KINETICS STUDY ON MELT GRAFTING ACRYLIC ACID ONTO LLDPE USING REACTIVE EXTRUSION

The kinetics of melt grafting acrylic acid （AA） onto linear low density polyethylene （LLDPE） by using reactive extrusion was investigated. The polymeric peroxides （POOP and POOH） generated by electron beam irradiation were used to initiate the graft reaction. The samples taken out from the barrel at five ports along screw axis were analyzed by FTIR. The spectra show that both the graft copolymerization and homopolymerization proceed in two stages： the graft degree （or mass of homopolymer） increases linearly with the reaction time in the initial stage, and then gradually in the second stage. The rate of graft copolymerization Rg is always faster than that of homopolymerization Rh in the present system and the activation energy is 131 kJ · mol^-1 for graft copolymerization and 127 kJ · mol^-1 for homopolymeirzation. These results were interpreted in terms of solubility and diffusion of monomer, as well as the reactivity and the concentration of reactive species. The relationships between reaction rate and monomer concentration and peroxide concentration were found to be： Rg ∞ [M]^1.46[POOP＋POOH]^0.53 and Rh ∞ [M] ^1.08[POOH]^0.51, which indicate that the addition of monomer to polymeric radicals is a slow step for the graft copolymerization.

Styrene/Butadiene Copolymer Synthesized by Reactive Extrusion

In this study, we present a method to synthesize styrene-butadiene copolymer, using anionic polymerization in a co-rotating closely intermeshing twin-screw extruder. The weight content of polybutadiene in these copolymers was above 50% although in the past studies it had been possible to accomplish levels higher than 30%. ^1H-NMR and GPC show that the molecular structure of the two polymers is different due to different feeding method. In terms of the structure of the polymerized products, the mechanism of polymerization in the bulk polymerization is discussed. TEM and DMA show that two phases in the block copolymer are completely incompatible, leading to sharp phase separation, while the case is complicated in the copolymer through the mixture feeding. Traditionally, styrene-butadiene rubber is mainly synthesized by solution polymerization. Reactive extrusion in this paper provides a possibility to synthesize these products in an environmentally friendly way.

Improving Interfacial Adhesion of PLA/Lignin Composites by One-Step Solvent-Free Modification Method

To clarify the effects of lignin as a biodegradable filler added into the PLA matrix,PLA/lignin composites with or without silane coupling agent ofγ-(2,3-epoxypropoxy)propy trimethoxysilane(KH560)were prepared by a one-step solvent-free modification method.The effects of KH560 as a compatibilizer on the morphology,chemical structure,crystallization behavior,thermal degradative behavior as well as mechanical strength of the PLA/lignin composites were analyzed in detail.It was found that,after modification by KH560,the fractured surfaces of composites became smooth,suggested sufficient bonding between the lignin and PLA in the composites with KH560 coupling agent molecules.This result further proved by 1H NMR and ATR spectra of the composites that lignin and PLA formed stable chemical bonds with KH560.Due to the toughening effect of KH560,mainly affect the molecular chain mobility,the thermodynamic properties of LG-KH560/PLA composites were all reduced.When compared to the conventional solution modification method of adding silane coupling agents into PLA/lignin,the composites were synthesized via a single-step reactive extrusion modification procedure in this work showed relatively low tensile strength,which mainly because the existence of the free radicals due to coupling agents result in the composite’s deterioration and subsequent weakening of the tensile properties.

IN SITU COMPATIBILIZATION OF LDPE/NYLON-6 BLEND USING LOW MOLECULAR WEIGHT INTERFACIAL AGENT AS A CHEMICAL COMPATIBILIZER

In situ, compatibilization of low density polyethylene (LDPE) (30%) and nylon-6 (70%) blends through one-step reactive extrusion using t-BuOOH as an initiator and low molecular weight interfacial agents as compatibilizers was studied. The compatibilizer contained a long chain hydrocarbon, double bond and two polar functional groups which was capable of reacting with both LDPE and nylon-6 in the presence of initiator to form a copolymer at the interface of the two polymer phases. The extruded blends exhibited significant enhancement in their compatibility based on morphological, thermal analysis and mechanical studies. The effect of the hydrocarbon chain length and structure of the functional group of the compatibilizer was also examined. It was found that blends prepared by using the compatibilizer containing longer hydrocarbon chain and amide group had better mechanical properties.