GMA接枝反应PLA及其对竹纤维/PLA复合材料的增容效应

为改善竹纤维(bamboo fiber, BF)与聚乳酸(polylactic acid, PLA)的界面相容性,以过氧化二异丙苯(DCP)为引发剂,采用熔融反应制备了甲基丙烯酸缩水甘油酯接枝聚乳酸(GMA-g-PLA, GPLA)高分子增容剂,考察了GPLA添加对BF/PLA复合材料结构与性能的影响,并与常用界面改性剂硅烷偶联剂(KH550)和异氰酸酯偶联剂(MDI)进行了比较。结果显示,GPLA添加对BF/PLA复合材料具有良好的界面增容和性能改善作用,其增容效果明显高于KH550和MDI,并在其占复合材料的质量分数为16%时,复合材料力学性能最佳。与未增容复合材料相比,其拉伸、弯曲及缺口冲击强度分别提高了72.1%、118.1%和81.6%,断裂伸长率提高了200.0%,维卡软化点提高28.4%,而浸水24h后吸水率下降31.6%。     

滑石粉和PLA-g-MAH对聚乳酸结晶性能和熔体强度的改善

采用混沌混炼单螺杆挤出机,制备马来酸酐接枝聚乳酸(PLA-g-MAH),进而制备PLA/滑石粉(5%,10%和20%,质量分数)和PLA/滑石粉(20%)/PLA-g-MAH(5%和10%)复合材料.复合材料样品中滑石粉的分散状态良好,滑石粉含量高达20%时未发生团聚.20%滑石粉和10%PLA-g-MAH使复合材料中PLA的α晶含量明显增加,结晶度提高至31.6%.在175℃下,PLA样品的熔体强度仅为3.6 mN,20%滑石粉明显提高了PLA的熔体强度(11.6 mN),这是由于分散较均匀的片状滑石粉对PLA熔体起增强效应并可提高PLA结晶速率,对PLA结晶有促进效应.与PLA样品对比,PLA/滑石粉(20%)/PLA-g-MAH(5%)复合材料的杨氏模量和冲击强度分别提高了51.7%和16.9%.     

接枝聚乳酸/塑化淀粉共混物的制备与性能研究

为提高聚乳酸(PLA)/淀粉共混物界面作用和降低成本,引入甲基丙烯酸缩水甘油酯(GMA)接枝聚乳酸和塑化淀粉(TPS),通过挤出和注射成型制备接枝聚乳酸/塑化淀粉共混物(PLA-g-GMA/TPS)。红外光谱分析证实,GMA成功接枝到PLA分子链上。对共混物的力学性能、热机械性能、微观形貌、热性能及亲水性等进行了系统研究,结果表明,选择GMA用量为6%(接枝率为1.51%)和TPS用量为10%时的拉伸强度、断裂伸长率及弹性模量最佳,分别为42.6MPa、8.9%及260MPa。FE-SEM观察结果表明,低含量TPS中颗粒被基体包覆或嵌入,界面平整,界面结合力强。DMA和DSC结果显示,不同质量配比的PLA-g-6%GMA/TPS共混物的Tg、储存模量、结晶度、结晶温度及熔融温度仅在小范围内发生变化。吸水率和接触角结果表明,低含量TPS的共混物吸水率和接触角变化幅度均小于高含量TPS体系。     

环氧化淀粉基核壳纳米粒子增韧聚乳酸的研究

通过酰氯接枝反应在淀粉大分子链上引入长烷基链和碳碳双键,使淀粉具有自乳化性能并增加反应位点,采用无皂乳液聚合将丙烯酸乙酯(EA)与酯化改性淀粉接枝共聚制备以淀粉为核的核壳粒子,即核壳粒子为硬核软壳的结构,通过添加甲基丙烯酸缩水甘油醚(GMA)进一步制备环氧化核壳粒子.将环氧化核壳粒子与聚乳酸(PLA)进行熔融共混改性,研究不同环氧化程度的核壳粒子对PLA性能的影响.结果表明,环氧化淀粉核壳粒子粒径约250 nm,与PLA共混改性后,环氧化核壳粒子能够明显提高PLA的韧性,而且其拉伸强度维持在较高水平,共混物缺口冲击强度提高至纯PLA的17倍.进一步研究表明环氧官能团的引入提高了核壳粒子与PLA的相容性同时增加了界面相互作用.     

