Subject Index

Ab initio method (see MO calculations) . Acceleration, in polymerization

description 8, 9 duration 16, 25, 28, 47 interpretations 25-33, 34, 123, 131, 132 poisons, role in 33, 131

Acetone 173, 174 Acetylene 121, 178, 185, 186, 212

copolymerization 185, 186, 381 poisoning effects 178, 185,212,381,

402 polymerization 185, 402 polymerization mechanism 402, 403

Activated complex chemical structures 379-387 kinetic manifestations 210--213 MO calculations 392-402 steric structures 413-423

Activation energy, of polymerization 52, 71

Active centers concentration 10, 16--18,51,94, 125-

139, 144, 157-159, 180--183, 188-200

measurement methods 116, 117, 157-159, 162-167, 181-183, 188

decay rates 36

direct observations 118-122, 196, 200--205

distribution on activity 16, 353, 354, 356--360

distribution on isospecificity 331-339 fonnation 109-118, 123-125 in homogeneous catalysts 128, 373-377 MO calculations 392-402 poisoning of 128, 155, 156, 157, 178-

188 reactivity stability structure

74-79, 149-153 10, 11,94, 125-128,207-210

chemical 109-118, 122, 373-379 electronic 392-402 steric 413-423

syndiospecific 330, 331 Adsorption

of monomers 210--213, 380--387, 397, 414, 418, 420, 421

of organometallic compounds Ill, 112, 114,117, 130--139, 144-153

of poisons 157-159, 178-188, 212 Aging of catalysts 10, 132, 133, 155-157,

172 AgNO, 244 Al(benzyl)4 299

430

AlBr, 278 AICl,

effect on catalyst activity 127, 128, 205-207, 351, 402

presence in catalysts 9, 98, 105, 109, 127,128,205,207,210,292,294, 374

reactions in catalysts 128, 150, 157, 164, 178, 205, 209

Alcohols effects on polymerization 159-162, 345 organometallic compounds, reactions with

148, 159, 160, 345 transition metal halides, reactions with

160, 161 tritiated, applications 163-167

Al(Decyl), 252 AIEt,

in catalysts 7-9, 11, 12, 15, 17, 20-22, 24-26,28-32,36,37,40,41,43-45, 47, 49, 50, 53, 54, 56, 59, 69, 70, 73, 76, 83, 108, 110, 112, 114, 117,118,120-122,124-127,135, 136, 138-140, 142, 143, 145, 147-160, 162, 167-178, 182-184, 188-191, 193-196,201,203,206,208-210, 227, 228, 239, 252, 273-278, 280-284,286,288-291,295,299, 310,312,326,327,329,331,332, 334-338, 340-342, 344-348, 360, 361,363,364,366,410

deactivation effects 125-127 reactions

with alcohols 148, 159 with catalysts 110-118, 124 with modifiers 108, 170-177 with water 147, 148, 154, 155

reactivity 139, 140, 143, 144, 148, 151-153

AIEt,Br 20, 128, 135, 140, 141, 146,227, 252, 278, 282, 347, 348

AIEtBr, 278 AIEtBrCl 128 AIEt,Cl

in catalysts 1,7,8, 11, 13, 17,20-24, 28,32-34,41,42,45-48,50,51, 53, 54, 56, 58-63, 66, 67, 69, 70, 73, 76, 108-110, 112-116, 120, 121, 123-125, 127-129, 131-136, 139, 140, 142, 143, 145, 146, 150-152,

Subject Index

164, 166, 167, 170, 176, 178-185, 187-194, 196,206,208-210,227, 252,274,275,277,278,282-284, 295,310,312,325,326-329,331-336,347,348, 352, 355, 357-359, 367, 374, 383, 403

deactivation effects of 133, 142 reactions

with catalysts 113, 114, 123 with poisons 157, 159, 169

reactivity 139, 140, 145, 146, 150, 151 Al,Et,Cl, 141-143, 146, 151 AIEtCl, 115,121,127,128,135,141,

