydrogen bonding, and GMA as a crosslinking agent was used to generate post‐covalent‐crosslinking networks through radical polymerization. This enhanced the cohesion so the diffusion of water molecules could be overcome. Fourier transform infrared spectroscopy, thermogravimetric analysis, underwater adhesion measurements, and tensile tests were used to characterize the chemical and mechanical properties of the as‐obtained adhesive. This led to an adhesive with a better mechanical strength and interfacial adhesion in water, and the results show that the mechanical properties (tensile strength, Young's modulus, and tensile elongation) of the GMA–PU adhesive were higher than those of the pure PU. As for the 4% GMA, the tensile strength was enhanced by 24.3% and the elongation was enhanced by 125.23% over those of the pure PU. This confirmed that the incorporation of GMA into the PU matrix indeed induced increasing cohesion, and the sample's adhesive strength was 21.19 ± 3.9 MPa; this indicated a superior adhesive strength over that of the pure PU. In addition, we can foresee that underwater adhesion will play an important role in prospective surgery and engineering areas. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46579.     

Interfacial structures and mechanical properties of PVC composites reinforced by CaCO3 with different particle sizes and surface treatments

The effects of particle size and surface treatment of CaCO₃ particles on the microstructure and mechanical properties of poly(vinyl chloride) (PVC) composites filled with CaCO₃ particles via a melt blending method were studied by SEM, an AG‐2000 universal material testing machine and an XJU‐2.75 Izod impact strength machine. The tensile and impact strengths of CaCO₃/PVC greatly increased with decreasing CaCO₃ particle size, which was attributed to increased interfacial contact area and enhanced interfacial adhesion between CaCO₃ particles and PVC matrix. Titanate‐treated nano‐CaCO₃/PVC composites had superior tensile and impact strengths to untreated or sodium‐stearate‐treated CaCO₃/PVC composites. The impact strength of titanate‐treated nano‐CaCO₃/PVC composites was 26.3 ± 1.1 kJ m⁻², more than three times that of pure PVC materials. The interfacial adhesion between CaCO₃ particles and PVC matrix was characterized by the interfacial interaction parameter B and the debonding angle θ, both of which were calculated from the tensile strength of CaCO₃/PVC composites. Copyright © 2005 Society of Chemical Industry     

Synthesis and characterization of elastomeric polyurethane/clay nanocomposites

An elastomeric polyurethane/clay (PU/clay) nanocomposite based on poly(propylene glycol) (PPG), glycerol propoxylate, and toluene‐diisocyanate (TDI) was synthesized by intercalative polymerization technology. The results of wide angle X‐ray diffraction (WAXD) studies showed that the gallery distance of the clay in the hybrid was enlarged from 1.9 to 4.5nm or more. Introducing clay in the PU matrix resulted in an increase in both the tensile strength and elongation at beak. When the clay content reached about 8%, the tensile strength and elongation at break were two times and five times respectively to that of the pure PU. In addition, the clay intercalative route to the nanocomposite synthesis also effected the thermal properties of the nanocomposites. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1444–1448, 2001     

Preparation and properties of novel poly(propylene oxide)‐block‐polylactide‐based polyurethane foams

A novel degradable flexible polyurethane (PU) foam was prepared by varying the ratio of poly(propylene oxide) (PPO) and triarm poly(propylene oxide)‐block‐polylactide copolymer (PPO‐b‐PLA), and was compared with conventional PU foams based on toluene diisocyanate (TDI) and PPO. Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) showed that introducing PLA segments were able to result in a transition from a microphase separated state to a microphase mixed state and improve the microphase mixing. The changes in structure and domain size distribution associated with this transition were found to have led to enhanced mechanical properties such as the tensile strength, the elongation at break, and the rebound resilience for the PU foams containing PLA segments. Furthermore, it was observed that the network structure was destroyed by hydrolytic degradation in alkali solution (10 wt%/vol%) at 80°C for 50 h, and that as the PLA content increased, the degradation rate of PU foams enhanced. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Physical properties and crystallization behavior of poly(lactide)/poly(methyl methacrylate)/silica composites

