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KINETICS OF POLYMERISATION REACTION

POLYMERISATION
In polymer chemistry, polymerization is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks.[1][2][3] There are many forms of polymerization and different systems exist to categorize them. Introduction In chemical compounds, polymerization occurs via a variety of reaction mechanisms that vary in complexity due to functional groups present in reacting compounds[3] and their inherent steric effects. In more straightforward polymerization, alkenes, which are relatively stable due to bonding between carbon atoms, form polymers through relatively simple radical reactions; in contrast, more complex reactions such as those that involve substitution at the carbonyl group require more complex synthesis due to the way in which reacting molecules polymerize.[3] As alkenes can be formed in somewhat straightforward reaction mechanisms, they form useful compounds such as polyethylene and polyvinyl chloride (PVC) when undergoing radical reactions,[3] which are produced in high tonnages each year[3] due to their usefulness in manufacturing processes of commercial products, such as piping, insulation and packaging. In general, polymers such as PVC are referred to as "homopolymers," as they consist of repeated long chains or structures of the same monomer unit, whereas polymers that consist of more than one molecule are referred to as copolymers (or copolymers).[4] Other monomer units, such as formaldehyde hydrates or simple aldehydes, are able to polymerize themselves at quite low temperatures (ca. 80 C) to form trimers; [3] molecules consisting of 3 monomer units, which can cyclize to form ring cyclic structures, or undergo further reactions to form tetramers,[3] or 4 monomer-unit compounds. Further compounds either being referred to as oligomers[3] in smaller molecules. Generally, because formaldehyde is an exceptionally reactive electrophile it allows nucleophillic addition of hemiacetal intermediates, which are in general shortlived and relatively unstable "mid-stage" compounds that react with other molecules present to form more stable polymeric compounds. Polymerization that is not sufficiently moderated and proceeds at a fast rate can be very hazardous. This phenomenon is known as hazardous polymerization and can cause fires and explosions. Step-growth Step-growth polymerization Step-growth polymers are defined as polymers formed by the stepwise reaction between functional groups of monomers, usually containing heteroatoms such as nitrogen or oxygen. Most step-growth polymers are also classified ascondensation polymers, but not

all step-growth polymers (like polyurethanes formed from isocyanate and alcohol bifunctional monomers) release condensates; in this case, we talk about addition polymers. Step-growth polymers increase in molecular weight at a very slow rate at lower conversions and reach moderately high molecular weights only at very high conversion (i.e., >95%). To alleviate inconsistencies in these naming methods, adjusted definitions for condensation and addition polymers have been developed. A condensation polymer is defined as a polymer that involves loss of small molecules during its synthesis, or contains heteroatoms as part of its backbone chain, or its repeat unit does not contain all the atoms present in the hypothetical monomer to which it can be degraded. Chain-growth Chain-growth polymerization Chain-growth polymerization (or addition polymerization) involves the linking together of molecules incorporating double or triple carbon-carbon bonds. These unsaturated monomers (the identical molecules that make up the polymers) have extra internal bonds that are able to break and link up with other monomers to form a repeating chain, whose backbone typically contains only carbon atoms. Chain-growth polymerization is involved in the manufacture of polymers such as polyethylene, polypropylene, and polyvinyl chloride (PVC). A special case of chaingrowth polymerization leads to living polymerization. In the radical polymerization of ethylene, its bond is broken, and the two electrons rearrange to create a new propagating center like the one that attacked it. The form this propagating center takes depends on the specific type of addition mechanism. There are several mechanisms through which this can be initiated. The free radical mechanism is one of the first methods to be used. Free radicals are very reactive atoms or molecules that have unpaired electrons. Taking the polymerization of ethylene as an example, the free radical mechanism can be divided in to three stages: chain initiation, chain propagation, and chain termination.

Polymerization of ethylene Free radical addition polymerization of ethylene must take place at high temperatures and pressures, approximately 300 C and 2000 atm. While most other free radical polymerizations do not require such extreme temperatures and pressures, they do tend to lack control. One effect of this lack of control is a high degree of branching. Also, as termination occurs randomly, when two chains collide, it is impossible to control the length of individual chains. A newer method of polymerization similar to free radical, but allowing more control involves the Ziegler-Natta catalyst, especially with respect to polymer branching. Other forms of chain growth polymerization include cationic addition polymerization and anionic addition polymerization. While not used to a large extent in 3

industry yet due to stringent reaction conditions such as lack of water and oxygen, these methods provide ways to polymerize some monomers that cannot be polymerized by free radical methods such as polypropylene. Cationic and anionic mechanisms are also more ideally suited for living polymerizations, although free radical living polymerizations have also been developed. Esters of acrylic acid contain a carbon-carbon double bond which is conjugated to an ester group. This allows the possibility of both types of polymerization mechanism. An acrylic ester by itself can undergo chain-growth polymerization to form a homopolymer with a carbon-carbon backbone, such as poly(methyl methacrylate). Also, however, certain acrylic esters can react with diamine monomers by nucleophilic conjugate addition of amine groups to acrylic C=C bonds. In this case the polymerization proceeds by step-growth and the products are poly(beta-amino ester) copolymers, with backbones containing nitrogen (as amine) and oxygen (as ester) as well as carbon.[5]