142, 145-147, 151, 164, 177,209, 332, 333, 374-376

dismutation of 177, 178 poisoning effect of 141, 145, 146

AIEt,F 140,227,282,331,361 AIEt,1 17,20, 115, 135, 141, 142,145,

227,278,279,282,284 AIEtl, 278 AIEt,OH 142, 147, 148, 155 AIEt,SPh 282 AIEt,SePh 282 AIEt(OEt)Cl 141, 150 AIEt(Oi-Pr)Cl 141, 150 Alfin catalysts 403 Al Hex, 150, 194, 363 Ali-Bu,

in catalysts 11,15,17,19,20,22,25, 28,29,31,38,67,69,70,73,112, 113, 115, 116, 120, 125, 126, 139, 140, 142, 145, 151, 152, 167, 175, 194, 195,209,227,229,276,280, 281, 283, 289, 292, 299-302, 329, 335,337,367,368,383,403

reactivity 140, 145, 151, 152 Ali-Bu,Cl 120, 141, 151, 152, 164,227 Ali-BuCl, 141, 164 Ali-Bu,H 142, 145 Alkylation, of transition metal compounds

in the gas phase III in solution 374 in suspension 112-115

Allene, effect on polymerization 178, 186-188,212,381

Allylmetallic compounds 225 Allyl radical 323 AIMe,

Subject Index

in catalysts 77,84,119,150,189,200, 227,305,389,410,411

reactions 111, 119 reactivity 150

AIMeBr, 178 AIMe,CI 119,146,177,178,374,410,

411 AIMeCI2 146, 177, 178,377 AIMe,I 282, 335, 378, 410, 411 AIMeI, 178 Aln-Bu, 150, 194 Aln-Pr3 140 AIOct, 49,192, 195,292,358 AIPh, 140, 378 a-TiC I, (see TiCI" a-fonn) Alumina (AI20,), as support 105, 106,

199, 292, 295 Aluminoxanes 142, 147, 148, 155,374,

377 Aluminum alkoxides

effect on polymerization 141, 142, 148-150, 159, 160, 168, 169, 171, 173, 345

fonnation 159, 168, 171, 174,345 sterically hindered 171, 345

Aluminum amides 176, 177 Amines

as co-catalysts 164, 165, 192 modification of catalysts 173, 175-177,

291,340 reactions 17 6-178

Anionic polymerization 11, 71, 80, 87 Anisole 424 Antibonding orbitals, in ole fins 380, 381,

393-396, 398, 402 Aromatic acid esters

as catalyst components 107, 108, 118, 121, 122, 170-172,292,294,301, 340, 342, 344, 345

reactions with organometallic compounds 171, 172

Asymmetric carbon atoms in polymer chains 222, 295-306, 412 in side groups 295-306

Atactic polyolefins 223, 323, 324, 377 Atom-atom potential method 421

BaCl, 294 BBr, 278

Benzene 3,4 Berillium alkyls

in catalysts 17,20,22,23,25, 115, 139, 140,280,281

Bemulli chains 263 r3-TiCI, (see TiCI" r3-fonn) BET method 100, 102, 103, 196,206 Bipyramidal structure, of active centers

386, 394--400 Block-copolymerization 54-61

conditions 55, 56, 59, 60 kinetic features 56-58 monomer reactivity in 61-63

Block-copolymers conditions of formation 55, 56 fractionation 58, 59 NMR spectra 60, 61 structure 54-56, 60

431

Bonding orbitals, in olefins 380, 381, 393, 402,403

Butadiene 55 I-Butene

copolymerization 55, 67 polymerization 14,50,51,122,194,

229, 410 reactivity 67,70,73,76,78,81,82,

85-87 2-Butenes 229

Cadmium alkyls 115, 135, 280 Carbenes 378 Carbon dioxide

effects in polymerization 178-183, 358, 359,381,382

insertion into M-C bonds 180, 381 labeled, applications 180, 181

Carbon disulfide 183-185 Carbon monoxide

effects, in polymerization 178-183, 358, 381, 382

insertion into the Mn-C bond 210, 211, 380

insertion into the Ti-C bond 180, 182, 381

labeled, applications 180, 181 Catalysts, Ziegler-Natta

composition 96-99, 105-109 grinding 26,99-105, 196-200,290 monometallic 110

432

Catalysts, Ziegler-Natta (cont.)

