18 Chemical Marketing Reporter (Rebranded as ICIS) http://wwwicis.com/chemicals/channel-info-chemicals-a-7/ Monomer Polymer Monomer __| Price Polymer | Price Polymer/Monomer Sib Sib Ethylene 0.46 LLDPE |__0.79 1.717391304 Propylene 0.46 PP 0.68 1.47826087 Styrene 04 PS 08 2 Vinyl chloride 032 PVC 0.55 1.71875 Bisphenol A 0.94 PC 1.35 1.436170213, Monomer, Polymer Prices 15557% Polymer prices, $/lb os +—— 0. {__ ay 0.2 +— mace ° oz o4 os Monomer prices, $/lb | Chapter 2 2-1 Mol. we. (100 A) (weight/molecule) x 6.02 x 1023 = (0%9/6).x 6.02 x 10° g/e-mole 100A) x 108 = 3.15 x 101% g/g-nole (100 A) x 10%8= 3.15 x 10% g/g-nole Mol. We. (1 micron) = Mol, Mol. We. (1 ém) = Wl. 232-2 Possible stereoisomers are: 8) .cis, trans, mixture (because of double bond) b) “Asotectic, syndictactic, atactic (because of -CHCl- group). However, because of distance between -CHC1- groups tacticity is unlikely to influence ability to crystallize unless rest of groups are all eis or trans. Use 1.45 A for c-O=a 108" for C-0-0 =0 15k" " Coad lo* for C-c-0 =a 2-3 Graphical solution is easiest using protractor and ruler. Vector sumation can be used, also. eu; [_—7424 ——__+] If by syndictactic we mean a succession of 4 and 1 monomer units, the distance turns out to be the sane. Another structure ds possible with methyls alternating so that the repeat distance would be doubled. 2-4 = Refer to Table 2-h, Fig. 2-4. -Folyiscbutylene in cyclohexene: = 0.436, Vi = 108, ve = 0.10 WW, = 2.45 x 10°, 90 that W = 2.27 x 10-5 mole/en® Sane in toluene: ‘% =0.557, Vi = 106, Wi = 2.40 x 10°, then vo = 0.21 See, swells to 473 x origina) volume. "2-5 m= p/m, moles/volume = (g/vol)/(g/mole) If M, = Mol.Wt. per repeat unit = 58 for CaHe0 (3 chain atoms) then M, = MoL.We. between cross-Links = 5o08 2 5k B/nole 1.20 x 5 n= 2032, = Leh x 10 mole/en? WV, = 102 x 1.24 x 10° /o.800 = 1.58 xio73 From Fig. 2-4: vz = 0.069 Assume additive volumes. Basis: Total volume = 1 cm 1.0 cx? svev, +¥2= 0.931 + 0.0692-5 (cont'a): total weight/cm® = 0,931 x 0.80 + 0.069 x 1.2 = 0.745 + 0.083 = 0.826 g/en® (sample density) 2-6 Let y = dose, R = cross-link density of lowest dose, GA) sy, y= 1, 2, b, 8, 16 Substitute in Eq. 2-5: = byBva(wai/3 - va/2) = In(Levg) + ve + aX Rearrange to Y = onvx +H where ¥ = (In(1-v2) + v2)/ve? and x = y(vat/® - va/2)/ve® See plot (p. 7). Intercept gives “Xe 0.49, slope sizes eV, = 6.5 x 10+ Therefore, (N/2)ig = + x 10° mole/cu®, 2-7 (a) Si = 1.6i(cos 70° + cos 32° + cos 38° + cos 0°) = 1.6% x 2.978 y = 1.64(sin 70° + sin 