HIPS的官能化及HIPS/PBT共混体系的研究

以过氧化二异丙苯（DCP）为引发剂，甲基丙烯酸缩水甘油酯（GMA）为活性单体，高抗冲苯乙烯（HIPS）通过熔融接枝制得了动能化的高抗冲聚苯乙烯接枝物（HIPS－g-GMA)。用红外光谱和电子能谱对其结构进行了表征。HIPS－g-GMA的红外谱图，证明GMA已经接枝到HIPS上。电子能谱分析也提供了相似的结论。研究了单体浓度和DCP用量对产物接枝率的影响，并用化学滴定方法测定了接枝物的接枝率。用DSC、SEM、WAXD、DMA等研究了PBT／HIPS和PBT、HIPS－g-GMA的结晶、形态结构、动态力学性能及力学性能随组成的变化。SEM及DMA分析表明增容后体系的相容性得到改善，力学性能有较大提高。     

原位固相接枝改性碳酸钙/聚丙烯复合材料的制备

用马来酸酐（MAH）在碳酸钙（CaCO3）表面引入双键,通过原位固相接枝法将聚丙烯蜡（PPW）化学键合在CaCO3表面,制得3种接枝率的CaCO3-MAH-PPW。 将这3种改性CaCO3填充聚丙烯（PP）制备复合材料,研究了PP/CaCO3界面作用对复合材料强度的影响。 结果表明,CaCO3表面经PPW接枝改性后在PP中的分散性提高,与PP相容性变好;随着改性CaCO3表面PPW接枝率的提高,CaCO3与PP之间界面作用逐渐增强。 当PPW接枝率为4.48 mg PPW/g CaCO3时,CaCO3与PP之间的界面作用最强,复合材料拉伸强度下降最小,杨氏模量提升最大,当m(PP)∶m(CaCO3)=100∶50时,杨氏模量达0.86 GPa,是纯PP的1.63倍;而PPW化学接枝率为2.49 mg PPW/g CaCO3时,CaCO3与PP之间的界面作用适中,复合材料缺口冲击强度提升最大,且当m(PP)∶m(CaCO3)=100∶10时,缺口冲击强度达3.91 kJ/m2,是纯PP的1.35倍。     

几种不同生物质复合材料的力学性能研究

以聚乳酸(PLA)为基体,以菠萝叶粉(PALF)、玉米秸秆芯粉(CF)、芝麻秸秆粉(SF)及甘蔗渣纤维粉(BF)作增强体,通过挤出加注塑工艺,制备可降解生物质复合材料(BBC),考察了秸秆粉用量对BBC力学性能的影响。并以PALF/PLA复合材料为例,研究了材料的断裂特性。结果表明,随着纤维粉用量的增加,所有BBC的拉伸强度均逐渐降低,当纤维粉添加量相同时,PALF/PLA的拉伸强度始终最低;CF/PLA、SF/PLA复合材料的弯曲模量随着秸秆粉用量的增加逐渐增大,当秸秆粉用量为40%时,弯曲模量分别比纯PLA增加74.15%和71.84%,BF/PLA复合材料的弯曲模量先增加后减小,但始终低于CF/PLA和SF/PLA,PALF/PLA的变化趋势较为复杂,呈现先增后减再增加的趋势;随着纤维粉含量的增加,PALF/PLA复合材料的冲击强度逐渐增加,其它三种均呈现先增加后减小趋势。PALF/PLA复合材料的断裂面无纤维拔出,应力-应变曲线无屈服点,断裂伸长率仅4.80%,属于典型的脆性断裂。     

EPM-g-GMA接枝率的测定及其增韧PBT的力学性能和形态结构研究

在同向双螺杆挤出机中通过熔融接枝反应制备了EPM g GMA ,将其与PBT在转矩流变仪中熔融共混可以获得增韧的PBT工程塑料 .实验中EPM g GMA接枝率的测定采用红外工作曲线法 ,选用CCl4 做溶剂以避免溶剂对样品吸收峰的干扰 .随着EPM g GMA接枝率的增加 ,PBT EPM g GMA的缺口冲击强度相应提高 ,共混物中EPM g GMA的粒径尺寸减小 ,当EPM g GMA的接枝率为 4 7mL 1 0 0gEPM时 ,EPM g GMA的粒径尺寸可达 0 5 μm ,PBT EPM g GMA的缺口冲击强度达到 5 1 6kJ m2 ,是纯PBT的 3 1倍     