preformed 32, 33 reactivity 139-142 soluble 347, 348, 360, 374-378 structure 96-99 supported, for ethylene polymerization

105-107 supported, for propylene polymerization

107-109, 118, 339-346 surface

measurement methods 100--102 structure 98, 99, 200--205

syndiospecific 331,348,391,424 Cationic polymerization 71, 226, 239, 307,

323,337,424 CdCI, 96, 294 Chain and control mechanism 250, 251,

253, 261-264, 269, 270, 306-308, 310

Chain initiation reactions 15, 16, 27-30, 34,37,116,123

Chain propagation reactions 16, 34, 61-72, 225

Chain transfer (termination) reactions 34 with hydrogen 24, 225 with monomer 15, 17, 34, 53, 225 with organometallic compounds 15, 17,

23-25,34,53,116,163,167,225 spontaneous 17, 24, 116, 134, 389

Chirality, of active centers 300, 306, 405, 412,417,418,423,425

Chromium-containing catalysts 96, 97, 109,252,274-276,294,351,423

isospecificityof 252, 274, 275, 276, 279, 294,423

Cis-opening of the double bond 390--392, 402, 422

CoCl, 294, 295 Concentration

of active centers (see Active centers, concentration)

estimations 2, 3 of monomer 5, 14 reaction kinetic order on 14, 15, 25,

211-213 Coordination-anionic mechanism 223, 394,

424,425 Coordination, of monomers 210--213, 380--

388, 393, 395-397, 403 Copolymerization

consecutive 61-63

statistical 360--368 kinetics 63-67 statistics 264-270

Subject Index

stereoregularity in 265-270, 306-314 Copolymers, ethylene-propylene 307-313 COS 183 Cresol, p- 118, 121 Cyclohexane 3 Cyclopentadienyl titanium compounds 128,

295,374-377,389 Cyclopolymerization 228, 229 Cyclotron resonance drift 379

Dative bonds 381, 382 Deactivation of catalysts

kinetic features 9, 33-38, 115, 117, 118 mechanisms 118, 122, 125-128,207-

210 Decalin 4, 41 I-Decene 33, 73, 82, 83, 85 Defects

on catalyst surface 130, 201-203 in polymer chains

chemical 226-228 effects on infrared spectra 240--242 effects on melting points 248, 249 steric, in polymer chains 249-253

8-TiCI3 (see TiCI" 8-form) Deuterium-containing monomers 119, 234,

239,252,310,311,379,390--392 Dichlorobenzene 3-5 Dienes (see Diolefins) Diffusion of monomers

effects on molecular weight distribution 349-351

effects on polymerization kinetics 1, 94, 95, 208, 209

3,3'-dimethyl-I-butene 84,86 3,7 -dimethy I-I-octene 296, 298, 300--302,

305 Diolefins (dienes)

conjugated 8, 55, 350, 424 non-conjugated 228, 229

Dissociation energy, of the Ti-C bond 374, 388

Distribution, of active centers 16, 51, 322-368

Distribution of monomer units in copolymers

Subject Index

experimental data 306-314 statistics 264--270

of propagation rate constants 16. 40. 351-360

Double bonds. in ole fins 223-226, 323 position, in coordination stage 383-387.

414. 416-423

Effective rate constant 2 Electron donors, effects in polymerization

108, 109, 177, 178 Electronic effects, on monomer reactivity

79-84,87 Electron microphotography

of catalyst surface 98, 99 of growing polymers 200-205

Electron spin resonance, of catalysts 103, 104. 107. 108, 118, 120-122,375

Enantiomorphous statistical model 249-253, 256-261, 265-269, 330

Epimerized polyolefins 234, 235, 238, 264 Equilibrium effects, in catalyst functioning

130, 131, 143-145 Esters

effects on polymerization 170-173, 252, 291,292,294,295,334.336,340, 342,344

reactions with organometallic compounds 171, 172

Ethers, effects on polymerization 174, 175, 291

Ethyl acetate 172, 173 Ethyl anisate 172, 340, 342 Ethyl benzoate 40, 118, 121, 170-172.

