Microstructure Characterization of Short-chain Branching Polyethylene with Differential Scanning Calorimetry and Successive Self-nucleation/Annealing Thermal Fractionation

A series of the copolymers of ethylene with 1-hexene （M1-M9） synthesized by metallocene catalyst Et[Ind]2ZrC1JMAO was studied by differential scanning calorimetry and successive self-nucleation and annealing （SSA） thermal fractionation. The distribution of methylene sequence length （MSL） in the different copolymers was determined using the SSA method. The comonomer contents of samples M4 and M5 are 2.04 mol% and 2.78 mol%, respectively. Both M4 and M5 have low comonomer content and their MSL distribution profiles exhibit a monotonous increase trend with their MSL. The longest MSL of M5 is 167, and its corresponding molar percent is 43.95%, which is higher than that of M4. Moreover, the melting temperature （Tm） of M5 is also higher than that of M4. The comonomer contents of samples M7, M8, and M9 are 8.73 mol%, 14.18 mol% and 15.05 mol%, respectively. M7, M8, and M9 have high comonomer contents, and their MSL distribution profiles display unimodality. M7 has a lower peak value of 33 and a narrow MSL distribution, resulting in a Tm lower than that of M8 and M9. The MSL and its distribution are also key points that influence the melting behavior of copolymers. Sometimes, MSL and its distribution of copolymers have a greater impact on it than the total comonomer contents, which is different from traditional views.

Comparison of Different Methods for Determining the Imidization Degree of Polyimide Fibers

In this study, polyimide fibers at different stages of imidization were characterized by TGA, DSC, and FTIR. The imidization degree （ID） calculated by TGA was based on the weight loss of each sample, which was caused by the imidization of residual amic acid groups. The results of TGA showed good regularity with the thermal treatment temperature of the PI fibers. For DSC, the ID was calculated based on the area of endothermal peak of each sample. Compared with TGA, DSC showed a relatively higher value because the endothermal peak was reduced by the exothermic re-formation of polyamic acid which may be partially degraded during thermal treatment. The IDs obtained by the FTIR spectra generally showed poorer regularities than those obtained by both TGA and DSC, especially for the results calculated using the 730 cm^-1 band. Based on the 1350 cm^-1 band, the obtained IDs showed better agreement with the TGA or DSC results. The results obtained by these three methods were compared and analyzed. The ID obtained by TGA showed much more reliability among these three methods.

Calibration Curve Establishment and Fractionation Temperature Selection of Polyethylene for Preparative Temperature Rising Elution Fractionation

A series of copolymers of ethylene with 1-hexene synthesized using a metallocene catalyst are selected and mixed. The blend is fractionated via preparative temperature rising elution fractionation（P-TREF）. All fractions are characterized via high-temperature gel permeation chromatography（GPC）, 13 C nuclear magnetic resonance spectroscopy（13C-NMR）, and differential scanning calorimetry（DSC）. The changes in the DSC melting peak temperatures of the fractions from P-TREF as a function of elution temperature are almost linear, thereby providing a reference through which the elution temperature of TREF experiments could be selected. Moreover, the standard calibration curve（ethylene/1-hexene） of P-TREF is established, which relates to the degree of short-chain branching of the fractions. The standard calibration curve of P-TREF is beneficial to study on the complicated branching structure of polyethylene. A convenient method for selecting the fractionation temperature for TREF experiments is elaborated. The polyethylene sample is fractionated via successive self-nucleation and annealing（SSA） thermal fractionation. A multiple-melting endotherm is obtained through the final DSC heating scan for the sample after SSA thermal fractionation. A series of fractionation temperatures are then selected through the relationship between the DSC melting peak temperature and TREF elution temperature.

Microstructure Characterization of a Complex Branched Low-density Polyethylene

A low-density polyethylene （LDPE） resin with excellent processing and film-forming properties is fractionated through temperature rising elution fractionation （TREF） technique. The chain structures of both the original resin and its fractions are further analyzed using high-temperature gel permeation chromatography （GPC） coupled with triple detectors （refractive index （RI）-light scattering （LS）-viscometer （VIS））, ^13C-nuclear magnetic resonance spectroscopy （^13C-NMR）, Fourier transform infrared spectroscopy （FTIR）, differential scanning calorimetry （DSC） and successive self- nucleation/annealing （SSA） thermal fractionation. The ^13C-NMR results show that the original resin has both short chain branch （SCB） （2.82 mol%） and long chain branch （LCB） （0.52 mol%） structures. The FTIR results indicate that the methyl numbers （per 1000 C） of the fractions gradually decrease from 81 to 46 with increasing elution temperature from 25 ℃ to 75 ℃. The TREF-GPC cross-fractionation results show that the main component is collected at around 68 ℃. The molecular weight of the components in the high elution temperatures of 60 ℃ to 75 ℃ is from 2.0× 10^3 g/mol to 2.0 × 10^6 g/mol, and the relative amount is more than 80%. In the low elution temperature region below 50 ℃, the molecular weights of the components range from 1.0 × 10^3 g/mol to 1.6 × 10^4 g/mol, and the relative amount is less than 10%. In the DSC results, the melting peaks of the fractions gradually increase from 80.1℃ to 108.8 ℃ with elution temperature. In the SSA thermal fractionation, each resin fraction shows a broad range of endotherm with multiple melting peaks （more than eight peaks）. The melting peaks shift toward high temperatures with the elution temperature. The characteristic chain microstructure for the resin is also discussed in detail.

Comparison of Chain Structures between High-speed Extrusion Coating Polyethylene Resins by Preparative Temperature Rising Elution Fractionation and Cross-fractionation

Two polyethylene（PE） resins（samples A and B） are synthesized as high-speed extrusion coatings with similar minimum coating thickness and neck-in performance but different maximum coating speeds. Both samples are separated into seven fractions using preparative temperature rising elution fractionation. The microstructures of the original samples and their fractions are studied by high-temperature gel permeation chromatography, Fourier transform infrared spectroscopy, 13 C nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and successive self-nucleation/annealing thermal fractionation. Compared with sample B, sample A has a broader MWD, more LCB contents, and less SCB contents. Moreover, sample A contains slightly more 30 ℃ and 50 ℃ fractions with lower molecular weights, and more fractions at 75 ℃ and 85 ℃ with higher molecular weight. The chain structure and its distribution in the two PE resins are studied in detail, and the relationship between the chain structure and resin properties is also discussed.