scholarly journals The Crystallization, Melting Behavior, and Thermal Stability of Poly(L-lactic acid) Induced byN,N,N′-Tris(benzoyl) Trimesic Acid Hydrazide as an Organic Nucleating Agent

2014 ◽  
Vol 2014 ◽  
pp. 1-8 ◽  
Author(s):  
Yan-Hua Cai ◽  
Yan-Hua Zhang
Keyword(s):  
Thermal Stability ◽  
Lactic Acid ◽  
Cooling Rate ◽  
Acid Hydrazide ◽  
Nucleating Agent ◽  
Melting Behavior ◽  
Crystallization Peak ◽  
Trimesic Acid ◽  
Neat Plla ◽  
Thermal Stability Of

N,N,N′-Tris(benzoyl) trimesic acid hydrazide (TTAD), as a novel nucleating agent of poly(L-lactic acid) (PLLA), was synthesized and characterized by FT-IR and1H NMR. The crystallization, melting behavior, and thermal stability of PLLA induced by TTAD were investigated through DSC, TGA, depolarized-light intensity measurement, and so forth. The crystallization behavior indicated that the presence of TTAD accelerated the overall PLLA crystallization. Compared to neat PLLA, the crystallization onset temperature of PLLA/1%TTAD increased from 101.36°C to 125.26°C, the melt-crystallization peak temperature increased from 94.49°C to 117.56°C, crystallization enthalpy increased from 0.1023 J·g−1to 33.44 J·g−1at a cooling rate of 1°C/min from melt, and the crystallization half-time of PLLA/TTAD decreased from 2997.2 s to 108.9 s at 110°C. Moreover, the nonisothermal crystallization measurements also indicated that the crystallization peak became wider and shifted to a lower temperature with increasing cooling rate. With the presence of TTAD, the melting behavior of PLLA was affected significantly, and a double-melting peak occurred due to melting-recrystallization. Thermal stability research showed that there existed one degradation stage of PLLA and PLLA/TTAD samples, and the thermal degradation temperature of PLLA/TTAD decreased compared to neat PLLA.

A 1H-Benzotriazole Derivative Nucleated Poly(L-lactic acid): Thermal Behavior and Physical Properties

2020 ◽  
Vol 42 (3) ◽  
pp. 383-383
Author(s):  
Li Sha Zhao and Yan Hua Cai Li Sha Zhao and Yan Hua Cai
Keyword(s):  
Thermal Stability ◽  
Lactic Acid ◽  
Melting Process ◽  
Nucleating Agent ◽  
Melting Behavior ◽  
Cold Crystallization ◽  
Melt Crystallization ◽  
Nucleation Effect ◽  
Lower Temperature ◽  
Thermal Stability Of

In this study, a 1H-benzotriazole derivative, N, Nand#39;-bis(1H-benzotriazole) succinic acid acethydrazide (SABHA), was synthesized to nucleate Poly(L-lactic acid) (PLLA). A series of comparative studies on the melt-crystallization, the cold-crystallization, the melting behavior, the thermal stability, as well as the fluidity between the pure PLLA and PLLA/SABHA were performed. The melt-crystallization behavior revealed that the SABHA as a heterogeneous nucleating agent could significantly facilitate the crystallization of PLLA, and a larger amount of SABHA concentration exhibited the better nucleation effect. However, for the cold-crystallization process, the crystallization peak shifted toward the lower temperature with increasing of SABHA concentration. The melting behavior after crystallization at different crystallization temperatures showed that the melting process of PLLA/SABHA samples depended on the crystallization temperature, and the appearance of the double melting peaks was attributed to the melt-recrystallization. The thermal decomposition profile of PLLA was not affected by SABHA, but the addition of SABHA reduced the thermal stability of PLLA. Fortunately, the presence of SABHA improved the fluidity of PLLA, and the effect of SABHA concentration on the fluidity was positive.

scholarly journals Poly (L-lactic acid) Modified by N, N -bis(Stearic acid)-1,4-Dicarboxybenzene Dihydrazide: Studies of Crystallization, Melting Behavior and Thermal Decomposition

2022 ◽  
Vol 58 (4) ◽  
pp. 73-83
Author(s):  
Hao Huang ◽  
Shuang-Qing Liu ◽  
Cheng-Pei Li ◽  
Shi-Tianle Luo ◽  
Li-Sha Zhao ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Thermal Decomposition ◽  
Lactic Acid ◽  
Stearic Acid ◽  
Isothermal Crystallization ◽  
Crystallization Process ◽  
Nucleating Agent ◽  
Melting Behavior ◽  
Melt Crystallization ◽  
Thermal Stability Of

