马来酸酐接枝聚乳酸增容聚碳酸亚丙酯/聚乳酸共混体系的结构与性能研究

采用熔融接枝技术将马来酸酐(MAH)接枝到聚乳酸(PLA)上,制备不同MAH含量的PLA-g-MAH接枝共聚物,将聚碳酸亚丙酯(PPC)、PLA、PLA-g-MAH熔融共混,制备PPC/PLA/PLA-g-MAH共混物,分析接枝物中MAH含量对PPC/PLA/PLA-g-MAH共混体系的热学性能以及力学性能的影响。结果表明:PLA-g-MAH可以改善PPC与PLA二者的相容性,使PLA在降温过程中更容易结晶。引入接枝物后,共混物的起始分解温度及完全分解温度分别提高30℃和60℃。共混物的力学性能随着接枝物中MAH含量的增加呈现先增加后减小的趋势,当MAH的加入量为3%,共混体系力学性能最佳,冲击断面塑性形变程度更加显著,呈现褶皱状韧性断裂特征,拉伸强度达到42.8 MPa,断裂伸长率为120%左右,同时冲击强度最大。     

甲基丙烯酸缩水甘油酯接枝聚乳酸共聚物的制备与表征

在哈克转矩流变仪中,用甲基丙烯酸缩水甘油酯(GMA)熔融接枝聚乳酸(PLA),制备高耐热性、良好拉伸强度和较好接枝率的GMA接枝PLA(PLA-g-GMA)共聚物。对PLA-g-GMA进行了傅里叶变换红外光谱分析、接枝率测试、热失重分析和力学性能测试。结果表明,在恒温175℃的密炼机中,以过氧化苯甲酰(BPO)为引发剂,当GMA单体用量为4 g,反应时间8 min,能成功地制备出接枝率为0.950 5%的PLA-g-GMA共聚物。与纯PLA相比PLA-g-GMA的起始分解温度和完全分解温度均提高60℃以上;在一定实验条件下,PLA-g-GMA的拉伸强度有所提高。     

反应性增容制备高性能PLA/PA11共混物

由于聚乳酸(PLA)与尼龙11(PA11)的相容性较差,因此,利用熔融接枝法制备了PLA与甲基丙烯酸缩水甘油酯(GMA)的接枝物PLA-g-GMA,并充当共混物的增容剂。在共混的过程中,利用增容剂原位反应性,增容PLA与PA11的共混体系。对共混物进行力学性能测试,结果表明,在没有添加增容剂的条件下,共混物的力学性能较差;随着接枝物的加入,共混物的力学性能显著提高。在PLA/PA11(80/20)组分中,当增容剂的含量达到20%时,共混物的断裂伸长率和拉伸强度均达到了最大值分别为281. 14%、53. 16 MPa,且材料抗冲击性能也有一定的改善,与纯PLA相比,增加了132%。     

GMA接枝聚乳酸对聚乳酸/淀粉共混物性能的影响

首先制备了聚乳酸与甲基丙烯酸缩水甘油酯(GMA)的接枝共聚物(PLA-g-GMA)和丁二酸酐功能化改性淀粉,并利用红外光谱和核磁共振谱对二者的结构进行了表征。进一步通过熔融共混法制备了聚乳酸(PLA)/改性淀粉/PLA-g-GMA三元共混物,并利用转矩流变仪、扫描电子显微镜、差示扫描量热仪和万能拉力试验机等手段研究了接枝物对共混物的流变性能、形貌结构、热性能以及力学性能的影响。结果表明,PLA-g-GMA的加入促进了淀粉在PLA基体中的分布,淀粉粒径最小在0.5μm以下;同时也抑制了PLA的热降解,提高材料的力学性能,尤其是断裂伸长率,最高达到260%;另外也抑制了PLA的结晶。     

