纳米粒子改性PET的非等温结晶动力学

研究了有机纳米丁苯吡粉末橡胶、无机纳米粒子添加到聚对苯二甲酸乙二酯(PET)后对PET结晶行为的影响.并探讨了不同降温速率下3种体系降温过程中的结晶行为及基于Jeziomy理论和莫氏理论的结晶动力学.研究表明,3种纳米粒子对PET结晶动力学的影响是不同的,纳米粉末橡胶在较低结晶度时符合Jeziorny理论,而无机纳米粒子则对莫氏理论有较好的相关性.由莫氏理论计算出的参数表明,达到同样结晶度时有机化黏土促进PET结晶的效果比纳米CaCO3好.     

液相增黏再生聚酯非等温结晶动力学研究

将废旧聚酯(PET)纺织品摩擦成形制成摩擦料,再经螺杆熔融挤出制得其共混摩擦料,然后采用立卧双釜串联系统对共混摩擦料进行液相增黏制得再生PET(R-PET),实现废旧PET纺织品的再生利用;利用差示扫描量热(DSC)对R-PET进行非等温结晶动力学研究,并与常规PET切片进行比较。结果表明:R-PET的特性黏数由未增黏前的0.580~0.595 d L/g增加至0.635~0.655 d L/g;DSC分析中,在同一降温速率下,R-PET的结晶峰温度高于常规PET切片,半结晶时间小于常规PET切片;利用Mo法可以较好地描述R-PET及常规PET切片的非等温结晶过程。     

含较高立构缺陷聚乳酸的非等温结晶动力学

用非等温结晶动力学研究了聚乳酸(PLA)的结晶行为,利用Hoffman-Weeks外推法以及Baur等提出的方程反推出PLA中的右旋组分摩尔分数为7.2%.较高的右旋组分摩尔分数是PLA结晶过程中成核速率低的主要因素.添加质量分数为2%滑石粉等成核剂后,PLA结晶速率没有明显提高;含10%滑石粉的PLA结晶速率略上升,...     

超支化聚酯共混聚合物等温结晶动力学研究

采用三羟甲基丙烷、2,2-二羟甲基丙酸、对甲苯磺酸反应制备第2～5代超支化聚酯(HBP),将其按质量分数10%分别与聚丙烯(PP)和聚甲醛(POM)共混,用差示扫描量热法(DSC)研究了共混物的等温结晶动力学。结果表明,用Avrami方程描述PP/HBP和POM/HBP的结晶动力学较理想。在PP中,HBP主要起成核作用;在POM中,HBP主要起稀释作用;第2代HBP成核作用最弱,稀释作用最强,第5代HBP稀释作用最小。     

回收PET共混物的非等温结晶和熔融行为

采用双螺杆挤出机制备了聚丙烯(PP)/回收聚对苯二甲酸乙二酯(r-PET)、r-PET/马来酸酐接枝PP(PP-g-MAH)和r-PET/甲基丙烯酸缩水甘油酯接枝PP(PP-g-GMA)共混物,并研究了共混物组成、熔融温度与时间以及降温速率对共混物非等温结晶与熔融行为的影响.结果表明,r-PET与PP共混,结晶温度均提高,这与组分间起到异相成核诱导结晶作用有关.r-PET结晶温度随PP-g-MAH用量增加而降低,但受PP-g-GMA用量影响较小;r-PET可提高PP-g-MAH结晶温度,但降低PP-g-GMA结晶温度.熔融温度提高,共混物中PP结晶温度和熔点均降低,r-PET熔融峰形和熔点取决于共混物的熔融温度及界面相互作用.     

