Modern Polymer Spect..

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3.12 CIS-trans Opening @the Double Bond 139 The question which remained to be answered for inore than a decade was whether the opening of the double bond occurs in cis or trans. The understanding of this reaction mechanism was of fundamental importance for the development of other similar reactions for other classes of materials. One way to solve the problem was to polymerize deuterated derivatives of ethylene with the same Ziegler-Natta catalysts. If cis di-deutero ethylene (monomer A) is polymerized and the opening of the double bond is CIS. the resulting polymer should be rich in the so-called ‘cridzro’ units HH c-c 7 DD c-c-c-c HDDH DHHD a 1 2 If the opening is cis for the case of monomer B (tram-dideuteropolyethylene) the reaction should yield a polymer rich in the so-called ‘threo’ units. DH c-c 7 HD c-c-c-c HHDD DDHH b 1 2 The opposite should occur if the catalyst forces the double bond to open in trans configuration. The polymers were made by chemists, but the identification of the configuration of the deuterium and hydrogen atoms remained unsettled for a long time. The vibrational spectra were recorded, but their interpretation was impossible on the basis of the classical techniques of polymer spectroscopy. An example of the procedure followed in the identification of the spectra is the following. Let the configurations of monomeric units be indicated as follows HD DH HH DD c-c- 7 -c-c- - -c-c- i -c-c- 4 DH HD DD HH I I1 111 IV From the viewpoint of calculations a computer program which generates a sequence of 1-andoni numbers was used in order to generate a random sequence g( 1’)
c 40’ r <strong>Polymer</strong> 8 (100) .? Wave number (cm-’ a Figure 3-24. (a) Calculated density of vibrational slates of polymers A and B with 100 monomeric unit. (b) Observed infrared spectra of poly(ci.v- CHD=CHD) and poly(rrrrris- CHD=CHD). for both chains with 50150 concentration of a and b. The sequence is the following: bbaabbaabbbbaabaaabababa bbbbaabaaabbbabbbbaaabba aaabababbbaabababbbaabaa ababbabbbabbaaababaaaabbb The two cases considered here are: (i) polymer A, generated by replacing a with unit I and b with unit 11; and (ii) polymer B, obtained by replacing a by unit 111 and b by unit IV. Each chain contains 600 atoms. The corresponding GR and FR matrices (of dimension 1800 x 1800) were constructed and NET applied for the calculation of got). The calculated g( v) (Figure 3-24a) compared with the experimental infrared spectra (Figure 3-24b) clearly shows that the calculated g(v)(A) corresponds to
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Modern Polymer Spectroscopy Edited
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Modern Polymer Spectroscopy Edited
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Preface For unfortunate reasons the
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However, theory and calculations yi
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Contents 1 Two-Dimensional Infrared
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Con ten t~ xi Index 5.2 Force Field
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Contributors M. Del Zoppo Dipartime
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1 Two-Dimensional Infrared (2D IR)
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1.2 Brick~qrorrnrl 3 . Figure 1-3.
