含氟PET的非等温结晶动力学

通过分子设计,在聚对苯二甲酸乙二酯(PET)大分子主链上同时引入耐热性的芳杂酰亚胺环和含氟基团。以六氟二酐和氨基十一酸为原料,通过热环化反应合成酰亚胺二酸,再用制备的酰亚胺二酸单体按照不同配比和对苯二甲酸二甲酯、乙二醇按一定比例调节投料比进行酯化缩聚反应,合成一系列含氟PET。利用差示扫描量热(DSC)法研究了聚合物非等温结晶行为,发现纯PET的结晶能力最强,随着含氟量的增加,结晶能力减弱。采用Jeziorny法分析了纯PET和含氟PET的非等温结晶动力学,发现结晶速率常数随着含氟链段的加入而减小,表明含氟链段的加入降低了PET的结晶能力。     

聚酰胺612的非等温结晶动力学研究

采用差示扫描量热仪研究了聚酞胺612在不同降温速率下的非等温结晶行为,并用Jeziorny法、Ozawa法和莫志深法对DSC测试数据进行了处理。结果表明,随降温速率的增加,其结晶峰从高温向低温方向移动,峰形变宽,结晶时间缩短,结晶加快。聚酚胺612的非等温结晶动力学能较好地符合莫志深法和Jeziomy法。采用Kissinger方程计算出聚酞胺612的非等温结晶活化能为293.0U/mol。     

SEBS-g-MAH对聚乙烯等温及非等温结晶动力学的影响

利用差示扫描量热法结合Avrami方程研究了苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物接枝马来酸酐(SEBS-g-MAH)对线型低密度聚乙烯(LLDPE)等温及非等温结晶动力学的影响。结果表明,热塑性弹性体SEBS及其接枝物的加入阻碍了LLDPE分子链的规则排列,影响了链段在结晶扩散迁移规整排列的速度,使得结晶速率变慢,对LLDPE晶体生长起了抑制作用;LLDPE/SEBS-g-MAH共混体系的半结晶时间t1/2和结晶活化能E明显增大,Avrami指数n对结晶温度有依赖性,kn值随温度的升高而减小。通过Jeziorny法对非等温结晶过程进行处理,试样的Avrami指数n值均在1.1~1.5,表明LLDPE的结晶成核机理和生长方式没有改变。     

聚乳酸的非等温结晶动力学研究

采用差示扫描量热仪研究了聚乳酸(PLA)样品在5种不同升温速率下的非等温结晶行为,采用Jeziorny法、Ozawa法、Mo法等分析了PLA的非等温结晶动力学。结果表明：随着升温速率的增加,PLA的熔融结晶峰向高温端移动,结晶峰变宽,结晶时间变短,同时结晶也变差。利用Jeziorny法和Mo法求得Avrami指数n和Ozawa指数m,在不同升温速率下,结晶初期的Avrami指数n和Ozawa指数m接近,均处于2～3,说明PLA的均相成核以一维方式为主、二维方式为辅;在升温速率为5～20 K/min时,结晶中期的PLA Avrami指数n>5、Ozawa指数m>3.5,均高于结晶初期的Avrami指数n与Ozawa指数m,表明PLA除了呈现均相成核的三维生长方式之外,还出现了结晶堆积的现象;当升温速率为30～40 K/min时,结晶中期的Avrami指数n和Ozawa指数m均与初期表现一致,Avrami指数n在3.5左右,Ozawa指数m为2.5～3.5,表明该条件下PLA以均相一维和二维2种方式共存结晶。应用Mo法得到的升温速率F(T)随着相对结晶度的增加而增加,表明随着结...     

