A New Ether Process Solvent: Cyclopentyl methyl ether (CPME) for Green Chemistry and Process Innovation

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1 A New Ether Process Solvent: Cyclopentyl methyl ether (CPME) for Green Chemistry and Process Innovation Sustainability Awards in Informex 2011 The Bronze prize in CPhI Innovation Awards 2010 OMe

2 Positioning Among Other Solvents 180 Glycol-ethers DMSO Boiling Point 100 Toluene Dioxane MTBE CPME AcOEt IPE MeTHF THF DMF Et2O Low Polarity (Dielectric Constant) High

3 Comparison with other Ethers CPME THF MeTHF Et 2 O Dioxane MTBE Density (20 C) [g/cm 3 ] Vapor specific gravity (air = 1) Boiling point [ C] Melting point [ C] < Viscosity (20 C) [cp] (25 C) Surface tension (20 C) [mn/m] Unknown Vaporization energy (bp) [Kcal/kg] Specific heat (20 C) [Kcal/kg K] Unknown Refractive index (20 C) Solubility parameter [cal/ml] Unknown Unknown Dielectric constant (25 C) Dipole moment [D] 1.27 (calcd.) 1.7 Unknown Azeotropic temperature with water [ C] 83 (a) (b) (c) Solubility of solvent in water (23 C) [g/100g] 1.1 Infinite Infinite 4.8 Solubility of water in solvent (23 C) [g/100g] 0.3 Infinite Infinite 1.5 Flash point [ C] Auto Ignition Temperature [ C] ~ LogPow Unknown Explosion range [vol%] Lower limit Upper limit

4 CPME Benefits 1. Green Chemistry Innovation Extraction solvent is not necessary Hydrophobicity Low peroxide formation High recovery rate >90% Reduce amount of wastes and CO 2 Azeotropic with water : 84% CPME, 16% water at 83 Low vaporization energy save energy

5 CPME Benefits 2. Process Innovation Reduction of fixed cost and variable cost Productivity up Reduce process time Wide temperature range -140 ~ 106 High resistance to acids or bases

6 Reduction of wastes and CO 2 Emissions with CPME

7 Fixed Cost Reduction with CPME CPME plays both as a reaction and as an extraction solvent. You can save process time --- reduce fixed cost per unit

8 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% $12 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 product 4 weight times of water to product 4 weight times of water to Solvent Extraction solvent: unnecessary! AcOEt ($1.2/kg) $1.2 x 10 x 0.1 = $1.2 B Extraction Solvent Cost AcOEt ($1.2/kg) $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) CPME: $0.5 x 10 x 0.1 = $0.5 water: $0.5 x 3 = $1.5 MeTHF: $0.5 x 10 x 0.3 = $1.5 AcOEt: $0.5 x 10 x 0.1 = $0.5 water: $0.5 x 6 = $3 (Waste solvent, Waste water) THF: $0.5 x 10 x 0.4 = $2.0 AcOEt: $0.5 x 10 x 0.1 = $0.5 water: $0.5 x ( ) = $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.

9 Comparison of Formation of Peroxide in CPME versus other ethers (THF, IPE, MTBE)

10 Comparison of Formation of Peroxides in MeTHF versus THF Aycock, D. Org. Process Res. Dev., 2007, 11 (1), pp Peroxide formation of MeTHF is very similar to that of THF.

11 High Resistance to Strong Acid or Base very stable

12 Comparison of Properties of CPME versus MeTHF, THF excellent good poor CPME MeTHF THF Solubility in water g/100g-water Infinite Recovery rate from water % Waste rate (1 - recovery rate) % Explosive Peroxide formation slower faster faster Stability to acid more stable less stable unstable Boiling Point C Flash Point C Vaporization Energy (at bp) kcal/kg

13 Conclusion CPME contributes to: 1. Green Chemistry Innovation Reduction of wastes and CO 2 Extraction solvent is not necessary by High Hydrophobicity High recovery rate Lower Peroxide formation 2. Process Innovation Fixed cost reduction reduce process time and vessels by solvent unification Variable cost reduction Extraction solvent is not necessary by High Hydrophobicity High recovery rate Better stability under acidic conditions

14 CPME 展示会での受賞 CPME won Awards Bronze Prize in Innovation Awards 2010 Product Category Profiles in Sustainability 2011

15 OMe Thank you for listening OMe

16 Acid and Base solutions in CPME

17 ACS / GCI Solvent Selection Guide CPME is one of green solvent candidates in discussion of ACS / Green Chemistry Institute.

18 Specifications

19 Toxicity Data

20 ICH Guideline for Residual Solvents 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.

21 Grignard Reaction

22 Example of Process & Green Chemistry Innovation PINNER REACTION (under acidic conditions) R CN 4M-HCl solution, CH 3 OH solvent, 0 o C, 1 h, then 0-5 o C, 48 h NH HCl R OCH 3 H 3 CO R CH 3 solution solvent Yield (%) 1,4-Dioxane Et 2 O 86 a) CPME CPME 90 b) CPME CPME 89 b) Solvent Requirements - stable to acid - solubility of raw materials - insolubility of product CPME CPME 91 b) a) U.S.Pat.No.: US B2 b) Work-up of CPME process is only filtration and washing. CPME Telescoping Cost Reduction

23 Example of Process Pinner & Green Reactions Chemistry Innovation PINNER (Telescoping&Green REACTION (under Chemistry) acidic conditions) 1. Reaction: Et 2 O - Dioxane 2. Cooling: 1. Reaction: CPME 2. Cooling 3. Warmed at 40 Telescoping 3. Filtration HCl 4. N 2 Bubbling Steps: Drying Et 2 O Dioxane 5. Removal of solvent in vacuo Solvents:2 1 Product Waste 6. Precipitated by cooling 7. Addition of Et 2 O CPME process 4 steps without dangerous solvents Et 2 O 8. Filtration 9. Drying Product Green Process Avoid Dangerous Solvent Patent process 9 steps with dangerous solvents