●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 lti-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 lti-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