PLA-g-GMA的制备及其对PBAT/PLA共混物结晶性能的影响

以制备的聚乳酸(PLA)-甲基丙烯酸缩水甘油酯(GMA)接枝物(PLA-g-GMA)为聚(对苯二甲酸/己二酸丁二酯)(PBAT)与PLA共混物的相容剂，制得了PBAT/PLA共混物。采用FTIR、¹HNMR分析了GMA质量分数对PLA-g-GMA接枝率的影响。发现当GMA质量分数为20%时，制备的PLA-g-GMA(G-20)有效接枝率为6.44%。通过DSC、SEM考察了G-20质量分数对PBAT/PLA共混物(BAx，其中，x%为G-20的质量分数，下同)结晶以及微观形貌的影响。结果表明，G-20的加入使共混物中PLA在降温过程中形成的结晶结构更完善，BA6冷结晶峰消失；BA4结晶温度由未添加相容剂共混物(BA0)的75.4℃降至68.0℃；G-20的加入使共混物在结晶初期速率常数由0.83(BA0)降至BA10的0.68，抑制了初期PLA晶核产生，但促使第2阶段结晶速率由1.28(BA0)提高到1.38(BA2)，促进了PBAT晶体生长；G-20使脆断截面中PLA与PBAT之间剥离程度减小；BA8纤维强度由BA0的0.25 cN/dtex提高至0.33 cN...     

长链型超支化聚合物对PLA/PPC共混体系的增容改性研究

将“一步法”合成的超支化聚酯进行接枝改性,得到末端带有大量脂肪酸长链的超支化聚合物（长链型超支化聚合物,LCHBP）,并采用红外光谱、核磁共振、羟值滴定等方法对其进行表征。以LCHBP为改性剂,对聚乳酸（PLA）/聚碳酸亚丙酯（PPC）进行不同程度的改性,制备了PLA/PPC/LCHBP熔融共混物,采用差示扫描量热仪、电子万能试验机、扫描电镜等,对其热性能、力学性能、断面形貌等进行表征。结果表明,加入不同含量的LCHBP后,共混体系的ΔTg出现不同程度降低,表明LCHBP的加入改善了PLA与PPC的相容性;与PLA/PPC体系相比,LCHBP的加入可使共混体系在保持拉伸强度基本不变的情况下,大幅提升断裂伸长率和冲击强度,其中当LCHBP的加入量为2.0 %时,冲击强度提高61 %,断裂伸长率提高367 %。     

聚碳酸亚丙酯增韧聚乳酸研究

利用双螺杆挤出机研究了聚碳酸亚丙酯(PPC)对聚乳酸(PLA)的增韧效果.结果表明:PPC树脂对PLA有明显的增韧作用,但增韧的同时会引起PLA拉伸强度和维卡软化温度的降低,随PPC用量增加,冲击强度持续提高,而拉伸强度和维卡软化温度持续降低;PLA/PPC共混体系中加入二苯基甲烷二异氰酸酯(MDI)后,可提高两者的相容性,从而起到增韧的作用,随MDI用量增加,PLA/PPC共混物的冲击强度和拉伸强度呈现先增加后减小的趋势.     

制备方法对聚乳酸/聚丙撑碳酸酯性能的影响

通过熔融共混法和溶液浇注法制备了聚丙撑碳酸酯(PPC)与聚乳酸(PLA)的共混物。采用转矩流变仪、差示扫描量热仪、扫描电子显微镜、紫外可见近红外分光光度计等对共混物进行了表征,研究了共混方法对材料性能的影响。实验结果表明:PLA/PPC为部分相容性共混物,常温下放置体系会发生物理老化;PPC的加入使共混物的水蒸气阻隔性提高,随着温度的升高,共混物的水蒸气阻隔性明显降低,特别是PPC含量多的组分;PPC的加入还使共混物拉伸强度和杨氏模量降低,断裂伸长率提高。熔融共混会造成PPC和PLA的降解,降低体系黏度;相对于溶液浇注制备的共混物,其断裂伸长率较低,水蒸气阻隔性较好。     

聚丁二酸丁二醇酯与聚乳酸共混型全生物降解材料的结构和性能研究

通过机械共混法,使聚丁二酸丁二醇酯(PBS)、聚乳酸(PLA)熔融共混,制备了一种完全生物降解塑料。用红外光谱(FTIR)法、DSC(DifferentialScanningCalorimetry)法、扫描电镜法(SEM)及力学测试等手段研究了不同组分配比情况下共混物的结构、热性能以及力学性能变化。并研究了聚丙撑碳酸亚丙酯(PPC)的加入对共混体系性能的影响。结果表明:随着PBS含量的增加,PBS/PLA共混体系的拉伸强度降低不多,而断裂伸长率显著提高。而PPC的加入能够提高共混体系的相容性并显著提高体系的韧性。     

