橡胶加工工艺(Elastomer Engineering)

前言
橡胶行业是国民经济的重要基础产业之一。它不仅为人们提供日常生活不可或缺的日用、医用等轻工橡胶产品，而且向采掘、交通、建筑、机械、电子等重工业和新兴产业提供各种橡胶制品、生产设备或橡胶部件。橡胶行业的产品种类繁多，服务产业十分广阔。橡胶工业是随着汽车工业发展起来的。二十世纪六十年代汽车工业与石油化学工业高速发展，使橡胶工业生产水平有了很大的提高；进入二十世纪七十年代，为适应汽车的高速、安全和节约能源，消除污染，防止公害等方面的需要，促进了轮胎新品种的不断出现，而原料胶消耗在交通运输领域占有相当大的比重。
橡胶弹性体材料具有长的柔性大分子网状链结构，在外力作用下可以发生大的变形，本体黏度随温度和应变速率的变化而变化，研究弹性体材料的高弹性具有重要的意义。全书重点介绍橡胶弹性体材料的合成、表征、力学性能、流动性能、胶料配合以及硫化成型加工工艺、橡胶弹性理论及测定。
本书第1章由张宏志老师编写，第3章由常海涛老师编写，第4章由巩学勇老师编写，第6章由孙红老师编写，第10章由刘光耀老师编写，其余章节由王者辉老师编写，最后由王者辉老师统一校订全稿。尽管我们常年从事橡胶学科的教学和科研工作，终因学识有限，错误和疏漏之处在所难免，恳请读者指正。

编者
2021年8月



Preface
Rubber industry is one of the important fundamental industries of national economy.It not only provides light industrial rubber products， for both daily and medical use， which are indispensable for people’s daily life， but also provides various rubber products， production equipment or rubber parts to heavy industries and emerging industries such as mining， transportation， construction， machinery， electronics， etc.There are many kinds of products in rubber industry， which depends on very broad supporting industries.The rubber industry is developing with the automobile industry.In the 1960s， with the rapid development of automobile industry and petrochemical industry， the production level of rubber industry has been greatly improved.In the 1970s， in order to meet the needs of high rapidity， safety， energy saving， pollution elimination and prevention of public hazards， new tire varieties were promoted， and the consumption of raw rubber accounted for a considerable proportion in the field of transportation.
　For elastomers， in particular， it is most instructive to derive the unique features of high elasticity from those of long flexible chain molecules in their matted and netted state and the changes imposed by large deformations， including the key role played by the internal viscosity as a function of temperature and rate.The book takes the reader from an introduction through synthesis，characterization， mechanical behavior， and flow to the major processing steps of filling， compounding， and vulcanization and to the theories and measurement of elastomeric performance， leaning strongly on the “materials” approach.
　Mr.Zhang Hongzhi， Chang Haitao， Gong Xueyong， Liu Guangyao and Mrs.Sun Hong edited part of the book （Chapter 1， 3， 4， 6， and 10 respectively）and Mr.Wang Zhehui made the final edition.The authors would like to acknowledge with appreciation the numerous and valuable comments， suggestions， constructive criticisms and praise from evaluators and reviewers.
　All chapters， while presenting theory， mechanism， and the author’s overview of the internal consistency of the material’s pattern of behavior， serve also as substantial sources of data and as guides to the relevant literature and to further self study.As such， this book should be suitable not only as a basis for elastomer course， but also as an instrument of instruction for students， teachers， and workers in all fields of polymer and， indeed， of material science.

Author
December 2020

《橡胶加工工艺（Elastomer Engineering）》主要内容包括：第1章“高分子化学：橡胶合成（Polymer Chemistry ： Elastomer Synthesis）”；第2章“橡胶高弹性：基本原理与性质（Polymer Elasticity： Basic Concepts and Behavior）”；第3章“橡胶配合（Rubber Compounding）”；第4章“橡胶补强剂（Reinforcement of Elastomers by Particulate Fillers）”；第5章“橡胶硫化（Vulcanization）”；第6章“生胶加工工艺（Processing of Unvulcanized Elastomer）”；第7章“橡胶加工流变性（Rheological Behavior in Elastomer Processing）”；第8章“热塑性弹性体（Thermoplastic Elastomers）”；第9章“橡胶共混（Elastomer Blends）”；第10章“橡胶化学改性（Chemical Modification of Elastomers）”；第11章“橡胶强度（Strength of Elastomers）”；第12章“轮胎工艺（Tire Engineering）”；第13章“橡胶再生（Elastomer Recycling）”。本书内容全面，不仅综述性强，而且前沿性强，将橡胶加工新技术与新工艺呈现给读者。
《橡胶加工工艺（Elastomer Engineering）》可供高等学校橡胶工程技术、高分子材料工程技术专业，以及与高分子材料、橡胶工程专业相关的高分子材料与工程、复合材料、材料工程应用技术等本科专业作为教材，也可供橡胶企业工程技术人员和各类橡胶技术培训班学员等参考使用。