马来酸酐-苯乙烯熔融接枝聚丙烯的影响因素及其性能研究

用单螺杆挤出机制备了马来酸酐 (MAH) 苯乙烯 (St)对聚丙烯 (PP)的多组分单体自由基熔融接枝体系 .研究证实了当两种单体物质的量比约为 1∶1时 ,接枝物的接枝率最高 ,而熔体流动速率 (MFR)最大 .对反应体系影响因素的研究表明单体用量和引发剂用量对不同单体用量比的系列接枝物的接枝率会产生不同的影响 ;另外 ,单体用量增加 ,接枝物的MFR减小 ,过氧化二异丙苯 (DCP)用量增加 ,接枝物的MFR增加 .对多单体熔融接枝聚丙烯PP g (MAH co St)的力学性能研究发现 ,选用合适的单体用量比、单体用量和DCP用量时 ,所制备的接枝物可具有与纯PP相当或更佳的力学性能     

环氧呋喃树脂反应性增容改性聚乳酸/淀粉复合材料的研究

研究了环氧呋喃树脂反应增容改性聚乳酸/淀粉复合材料,对索氏提取法得到的淀粉进行1H-NMR、FTIR、XPS和静态接触角测试表征.结果表明在熔融共混过程中环氧呋喃树脂(FER)与淀粉及聚乳酸(PLA)发生化学反应,从而起到反应性增容的作用.另外,利用SEM、万能材料试验机和DSC分别对复合材料的界面相容性、机械性能以及热性能进行了表征,结果表明FER能够显著改善PLA和淀粉之间的界面相容性,在保持PLA高强度高模量的基础上,显著提高了PLA/starch复合材料的综合机械性能和结晶性能.     

Influence of chemical surface modification of cellulose nanowhiskers on thermal,mechanical, and barrier properties of poly(lactide) based bionanocomposites

In the aim of producing fully organic bionanocomposite based on poly(lactide) (PLA), cellulose nanowhiskers (CNW) were grafted by n-octadecyl-isocyanate (CNW-ICN) applying an in situ surface grafting method. The compatibilizing effect of the long aliphatic grafted chain was investigated by thermal, mechanical and permeability analysis of solvent cast nanocomposite films. The grafted CNW-ICN could be successfully dispersed in the polymer matrix. The gained compatibility brought about a nucleating effect, decreasing the half time of isothermal crystallization from 25 min for the neat PLA to 8.4 min for the nanocomposite including 2.5 wt% CNW-ICN, e.g., tensile strength was improved by 10 MPa for the same 2.5 wt% CNW-ICN/PLA composite. Mechanical reinforcement was also effective in the rubbery state of PLA and increased the tensile modulus of the rubbery plateau providing thereby thermal resistance to the polymer. Oxygen barrier properties did not change significantly upon the inclusion of CNW-ICN, even when the quantity of CNW-ICN was increased to 15 wt%. More interestingly, the water vapour permeability of the CNW-ICN nanocomposite was always lower than the one of ungrafted CNW composites, which led to the conclusion that the hydrophobic surface graft and improved compatibility could counteract the effect of inclusion of hydrophilic structures in the matrix on water vapour transport. In conclusion, the surface grafting of CNW with isocyanates might be an easy and versatile tool for designing fully organic bionanocomposites with tailored properties.     

Compatibility and phase structure of binary blends of poly(lactic acid) and glycidyl methacrylate grafted poly(ethylene octane)

This work study is the compatibility, phase structure, and component interaction of poly(lactic acid) (PLA) and glycidyl methacrylate grafted poly(ethylene octane) (GMA-g-POE denoted as mPOE) blend by Fourier transform infrared (FTIR) spectra, dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), and wide-angle X-ray diffraction (WAXD), respectively. All the binary blend compositions exhibit two distinct glass transition temperatures corresponding to the mPOE-rich and PLA-rich phases, respectively. Moreover, these two peaks approach each other with increasing mPOE content, indicating partial compatibility between the PLA and mPOE. Chemical reactions between the end carboxyl groups of the PLA and epoxy groups of the mPOE are considered as the driving force of the enhanced compatibility. They lead to an increase in viscosity of the blends and a decrease in the structural symmetry of PLA. This result brings about a decrease in the spherulite growth rate and the degree of crystallinity. Glass transition temperature (T_g) depression of mPOE is attributed to the negative pressure imposed on the dispersed rubber phase, resulting from differential contraction due to the thermal shrinkage mismatch upon cooling from the melt state. The negative pressure in the dispersed particles, in turn, would cause a dilational effect for the matrix ligament between the particles, and therefore increases the ductility and toughness of PLA.     

