Table of Contents
Cover
Title Page
Copyright
List of Contributors
Chapter 1: Introduction
1.1 Introduction
1.2 Sustainable Polymers
1.3 Biomass Resources for Sustainable Polymers
1.4 Conclusions
References
Chapter 2: Polyhydroxyalkanoates: Sustainability, Production, and Industrialization
2.1 Introduction
2.2 PHA Diversity and Properties
2.3 PHA Production from Biomass
2.4 PHA Application and Industrialization
2.5 Conclusion
Acknowledgment
References
Chapter 3: Polylactide: Fabrication of Long Chain Branched Polylactides and Their Properties and Applications
3.1 Introduction
3.2 Fabrication of LCB PLAs
3.3 Structural Characterization on LCB PLAs
3.4 The Rheological Properties of LCB PLAs
3.5 Crystallization Kinetics of LCB PLAs
3.6 Applications of LCB PLAs
3.7 Conclusions
Acknowledgments
References
Chapter 4: Sustainable Vinyl Polymers via Controlled Polymerization of Terpenes
4.1 Introduction
4.2 β-Pinene
4.3 α-Pinene
4.4 Limonene
4.5 β-Myrcene, α-Ocimene, and Alloocimene
4.6 Other Terpene or Terpenoid Monomers
4.7 Conclusion
References
Chapter 5: Use of Rosin and Turpentine as Feedstocks for the Preparation of Polyurethane Polymers
5.1 Introduction
5.2 Rosin Based Polyurethane Foams
5.3 Rosin-Based Polyurethane Elastomers
5.4 Terpene-Based Polyurethanes
5.5 Terpene-Based Waterborne Polyurethanes
5.6 Rosin-Based Shape Memory Polyurethanes
5.7 Conclusions
References
Chapter 6: Rosin-Derived Monomers and Their Progress in Polymer Application
6.1 Introduction
6.2 Rosin Chemical Composition
6.3 Rosin Derived Monomers for Main-Chain Polymers
6.4 Rosin-Derived Monomers for Side-Chain Polymers
6.5 Rosin-Derived Monomers for Three-Dimensional Rosin-Based Polymer
6.6 Outlook and Conclusions
Acknowledgments
References
Chapter 7: Industrial Applications of Pine-Chemical-Based Materials
7.1 Pine Chemicals Introduction
7.2 Crude Tall Oil
7.3 Terpenes
7.4 Tall Oil Fatty Acid
7.5 Rosin
7.6 Miscellaneous Products
References
Chapter 8: Preparation and Applications of Polymers with Pendant Fatty Chains from Plant Oils
8.1 Introduction
8.2 (Meth)acrylate Monomers Preparation and Polymerization
8.3 Norbornene Monomers and Polymers for Ring Opening Metathesis Polymerization (ROMP)
8.4 2-Oxazoline Monomers for Living Cationic Ring Opening Polymerization
8.5 Vinyl Ether Monomers for Cationic Polymerization
8.6 Conclusions and Outlook
References
Chapter 9: Structure–Property Relationships of Epoxy Thermoset Networks from Photoinitiated Cationic Polymerization of Epoxidized Vegetable Oils
9.1 Introduction
9.2 Photoinitiated Cationic Polymerization of Epoxidized Vegetable Oils
9.3 Conclusions
Acknowledgment
References
Chapter 10: Biopolymers from Sugarcane and Soybean Lignocellulosic Biomass
10.1 Introduction
10.2 Lignocellulosic Biomass Composition and Pretreatment
10.3 Lignocellulosic Biomass from Soybean
10.4 Production of Polymers from Soybean Biomass
10.5 Lignocellulosic Biomass from Sugarcane
10.6 Production of Polymers from Sugarcane Bagasse
10.7 Conclusion and Future Outlook
Acknowledgments
References
Chapter 11: Modification of Wheat Gluten-Based Polymer Materials by Molecular Biomass
11.1 Introduction
11.2 Modification of Wheat Gluten Materials by Molecular Biomass
11.3 Biodegradation of Wheat Gluten Materials Modified by Biomass
11.4 Biomass Fillers for WG Biocomposites
11.5 Conclusion and Future Perspectives of WG-Based Materials
References
Chapter 12: Copolymerization of C1 Building Blocks with Epoxides
12.1 Introduction
12.2 CO2 /Epoxide Copolymerization
12.3 CS2 /Epoxide Copolymerization
12.4 COS/Epoxide Copolymerization
12.5 Properties of C1-Based Polymers
12.6 Conclusions and Outlook
References
Chapter 13: Double-Metal Cyanide Catalyst Design in CO2/Epoxide Copolymerization
13.1 Introduction
13.2 Polycarbonates and Their Synthesis Methods
13.3 Copolymerization of CO2 and Epoxides
13.4 Double-Metal Cyanides and Their Structural Variation
13.5 Methods of DMC Synthesis
13.6 Factors Influencing Catalytic Activity of DMCs
13.7 Role of Co-catalyst on the Activity of DMC Catalysts
13.8 Copolymerization in the Presence of Hybrid DMC Catalysts
13.9 Copolymerization with Nano-lamellar DMC Catalysts
13.10 Effect of Crystallinity and Crystal Structure of DMC on Copolymerization
13.11 Effect of Method of Preparation of DMC Catalysts on Their Structure and Copolymerization Activity
13.12 Reaction Mechanism of Copolymerization
13.13 Conclusions
References
Index
End User License Agreement
Pages
xi
xii
xiii
xiv
1
2
3
4
5
6
7
8
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
35
36
37
38
39
40
41
42
43
44
45
47
48
49
50
51
52
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
91
92
93
94
95
96
97
98
99
100
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
128
129
130
132
133
135
136
137
138
139
140
141
142
143
144
145
146
147
148
151
152
153
154
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
206
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
227
228
229
230
231
232
233
234
236
238
239
240
241
245
246
247
248
249
250
251
252
255
256
257
259
260
261
262
263
264
265
267
268
270
271
272
273
274
275
276
277
279
280
281
282
283
284
285
286
287
288
290
291
292
293
294
295
296
297
298
299
300
301
302
303
304
305
306
307
308
309
310
311
312
315
316
317
318
319
320
321
322
323
324
326
327
328
329
330
331
332
333
334
335
336
337
338
339
341
342
343
344
347
348
349
350
351
352
353
354
355
356
Guide
Cover
Table of Contents
Begin Reading
List of Illustrations
Chapter 1: Introduction
Figure 1.1 A comparison between traditional petrochemical-based polymers and sustainable polymers.