Poly(lactide)/poly(methyl methacrylate)/silica (PLA/PMMA/SiO₂) composites were fabricated using a twin‐screw extruder. Nanosilica particles were incorporated to improve the toughness of the brittle PLA, and a chain extender reagent (Joncryl ADR 4368S) was used to reduce the hydrolysis of the PLA during fabrication. Highly transparent PLA and PMMA were designated to blend to obtain the miscible and transparent blends. To estimate the performance of the PLA/PMMA/SiO₂ composites, a series of measurements was conducted, including tensile and Izod impact tests, light transmission and haze measurements, thermomechanical analysis, and isothermal crystallization behavior determination. A chain extender increases the ultimate tensile strength of the PLA/PMMA/SiO₂ composites by ～43%, and both a chain extender and nanosilica particles increase Young's modulus and Izod impact strength of the composites. Including 0.5 wt % nanosilica particles increase the elongation at break and Izod impact strength by ～287 and 163%, respectively, compared with those of the neat PLA. On account of the mechanical performances, the optimal blending ratio may be between PLA/PMMA/SiO₂ (90/10) and PLA/PMMA/SiO₂ (80/20). The total light transmittance of the PLA/PMMA/SiO₂ composites reaches as high as 91%, indicating a high miscible PLA/PMMA blend. The haze value of the PLA/PMMA/SiO₂ composites is less than 35%. Incorporating nanosilica particles can increase the crystallization sites and crystallinities of the PLA/PMMA/SiO₂ composites with a simultaneous decrease of the spherulite dimension. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42378.     

原位反应法制备聚乳酸/聚氨酯共混物及性能

以聚乳酸（PLA）、聚四氢呋喃醚二醇（PTMG）和液化4,4′-二苯基甲烷二异氰酸酯（L-MDI）为原料,通过原位反应法制备了PLA/聚氨酯（PU）共混物,研究了PLA/PU共混物的反应原理、力学性能、断面形貌、动态流变性能以及结晶性能。结果表明,在原位反应中有微交联结构PU生成,且伴随着PLA的扩链和枝化反应;PLA/PU共混物的韧性得到显著提高,当PU含量为30 %（质量分数,下同）时,共混物的断裂伸长率、断裂韧性和缺口冲击强度分别达到230 %、134.13 MJ/m3和34.19 kJ/m2,较纯PLA分别增加了16.6、8.1和11.1倍,此时拉伸强度仍保持在较高水平（49.7 MPa）;纯PLA和PLA/PU共混物熔体均为假塑性流体,共混物具有更高的储能模量和复数黏度;PLA/PU共混物比纯PLA的结晶速率高,晶体完善程度高。     

Effect of matrix graft modification using acrylic acid on the PP/Mg(OH)2 composites and its possible mechanism

The matrix graft modification using an acrylic acid (AAc) was employed on the polypropylene/Mg(OH)₂ flame-retardant composite. The graft modification of PP matrix was carried out via an in-situ reactive extrusion by a twin-screw extruder. The tensile strength of the composites was analyzed using an equation developed by Pukanszky from which both matrix tensile strength σ₀ and interfacial adhesion strength were found to be increased. The enhancement of σ₀ is due to the intermolecular crosslinking of PP by AAc grafting. This crosslinking causes increases of tensile strength, Young’s modulus, impact resistance, and thermal resistance, but decreases the elongation at break of the composites.     

Toughening polylactide with epoxidized styrene–butadiene impact resin: Mechanical,morphological, and rheological characterization

Styrene–butadiene impact resin (SBC) was chosen as the toughening agent to improve the tensile toughness of polylactide (PLA). Epoxidized SBC (ESBC) with different epoxidation degree were prepared by epoxidation using in situ peroxoformic acid method and a series of PLA/SBC(ESBC) blends were prepared by melt blending. The elongation at break of the PLA/ESBC blends was greatly improved, which was reflected in the slight decrease in the tensile strength and tensile modulus. Moreover, the tensile strength and tensile modulus were not significantly affected by the epoxidation degree of ESBC. For example, the incorporation of ESBC28.8% (30 wt %) to PLA caused an obvious increment of elongation at break from 3.5% of pure PLA to 305.0%, while the tensile modulus and tensile strength decreased to 80 and 78% of pure PLA, respectively. Scanning electron microscopy observations of cryo‐fractured surface morphology and particle size analysis demonstrated that the compatibility of the PLA/ESBC blends was improved significantly compared to PLA/SBC blend. PLA/ESBC(70/30) blends exhibited shear‐thinning behavior over the range of the studied shear rate. With an increase in shear rate, the non‐Newtonian index of the blends decreased gradually. Furthermore, the flow behavior of PLA/ESBC(70/30) blends was more sensitive to the shear rate than pure PLA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46058.     

