Index

A
Acetyl (CH3C) groups, 11
Activation energies of PLA, 129t
Aliphatic polyesters, 34
41
Amorphous-made PLA films,
characteristics of, 258t
Analytical technique of PLA
CH symmetric stretching,
159
161
Fourier transform infrared
spectroscopy (FT-IR),
157
159
1
H and 13C NMR spectra,
154
156, 155f, 156f, 157f
infrared (IR) spectroscopy,
157
162
nuclear magnetic resonance
(NMR) spectroscopy,
154
157
aOH stretching band,
157
159
presence of aCQO carbonyl,
157
159
Applications of PLA, 25t
biomedical, 43
57, 52t,
143
144, 317, 324t
domestic, 33
42, 302
317,
303t
engineering, 317, 318t

B
Bagley correlation, 221
222
Bakelite, 2
Bio-based polyethylene, 17
19

Biodegradability and
biodegradation of PLA
aerobic and anaerobic
biodegradation, 266
267,
266t
chemical bonding and,
249
251
copolymer compositions,
effect of, 251
252
degradation time, 251t
environmental degradation,
265
278
factors affecting, 248
255
flame resistance, 288
295
fungal strains involved in,
273
275, 274t
high-molecular-weight
polyesters, 253
hydrolytic and enzymatic
degradation, 255
265
microorganisms involved in,
273
molecular weight and
crystallization, effect of,
252
253
test under controlled
composting conditions,
275
278, 276t, 277f, 278f,
279f
thermal degradation,
278
287
using cumulative
measurement respirometric
(CMR) system, 269
272

329

330
Biodegradability and
biodegradation of PLA
(Continued)
in vivo degradation
mechanisms, 254
255
water uptake and acidity,
253
254
Biodegradable polyesters, 10f, 12
Biodegradable polymers, 3,
17
19
background, 1
13
biological applications, 6
10
common, 7t
definitions of common
biological terms, 250t
degradation modes, 256f
degradation time, 251t
evolution after 28 days, 268f
hydrolyzable polymers, 251t
market potential, 13
33
petroleum-derived, 12, 16
physical properties of
synthetic, 50t
weight losses due to
hydrolysis, 257
261, 258t,
259f, 260t, 263f
Bio-ethanol, 17
19
Bio-Flexs, 41
BioFoams, 24
31
BIOFRONTt, 23
24, 31
32
Biomaxs, 211
Biomedical applications, of
PLA, 43
57, 52t,
143
144, 317, 324t
Bionollet, 12
Bionolles, 199
200
Bionollet PTT 1100, 13
Blendex 338, 210
Blends, polymer. see polymer
blends

INDEX
Brabender extruder, 224
226
Branching in PLA, 230
232
Bulk production PLA, 20
22

C
Capillary rheometers, 221
222
e-caprolactone, 46
51, 80
83,
95
monomer, 98
Capronors, 6
10
Cargill Dow Polymer LLC, 5
Carothers, Wallace, 5
Carreau
Yasuda model
parameters, 231t
Cellulose acetate, 11
fabric, knitted, 11
Cellulose polymers, 19
20
C
H bending bands, 126
128
Chemical properties of PLA
copolymerization effects,
148
149
crystallinity and supercooling,
149
152, 150f
crystallization half-time,
148
152, 150t
-form, -form and -form,
152, 159
161, 160f
infrared (IR) spectroscopy,
157
162
lactide isomers, 147
148
nuclear magnetic resonance
(NMR) spectroscopy,
154
157
permeation properties,
164
172, 168t, 169f
revised tetrad stereosequence,
154
155
solubility, 163
164, 165t, 166t
solution-diffusion model,
170
171

INDEX
stereochemistry, 146
153
stereoregularity, 154
stereosequence distribution,
154
155
stereospecific isomer,
171
172
thermodynamic criterion of
solubility, 163
164
water vapor transmission
rates, 170t
China, PLA in, 32
33
Climate change, PLA and, 61f
Cloisite 25A, 201
202
Columbus, Christopher, 1
Commercial-grade branched
material, 230
Condensation polymerization of
lactic acid, 89
90, 90f
Copolymerization
of lactide and glycolide,
97
99
of L and D stereochemistry,
34
41
Copolymers, 24
31
Cross
WLF model coefficient,
225t
Cup system, 63
64
b-cyclodextrin, 104

