Macromolecules Containing Metal and Metal-Like Elements, Group IVA Polymers

by Abd-El-Aziz, Alaa S.; Carraher, Charles E.; Pittman, Charles U.; Zeldin, Martel

• ISBN13: 9780471682387
• ISBN10: 0471682381
• Format: Hardcover
• Copyright: 2005-03-17
• Publisher: Wiley-Interscience

Summary

This series provides a useful, applications-oriented forum for the next generation of macromolecules and materials. Volume 4 provides useful descriptions of Group IV metals and their applications, including silicon-, organogermanium-, organotin-, and organolead-containing polymers. A high-quality team of macromolecular experts from around the world have put together these leading macromolecule titles.

Table of Contents

Preface	xv
Series Preface	xvii
1. Overview-Group IVA Polymers	1	(6)
Charles E. Carraher, Jr., Charles U. Pittman, Jr., Martel Zeldin, and Alaa S. Abd-El-Aziz
I. Introduction	2	(2)
II. Group IV Polymers	4	(1)
III. References	5	(2)
2. Hyperbranched Poly(silylenearylene)s	7	(30)
Ronghua Zheng, Hongchen Dong, and Ben Zhong Tang
I. Introduction	8	(2)
II. Results and Discussion	10	(17)
A. Monomer Synthesis	10	(1)
B. Polymerization Behaviors	11	(2)
C. Structural Characterizations	13	(11)
D. Polymer Properties	24	(3)
III. Conclusions	27	(1)
IV. Experimental Section	27	(8)
A. Materials and Instruments	27	(1)
B. Synthesis of (4-Bromophenylethynyl)- trimethylsilane	27	(1)
C. Synthesis of (4-Bromo-3-methylphenylethynyl)- trimethylsilane	28	(1)
D. Synthesis of (4-Bromo-2, 5-dimethylphenylethynyl)- trimethylsilane	28	(1)
E. Synthesis of Bis[4-(2-trimethylsilyethynyl)phenyl]- dimethylsilane	29	(1)
F. Synthesis of Bis[4-(2-trimethylsilyethynyl)phenyl]- methylphenylsilane	29	(1)
G. Synthesis of Bis[4-(2-trimethylsilyethynyl)phenyl]- diphenylsilane	30	(1)
H. Synthesis of Bis[2-methyl-4-(2-trimethylsilylethynyl)-phenyl]dimethylsilane	30	(1)
L Synthesis of Bis[2,5-dimethyl-4-(2-trimethylsilylethynyl)- phenyl]dimethylsilane	30	(1)
J. Synthesis of Bis(4-ethynylphenyl)dimethylsilane	31	(1)
K. Synthesis of Bis(4-ethynylphenyl)methylphenylsilane	31	(1)
L. Synthesis of Bis(4-ethynylphenyl)diphenylsilane	31	(1)
M. Synthesis of Bis(4-ethynyl-2-methylphenyl)- dimethylsilane	32	(1)
N. Synthesis of Bis(2,5-dimethyl-4-ethynylphenyl)- dimethylsilane	32	(1)
O. Diyne Polycyclotrimerization	32	(1)
P. Polymer Characterization	33	(1)
Q. Synthesis of Model Compounds 1,3,5- and 1,2,4- Triphenylbenzenes	34	(1)
R. Decomposition of Hyperbranched Polymers	35	(1)
S. Structural Simulation	35	(1)
V. Acknowledgments	35	(1)
VI. References	36	(1)
3. Silole-Containing Conjugated Polymers	37	(14)
Jacky W.Y. Lam, Junwu Chen, Hongchen Dong, and Ben Zhong Tang
I. Introduction	38	(1)
II. Polymer Syntheses	38	(3)
III. Thermal Stability	41	(1)
IV. Photoluminescence	42	(2)
V. Electroluminescence	44	(3)
VI. Optical Limiting	47	(1)
VII. Conclusions	48	(1)
VIII. Acknowledgments	48	(1)
IX. References	48	(3)
4. Silica Polyamine Composites: Advanced Materials for Metal Ion Recovery and Remediation	51	(28)
Edward Rosenberg
I. Introduction	52	(3)
II. Relationships between Composite Characteristics and the Starting Materials Used	55	(3)
