Synthesis, Structure And Properties Of Polyethylene/Polypropylene In-Reactor Alloys And Their Graft Polymerization Products

Chlorided derivative of Fullerenes(C60/C70=7/3), C60Cln(the value of n is 18-22,the average value is 20) has been used as a novel initiator in atom transfer radical polymerization(ATRP) for the first time. C60 bonded Polystyrene(PSt), poly(N-vinylcarbazole) (PVK) and polymethylmethacrylate(PMMA) were prepared by C60Cl20/CuCl/2,2'-bipyridine(Bpy) and C60Cl20/Ni(naph)2/P(Ph)3 initiator system, respectively. Polymeric processes, polymerization mechanism and the structure of polymers were studied in more detail. C60Cl20 was also used as a novel coupling agent in n-BuLi initiating anionic polymerization of butadiene (Bd) and styrene (St) in the first instance. With the two methods, star-shaped polymer with a chlorided derivative of C60 as core and with predictable average molecular weights and narrow polydispersity indices (PDI) polymer chain arm could be synthesized.C60-bonded polystyrene was prepared by C60Cl20/CuCl/ 2,2'-bipyridine(Bpy) initiator system. The mole ratio of styrene: C60Cl20:CuCl:Bpy was 100:1/20:1:2 and polymerization temperature was 130 C.Compared with ordinary initiator system,CCl4CuCl/Bpy, this initiator system showed better phone state dispersion and similar activity in toluene. There were two peaks(peak a and peak b) in the Gel-permeation chromatography(GPC) of PSt initiated by C60Cl20 detected by refractive index (RI) detector. The peak(b), and a smell part of peak(a), consisted with the GPC curve detected by ultra-violet absorption (UV) detector. The working wavelength for the UV detector was set at 340nm where the polystyrene could not be detected and only C60 and its derivative can be recorded. Which indicted that C60 was chemical bonded into the main chain for the part of polystyrene. The linear increasing of molecular weights (Mn,GPC obtained by UV detector) with conversion indicated that this part of polymerization was ATRP initiated by C60Cl20.The peak(a) of the GPC curve detected by RI detector didn't move with the conversion increasing, and without C60 in the part of polymer. Therefore the part of polymerization was designed therm polymerization. At the same time,a small quantity of C60-PSt existed in peak(a) ,which was initiated by C60Cl20. After styrene polymerized completely, by adding methymethacrylate the copolymer of polystyrene-block-polymethylmethacrylate can also be compounded.Which also verified a "living" nature of the polymerization. In this initiator system, the polymerization rate and the Mn of PSt were decreased as increasing the content of CuCl. The best mole rate of Bpy/CuCl was about 1.2. The part of ATRP in whole polymerization was decreased as decreasing the content of C60Cl20.As decreasing the value of n in C60Cln, the polymerization activity and the molecular weight of polymer were decreased. As increasing the content of monomer, the molecular weight of polymer increased. The apparent activation energy of this polymerization reaction (Ea) was 93.0KJ.mol-1. This initiator system can be used to initiate MMA too. The fluorescence spectra of C60-PSt which was initiated by C60Cl20 initiator system and PSt in dichloromethane at room temperature and the ex was 248nm were detected. The peak of C60Cl20 in 650nm was found in the fluorescence spectrum of C60-PSt, which also indicted that C60 was chemically bonded to PSt linear. With the "living" nature of this polymerization system, the arm number of this C60-bonded polystyrene was roughly calculate by the formula of Mn,GPC=([M]C%/[I])WM, which was about 4-6. The microstructure of C60-PSt was atactic detected by IR,1H-NMR and 13C-NMR. The photoconducting properties of C60-PSt were studied preliminarily. C60-PSt exhibit a higher charge acceptance (V0=1720) than ordinary PSt(V0=1320) and C60-PSt has a shorter t1/2(0.81s) than PSt2 (0.92s). So C60 bonded polystyrene exhibits better photoconductivity than ordinary PSt.C60 bonded poly(N-vinylcarbazole) has been synthesized in present of C60Cl20 in toluene at 120 C ,VK: C60Cl20 was 100:1 (mole ratio) and the concentration of VK was 0.25g/mL. The fullerenated PVK has a...