D
Decomposition temperature of
PLA, 123
131
Depolymerization of PLLA, 126
Development of PLA, in early
days, 144
145
Dextrose, biological
fermentation of, 10
11
Directive 94/62/EC on
Packaging and Packaging
Waste, 16
17

331
Directive 1999/21/EC on the
Landfill of Waste, 16
17
Directive 2008/98/EC on waste
(Waste Framework
Directive), 16
17
Distortion/deflection
temperature, impact on, 41
D-lactic acid, 74, 80
83, 88
89,
95
96, 163, 247
248,
251
252, 254
255
content in PLA, calculations,
104
105
presence, evaluation of,
103
105
D-lactide, 34
41, 92
93, 229
Domestic application, PLA for,
33
42, 302
317, 303t
Downstream processing, 20
22
Drug carrier medium, PLA as,
51, 54t
Durect Lactels, 57t

Eastar Bios, 12
13

Eastar Bios Ultra, 12
13
Ecodeart, 31
32
Eco-efficiency, of PLA postconsumer, 63
Ecoflexs, 12
13
Eco-indication points, 63
64,
65f
Ecological aspects of PLA
production, 61
63
Eco-plastic products, 17
Ecoprofile of PLA in mass
production, 58
63
Ecovios, 12
13, 20
22
Elastic poly(e-caprolactone/
L-lactide) (PCL/L-LA)
copolymer with PLLA, 193

332
Engineering applications, PLA
for, 317, 318t
Environmental degradation of
PLA, 265
278
Environmental impact of PLA,
63
66
Environmental profile of PLA,
57
58
European standard EN 13432,
16
17
European Union, PLA in, 31
Extensional viscosities of PLA,
232
233

F
Fibers, PLA, 145
146
First generation PLA, 63
64
FKuR Kunststoff GmbH grade,
44t
Flame resistance of PLA,
288
295
Food packaging polymer, PLA
as, 145
146
Fossil energy requirement for
PLA, 59
61, 60f
Fremy, 73
74
Futerros, 41
Futerro specification, 48t

Galacids, 84
85, 85t

Glycolide, 95
Glycolide-content copolymer,
97
99
Goodyear, Charles, 1
green credentials of PLA,
145
146
Green plastic technologies,
23
24

INDEX

H
Heat capacity of PLA, 132, 133t
High-molecular-weight PLA,
23
24, 145
146
Hisun Biomaterial PLA
specification, 47t
Hydrolisis of PLA, 124f
Hydroxycyclic ester initiators,
230

I
Ingeot, 5, 23
24, 34
41,
58
61, 63
66, 66t
IngeosPLA, 80
83
IR spectrum of PLA, 157
162

L
Lactate ester, 86
Lactels, 51
57
Lactic acid
with addition of bases,
production, 77
80
during anaerobic exercise,
production, 73
bacteria, 74
75, 75t, 77
80,
146
147
from bacteria fermentation,
74
75
broth from the fermentor, 80
chemical synthesis approach,
83
commercial purified, 84
85
condensation polymerization,
90f
evaporation and
prepolymerization stages,
90
92
and feeling of soreness, 73
fermentation process, 74
75,
77
80, 84, 146
147

INDEX
industrial, 84
85
laboratory scale production,
85
86
NatureWorks, 80
pharmaceutical grade, US, 85
physical properties, 73t
polylactide (PLA) from,
43
46
production, 72
85
Puracs, 30f, 57
58, 61
63
purification technologies, 80,
81t
reaction of polymerization
and depolymerization
reaction, 90
92, 91f
sugarcane-based production,
57
58
synthesis in lactate form, 85b
water removal during
production, 89
90
yield corresponding to type of
starchy and cellulosic
material and to
microorganism, 78t
Lactide, 5
coordination-insertion chain
growth reaction scheme,
96f
Lactide copolymer, 97
99
Lactide
dioxanone copolymer,
98
99, 100f
Lactide
glycolide copolymers,
97
98
tensile strength, 99t
Lactide polymerization, 95
96
Lactide production technology,
88
93
anionic initiators used, 94
95
cationic initiators used,
94
95

