苯乙烯—丙烯嵌段共聚物等温结晶动力不宾研究

用ＤＳＣ法研究苯乙烯－丙烯嵌段共聚物（ｉＰＳ－ｂ－ｉＰＰ）的等温结晶动力学，结果表明，在所选择的结晶温度（１２７－１３２℃）范围内，共聚物很好地符合Ａｖｒａｍｉ动力学方程；共聚物结晶温度，结晶速率，结晶成和生长方式都与共聚物结构和组成比在关，随着嵌段共的中ｉＰＳ段含量的增加，结晶速率和Ａｖｒａｍｉ指数（ｎ）明显降低。     

苯乙烯-丙烯等规立构嵌段共聚物(iPS-b-iPP)的非等温结晶动力学的研究

用DSC法研究了苯乙烯-丙烯等规立构嵌段共聚物的非等温结晶动力学。结果表明:冷却速率在5～20℃/min范围内,共聚物的非等温结晶动力学参数能很好地符合Avrami动力学方程,非等温结晶速率常数与冷却速率有关,动力学结晶能力则同时受到冷却速率和共聚物组成比的影响。文中还讨论了在非等温结晶条件下共聚物的结晶成核和生长方式与共聚物组成和结构的关系。联合Avrami方程和Ozawa方程推导的非等温结晶动力学方程较好地描述了iPS-b-iPP嵌段共聚物的非等温结晶动力学过程。     

聚苯乙烯-b-聚右旋乳酸二嵌段共聚物的热性能和结晶行为研究

合成了系列聚右旋乳酸(PDLA)嵌段重量分率(fw=0～0.61)的窄分子量分布聚苯乙烯-b-聚右旋乳酸二嵌段共聚物(PS-b-PDLA).运用温度调制示差扫描热分析仪(TMDSC)和热台偏振光显微镜(POM)等研究手段,对制备所得的结晶性二嵌段共聚物的热性能、结晶速率与结晶形貌等进行了研究.研究结果表明,与聚右旋乳酸均聚物相比,随着PS-b-PDLA中结晶性PDLA嵌段重量分率fw减少,无定形聚苯乙烯嵌段(PS)对PDLA嵌段链段的结晶抑制作用增强,PS-b-PDLA的热结晶性能与结晶形貌发生显著变化;相对于PDLA均聚物,PS-b-PDLA的冷结晶温度(Tcc)和结晶平衡熔点(Tm0)分别下降14℃和38℃,球晶生长速率明显降低.在无定形PS嵌段链段的玻璃化温度(Tg)附近,二嵌段PS-b-PDLA的结晶行为出现拐点,揭示PS嵌段由于相分离所形成纳米微相空间对PS-b-PDLA中PDLA链段的结晶产生影响,并且该影响作用程度与PDLA嵌段的重量分率fw和结晶温度(Tc)相关。     

聚对苯二甲酸乙二醇酯/聚乙二醇醚插层嵌段共聚物的结晶性能

合成了不同用量、不同分子量的聚乙二醇醚(PEG)或聚丁二醇醚(PTMC)与聚对苯二甲酸乙二醇酯(PET)/蒙脱土(MMT)的嵌段共聚物。研究了MMT在共聚物中的分散状态及PEG或PTMG对PET/MMT插层聚合物结晶性能的影响。结果表明,MMT在共聚物中以纳米尺寸分散;加入PEG或PTMG增强了聚酯链段的柔顺性,使共聚物熔体降温过程的结晶温度提高,冷结晶温度降低,即插层嵌段共聚物的结晶速率提高;在合成的共聚物中,分子量为2000,用量为DMT的6%的PEG对插层共聚物结晶速率的促进作用最大     

聚丙烯-聚乙烯嵌段共聚物和相应共混物的热分析

用DSC研究了预期为聚丙烯-聚乙烯两嵌段共聚物(PP-PE)和相应共混物(PP+PE)在热学性能上的差异。经用不同分子量的PP和PE及其共混物进行试验后发现,由于PP和PE在结晶时出现过冷的难易不同。在共混物降温热分析曲线上,当降温速率较快时仅出现一个放热峰,而降温速率较慢时出现PP和PE各自的结晶放热峰,从而解释了文献中的不同结果。并发现共混物的PP和PE熔融、结晶温度均较组分相同的嵌段共聚物的相应温度为高;嵌段共聚物中PP和PE的△H_f值均低于均聚物的△H_f值,而PE的值降低尤甚。我们认为这与嵌段间的共价键限制嵌段活动和结晶过程有关,从而确认DSC热分析可以作为识别是否为嵌段共聚物的一种方法. 本工作的结果表明,所研究的PP-PE试样具有嵌段结构。     