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1.0 , Figure 1-6. The in-phtrse and
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1.2 Bcrckgroinizd 7 where AA (i~) i
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1.2 Background 9 1.2.5 Two-Dimensio
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1.3 Bnsic Properties of 20 IR Corre
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2D IR spectrometer coupled with a d
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1.5 Applirtrtions 15 Unlike a dispe
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\ '\ Melliyleiie 1'7- -3000 Posiliv
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11 Amorphous Crystalline ,...." I F
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1.5 Applications 21 / I 1430 Figure
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1.5 Appliccitioiis 23 Methylene Fig
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1.5 Ajqdicrrtions 25 3024 Figure 1-
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1.5 Applicutions 27 Furthermore. th
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1.7 Coizclirsions 29 derived in a s
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1.9 References 31 [9] Colthup, N. B
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2 Segmental Mobility of Liquid Crys
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SRMPLE/DETECTOR e3 ‘retardation
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2.4 Srvuc me-Dependenr Alignment 37
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2.5 Electric Field-Innductid Orirnt
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2.5 Electric Field-nclticetl Orient
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a -@ COWER SRHPLE ._ 2.5 Elec tric
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2.5 Electric Field-Itzduced Orienta
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2.5 Electric Field-IwrElrced Orient
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2.5 Electric Field-Im/irced Orientu
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2.5 Electric Field-Induced Orientli
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2.5 Electric Field-Induced Orientat
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2.5 Electric Field-Induced Orienfat
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2.5 Elrc tric Field-Iiidircwl Orim
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2500 2008 I s00 WRVtNdMRtR CM-I Fig
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-3.6 Aligmient OJ' Side- Clinin Liy
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~ polyester 2.6 Alignnient qf Side-
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I." 0.9 0.8 Figure 2-34. FTlR 0.7 p
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induced alignment of the investigat
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2.7 Orientation oj Liquid Ci:i,stal
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2.7 Orieritation of Liquid Ciysttrl
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0 8 18 16 1 a W u z a m a 0 Ln m Q
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2.7 Orientation oj Liquid Crystals
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2.7 Orientation of Liquid Crjvtals
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2.7 Orientatioiz of Liquid Crystals
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2.8 Conclusions 81 strain. As A0 is
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3. I0 Refcreiice.r 83 [I 71 Hoffina
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2.10 References 85 [92] Wiesner, U.
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t Order/Disorder in Chain Molecules
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Page 106 and 107: 3.2 The Dyriamical Case qf Simll ar
Page 108 and 109: 3.2 The Dyrinniical Case of Sinnll
Page 110 and 111: 3.4 S11or.f- and Loizg-Rcrizye Vibr
Page 112 and 113: 3.4 Slzort- and Loiig-Range Vibrati
Page 114 and 115: eyularity), e.g., 2. During the pol
Page 116 and 117: 3.5 Towards Lnrger Molecules: From
Page 118 and 119: 3.5 TOIIYW~ Laiyer Molertiles: Fvoi
Page 120 and 121: 3.5 Towmu" Larger Molecules: F~om O
Page 122 and 123: 1700 - CIO --- ca c 22 _- c 12 l l
Page 124 and 125: 3.6 From Dynamics to Vibrational Sp
Page 126 and 127: 3.6 Froin Dynaiiiics to T’ihratio
Page 128 and 129: 3.7 The Case of Isotactic Polypropy
Page 130 and 131: 3.7 The Cuse of Isotactic Polypvop.
Page 132 and 133: 3.8 Density of Vibrational States a
Page 134 and 135: 3.8 Dtvz.sit,v of L’ihrntioizal S
Page 136 and 137: 3.8 Driisity of Vibratioiid StLitrs
Page 138 and 139: 3 9 Mouiiiq ToIvmds Rerrlitv: From
Page 140 and 141: 3.9 Moving Towards Reality: From Or
Page 142 and 143: 3.9 Moving Towards Reality: Froin O
Page 144 and 145: 3.10 Wlmt Do We Learn from Cnlcailc
Page 146 and 147: + 3.11 A Very Siriiple Ccrse: Latti
Page 148 and 149: 3 I1 A Yey) Siiiiple Case: LLittice
Page 150 and 151: 3.11 A Vq> Siiiiplc Crrw: Luttice D
Page 152 and 153: Figure 3-22. Sample eigenvectors in
Page 156 and 157: 3.13 Defect Modes cis Structtrr.al
Page 158 and 159: 3.13 Defect Mo&s cis Structurcil Pr
Page 160 and 161: 0 3.14 Case Studies N 0 d - Y N o m
Page 162 and 163: 3.14 Case Studies 147 OC 60 58 57.
Page 164 and 165: 3.14 Case Studies 149 GI A V E N U
Page 166 and 167: 3.14 Case Studies 15 1 correspond t
Page 168 and 169: 3.14 Case Studies 153 (I10 + 200) +
Page 170 and 171: 3.14 Case Studies 155 1500 1480 146
Page 172 and 173: 3.14 Case Studies 157 the molecular
Page 174 and 175: 17E (ir 1, R): (iii) z = 4, t = 1,
Page 176 and 177: 3.16 Stnictural Znlioi~zogeneity an
Page 178 and 179: 3.1 7 Fermi Resonancrs 163 stants.