Physical and degradation properties of binary or ternary blends composed of poly (lactic acid), thermoplastic starch and GMA grafted POE

Binary and ternary blends composed of poly (lactic acid) (PLA), thermoplastic starch (TPS) and glycidyl methacrylate grafted poly (ethylene octane) (GPOE) were prepared using Haake Mixer. The mechanical morphology, thermal properties, water absorption, and degradation properties of the blends were also investigated. The elongation at break and impact strength of the ternary blends were greatly increased by the filling of GPOE. Compared to non-GPOE binary blends, the morphology of ternary blends with GPOE indicated that starch granules melted and there was good compatibility between PLA matrix and TPS. The mechanism and schematic diagram of the reactions in PLA, TPS, and GPOE were proposed and proved by testing and observing the morphology. Moreover, the biodegradation and thermal decomposition were studied through compost testing and thermal gravimetric analysis, respectively. Biodegradation results indicated that the blends have the excellent biodegrade ability.     

PLA/PBS/DCP反应共混体系的结晶行为研究

通过熔融共混法制备了一系列聚乳酸(PLA)/聚丁二酸丁二醇酯(PBS)物理共混试样及PLA/PBS/过氧化二异丙苯(DCP)反应共混试样,采用示差扫描量热分析(DSC)法研究了物理共混试样结晶行为及反应共混试样的特殊结晶行为.结果发现,PLA与PBS的物理共混并未改善PLA的结晶性,而PLA/PBS/DCP反应共混时生成的交联/支化结构可起到异相成核作用,从而明显改善了反应共混体系的结晶性能,且随着DCP含量的增加,共混体系中两相结晶行为出现交替变化.     

Effect of ethylene-co-vinyl acetate-glycidylmethacrylate and cellulose microfibers on the thermal,rheological and biodegradation properties of poly(lactic acid) based systems

The properties and biodegradation behavior of blends of poly(lactic acid) (PLA) and ethylene-vinyl acetate-glycidylmethacrylate copolymer (EVA-GMA), and their composites with cellulose microfibers (CF) were investigated. The blends and composites were obtained by melt mixing and the morphology, phase behavior, thermal and rheological properties of PLA/EVA-GMA blends and PLA/EVA-GMA/CF composite films were investigated as a function of the composition. The disintegrability in composting conditions was examined by means of morphological, thermal and chemical analyses to gain insights into the post-use degradation processes. The results indicated a good compatibility of the two polymers in the blends with copolymer content up to 30 wt.%, while at higher EVA-GMA content a phase separation was observed. In the composites, the presence of EVA-GMA contributes to improve the interfacial adhesion between cellulose fibers and PLA, due to interactions of the epoxy groups of GMA with hydroxyls of CF. The addition of cellulose microfibers in PLA/EVA-GMA system modifies the rheological behavior, since complex viscosity increased in presence of fibers and decreased with an increase in frequency. Disintegration tests showed that the addition of EVA-GMA influence the PLA disintegration process, and after 21 days in composting conditions, blends and composites showed faster degradation rate in comparison with neat PLA due to the different morphologies induced by the presence of EVA-GMA and CF phases able to allow a faster water diffusion and an efficient PLA degradation process.     

Characterization of the effect of REC on the compatibility of PHBH and PLA

This study reports the compatibility of the biobased polymers poly(3-hydroxybutyrate-co-3- -hydroxyhexanoate) (PHBH) and poly(lactic acid) (PLA), as well as the effect of the addition of a reactive epoxy compatibilizer (REC) to the PHBH/PLA blend. The chemical structure, thermal performance, surface morphology and mechanical properties of the blends were measured using fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic thermo-mechanical analysis, thermogravimetric analysis, scanning electron microscopy, and impact and tensile testing.PHBH and PLA were partially compatible, and a PHBH/PLA mass ratio of 80:20 was selected for evaluation with an REC. The REC decreased the difference between the glass-transition temperatures of PHBH and PLA, decreased the particle size of the dispersed phase of the PHBH/PLA blend and produced uniform particle distribution. Moreover, the REC improved the elongation at break and impact strength of the PHBH/PLA blend. These results show that the addition of an REC improves the compatibility of PHBH and PLA.     