333
mass-scale production, 88
polymerization and
copolymerization, 94
97
process flow, 89f
US Patent 5 274 073, 88
89
Lactobacillus species, 74
77,
75t, 76t
Le Chateliers principle, 90
92
Lignocellulosics, 2
3
Limiting oxygen index (LOI),
288
290
Linear-branched PLA, 231
L-lactic acid, 43
46, 79t,
80
83, 88
89, 251
252,
254
255
L-lactide, 74, 92
93
Long-chain poly(p-dioxanone),
98
99
Low-molecular-weight PLA,
86
87

M
Mark
Houwink equation, 233,
234t
Market potential of PLA, 13
33
Mass production, ecoprofile of
PLA in, 58
63
MaterBis sample, 266
267
MBA900H, 23
24
Mechanical properties of PLA
of annealed poly (D,L-lactide)
specimens, 181t
of blends of polylactide with
nondegradable polymers,
213t
crystallinity and molecular
weight, effect of, 179
182
electron irradiation and,
286
287
elongation at break, 190
191

334
Mechanical properties of PLA
(Continued)
glucose monoester or partial
fatty acid ester, effect of,
188
nanocomposites, 212
215
from NatureWorks LLC, 178t
of nonannealing poly (D,Llactide) specimens, 181t
oligomeric lactic acid, effect
of, 189
190
PBOH, AGM and DBS, effect
of, 190
191
PLA/organoclay
nanocomposites, 195
for PLA/PCL, 195, 196t, 198
PLA
PCL
PLA triblock
copolymer, 195
PLA/polystyrene blend,
239
240
plasticizers and modifiers,
effect of, 182
191, 183t
with polycaprolactone (PCL),
blending with, 192
197
poly(ethyleneco-vinyl acetate)
(EVA), effect of, 189
190
polyethylene glycol
monolaurate, effect of,
189
190
poly(ethylene glycol) (PEG),
effect of, 189
191
of polylactide/PHA blends,
208t
of poly(L-lactide) specimens,
180t
polymer blends, 191
215
with poly(tetramethylene
adipate-co-terephthalate)
(PTAT), 198
199
triacetin (TAC), effect of, 190

INDEX
Meso-lactide, 34
41, 88
89,
156
157
Methyl trifluoromethane
sulfonic acid, 94
95
Microorganism-derived
biodegradable polymers, 3
Mineralization of PLA, 272,
272f
Mirelt, 10
11
MMT nanoclays, 210
Moldflows software, 224
226
Multicyclic esters, 230
Multifunctional polymerization
initiators, 230

N
NatureWorks, PLA by, 58
61,
59f
NatureWorks grades, 35t, 37t,
39t
NMR spectrum of PLA,
154
157
N,N,N0 ,N0 -tetramethyl-1,4phenylenediamine (TMPD),
284
286
Nodaxt, 206
207

O
oligoNodax, 206
207
oligoNodax-b-poly(L-lactide)
diblock copolymers,
206
207
Organically modified
montmorillonite (OMMT),
294
295, 294t
Oxo-biodegradable plastics,
3
4
Oxo-biodegradable polymers,
3
4

INDEX

335
s

PaperMate , 10
11
Patents published about PLA, 6f
PBS/PBSA, 12
p-dioxanone monomer, 98
99
PE-coated cardboard cup, 63
64
Pellethanet 2102-75A, 210
Permeation properties of PLA,
207
215
Petrochemical polymers and
climate change, 61f
Petroleum-derived
biodegradable polymers, 3,
12, 16
Phenol-formaldehyde resin, 2
Picea sitchensis, 121
122
PLA-copolymer-related drug
delivery system, 51
57
PLAGA copolymer, 273
275
Plastics
ban on non-degradable,
16
17
certification of compostable,
18t
degradability of, 2
3
global producers, 13
14
products, 15
16
renewable biodegradable, 20f
reusable plastic bags, 17
world production, 13
14
worldwide demand, 14
15
Plastic surgery, PLA in, 51
Polybutylene adipate/
terephthalate (PBAT), 13
Polycaprolactone (PCL), 6
10
Polydioxanone (PDO), 6
10
Poly(D-lactide)/poly(D-lactic
acid) (PDLA), 43
51,
109
112, 143
144
copolymers, 113

