Subject Index978-1-4612-5084...Berillium alkyls in catalysts 17,20,22,23,25, 115, 139, 140,280,281...
Transcript of Subject Index978-1-4612-5084...Berillium alkyls in catalysts 17,20,22,23,25, 115, 139, 140,280,281...
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