32° - sin 38°) = 1.64 x 0.854 L = 1.6% x 3.098 = 5.080 2/2 units, so for 1000 units, HL = 2,500 Zor 254 mm.2-7 (cont'd): (b) X = 1.54008 70.5% cos F) + 1.43(cos 0% cos 6.5% cos 73.5° 2 + cos 67°) 1.54(sin 70.5% sin 3°)~ 1.43(sin 6.5° + sin 73.5° + sin 67°) 5:87, y= 4.38, L = 7.32/2 units For 1000’ units, HL = 366 na 228 xe x = 1.43(cos 72° + cos 2° + cos 70° + cos 0°) = 3.790 £ y = 1.43(sin 72° + sin 2° ~ sin 70°) = 0.066 & L = 3.79 2/2 units, For 1000 units, 5L = 189.5 nm -6-a ooz ive a a ee? pI PSION bnorX X- EW YT a |,0 iartery 5-72 ee ee2-8 2) In planar, zig-cag form, repeat distance is about 0.25 nm for every two chain atoms. Molecular weight per two chain atoms is 12. Length = 2x10 5 0.05 x 10° om = 1.2 x 10°? on ») Votuse = <5 Sosssracale x OE G7 OST = OMT owt * 25.7210? m® = 5.7 x 108 IF 2-9 N=2x (0.1 mol)/1000 cm3 = 0.2 x 10-3 movem3 NV =Nx92.14 gimoV0.867 gicm> = 0.00212 v2= 1435 =0.23 1n(O.77) + 0.23 + 4(0.23) = -0.00212 (0.23) 1/3 - 0.2372) 0.003136 + + 4(0.23)? =-0.001055 So x= 0.002081/(0.23)2 = 0,393 {Nomograph gives = 0.41] New value of v2 = 1/3.45 = 0.29 Using x = 0.39 gives NV = 0.0039 Using x =0.41 gives NV = 0.0037 ‘Thus N/2 = (NV4/2)x(0.867/92.14) 83 x 10-4 crosslinks/em3 Also Amount of sulfur = (28 x 10-3 /32) = 0.875 x 10°3 mols of S/em3 ‘Therefore, each crosslink contains an equal amount of sulfuir ‘The amount of sulfur in each crosslink is = 0.875 x 10°3/1.83 x 10-4 = 4,78 S/crosslink2-10 Case I: Concentration of 0.020 g A/100 gP =c1 v2 = 5/75 = 0.067 1= B+ (VURT\61~- 52)? andsox= B 50.475 ‘Therefore (NV1)1 = 5.8 x 10-4 from equation 2-5 using v2 and x. Case II: Concentration =c2 We want v2 = 5/25 = 0.200 (NV) = 0.85 x 10-2 from equation 2-5 using new v2 and same x . ‘Since V1 does not change, the concentrations used are just proportional to N or NV1: cafe1 = (NVIDIMINV 1) = 0.0085/0.00058 = 14.6 ‘Thus we need 0.020 x 14.6 = 0,29 g of A/100 gP=c? 2-11 Im solvent A: Aq Ba + (a/RT)(8, = 5)? sop, = 0.33 8, = (cp)? = (&)/2 = 9, From Fig. 2-h, if x, = 0.33 at v2 = 0.1, then at v2 = 0.2, Xj mst equal 0.52. That is, (1WV,) = 5.0.x 10" in either solvent. Then %, = 61 + (V/RT)(8, - 8,)* * or 0.52 = 0.33 + (100/600)( 8 - 9.22)" 8,7 222 Lots 8.15 or 10.29. But all lactones (piguee®2-6) have inigh solubility paremeters, so lover value is ruled out. b= 10.29 (cat/en?)2/2 a 2-12 m = 2C where C = mmber of moles of crosslinks a) C= (1) = (0.5/2k2) x 0.97 = 2.0 x 10% moles/en® W = 4.0 x 10% moles of cheins/cn® bv) Wy = 4.0 x 89x 10S =35.56 x10, x = 0.40 Figure 2-4 gives (a =3) ve = 0-105 . Swollen volume = 1/v2 = 9.5 ox® 9b2-13 W = 1.00 mole/(425 x 78) c® = 3.017 x 10°S mole/cn® ‘Vi = 104/0.705 = 162 cm/mole AV, = 4.89 x 10S From Figure 2-4, v2 = 0.175. Swollen volume = 1/ve = 5.71 cx? 2-14 “nS: vq=1/4.55=0220 and %=05 so NV] =8.63x10-3 Eq. or graph) InQ@ 8Q= (29,900 x 0.860/88.0)1/2 = 17.1 (MPa)l/2 InQ = 0.40 + (88.0/0.86)(1/300)(1/8.31)(17.1 -16.0)2 = 0.450 ‘New value of (NV) in Q=(NV1) in S x (Vi(QVV1S)} = 8.63 x10-3x(88.0/0.86/216) So f(NV1)inQ=4.09x10-3 and Eq, or graph gives v2 =0.133 = 1/7.52 ‘That is, the polymer swells in Q to 7,52.times its original (dry) volume. * 15 = 0.300 + [100/(2x300)]17.00 - 8,]* = 0.300 + [100(2x300)1[8.80 — 8,1 So +(7.00 - 6,) = 880 - 5, By = (7.70 + 8.80)/2 = 15.802 =7.90_ - a= Ye = 0.435 Ina: vg= 0.25 So NV; = 2.1 x10 (Using nomograph, Eq. gives = 2.08 x10") Tn CHNV c= 25 (NVA = 52x10 Xe = 0.300 + {250/(2 x 300)\(8.20- 7.90" = 0.3375 Nomograph gives v2 = 0.30 so swollen volume = (1/v2) = S 33 em® 2-16 4 = 043, Vy = MI2S/L.10 = 102 enol mf ef sume em alvin esac ci (oa in cco ese) ‘Concentration of chains = 0.5 x concentration of nitrogen Cone. of nitrogen = (2.10 gfliter)/(14.0 g/ mol of nitrogen) = 0.15 moViiter Cone. of chains =0.15/2= 0.075 mol/liter NV, = (0.075 molfter)x( 102 ca /mol) x(liter/1000 ni) = 7.65 x10 From equation or nomograph, vz = 0.167 = 1/6.00 So 1 cm? swells to 6.0m. -10-2-17 Each PE is a crosslink and corresponds to two chains: Pe. 200 x 58 = 11,600 “N fag oT ~ 1x136= 136 - NO a { 2 2xll0= 120 Pe. ny. Total 11,956 g = 2 mols of chains > e N = (2mols/11,956 g)x1.06 glem® =0.177 x 10° moliem? V, = (92.14 g/mol) (0.862 giom®) = 106.9 om/mol NV, = 189x107, and v2 = 13.57 = 0.280 bi +, (from nomograph or equation) = 0.50 (actually 0.495 from equation) x=B + (VyRTIG, - 82)” 0.495 = 0.300 + [106.9(1.987x300)1[8.90 - 82)" S 0.195x5.576 = 1.087 = [8.90 - 8,]” 8 = 890 £1.04 (but 9.94 is more likely than 7.86 on basis of polarity.) 2-18 =0.48 Calculate NV} from equation 2-5 using known v2: é "Doubly cross-linked” ‘ v2 = 10/55.6 = 0.180 (NV) =6.11 x 103 * "After hydrolysis" : v2 = 10/83.3 = 0.120 QV) =2.13x 103 Mols crosslinks/volume = N/2 (One crosslink for each two chain segments) Covalent crosslinks/Total crosslinks = 2.13/6.11 = 0.349 ‘Therefore, ester bonds were 1.000 - 0.349 = 0,651 of original total. 