Figure 1.2 Scientific publications with the keyword “sustainable polymers” published from 1995 to 2016.
Figure 1.3 A schematic diagram to illustrate the concepts of sustainable polymers from biomass.
Figure 1.4 Examples of a few naturally occurring biopolymers.
Figure 1.5 Sustainable polymers derived from biotechnologically derived monomers.
Figure 1.6 Top biomass platform molecules produced from sugars recognized by the US Department of Energy.
Figure 1.7 Terpene-based compounds used in renewable polymers.
Figure 1.8 Copolymerization of limonene oxide and CO2 .
Chapter 2: Polyhydroxyalkanoates: Sustainability, Production, and Industrialization
Figure 2.1 Intracellular PHA and the classification of its monomers. The white granules are PHA accumulated in bacteria. 3HB, 3-hydroxybutyrate; 3HV, 3-hydroxyvalcrate; 3HHx, 3-hydroxyhexanoate; 3HO, 3-hydroxyoctanoate; 3HD, 3-hydroxydecanoate; 3HDD, 3-hydroxydodecanoate.
Figure 2.2 PHA classifications based on the microstructure [11, 12].
Figure 2.3 Constituents of PHA production cost.
Figure 2.4 Required properties as an ideal strain for PHA industrial production [7].
Figure 2.5 Metabolic pathways for PHA synthesis. PhaA: β-ketothiolase; PhaB, NADP dependent acetoacetyl-CoA reductae; PhaC, PHA synthase; PhaG: 3-hydroxyacyl-acyl carrier protein-coenzyme A transferase; PhaJ: enoyl-CoA hydratase; scl PHA, short chain length PHA; mcl PHA, medium chain length PHA.
Figure 2.6 P3HB4HB synthesis pathway in recombinant E. coli from unrelated carbon source [61]. phaA : gene encoding β-ketothiolase; phaB : gene encoding acetoacetyl-CoA reductase; phaC : gene encoding PHA synthase; sucD : gene encoding succinate semialdehyde (SSA) dehydrogenase; orfZ : gene encoding CoA transferase; 4hbD : gene encoding 4-hydroxybutyrate dehydrogenase; sad and gabD : genes encoding succinate semialdehyde dehydrogenase of E. coli . The black cross indicates deletion.
Figure 2.7 Scanning Electron Microscope (SEM) and TEM results of enlarged E. coli cells for P3HB4HB production [61]. (a) SEM images of normal rod shape E. coli with PHA accumulation; (b) SEM images of elongated E. coli with PHA accumulation; (c) TEM images of PHA granules accumulated in normal rod shape E. coli ; and (d): TEM images of PHA granules accumulated in elongated E. coli. The white bar in (a) and (b) represents 10 µm. The bar in black color in (c) and (d) represents a length of 1 µm.
Figure 2.8 Gravity precipitation of elongated E. coli.
Figure 2.9 Engineered metabolic pathway for PHBV production by Halomonas TD strains from various carbohydrates [58]. PhaA: β -ketothiolase; PhaB, NADP dependent acetoacetyl-CoA reductae; PhaC, PHA synthase; ThrA-ak: aspartokinase; ThrA-hom: homoserine dehydrogenase; ThrB: homoserine kinase; ThrC: threonine synthase; IlvA: threonine dehydrogenase; PrpC: 2-methylcitrate synthase; PhaZ: PHA depolymerase; PEP: phosphoenolpyruvate; MCC cycle: methylcitrate cycle. The black bold arrows indicate overexpression, and the black cross indicates deletion.
Figure 2.10 Various applications of PHA.
Chapter 3: Polylactide: Fabrication of Long Chain Branched Polylactides and Their Properties and Applications
Scheme 3.1 Illustration of reactions of epoxide and isocyanate groups with PLA end groups.
Scheme 3.2 Illustration of general formula of commercially available epoxide-functionalized copolymer.
Scheme 3.3 Synthetic illustration of preparation of prepolymers and long chain branched polylactides.
Scheme 3.4 Structural formulae for three types of free radicals from PLA backbone chain induced by irradiation of gamma rays (I, II, and III) and for trifunctional monomer, trimethylolpropane triacrylate (TMPTA) (IV) and schematic demonstration of degradation and formation of long chain branched structures for PLA (V).
Figure 3.1 (a) Differential molecular mass distributions, (b) changes of root-mean-square radius of gyration, , and (c) changes of intrinsic viscosity, [η ] as functions of molecular mass for linear PLA and LCB-PLAs as determined from SEC-MALLS. The solid lines in (a) represent the fitted log-normal bimodal distributions in LCB-PLA2 and LCB-PLA3.
Figure 3.2 (a) van Gurp–Palmen plot and (b) activation energy spectra for LCB PLA samples prepared by gamma-radiation-induced reaction.
Figure 3.3 Change of zero-shear viscosity, η 0 as a function of M w for linear PLA samples and LCB-PLAs at 180 °C, indicating a tree-like highly branched structure.
Figure 3.4 Linear viscoelastic spectra for (a) P and P-P03; (b) P-T04; (c) P-DCP; and (d) P-P02-T04. Lines are the results of simulation by using the BOB model.
Figure 3.5 The changes of (a) viscosity from dynamic and steady shear experiments and (b) storage modulus as functions of frequency for neat PLA and LCB PLA samples prepared by reactive extrusion with epoxide copolymer.
Figure 3.6 Changes of elongational viscosity as functions of time at different elongational flow rates (0.05, 0.1, 0.3, and 0.5 s−1 ) for (a) PLA0, (b) LCB-PLA1, (c) LCB-PLA2, (d) LCB-PLA3, and (e) LCB-PLA4. The LCB PLA samples were prepared by gamma-radiation-induced reactions.
Figure 3.7 Selected POM images taken during isothermal crystallization at different temperatures for (a) PLA0, (b) LCB-PLA1, (c) LCB-PLA2, and (d) LCB-PLA3. The crystallization temperatures and times are marked on the micrographs.
Figure 3.8 Changes of spherulitic growth rate, G as functions of isothermal crystallization temperature, T c for linear PLA and LCB PLA samples. The solid lines represent the theoretical curves fitted with the data points on the basis of the Hoffmann–Lauritzen theory.
Figure 3.9 Selected POM images taken at the early stage of crystallization for linear PLA and LCB PLAs at 130 °C after pre-shear with the shear rate of 1 s−1 for different shear times.