Page 180 and 181: 3.1 7 Femi Resorinnces 165 2 L 1 29
Page 182 and 183: lowing. The CHl-bending mode 6 [cer
Page 184 and 185: 3.17 Ferini Re.sonrriire.s 169 a Fi
Page 186 and 187: 3. I7 Fernii Resoiiances 17 1 terin
Page 188 and 189: 3.18 Band Broadening and Confonnati
Page 190 and 191: 3.18 Bmd Brourleiziriy md Cmforrnat
Page 192 and 193: 3.18 Band Bvoaderiing arid Conjonna
Page 194 and 195: 3.18 Band Broadening and Confornmti
Page 196 and 197: 3.19 A Worked E.utinple 181 pre-mel
Page 198 and 199: 3.19 A Wovh-ecl E.uanzple 183
Page 200 and 201: 3.19 A Worked Example 185 19 5°C 2
Page 202 and 203: 3.19 A Workrd Example 187 Figure 3-
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3.19 A Worked E.rcnniplr 189 LAM I
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3.19 A Worked E.xuniple 191 Figure
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3.19 A Worked E.vnn~yle 193 Figure
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3.19 A Worked E.vnrqde 195 009.1 00
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3.19 A Worked Example 197 existence
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3.1 9 A Worked Example 199 The soli
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3.20 References 201 very important,
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3.20 References 203 [41] M. Gussoni
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3.20 Refeeveiicrs 205 [I 171 P. Jon
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4 Vibrational Spectroscopy of Intac
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4.3 Georrietvy oj Intuct Po1vniev.r
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1'45 4.4 Geometric Chunges I?zditce
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4.4 Geometric Chmges Iiid~lrcecl bj
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4 5 Mer1iodolog.v of Raiii~11 Studi
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4.7 Poly(p-pheiq.lene) 217 with an
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4.7 Pol)~(p-pheiz~~lene) 219 ENERGY
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is worthwhile pointing out that the
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~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 801 Table 4-3
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4.7 Poly(y-phenylene) 225 Figure 4-
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Table 4-4. Observed Raman frequenci
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4.8 Other Polwieys 229 Table 4-5. T
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under various models. According to
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4. I0 Mechnriism oj Charge. Transpo
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4.12 Reftrences 235 [ 131 Kuzmany,
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4.12 References 237 [98j Matsunuma,
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5 Vibrational Spectroscopy of Polyp
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5.2 FOYCC Fields 241 such calculati
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5.2 Force Fields 243 accounts for o
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5.2 Force Fields 245 centers of the
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5.2 Force Fields 247 ture with conf
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5.3 Amide Modes 249 to the nh initi
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5.3 Ainide Modes 251 Table 5-1. Ami
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Table 5-2. Some amide modes of four
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5.3 Amidc Modes 255 Figure 5-1. Opt
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5.4 Polypeptides 257 nonhydrogen-bo
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5.4 Polvpeptida 259 Figure 5-2. Ant
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I 5.4 Polypeptides 261 )I .- + $ 80
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1226M 1222s (1 1165W 1167s (1 1120V
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135s 9 1 Ms1i 122Wbr 147 NH ob(37)
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5.4 Polypeptides 267 glycine residu
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5.4 Polypeptides 269 Raman bands in
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5.4 Polypeptides 271 Figure 5-7. St
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Frequency (cm-'1 100% b 700 500 300
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5.4 Polypptidt~s 215 Table 5-9. Obs
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~~ ~~ ~~~ ~ ~ ~~ 5.4 Polypeptides 2
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5.4 Poliyeptides 219 Table 5-11. Co
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Table 5-12. Aniide mode frequencies
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1351 Lifson, S., Stern, P. S., J. C
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5.6 Refeverices 285 [130] Tiffany,
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Index Amide modes 249 Amorphous pol
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Step-scan FTIR spectroscopy 14,34 -
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