Chapter 1Polymer Chemistry：Elastomer Synthesis1
1.1Introduction2
1.2Classification of Polymerization Reactions and Kinetic Considerations3
1.3Polyaddition/ Polycondensation6
1.4Chain Polymerization by Free Radical Mechanism8
1.5Emulsion Polymerization14
1.6Copolymerization23
1.7Chain Polymerization by Cationic Mechanism28
1.8Chain Polymerization by Anionic Mechanism34
1.9Stereospecific Chain Polymerization and Copolymerization by Coordination Catalysts43
1.10Graft and Block Copolymerization51
References57

Chapter 2Polymer Elasticity： Basic Concepts and Behavior65
2.1Introduction66
2.2Elasticity of a Single Molecule66
2.3Elasticity of a Three-Dimensional Network of Polymer Molecules69
2.4Comparison with Experiment72
2.5Continuum Theory of Rubber Elasticity74
2.6Second-Order Stresses80
2.7Elastic Behavior Under Small Deformations81
2.8Some Unsolved Problems in Rubber Elasticity84
References85

Chapter 3Rubber Compounding87
3.1Introduction87
3.2Polymers87
3.3Filler Systems98
3.4Stabilizer Systems108
3.5Vulcanization System113
3.6Special Compounding Ingredients120
3.7Compound Development123
3.8Compound Preparation126
3.9Environmental Requirements in Compounding126
3.10Summary129
References129

Chapter 4Reinforcement of Elastomers by Particulate Fillers131
4.1Introduction131
4.2Preparation of Fillers131
4.3Morphological and Physicochemical Characterization of Fillers134
4.4The Mix：a Nanocomposite of Elastomer and Filler143
4.5Mechanical Properties of Filled Rubbers148
References157

Chapter 5Vulcanization158
5.1Introduction158
5.2Definition of Vulcanization158
5.3Effects of Vulcanization on Vulcanizate Properties159
5.4Characterization of the Vulcanization Process161
5.5Vulcanization by Sulfur without Accelerator164
5.6Accelerated-Sulfur Vulcanization165
References194

Chapter 6Processing of Unvulcanized Elastomer195
6.1Introduction195
6.2Two Roll Mill195
6.3Internal Mixers197
6.4Continuous Mixers201
6.5Trouble Shooting the Mixing Process202
6.6Extrusion Process203
6.7Calendering206
6.8Continuous Vulcanization System211
6.9Moulding212
References217

Chapter 7Rheological Behavior in Elastomer Processing219
7.1Introduction219
7.2Basic Concepts of Mechanics223
7.3Rheological Properties225
7.4Boundary Conditions241
7.5Mechanochemical Behavior244
7.6Rheological Measurements246
7.7Processing Technology251
7.8Engineering Analysis of Processing261
References270

Chapter 8Thermoplastic Elastomers281
8.1Introduction281
8.2Synthesis of Thermoplastic Elastomers286
8.3Morphology of Thermoplastic Elastomers292
8.4Properties and Effect of Structure309
8.5Thermodynamics of Phase Separation315
8.6Thermoplastic Elastomers at Surfaces320
8.7Rheology and Processing326
8.8Applications329
References330

Chapter 9Elastomer Blends331
9.1Introduction331
9.2Miscible Elastomer Blends333
9.3Immiscible Elastomer Blends338
9.4Conclusion350
References350

Chapter 10Chemical Modification of Elastomers355
10.1Introduction355
10.2Chemical Modification of Polymers within Backbone and Chain Ends356
10.3Esterification，Etherification，and Hydrolysis of Polymers357
10.4The Hydrogenation of Polymers360
10.5Dehalogenation，Elimination，and Halogenation Reactions in Polymers361
10.6Other Addition Reactions to Double Bonds364
10.7Oxidation Reactions of Polymers366
10.8Functionalization of Polymers367
10.9Miscellaneous Chemical Reactions of Polymers367
10.10Block and Graft Copolymerization368
References380

Chapter 11Strength of Elastomers382
11.1Introduction382
11.2Initiation of Fracture383
11.3Threshold Strengths and Extensibilities388
11.4Fracture Under Multiaxial Stresses390
11.5Crack Propagation394
11.6Tensile Rupture401
11.7Repeated Stressing：Mechanical Fatigue406
11.8Surface Cracking by Ozone408
11.9Abrasive Wear409
References412

Chapter 12Tire Engineering415
12.1Introduction416
12.2Tire Types and Performance417
12.3Basic Tire Design419
12.4Tire Engineering421
12.5Tire Materials431
12.6Tire Testing444
12.7Tire Manufacturing448
12.8Summary452
References454

Chapter 13Elastomer Recycling456
13.1Introduction456
13.2Retreading of Tire458
13.3Recycling of Rubber Vulcanizates459
13.4Use of Recycled Rubber474
13.5Pyrolysis and Incineration of Rubber484
13.6Concluding Remarks485
References485

Appendix ⅠDemonstration492

Appendix ⅡAcronyms for Common Elastomers498