Figure 3.10 Schematic illustration of the mechanism of enhancement of nucleation ability and evolution of crystalline morphology for linear PLA and LCB PLA after sheared for sufficient time. Wang 2013 [44, 45]. Reproduced with permission of American Chemical Society.
Figure 3.11 Pictures of neat PLA bubble with die temperature at 150 °C and LCB PLA with die temperature at 180 °C. The LCB PLA sample was prepared by reactive extrusion of PLA with 0.5 wt% of commercial available epoxide-functionalized copolymer (Scheme 3.2).
Figure 3.12 SEM images of (a) 4032D and (b) 4032D/8%-75-TN foams and (c) photograph of 4032D/8%-75-TN before and after foaming.
Chapter 4: Sustainable Vinyl Polymers via Controlled Polymerization of Terpenes
Figure 4.1 Terpenes and terpenoids for vinyl polymers. The compounds in a square bracket are not naturally occurring but obtained from natural compounds via relatively simple chemical transformations.
Figure 4.2 Cationic polymerization of β-pinene via β-scission of the four-membered ring.
Figure 4.3 Living cationic polymerization of β-pinene with the R–Cl/MXn /additive initiating system followed by hydrogenation.
Figure 4.4 Block copolymers of β-pinene and other vinyl monomers via living cationic polymerization of β-pinene and the subsequent block copolymerization [55–57].
Figure 4.5 RAFT copolymerization of β-pinene and other vinyl monomers and the obtained copolymers [62–69].
Figure 4.6 Proposed mechanism for cationic polymerization of α-pinene with AlCl3 /SbCl3 [84].
Figure 4.7 α-Pinene-derived monomers: radical polymerization of pinocarvone [87] and ROMP of apopinene [88].
Figure 4.8 Proposed mechanism for cationic polymerization of limonene [37].
Figure 4.9 Proposed mechanism for 1 : 2 alternating radical copolymerization of limonene and maleic anhydride via cyclopolymerization [93].
Figure 4.10 1 : 2 alternating radical and RAFT copolymerization between limonene or its derivatives and maleimide derivatives in fluoroalcohol [68, 105, 106].
Figure 4.11 Coordination copolymerization of ethylene and limonene with titanium catalysts [107].
Figure 4.12 Possible microstructures of poly(β-myrcene).
Figure 4.13 RAFT polymerization of myrcene [119].
Figure 4.14 Proposed structures via cationic polymerization of alloocimene.
Figure 4.15 ABA-triblock copolymer and end-functionalized polymer obtained by living anionic polymerization of myrcene [132–134].
Figure 4.16 Metal catalysts for regioselective coordination polymerization of myrcene [135–139].
Figure 4.17 Ring-closing metathesis of myrcene into 3-methylenecyclopentene and its living cationic polymerization followed by hydrogenation [140].
Figure 4.18 Cationic polymerizations of α- and β-phellandrene followed by hydrogenation [46, 142].
Figure 4.19 α- and β-Farnesene and obtained structure in polymerization of β-farnesene.
Figure 4.20 ROMP of β-caryophyllene and humulene followed by hydrogenation [145].
Figure 4.21 Alternating living cationic copolymerization of vinyl ether and naturally occurring aldehydes followed by acid hydrolysis of the alternating copolymers [147, 148].
Chapter 5: Use of Rosin and Turpentine as Feedstocks for the Preparation of Polyurethane Polymers
Figure 5.1 The schematic synthesis routes of rosin-based polyester polyol [5].
Figure 5.2 The mechanism of synthesis of formaldehyde-modified rosin acid [9].
Figure 5.3 Synthesis of rosin-based polyether polyol [7].
Figure 5.4 Synthesis of polyols from hydrogenated terpene-maleic ester type epoxy resin [11].
Figure 5.5 Schematic synthesis of a cationic polyol based on hydrogenated terpene-maleic ester type epoxy resin [13].
Figure 5.6 The synthesis route of FAPP.
Figure 5.7 Schematic synthesis route of RWPU [14].
Figure 5.8 Synthetic pathway of R-CE [19].
Chapter 6: Rosin-Derived Monomers and Their Progress in Polymer Application
Figure 6.1 Representative structures of resin acids.
Figure 6.2 Synthesis of MPA.
Figure 6.3 Synthesis of MPA-derived monomers with di-carboxyl group.
Figure 6.4 Preparation of rosin-based polyesterimides via esterification.
Figure 6.5 Preparation of rosin-based polyamideimides.
Figure 6.6 Structure of rosin-based polyesterimides.
Figure 6.7 Synthesis of MPA-derived monomers bearing a carboxyl group and an amine group.
Figure 6.8 Preparation of rosin-based polyamideimides via self-polycondensation.
Figure 6.9 Synthesis of APA.
Figure 6.10 Preparation of rosin-based polyester from APA.
Figure 6.11 Preparation of rosin-based polyamides from APA.
Figure 6.12 Synthesis of APA-derived monomers bearing a carboxyl group and hydroxyl group.
Figure 6.13 Synthesis of DAK.
Figure 6.14 Chemical structure of ketonic type rosin-derived macro-monomers.
Figure 6.15 New rosin-based polyamide derived from ketonic type rosin derived macro-monomers.
Figure 6.16 New rosin-based polyamideimides derived from ketonic type rosin derived macro-monomers.
Figure 6.17 Synthesis of rosin-derived monomer with bi-vinyl group.
Figure 6.18 Synthetic strategy of novel rosin-based polymer via ADMET.
Figure 6.19 Chemical structure of rosin-derived monomers with vinyl ester group.
Figure 6.20 Synthesis of rosin-derived monomers with acrylate group.
Figure 6.21 Scheme of synthesis of rosin-derived monomers with acrylate group.
Figure 6.22 Synthesis of rosin-based acrylic monomer with cationic group.
Figure 6.23 ATRP of vinyl monomers derived from DA.
Figure 6.24 GPC traces and 1 H NMR spectra of PABDA and PMAEDA prepared by ATRP.
Figure 6.25 DSC traces of poly(13) (PAEDA), PABDA, and PMAEDA polymers prepared by ATRP.
Figure 6.26 Chemical structure of rosin-derived cationic monomer.
Figure 6.27 Preparation of rosin-derived acrylic polymers by RAFT.
Figure 6.28 Preparation of rosin-derived cationic polymers by RAFT.
Figure 6.29 Preparation of di-block copolymers containing ε-Caprolactone (CL) and 13 (AEDA) by two-step sequential polymerization and one-pot polymerization.