A. Wide-Pore Amorphous Silica	55	(1)
B. Particle Size and Back Pressure	56	(1)
C. Capacity, Longevity, and Polymer Molecular Weight	57	(1)
III. Comparison with Other Resin Technologies	58	(3)
IV. Structural Considerations	61	(5)
A. The Nature of the Polymer Graft to the Silica Surface	61	(1)
B. Polymer Structure and Metal Ion Coordination	62	(2)
C. Molecular Modeling Studies	64	(2)
V. Applications	66	(10)
A. Metal Chromatography: Separation and Concentration of Multicomponent Metal Mixture from Acid Mine Drainage	66	(2)
B. Selective Recovery of Copper from Solvent Extraction Circuit Waste Streams of Acid Mine Leaches	68	(3)
C. Separation of Cobalt and Copper Using Two Different Polyamine Composites in Tandem Columns	71	(1)
D. Removal of Mercury from Waste Solutions Using Sulfur-Modified Silica-Polyamine Composites	72	(4)
VI. Future Work	76	(1)
VII. Acknowledgments	77	(1)
VIII. References	77	(2)
5. Polyhedral Oligomeric Silsesquioxane (POSS) Polymers, Copolymers, and Resin Nanocomposites	79	(54)
Guizhi Li and Charles U. Pittman, Jr
I. Introduction	80	(2)
II. Synthesis of Polyhedral Oligomeric Silsesquioxanes	82	(4)
A. Monofunctional POSS Synthesis	83	(1)
B. Multifunctional POSS Synthesis	84	(2)
III. POSS Polymers and Copolymers (Thermoplastics)	86	(20)
A. Styryl-POSS Polymers, Copolymers, and Nanocomposites	87	(6)
B. Methacrylate-POSS Polymers, Copolymers, and Nanocomposites	93	(5)
C. Norbornenyl-POSS Copolymers and Nanocomposites	98	(6)
D. POSS-Olefin Copolymers and Nanocomposites	104	(1)
E. Siloxane-POSS Copolymers	105	(1)
IV. Crosslinked POSS-Containing Resins and Materials	106	(17)
A. Vinyl Ester, Epoxy, and Phenolic Resins Containing POSS	108	(7)
B. Dicyclopentadiene Resins Containing POSS	115	(2)
C. Styrene and Methyl Methacrylates Resins Containing POSS	117	(6)
V. Other Applications	123	(3)
VI. Summary	126	(1)
VII. Acknowledgments	126	(1)
VIII. References	127	(6)
6. Silica- and Silsesquioxane-Containing Polymer Nanohybrids	133	(28)
Mohammad A. Wahab, Il Kim, and Chang-Sik Ha
I. Introduction	134	(1)
II. Polymer-Silica or Polymer-Silsesquioxane Nanohybrids	135	(8)
A. Key Parameters for Forming Nanohybrids	135	(3)
B. The Sol-Gel Method and Its Related Parameters	138	(2)
C. Polymer-Silica Nanohybrids	140	(1)
D. Polymer-Silsesquioxane (SSQ) Nanohybrids	140	(2)
E. Other Metal Oxide or Metal-Like Materials Containing Polymer Nanohybrids	142	(1)
III. Polyimide-Silica or Polyimide-Silsesquioxane Nanohybrids	143	(13)
A. Polyimide	143	(1)
B. Polyimide-Silica Nanohybrids Their Characterization and Properties	143	(8)
C. Polyimide-Silsesquioxane Nanohybrids-Their Characterization and Properties	151	(3)
D. Polyimide-Silica-Titania Nanohybrids	154	(2)
IV. Conclusions	156	(1)
V. Acknowledgments	157	(1)
VI. References	157	(4)
7. Siloxane Elastomers and Copolymers	161	(42)
Sakuntala Chatterjee Ganguly
Part 1. Siloxane-Divinylbenzene Copolymers as Elastomers	163	(12)
I. Introduction	163	(1)
A. Silicone Elastomers by Radical Polymerization	163	(1)
B. Synthesis of Silicone Elastomers by Combining Radical Polymerization and Hydrosilation	166	(1)
C. Synthesis of Silicone Elastomers by Polycondensation Reaction	167	(1)