半芳香族聚酰胺6T/6I/6的合成及其非等温结晶动力学研究

采用成盐、高温溶液缩聚两步法成功制备了半芳香族聚酰胺（PA）6T/6I/6。通过傅里叶变换红外光谱（FTIR）、氢核磁共振（¹H⁃NMR）分析了其分子链结构,并对其力学性能进行了测试表征,利用差示扫描量热法（DSC）对PA6T/6I/6的非等温结晶动力学进行了研究,使用Jeziorny法、Oazawa法和莫志深法修正的Avrami方程分别分析了PA6T/6I/6的非等温结晶行为。结果表明,通过Jeziorny法处理发现结晶过程分为主期结晶和次期结晶2个阶段,主期结晶阶段Avrami指数在1.08~1.09之间,晶体为异相成核,呈一维针状生长,次期结晶阶段Avrami指数在2.13~2.21之间,晶体为二维片状生长方式;Ozawa法处理曲线相关性低,表明不适用于描述PA6T/6I/6的非等温结晶过程;莫志深法修正的Avrami方程能较好地描述结晶过程,a值在0.89~0.90之间,F（T）值在7.24~15.85之间;采用Kissinger方程计算求得PA6T/6I/6的非等温结晶活化能为-294.17 kJ/mol。     

PBT非等温结晶动力学

用差示扫描量热法研究聚对苯二甲酸丁二酯（PBT）的非等温结晶动力学，并分别用Ozawa,Jeziorny和考虑综合因素法来处理PBT的非等温结晶数据。结果表明，PBT非等温结晶过程与Ozawa动力学方程相吻合，但不符合用Jeziorny方法处理的Avrami动力学方程；综合考虑温度和结晶程度对聚合物结晶速度的影响。PBT非等温结晶过程符合结晶动力学方程。     

半芳香族耐高温PA10T/1010的非等温结晶动力学研究

利用对苯二甲酸、癸二胺、癸二酸合成了聚对苯二甲酰癸二胺(PA10T)和聚酰胺(PA)1010的共聚物PA10T/1010,通过差示扫描量热法研究了PA10T/1010的非等温结晶动力学,结果表明随着降温速率的增加,结晶温度和熔点不断降低,同时结晶温度的范围变宽,结晶所需时间减少。用Jeziorny法描述了PA10T/1010的非等温结晶过程,发现其结晶过程分为两段,晶体生长方式在前期为二维盘状生长,后期为多维生长。通过Mo法描述了PA10T/1010的非等温结晶动力学,发现降温速率越大,在单位时间内PA10T/1010所能达到的相对结晶度越高。最后通过Kissinger方法计算得到PA10T/1010非等温结晶活化能为–171.47 k J/mol。     

PEN非等温冷结晶动力学的研究

采用差示扫描量热(DSC)法对聚萘二甲酸乙二醇酯(PEN)的非等温冷结晶动力学进行研究;通过改变升温速率,讨论了PEN冷结晶起始温度与峰顶温度之间存在差值的原因;对比了两种不同的冷结晶起始点的确定方法对冷结晶动力学常数的影响。结果表明:以DSC曲线偏离基线作为PEN冷结晶的起始点,得到的表观Avrami指数很大;用基线延长线与DSC曲线的切线的交点作为冷结晶的起始点和结束点,得到的表观Avrami指数为2.55,且不随升温速率的变化而变化,与等温熔融热结晶方法得到的结果接近,具有相似的结晶生长方式。     

PP/CNFs复合材料非等温结晶动力学研究

采用聚丙烯蜡乳液(PP-wax)改性纤维素纳米微纤(CNFs),再通过HAKKE转矩流变仪熔融混合制备了聚丙烯(PP)/CNFs复合材料。利用差示扫描量热仪(DSC)研究了改性CNFs对PP非等温结晶行为的影响,并分别用Jeziorny、Ozawa和Mo模型对数据进行了处理。结果表明:改性CNFs对PP结晶的影响主要由改性剂PP-wax决定。一方面,低分子量PP-wax降低了PP基体的规整性,抑制了PP的成核,使得PP结晶温度下降;另一方面,PP-wax提升了基体PP分子链的运动能力,使PP晶体的生长速度加快,进而提高了PP基体的结晶速率。另外,Kissinger公式计算结果表明,CNFs的引入降低了PP结晶的活化能。     

取向PET/PEG共聚酯纤维的非等温结晶动力学

研究了取向ＰＥＴ／ＰＥＧ共聚酯纤维的非等温结晶动力学，提出了解析结晶动力学参数的新方法。结果表明，随ＰＥＧ含量的增加共聚酯纤维的结晶扩散活化能降低，结晶速率加快。与各向同性试样比较，取向试样的结晶峰明显向低温方向扩散。取向试样在较低温度下的结晶速率高于各向同性试样，而在较高温度下的结晶速率低于各向同性试样。     