Poly(DL-lactide)/poly(DL-lactic
acid) (PDLLA), 109
111,
114f, 143
144
Polyethylene, 2
4
Poly (ethylene oxide) (PEO),
188
189
Polyethylene terephthalate
(PET), 13, 164
permeability, 166
169
Polyglycolic acid (PGA), 6
10
Poly(3-hydroxyalkanoate)
(PHA)/PLA blends,
205
206
Polyhydroxyalkanoates (PHA),
10
11
Poly(b-hydroxybutyrateco-hydroxyvalerate)
(PHBV), 169
170
Poly-3-hydroxybutyratecovalerate (PHBV), 10
11
Polyhydroxybutyrate (PHB),
10
11
Poly(lactic acid)/polylactide
(PLA), 3, 5
applications, 25t
arrangement of molecules of
semicrystalline, 222
223
average prices, 22
23
biodegradability, 144.
see also biodegradability
and biodegradation of PLA
biomedical applications,
43
57, 52t, 143
144, 317,
324t
bulk production, 20
22
Carreau
Yasuda model
parameters, 231t
characteristics of amorphousmade, 258t
in China, 32
33

336
Poly(lactic acid)/polylactide
(PLA) (Continued)
and climate change, 61f
copolymers, 24
31
cross
WLF model
coefficient, 225t
cup system, 63
64
development, early days,
144
145
direct method of synthesizing,
144
145
distortion/deflection
temperature, impact on,
41
domestic application, 33
42,
302
317, 303t
downstream processing,
20
22
as a drug carrier medium, 51,
54t
eco-efficiency, postconsumer, 63
eco-indication points, 63
64,
65f
engineering applications, 317,
318t
environmental profile of,
57
58
in the European Union, 31
family, 144
fibers, 145
146
first generation, 63
64
FKuR Kunststoff GmbH
grade, 44t
as a food packaging polymer,
145
146
fossil energy requirement,
59
61, 60f
Futerro specification, 48t
green credentials, 145
146

INDEX
high-molecular-weight,
23
24, 145
146
Hisun Biomaterial
specification, 47t
impact on environment,
63
66. see also
biodegradability and
biodegradation of PLA
from L-lactic acid, 43
46
market potential, 13
33
mass production and
ecoprofile, 58
63
by NatureWorks, 58
61, 59f
NatureWorks grades, 35t, 37t,
39t
patents published, 6f
PLA-coated cable vs PVCcoated cable, 323t
in plastic surgery, 51
power
law equation, 225t,
236
Puracs product range,
24
31, 51
57
research publications
(1950
2009), 6f
routes for synthesis, 144f
second generation, 59
61
Toyobo grade, 46t
Unitika
Terramacs grade,
42t, 43t
virgin PET (vPET) vs
recycled PET (rPET),
66t
Polylactic acid resin producers,
32t
Polylactide bottles,
biodegradability study of,
267
269
in compost pile, 270f
evolution after 28 days, 268f

INDEX
Poly(L-lactic acid)/poly(L-lactide)
(PLLA), 109
111,
143
144
activation energy, 128
129
calcium-ion end-capped,
128
129
carboxyl-type, 128
129
depolymerization, 126
effects of pyrolysis, 128
129
functional groups of endcapped, 128
129
IR spectra, 161
162
melting range, 112
113
PBS/PBSL blends, 200
PLLA/HDPE blends,
211
212
PLLA/LLDPE blends,
211
212
PLLA/Nodaxt blends,
206
207
PLLA/PBSA composites with
C25A and TFC, 200
201
PLLA/PBS blends, 201
PLLA
PEG
PLLA triblock
copolymer, 205
PLLA/PEO, 207
210
PLLA/PHB blends, 205
PLLA/PHBV blends,
202
205
PLLA/PTAT blends,
198
199
rate of hydrolysis, 264t
re-crystallization process, 261
stereochemical defects and
crystallization, 121
122
thermal decomposition,
123
125
thermal properties of
hydrolytically degraded,
261
264, 262t