Crystallization Behavior and Dynamic Mechanical Properties of Poly(ε-caprolactone)/Octaisobutyl-Polyhedral Oligomeric Silsesquioxanes Composites Prepared via Different Methods

Two octaisobutyl-polyhedral oligomeric silsesquioxanes(oib-POSS)reinforced biodegradable poly(ε-caprolactone)(PCL)composites were prepared via two different methods,i.e.,melt compounding and solution casting,which were named as m PCL/oib-POSS and s PCL/oibPOSS,respectively,in this work.Oib-POSS dispersed finely in both composites;moreover,oib-POSS aggregates were larger in m PCL/oib-POSS than in s PCL/oib-POSS.Despite the different preparation methods,oib-POSS obviously promoted the crystallization of PCL,especially in s PCL/oib-POSS,but did not modify the crystal structure of PCL.The storage moduli of PCL were improved significantly in both composites.PCL/oib-POSS composites with enhanced crystallization behavior and improved dynamic mechanical properties were successfully prepared through both methods;moreover,the solution casting method was more effective than the melt compounding method.     

New approach on the development of plasticized polylactide (PLA): Grafting of poly(ethylene glycol) (PEG) via reactive extrusion

In this work, new ways of plasticizing polylactide (PLA) with low molecular poly(ethylene glycol) (PEG) were developed to improve the ductility of PLA while maintaining the plasticizer content at maximum 20 wt.% PLA. To this end, a reactive blending of anhydride-grafted PLA (MAG-PLA) copolymer with PEG, with chains terminated with hydroxyl groups, was performed. During the melt-processing, a fraction of PEG was grafted into the anhydride-functionalized PLA chains. The role of the grafted fraction was to improve the compatibility between PLA and PEG. Reactive extrusion and melt-blending of neat and modified PLA with PEG did not induce any dramatic drop of PLA molecular weight. The in situ reactive grafting of PEG into the modified PLA in PLA/PEG blends showed a clear effect on the thermal properties of PLA. It was demonstrated by DSC that the mobility gained by PLA chains in the plasticized blends yielded crystallization. The grafting of a fraction of PEG into PLA did not affect this process. However, DSC results obtained after the second heating showed an interesting effect on the T_g when 20 wt.% PEG were melt blended with neat PLA or 10 wt.% MAG-PLA. In the latter case, the T_g displayed by the reactive blend was shifted to even lower temperatures at around 14 °C, while the T_g of neat PLA and PLA blended with 20 wt.% PEG was around 60 and 23 °C, respectively. Regarding viscoelastic and viscoplastic properties, the presence of MAG-PLA does not significantly influence the behavior of plasticized PLA. Indeed, with or without MAG-PLA, elastic modulus and yield stress decrease, while ultimate strain increases with the addition of PEG into PLA.     

Effect of poly(vinyl acetate) (PVAc) on thermal behavior and mechanical properties of poly(3-hydroxybutyrate)/poly(propylene carbonate) (PHB/PPC) blends

To assess the compatibility of blends of synthetic poly(propylene carbonate) (PPC), with a natural bacterial poly(3-hydroxybutyrate) (PHB), a simple casting procedure of blend was used. poly(3-hydroxybutyrate)/poly(propylene carbonate) blends are found to be incompatible according to DSC and DMA analysis. In order to improve the compatibility and mechanical properties of PHB/PPC blends, poly(vinyl acetate) (PVAc) was added as a compatibilizer. The effects of PVAc on the thermal behavior, morphology, and mechanical properties of 70PHB/30PPC blend were investigated. The results show that the melting point and the crystallization temperature of PHB in blends decrease with the increase of PVAc content in blends, the loss factor changes from two separate peaks of 70PHB/30PPC blend to one peak of 70PHB/30PPC/12PVAc blend. It is also found that adding PVAc into 70PHB/30PPC blend can decrease the size of dispersed phase from morphology analysis. The result of tensile properties shows that PVAc can increase the tensile strength and Young’s modulus of 70PHB/30PPC blend, and both the elongation at break and the tensile toughness increase significantly with PVAc added into 70PHB/30PPC.     

环氧基团功能化弹性体增韧聚乳酸的性能

以2种不同结构的弹性体乙烯-辛烯共聚物接枝甲基丙烯酸缩水甘油酯(POE-g-GMA)和乙烯-丙烯酯甲酯-甲基丙烯酯缩水甘油酯三元共聚物(E-MA-GMA)增韧聚乳酸(PLA), 研究了接枝型与嵌段型弹性体的结构对聚乳酸增韧效果的影响. 结果表明, 接枝型聚合物POE-g-GMA与基体PLA之间具有良好的界面相互作用, 当POE-g-GMA的质量分数为15%时, 共混体系的缺口冲击强度为72.4 kJ/m², 而E-MA-GMA的质量分数为15%时, 共混体系的缺口冲击强度为32.4 kJ/m², 结果表明, 接枝型聚合物POE-g-GMA增韧效果明显优于嵌段型E-MA-GMA.