193,227,273,295,340-342,344 Ethylcellosolve 360 Ethylcyclohexenes 229 Ethylene

block-copolymers of 55-61 catalysts for polymerization 105-107,

374-377 copolymerization of 63,73. 115, 116.

297,307-313,323,361-368.413 deuterated 228, 379, 390 isolated units, in copolymers 297, 307-

310 monomer unit distribution, in copolymers

310-314 polymerization of 2, 5, 9, II, 14, 20-

22,34,40,49,112,115,377

433

reactivity 63,69,71-73,76-79,81-87 solubility 3

Ethylidenecyclohexane 229 3-ethyl-I-pentene 86

FeCI) 96, 274, 276, 294 Flory distribution 347. 356 Flory equation 248, 324, 326 Formation, of acti ve centers

in gas phase systems 111, 112 in supported catalysts 106, 107 in suspension catalysts 112-118

Fractionation of block-copolymers 58, 59 of polyolefins 322-339 of statistical copolymers 360-368

Gallium alkyls. in catalysts 115, 280. 330, 331

"1-TiCI, (see TiCI,. "I-form) Gas phase polymerization 59 Gel-effect 362 Gel permeation chromatography 3, 5. 347 Grinding. of catalysts

effect on isospecificity 290. 291 effect on kinetics and reactivity 26. 196-

200 effects on S" 99-105

Growing polymer chains in block-copolymerization 54-58 kinetic effects 39-43,51-54. 74-79

Hammett parameter (a) 74, 75, 80 Hartree-Fock method 388, 392 HCI

effect on polymerization 167, 168 role in catalyst formation 106

"Head to head" chain growth (see Inversion of monomer units)

"Head to tail" chain growth 223, 225, 226 Heat of fusion 249 Helices

of isotactic polymers 221, 223. 224, 307, 3 10, 3 1 I, 3 13

role in stereoregulation 307, 310 Hemi-alkoxides 148, 149. 159, 162

434

Henry constants 3 Henry law 3 1,5-Heptadiene, polymerization 229 I-Heptene 73, 82, 85 Heterotactic triad, definition 231 Hexa-coordinated centers 383-386, 392-

396 1,5-Hexadiene 228, 229 Hexamethylphosphorous triamide 177 ,

178, 332, 333 I-Hexene

copolymers of 312-314,367 polymerization 14, 20, 194 reactivity 73, 81-83, 85

2-Hexene 229 Homolytic bond dissociation 390 H2S 170 Hydrogen, as chain transfer agent 24, 25,

119, 225, 335, 349, 355, 357

Induction periods, in polymerization 28, 33, 123, 154, 155

Infrared spectra in catalyst studies 118-120, 171 of copolymers 185,310-312,314,323 of poly-I-butene 240, 246, 259 of polyethylenes 390, 391 of poly-3-methyl-I-butene 246, 247, 259 of poly-4-methyl-l-pentene 228,247,

248,259 of polypropylene 226, 240, 242-246,

259, 329, 336 of polystyrene 240, 248, 259 stereoregularity measurements with 242,

244-248 of stereoregular polymers 240-242

Initiation reactions (see Chain initiation reactions)

Insertion reactions of acetylene 185, 186,403 of carbon monoxide 180-182,210,211,

380 of olefins 210, 212, 380, 387-389

Intrinsic viscosity 3, 11, 21 Inversion, of monomer units 226-228,

253,310,331 Isobutene 115, 116, 350 Isomerization

of double bonds 228, 229

Subject Index

of monomer units 225, 226, 228, 229 Isoprene 8, 15, 55 Isotactic index 331,334,340,341,343-

