Mechanisms of polyemerization (Note: Polyethylene falls under the category of chain-growth polymerization) POLYMERIZATION REACTIONS Types of Polymerization Polymerization can proceed according to two different mechanisms, referred to as chain-growth and step-growth polymerization. In chain-growth polymerization (also called addition polymerization) reaction occurs by successive addition of monomer molecules to the reactive end (e.g. a radical end) of a growing polymer chain. The most important group of chain-growth polymerizations is polymerization of vinyl monomers such as ethene, propene, styrene, and vinyl chloride: nCH2= CHX → - (-CH2-CHX)n – in which X = H, CH3, C5H6, or Cl, respectively. An initiator or a catalyst is usually required to start the chain-growth reaction. Step-growth polymerization involves the reaction between the functional groups (HO-, HOOC-, etc.) of any two molecules (either monomers or polymers). By repeated reaction long chains are gradually produced. Most commonly, the reactions are condensation reactions resulting in the elimination of a small molecule like water or methanol. Examples are the production of poly (ethene terephthalate) by reaction of ethene glycol with either terephthalic cid or dimethyl terephthalate (see Scheme 1). Scheme 2 shows the principle reactions taking place when two different functional groups are present on the same molecule (indicated as AB. e.g. in the production of caprolactam), and when two different molecules each contain two identical functional groups (indicated as AA and BB, e.g. in production of PET). O || n HO-C-- O || ___ C-OH + n HO-CH2-CH2-OH → terephthalic acid O || -O-CH2-CH2-O-C- ethene glycol O || -C- + 2n-1 H2O poly-ethene terephthalate O || n H3C-O-C - O || ___ C-O-CH3 + n HO-CH2-CH2-OH → dimethyl terephthalic O || -O-CH2-CH2-O-C- ethene glycol O || -C- + 2n-1 CH3OH poly-ethene terephthalate Scheme 1 Reactions for the production of polyethene terephthalate (PET) In chain-growth polymerization, a high molecular weight product is produced right from the start, while the monomer quantity deceases slowly with time. In contrast, in step-growth polymerization there is a slow increase in average molecular weight of the product. The molecular weight is usually not as high as in chain-growth polymerization, and relatively small amounts of unreacted monomer are present after the start of the reaction. Chain-growth polymerization generally is fast, irreversible, and moderately to highly exothermic. On the other hand, step-growth polymerization is usually slow, equilibrium-limited, and isothermal to slightly exothermic. Polymerization of bifunctional monomer (A,B: two different functional groups): AB + AB → ABAB (or AB)2 ) AB + (AB)2 → (AB)3 AB + (AB)3 → (AB)4 (AB)2 + AB)2 → (AB)4 … (AB)r + (AB)s → (AB)r+s Polymerization of two monomers with different functional groups: AA + BB → AABB AABB + AA → AABBAA AABBAA + BB → AABBAABB AABB + AABB → AABBAABB Scheme 2 Reactions in step-broth polymerization. Mechanisms of Chain-Growth Polymerization Chain-growth polymerization can be classified (in order of commercial importance) as radical, coordination, anionic, or cationic polymerization, depending on the type of initiation. The next two sections will briefly discuss radical and coordination polymerization respectively. Radical polymerization Scheme 3 outlines a typical reaction scheme for radical polymerization. Most radical polymerizations need an initiator to produce the first radical and thus start the chain of addition reactions. The most common initiation reaction is the thermal decomposition of molecules containing weak bonds, e.g. peroxides (-O-O-) or azo compounds (-N=N-). The formed radicals then react with the monomers. Once initiated, a chain will grow by repeated additions of monomer molecules with simultaneous creation of a new radical site. This propagation is very fast, so very long polymer chains will form already in the earliest stage of the reaction. Termination can occur by disproportionation or recombination. Initiation: R-R → R• R• + M →RM1• Propagation: RM1• + M → RM2• ki ≈ 10-4 – 10-6 s-1 (300-350 K) kp ≈ 102 – 104 m3 kmol-1 s-1(300 350 K) RM2• + M → RM3• Etc. RMn-1• + M → RMn• Termination by