增容剂种类对PLA/PCL共混体系性能影响的研究

采用熔融共混法制备了PLA/PCL(聚乳酸/聚己内酯)共混母粒,并选用甲基丙烯酸缩水甘油酯(GMA)与L-赖氨酸三异氰酸酯(LTI)作为PLA/PCL体系的增容剂。研究选取合适的增容剂用量并探究了两种增容剂对PLA/PCL体系熔体流动速率、力学性能以及热性能的影响。PLA/PCL共混母粒的力学性能表明,PCL的加入会增加体系的断裂伸长率,提升体系的冲击强度。而以GMA作为增容剂的共混体系造成的强度下降更少。DSC数据表明,GMA和LTI对PLA/PCL共混体系均有增容效果。而GMA对Tg、Tc的减小程度更明显,说明GMA的增容效果更好。PLA/PCL共混母粒FTIR谱图表明共混体系制备成功。SEM分析表明,PLA/PCL/GMA纤维相界面更为平整,进一步证明了GMA的增容效果更明显。     

High-toughening modification of polylactic acid by long-chain hyperbranched polymers

The hyperbranched polyester synthesized by “one-step method” was grafted with stearic acid to obtain long-chain hyperbranched polymers (LCHBPs) with a large number of long stearic acid chains at the end. By means of FTIR and ¹³C-NMR characterization, it was proved that stearic acids were grafted onto hyperbranched polyesters (HBPE) to yield LCHBPs successfully. It was determined by GPC and hydroxyl value titration that the number average molecular weight of HBPE was 4.86 × 10³ and the grafting rate of stearic acid was 47%. Polylactic acid (PLA)/LCHBPs blends were prepared by melt processing method. The results showed that comparing with neat PLA, the tensile strength of PLA/LCHBPs blends decreased slightly with the increase of LCHBPs, but still maintained a high level, while the elongation at break and the impact strength of the PLA with 3.0 phr LCHBPs were greatly improved by 1360.0% and 119.8%, respectively. In addition, the impacted fracture characteristics of PLA changed significantly from brittle fracture to ductile fracture after LCHBPs incorporation, with the formation of a large number of filamentous structures. Thus, LCHBPs was an excellent toughening modifier for PLA and the resulting blends with improved performance possess wider applications.     

PE-LLD-g-(GMA-co-St)对PLA/PE-LLD共混体系的反应性增容研究

在聚乳酸(PLA)中加入线形低密度聚乙烯(PE-LLD)进行增韧,并通过相容剂 PE-LLD-g-(GMA-co-St)增容PLA 和 PE-LLD。采用红外光谱、动态流变测试和扫描电子显微镜对共混物进行了表征,测试了共混物的冲击强度。结果表明,加入 PE-LLD-g-(GMA-co-St)能明显提高 PLA/PE-LLD 的冲击韧性,最高比 PLA/PE-LLD 简单共混物提高了144%,熔体的损耗模量G″明显增大,PE-LLD 分散相在 PLA 基体中有更加细微的分散,界面更加模糊,PE-LLD-g-(GMA-co-St)在共混体系中起到了反应性增容作用。     

PLA/PBS共混物增黏改性的研究

采用熔融反应共混法,通过引入过氧化二苯甲酰(BPO),对聚乳酸/聚丁二酸丁二醇酯(PLA/PBS)进行增黏改性。研究了该PLA/PBS反应共混物的流变性能、凝胶分数、热性能、力学性能和断面微观形貌。结果表明:随着BPO用量的增加,PLA/PBS反应共混物的转矩和凝胶分数均增大;PLA/PBS反应共混物的结晶性和熔点(Tm)随着BPO用量的增加而降低,且出现熔融双峰,当BPO用量增至1 phr时,熔融双峰消失,PLA和PBS间的相容性显著改善;随着BPO用量的增加,PLA/PBS反应共混物的断裂伸长率、拉伸强度、冲击强度均有所提高,而玻璃化转变温度(Tg)先降后升,体系的内耗则逐渐降低。     

Reactive compatibilization of high‐impact poly(lactic acid)/ethylene copolymer blends catalyzed by N,N‐dimethylstearylamine