337
thermograms, 114f, 259f
unit cell parameters for
non-blended, 143
144
Polymer blends, 191
215
with dicumyl peroxide (DCP),
194
elastic poly(e-caprolactone/
L-lactide) (PCL/L-LA)
copolymer with PLLA, 193
with nondegradable polymers,
207
215
PEO/PLLA blends, 207
210
PLA/Cloisite 30B blends,
210
PLA/ePHA blends, 205
206
PLA/PHA blends, 205
206
PLA/poly(butylene adipateco-terephthalate) (PBAT),
199
PLA/polyisoprene/poly(vinyl
acetate) blends, 210
PLLA/Nodaxt blends,
206
207
PLLA/PBS blends, 201
PLLA/PBSL blends, 200
PLLA
PCL diblock
copolymer, 193
194
PLLA
PCL
PLLA triblock
copolymer, 193
PLLA/PHB blends, 205
PLLA/PHBV, 202
205
PLLA/PHBV blends, 202
with polycaprolactone (PCL),
192
197
with poly(ethylene/butylene
succinate), 199
200
with polyhydroxyalkanoates
(PHAs), 202
207
of polylactide with
degradable or partially

338
degradable polymers,
198
202, 203t
poly(TMC/CL), 194
195
polyurethane/PLA networks,
194
with poly(vinyl acetate)
(PVAc), 207
solution and melt blending,
207
using triphenyl phosphite, 193
at XPLLA, 193
194
Polymerize lactide, 95
96
Polymers, 1
average prices, 22f
biodegradable, 3, 21f
global development, 2, 2f
oxo-biodegradable, 3
4
petroleum price and, 15
16
synthetic, 2
worldwide consumption, 15t
Polypropylene, 2
4
Polystyrene (PS), 2, 194
195
Polytetramethylene adiphate/
terephthalate (PTMAT), 13
Poly(vinyl acetate), 3
Poly(vinyl alcohol) (PVOH),
3
5, 249
251
average prices, 22
23
Poly(vinyl chloride) (PVC), 2
Potassium methoxide, 94
95
Power
law equation, 225t, 236
Prepolymer reactor, 89
92
PRO-BIP 2009, 17
19
Production of poly(lactic acid)/
polylactide (PLA),
86
105
application of coupling agents
in, 86
105
calculation of residual lactide,
102
103

INDEX
catalyst used, 94t
coordination-insertion chain
growth reaction scheme of
lactide, 96f
direct polycondensation (DP)
route, 71
72
evaluation of D-lactic acid
presence, 103
105
evaporation and
prepolymerization stages,
90
92
formation of free radicals,
86
87
GC/FID method of residual
lactide quantification,
100
102, 101t
from initial fermentation
process, 92f
from lactate ester, 86
low-molecular weight, 86
87
low-molecular-weight
byproducts, 92
93
quality control, 99
100
quantification of residual
lactide in, 99
103
reaction of polymerization
and depolymerization
reaction, 90
92, 91f
ring-opening polymerization
(ROP) route, 71
72,
86
87
sample preparation for
testing, 104b
stereocomplex composition,
92
93
testing procedures, 99
100
transesterification mechanism,
90
92
US Patent 6 569 989,
92
93

INDEX
Proteinase K, 265t
Puracs product range, 24
31,
51
57
PURALACTt, 24
Purasorbs, 51
57, 55t, 56t
PVC-coated cable
PLA-coated cable vs, 323t
PVT relationship of PLA,
132
138, 136t, 137t
Pyramid Bioplastics Guben
GmbH, 31