支化PET的非等温结晶性能研究

采用直接酯化缩聚法,以3-羟甲基丙烷(TMP)或季戊四醇(PER)为支化剂,制备支化PET;探讨了支化剂对其结晶性能的影响;利用差示扫描量热(DSC)法研究了支化PET的非等温结晶性能。结果表明:支化剂TMP或PER的加入可以有效增强PET的结晶能力,但过量的支化剂会抑制PET的结晶;支化PET的非等温结晶Avrami指数为3.03~4.42,其结晶机理为均相成核和异相成核相结合;支化PET的结晶活化能比常规PET的低,支化PET结晶对温度的依赖性降低。     

聚丙烯复合材料的非等温结晶动力学

采用差示扫描量热仪研究了β成核剂和水滑石(LDH)/β成核剂复配的成核剂对聚丙烯(PP)非等温结晶动力学及熔融行为的影响。结果表明:加入成核剂后,PP中晶体分布不均匀且分散度增大。莫志深方法采用F(θ)表征聚合物在单位时间内达到某一结晶度时所需的冷却(或加热)速率,结晶度达到40%时,纯PP的F(θ)为3.82,加入β成核剂的PP的F(θ)为3.30,加入LDH/β成核剂的PP的F(θ)为2.49。与纯β成核剂相比,LDH/β成核剂能更好地提高PP的结晶温度、结晶速率,增强PP的β晶熔融峰,减弱β晶和α晶共存熔融峰和α晶熔融峰。     

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。     

Photopolymerization kinetics of hyperbranched acrylated aromatic polyester

The influences of the irradiation temperature, comonomer content, sample thickness, and photoinitiator concentration on the polymerization kinetics of hyperbranched acrylated aromatic polyester (HAAPE) were investigated with photo‐differential scanning calorimetry and IR measurements. The maximum photopolymerization rate increased with the temperature rising up to 110°C but decreased beyond 110°C. An activation energy of 16 kJ mol^?1 for the photopolymerization was obtained below 110°C from an Arrhenius plot, but it was negative beyond 120°C. A remarkable synergistic effect between HAAPE and the comonomer trimethylolpropane triacrylate with a molar fraction of around 0.4 was observed from a photopolymerization kinetic study of the resins. The final unsaturation conversion in an ultraviolet‐cured film decreased with the sample thickness, and this became more remarkable as the photoinitiator concentration increased. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1500–1504, 2003     

PBT蓄能发光复合材料非等温结晶动力学研究

采用差示扫描量热(DSC)法研究非等温条件下环形对苯二甲酸丁二醇酯(CBT)反应性挤出加工所制聚对苯二甲酸丁二醇酯(PBT)蓄能发光复合材料的结晶行为,分别采用Ozawa,Jeziorny及Mo方程拟合分析复合材料的非等温结晶动力学。结果表明:采用Ozawa及Jeziorny方程所获拟合曲线均不成线性;Mo方程可很好地描述PBT蓄能发光复合材料的非等温结晶过程,拟合所得PBT复合材料的单位时间里体系到达结晶度时的降温速率(F(T))值均较纯PBT的低,且粉体质量分数为15%时,其F(T)值最小,表明加入发光粉体可加速体系的结晶过程,然而在高降温速率下,较高浓度的发光粉体反而会降低体系的结晶速率。     

改性聚乙烯醇的非等温结晶动力学研究

通过差示扫描量热法(DSC)测定了己内酰胺水溶液改性的聚乙烯醇(PVA)降温结晶过程,并用Ozawa方法,Jeziorny方法和莫志深方法分析了改性PVA的非等温结晶动力学。结果表明:随着冷却速率增加,改性体系内起增塑作用的小分子由于其蒸发升华的减缓,改性PVA体系的运动能力增强,结晶度提高;莫志深方法能够较好地解释改性PVA的非等温结晶过程,即在单位时间内达到较大结晶度需较大的降温速率,且随着体系相对结晶度的增加,结晶速率降低。     

超支化聚酯的合成及其对PET纤维的改性研究

以三羟甲基丙烷作为中心核,二羟甲基丙酸为合成单体,对甲苯磺酸作为催化剂,采用一步法分别合成了第二代、第三代、第四代不同代数的端羟基超支化聚酯(HBP),并对其结构进行了表征.将不同代数的HBP与聚对苯二甲酸乙二醇酯(PET)共混纺丝制备了HBP/PET共混纤维,研究了纤维的流变性能、力学性能、染色性能和吸湿性能.结果表...     