The inherent brittleness of poly(lactic acid) (PLA) limits its wide application in many fields. Here, high‐impact PLA/ethylene–methyl acrylate–glycidyl methacrylate random terpolymer (EMA–GMA) blends were prepared with the addition of a small amount of N,N‐dimethylstearylamine (DMSA) catalyst. It was found that the notched impact resistance of various PLA/EMA–GMA blends could be considerably improved by adding DMSA. In particular, the notched Izod impact strength of the blend with 20 wt% EMA–GMA increased from 35.6 to 83.5 kJ m^?2 by adding 0.2 wt% DMSA. Reactive compatibilization between PLA and EMA–GMA with DMSA was studied using Fourier transform infrared spectroscopy. The results indicated that DMSA promoted the reaction between the epoxide group of EMA–GMA and end groups (–OH, –COOH) of PLA. This considerably improved the interfacial adhesion, leading to better wetting of the dispersed phase by the PLA matrix and finer dispersed EMA–GMA particles. Therefore, the significant increase in notched impact strength was attributed to the effective reactive compatibilization promoted by DMSA. © 2013 Society of Chemical Industry     

Rheological properties and crystallization behavior of modified polylactic acid using lauroyl peroxide and glycidyl methacrylate

The molecular structure of polylactic acid (PLA) was modified by lauroyl peroxide (LP) as an alkyl free radical and glycidyl methacrylate (GMA) as a reactive co-monomer. We investigated the effect of different preparation methods, that is, the melt and solution, on the structure and physical and mechanical properties of glycidyl methacrylate grafted polylactic acid (PLA-g-GMA). The Fourier transformed infrared spectroscopy (FTIR) was implemented to characterize the final products in order to confirm that GMA was successfully grafted onto PLA. The gel permeation chromatography showed that the molecular weight and polydispersity of the modified PLA were increased by grafting. However, by varying other parameters such as the reaction time and the LP and GMA concentrations, we observed that the resulting products from the melt method are richer in the rheological properties compared with those properties from the solution method. This is due to the different molecular weights resulted from the either preparation methods. From the DSC characteristics of PLA-g-GMA samples, the crystallization degree of the samples prepared from the melt method is greater than that of the solution method. Meanwhile, the cold crystallization for the PLA-g-GMA samples derived from the solution method occurs at higher temperatures compared with the cold crystallization of the samples resulted from the melt method.     

胺端基型超支化乙二胺三嗪聚合物对PLA/PPC的增韧改性研究

以乙二胺和三聚氯氰作为原料,以丙酮为溶剂,通过“一步法”合成了胺端基型的超支化乙二胺三嗪聚合物(HBETP)。以HBETP作为改性剂,采用双螺杆挤出机熔融共混和注射成型法制备了聚乳酸(PLA)/聚碳酸亚丙酯(PPC)共混物,并用差示扫描量热仪(DSC)、 热失重分析仪(TGA)、电子万能试验机、扫描电字显微镜(SEM)等测试手段对共混物的热性能、力学性能以及断面形貌等进行表征与测试。结果表明,与PLA/PPC共混物相比,当HBETP含量为0.6份时,PLA/PPC/HBETP共混体系在保持拉伸强度基本不变的基础上,断裂伸长率和冲击强度分别提高了266.0 %和122.9 %;HBETP是一种增韧PLA/PPC共混物的有效助剂。     

High impact poly(lactic acid)/poly(ethylene octene) blends prepared by reactive blending

Poly(ethylene octene) grafted with glycidyl methacrylate (POE‐g‐GMA) was prepared and used to toughen poly (lactic acid) (PLA) via reactive blending. It was found that the notched Izod impact strength of PLA/POE‐g‐GMA blends improved dramatically when the content of elastomer was higher than 10 wt%. Reactive compatibilization between PLA and POE‐g‐GMA were studied by Fourier transform infrared spectroscopy (FTIR) and “Molau test,” the results showed the end carboxyl groups of PLA reacted with the epoxide groups of POE‐g‐GMA during blending. This considerably improved the compatibilization, leading to better wetting of the dispersed phase by the PLA matrix and finer dispersed POE‐g‐GMA particles with narrow distribution. Moreover, the critical interparticle distance (L_c) of the dispersed domains for PLA/POE‐g‐GMA blends system at room temperature was also identified. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Thermal properties and characterization of surface-treated RSF-reinforced polylactide composites