346 Isotactic polyolefins 221-223 Isotactic triads, definition 230 Isotope effects 166

Kinetics of active center decay 9, 207-210 of ester-AIR, interaction 171, 172 of polymerization 5-38

Labeled compounds 1 10 I3C,I'C-containing 110,114,116,117,

180-182, 189, 191, 192,210,235, 303, 304, 308, 309, 375-378, 410

deuterium-containing 112, 119, 228, 232, 234, 238, 252, 310, 311, 379, 390-392

tritium-containing 163-167, 189-193 Langmuir adsorption equation 130, 144,

179, 187 Langmuir-Hinshelwood kinetics 212,351 Laplace method 353 Lattice defects, in catalysts 105, 120 Lattices, of MX, 96-98 Laue-Scherrer equation 100 Lennard-Jones potential 416 Lewis bases 346, 359 Lithium alkyls, in catalysts 115,331,348 Living chains, of polyolefins 11, 43, 45

Magnesium alkyls 280 Magnesium chloride, as support 72, 107,

118, 121,252,292,294,295,299, 300, 302, 340

Magnesium derivatives, as supports 105, 106, 190, 193,292-294,358

Mark-Houwink equation 3, 5 parameters of 4

Markoff chains 256, 257, 264 Mean lifetime of chain growth (L) 51-54 Melting points, of polyolefins 248, 249,

259, 324-326, 328, 332 Mentyl anisate 301, 302 Meso-dyads 230, 231

Subject Index

Metal-polymer bonds 163, 165-167 Methyl acetate 295 3-Methyl-I-butene

copolymerization of 67, 73, 413 polymerization 14, 117, 226 polymers, characterization 246, 247 reactivity 70, 73, 76, 77-79, 82, 84-86

5-Methyl-I-heptene 298 4-Methyl-I-hexene 83,85,296,298-300,

302, 305, 368 5-Methyl-I-hexene 83,85 Methyl methacrylate 171 3-Methyl-I-pentene 83-85,296,301,303-

305 4-Methyl-I-pentene

copolymerization of 73,312-315,367, 413

polymerization 7,8, II, 14,20,47,48, 167, 175, 194,337

polymers, characterization 247,248,259 reactivity 20, 33, 70, 76, 79, 81, 83, 85

Methyl-p-toluate 118, 173,340,344 Methyl styrene 116, 195 MeTiCI, 33, 119, 123,379,386,388 Michaelis-Menten kinetics 211, 400 MnCI, 227, 294, 295 Molecular orbital (MO) calculations

ab initio method 392, 396-400, 402 CNDO method 394-396 for crystal lattices 400-402 semi-empirical methods 392-394

Molecular weight distributions 21 effects of

active center inhomogeneity 351-360 hydrogen 355, 357 reaction time 356--358

measurement methods 3, 5 Molecular weight of polymers

change, in polymerization reactions 9, 11-13, 15,39-51

control, by hydrogen 24, 25, 225, 335, 349, 355, 357

equilibrium, in polymerization II, 18, 19

measurement methods 3-5 number average 3, 347 organometallic compounds, effects on

18-25, 34 viscosimetric average 3 weight average 3, 347

NEt, (see Triethylamine) NiCI, 294 Nuclear magnetic resonance spectra

I3C-NMR of copolymers 387 of ethylene-propylene copolymers

308-310,312,313 of model hydrocarbons 407, 408

435

of poly-I-butene 236, 238, 410, 411 of poly-3-methyl-I-pentene 303-306,

387 of polypropylene 225, 235-237, 250-

252,262,264,325-327,330,336, 407, 409--411

of polystyrene 236, 238-240 of soluble catalysts 374-377 stereoregularity measurements with

235, 236, 239, 240 'H-NMR, stereoregularity"measurements

with 232-238, 330 Number of active centers (see Active cen­

ters, concentration)

I-Octadecene 82, 83, 85, 229 Octenes 229 Oletins

branched, reactivity 73, 79-87 ionization potentials of 82, 83 linear II, 73, 81-87, 228, 229 substituents in, effects on reactivity 72-