In this study, a new organic nucleating agent N, N -bis(stearic acid)-1,4-dicarboxybenzene dihydrazide (PASH) to improve crystallization behavior of poly(L-lactic acid) (PLLA) along with the effect of PASH on melting behavior, thermal stability of PASH-nucleated PLLA was holistically reported. The melt-crystallization process illustrated that PASH as an effective heterogeneous nucleating agent could boost PLLA�s crystallization rate, but increasing PASH concentration and cooling rate conversely inhibited melt-crystallization process of PLLA in this study. With respect to melt-crystallization process, a larger amount of PASH leaded to a shift of cold-crystallization peak to lower temperature level. Isothermal crystallization revealed, in comparison to pure PLLA, that the half time of overall crystallization of PLLA/PASH was significantly decreased with PLLA containing 3 wt% PASH having the minimum t1/2= 67.3 s at 105şC. The different melting behaviors of PLLA/PASH under different conditions were attributed to the nucleating effect of PASH within PLLA. In particular, the melting behavior at a heating rate of 10�C/min after isothermal crystallization depended primarily on the crystallization temperature. Whereas, the impact of crystallization time on melting behavior was negligible. Nonetheless, the melting behavior was influenced by the heating rate after non-isothermal crystallization. The thermal stability of PLLA was detrimental with the addition of PASH owing to a typical drop in onset thermal decomposition temperature.

scholarly journals Heterogeneous Nucleation Effect of N, N'-Adipic Bis(4-phenylbutyric Acid) Dihydrazide on Crystallization Process of Poly(L-lactic Acid)

2019 ◽  
Vol 25 (4) ◽  
pp. 446-454
Author(s):  
Yan-Hua CAI ◽  
Li-Sha ZHAO
Keyword(s):  
Thermal Stability ◽  
Lactic Acid ◽  
Heterogeneous Nucleation ◽  
Isothermal Crystallization ◽  
Crystallization Process ◽  
Melting Behavior ◽  
Light Transmittance ◽  
Crystallization Peak ◽  
Nucleation Effect ◽  
Phenylbutyric Acid

Enhancing crystallization ability is a fundamental challenges in Poly(L-lactic acid) (PLLA) industry, therefore, the goal of this work was to synthesis a new organic nucleating agent N, N'-adipic bis(4-phenylbutyric acid) dihydrazide (APAD), and investigate its effect on non-isothermal crystallization, isothermal crystallization, melting behavior, thermal stability, and optical property of PLLA. Non-isothermal melt crystallization results showed that APAD acted as more effective nucleating and accelerating agent for the crystallization of PLLA, as a result, upon cooling at 1 °C/min, PLLA/0.5 %APAD had the highest onset crystallization temperature 136.4 °C and the crystallization peak temperature 132.0 °C, as well as the largest non-isothermal crystallization enthalpy 48.1 J/g. However, with increasing of APAD concentration from 0.5 wt.% to 3 wt.%, the crystallization peak shifted to the lower temperature. In contrast, for the non-isothermal cold crystallization process, the effect of APAD concentration on the crystallization behavior of PLLA was negligible. Additionally, the non-isothermal crystallization process was also depended on the cooling rates and the final melting temperature. In isothermal crystallization section, to compare with the primary PLLA, the crystallization half-time of PLLA/APAD could decrease from 254.3 s to the minimum value 29.4 s, with 0.5 wt.% APAD contents at 125 °C. Melting behavior of PLLA/APAD samples under different conditions further confirmed the heterogeneous nucleation effect of APAD for PLLA, and the appearance of the double melting peaks was attributed to the melting-recrystallization. Finally, the addition of APAD decreased the thermal stability to some extent, although APAD could not change the thermal decomposition profile of PLLA. And a drop of PLLA/APAD samples in light transmittance resulted from the double influence of the enhancement of crystallization and the opaqueness of APAD.

Thermal behavior of modified poly(L-lactic acid): effect of aromatic multiamide derivative based on 1H-benzotriazole

e-Polymers ◽  
2016 ◽  
Vol 16 (4) ◽  
pp. 303-311 ◽  
Author(s):  
Yan-Hua Cai ◽  
Li-Sha Zhao
Keyword(s):  
Thermal Stability ◽  
Thermal Decomposition ◽  
Lactic Acid ◽  
Isothermal Crystallization ◽  
Crystallization Behavior ◽  
Nucleating Agent ◽  
Melting Behavior ◽  
Decomposition Temperature ◽  
Scanning Calorimetry ◽  
Onset Crystallization Temperature