Non-isothermal polymer crystallization kinetics and Avrami master curves

The kinetic crystallization model of Avrami is generally accepted as a starting point for the analysis of isothermal polymer crystallization. It is shown in this paper that, in the case of non-isothermal crystallization kinetics with constant heating or cooling rates, an apparent m -order reaction model is approximately equivalent to the nucleation and growth model of Avrami in the vicinity of the inflection points of the corresponding crystallization curves. Since the apparent m -order reaction model is defined for every real, positive apparent reaction-order m , a distinct Avrami index n , which is valid for the characterization of isothermal and non-isothermal crystallization experiments with constant heating or cooling rates, can always be related to any apparent reaction-order m . Therefore, two types of Avrami master curves, which are dependent merely on the Avrami index n and which describe the isothermal polymer crystallization thoroughly, can be obtained by performing non-isothermal experiments with constant heating or cooling rates.     

PBT/PTT合金的非等温结晶行为

采用差示扫描量热法(DSC)研究了聚对苯二甲酸丁二酯(PBT)/聚对苯二甲酸丙二酯(PTT)合金的非等温结晶动力学.随着降温速率的增大,PBT/PTT合金的结晶峰温均降低,结晶峰均加宽.采用Jeziorny法、莫志深法和Flyn-Wall-Ozawa法分析非等温结晶过程,Jeziorny法能够描述PBT/PTT合金的初期结晶过程,对后期结晶存在一定偏差,各PBT/PTT合金的结晶维数变化不大;莫志深和Flyn-Wall-Ozawa法能很好地描述PBT/PTT合金的非等温结晶过程,随PTT含量增加,由Flyn-Wall-Ozawa法求得PBT/PTT合金的活化能呈增加趋势.相对结晶度为0.5,m(PBT)/m(PTT)分别为90∶10,70∶30,50∶50时,PBT/PTT合金的活化能分别为-201.9,-116,0,-66.6 kJ/mol;相对结晶度为0.5时,m(PBT)/m(PTT)为50∶50的合金活化能比PTT(-77.4 kJ/mol)还高.     

Non-isothermal crystallization kinetics of polypropylene/MAP-POSS nanocomposites

Non-isothermal crystallization kinetics of polypropylene (PP)/methylacryloypropy polyhedral oligomeric silsesquioxanes (MAP-POSS) nanocomposites (PP/MAP-POSS) were investigated by DSC at various cooling rates. Jeziorny and Mo method were used to study the non-isothermal crystallization kinetics. The results show that the Jeziorny and Mo method are all successful in describing the non-isothermal crystallization kinetics of PP/MAP-POSS nanocomposites. The MAP-POSS can act a role of heterogeneous nucleation and increase the crystallization rate constant Z _c and decrease crystallization half time t _1/2, and the spherulite crystal size decreases, the inter-spherulitic action or crosslinking structure each other appear at the appropriate content. The DSC peak temperature T _p increase about 5 °C, t _1/2 reduce 0.21 min at 6 % content of MAP-POSS and heating rate of 10 °C/min. The MAP-POSS can also increase the mechanical property of PP/MAP-POSS nanocomposites, the tensile strength and impact strength increase from 12.97 to 19.93 MPa and from 33.2 to 52.6 kJ/m², respectively, at 4 % content of MAP-POSS. But the spherulitic crystal becomes larger and boundaries become clearer again; the macrophase separation will occur and mechanical properties decrease when more and more MAP-POSS was added. The nanocomposite has the best mechanical property at 4 % content of MAP-POSS.     

