增塑剂绿色催化技术(英文版) 刘仲毅 著 专业科技 文轩网

Contents
1  Introduction  1
1.1  Background  1
1.2  Fundamentals of Plasticizers  6
1.2.1  Symbols and Abbreviations  6
1.2.2  Major Functions of Plasticizers  6
1.2.3  Major Performance-Determining Factors for Plasticizers  10
1.2.4  Mechanism for Plasticity Increase by Plasticizers  11
1.2.5  Property Requirements for Plasticizers  13
1.2.6  Inspection Standards for Plasticizers  18
1.2.7  Types of Plasticizers  18
1.3  Cyclohexane-1, 2-Dicarboxylate Plasticizers  22
1.4  Environmentally Friendly Plasticizers  25
1.5  Developmental Direction of Plasticizer Industry in China  26
1.6  Main Contents of This Book  27
References  27
2  Foreign and Domestic Plasticizer Laws  33
2.1  Foreign Plasticizer Laws, Evolution  33
2.2  Domestic Plasticizer Laws and Evolution  33
2.3  Interpretations of Foreign and Domestic Plasticizer Laws  37
2.3.1  EU Bans  37
2.3.2  EU’s REACH Policy [1,2]  39
2.3.3  The EU’s RoHS [1,3]  40
2.3.4  USA’s CPSIA  42
2.3.5  Related Phthalate Laws in Other Countries  44
2.3.6  Domestic Laws [4–6]  44
2.4  Comparison and Trend of Plasticizer Laws for Food Contact Applications  47
2.4.1  Current Status  47
2.4.2  Chinese Laws and Regulations  47
2.4.3  EU’s Laws and Regulations  47
2.4.4  USA’s Laws and Regulations  48
2.5  Conclusion  48
References  49
3  Current Status of Plasticizer Research  51
3.1  Foreign Research Status  51
3.1.1  Phthalate Hydrogenation Technology  51
3.1.2  Research on Toxicity of Phthalate Compounds  55
3.2  Domestic Research Status  55
3.2.1  Synthesis of DIBCH(1999)[9]  55
3.2.2  Synthesis of HHPA(2000)[10]  57
3.3  Di(2-Propylheptyl) Phthalate (2006) [13]  59
3.3.1  Physical Properties  59
3.3.2  Performance  60
3.4  Cyclohexane Dicarboxylate Plasticizers (2010)[14]  64
3.4.1  Preparation of Cyclohexane Dicarboxylate Plasticizers  65
3.4.2  Properties and Assessment of Cyclohexane Dicarboxylate Plasticizers  66
3.4.3  Application Examples of Formulation  71
3.4.4  Conclusion  72
3.5  Development Status of Plasticizers (2010, 2011) [18,19]  73
3.5.1  Status of Plasticizers in Foreign Countries  73
3.5.2  Status of Plasticizers in China  73
3.5.3  New Environmentally Friendly Plasticizers  75
3.5.4  Sustainable Development of Plasticizers in China  75
3.6  Diisononyl Cyclohexane-1,2-Dicarboxylate(2010,2014)[20,21]  76
3.6.1  Physical Properties  77
3.6.2  Production Routes of DINCH  77
3.6.3  Applications of DINCH  79
3.7  Environmentally Friendly Plasticizers  81
3.7.1  Di(2-Ethylhexyl) Cyclohexane-1,2-Dicarboxylate Plasticizer(2011)[22]  81
3.7.2  Research and Application Progress of Catalytic Synthesis of Environmentally Friendly Plasticizers(2012)[15]  83
3.7.3  Innovations and Applications of Green Plasticizers[97]  91
3.7.4  Technological Innovation and Market Dynamics of Green Plasticizers(2017)[98]  93
3.8  Hydrogenation of Dioctyl Phthalate (2012)[34]  94
3.9  Liquid-Phase Catalytic DOP Hydrogenation and Kinetics(2012)[50]  94
3.10  Synthesis and Application of Environmentally Friendly DEHCH Plasticizer(2013)[38,113,114]  97
3.11  Synthesis and Application of Environmentally Friendly DEHCH Plasticizer(2014–2015)  100