Figure 6.30 (a) Kinetic plot of chain-extension reaction from PCL-Br to PAEDA by ATRP and (b) GPC traces of PCL-Br and PCL-b -PAEDA-Br, and degraded block copolymers.
Figure 6.31 1 H NMR spectra of PCL-Br, PAEDA-OH, and PCL-b -PAEDA block copolymers.
Figure 6.32 Synthesis of linear PEG-b -PMAEDA block copolymer
Figure 6.33 (a) 1 H NMR spectrum of block copolymer PEG-b -PMAEDA and (b) GPC traces of macroinitiator PEG-Br and block copolymer PEG-b -PMAEDA.
Figure 6.34 The morphology of PLGM-loaded PEG-b -PMAEDA nanoparticles (19.5% drug loading) by (a) TEM and (b) SEM; (c) size distribution of PLGM-loaded PEG-b -PMAEDA nanoparticles in aqueous solution measured by DLS.
Figure 6.35 Mechanism of azide/alkyne click reaction.
Figure 6.36 Synthesis of rosin-based monomers with alkyne group.
Figure 6.37 Synthetic strategy of rosin-grafted PCL copolymer (PCL-g -DAPE).
Figure 6.38 1 H NMR and FTIR spectra of poly(αClεCL), poly(αN3 εCL), and PCL-g -DAPE.
Figure 6.39 GPC traces of poly(αClεCL), poly(αN3εCL), PCL-g -DAPE, and acid-degraded PCL.
Figure 6.40 Synthesis of rosin-based cationic monomers with alkyne group.
Figure 6.41 Synthetic strategy of quaternary ammonium-containing rosin-grafted PCL copolymer.
Figure 6.42 1 H NMR spectra of quaternary ammonium-containing rosin propargyl ester 3 in methanol-d 4 , azide-substituted PCL in CDCl3 , and quaternary ammonium-containing rosin-substituted PCL 4 in methanol-d 4 .
Figure 6.43 Preparation of cellulose-rosin copolymers by a grafting strategy.
Figure 6.44 First-order kinetic plots for the polymerization of MAEDA, AEDA, MAHDA, and AHDA, ([M]/[I]/[Cu(I)]/[PMDETA] = 100 : 1 : 1 : 1, Temperature = 55 °C).
Figure 6.45 1 H NMR spectra of EC-grafted copolymers.
Figure 6.46 (a) UV-visible transmittance and (b) UV-visible absorption curves of EC, EC-DA, and EC-g -PMAEDA.
Figure 6.47 Synthesis of renewable graft copolymers Cell-g -P(BA-co -MAEDA) and Cell-g -P(LMA-co -MAEDA) by “grafting from.”
Figure 6.48 Typical 1 H NMR spectra of Cell-g -P(BA-co -MAEDA) and Cell-g -P(LMA-co -MAEDA).
Figure 6.49 DSC curves of (a) Cell-g -P(BA-co -MAEDA) and (b) Cell-g -P(LMA-co -MAEDA). In each plot, the MAEDA mole percent values increase for curves ordered from top to bottom.
Figure 6.50 Stress–strain curves for (a) Cell-g -P(BA-co -MAEDA) and (b) Cell-g -P(LMA-co -MAEDA) graft copolymers with different monomer feed ratios.
Figure 6.51 Synthesis of rosin polymer-grafted lignin composites (lignin-g -(rosin polymer)): LGEMA (X = 2, Y = CH3 ), LGEA (X = 2, Y = H), and LGBA (X = 4, Y = H).
Figure 6.52 Kinetic plots of graft polymerization of MAEDA, AEDA, and AEBA by ATRP.
Figure 6.53 Synthesis of rosin polymer-grafted chitosan.
Figure 6.54 Illustration of amphiphilic rosin-grafted cellulose composite.
Figure 6.55 Synthesis of DA-grafted ethyl cellulose (EC).
Figure 6.56 Synthesis of rosin acid-grafted lignin (lignin-g -DA).
Figure 6.57 Structure of rosin-modified phenolic resin.
Figure 6.58 Synthesis of rosin-derived monomer from abietic acid.
Figure 6.59 Synthesis of rosin-derived monomer for shape memory polyurethane.
Figure 6.60 Structure of rosin-derived epoxy resin.
Figure 6.61 Synthesis of rosin-derived monomers from ketonic type rosin-derived macro-monomers.
Figure 6.62 Structure of rosin oligomer-derived epoxy resin.
Figure 6.63 Synthesis of NCPT and comparative curing agents.
Figure 6.64 Synthesis of rosin-based acrylic monomers from MPA or APA.
Figure 6.65 Synthesis of rosin-based diacrylic monomers from MPA or APA.
Figure 6.66 Synthesis of rosin-based monomers with allyl group.
Chapter 7: Industrial Applications of Pine-Chemical-Based Materials
Figure 7.1 Representative components of crude tall oil.
Figure 7.2 Chemical structures of some common turpentine monoterpene components.
Figure 7.3 Alkyd resin from TOFA.
Figure 7.4 Common polyol motifs from tall oil derivatives.
Figure 7.5 Tall oil-modified epoxy resin ester.
Figure 7.6 Representative structure of epoxy resin cured with tall oil amidoamine.
Figure 7.7 Examples of rosin-based thermoplastic polymers.
Figure 7.8 Potential rosin-based polymer structure.
Chapter 8: Preparation and Applications of Polymers with Pendant Fatty Chains from Plant Oils
Scheme 8.1 Structures of (meth)acrylate monomers from fatty compounds. The structural components in black color originate from fatty compounds and in blue color come from coupling reagents. A dashed line means that both methacrylate and acrylate monomers have been prepared. A star indicates that the monomers were prepared from the mixture derivatives of plant oils.
Scheme 8.2 Preparation of branched acrylate monomers from the methyl esters of (a) ricinoleic acid and (b) oleic acid, (meth)acrylate monomers from the esterification of fatty acid (oleic acid as an example) (c) and fatty alcohols (d).
Figure 8.1 (a) GPC curves for polymer PMAEO with pendant oleic acid group, and chain extended block copolymers PMAEO-b -PMAEO, PMAEO-b -PMMA, PMAEO-b -PPEGMA.
Scheme 8.3 Schematic illustration of PMAEO and post-modifications through thiol–ene, epoxidation, and cross-linking.
Scheme 8.4 Chemical structures of (a) mono-functional initiator, (b) di-functional initiator, and (c) protected HEMA monomer for group transfer polymerization of LMA.
