Rigid Polymer Networks: Advances in Polymer Science Volume 118

Description

Table of Contents
List of Symbols
1 Introduction
General Classification of Liquid-Crystal Polymers
and Networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.2.1 Definition of Liquid-Crystal Polymers . . . . . . . . . . . . . . 8
1.2.2 Flexible Chain Polymers with Mesogenic Groups . . . . . . . 10
1.2.3 Networks with Flexible Chains and Stiff Mesogenic
Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.2.3.1 Networks with Stiff Main-Chain Mesogens,
Flexible Spacers and Flexible Junctions . . . . . . . . . 13
1.2.3.2 Networks with Stiff Main-Chain Mesogens,
Flexible spacers and Rigid Branchpoints . . . . . . . . 16
1.2.3.3 Networks with Stiff Pendant Mesogens, Flexible
Main-Chains and Flexible Junctions . . . . . . . . . . 18
1.2.3.4 Networks with Stiff Pendant Mesogens Connected
at Both Ends to Flexible Main Chains . . . . . . . . . 21
1.2.4 Networks Containing No Flexible Spacers . . . . . . . . . . . 25
1.2.4.1 Uniform Main-Chain Mesogenicity: Flexible,
Wormlike, Rodlike . . . . . . . . . . . . . . . . . . . . . 26
1.2.4.2 LCPs from Biological Origin and
Their Networks . . . . . . . . . . . . . . . . . . . . . . . 33
1.2.4.3 Networks with Uniform Main-Chain
Mesogeni-city and Flexible Crosslinking Residues . . 34
1.3 The Fractal Character of Pre-Gel and Post-Gel
Highly Branched Polymers . . . . . . . . . . . . . . . . . . . . . . . . 38
Exclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
Synthetic Highlights . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.1 One-Step and End-Capped Rigid Networks . . . . . . . . . . . . . . 46
3.1. t Networks with Stiff Hydrocarbon Segments . . . . . . . . . . 46
3.1.1.1 Polyphenylenes and Poly (Substituted Phenylenes).. 46
3.1.1.2 Hydrocarbon Networks with Very Short Aromatic
Segments . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.1.1.3 Stiff Aliphatic Segments . . . . . . . . . . . . . . . . . . 52
3.1.1.4 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.1.2 Aromatic Polyamide Networks with Stiff Segments
and Rigid Branchpoints . . . . . . . . . . . . . . . . . . . . . . 54
3.1.2.1 Rigid Polyamide Networks, Gels and Fractal
Polymers Prepared in Solution in the Presence
of Triarylphosphite . . . . . . . . . . . . . . . . . . . . . 54
3.1.2.2 Rigid Polyamide Networks and Fractal Polymers
Prepared in Solution by Other Procedures . . . . . . . 66
3.1.3 Rigid Aromatic Polyester Networks . . . . . . . . . . . . . . . 68
3,1.4 Rigid Aromatic Networks Containing Single-Atom Bridges . 70
3.1.4.1 Aromatic Hydrocarbons with Methylene Bridges... 72
3.1.4.2 Phenol-Formaldehyde Type Networks . . . . . . . . . 73
3.1.4.3 Furan-Containing Networks . . . . . . . . . . . . . . . 76
3.1.4.4 Aromatic Polyether and Ether-Containing
Networks . . . . . . . . . . . . . . . . . . . . . . . . . . 78
3.1.4.5 Bridged Aromatic Networks with Uncommon
Electronic Structure . . . . . . . . . . . . . . . . . . . . 80
3.1.4.6 Morphology and Possible Fractality . . . . . . . . . . 84
3.1.5 Rigid Networks with Triazine Branchpoints . . . . . . . . . . 85
3.1.6 Rigid Networks from Stiff End-Capped Segments . . . . . . . 92
3.t.6.1 Networks with Unsaturated Imide Junction
Precursors . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3.1.6.2 Networks Crosslinked by Strained-Ring Precursors . 96
3.1.6.3 Networks Crosslinked by Ethynyl End-Caps
and Pendant Groups . . . . . . . . . . . . . . . . . . . 102
3.2 Two-Step Aromatic Networks . . . . . . . . . . . . . . . . . . . . . 107
3.2.1 Two-Step Aromatic Polyamide Networks . . . . . . . . . . . 108
3.2.2. Two-Step Networks from Poly (Ether Ketone Ketone)
(PEKK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
3.2.3 Networks from Aromatic Linear Chains Created
by Reacting Backbone Diacetylene or Pendant
Acetylene Groups . . . . . . . . . . . . . . . . . . . . . . . . . 113
32.4 Potential Two-Step Polyarylene Networks . . . . . . . . . . 116
3.2.5 Supernetworks . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
Features . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
4.1 Pre-Gel State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
4.1.1 Fractal Nature of Growing One-Step Species
and Comparison with Two-Step Species . . . . . . . . . . . . 121
4.1.2 Co*, the Critical Concentration for Gelation . . . . . . . . . 135
4.2 Post-Gel State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
4.2.1 Fractal Nature of Gelled Rigid Networks . . . . . . . . . . . 142
4.2.2 Manifestations of Rigid Network Defects . . . . . . . . . . . 149
4.2.3 Mechanical Properties of Rigid Networks and Their Gels . 152
4.2.4 Observations on Effects of Gravity and Flow-Stress During
the Formation of Rigid Network Gels . . . . . . . . . . . . . 155
4.2.5 High Temperature Stability of Rigid Aromatic Networks.. 157
4.3 Some Properties of Liquid-Crystal Polymer Networks . . . . . . . 159
4.4 Modes of Segmental Deformation . . . . . . . . . . . . . . . . . . . 161
4.4.1 Description of Segments . . . . . . . . . . . . . . . . . . . . . 161
4.4.1.1 Mathematical Description of the Molecules . . . . . 161
4.4.1.2 General Empirical Description of Network
Segments . . . . . . . . . . . . . . . . . . . . . . . . . . 164
4.4.2 Deformation of Aromatic Segments with Bridges
Consisting Exclusively of Coaxial Single Bonds . . . . . . . 166
4.4.3 Deformation of Stiff Aromatic Segments with Bridges
Consisting of a Single Non-Coaxial Bond Connecting
Two Coaxial Bonds Between Aromatic Groups . . . . . . . 168
4.4.4 Deformation of Aromatic Segments with Swivels
Consisting of Two Single Bonds
Connected by a Single Atom . . . . . . . . . . . . . . . . . . 175
4.4.5 Deformation of Networks with Stiff Aromatic Segments
and Relatively Flexible Aliphatic Junctions Created
from Reactive End-Caps . . . . . . . . . . . . . . . . . . . . . 177
4.5 Questions of Elastic Constants . . . . . . . . . . . . . . . . . . . . 179
5. Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
5.1. The Problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
5.1.1 Responses of Flexible and Rigid Networks to Stress
Fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
5.1.2 Complexities Uniquely Linked to Network Rigidity . . . . 193
5.2 Theoretical Description of Rigid Networks . . . . . . . . . . . . . 194
5.2.1 One-Step Networks . . . . . . . . . . . . . . . . . . . . . . . 194
5.2.1.1 General Mathematical Description . . . . . . . . . . 200
5.2.1.2 Field Formalism for Deformation . . . . . . . . . . 203
5.3 Simpler Theoretical Approaches . . . . . . . . . . . . . . . . . . . 206
5.3.1 Simple Calculations of the Concentrated Rigid Network . 206
5.3.2 Simple Calculations in a Dilute Rigid Network . . . . . . . 208
6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
Author Index Volumes 101-118 . . . . . . . . . . . . . . . . . . . . . . . . . 233
Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239

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