3.11.1  Preparation of DOP Hydrogenation Catalyst(2014)[120]  100
3.11.2  DEHP Hydrogenation Product Analysis Using GC-MC (2015)[42]  100
3.12  Synthesis of DEHCH via Direct Esterification (2015)[121]  103
3.13  Cable Industry’s Response to EU’s Newest Environmental Laws  108
3.14  Applications of Environmentally Friendly Plasticizers in Disposable Gloves(2016)[127]  108
3.15  Development and Application of Environmentally Friendly Polyester Plasticizers (2016)[128]  109
3.16  How to Accurately Assess and Use Benzoate-Based Plasticizers?(2016)[129]  110
3.17  Production Study of Environmentally Friendly DEHCH Plasticizer(2016)[130]  113
3.18  Co-existing Opportunities and Challenges for DOP Market(2017)[115]  115
3.19  Conclusion  117
References  122
4  Foreign and Domestic Inventions and Patents  129
4.1  Foreign Inventions and Patents  129
4.1.1  Hydrogenation Methods  129
4.1.2  Esterification Methods  133
4.2  Domestic Inventions and Patents  134
4.2.1  A Catalyst for Hydrogenating Dimethyl Terephthalates to Dimethyl Cyclohexane-1,4-Dicarboxylates and the Preparation Thereof(2001)[11]  134
4.2.2  A Plasticizer Containing Cyclohexane Multi-carboxylate and its Preparation Method(2006)[12]  135
4.2.3  A Catalyst for Preparing Cyclohexane-1,2-Dicarbolxylates(2008)[13]  136
4.2.4  A Method for Preparing Cyclohexane-1,2-Dicarboxylates (2008)[14]  137
4.2.5  A Method for Preparing Environmentally Friendly Di(2-ethylhexyl) Cyclohexane-1,2-Dicarboxylate(DEHCH)(2009)[15]  139
4.2.6  A Method for Preparing Environmentally Friendly Di(2-ethylhexyl) Cyclohexane-1,2-Dicarboxylate(DEHCH)Plasticizer(2011)[16]  140
4.2.7  A Method for Preparing Cyclohexane-1,2-Dicarboxylates Using Organic Acid Catalysts(2010)[17]  141
4.2.8  A Method for Preparing Cyclohexane-1,2-Dicarboxylates Using Ionic Liquid Catalysts(2010)[18]  142
4.2.9  A Type of Catalysts for Hydrogenating Benzenecarboxylates to Cyclohexanecarboxylates and the Preparation Method Thereof(2012)[19]  143
4.2.10  A Type of Benzenecarboxylate Hydrogenation Catalyst and the Preparation and Application Thereof(2012)[21]  146
4.2.11  Catalysts for Hydrogenating Benzenecarboxylate to Cyclohexanecarboxylates and the Preparation and Application Thereof(2012)[20]  147
4.2.12  A Method for Preparing Diisooctyl Cyclohexane-1,2-Dicarboxylate Plasticizer(2012)[21]  150
4.2.13  A Method for Preparing the Catalysts for Hydrogenation-Based Cyclohexane-1,2-Dicarboxylates(2012)[22]  151
4.2.14  A Method for Preparing Diisooctyl Cyclohexane-1,2-Dicarboxylates via Hydrogenation(2012)[23]  153
4.2.15  A Method for Preparing Cyclohexane-1,2-Dicarboxylates via Hydrogenation(2012)[24]  154
4.2.16  A Method for Preparing Environmentally Friendly Cyclohexane-1,2-Dicarboxylates(2013)[25]  155
4.2.17  A Method for Preparing Phthalate Selective Hydrogenation Catalysts(2013)[26]  156
4.2.18  A Method for Preparing Phthalate Hydrogenation Catalysts(2015)[27]  158
4.2.19  An Integrated Method for Preparing Cyclohexane-1,2-Dicarboxylates(2015)  159
4.2.20  A Type of Efficient Plasticizer Hydrogenation Catalysts and their Preparation Method(2013)  161