4Lis2-19 AGget = RIG Ni v2+Niln vi) + B/2)RTEW37? - 1) Ea), -Cae LG, aN, Jam VON ™ AN Jay OMe, tra Blue] © an, [z see Car Need to determine sand : “ AN, Jey, LOM Jew, OM, Jr», uy a(_% \_{_"% _)_ =-~|—4_|- =Vy,= OM, Jey, ON M+, NM +, AAG, oe dem = RT (3 +m, tiny, +N, Q) where Vp is the volume of dry polymer. &y, ey, wy Because of the assumption +v2=1,} >] =—| (= 2 et 3) ‘ ON Joy, OM Jen, Mi i aan ray \. Ee) at n() 2m? 2 Kv? aN, 37 (aM) 3) (My 3 M8 OY where = NJ; +V,= total volume @ Substitution of Eqs. (2) — (4) into Eq. (1) yields: ety, y, =RT[2v) +In(1-v2)+¥% +NVv4"] -aa- avs + aM, tin (I-v)+y, to hoy " y, =RT[ gv} +In(1-v,)+¥, + Ny? ] where N= ¢/Vp is the density of elastic strands in the dry state. aaa, At equilibrium, (——™ Gan rai? =O and Eq, (2.17) Ofte tent is recovered. 2122-20 a) OD on — ae eu Ou a He- ™ ete a, == (4 J fié-m" » m0 * Substitution into Eq. (1) yields Eq. A2.7 of the text: a =) "= qi F a ng! [(alx—m)! <[3-2-20 (continued) b) Taking the natural logarithm of the preceding equation, we get: In Qqq = na(X-1)fIn(2-1) — In] + xnglnx — In ng! + x[]n(n/x)! — In(n/x - ny] Using Sterling’s approximation: Inn! ~nlnn—n and the fact that n= ny + xMg, we get: In Qyq = mG) [In(2-1) — Inn] + xnalnx ng In ng np + x{In(n/x)! — In(ny/x)!] In. Qy¢ = m9(¢-1fln(2-1) — Inn] + xnglnx ng In nz +n + x{(n/x)(Inn — Inx) — n/x — (nny/x)( Inn, ~ Inx) + my/x1] Further algebraic simplifications using n =n, + xnp give: In Qy= n(x = ln (2 1) + ny Inn ny In ny ~ n(x - 1) that can be rewritten as: In Qqq =~ npIn(ny/n) — ngln(ny/n) + g(x 1)In(z— 1) — max - 1) Finally, from Sy=k In Qu, we recover Eq. (A2.9) of the text: % a. Su = -{n In +m In ny +My ny + xm, | k(x=1)ny[In(z -1) -1] -14-2-21 From Eq. (A2.9), setting mz = 0, we get S) =-k{nilnl + 0] + 0= 0; w@ and for nj = 0, we get: S_=—k [0 + ngln(1/x)] + k(x — 1)no[In(z— 1) - 1]. 2) Substitution of Eqs. (A2.9), (1) and (2) into: ASm = Sm—- $1 -S2 gives: ASm= -#[n Initn, in? | kG, [in(e-1)-1] — km,{In(@)] + &— 1) [In - 1) - 1}. This can be rewritten as: ASy=~ A[mln(m/n) + mln(nx/n)] (3) Because x = V/V; , rnin = nyl(anet max) = my Vil Vict ma Va) = v1, and ngxin = my Val(ay Vit ma Vo) = v2. Substitution in Eq. (3) gives the desired result: ASw =~ Minlnvy+ mal») =— R(N Invi+ Nolnv2). 2-22 Use the group contribution method formula: 5=pEF/EM, where p, F) and M; are the density of the polymer, the attraction constant of group i and the molar mass of group i, respectively. For PE, we get: ps = 0.86 g/em?x 135 cal!cm>”/ 14 g = 8.29 cal”cm™” or 16.97 (MPa)'” approx.. 4.7% from experimental value. For PVC, we get: Seve = 1.39 g/em? x (135+60+230) 135 cal!cm*”/ 62.48 g = 9.45 cal!cm™? or 19.34 (MPa)'? approx. 2.3 % from experimental value. -15-