Polyethylene anionic polymerization

It may be shown that M > M. The two are equal only for a monodisperse material, in which all molecules are the same sise. The ratio MI /MI is known as the polydispersity index and is a measure of the breadth of the molecular weight distribution. Values range from about 1.02 for carefully fractionated samples or certain polymers produced by anionic polymerization, to 20 or more for some commercial polyethylenes. 

Polyethylene glycol), or Carbowax, is made by anionic polymerization of ethylene oxide using NaOH as catalyst. Propose a mechanism. 

Dynamic Mechanical Properties. The dynamic mechanical properties of branched and linear polyethylene have been studied in detail and molecular interpretation for various transitions have already been given, although not necessarily agreed upon in terras of molecular origin.(52-56) Transitions for conventional LDPE (prepared by free radical methods) when measured at low frequencies, are located around +70°C, -20°C and -120°C and are assigned to o, 5, and y transitions respectively. (53) Recently Tanaka et al. have reported the dynamic mechanical properties for a sample of HB which was also prepared by anionic polymerization, but contrary to our system the hydrogenation of the polybutadiene was carried out by a coordinate type catalyst.(12) The transitions reported for such a polymer at 35 Hz are very similar to those of LDPE.(12)... 

Polystyrene/polyethylene oxide dendrimers were prepared by ATRP using tri- and tetra (bromomethyl) benzene as the initiators [207]. Each bromine end-group of the resulting stars was transformed first to two - OH groups and subsequently to potassium alcholate, as shown in Scheme 114. These - OK sites served to initiate the anionic polymerization of EO. The synthesized dendritic copolymers were found to display monomodal and narrow molecular weight distribution. 

To the first category belong the homo- and copolymerization of macromonomers. For this purpose, macromolecules with only one polymerizable end group are needed. Such macromonomers are made, for example, by anionic polymerization where the reactive chain end is modified with a reactive vinyl monomer. Also methacrylic acid esters of long-chain aliphatic alcohols or monofunctional polyethylene oxides or polytetrahydrofurane belong to the class of macromonomers. 

Graft copolymer, polyclhylene-gra/f-poly(propylcnc oxide) (PE-g-PPG), has been synthesized by ring opening anionic polymerization of propylene oxide with a phosphazene catalyst and hydroxylated polyethylene (Mn = 12400, [OH] = 5 units/chain). Polymerization of propylene oxide was carried out in tetraline at 120 °C for 20 hours. The 13C NMR analysis of PE-g-PPG suggested that all the hydroxyl groups were consumed for propylene oxide polymerization (Fig. 6). 

Flaked caprolactam is supplied in polyethylene bags for general purposes or in aluminum coated paper bags for anionic polymerization. Flake caprolactam should be stored in dry warehouses and protected against direct sunlight. It is advisable to keep the ambient temperature below 45°C and the relative humidity below 65%264. 

Other important examples of ring-opening polymerizations are the synthesis of polyethylene oxide and the block copolymer of ethylene oxide and propylene oxide. Polyethylene oxide, also known as polyethylene glycol (PEG), is commonly produced by anionic polymerization and has a low molecular weight of less than 20,000. 

Polyethylene oxide)macromonomers have thus been synthesized by two-step processes. Poly(oxyethylene)mo nomethyl ethers with widely varying molecular weights are commercially available. They are obtained by anionic polymerization of oxirane initiated by monofunctional alkoxides261 such as potassium 2-methoxyethanol. 

Ordinarily anionic polymerizations must be run in the absence of oxygen, but the addition of polyethylene glycol serves to complex with the sodium ion just as 18-crown-6 does and enhances the catalytic activity of the sodium hydride. 

Though not as important as aluminum and magnesium alkyls, lithium alkyls are produced in million pound per year quantities, but have only an indirect role in the production of polyethylene. The primary merchant application for lithium alkyls is in anionic polymerization of dienes to produce synthetic elastomers... 

B-90 and B-91, respectively.390 Another route coupled with cationic ring-opening polymerizations is accomplished for polymer B-92 with the use of a hydroxyl-functionalized initiator with a C—Br terminal, where the OH group initiates the cationic polymerizations of 1,3-dioxepane in the presence of triflic acid.329 Polyethylene oxide)-based block copolymers B-93 are obtained by living anionic polymerization of ethylene oxide and the subsequent transformation of the hydroxyl terminal into a reactive C—Br terminal with 2-bromopropionyl bromide, followed by the copper-catalyzed radical polymerization of styrene.391... 

A number of block copolymers prepared with Ziegler-Natta catalysts have been reported however, in most cases the compositions may include significant amounts of homopolymer. The Ziegler-Natta method appears to be inferior to anionic polymerization for synthesizing carefully tailored block copolymers. Nevertheless, bock copolymers of ethylene and propylene (Eastman Kodak s Pofyallomers) have been commercialized. Unlike the elastomeric random copolymers of ethylene and propylene, these are high-impact plastics exhibiting crystallinity characteristics of both isotactic polypropylene and linear polyethylene. They also contain homopolymers in addition to block copolymers. 

---