AbstractThe goal of this work was to synthesis a novel aromatic multiamide derivative based on 1H-benzotriazole (PB) as an organic nucleating agent for poly(L-lactic acid) (PLLA), and investigate the effect of PB on the non-isothermal crystallization, melting behavior and thermal decomposition of PLLA. Here, PB was firstly synthesized through 1H-benzotriazole aceto-hydrazide and terephthaloyl chloride, then PB-nucleated PLLA was fabricated via melt-blending technology at various PB concentration from 0.5 wt% to 3 wt%. Finally, the thermal performances were evaluated through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The high thermal decomposition temperature of PB indicated that PB possessed possibility as a nucleating agent for PLLA, and the non-isothermal crystallization behavior confirmed the crystallization accelerating effectiveness of PB for PLLA. Upon optimum concentration of 2 wt%, the onset crystallization temperature, the crystallization peak temperature and the non-isothermal crystallization enthalpy increased from 101.4°C, 94.5°C and 0.1 J·g-1 to 121.3°C, 115.8°C and 35.1 J·g-1, respectively. In addition, the non-isothermal crystallization behavior was also affected by the cooling rate and the final melting temperature. The melting behavior further evidenced the advanced nucleating ability of PB, and the competitive relationship between PB and the heating rate, the nuclear rate and crystal growth rate. Thermal stability measurement showed that PB with a concentration of 1 wt%–2 wt% could slightly improve the thermal stability of PLLA.

scholarly journals Synthesis, Thermal Properties and Nucleating Effect ofN, N, N, N'-Tetra(benzoyl) Ethylene Diamine Tetraacetic Acid Dihydrazide as Nucleating Agent of Poly(L-lactic acid)

2012 ◽  
Vol 9 (3) ◽  
pp. 1575-1580 ◽  
Author(s):  
Yan-Hua Cai
Keyword(s):  
Thermal Stability ◽  
Lactic Acid ◽  
Ethylene Diamine Tetraacetic Acid ◽  
Nucleating Agent ◽  
Ethylene Diamine ◽  
Tetraacetic Acid ◽  
Melt Mixing ◽  
Good Thermal Stability ◽  
Benzoyl Hydrazine ◽  
Thermal Stability Of

N, N, N, N'-Tetra(benzoyl) ethylene diamine tetraacetic acid dihydrazide as nucleating agent of Poly(L-lactic acid) (PLLA) was synthesized from benzoyl hydrazine and tetraacetic acid by acylation and ammoniation. and the structure of this novel tetraamide compound had been characterized by FT-IR. The thermal stability ofN, N, N, N'-Tetra(benzoyl) ethylene diamine tetraacetic acid dihydrazide was investigated by TGA thermal analyzer. The result showed good thermal stability ofN, N, N, N'-Tetra(benzoyl) ethylene diamine tetraacetic acid dihydrazide under 170 °C.N, N, N, N'-Tetra(benzoyl) ethylene diamine tetraacetic acid dihydrazide modified PLLA sample was prepared by a melt-mixing technique. With incorporation of 0.5%N, N, N, N'-Tetra(benzoyl) ethylene diamine tetraacetic acid dihydrazide, Non-isothermal crystallization behavior at different cooling rate showed the crystallization peak of PLLA became sharper and shift to higher temperature, and indicated that the presence ofN, N, N, N'-Tetra(benzoyl) ethylene diamine tetraacetic acid dihydrazide accelerated the overall PLLA crystallization.

scholarly journals Non-isothermal Crystallization, Thermal Stability, and Mechanical Performance of Poly(L-lactic acid)/Barium Phenylphosphonate Systems

2017 ◽  
Vol 15 (1) ◽  
pp. 248-254 ◽  
Author(s):  
Yan-Hua Cai ◽  
Li-Sha Zhao
Keyword(s):  
Mechanical Properties ◽  
Thermal Stability ◽  
Lactic Acid ◽  
Isothermal Crystallization ◽  
Mechanical Performance ◽  
Nucleating Agent ◽  
Crystal Form ◽  
Decomposition Temperature ◽  
Scanning Calorimetry ◽  
Crystallization Peak

AbstractThe introduction of a nucleating agent in semi-crystalline polymers is a frequently utilized way to improve the crystallization performance, and the use of a nucleating agent has a very great effect on the performance of the polymer in other areas including thermal stability and mechanical properties. In this investigation, barium phenylphosphonate (BaP) was prepared as a crystallization accelerator for Poly(L-lactic acid) (PLLA), and the non-isothermal crystallization behavior, thermal stability, and mechanical properties of PLLA modified by BaP were investigated using differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and electronic tensile testing. Non-isothermal crystallization analysis showed that the BaP could significantly accelerate the crystallization of PLLA, and the non-isothermal crystallization peak shifted to a higher temperature with increasing concentration of BaP, however, the corresponding crystallization peak became wider. XRD results after non-isothermal crystallization confirmed the non-isothermal crystallization DSC results. Additionally, the addition of BaP did not change the crystal form of PLLA. A comparative study on thermal stability indicated that BaP decreased the onset decomposition temperature of PLLA, resulting from the formation of more tiny and imperfect crystals. Whereas the influence of BaP on the thermal decomposition profile of PLLA was negligible. In terms of mechanical properties, the tensile strength and elastic modulus of PLLA/BaP increased compared to the virgin PLLA, unfortunately, the elongation at break decreased.