聚乳酸/聚(已二酸-对苯二甲酸丁二酯)共混物的非等温结晶动力学

采用熔融挤出法制备了聚乳酸/聚(已二酸-对苯二甲酸丁二酯)共混物。利用差示扫描量热仪研究了聚乳酸及其共混体系的非等温结晶过程。用经Jeziorny修正的Avrami方程和Mo法对其非等温结晶动力学进行了分析。结果表明:Avrami方程和Mo法都适用于处理聚乳酸及其共混体系的非等温结晶过程,共混物的结晶速率大于聚乳酸的结晶速率。此外,用Huffman-Lauritzen理论计算了非等温结晶的结晶活化能,发现共混体系的结晶活化能绝对值小于聚乳酸。     

纳米CaCO3对FEP非等温结晶动力学的影响

采用熔融共混法制备了聚全氟乙丙烯（FEP）/纳米碳酸钙（nano-CaCO3）复合材料,利用差示扫描量热法研究了FEP及其复合材料的非等温结晶行为,并通过Avrami方程修正的Jeziorny法、Ozawa法以及Mo法对其非等温结晶动力学进行了处理分析。结果表明,Jeziorny法及Mo法均适用于处理FEP和FEP/nano-CaCO3的非等温结晶过程,但Ozawa法不合适;在同一降温速率下,FEP/nano-CaCO3复合材料的初始结晶温度、最大结晶温度均比相应的纯FEP高,且半结晶时间延长,这说明nano-CaCO3对FEP具有一定的诱导和促进成核的作用,但由于FEP/nano-CaCO3复合材料的长链分子结构及大的空间位垒导致FEP的结晶总速率下降。     

Poly(amide imide)s and poly(amide imide) composite membranes by interfacial polymerization

Novel amic acid diamines (AADs) (2‐carboxyterephthalamido‐bis(alkyl or aryl amine)s, H₂N? X? NH(O?)C? C₆H₃(COOH)? C(?O)NH? X? NH₂, where X is were synthesized by reacting trimellitic anhydride chloride with aromatic or aliphatic diamines in dimethylformamide at 5–10 °C. Poly(amide imide)s (PAIs) with an amide to imide ratio of three in the polymer chains were prepared by interfacial polycondensation of the AADs in aqueous alkaline solution with isophthaloyl chloride or terephthaloyl chloride in dichloromethane at ambient temperature to form poly(amide amic acid)s, followed by their subsequent thermal cycloimidization. All of the PAIs were soluble in polar aprotic solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide and N‐methylpyrrolidone, and have inherent viscosities in the range 0.15–0.48 dL g^?1. The polymers were characterized by IR and NMR spectroscopy, TGA and DSC techniques. The PAIs have initial decomposition temperatures in the range 250–460 °C in air, and glass transition temperatures of 128–320 °C, depending upon the structures of the monomers. Composite membranes containing a poly(amide amic acid) and poly(amide imide) barrier layer on the top of a porous polyethersulfone support were prepared by in situ interfacial polymerization of the AADs in aqueous alkaline solution with trimesoyl chloride in hexane, and subsequent curing. The performances of these membranes were evaluated by using aqueous feed solutions containing 2000 ppm NaCl, Na₂SO₄ or CaCl₂. Copyright © 2006 Society of Chemical Industry     

Reduction and cyclization to form poly(benzimidazole amide imide) copolymers

Poly(amide imide) copolymers were synthesized with different molar ratios of 4,4‐diphenylmethane diisocyanate, two types of aromatic dianhydrides (pyromellitic dianhydride (PMDA) and 3,3′,4,4′‐sulfonyl diphthalic anhydride (DSDA)), and a diacid, which was derived from 3,3′‐dinitrobenzidine and isophthaloyl chloride in a previous work. In this study, the copolymers were further reacted with a reducing agent, and the nitro groups in the copolymers were hydrogenated into amine groups. Then, the amine‐group‐containing poly(amide imide) copolymers were cyclized at 180°C to form the poly(benzimidazole imide amide) copolymers in poly(phosphoric acid), which acted as a cyclizing agent. The resultant copolymers were soluble in sulfuric acid and poly(phosphoric acid) at room temperature and in sulfolane or N‐methyl‐2‐pyrrolidone under heating to 100°C with 5% lithium chloride. According to wide‐angle X‐ray diffraction, all the copolymers were amorphous. According to thermal analysis, the glass‐transition temperature ranged from 270 to 322°C, and the 10% weight‐loss temperature ranged from 460 to 541°C in nitrogen and from 441 to 529°C in air. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 378–386, 2004     