聚己内酯/聚乳酸/竹纤维复合材料制备及性能

以聚己内酯（PCL）和聚乳酸（PLA）共混物为基材,竹纤维（BF）作为增强材料,硅烷偶联剂为改性剂,通过模压成型制备了PCL/PLA/BF复合材料。研究了PCL和PLA质量比、BF质量分数、硅烷偶联剂用量以及模压温度对复合材料性能影响。结果表明,适宜的PCL/PLA质量比为1∶1,BF质量分数为40 %时BF/PCL/PLA复合材料的冲击强度、拉伸强度和断裂伸长率分别达到最大值11.26 kJ/m2,12.68 MPa和5.2 %;硅烷偶联剂用量为1 %时复合材料的冲击强度、拉伸强度和断裂伸长率分别达到最大值15.11 kJ/m2、13.15 MPa和5.8 %;模压温度为150 ℃时,复合材料的冲击强度、拉伸强度和断裂伸长率分别达到最大值14.51 kJ/m2、13.75 MPa和5.8 %。     

Design of Janus particles based on silica@polystyrene and their compatibilization on poly(p-dioxanone)/poly(lactic acid) composites

The compatibility of poly(p-dioxanone) (PPDO) and poly(lactic acid) (PLA) is very important when they are blended. Herein, three kinds of snowman-like Janus particles (JPs) with different hydrophilic–lipophilic balance (HLB) were prepared by one-pot method by adjusting the surficial functional groups of polystyrene (PS) side and used as the compatibilizer of PPDO/PLA composites. JPs self-assemble at the cell-structure PPDO/PLA interface, which provides channels for the migration of PPDO. The silica (SiO₂) side forms hydrogen bond with PLA, and the PS side forms hydrophobic action with PPDO. Therefore, JPs improve interfacial adhesion and suppress phase separation. Among the three JPs, silica@polystyrene-graft-polymethylmethacrylate (SiO₂@PS-PMMA) possesses the most excellent interfacial behavior because its HLB value is similar to that of PPDO/PLA composites. Tensile strength was increased from the original 14.59 MPa to the maximum 24.18 MPa at 1.5 phr of SiO₂@PS-PMMA JPs, and the elongation at break increased from 39% to 203%.     

Polylactide,nanoclay, and core–shell rubber composites

Three types of composites, namely, polylactide (PLA)/nanoclay, PLA/core–shell rubber, and PLA/nanoclay/core–shell rubber, were melt compounded via a corotating twin‐screw extruder. The effects of two types of organically modified montmorillonite nanoclays (i.e., Cloisite®30B and 20A), two types of core (polybutylacrylate)–shell (polymethylmethacrylate) rubbers (i.e., Paraloid EXL2330 and EXL2314), and the combination of nanoclay and rubber on the mechanical and thermal properties of the composites were investigated. According to X‐ray diffraction and transmission electron microscopy analyses, both types of PLA/5 wt% nanoclay composites had an intercalated morphology. In comparison with pure PLA, both types of PLA/5 wt% nanoclay composites had an increased modulus, similar impact strength, slightly reduced tensile strength, and significantly reduced strain at break. On the other hand, PLA/EXL2330 composites with a rubber loading level of 10 wt% or higher had a much higher impact strength and strain at break, but a lower modulus and strength when compared with pure PLA. The simultaneous addition of 5 wt% nanoclay (Cloisite®30B) and 20 wt% EXL2330 resulted in a PLA composite with a 134% increase in impact strength, a 6% increase in strain at break, a similar modulus, and a 28% reduction in tensile strength in comparison with pure PLA. POLYM. ENG. SCI. 46:1419–1427, 2006. © 2006 Society of Plastics Engineers     

