Synthesis of Well-defined Long Chain Branched Polyethylene via Anionic Polymerization Combined with Graft-onto Method

Comb-like polyethylene（PE） was prepared via anionic polymerization combined with ＂graft-onto＂ process. The polybutadiene（PB） backbone underwent hydroxylation at 1,2-vinyl groups to obtain a controlled number of hydroxyl groups along the main chain. After the translation of hydroxyl groups to tosyl groups, a nucleophilic substitution by living anionic PB chains was achieved. The comb PE was finally obtained by the hydrogenation of the obtained unsaturated comb polymer. Since the living anionic polymerization was used to prepare the backbones and the branch chains, molecular weight to molecular weight distribution（Mw/Mn〈1.5） can be well-controlled in the final comb polymer, including the average number and length of branches.

The Rheological Property and Foam Morphology of Linear Polypropylene and Long Chain Branching Polypropylene

The rheological behavior, thermal properties and foam morphology of linear polypropylene and long chain branching polypropylene prepared through UV irradiation reactive extrusion were studied by rheological test, melt index test, DSC and supercritical carbon dioxide foaming technology. Rheological test and melt index test confirmed that under UV irradiation and extrusion, adding photo-initiator and cross- linking agent could achieve the purpose of branching, thus improved the melt strength of polypropylene effectively. The DSC results revealed that with the introducing of long chain branching, the melting range of the polypropylene broadened and the crystallization temperature increased. Owing to the introduction of long chain branches, polypropylene exhibited higher melt strength and strain hardening behavior. Compared with linear polypropylene, the foam morphologies of long chain branching polypropylene were more uniform.

Preparation and Rheological Characterization of Long Chain Branching Polyglycolide

The long chain branching(LCB)polyglycolide(PGA)was successfully prepared by the successive reactions of the terminal hydroxyl groups of PGA with triglycidyl isocyanurate(TGIC)and pyromellitic dianhydride(PMDA).The influence of LCB produced by functional group reaction on rheological and crystallization behavior was studied and discussed through linear rheology,uniaxial elongation and DSC(differential scanning calorimetry).The much higher viscosity and the more notable strain hardening behavior of modified PGA indicates the LCB with high degree of entanglements are created.The melt strength of PGA is finally improved greatly and can make su re that the supercritical CO_(2)foaming can be carried out successfully.

Effect of Long Chain Branching on the Rheological Behavior,Crystallization and Mechanical Properties of Polypropylene Random Copolymer

Long chain branched polypropylene random copolymers （LCB-PPRs） were prepared via reactive extrusion with the addition of dicumyl peroxide （DCP） and various amounts of 1,6-hexanediol diacrylate （HDDA） into PPR. Fourier transform infrared spectrometer （FTIR） was applied to confirm the existence of branching and（ investigate the grafting degree for the modified PPRs. Melt flow index （MFI） and oscillatory shear rheological properties including complex viscosity, storage modulus, loss tangent and the Cole-Cole plots were studied to differentiate the LCB-PPRs from linear PPR. Differential scanning calorimetry （DSC） and polarized light microscopy （PLM） were used to study the melting and crystallization behavior and the spherulite morphology, respectively. Qualitative and quantitative analyses of rheological curves demonstrated the existence of LCB. The effect of the LCB on crystalline morphology, crystallization behavior and molecular mobility, and, thereby, the mechanical properties were studied and analyzed. Due to the entanglements between molecular chains and the nucleating effect of LCB, LCB-PPRs showed higher crystallization temperature and crystallinity, higher crystallization rate, more uniformly dispersed and much smaller crystallite compared with virgin PPR, thus giving rise to significantly improve impact strength. Moreover, the LCB-PPRs exhibited the improved yield strength. The mobility of the molecular chain segments, as demonstrated by dynamic mechanical analysis （DMA）, was improved for the modified PPRs, which also contributed to the improvement of their mechanical properties.

Synthesis and Rheological Investigation of Model Symmetric 3-Arm Star Polyethylene

A variety of linear and 3-arm star polyethylene （PE） model polymers covering a wide range of molecular weight are synthesized by the living polymerization of butadiene and the subsequent hydrogenation. Several rheological parameters of these model linear and 3-arm star PE samples are analyzed for detecting the long chain branching （LCB） structure. It is found that the analyses based on zero shear viscosity, vGP plot and flow activation energy are very sensitive to the 3-arm star PEs. The information on the presence of LCB can be obtained with these methods even for low molecular weight samples, which can not be determined by GPC-MALLS. However the information about the LCB structure can not be obtained by the rheological methods alone.