D. Synthesis of Silicone Elastomers by Side-Chain and Main-Chain Hydrosilation Reactions	168	(3)
II. Experimental Section	171	(1)
A. Materials and Instruments	171	(1)
B. Synthesis of Poly(tetramethyldisiloxane-divinylbenzene) (PTMS-DVB)	171	(1)
III. Results and Discussions	171	(3)
IV. Conclusions	174	(1)
Part 2. Polyviologen and Siloxane-Based Polyviologen Copolymers	175	(8)
I. Introduction	175	(1)
A. Polyviologen Based on 4,4'Bipyridinium Salts	176	(1)
B. Miscellaneous Polyviologens	176	(1)
C. Modified Route to Pyridino-Terminated Oligo-(dimethylsiloxane)	178	(1)
D. Alternate Viologen Polymers from Vinylbenzyl Chloride-Modified Tetramethyldisiloxane and 4,4'-Bipyridine	179	(1)
II. Experimental Section	180	(1)
A. Materials and Instruments	180	(1)
B. Synthesis of Bis(4-Chloromethylphenyl)tetramethyl-disiloxane (BCTD)	181	(1)
C. Synthesis of Viologen Polymer from BCTD and 4,4'-Bipyridine	181	(1)
III. Results and Discussions	181	(1)
IV Conclusions	182	(1)
Part 3. Siloxane-Based Polyurethane Copolymers	183	(21)
I. Introduction	183	(1)
A. Blends of Polysiloxane with Poly(etherurethane) and Blends of Polydimethylsiloxane with Thermoplastic Polyurethane-True and Semi-Interpenetrating Networks of Silicone-Urethanes	184	(1)
B. Siloxane Groups and Urethanes Linking Units into PEO	185	(1)
C. Side-Chain Polyurethane Based on Polysiloxanes with Pendant Primarily Alcohol and Quaternary Ammonium Groups	185	(1)
D. End-Chain Silicone-Modified Segmented Polyurethane Membrane as Blood-Compatible Ion-Selective Electrode	186	(1)
E. Polyurethane Containing Side-Chain Polyhedral Oligometric Silsesquioxanes (POSS)	187	(1)
F. Diphenylsilanediol-Based Polyurethanes	187	(1)
G. Siloxane-Urethane Containing Block Copolymers	188	(1)
H. Polyurethane Modified with an Aminoethylaminopropyl-Substituted Polydimethylsiloxane	192	(1)
I. Synthesis of Waterborne Polyurethane Modified with an Aminoethylaminopropyl-Substituted Polydimethylsiloxane	193	(1)
J. Alternate Siloxane-Urethane Copolymer by Three-Step Reaction	194	(2)
II. Experimental Section	196	(1)
A. Materials and Instruments	196	(1)
B. Synthesis of Bis(3-trimethylsiloxypropyl)tetramethyl Disiloxane (BTTD) from Allyloxytrimethylsilane	197	(1)
C. Synthesis of Bis(3-hydroypropyl)tetramethyl Disiloxane (BHTD)	197	(1)
D. Synthesis of Siloxane-Urethane Copolymer from BHTD and 2,5-TDI	197	(1)
III. Results and Discussions	197	(2)
IV Acknowledgments	199	(1)
V References	199	(4)
8. Bioinspired Silica Synthesis	203	(22)
Siddharth V. Patwardhan and Stephen J. Clarson
I. Introduction	204	(4)
A. Silica	204	(1)
B. Silica: Existence, Solubility, and Synthesis	204	(1)
i. Silica Synthesis by Sol-Gel Processing	206	(1)
a. Hydrolysis	206	(1)
b. Condensation	206	(1)
ii. Silica Particle Synthesis	207	(1)
C. Biosilica: Existence and Importance	207	(1)
II. Biosilicification and Protein Interactions	208	(3)
A. Diatoms	208	(2)
B. Grasses	210	(1)
C. Sponges	211	(1)
III. Bioinspired and Biomimetic Synthesis: The Use of Poly(allylamine Hydrochloride)	211	(5)
A. Synthesis of Spherical Silica Particles	212	(1)
B. Synthesis of Nonspherical Silica Structures	213	(1)
