LA (a) All monomers are diftnetional except for pentaerythritol and diallyl isophthalate which are tetrafunctional, This includes phthalic anhydride and the functionality of this monomer can be understood by considering that phthalic anhydvide effectively acts as a diacid. (b) the monomer's structures for the difuactional monomers are reported below, together with the corresponding polymer repeat unit. Monomer’ Polymer repeat unit Hyc=cE-cH Sacare—cHr isoprene © Polyisoprene” g g wo Lense on ~ no-enycon — Cerne oreryeo- hexanedioic acid + 1,10-decamethylene glycol a BANCH)AH, + ACOKCH.Coa o 9 pentametiylenediamine + heptanedioy! chloride —#N(CHISSE CCH a yO GH YC-CB- Co0csHis COOCsS ethyl acrylate avy Poly(ethyl acrylate) ‘The seaction between pentaerythritol and phthalic anhydride: ° iRoR S rong cmon OY leads to a complex polymeric structure, as a result of the tetrafnctionality of pentaerythritol. As shown below, linear postions of chains are possible as well as branching: ” ; This is the polymer resulting from the 1,4 polymerization but other structures are ‘possible (see example 3.1)12 13 ” Furthermore, reactions between the two acid groups phthalic anhydride and two of the hydroxyl groups of pentaerythritol causes chain termination. ‘Similarly, diallylisophthalate is a tetrafunctional monomer and free radical polymerization produces a network stnueture tore, Gh oe on Ch te garg (©) Structures (D, (IV) and (VD) will polymerize via a chain growth mechanism but for all other polymer structures polymerization will proceed by step-growth, Glycerol is a trifuctional monomer, 1.4-butancdiol is difunctional and butanol ‘monofuetional. Reaction of adipic acid with the latter will not lead to a polymer chain, since a minimum functionality of two is required. The trifunctional monomer will generate ‘a network structure when seacting with adipic acid. Condensation reaction between adipic acid and 1 4-butanediol, with elimination of water gives the linear structure: —€-(cr i d-0-(CH YO Both monomers are difimstional and have two different functional groups at each end, Reaction of monomer 1 gives the polyester: g g HO-(CH)s¢-08 ——- —o-(cHy)gs¢— + 0 om‘Whereas for monomer 2 a polyamide is formed: mycHjct-on = ——— —Raay,d— + no wm The two polymers differ in the nature of the functional groups. Polymer (VII) is polar and dipole-dipole interactions are active between chains. The strength of the intermolecular forces is greater for polymer (VIID as hydrogen bonding between —NH— and —CO— ‘2toups is possible, The melting point of polymer (VIM) is therefore expect to be higher than that of structure (VID. 1.4 The mumber average molar mass y s defined by: =, “EN, (M), =nM, oO where Ny is the number of molecules of species i of molar mass Mj. By considering that LN, represents the total mumber of molecules, (Mf), can be defined in terms of the mole fraction, x, Similarly, the weight average molar mass (4 ,is given by: A ENME Ew, =NM, Dw, where wv; is the weight of molecules of species i of molar mass Mj. Since cach a, @ termw, | E.w,represents a weight fraction. a. equation (2) ean be rewritten as: rN M? _INM, Values required for the calculation are tabulated below: M. =2aM, @) ™ | Mi w Mi @ aM, 0.083 | 10000 oss 5300 0.152 1523 0.035 | so000 03s 17500] 0.50 asia 0.012 | 100000 012 12000] 0.345 34ass 34800 | (M), = EoM, = | 1148 The polydispersity is: 4), 61149 (MD), 34800 1.76 @LS The IUPAC names are listed below: Polymer repeat unit TUPAC name @) tor-cHs), Poly(I-decyl ethylene) ‘Ee ) {o-gH-cHy}, Poly[oxy(1-bromoethylene)] Be © fo-cascrsh Poly(oxyethylene) @ Auxcorcx),conuica),)__ Poly(iminoadipoyliminchexane-1,6-diyl) 1.6 The corresponding IUPAC names are (a) poly(-hydroxyethylene) for Elvanol® (b) poly(imino-p-phenyleneimino= terephthaloyl) for Kevlar and (©) poly[(S.7edinydro =1.3,5,7etetraoxobenzo[1.2c: 4.S-c'ldipyrole -2.6(1H.3H)-diyl) pe phenyleneoxy -p-phenylene] for Kapton. 1.7 The number average molar mass , has been defined as: ==" =N, E(w, /M,) where N; and w, are the number and the mass of molecules of species / of malar mass Mj. Oo, 3 ‘Since in this ease values of mass are given, the expression on the right hand of equation (5) gives a direct route for ealeulating (M),. As for the weight average molar mass (4f), this is expressed as: -ENMG EM, NM, Dw, ‘Values required for the calculation are (The M, values tabulated corresponds to the mide OM), co) mange)Mi, we eo wi, 40000 | 0.040 1.00 1600 0000 | 0.160 2.00 12800 120000] 0.360 3.00 43200 160000] 0.720 4.50 115200 200000] 0.440 20 88000 240000) 0.228, 095 54720 280000) 0.140 0.0 39200 Dw, =2.088 | EN, = 14.1510" | Dw, = 354720 The mumber average molas mass is then: And the weight average The polydispersity is: The distribution, expressed as number fraction versus M; is shown in the figure below. co) ° 03 Number fraction Ma My 0.0 ° 40000 80000 120000 160000 200000 240000 280000 Molar Mass 0