CHDM改性PBT共聚酯的非等温结晶动力学研究

采用直接酯化熔融缩聚工艺路线,以1,4-环己烷二甲醇(CHDM)为第三单体,制备了CHDM改性聚对苯二甲酸丁二醇酯(PBT)共聚酯(PBTG),利用差示扫描量热仪测定了PBT及PBTG在不同降温速率下的降温曲线,并采用Jeziorny方法分析了PBTG的非等温结晶动力学。结果表明:随着降温速率的增加,PBT及PBTG的结晶温度降低,结晶曲线变宽;在相同降温速率下,相比PBT,加入第三单体CHDM后的PBTG的非等温结晶动力学速率常数降低,证明PBTG的非等温结晶能力降低,结晶速率变慢; CHDM的加入不利于PBT结晶。     

Non-isothermal crystallization kinetics of poly(ethylene terephthalate)/mica composites

The non-isothermal crystallization kinetics of pure poly(ethylene terephthalate) (PET), PET/mica and PET/TiO₂-coated mica composites were investigated by differential scanning calorimetry with different theoretical models, including the modified Avrami method, Ozawa method and Mo method. The activation energies of non-isothermal crystallization were calculated by Kissinger method and Flynn–Wall–Ozawa method. The results show that the modified Avrami equation and Ozawa theory fail to describe the non-isothermal crystallization behavior of all composites, while the Mo model fits the experiment data fair well. It is also found that the mica and TiO₂-coated mica could act as heterogeneous nucleating agent and accelerate the crystallization rates of PET, and the effect of TiO₂-coated mica is stronger than that of mica. The result is further reinforced by calculating the effective activation energy of the non-isothermal crystallization process for all composites using the Kissinger method and the Flynn–Wall–Ozawa method.     

Non-isothermal cold crystallization behavior and kinetics of poly(l-lactide): effect of l-lactide dimer

The effects of l-lactide dimer as additives on the crystallization behavior of poly(l-lactide) (PLLA) films were studied. Hence, neat PLLA films and PLLA containing l-lactide (5 % w/w) (PLLA/La) were prepared in dichloromethane at room temperature via solution casting. The non-isothermal cold crystallization of PLLA films were studied using differential scanning calorimetry at various heating rates including 2.5, 5, 7.5, 10 and 15 °C/min. However, the X _C% was increased for PLLA/La films in comparison with neat PLLA films. The crystallization kinetics was then analyzed by the Avrami, Jeziorny, Ozawa and Mo kinetic models. It is found that all the kinetic models were established to describe the experimental data fairly well except the Ozawa model. The values of t _1/2, Z _C and F(T) indicated that the crystallization rate increased with increase in heating rates for PLLA and PLLA/La films. However, l-lactide dimer incorporated in PLLA films accelerates the crystallization process of PLLA at the high heating rate. The nucleation constant (K _g) and the surface free energy (σ _e) based on Lauritzen–Hoffman theory indicated that these parameters for PLLA/La films is lower than neat PLLA.     

Non-isothermal crystallization kinetics assessment of poly(lactic acid)/graphene nanocomposites

In this work, the effects of the presence and modification of graphene nanoplatelets (GNps) on the crystallization of the poly(lactic acid) (PLA) were studied. Functionalization of GNps was accomplished by acid treatment. Nanocomposite samples were prepared by solution method containing pristine and functionalized graphene. In contrast to pristine PLA, crystallization of the samples contains nano filler initiates at higher rates that showed the role of heterogeneous nucleating effects of these particles in crystallization of the PLA. Then, the effect of nano filler functionalization was comprised. Initial slope of the crystallization (S _i) and full width at the half height maximum of crystallization peak are indicative of nucleation rate and spherulite size distribution, respectively; which upon the addition of the functionalized graphene nanoplatelets (FGNps), S _i increased and spherulites gained normal size distribution. Non-isothermal and crystallization kinetics of the samples were studied using differential scanning calorimetry at heating rates of 2, 4, 6 and 10 °C/min. Performed techniques such as furrier transform infrared, dynamic-mechanical thermal analysis and visual observation of sediments confirmed the successful modification of the graphene platelets. Also, non-isothermal analysis pinpointed the fact that crystallization temperature (T _c) of the nanocomposites has increased by 11–21 °C, compared to the neat PLA. Upon verification of Avrami’s theory, it was conducted that dominant mechanism of nucleation of the nanocomposite samples was 2D circular diffusion; wherein, Avrami’s exponent (n) was determined as 2. Moreover, it was deduced from Avrami’s equation that “n” have no discernible changes in nanocomposites containing GNps or FGNps. Electrical devices and shape memories can be the main application of these nanocomposites.