87 Organometallic compounds

dissociation, in solution 23, 24, 130, 131,146,147

effects of polymerization 14, 15, 17,21, 23,24,37,340-343,389,390

reactions 146--148, 152, 159, 167, 168, 170, 171, 174, 176--178, 180, 183, 210,211

Oxygen, effect on polymerization 168-170

Particles, of catalysts, structure 98-100, 198, 199

Penta-coordinated centers 386, 394--400 I-Pentene 8, 14,78,82,85, 122 Phenylacetylene 377 Phenyldimethyl carbinol 345

436

Phenyl group, substituted, effect on olefin reactivity 79, 80, 87

'IT-complexes, of olefins 380--383, 386, 387 Piperidine 291 Poisons, of active centers

effects on polymerization 153, 154 reactions

with active centers 155-159, 163, 178-188

with organometallic compounds 147, 148, 154, 159, 167-170, .174, 176-178

with transition metal compounds 155, 160, 175

types of 153, 154 Polyallomers (see Block-copolymers) Poly-I-butene 2,50,51,199,251,279

13C-NMR spectra 236, 238, 251 infrared spectra 240, 246, 259 molecular weight measurement 3, 4 stereoregularity measurements 236, 246

Poly-3,7-dimethyl-I-octene 296,300 Polyethylene 59, 60, 199, 249

catalysts for synthesis 105-107 molecular weight distribution 347-349,

357, 358 molecular weight measurements 3, 4

Polymerization centers (see Active centers) Polymerization degree (v) 16, 18, 19,23,

39,41,43-54 Polymerization rate, definition 2 Polymerization reaction, conditions 2, 5 Poly-3-methyl-l-butene 226,246,247,276 Poly-4-methyl-I-hexene 296, 300 Poly-3-methyl-I-pentene 297, 299, 303 Poly-4-methyl-I-pentene 4, 199,228,247,

248,337,403,416 Poly-I-octene 226 Poly-I-pentene 226 Polypropylene 59,60, 199

atactic 264, 323, 324, 331, 335, 336, 377

catalysts for synthesis 107-109, 118, 121,122,170,292-295

chemical structure 225-228 fractionation 322-331 infrared spectra 226, 240, 242-246,

262, 329, 330, 391 insoluble fractions, stereoregularity of

271-295, 325-330, 332, 335

Subject Index

isotactic index 331, 334, 340, 341, 343-346

Lewis acids, effects on 340--346 melting point of 249, 279, 324, 326 molecular weight distribution 347-349,

352-360 molecular weight measurement 3, 4 NMR spectra 232-235,237,251-253,

262, 264, 325-327, 330, 336, 410 soluble fractions, structure of 227, 323,

325,327,328,330,331,335-337 stereoregularity distribution 322-339 stereoregularity measurements 234, 235,

242, 244-246 steric purity 249-252, 271-273, 279 steric structure 222, 223, 232, 264 syndiotactic 222, 330, 331

Polystyrene 164, 199,249,323,337,416 atactic 5, 323 infrared spectra 240, 248, 259 molecular weight measurement 3,4 NMR spectra 236, 238-240 solubility 3

Propagation reactions (see Chain propagation reactions)

Propylene block-copolymers of 55-63 catalysts for polymerization 107-109,

118,121,122,170,292-295 copolymerization 61-67,73,307-313,

323, 361-366 deutero-substituted 232, 234, 235, 252,

310,311,391 polymerization of 5,7,8, 10-12, 14,

19-23, 25, 33, 34, 36, 37, 38, 40, 41-44,46-48,52,377,383

reactivity 33,63,67,69,72-87 solubility 3, 23

Proton magnetic resonance (see Nuclear magnetic resonance spectra)

Pyridine 20,25, 178,283,291,329,335

Racemic diad 230 Radical polymerization II, 307, 323, 424 Rate-determining step, in polymerization re-

actions 210--213 Reactivity ratios

in copolymerization (r" r 2) 64, 73-81,

Subject Index

266,270,301,311,312,314,362, 363,413

in stereoselection 297-299, 305 Reduction

of active centers 122, 374 of transition metal halides 110-112,

115,116 Riedel kinetics 212,351

ScCI3 110 Secondary monomer insertion 228 SeOCl, 170 Silica, as support 105, 106, 292, 294, 295 Soluble catalysts, for olefin polymerization