Scheme 8.5 Chemical structures of ligands and hydrophobic quaternary ammonium used for ATRP of monomers with long fatty chains.
Figure 8.2 Structure of tri-block copolymer PSMA-b -PtBA-b -PSMA prepared by ATRP with GPC traces of PtBA macroinitiator (M n = 42400 g mol-1, Ð = 1.12, solid line) and the tri-block copolymers (M n = 75900 g mol-1, Ð = 1.14, dashed line) (a). Tapping mode AFM phase image of the triblock copolymers thin film (b).
Figure 8.3 Synthesis of brush polymers containing PLMA chains with (a) GPC curves of the macro-initiators PBIEM-1 and two polymer brushes (n = 130 for brush 1, n = 162 for brush 2 as determined from the cleaved side chains; (b) AFM image of a polymer brush with n = 164.
Figure 8.4 Chemical structure of tri-block copolymer PS-b -(PMA-r -PSA)-b -PS prepared by RAFT polymerization and its stress-strain-temperature cycling demonstrating its shape memory property. On the plot, S indicates the start of the test and E indicates the end of the test.
Figure 8.5 Chemical structure of tri-block copolymers PS-b -(PSA-r -PLA)-b -PS with TEM images showing phase separation and a representative stress-strain curve of the tri-block copolymers.
Scheme 8.6 Amidation of plant oils by amino alcohols and further derivatization into monomers.
Scheme 8.7 Synthesis of PS-b -PSBA-b -PS and PS-b -PSBMA-b -PS tri-block copolymers by ATRP.
Scheme 8.8 Preparation of norbornene monomers from saturated fatty alcohols through esterification.
Scheme 8.9 Structure of oxazoline monomers prepared from fatty acids.
Scheme 8.10 Schematic overview of the derivatization methods based on DecenOx as reported by Litt’s group.
Scheme 8.11 Schematic representation of cross-linking of DecenOx based random copolymers via thiol–ene reaction.
Figure 8.6 Structure illustration for the formation of RGD containing hydrogel based on P(MeOx-co -DecenOx) and fibroblast adhesion onto the surface of hydrogels: (a) polymer cross-linked with DTT; (b) polymer cross-linked with DTT and 2-mercaptoethanol; (c) cross-linked hydrogel with RDG ; and (d) cross-linked hydrogel with RGD. Scale bar = 50 μm.
Figure 8.7 Schematic structure of P(EtOx-b -SoyOx) (top) together with AFM images of micelles in a solution of water (a), after UV-cross-linking in water (b), after UV-cross-linking in acetone (c), and after UV-cross-linking and re-dissolved in water (d).
Scheme 8.12 Chemical structures of vinyl ether monomers prepared from fatty acids.
Figure 8.8 Scheme for the preparation and polymerization of 2-VOES (a) and number average molecular weight as a function of monomer conversion from the cationic polymerization (b).
Figure 8.9 Preparation of amphiphilic random copolymer poly(2-VOES-ran-TEGEVE) with an image of 30 wt% of a random copolymer (50 wt% of 2-VOES) in water (a) and 30 wt% mixture of soybean oil in water (b).
Figure 8.10 Structure of 2-VOES based tri-block copolymer PCHVE-b -P(2-VOES)-b -PCHVE and DSC curves for PCHVE (empty circles), P(2-VOES) (solid square), and tri-block copolymer (solid triangle).
Chapter 9: Structure–Property Relationships of Epoxy Thermoset Networks from Photoinitiated Cationic Polymerization of Epoxidized Vegetable Oils
Figure 9.1 (a) Price history of soybean oil and crude oil since 1995. Crude oil price represents a simple average of three spot prices; Dated Brent, West Texas Intermediate, and the Dubai Fateh. (b) Annual production of soybean oils in the United States and China over four decades.
Figure 9.2 UV absorption spectra of a series of (a) diaryliodonium salts and (b) triarylsulfonium salts. All the spectra had been obtained from 0.05 mg mL−1 solutions in ethanol.
Figure 9.3 Photo-initiated cationic polymerization scheme using diaryliodonium salts to prepare sustainable thermosets from vegetable oils using multifunctional epoxidized vegetable oils from soybean or linseed.
Figure 9.4 (a) Reaction schematic diagram to convert the carbon–carbon double bonds in vegetable oil to epoxide group in epoxidized vegetable oil using W-based phase transfer catalyst. (b) Picture of the emulsified reaction mixture for the preparation of EVO using the phase transfer catalyst.
Figure 9.5 H NMR spectra of (a) soybean oil (SO) and (b) epoxidized soybean oil (ESO), prepared by reacting soybean oil with W-based phase transfer catalyst and 30% H2 O2 solution for 2 h.
Figure 9.6 (a) Reaction schematics for the cross-linking of epoxidized linseed oils by photo-initiated cationic ring-opening polymerization and (b) the network density descriptions by correlating the average epoxy functionality (i.e., average number of epoxide group per monomer, f epoxy ) in EVOs with the average molecular weights between cross-linked junctions (M x ), which was estimated by the rheological plateau modulus, G N .
Figure 9.7 (a) Dynamic mechanical analysis results of cross-linked ESO_2.8 (i.e., ESO with f epoxy = 2.8) films under tension mode to suggest the glass transition temperature of 0 °C. (b) Frequency sweep results from oscillatory shear rheology of crosslinked ESO_2.8 (thickness = 0.5 mm) using 25 mm parallel plates at 50 °C. The rubbery plateau modulus (GN ) measured from the shear rheology was used to estimate the average molecular weight between crosslinks (M x ).
Figure 9.8 Representative chemical structures of (a) ESO_2.8 and (b) SO used for ESO/SO blends.
Figure 9.9 Frequency sweep results for the elastic shear modulus (G ′) using oscillatory shear for (a) epoxidized soybean oils with different average degree of epoxide functionality (f epoxy ) per monomer and (b) ESO_2.8/SO blends at different compositions. The G N values are measured by averaging the frequency independent plateau regions of G ′ from the frequency sweep results.
Figure 9.10 (a) Rubbery plateau network modulus (G N ) and (b) average molecular weight between cross-links (M x ) as a function of average epoxy functionality ( ) per epoxidized soybean oils monomers. ESO with different average epoxy functionality (f epoxy ) is used as well as the blends of ESO_2.8 and soybean oil (SO).
Figure 9.11 Schematic diagram to show the ESO network structure formation as a function of .