The thermal, mechanical, and biodegradation properties of composite materials made from polylactide (PLA) and rice straw fibre (RSF) were evaluated. To improve the properties of PLA/RSF composites, glycidyl methacrylate (GMA)-grafted polylactide (PLA-g-GMA) and treated (crosslinked) rice straw fibre (TRSF) were used to prepare the composites. The result showed that PLA-g-GMA/TRSF had noticeably superior mechanical properties compared with PLA/RSF because of greater compatibility between the polymer and TRSF. The dispersion of TRSF in the PLA-g-GMA matrix was more homogeneous, because branched and crosslinked macromolecules formed via condensation of the glycidyl methacrylate groups of PLA-g-GMA and the hydroxyl groups in TRSF. In addition, the PLA-g-GMA/TRSF composites were more easily processed because of their lower melt viscosities. The water resistance of PLA-g-GMA/TRSF was higher than that of PLA/RSF, although the weight loss of composites buried in soil compost indicated that both were biodegradable, especially at high levels of RSF substitution. The PLA/RSF and PLA-g-GMA/TRSF composites were more biodegradable than was pure PLA.     

Blends of polylactic acid with thermoplastic copolyester elastomer: Effect of functionalized terpolymer type on reactive toughening

This study is an attempt to explore the effectiveness of thermoplastic copolyester elastomer (TPCE) as a toughening agent for improving the impact strength of PLA. Biobased Hytrel^® thermoplastic copolyester of polyether glycol and polybutylene terephthalate was selected as the TPCE of choice for this study. Blends of PLA/Hytrel at varying weight ratios were prepared using extrusion followed by injection molding technique. Optimal synergies of two polymers were found in the PLA/Hytrel (70/30) blend, showing impact strength of 234 J/m, a sixfold increase compared to neat PLA. In order to obtain further enhancement in toughness, different functionalized terpolymers were added to accomplish reactive compatibilization. A series of functionalized terpolymers, ethylene methyle acrylate‐glycidyl methacrylate (EMA‐GMA), ethylene butyl acrylate‐glycidyl methacrylate (EBA‐GMA), ethylene methyl acrylate‐maleic anhydride (EMA‐MaH), and ethylene butyl acrylate‐maleic anhydride (EBA‐MaH) were selected. Comparing PLA ternary blends with different terpolymers, GMA containing terpolymers showed better impact toughness compared to MaH terpolymer blends. Unique fracture surface morphology showing debonding cavitation and massive shear yielding in the ternary blends containing EMA‐GMA resulted in super toughened blends. Highest zero shear viscosity and storage modulus was also observed for ternary blends with EMA‐GMA. Under the processing conditions and blend ratio investigated, EMA‐GMA showed better efficiency in improving the toughness of the PLA blends. POLYM. ENG. SCI., 58:280–290, 2018. © 2017 Society of Plastics Engineers     

MCC对PLA/PPC复合材料力学性能与热稳定性的影响

以微晶纤维素(MCC)作为改性剂,马来酸酐接枝聚乳酸(PLA g MAH)为界面相容剂,聚乳酸(PLA)、聚碳酸亚丙酯(PPC)为基体,通过熔融共混法制得PLA/PPC/MCC三元复合材料。采用控温拉伸、动态热分析、扫描电子显微镜以及热失重分析等方法研究了MCC对PLA/PPC的力学性能和热稳定性。结果表明,PLA/PPC/MCC三元复合材料的拉伸强度提高了12.7 %,玻璃化转变温度（Tg）提高了9.8 ℃;PLA g MAH的加入可以改善PLA/PPC/MCC三元复合材料的界面性质,从而提高力学性能和热稳定性;当PLA g MAH的添加量为5 %（质量分数,下同）时,三元复合材料在常温下的拉伸强度、弯曲强度和冲击强度分别提高了53.7 %、43.1 %和18.5 %;在60 ℃下三元复合材料的断裂强度提高了80 %;热降解温度以及最大失重温度与PLA/PPC相比分别提高了25.31 ℃和61.83 ℃。