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增塑劑綠色催化技術(英文版) 版權信息
- ISBN：9787030724748
- 條形碼：9787030724748 ; 978-7-03-072474-8
- 裝幀：一般膠版紙
- 冊數：暫無
- 重量：暫無
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增塑劑綠色催化技術(英文版) 內容簡介
本書在國內外文獻調研和實驗室研究基礎上，從物質結構和分子水平上闡述鄰苯類增塑劑分子結構改性的微觀機制，闡明苯環改性和酯基調控的多相催化機理以及產物分離、產品應用的科學依據，以及國內外相關法律法規，為增塑劑行業實現轉型發展、綠色發展提供有益借鑒。
增塑劑綠色催化技術(英文版) 目錄
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
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
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增塑劑綠色催化技術(英文版) 節選
Chapter 1 Introduction 1.1 Background Phthalate plasticizers， such as dioctyl phthalate (DOP)， di(iso-octyl) phthalate (DIOP)， di(2-ethylhexyl) phthalate (DEHP)， dibutyl phthalate (DBP)， di(iso-butyl) phthalate (DIBP)， and di(iso-nonyl) phthalate (DINP)， have the earliest use， the best performance， the broadest application， and the most production globally. Phthalate compounds have achieved an annual production capacity of 5 million tons in China and a consumption capacity of3.6 million tons， about 1/5 of the global numbers. They are also one of the fundamental raw materials for a number of strategic industries. A plasticizer is a manufacturing additive for polyvinyl chloride (PVC) resins， 40-50% in the final soft PVC articles. It can modify the PVC resin structure， weaken the interactions between polymer chains， decrease the glass transition temperature， reduce the tensile strength， increase the elongation at break， improve the plasticity， soften the articles， and harvest better low-temperature performance， thus enhancing the processability of PVC resins. As a type of commodities， plasticizers are widely applied in hundreds of areas in our economics and society， including tubes， plastics， adhesives， celluloses， lubricants， inks， paints， toys， food wraps， personal care articles (such as nail oils， hair sprays， soaps， and shampoos)， etc. Despite the increasingly wider uses， the toxicity of plasticizers has attracted a great deal of global attention with the focus on their side effects on the embryos， kidneys， hearts， livers， and reproductive systems of mammals [1-6]. Many years of experimental data and patient cases have indicated the harmful effects of the benzene ring structure on humans， animals， plants， and the environment. Phthalate compounds are a family of substances that can accumulate in the human body， are potentially mutagenic， carcinogenic， and teratogenic， and can cause damage to livers and kidneys after long-term exposure to them [7-14]. They are also considered as a type of environmental estrogens or endocrine-disrupting chemicals that have reproductive toxicity and developmental toxicity， a serious threat to ecological security and human reproductive health [15-17]. In 2005， the EU issued an official law to prohibit the use of phthalate plasticizers in human contact articles including food， drugs， and toys. The “Registration， Evaluation， Authorisation and Restriction of Chemicals (REACH)” regulation， effective since 2007in theEU， lists phthalate compounds as substances of veryhigh concern (SVHC) that may cause serious and irreversible damages to human health and the environment. The Consumer Product Safety Improvement Act (CPSIA) of the USA issued in 2008prohibits the sale， manufacturing， and import of any articles containing >0.1% phthalates. The Restriction ofHazardous Substances (RoHS) implemented by EU in 2006 officially lists the following 6 phthalates as restricted substances in electronics and cables: DOP， DIOP， DEHP， DBP， DIBP， and DINP. In China， the toxicity of phthalates has attracted broad attention among the communities of the press， drug， food science， etc. In 2011， a “plasticizer incident” happened in Taiwan. In 2012， a “Chinese spirits plasticizer incident” was reported. In 2013， a “toxic capsule plasticizer incident” was noticed; the China Central Television (CCTV) reported the use of a prohibited plasticizer in 15 types of PVC food wraps. In 2014， the CCTV reported an incident of the plasticizer content 368 times over the standard number in “toxic toys”. In 2015， the plasticizer incident was labeled as one of the annual top-ten food contamination incidents. Dr. James-Todd from Brigham and Women’s Hospital ofHarvard Medical School discovered that women with higher phthalic acid ester (PAE) levels are more susceptible to diabetics. Later in October 2016， Dr. Fan Qu’s research team from the Department of Traditional Chinese Medicine at the Women’s Hospital of Zhejiang University Medical School found that long exposure to DEHP causes significant changes to the transcription of the key granulosa cell-related signaling pathway factors. Such changes will lead to dysfunctions in the anabolism， cell cycle， proliferation， and apoptosis of granulosa cells， and thus failure of ovulation will occur for women， i.e.， polycystic ovary syndrome (PCOS). Simply saying， extensive exposure to plastics will cause ovulation dysfunction and infertility. Meanwhile， DEHP also greatly affects the fertile functions of men’s sperms and causes gene mutations. In November 2016， according to the interview ofMr. Xin Liu who was a member of National Committee of the Chinese People’s Political Consultative Conference (CPPCC) and also the Chair of the Department of Health Food in the Chinese Institute of Food Science and Technology (CIFST)， the China Food Daily published a report titled “High Hopes for Environmentally Benign Plasticizer Industry in China”. According to the
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