Figure 9.12 Schematic diagram to show the procedure of preparing the UV-cured ELO films for the measurement of film thickness at different UV irradiation conditions.
Figure 9.13 UV-cured ELO_4.1 film thickness as a function of accumulative UV irradiation dose. The 2200 mJ cm−2 is the approximate UV dose for 40 s UV irradiation under a UV curing conveyor system from Dymax.
Figure 9.14 Chemical structure of (4-n -octylphenyl)phenyliodonium hexafluoroantimonate (IOC-8), the cationic photo-initiator used for the UV-curing of ELO.
Figure 9.15 (a) Schematic diagram to show the front and back surfaces of the UV-cured ELO film (400 µm thick) and (b) ATR FTIR spectra from the front and back surfaces of the film after UV irradiation for 40 s at an intensity of 55 mJ (cm2 × s)−1 . The peak near 1150 cm−1 (designated as “ether” A) came from the ether bonds in the triglyceride ester bonds of ELOs, while the peak near 1070 cm−1 (designated as “ether” B) originated from the ether bonds from the ring-opened epoxide groups in ELO. A broad and weak peak between 800 and 1000 cm−1 represent the existence of epoxide groups remaining after the UV-curing on the front and back surfaces.
Chapter 10: Biopolymers from Sugarcane and Soybean Lignocellulosic Biomass
Figure 10.1 Photographs of (a) soybean straw, (b) soybean hulls, and (c) sugarcane bagasse from Brazil.
Figure 10.2 Chemical structure of (a) cellulose, (b) hemicellulose, and (c) lignin.
Figure 10.3 Pretreatments and treatment strategy for lignocellulosic biomass.
Figure 10.4 TEM images of cellulose nanofibrils and nanocrystals obtained by (a) enzymatic or (b) acid hydrolysis of soybean straw, respectively [64].
Figure 10.5 Reducing sugar production after enzymatic treatment (VR 315 CMCU/g of fiber) for samples milled in knife mill (KM) and submitted to chemical treatments (T1: NaOH 5% at 90 °C for 1 h-twice and H2 O2 4% at 90 °C for 3 h, and T2: NaOH 17.5% at 90 °C for 1 h-twice and H2 O2 4% at 90 °C for 3 h). Results are expressed as g of glucose per 100 g of holocellulose content. (Holocellulose corresponded to the fraction that contained cellulose and hemicelluloses.) KM without enzyme was the “control.”
Figure 10.6 Mechanical properties of cassava starch films (Control) added with 1% (g of fiber/100 g of starch) of soybean straw fibers milled in knife (KM), ball (BM), or cryogenic (CM) mill.
Figure 10.7 Scanning Electron Microscopy (SEM) images of (a) Cassava starch film, soybean straw milled with (b) knife mill (KM), (d) ball mill for 2 h at 5 Hz (BM1), and (f) cryogenic mill for 20 min (CM2). The milled straw was incorporated into cassava starch matrix, to give composite films: (c) cassava starch/KM film, (e) cassava starch/BM film, and (g) cassava starch/CM film.
Chapter 11: Modification of Wheat Gluten-Based Polymer Materials by Molecular Biomass
Figure 11.1 Tensile strength and elongation of the WG-AF and WG-AFTR materials.
Figure 11.2 Dynamic mechanical analysis results for WG-AF or WG-AFTR materials.
Figure 11.3 CP (a) and SPE (b) 13 C solid-state NMR spectra of WG-AFTR materials. (
Figure 11.4 1 H MAS NMR spectra of the WG samples measured by CPMG pulse sequence at the τ delay of 0.1 ms (a) and 3 ms (b).
Figure 11.5 13 C SPE/MAS NMR spectra of A-WG-0 (pH 6), A-WGESO-20 (pH 6), B-WGESO-20 (pH 11), and 13 C solution NMR spectra of ESO and WG-lipid. bs: background signal from the spinning and * peaks: epoxy groups in ESO.
Figure 11.6 1 H NMR spectra of WG-0 and WGESO-20 (A-pH 6; B-pH11).
Figure 11.7 Tensile strength data of WG-glycerol and WGESO-glycerol at pH 6 and 11.
Figure 11.8 Contact angle data of WG-glycerol and WGESO-glycerol samples at pH 11.
Figure 11.9 SEM images of the WG-AFTR sample after composting for 7 days.
Figure 11.10 Biodegradation process of the chemically modified WG materials detected as conversion to CO2 (error bar of 3–5%).
Chapter 12: Copolymerization of C1 Building Blocks with Epoxides
Figure 12.1 The formation of new carbon–oxygen bond between CO2 and epoxide (R1 and R2 are alkyl and aryl groups, Pn represents the propagating chain).
Figure 12.2 (a) Bulk structure of ZHCC [61] and (b) the proposed Zn─OH bond of Zn─Co(III) DMCC [62] for initiating copolymerization. Herein, two CN− groups are shared by Zn2+ and Co3+ ions. Such a proposed site contains one OH− (or Cl− ) in one tetrahedral Zn2+ structure, and thus meets the electroneutrality principle. CA is the complexing agent (generally tert -butyl alcohol, t -BuOH); (c) carbonic anhydride zinc enzyme.
Figure 12.3 Zn─Co(III) DMCC-catalyzed CO2 /PO and CO2 /CHO copolymerization and chain structure of the resulting copolymer [62, 72]. H2 O acts as chain transfer agent for the copolymerization.
Figure 12.4 The proposed catalytic cycle with Zn─OH initiation for Zn─Co(III) DMCC (take CO2 /CHO copolymerization as an example), 1 and 2: initiation, 3, chain propagation, and 4, chain transfer reaction to water.
Figure 12.5 SEM images of Zn─Co(III) DMCC catalyst synthesized at 75 °C [62].