Crystallization and properties of nucleated poly(l-lactic acid): Effect of cyclopentanecarboxylic acid derivative as a new nucleating agent

2021 ◽  
pp. 089270572110019
Author(s):  
Lisha Zhao ◽  
Xuhua Liu ◽  
Yanhua Cai ◽  
Wei Chen
Keyword(s):  
Lactic Acid ◽  
Cooling Rate ◽  
Melting Temperature ◽  
Tensile Modulus ◽  
Nucleating Agent ◽  
Orbital Energy ◽  
Melt Crystallization ◽  
Promoting Effect ◽  
Crystallization Peak ◽  
Lower Temperature

In this study, the potential effects of N, N’-dodecanedioic bis(cyclopentanecarboxylic acid) dihydrazide (BCADD) as a new additive in poly(L-lactic acid) (PLLA) was estimated. The comparative study on the melt-crystallization showed that the BCADD as heterogeneous nuclei facilitated crystallization of PLLA in cooling, which indicated by the obvious crystallization exotherms and sharp melt-crystallization peak. Unfortunately, with increasing of BCADD from 0.5 wt% to 3 wt%, it is unexpected that the melt-crystallization peak of the BCADD-nucleated PLLA shifted toward the lower temperature and became flatter, evidencing the importance of BCADD loading for PLLA’s crystallization. Additionally, the cooling rate and the final melting temperature were also proved to be important influence factors during PLLA’s melt-crystallization process, but in contrast with the effect of the final melting temperature on the melt-crystallization, a higher cooling rate could more seriously weaken crystallization ability of the BCADD-nucleated PLLA. The chemical nucleation mechanism was proposed to explain the promoting effect of BCADD on the crystallization of PLLA via the analysis of frontier orbital energy. The melting behaviors after crystallization further confirmed the crystallization accelerating role of BCADD, and the melting behaviors were affected by the heating rate, crystallization temperature and BCADD loading. Although the onset thermal decomposition of the BCADD-nucleated PLLA occurred at lower temperature comparing with the pure PLLA, the intermolecular interaction of PLLA with BCADD attempted to prevent the decrease of thermal stability. Overall, the addition of BCADD resulted in the complicated effect on the tensile modulus and tensile strength of PLLA, but the elongation at break continuously decreased when increasing BCADD loading.

scholarly journals N, N’-sebacic bis(hydrocinnamic acid) dihydrazide: A crystallization accelerator for poly(L-lactic acid)

e-Polymers ◽  
2019 ◽  
Vol 19 (1) ◽  
pp. 141-153 ◽  
Author(s):  
Li-Sha Zhao ◽  
Yan-Hua Cai ◽  
Hui-Li Liu
Keyword(s):  
Thermal Stability ◽  
Lactic Acid ◽  
Isothermal Crystallization ◽  
Nucleating Agent ◽  
Melting Behavior ◽  
Cold Crystallization ◽  
Light Transmittance ◽  
Nucleation Density ◽  
Melt Crystallization ◽  
Hydrocinnamic Acid

AbstractDeveloping more organic nucleating agent with different molecular structure is very instructive to improve the crystallization of poly(L-lactic acid) (PLLA) and explore the crystallization mechanism. In this study, N, N’-sebacic bis(hydrocinnamic acid) dihydrazide (HAD) was synthesized to serve as a nucleating agent for PLLA. The effects of HAD on the non-isothermal crystallization, melting behavior, thermal stability and optical performance of PLLA were investigated by differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), and light transmittance meter. The melt crystallization behavior showed that HAD was able to promote the crystallization of PLLA via heterogenous nucleation in cooling, and it was found that, upon the cooling of 1°C/min, the incorporation of 1 wt% HAD made the crystallization temperature and non-isothermal crystallization enthalpy increase from 94.5°C and 0.1 J/g to 131.6°C and 48.5 J/g comparing with the pure PLLA. Additionally, the melt crystallization significantly depended on the cooling rate and the final melting temperature. For the cold crystallization, when the nucleation density from HAD and PLLA itself was saturated, the influence of the HAD concentration on the cold crystallization process of the PLLA/HAD samples is negligible. The melting behavior after isothermal or non-isothermal crystallization further confirmed the crystallization accelerating effect of HAD for PLLA, and the appearance of the double melting peaks was attributed to the melting-recrystallization. Unfortunately, the addition of HAD decreased the thermal stability and light transmittance of PLLA.

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