Biobased chain extended polyurethane and its composites with silk fiber

The biobased chain extended polyurethane (PU) was synthesized by reacting castor oil based polyol with different diisocyanates [toluene‐2,4‐diisocyanate (TDI) and hexamethylene diisocyanate (HMDI)] and chain extender such as glutaric acid. Biocomposites have been fabricated by incorporating the silk fiber into both TDI‐ and HMDI‐based PUs. The effect of incorporation of silk fiber into TDI‐ and HMDI‐based neat PU on the physicomechanical properties such as density, surface hardness, tensile strength, and percentage elongation have been investigated. The dynamic mechanical properties and the thermal stability of neat PUs and the silk fiber incorporated PU composites have been evaluated. The TDI‐based neat PU has showed higher mechanical properties compared to HMDI‐based PU. The incorporation of 10% silk fiber into TDI‐ and HMDI‐based PU resulted in an enhancement of tensile strength by 1.8 and 2.2 folds, respectively. The incorporation of silk fiber into biobased chain extended PU increased the glass transition temperature (T_g) of the resultant biocomposites. The morphology of tensile fractured neat PUs and their biocomposites with silk fiber was studied using scanning electron microscope (SEM). POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Properties of grafted wood flour filled poly (lactic acid) composites by reactive extrusion

Composites of poly(lactic acid) with wood flour which was grafted by melt extruding with methyl acrylate in the presence of benzoyl peroxide (BPO) were investigated. The modification of filler (WF-g-PMA) was carried out to enhance the filler-matrix interactions, while the treated component was characterized by infrared spectrum. Properties of binary (PLA/WF, PLA/WF-g-MA) composites were analyzed as a function of the grafting monomer amount by scanning electron microscopy, differential scanning calorimeter, thermogravimetric analysis, water absorption and mechanical tests. Compared with the untreated system (PLA/WF), all treated composites showed higher interfacial compatibility as a result of chemical bonding between WF and grated monomer. All composites showed higher tensile modulus and lower strength and elongation at break as compared to pure PLA; grafting modification with methyl acrylate led to an increased stiffness and decreased water absorption of the composites because of an enhanced filler-matrix interfacial compatibility.     

Mechanical and thermal properties of chitosan‐filled polypropylene composites: The effect of acrylic acid

The mechanical properties, morphology, and thermal properties of chitosan‐filled polypropylene (PP) composites have been studied. The effect of the chemical modification of chitosan by acrylic acid treatment was also investigated. Results showed that the tensile strength and elongation at break decreased but that the Young's modulus of the composites increased with increasing filler loading. Chemical modification of chitosan with acrylic acid improved the tensile strength and Young's modulus of the composites but reduced the elongation at break. Thermogravimetric analysis showed that the addition of chitosan improved the thermal stability of the PP/chitosan composites as compared to that of neat PP. Chemical modification of chitosan had a positive effect on the thermal stability of the composites. This change was attributed to improvement of the interfacial adhesion between the chitosan and PP matrix due to formation of a covalent bond between chitosan and acrylic acid. Meanwhile, differential scanning calorimetric analysis showed that the addition of filler did not significantly change the melting temperature (T_m) of the PP/chitosan composites. The degree of crystallinity of the composites decreased with the addition of chitosan. At a similar chitosan loading, the chemically treated PP/chitosan composites exhibited higher crystallinity than the untreated composites and exhibited slightly increased T_m. A scanning electron microscopy study of the tensile fracture surface of chemically treated PP/chitosan composites indicated that the presence of acrylic acid increased the interfacial interaction between chitosan and the polypropylene matrix. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

Preparation and mechanical characterization of chicken feather/PLA composites

Green composites, a bio‐based polymer matrix is reinforced by natural fibers, are special class of bio‐composites. Interest about green composites is continuously growing because they are environment‐friendly. This study describes the preparation and mechanical characterization of green composites using polylactic acid (PLA) matrix including chicken feather fiber (CFF) as reinforcement. Extrusion and an injection molding process were used to prepare CFF/PLA composites at a controlled temperature range. CFF/PLA composites with fiber mass content of 2%, 5%, and 10% were manufactured. The effects of fiber concentration and fiber length on mechanical properties of CFF/PLA composites have been studied. Mechanical properties of composites were investigated by tensile, compression, bending, hardness, and Izod impact testing. The results of experiments indicated that Young's modulus, compressive strength, flexural modulus, and hardness of the PLA reinforced CFF composites are higher but tensile strength, elongation at break, bending strength and impact strength of them are lower than pure PLA. The results indicate that these types of composites can be used for various applications. POLYM. COMPOS., 38:837–845, 2017. © 2015 Society of Plastics Engineers