Figure 12.6 Selected epoxides with various side groups for the copolymerization with CO2 . (A) ethylene oxide, (B) propylene oxide, (C) 2-ethyloxirane (1,2-butene oxide), (D) 2-butyloxirane (1,2-hexeneoxide), (E) 2-hexyloxirane (1,2-octeneoxide), (F) 2-decyloxirane (1,2-epoxydodecane), (G) isobutene oxide, (H) 2-(tert -butyl)oxirane, (I) 2-cyclohexyloxirane, (J) styrene oxide, (K) 2-benzyloxirane, (L) epichlorohydrin, (M) phenyl glycidyl ether, (N) glycidyl methyl ether, (O) glycidyl methacrylate, (P) allyl glycidyl ether, (Q) glycidyl isopropyl ether, (R) 2-((2-(2-methoxyethoxy)-ethoxy)methyl)oxirane, (S) ethoxy ethyl glycidyl ether, (T) 1,2-isopropylidene glyceryl glycidyl ether, (U) tert -butyl glycidyl ether, (V) butyl glycidyl ether, (W) benzyl glycidyl ether, (X) epoxy methyl 10-undecenoate, (Y)vinyl oxide, (a) cyclohexene oxide, (b) 1,2-epoxy-4-cyclohexene, (c) 1,2-epoxy-3-cyclohexene, (d)1,4-dihydronaphthalene, (e) cyclopentene oxide, (f) indene oxide, (g) 3,5-dioxa-epoxides, (h) 1,2-epoxy-4-vinylcyclohexane, (i) limonene oxide, and (j) functionalized cyclohexene oxide.
Figure 12.7 Copolymerization of limonene oxide and CO2 to enantiomerically pure, regioregular isotactic copolymers, and formation of semi-crystalline stereocomplex.
Figure 12.8 DA reaction of N -phenylmaleimide and the polycarbonate obtained from furfuryl glycidyl ether and CO2 .
Figure 12.9 Synthesis of bio-based epoxide from 10-undecenoic acid, alternating copolymerization of methyl 10-undecenoate epoxide and CO2 via Zn─Co(III) DMCC catalysis and corresponding tri-block copolymer from ROP of l-lactide at 25 °C [82].
Figure 12.10 Synthesis of 1,4-cyclohexadiene oxide (CHDO), cyclohexene oxide (CHO), and two bis-epoxides (syn -1,4-cyclohexadiene diepoxide, anti -1,4-cyclohexadiene diepoxide) from 1,4-cyclohexadiene (CHD) and the copolymerization of CO2 with CHDO.
Figure 12.11 The CO2 /epichlorohydrin copolymerization catalyzed by Zn─Co(III) DMCC catalyst at 25–60 °C.
Figure 12.12 Lactones and cyclic anhydrides derived from biomass which could be terpolymerized with epoxides and CO2 .
Figure 12.13 Copolymerization of CHO and subsequent block copolymerization with lactide [97].
Figure 12.14 Tandem strategy for the synthesis of CO2 -based model A–B diblock copolymer and the related catalyst system. X = 2,4-dinitrophenoxide [106].
Figure 12.15 Terpolymerization of CHO, DGA, and CO2 to a diblock copolymer via one-pot reaction [98].
Figure 12.16 MA/CHO/CO2 terpolymerization catalyzed by Zn─Co(III) DMCC in tetrahydrofuran (THF).
Figure 12.17 The one-pot coupling reaction of PO, bis-epoxide, and CO2 catalyzed by Zn─Co(III) DMCC/CTAB binary catalyst system and polyaddition of bis(cyclic carbonate)s and 1,6-hexamethylenediamine. Note that two pathways (a and b) to the ring opening of the cyclic carbonate occur randomly during the reaction, leading to the formation of the secondary and primary hydroxyl groups [112].
Figure 12.18 The copolymerization of propylene oxide with carbon disulfide.
Figure 12.19 The copolymerization of PO with CS2 catalyzed by Zn─Co(III) DMCC catalyst. (a) O/S atom-exchange reaction of PO and CS2 . (b) Copolymerization and coupling reaction among CS2 , PO, COS, PS, and CO2 .
Figure 12.20 The copolymerization of CHO with CS2 catalyzed by (salen)CrCl/PPNCl catalyst and Zn─Co(III) DMCC catalyst.
Figure 12.21 The coupling reaction of cyclopentene oxide with CS2 catalyzed by (salen)CrCl/PPNCl catalyst.
Figure 12.22 The copolymerization of oxetane with CS2 .
Figure 12.23 The 1 H NMR spectra of entries from different cocatalysts. In this 1 H NMR spectrum, peaks for different thiocarbonate units are separated and thus O/S scrambling could be quantitatively investigated. (CS2 /OX = 1, catalyst/cocatalyst = 1, catalyst/epoxides = 1/1000, 80 °C, PPN = bis(triphenylphosphine)iminium, Cl = chloride; Y = 2,4-nitrophenoxide; N3 = azide; SCN = sulfocyanate, TBD = 1,5,7-triazabicyclo[4.4.0]dec-5-ene, Bu4 NCl = tetrabutylammonium chloride.). (
Figure 12.24 The copolymerization of propylene oxide with COS.
Figure 12.25 Different routes for the propagating process in PO/COS copolymerization.
Figure 12.26 A plausible mechanism for the O/S exchange reaction in the PO/COS copolymerization. (
Figure 12.27 The copolymerization of CHO with COS catalyzed by Zn─Co(III) DMCC catalyst.
Figure 12.28 The copolymerization of CHO with COS and terpolymerization of CHO/PO/COS.
Figure 12.29 The copolymerization of COS with phenyl glycidyl ether.
Figure 12.30 The copolymerization of COS with styrene oxide.
Figure 12.31 Two different routes of the ring opening of styrene oxide. The structures of the three different catalysts used in the copolymerization of COS with styrene oxide.
Figure 12.32 Copolymerization of 1,4-dihydronaphthalene oxide (CDO) with CO2 .
Figure 12.33 The substituent effect of selected epoxides on T g s of the resulting CO2 /epoxide copolymers ( = 91.5–99%; M n : 6.6–93.2 kg mol−1 ) [81].
Figure 12.34 The variation of the refractive indices (n ) via the wavelength from 400 to 800 nm (n d is refractive index at wavelength 587.6 nm).
Chapter 13: Double-Metal Cyanide Catalyst Design in CO2/Epoxide Copolymerization
Scheme 13.1 Synthetic routes for aliphatic polycarbonates.
Figure 13.1 Structures of (a) cubic Zn3 [Co(CN)6 ]2
Scheme 13.2 Method for the synthesis of Fe–Zn DMC and its tentative structure [35].
Figure 13.2 Effect of unsaturated complexing agents on activity of Co–Zn DMC in PO/CO2 copolymerization [44].
Figure 13.3 Illustration showing the crystallization of DMC catalyst in the presence of co-complexing agents.
Figure 13.4 Mechanism of copolymerization of ECH and CO2 over a nano-lamellar DMC catalyst.
Figure 13.5 Scanning electron microscopic images of Co–Zn DMC catalysts prepared by different methods. (a) DMC with cubic crystal structure, (b) DMC with cubic/monoclinic crystal structure, and (c) DMC with monoclinic/rhombohedral crystal structure.