disproportionation: RMn• + RMn• → RMm= + RMn Termination by recombination: RMm• + RMn• → RMm-MnR Transfer to solvent: RMn• + S → RMn + S• Transfer to monomer: RMn• + M → RMn + RM• Scheme 3 Steps in radical polymerization; M1, Mn, number of monomers in chain. H H | | C–CH2–CH2–CH2–CH2- C • | H CH2 – CH2 H | C H H C | H H | CH2 CH2 H | CH = CH 2 2 C –CH2–CH2–CH2–CH2-CH3 ⎯⎯⎯ ⎯⎯ → • C-CH2-CH2-CH2-CH2-CH3 | CH2 | H–C–H C • Figure 1 Backbiting in the synthesis of LDPE by radical polymerization. In the first case, the final polymers on an average have the same length as the growing chains. Termination occurs by transfer of a hydrogen atom from one of the radicals to the other, leading to unsaturation at one chain end. Recombination results in polymers with on average double the length of the growing chains. Chain transfer is common in many radical polymerization processes. It involves the transfer of the radical end of a growing polymer chain to another species, for instance a monomer or a solvent. Chan transfer reduces the average polymer size and molecular weight. It is possible to add a special agent, a modifier, in order to control the average degree of polymerization. In the production of low-density polyethene (LDPE), side chains are generated by internal chain transfer, in which the end of the chain abstracts a hydrogen atom from an internal –CH2- group, a process termed backbiting. Figure 1 illustrates this process. A branch starts to grow from the internal carbon radical. In this branch, backbiting is also possible resulting in widely branched chains. Backbiting has a significant influence on the structure, and hence, the properties of the final polymer. Coordination polymerization In coordination polymerization, usually transition-metal catalysts are involved. Figure 2 indicates the main features of chain propagation in the coordination polymerization of ethene. A growing polymer chain is coordinatively bound to a metal atom that has another coordinative vacancy (partially empty dorbitals). A new ethene molecule is inserted by the creation of bonds between one of its carbon atoms and the metal and between the other carbon atom and the innermost carbon atom of the existing chain. Branching will not occur through this mechanism since no radicals are involved; the active site of the growing chain is the carbon atom directly bonded to the metal. High density polyethene (HDPE) is produced by this type of polymerization. When higher 1-alkenes are added, the resultant polymer chain will have a few short branches. These are all of the same length since they are simply the rest of the 1-alkene molecule. Figure 3 shows the incorporation of 1-butene in a growing polyethene chain The ethene copolymer known as linear-low-density polyethene (LLDPE) is produced polymerization of ethene and 1-butene or 1-hexane. by coordination The most important catalysts for coordination polymerization are socalled Ziegler-Natta or Ziegler catalysts, and ‘Phillips’ catalysts, both discovered to be effective for alkene polymerization in the 1950s. Ziegler catalysts combine transition-metal compounds such as titanium and vanadium with organometallic compounds. An important property of these catalysts is that they yield stereoregular polymers when higher alkenes are polymerized, e.g. polymerization of propene produces isotactic polypropene with high selectivity. On Ziegler catalysts, the polymer chains grow to a very long length. Therefore, a chain-transfer agent is added to the system. Most commonly H2 is used, which donates a hydrogen atom to terminate and detach the chain from the metal atom. In catalyst systems developed at Phillips Petroleum Co., chromium oxide supported on silica is the most important constituent. Phillips catalysts are less active than Ziegler catalysts, and therefore are limited to the production of polyethene. They produce a polymer with a large molecularweight distribution, with chains varying in molecular weight from 103 to 106 g/mol. It is not surprising that polymerization catalysis draws a lot of attention, and many new systems have been discovered. Even plastic materials that only melt at temperatures of over 770 K (!) can be produced.
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