R
Recycled PET (rPET)
virgin PET (vPET) vs, 66t
Recycling of biowaste, 16
17
Regular solution theory (RST),
164
Research publications about
PLA (1950
2009), 6f
Residual lactide, quantification
of, 99
103
calculations, 102
103
GC/FID method, 100
102,
101t
REVOD201, 41
REVODE101, 41
Rheological properties of PLA,
222
226
blends with layered silicate
nanocomposites, 237
239
branching effects, 230
232
extensional viscosities,
232
233
flow activation energy for
PLA70 blend, 243t
molecular weight, effect of,
226
229, 227t, 228f
non-Newtonian pseudoplastic
behavior of PLA, 224
226

339
of PLACNs, 237
239, 238f
PLA-melt viscosity, 223f,
224f
PLA/PBAT melts, 235
237
PLA/polystyrene blend,
239
243
of polymer blends, 233
243
shear viscosities, 222
224
solution viscosity, 233
true viscosity vs 1/T for
PLA70, 242, 242f
viscoelastic properties,
226
227
zero-shear viscosity,
227
229, 227t
Rheometric Dynamic Analyzer
(RDAII), 237
Rheometrics RDSII torsional
rheometer, 226
227
Rhizopus oryzae, 75
77
Ring-opening polymerization of
lactide, 86
87
Rotational rheometers, 221
222
Rubber, natural, 1

S
Scheele, Carl Wilhelm, 73
74
Second generation PLA, 59
61
Semicrystalline, arrangement of
molecules of, 222
223
Solution viscosity of PLA, 233
Stannous (Sn) complexes,
95
96
Starch-based plastics, 22
23
Starches, 2
3
Starch
polymer blends, 19
20
Stereochemistry of PLA,
146
153
Stereoisomer D-lactic acid,
43
46

340
Sulfur vulcanization, 1
Synthesis of PLA, routes for, 144f
Synthesizing PLA, direct
method of, 144
145
Synthetic polymer, 2

T
Tellest, 10
11
Teramacs, 31
32
Terramacs, 41
Thermal conductivity of PLA,
131
132, 135t
Thermal degradation of PLA,
278
287, 281t, 282f, 283f
Thermal properties of PLA
activation energies, 129t
annealing point, 115
116
crystallization, 111
123
degradation under isothermal
conditions, 125
126
determination, 109
111
DSC thermograms, 117f
fiber incorporation and
thermal transition, 121
122
food grade plasticizer, effects
of, 116
121, 120t
FTIR spectra, 126
128, 127f
glass transition behavior,
114
115
glass transition temperature,
112
115
heat capacity, 132, 133t
isomers, effects of, 111t
lactide and, 118
maleic anhydride (MA)compatibilized blends,
122
123
melting temperature and
enthalpies, 114
115, 119t,
149f

INDEX
microstructure rearrangement
upon cooling, 111
molten polymer, 132
138
monomer types, impact on
structural properties,
121
122
PLA
starch blends,
122
123, 122t, 123f
pure PLA, 121
122
PVT relationship, 132
138,
136t, 137t
shear viscosity, 112
113
solubility parameters, 118t
stereocomplexed
PLLA
PDLA blend,
112
113
stereoform of lactides, 110f
thermal conductivity,
131
132, 135t
thermal decomposition,
123
131
thermogravimetry, 130f
transition temperature,
112
123
WF accelerated thermal
decomposition, 129
131
Tin octoate catalyst, 96
97
Titration reaction scheme,
271, 271
Toyobo PLA specification, 46t
Transesterification of PLA,
124f
Triallyl isocyanurate (TAIC),
286
287, 287f
Trifluoromethane sulfonic acid,
94
95
Tris(nonylphenyl), 231
Tris (nonylphenyl) phosphate,
231
Tweens80, 77
80

INDEX

U
UL-94, 288
290, 289t, 291t,
292t
Unitika
Terramacs PLA
grade, 42t, 43t

V
Vinegar syndrome, 11
Virgin PET (vPET) vs recycled
PET (rPET), 66t
Vuitton, Louis, 11

341
Vulcanization of rubber, 1
Vyloecols, 24
31, 41

W
Weissenberg
Rabinowitsch
correlation, 221
222
Williams
Landel
Ferry
equation (WLF), 229

Zoladexs, 51