Polymerization Kinetics Chain Polymerization Process Activated monomer, M*, attacks another monomer and adds to it Resultant species then attacks new monomer and adds, etc. Monomer used up slowly High polymers formed rapidly Average molar mass increased by long reaction times Step Polymerization Any two monomers can link at any time Monomer used quickly

Chain Polymerization Examples ethene, metyl methacrylate and styrene -CH2CHXl + CH2=CHX -> -CH2CHXCH2CHXl Rate of polymerization, v is proportional to the square root of the initiator concentration, v = k[I]1/2[M] Proof: Steps: {Initiation} I -> Rl + Rl v = ki[I] (I= initiator, R = radical) M + Rl -> M1l fast (M=monomer, M1l monmer radical) {Propagation} M + Mn-1l -> Mnl v = kp[M][Ml]

Rate of monomer radical production is determined by initiation step so d[Ml]/dt = 2f ki[I] 4

{2 because 2 radicals produced and f is the fraction of radicals which initiate a chain} {Termination} Mnl + Mml -> Mm+n v = kt[Ml]2 ; d[Ml]/dt = -2kt[Ml]2

Proof (continued) Apply steady state approximation d[Ml]/dt = 2f ki[I] -2kt[Ml]2 = 0 2f ki[I] =2kt[Ml]2 or 2f ki[I] =2kt[Ml] 2 [Ml] = (2f ki[I]/2kt)0.5 = (f ki[I]/kt)0.5 ([I] )0.5

Rate of propagation = - rate of monomer consumption = kp[M][Ml] Rate of monomer consumption=-v = -kp[M] (f ki[I]/kt)0.5 ([I] )0.5 This is same as v = k[I]1/2[M] where k = kp(f ki[I]/kt)0.5

Chain length Kinetic chain length, n, ratio of the number of monomer units consumed per active center in the initiation step Measure of the efficiency of chain propagation n = # of monomer units consumed/#number of active centers n = propagation rate/initiation rate Since initiation rate = termination rate, n =kp[M][Ml]/ -2kt[Ml]2 or n =kp[M]/ 2kt[Ml] But from steady state approximation, [Ml] = (f ki[I]/kt)0.5 ([I] )0.5 so n =kp[M][Ml]/ -2kt[Ml]2 becomes n =kp[M]/ -2kt (f ki[I]/kt)0.5 ([I] )0.5 n =k [M ][I]-0.5 where k = kp/ -2kt (f ki[I]/kt)0.5 ([I] )0.5 The slower the initiation, the greater the kinetic chain length

Average Number of Monomers in a Chain Example Average Number of Monomers in a Chain, <n> depends on termination mechanism

If it is two radicals combining, Mnl + Mml -> Mm+n,<n> is twice the kinetic chain length since two combine to terminate the reaction <n> = 2n = 2k [M ][I]-0.5 If it is disproportionation, Ml + Ml -> M + :M,<n> is the kinetic chain length termination results in two chains <n> = n = k [M ][I]-0.5

Stepwise Polymerization Any monomer can react at any time Proceeds via a condensation reaction in which a small molecule is eliminated in the step Usually water Example polyesters HO-M-COOH + HO-M-COOH -> HO-M-COO-M-COOH Rate (A is COOH) d[A]/dt = -k[OH][A] = k[A]2 {there is one OH for every A} Solution [A] = [A0]/(1 + kt[A0]) Fraction of groups condensed at t is p p = [A0]- [A]/ [A0] = kt [A0]/(1+kt [A0]) <n> = [A0]/[A] = 1/(1-p) = 1 + kt [A0]

Catalysis Catalyst accelerates the reaction Undergoes no change Lowers the activation energy Provides alternate pathway for reaction Homogeneous catalyst is in the same phase as the reaction mixture Heterogeneous catalyst is a different phase In auto catalysis, products accelerate the reaction Example A-> P v= k[A][P] Rate initially slow. As P increases, rate increases. As [A] gets small, reaction slows down Demonstrated by integration of rate law:

Oscillating Reactions Because of autocatalysis, reactants and products may vary periodically

Important in biochemistry Maintain heart rhythm Glycolytic cycle Lotka-Volterra mechanism Steps (1) A + X -> X + X d[A]/dt = -ka[A][X] (2) Y + X -> Y + Y d[X]/dt = -kv[X][Y] (3) Y -> B d[B]/dt = kc[Y] (1) & (2) Autocatalytic Conditions: [A] is constant {steady state condition not approximation} Numerical solution of [X] and [Y] gives periodic variation

Bibliography Books Physical Chemistry -Keith Lailder Physical Chemistry - Atkins Website www.google.com