47, 73, 128, 347, 348, 360, 374-377,403

co-catalysts for 128, 374 molecular weight distribution, of polyole­

fins 347, 348 polymei-ization mechanism with 374-378

Solubility, of olefins 2, 3, 23 Solvents

for molecular weight measurements 3-5 for polymerization 2

Specific polymerization rate, yield (defini­tions) 2

Specific surface area, of catalysts 95, 98-109, 113, 125, 205-207

effects on catalyst activity 196-199, 205,206

effects on grinding on 102-105 measurement methods 100-102, 206

Spontaneous chain termination reaction (see

Chain termination reactions) SrCI2 294 Stability, of active centers I, 10, 207-210 Stationary polymerization 7,8, 10, 13,

14-25 duration 10 kinetics of 16-25 temperature effects on 10, 11

Statistics of copolymer chains 264-270 stereochemical, of homopolymers 253-

264 Stereochemical control

in copolymerization 306-310 mechanism 249-253, 256

437

in stereoselective polymerization 295-306

Stereoselective polymerization 300-303 Stereoregularity, of polyolefins

definition 221-223 measurement methods 232-240, 242-

249 Stereoselective polymerization 296-300,

303-306 Stereosequences 229-231 Stereospecificity, of Ziegler-Natta catalysts

definitions 271-273 distribution of active centers on 322-346 effects on

of modifiers 289, 290, 291, 292 of organometallic compounds 279-283 of supports 292-295 of temperature 283-289 of transition metal halides 273-279

Steric effects, in olefin reactivity 79-87 Stereoregularity ratios (R) 254, 256, 261,

265, 269, 272, 286, 287 Stop-flow method 49 Styrene

copolymerization of 73,323,367,368, 413

polymerization of 8, 9, 11, 15, 20, 45, 55,116,117,122,195,383,424

reactivity 20,70,71,74,75,79,81,83 Styrenes, substituted 79,80, 116, 195,

212,367,424 Supported catalysts 9

activity 70, 72 co-catalysts for 106, 108, 109, 170, 171 for ethylene polymerization 40, 105-

107,292 for propylene polymerization 47, 107-

109,118,121,122,252,293-295, 339-346

synthesis 106-109 Supports, for polymerization catalysts

effects on activity 199, 200 synthesis 105-109 types 105-109, 293-295

Syndiospecific polymerization 222, 391, 424

Syndiotactic triads 231, 232

Tacticity function 261, 293

438

Taft equation 84 Taft parameters (cr*, EJ 77, 78, 80, 82-86 Temperature effects, in polymerization 10,

11,71,125,283-289,382 Ternary carbon atoms 222 Tetracyanoethylene 185 Tetralin 4, 53 Thiele modulus 95, 209 Thiourea 291 Ti(acac)2CI2 403 Ti(Benzyl)4 299 TiBr, 277-279, 423 TiCI, 28,69,110,164,190,199,227,

252, 274, 277 TiCI,

a-form 1,7-9, 12, 15,20--23,25,26, 28, 30--32, 34, 37, 43, 45, 53, 54, 56, 59, 69, 96-99, 102, 103, 105, 110--112, 114, 120, 123-125, 127, 130, 137, 139, 140, 143, 147-150, 154-158, 160, 162-165, 167, 169, 172, 173, 183, 189, 195-198,200--203,205-207; 227, 274, 276-281, 283,284,286,288,290,310,329, 331, 332, 334, 335, 337, 367

