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Cyclopentyl Methyl Ether (CPME) for Green Chemistry and Process Innovation

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Cyclopentyl Methyl Ether (CPME) for Green Chemistry and Process Innovation A New Ether Process Solvent: Cyclopentyl methyl ether (CPME) for Green Chemistry and Process Innovation OMe Industrial Green Chemistry World, 7 December 2013, Mumbai Shunji Sakamoto Positioning of CPME Among Other Solvents Glycol-ethers DMSO 180℃ Boiling Boiling Point DMF Toluene CPME 100℃ Dioxane MeTHF AcOEt IPE THF MTBE Et2O Low Polarity High (Dielectric Constant) Comparison with other Ethers CPME THF MeTHF Et2O Dioxane MTBE Density (20°C) [g/cm3] 0.86 0.89 0.85 0.71 1.03 0.74 Vapor specific gravity (air = 1) 3.45 2.49 2.97 2.56 3.3 3.03 Boiling point [°C] 106 65 80 34.6 101 55 Melting point [°C] <-140 -108.5 -136 -116.3 11.8 -108.7 Viscosity (20°C) [cP] 0.55 0.55 0.6 (25˚C) 0.2448 1.31 0.35 Surface tension (20°C) [mN/m] 25.17 26.4 Unknown 17.3 33.74 19.8 Vaporization energy (bp) [Kcal/kg] 69.2 98.1 89.7 86.08 98.6 81.7 Specific heat (20°C) [Kcal/kg∙K] 0.4346 0.469 Unknown 0.5385 0.41 0.51 Refractive index (20°C) 1.4189 1.407 1.406 1.353 1.422 1.369 Solubility parameter [(cal/cm3)1/2] 8.4 9.5 8.52 7.4 Unknown Unknown Dielectric constant (25°C) 4.76 7.58 7 4.197 2.227 2.6 Dipole moment [D] 1.27 (calcd.) 1.7 Unknown 1.12 0.45 1.4 Azeotropic temperature with water [°C] 83 (a) 64 71 (b) 34.2 87.8 52.9 (c) Solubility of solvent in water (23°C) [g/100g] 1.1 Infinite 14 6.5 Infinite 4.8 Solubility of water in solvent (23°C) [g/100g] 0.3 Infinite 4.4 1.2 Infinite 1.5 Flash point [°C] -1 -14.5 -11 -45 12 -28 Auto Ignition Temperature [°C] 180 205 270 180~190 180 224 LogPow 1.59 0.47 Unknown 0.89 -0.42 0.94 Explosion range [vol%] Lower limit 1.1 1.84 1.5 1.85 2 1.6 Upper limit 9.9 11.8 8.9 48 22 8.4 Summary of CPME Benefits 1. Green Chemistry High Recovery Rate > 90% --- High Hydrophobicity Reduces amount of wastes and CO2 Diverse uses as reaction, extraction and crystallization solvents --- Solvent unification, Reduction of solvent amount Low peroxide formation Manufactured by atom economical process Makes Azeotrope with water : 16% water at 83℃ 2. Process Innovation Diverse uses as reaction, extraction and crystallization solvents --- Reduction of solvent exchange Process simplification and shortening One-pot synthesis and telescoping Stable under acidic and basic conditions The Contribution of CPME to Green Chemistry Reduction of wastes and CO2 Emissions with CPME ZEON’s Manufacturing Process of CPME OMe + MeOH Acid Cat. Molecular Weight 68.12 + 32.04 = 100.16 100% Atom Economical Reaction No atom waste One-step continuous system --- energy saving Peroxide Formation in CPME versus other ethers The 12 Principles of Green Chemistry 1. Prevention CPME meets 8 principles Significant reduction of water and solvent waste 2. Atom Economy We manufacture CPME by the atom economical reaction. 3. Less Hazardous Chemical Syntheses 4. Designing Safer Chemicals 5. Safer Solvents and Auxiliaries CPME makes slight peroxides. We manufacture CPME with minimum auxiliaries. 6. Design for Energy Efficiency CPME can save energy by simplification and shortening of production processes. 7. Use of Renewable Feedstocks 8. Reduce Derivatives We manufacture CPME in the one-step continuous system without derivatizations. 9. Catalysis We manufacture CPME in the catalytic process in the presence of the solid acid. 10. Design for Degradation 11. Real-time analysis for Pollution Prevention The flow reaction process is continuously monitored. 12. Inherently Safer Chemistry for Accident Prevention CPME has lower formation of peroxides in comparison with common ethers. The Contribution of CPME to Process Innovation Fixed cost reduction with CPME CPME shortens and simplifies the process --- saves process time, facilities and labor --- fixed cost reduction Variable Cost Reduction with CPME (with solvent recovery) A Reaction Solvent Cost Solvent/Product = 10/1(by weight) CPME MeTHF THF ($8/kg) ($6/kg) ($4/kg) recovery rate = 90% recovery rate = 70% recovery rate = 60% $8 x 10 x 0.1 = $8//kg - product $6 x 10 x 0.3 = $18/kg - product $4 x 10 x 0.4 = $16/kg - product equal weight of water to 4 weight times of water to 4 weight times of water product product to Solvent Extraction solvent: B Extraction Solvent Cost unnecessary! AcOEt ($1.2/kg) AcOEt ($1.2/kg) $1.2 x 10 x 0.1 = $1.2 $1.2 x 10 x 0.1 = $1.2 equal weight of water, aqNaCl to product 2 weight times of water, aqNaCl to Solvent C Waste Disposal Cost ($0.5/kg) (Waste solvent, Waste water) CPME: $0.5 x 10 x 0.1 = $0.5 MeTHF: $0.5 x 10 x 0.3 = $1.5 THF: $0.5 x 10 x 0.4 = $2.0 AcOEt: $0.5 x 10 x 0.1 = $0.5 AcOEt: $0.5 x 10 x 0.1 = $0.5 water: $0.5 x 3 = $1.5 water: $0.5 x 6 = $3 water: $0.5 x (40+20+20) = $40 Total Variable Cost (A+B+C) CPME MeTHF THF $10.0/kg-product $24.2/kg-product $59.7/kg-product * The prices used here are only to demonstrate their cost reduction with CPME. The actual prices would vary according to conditions such as quality, quantity, location, time, etc. Stability of CPME to Acid and Base Example of Green Chemistry & Process Innovation PINNER REACTION (1) 4M-HCl solution, CH3OH NH HCl R CN o o solvent, 0 C, 1 h, then 0-5 C, 48 h R OCH3 Requirements for Solvent R solution solvent Yield (%) stability to acid a) 1,4-Dioxane Et2O 86 solubility of raw materials H3CO CPME CPME 90b) insolubility of product CPME CPME 89b) CH3 b) CPME CPME 91 Solvent Unification a) U.S.Pat.No.: US 6806380 B2 b) Work-up of CPME process is only filtration and washing. Example of Green Chemistry & Process Innovation PINNER REACTION (2) Original Process CPME Process 9 steps with dangerous solvents 4 steps without dangerous solvents 1. Reaction: Et2O - Dioxane 1. Reaction: CPME 2. Cooling: 2. Cooling ℃ Telescoping 3. Warmed at 40 3. Filtration Steps: 9 to 4 HCl 4. N2 Bubbling Solvents: 2 to 1 4. Drying Et O 2 5. Removal of Product Dioxane solvent in vacuo Waste 6. Precipitated by cooling 7. Addition of Et2O Greener Process Without: Et2O 8. Filtration Dangerous Solvents 9. Drying Product Comparison of Properties of CPME & MeTHF versus THF excellent good poor CPME MeTHF THF Solubility in water g/100g-water 1.1 14 Infinite Recovery rate from water % 90 70 60 Waste rate (1 - recovery rate) % 10 30 40 Explosive Peroxide formation slower faster faster Stability to acid more stable less stable unstable Boiling Point °C 106 80 65 Flash Point °C -1 -11 -14.5 Vaporization Energy (at bp) kcal/kg 69.2 89.7 98.1 Acid and Base solutions in CPME Conclusion CPME contributes to: 1. Green Chemistry – Cradle to Greave Manufactured by Atom economical process Solvent unification and reduction of solvent used Reduction of wastes and CO2 Saving energy Lower Peroxide formation 2. Process Innovation Process simplification - Fixed cost reduction Solvent unification - Variable cost reduction Facilitate one-pot synthesis and Telescoping Better stability under acidic and basic conditions Thank you for your attention OMe Please visit our stall at Exhibition for further information Specifications Toxicity Data ICH Guideline for Residual Solvents (Zeon) CPME has not yet classified in ICH guideline for residual solvents (Q3C). However, it is assumed to be in Class 2 according to Zeon's own calculation. 1) Formula PDE = (NOEL x Weight Adjustment)/(F1+F2+F3+F4+F5) Concentration Limit (PPM) = 1000 x PDE / dose *PDE: Permitted Daily Exposure 2) Calculation PDE = (15x50) / (5 x 10 x 10 x 1 x 1)=1.5mg/day Concentration Limit = 1000 x 1.5/10 = 150ppm 3) Conclusion According to the above, Zeon assume CPME would be classified in Class 2. ICH Guideline for Residual Solvents (Merck) PDE (mg/day) CPME 7.4 MeTHF 6.2 THF 7.2* Toluene 8.9* *ICH Guideline Antonucci, V et al.: Org. Process Res. Dev., Article ASAP, 10.1021/op100303c, March 18, 2011 Grignard Reaction Variable Cost Reduction with CPME (without solvent recovery) A Reaction Solvent Cost Solvent/Product = 10/1(by weight) CPME MeTHF THF ($8/kg) ($6/kg) ($4/kg) $8 x 10 = $80//kg - product $6 x 10 = $60/kg - product $4 x 10 = $40/kg - product equal weight of water to 4 weight times of water to 4 weight times of water product product to Solvent Extraction solvent: B Extraction Solvent Cost unnecessary! AcOEt ($1.2/kg) AcOEt ($1.2/kg) $1.2 x 40 = $48 $1.2 x 40 = $48 equal weight of water, aqNaCl to product 2 weight times of water, aqNaCl to Solvent C Waste Disposal Cost ($0.5/kg) (Waste solvent, Waste water) CPME: $0.5 x 10 = $5 MeTHF: $0.5 x 10 = $5 THF: $0.5 x 10 = $5 AcOEt: $0.5 x 40 = $20 AcOEt: $0.5 x 40 = $20 water: $0.5 x 3 = $1.5 water: $0.5 x 6 = $3 water: $0.5 x (40+20+20) = $40 Total Variable Cost (A+B+C) CPME MeTHF THF $86.5/kg-product $136.0/kg-product $153.0/kg-product * The prices used here are only to demonstrate their cost reduction with CPME.
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