C. Synthesis Using a Mixture of Macromolecules	213	(1)
D. Electrostatically Self-Assembled Bilayers of PAAcid and PAH	214	(1)
E. Role of Polyelectrolytes	214	(2)
IV. Use of Other Macromolecular Systems to Synthesize Silica	216	(4)
A. Silica Synthesis Using Polyamino Acids	216	(1)
B. Silica Synthesis Using Polypeptides	216	(3)
C. Silica Synthesis Using Polycations	219	(1)
D. Silica Synthesis Using Polyanions and Other Systems	219	(1)
V. Summary	220	(1)
VI. Future Work	220	(1)
VII. Acknowledgments	221	(1)
VIII. References	221	(4)
9. Organogermanium Polymers	225	(38)
Charles E. Carraher Jr., Charles U. Pittman, Jr., Martel Zeldin, and Alaa S. Abd-El-Aziz
I. Introduction	226	(1)
II. Polygermanes	227	(7)
A. Wurtz Reactions	228	(2)
B. Catalytic Routes	230	(1)
C. Ligand Substitution	230	(1)
D. Electrochemical Synthesis	231	(1)
E. Chemical Properties	232	(1)
F. Physical Properties	232	(1)
G. Miscellaneous	233	(1)
III. Organogermanium-Carbon Backbone Polymers	234	(10)
A. Organogermanium Polymers Containing σ-π Conjugation	235	(8)
B. Simple Ge-C Polymers	243	(1)
IV. Polyferroceneylgermanes	244	(1)
V. Polymers Containing Oxygen, Nitrogen, Silicon, and Sulfur in the Backbone	245	(8)
A. Ge-O Polymers	245	(3)
B. Ge-N Polymers	248	(2)
C. Ge-S Polymers	250	(1)
D. Ge-Si Polymers	250	(1)
E. Other Mixed-Bonded Polymers	251	(2)
VI. Anchored Organogermanium Products	253	(2)
VII. Stacked Phthalocyanine Polymers	255	(1)
VIII. Hyperbranched Materials	256	(2)
IX. Summary	258	(1)
X. References	258	(5)
10. Organotin Polymers	263	(48)
Charles E. Carraher, Jr
I. Introduction	264	(1)
II. Mechanisms	265	(1)
III. Structures	266	(2)
IV. Organotin Polymers	268	(1)
V. Organotin Appendages	268	(14)
A. Vinyl Introduction	268	(1)
i. Organoesters and Ethers	268	(1)
ii. Organotin Carbon	273	(2)
B. Performed Polymer	275	(4)
C. Crosslinked Mixtures	279	(3)
VI. Organotin-Containing Backbones	282	(6)
A. Noncarbon-Linked Organotin Polymers	282	(4)
B. Organotin Polyolefins	286	(2)
VII. Polystannanes	288	(1)
VIII. Organotin Aluminoxanes and Titanoxanes	288	(1)
IX. Group VA-Containing Organotin Polymers	289	(1)
X. Stannoxy Titanoxane Polymers	290	(1)
XI. Stannoxane Polymers	290	(1)
XII. Bioactivity	291	(2)
XIII. General Physical Properties	293	(6)
A. Solubility	293	(1)
B. Stability	294	(1)
C. Physical Nature	294	(1)
D. Molecular Weight	294	(1)
E. Thermal Properties	294	(1)
F Electrical Properties	295	(1)
G. Mass Spectral Behavior	295	(4)
H. Miscellaneous	299	(1)
XIV. Interfacial Polymerization	299	(4)
XV. Summary	303	(1)
XVI. References	303	(8)
11. Organolead-Containing Polymers	311	(22)
Charles E. Carraher, Jr
I. Introduction	312	(1)
II. Polymerization and Copolymerization of Vinyl Lead Compounds	313	(2)
III. Chelation Polymers and Copolymers Derived from Poly(Acrylic Acid)	315	(1)
IV. Arylene-Bridged Products	316	(1)
V. Solid-State Products	316	(8)
A. Nitrogen-Coordinated Products	317	(2)
B. Sulfur-Coordinated Products	319	(2)
C. Halide-Coordinated Products	321	(1)
D. Oxygen Coordinated Products	322	(2)
VI. Condensation Products	324	(2)
VII. Miscellaneous	326	(2)
VIII. Summary	328	(1)
IX. References	328	(5)
Index	333