mLLDPE非等温结晶动力学研究

利用差示扫描量热仪(DSC)研究了茂金属线性低密度聚乙烯(mLLDPE)和传统线性低密度聚乙烯(LLDPE)的非等温结晶行为。采用Jeziorny法和莫志深法对所得的数据进行了分析。结果表明,采用莫志深法处理数据可得到较好的线性关系,且mLLDPE在相同的相对结晶度下的结晶速率低于LLDPE。     

Study on Thermal Properties and Crystallization Behavior of Blends of Poly(phenylene sulfide)/Poly(ether imide)

The thermal behavior of poly(phenylene sulfide) (PPS) blends with poly(ether imide) (PEI) was studied by differential scanning calorimeter (DSC). The crystallization temperature of PPS in blends shifted from 216.8°C to 226.4°C upon addition of 20–70% PEI contents. The heat of crystallization remained unchanged with less than 50% PEI in blends, whereas the heat of fusion decreased with increasing PEI content. The isothermal crystallization indicated that incorporating PEI would accelerate the crystallization rate of PPS. The activation energy of crystallization increased with addition of PEI. The equilibrium melting point of PPS/PEI blends was not changed with compositions.     

二苯基硅二醇改性涤纶的非等温结晶动力学研究

采用差示扫描量热仪,对二苯基硅二醇改性PET的非等温结晶动力学进行了研究,利用Jeziorny动力学模型对结晶过程进行拟合计算。结果表明:改性PET的Avrami指数偏大,其原因是由于二苯基硅二醇的加入,改变了其结晶成核方式;与纯PET相比,半结晶时间增加。用Ziabicki方法处理得出的结晶能力参数Gc值也说明了改性PET的结晶能力比纯PET好。     

用Avrami-Ozawa模型研究6-叔丁基间甲酚非等温结晶动力学

主要研究了6-叔丁基间甲酚（3M6TB）的静态熔融结晶动力学。通过差示扫描量热仪（DSC）在不同的降温速率下测定降温结晶过程中的放热曲线,然后对数据进行分析得到相对转化度随温度变化的关系。用Avrami-Ozawa模型处理试验数据得到3M6TB静态熔融结晶过程的力学参数F_T（达到给定结晶度所需要的冷却速率的值）以及θ（Avrami常数对Ozawa常数的比值）,F_T和θ均随着降温速率的增大而增大,导致在本研究试验条件下一定结晶时间内3M6TB的相对结晶度随降温速率的增加而提高。     

Synthesis and properties of fluorinated polyimides and fluorinated poly(imide amide)s containing pendent cyano groups

A series of fluorinated polyimides and fluorinated poly(imide amide)s containing pendent cyano groups were prepared and investigated to determine their dielectric constants as a function of relative humidity and thermal characteristics. The fluorinated polymides and fluorinated poly(imide amide)s containing pendent cyano groups were prepared by reaction of bis(4-aminophenoxy) benzonitriles with a fluorinated dianhydride and with a fluorinated di(acid chloride) containing preformed imide rings. The properties of the fluorinated polyimides and fluorinated poly(imide amide)s containing pendent cyano groups were compared with those of fluorinated polyimides and fluorinated poly(imide amide)s prepared from 1,3-bis(4-aminophenoxy)benzene. The introduction of the pendent cyano groups caused an increase in the dielectric constant and an increase in the glass transition temperature of the polymers compared with the polymers prepared without pendent cyano groups.     

聚对苯二甲酸丙二醇酯的非等温结晶动力学研究

采用DSC研究了聚对苯二甲酸丙二醇酯(PTT)在不同等速降温速率下的结晶过程,并利用由等温Avrami方程推导得到的两种不同的等速降温非等温结晶方程,研究了其结晶动力学,得出PTT的成核方式为异相成核,同时利用拟和法计算了PTT的结晶能力,发现在同等条件下PTT的结晶能力大于PET。