!)-form 97,98, 102, 105, 109, 119, 120, 123, 127, 133, 134, 140, 151, 152, 170, 189, 197,227,252,274-277, 292, 326, 327, 332-334

a-form 1,7-9,11,13,20--24,27,32-34,36,37,41,42,44-51,53,54, 56,58--63,66,67,69,70,84,96-99, 102-104, 108, 109, 115, 118, 120, 121, 124, 125, 127, 128, 131-133,135,138-140,146, 150, 151, 162, 164, 166, 167, 169, 170, 174-176, 178-185, 187-189, 191, 192, 194-199,205,207-209,227,252, 274-278, 283, 284, 291, 295, 299, 300,303,305,310,312,325,326, 328,329,332,334-337,340,348, 352,355,357, 358, 367, 378,410, 411

"i-form 20, 22, 24, 69, 96-98, 102-105, 189,205

TiCI4 8,17,49,54,105-109,118-121, 129, 134, 162, 170, 182, 186, 190, 199,227-229,239,252,274-276, 289, 292, 294, 340, 348, 368, 403

TiCI,I 279

Subject Index

TiCI4/MgCI, 33,40,47,70,72,83, 121, 171, 172, 182, 193, 198,209,227, 252, 273, 292, 295, 299, 300, 302, 326, 327, 332, 334, 336, 338

TiCIiMnCl, 227,252,295 TiCl/Mg(OEt), 40, 49, 358 TiI, 277-279, 410 Titanium alkoxides 105, 227, 295, 348,

361 Titanium chlorides

activity in polymerization 109, 205-207 catalysts with 98, 99, 205-207 elementary cell parameters 96, 97 grinding of 99-105, 196, 197 modifications 96-98, 196-199, 205-207

Titanium tetrabenzyl 295 Toluene 4 Transfer reactions (see Chain transfer

reactions) Transition metals, in catalysts 96,97, 105,

273-279 effect on stereospecificity 273-283

1,2,4-Trichlorobenzene 3,4 Triethylmine 164, 165, 173, 175, 192,291 Trigonal bipyramidal centers 386, 394-

400, 415 2,4,6-Trimethylheptane 407,408,410 2,4,6-Trimethylnonane 407 2,4,6-Trimethyloctane 407, 408, 410 Triplet instability, of the Ti-C bond 388 Tung function 349

Universal calibration principle, in GPC 5 Urea, derivatives 291, 335

V(acac)3 47,227,348,360,363,383 Vacancies, at transition metal atoms ~83-

386, 394, 415, 419, 420, 422 VBr3 277,278 VCI, 115, 125, 282 VCl3 11, 14, 15, 19, 20, 22, 25, 26, 28,

29,31, 33, 37, 38, 96, 110, 113, 115, 116, 119, 123, 125-127, 130, 137, 162, 164, 167, 175, 194, 195, 199, 200, 208, 209, 227, 228, 252, 275-277,280,283,284,286,288, 326,327,331-333,335,360,361, 363, 364, 366, 383, 410

Subject Index

VCl4 70, 105,227,228,252,282,289, 292,331,336,348,363

Vinyl acetate 171 Vinylcyclohexane

copolymerization 66,67,73,413 polymerization 8, 15, 25, 194, 229 reactivity 73, 76-79, 83-85

Vinyl double bonds 225, 323 Vinylene double bonds 225, 226, 323 Vinylidene double bonds 225, 323 Vinyl naphthalene 83 Viscosimetric average molecular weight (see

Molecular weight) VOCI3 1, 105, 186,227,228,289,363 VO(OR)3 105

Water effects on polymerization 147, 148,

154-159 reactions with organometallic compounds

147, 148 Wesslau function 348, 349

W-C, W-H bonds, insertion in 380

X-ray methods, for surface area measure­ments 100, 101, 197,206

439

Yields (Q), in polymerization reactions 2, 6,31,32,37

Zero-order reaction kinetics 15, 383 Zink alkyls 20, 22, 24, 25, 84, 110, 115,

135, 137, 139, 140, 142, 143, 145, 152,227,280,281,303,305,336, 378, 410, 411

efect on catalyst activity 24 effect on polymer molecular weight 24,

280, 303, 410 effect on stereoelectivity 300 hydrolysis 148, 303, 304

Zirconium tetrabenzyl 403 ZrCI4 252