苯乙烯—丙烯等规立构嵌段共聚物（iPS—b—iPP）的非等温结…

用ＤＳＣ法研究了苯乙烯－丙烯等规立构嵌段共聚物的非等温结晶动力学。结果表明，冷却速度在５－２０℃／ｍｉｎ范围内，共聚的非等温结晶动力学参数能很好地符合Ａｖｒａｍｉ动力学学方程，非等温结晶速率常数与冷却速率有关，动力学结晶能力则同时受到冷却速率和共聚物组成比的影响，文中还讨论了在非等温结晶条件下共聚物的结晶成核和生长方式与共聚物组成和结构的关系，联合Ａｖｒａｍｉ方程和Ｏｚａｗａ方程推导的非等温结晶动     

聚醚型多嵌段共聚物软链段结晶特性的研究

本文使用虹外光谱及膨胀计等方法,对聚四亚甲基醚二醇类多嵌段共聚物的软链段结晶性进行了研究。在聚醚-聚酯多嵌段共聚物中(PTMEG>60％),其软链段结晶的熔点和结晶速率均随PTMEG含量减少而下降。而在聚醚-聚脲胺酯多嵌段共聚物中,由于N—H和C—O—C之间氢键的作用,即使在低温下,其软链段也难于结晶。此外,高倍拉伸会提高上述二类多嵌段共聚物中软链段结晶的熔点和结晶速率。     

PDLA-PBS-PDLA三嵌段共聚物的合成及性能

合成了末端均为羟基的聚丁二酸丁二醇酯(PBS)预聚物,再以PBS的端羟基引发D-丙交酯(D-LA)开环聚合,得到聚右旋乳酸(PDLA)与PBS的三嵌段共聚物(PDLA-PBS-PDLA).通过凝胶渗透色谱和核磁共振氢谱进行了结构表征.随着m(D-LA)∶m(PBS)由0.51∶1逐渐增加至2.60∶1,PDLA-PDS-PDLA中PDLA链段的长度逐渐增加.随着PDLA嵌段长度的增加,PDLA嵌段对PBS嵌段的限制作用增强,并导致PBS嵌段结晶温度下降,结晶焓降低.当m(D-LA)∶m(PBS)=2.60∶1时,PBS嵌段不再能形成结晶.而m(D-LA)∶m(PBS)在0.51∶1~3.04∶1范围内,PDLA嵌段均可形成结晶,PDLA嵌段的熔点随其在嵌段共聚物中含量的增加而逐渐升高,但PDLA嵌段的熔融焓呈现先增加后降低的趋势.在部分嵌段共聚物中,PBS和PDLA嵌段可各自形成结晶,且PBS和PDLA的结晶结构不随组分的变化而发生改变,表明该嵌段共聚物中PDLA嵌段和PBS嵌段呈微相分离结构.     

结晶/无定形PMMA-b-PHBV-b-PMMA三嵌段共聚物的合成及热稳定性表征

以生物质聚酯聚(3-羟基丁酸酯-co-3-羟基戊酸酯)(PHBV)为结晶组分、聚甲基丙烯酸甲酯(PMMA)为无定形组分,通过原子转移自由基聚合法(ATRP)制备了ABA型结晶/无定形三嵌段共聚物.采用凝胶色谱法(GPC)、傅里叶红外光谱(FTIR)和核磁共振氢谱(1H-NMR)表征了三嵌段共聚物的分子量及其分子量分布和化学结构;使用热失重分析仪(TG)测试了三嵌段共聚物的热稳定性,并通过Horowitz-Metzger法计算了嵌段共聚物的降解表观活化能.研究表明,三嵌段共聚物的最大转化产率为92.39%;当单体与大分子引发剂的比例为8∶1时,三嵌段共聚物的T0、T5%、T max温度分别提高25 K、15 K和40 K,三嵌段共聚物降解表观活化能E a可由纯PHBV的428.25 kJ·mol-1降低至169.83 kJ·mol-1.     

聚苯乙烯嵌段对左旋聚乳酸/聚苯乙烯-b-右旋聚乳酸立构复合晶结晶行为的调控

聚乳酸较差的耐热性和较慢的结晶速率限制了其应用范围的扩展,左旋聚乳酸(PLLA)和右旋聚乳酸(PDLA)共混后形成的立构复合晶(SC)能够促进PLA均质晶(HC)的成核并提高其热稳定性,在改性PLA方面有着巨大应用前景.本研究通过可逆加成-断裂链转移聚合(RAFT)和开环聚合(ROP)法,制备了一系列不同聚苯乙烯(PS)分子量的PS-b-PDLA嵌段共聚物,并将其与PLLA共混,探究了嵌段共聚物及共混物的组成与结晶性能之间的关系.研究结果表明,分子运动性较差的PS嵌段的引入使共混物的结晶更加困难,而低分子量的PS嵌段由于抑制了均质晶(HC)的形成,反而有利于大量立构复合晶(SC)的形成,进而提高了共混物的结晶速率.     