Figure 13.6 Induction period of DMC catalysts in copolymerizations and terpolymerization.
Figure 13.7 Copolymerization in the presence of initiators [69].
Figure 13.8 Mechanism of copolymerization at different active centers [69, 70].
List of Tables
Chapter 2: Polyhydroxyalkanoates: Sustainability, Production, and Industrialization
Table 2.1 Thermal and mechanical properties of typical PHAs and traditional plastics [17–20].
Table 2.2 Known bacterial strains used for PHA industrial production [5].
Table 2.3 PHA projects by companies all over the world [5].
Chapter 3: Polylactide: Fabrication of Long Chain Branched Polylactides and Their Properties and Applications
Table 3.1 Parameters used to fit linear viscoelasticity for PLA samples with three components.
Chapter 5: Use of Rosin and Turpentine as Feedstocks for the Preparation of Polyurethane Polymers
Table 5.1 Some physical parameters and foaming behavior of cup foam for rosin-based polyester polyol and Daltola P744 [7].
Table 5.2 Some physical properties of RPUFsa) - [7].
Table 5.3 Properties of the cross-linked products of the polyols from HTEM [12].
Table 5.4 The recovery rate (Rr) at a 500% strain of the cyclic tensile testing [19].
Chapter 6: Rosin-Derived Monomers and Their Progress in Polymer Application
Table 6.1 Copolymer properties obtained from creep recovery tests.
Chapter 7: Industrial Applications of Pine-Chemical-Based Materials
Table 7.1 Crude tall oil composition by region [3].
Table 7.2 Simplified overview of the composition of turpentines of different origins.
Table 7.3 Copolymers of terpenes and petroleum-based hydrocarbons.
Table 7.4 Typical composition of TOFA (wt%).
Table 7.5 Typical composition of rosin acids (wt%).
Table 7.6 Method of extraction of Sterols from tall oil pitch.
Table 7.7 Uses of tall oil pitch in asphalt applications.
Table 7.8 Uses of Vinsol® resin as air-entraining agent in cement or concrete.
Chapter 8: Preparation and Applications of Polymers with Pendant Fatty Chains from Plant Oils
Table 8.1 ATRP polymerization of fatty alcohol derived (meth)acrylate monomers.
Chapter 9: Structure–Property Relationships of Epoxy Thermoset Networks from Photoinitiated Cationic Polymerization of Epoxidized Vegetable Oils
Table 9.1 General chemical structures of “onium salts” used for photo-initiated cationic polymerization.
Table 9.2 Hammett acidities of Brønsted acid, HMtXn .
Table 9.3 Relative fatty acid composition and average number of carbon–carbon double bonds per triglyceride molecule in various types of vegeTable oils.
Table 9.4 ESO thermoset resins with different values of f epoxy .
Chapter 10: Biopolymers from Sugarcane and Soybean Lignocellulosic Biomass
Table 10.1 Chemical composition of different lignocellulosic biomass types.
Table 10.2 Polymers produced from soybean hulls.
Table 10.3 Average diameter (D 50 ) and chemical composition of soybean straw ground by different milling processes: knife mill (KM), cryogenic mill (CM) for 10 or 20 min, and ball mill (BM) for 2 or 24 h, at 5 or 15 Hz.
Table 10.4 Lignocellulosic composition of soybean straw (SS) residues after grinding in knife mill (KM), ball mill for 2 h at 5 Hz (BM), and cryogenic mill for 20 min (CM), before and after pretreatments (Table 10.1).
Table 10.5 Polymers produced from sugarcane bagasse
Chapter 11: Modification of Wheat Gluten-Based Polymer Materials by Molecular Biomass
Table 11.1 Properties of wheat gluten films containing tannic acid [72].
Table 11.2 The 1 H T 1 and T 2 values of different components in the WG Materials [75].
Table 11.3 1 H T 2 (ms) data of lipid and ESO in WG-ESO materials at pH 6 (A) and 11 (B) [83].
Chapter 13: Double-Metal Cyanide Catalyst Design in CO2/Epoxide Copolymerization
Table 13.1 Effect of complexing agent on activity of Co–Zn DMC for CHO/CO2 copolymerization [42].
Table 13.2 Effect of co-complexing agent on the activity of Co–Zn DMC in the copolymerization of CHO and CO2 [45].
Table 13.3 Effect of co-complexing agents (Co–CA) on activity of Co–Zn DMC in the copolymerization of CHO and CO2 under microwave irradiation [46].
Table 13.4 Effect of different co-complexing agents on activity of Co–Zn DMC in the copolymerization of PO and CO2 [47].
Table 13.5 Influence of zinc precursors (ZnX2 ; X = Cl, Br, and I) on the activity of Co–Zn DMCs in the copolymerization of CHO, CPO, PO, and CO2 [48].
Table 13.6 Effect of co-catalysts on the copolymerization of PO and CO2 in the presence of Co–Zn DMC catalysts [53].
Table 13.7 Catalytic activity of nano-multimetal cyanides in the copolymerization of CHO and CO2 [59].
Table 13.8 Physicochemical properties of Co–Zn DMC catalysts with cubic, cubic/monoclinic, and monoclinic/rhombohedral crystal structures [67].
Table 13.9 Catalytic activity of Co–Zn DMCs (cubic/monoclinic and monoclinic/rhombohedral) in copolymerizations and terpolymerization of PO, CHO, and CO2 [67].
Sustainable Polymers from Biomass
Edited by Chuanbing Tang and Chang Y. Ryu
Editors
Prof. Chuanbing Tang
University of South Carolina
Dept. of Chemistry & Biochemistry
631 Sumter Street
SC
United States
Prof. Chang Y. Ryu
Rensselaer Polytechnic Institute
Dept. of Chemistry & Chemical Biology
110 8th Street
NY
United States
Cover
folded up sheet
fotolia/pico, pellets
fotolia/BillionPhotos.com, stack of wood
fotolia/Alberto Masnovo
All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.
Library of Congress Card No.: applied for
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library.
Bibliographic information published by the Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>.
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany
All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.
Print ISBN: 978-3-527-34016-3
ePDF ISBN: 978-3-527-34017-0
ePub ISBN: 978-3-527-34019-4
Mobi ISBN: 978-3-527-34018-7
oBook ISBN: 978-3-527-34020-0
Cover Design Schulz Grafik-Design, Fußgönheim, Germany