Plasticizers are organic esters, which is compounded into polymers to facilitate processing, and to improve flexibility and toughness of the final products through internal modification of the polymer morphology. Commercially, about 90% of plasticizers consumption is accounted for by the application for flexible polyvinylchloride (PVC).
There are increasing concerns over the traditional plasticizers like dioctyl phthalate (DOP) on its potential migration out of PVC compounds and release to the environment or human body. The concerns have caused the industry to move towards more eco-friendly plasticizers. The first trend is moving towards higher molecular weight and less migratory phthalates.
PEP Report 62B reviews the technology for producing alternative plasticizers.
• Dioctyl terephthalate (DOTP) from terephthalic acid and 2-ethylhexanol[1]
• Dioctyl adipate (DOA) from 2-ethylhexanol and adipic acid
• Diisononyl phthalate (DINP) from esterification of phthalic anhydride with isononyl alcohol[2]
• 1,2-Cyclohexanedicarboxylic acid diisononyl ester (DINCH) from catalytic hydrogenation of diisononyl phthalate[3]
PEP last covered vinyl plasticizers in PEP Report 62 (1970). The same processes for the manufacture of diethylhexyl pthalate (DEHP) were updated in PEP Report 62A. PEP report 62B, will review, and analyze technologies for production of some of the abovementioned eco-friendly plasticizers in its usual format, providing information on technology aspects like R&D status, technical review, process description, process design details, economic evaluation of production processes.
This report is beneficial to plasticizer producing companies as well as consumers of plasticizers products for the production of PVC and other plastics.

1. Introduction 12

Major Plasticizer Types 13

      Phthalates 14

      Specialty Plasticizers 15

Potential Alternatives to DEHP 19

      Phthalate alternates 19

      Non-phthalate alternates 19

2. Summary 21

European Union overview: 21

United States overview 21

Economics Summary 22

3. Industry Status 28

Prices 39

Environmental Issues 42

      United States 42

      Western Europe 43

      Classification and Labeling 43

      Risk Assessments 45

      REACH 45

4. Technology Review 47

Plasticizer Theory 47

      Lubricity Theory 47

      Gel Theory 47

      Free Volume Theory 48

      Mechanistic Theory 49

Plasticizer Classification 49

      Properties of Flexible PVC 53

Manufacturing Process 55

      Esterification Reactions 59

      Esterification Catalysts 61

      Operating Mode 69

      Carboxylic Acid Esters 69

      Epoxidized Vegetable Oils 72

      Phosphate Plasticizers 74

      Polymeric Plasticizers 76

5. Dioctyl terephthalate(DOTP) from terephthalic acid and 2-ethylhexanol in a continuous process 77

Process Description 79

      Investment Costs 82

      Production Costs 84

Process discussion 88

6. Dioctyl adipate (DOA) from 2-ethylhexanol and adipic acid in a semi-batch process 89

Process description 90

Cost estimates 95

      Investment costs 95

      Production costs 98

Process discussion 102

7. Diisononyl phthalate (DINP) from esterification of phthalic anhydride with isononyl alcohol 104

Process description 107

      Investment costs 112

Cost estimates 115

      Production costs 115

Process discussion 119

8. 1,2-Cyclohexanedicarboxylic acid diisononyl ester (DINCH) by continuous catalytic hydrogenation of diisononyl phthalate 121

Process description 124

      Investment Costs 126

      Production Costs 126

Process discussion 130

Appendix A: Patent summary 131

Appendix B: Design and cost bases 148

Design conditions 148

Cost bases 148

      Capital Investment 148

      Production Costs 149

      Effect of Operating Level on Production Costs 150

Appendix C: Plasticizers and their producers 151

Appendix D: Cited references 188

Appendix E: Process flow diagrams 189

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