聚丙烯-g-聚氨酯共聚物的非等温结晶动力学研究

用DSC法研究了聚丙烯 (PP)和聚丙烯接枝聚氨酯的共聚物 (PP g PU)在不同冷却速率下的非等温结晶动力学 .用Avrami方程和莫志深改进法对DSC测定结果进行了处理 ,结果表明 ,PP g PU的动力学参数能很好的符合Avrami方程和莫志深改进方程 .PP接枝了聚氨酯支链后 ,结晶速率增大 ,球晶的生长和成核机制也相应发生改变 ,而其变化规律与接枝物的组成和结构密切相关     

生物可降解聚丁二酸/苯基丁二酸丁二醇酯系列共聚物的合成及其结晶行为

合成了一系列聚丁二酸/苯基丁二酸丁二醇共聚酯(PBSBS),利用DSC、1H-NMR和X射线等测试手段对共聚物组成、热力学性能、结晶性能、等温结晶行为进行了表征和研究.结果表明,含苯基的共聚单元的引入显著改变了聚丁二酸丁二醇酯(PBS)的热力学性能4,利用Hoffman-Week曲线得到的共聚物平衡熔点随共聚组分含量的增加显著降低,玻璃化转变温度则明显升高,结晶熔点符合无规共聚物的Flory方程.此外,利用Avrami方程对均聚物PBS以及共聚物PBSBS-10分别进行了等温结晶行为研究,结果表明共聚使结晶速率降低,PBS和PBSBS-10的Avrami指数分别介于2.8~3.0和2.7~2.9之间,结晶方式为三维生长异相成核,X射线测试结果表明共聚不影响晶体结构.     

PET/LCP反应性共混物的非等温结晶动力学

采用DSC方法研究了聚对苯二甲酸乙二酯 (PET)和热致性液晶共聚酯 6 0PHB PET (LCP)体系在少量扩链剂双 (2 唑啉 ) (BOZ)存在下形成的反应性共混物的非等温结晶动力学 .结果表明反应性共混物的Avrami指数均在 3 0～ 4 5之间 ,BOZ的加入使反应共混物中PET组分的结晶速率降低 ;表明BOZ对酯交换的促进作用 ,使所生成的共聚酯中PET嵌段的数均序列长度变短 ,而使结晶在某种程度上较为困难 ,但对体系的成核和结晶生长机理无明显影响 .结果还表明 ,随冷却速率的增大结晶峰向低温方向移动     

Influence of molecular characteristics on overall isothermal melt-crystallization behavior and equilibrium melting temperature of syndiotactic polypropylene

Overall isothermal melt-crystallization and subsequent melting behavior of metallocene-catalyzed syndiotactic polypropylene resins of various molecular weights were investigated using differential scanning calorimetry (DSC) technique. Two sets of molecular weight range were synthesized with two different metallocene catalyst systems. The kinetics of the overall isothermal melt-crystallization process was analyzed based on various macrokinetic models, i.e. the Avrami, Malkin and Urbanovici-Segal models. The effective activation energy describing the overall isothermal crystallization process over the crystallization temperature range studied was estimated based on an Arrhenius approximation of the obtained Avrami crystallization rate constants. The equilibrium melting temperature for each of these resins was estimated based on the linear and non-linear Hoffman-Weeks extrapolative methods.     

茂金属间规立构聚丙烯结晶动力学研究

用ＤＳＣ和密度法对茂金属间规立构聚丙烯（ｓＰＰ）样品进行了等温和非等温结晶动力学研究．测得平衡熔点Ｔ０ｍ为１５８℃,平衡熔融热焓ΔＨ０ｍ为３７ｋＪ／ｍｏｌ,侧表面自由能σ＝５２ｅｒｇ／ｃｍ２,折叠链表面自由能σｅ＝６９ｅｒｇ／ｃｍ２,链堆砌功ｑ＝３３７５ｋＪ／ｍｏｌ．对非等温结晶过程研究表明,由熔体结晶的ｓＰＰ具有非均相成核,三维球状生长机理．成核与生长活化能ΔＥ＝７３１ＫＪ／ｍｏｌ     

Crystallization kinetics and crystallization behavior of syndiotactic polystyrene/clay nanocomposites