4.2.21  A Type of Non-linear Plasticizers and the Preparation and Applications Thereof(2013)  162
4.2.22  A Type of Apparatus for Preparing Dioctyl Cyclohexane-1,4-Dicarboxylate(2013)  163
4.2.23  The Esterification Reaction Protocols for DOTP Plasticizer(2015)  165
4.2.24  A Method for Preparing Cyclohexane-1,2-Dicarboxylates(2015)  166
4.2.25  A Method for Preparing Environmentally Friendly Plasticizers(2015)  168
4.2.26  A Method for Preparing Hexahydrophthalic Anhydride(2016)  169
4.2.27  A Method for Preparing Dioctyl Cyclohexane-1,4-Dicarboxylate(2016)  170
4.2.28  A Method for Preparing the Catalysts used for Preparing Cyclohexane Dicarboxylates(2016)  172
4.3  Conclusion  174
References  180
5  Catalytic Ring Hydrogenation of Phthalate Plasticizers  183
5.1  Ring Hydrogenation of Phthalates  183
5.1.1  Experimental  186
5.1.2  Effects of Various Factors  188
5.1.3  Effects of S Content in DOP  193
5.1.4  Qualitative Analysis of Products  197
5.1.5  Separation and Purification of Products  199
5.1.6  Repeatability of Catalytic Hydrogenation  201
5.1.7  Conclusions  202
5.2  Multi-phase Catalysis Kinetics of DOP Hydrogenation  204
5.2.1 Effects of Concentration on DOP Hydrogenation Rate  208
5.2.2  Arrhenius Equation of Phthalate Hydrogenation Reaction  218
5.2.3  Conclusions  220
5.3  Characterizations of Catalysts  220
5.3.1  XRD  221
5.3.2  Tem  222
5.3.3  Texture Analysis of Catalysts  223
5.3.4  XPS  226
5.4  Reaction Mechanisms of Catalytic Phthalate Hydrogenation  226
5.5  Characterizations of PVC Plasticized by Cyclohexane-1,2-Dicarboxylates and Phthalates  227
5.5.1  Mechanical Properties of PVC/DEHCH and PVC/DOP CompositeMaterials  228
5.5.2  Thermal Properties of PVC/DEHCH and PVC/DOP CompositeMaterials  233
5.5.3  Dynamic Mechanical Analysis of PVC/DEHCH and PVC/DOP CompositeMaterials  238
5.5.4  Rheology of PVC/DOP and PVC/DEHCH CompositeMaterials  240
5.5.5  Solvent Extraction Resistance of PVC Samples with Different DEHCH and DOP Contents  243
5.5.6  Evaporation Resistance of PVC Composite Materials with Different DEHCH and DOP Contents  245
5.5.7  Photonic Properties of PVC Composite Materials with Different DEHCH and DOP Contents  246
5.5.8  Conclusions  247
5.6  Third-Party Inspections  247
5.6.1  Physico-Chemical Property Inspection for Ring-Hydrogenated Products  248
5.6.2  Toxicity Test of Ring Hydrogenation Product  249
5.6.3  Ring-Hydrogenated Product Pellets and PVC Articles  252
References  258
6  Pilot Demo and Industrialization  261
6.1  Pilot Demo Studies  261
6.2  Industrialization Design of 50 k Ton/y Scale Phthalate Hydrogenation  264
6.2.1  Design Flowchart  264
6.2.2  Hydrogenation System  265
6.2.3  Separation and Purification System  266
6.2.4  Catalyst Recycling System  267
6.2.5  Exhaust Recycling System  268
6.3  Industrial Catalyst Production  270
6.4  Industrial Standards of Cyclohexane-Based Plasticizers  271
6.4.1  Scope  271
6.4.2  Normative References  271
6.4.3  Test Methods  272
6.4.4  Inspection Rules  275
6.4.5  Industrial Standard Numbers and Technical Index  276
6.5  Third-Party Inspections  279