We investigated the effects of montmorillonite (clay) on the crystallization kinetics of syndiotactic polystyrene (sPS) with isothermal differential scanning calorimetry analyses. The clay was dispersed into the sPS matrix via melt blending on a scale of 1–2 nm or up to about 100 nm, depending on the surfactant treatment. For a crystallization temperature of 240 °C, the isothermal crystallization data were fitted well with the Avrami crystallization equation. Crystallization data on the kinetic parameters (i.e., the crystallization rate constant, Avrami exponent, clay content, and clay/surfactant cation‐exchange ratio) were also investigated. Experimental results indicated that the crystallization rate constant of the sPS nanocomposite increased with increasing clay content. The clay played a vital role in facilitating the formation on the thermodynamically more favorable all‐β‐form crystal when the sPS was melt‐crystallized. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2097–2107, 2001     

Isothermal crystallization kinetics of Fe<Subscript>75</Subscript>Cr<Subscript>5</Subscript>P<Subscript>9</Subscript>B<Subscript>4</Subscript>C<Subscript>7</Subscript> metallic glass with cost-effectiveness and desirable merits

In this work, the isothermal crystallization kinetics of cost-effective Fe₇₅Cr₅P₉B₄C₇ metallic glass with a combination of desired merits synthesized by industrial ferro-alloys without high-purity materials was evaluated by Johnson–Mehl–Avrami approach using differential scanning calorimeter. The Avrami exponents at all isothermal annealing temperatures range from about 2.93 to 4.61, indicating a three-dimensional diffusion-controlled growth with an increasing nucleation rate during the isothermal crystallization. Meanwhile, the Avrami exponent firstly increases from 2.93 at the initial time to a maximum value of 4.61 and then decreases to 4.09 with the increment of the isothermal annealing temperature, which can be attributed to the atomic diffusion in the alloy. Additionally, the trend of the local Avrami exponent variations at different isothermal annealing temperatures reflects a variable crystallization mechanism during the crystallization process. Moreover, the local activation energy determined by Arrhenius equation gradually decreases from about 412 to 383 kJ mol^?1 during the present isothermal crystallization, further revealing that the process is dominated by a three-dimensional diffusion-controlled growth with an increasing nucleation rate, which provides useful insights into the formation of the present alloy.     

Crystallization kinetics of poly(glycolic acid-alt-6-aminohexanoic acid)

The crystallization behavior of a new regular poly(ester amide) constituted by glycolic acid and 6-aminohexanoic acid units under both isothermal and non-isothermal conditions is studied. Differential scanning calorimetry (DSC) is used to monitor bulk crystallization, and subsequently Avrami and Ozawa analyses are applied. A three-dimensional spherulitic growth from heterogeneous nuclei is deduced for isothermal crystallization, whereas higher exponents are obtained for non-isothermal crystallization when an Avrami equation is applied. However, modifications of the Ozawa methodology indicate a crystallization mechanism similar to that of the isothermal process.The maximum crystallization rate is deduced to take place at a temperature close to 91 °C by considering experimental data and theoretical equations with adjusted parameters. The equilibrium melting temperature is determined to be 168 °C by the characteristic Hoffman-Weeks plot. One crystallization regime is detected by using the Lauritzen-Hoffman kinetic theory for isothermal crystallization and also with an isoconversional method applied for non-isothermal crystallization. Activation energy of molecular transport and nucleation constant are close to 1500 cal/mol and 1.81 × 10⁵ K², respectively. Crystal morphology, nucleation, and spherulitic growth rates are also investigated with hot-stage optical microscopy (HSOM).     

Isothermal and nonisothermal crystallization kinetics of poly(propylene terephthalate)

The kinetics of crystallization of poly(propylene terephthalate) (PPT) samples of different molecular weights were studied under both isothermal and nonisothermal conditions. The Avrami and Lauritzen–Hoffmann treatments were applied to evaluate kinetic parameters of PPT isothermal crystallization. It was found that crystallization is faster for low‐molecular‐weight samples. The modified Avrami equation, and the combined Avrami–Ozawa method were found to successfully describe the nonisothermal crystallization process. Also, the analysis of Lauritzen–Hoffmmann was tested and it resulted in values close to those obtained with isothermal crystallization data. The nonisothermal kinetic data were corrected for the effect of the temperature lag and shifted alone with the isothermal kinetic data to obtain a single master curve, according to the method of Chan and Isayev, testifying to the consistency between the isothermal and corrected nonisothermal data. A new method for ranking of polymers, referring to the crystallization rates, was also introduced. This involved a new index that combines the maximum crystallization rate observed during cooling with the average crystallization rates over the temperature range of the crystallization peak. Furthermore, the effective energy barrier of the dynamic process was evaluated with the isoconversional methods of Flynn and Friedmann. It was found that the energy barrier is lower for the low‐molecular‐weight PPT. The effect of the catalyst remnants on the crystallization kinetics was also investigated and it was found that this is significant only for low‐molecular‐weight samples. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3775–3796, 2004