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綠色化學之內涵 中央研究院化學研究所 趙奕姼 2009年2月25日 東吳大學 綠色/永續化學的內涵

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  • 2009225

    /

  • 200024.68%37.39%22.84%(1.92)15.09%

    2005 2.95 2.82 1.43

  • 184/

    1912Itai Itaidisease

    500000170000800016000

    42/

    1984Bhopal disaster

    2265/

    1956Minamatadisease

  • CO2

  • Istvn T. Horvth- Acc. Chem. Res. 2002, 35(9)

    Chemist

    Molecular designer

  • E-factorE-factor

    (E-factor)

  • persistent chemicals

    DDT

    1874 1939 Paul Hermann Mller

  • The Natural Step(International movement started in Sweden)

    DDT CFCs

  • 1987

    meeting the needs of the present without compromising the ability of future generations to meet their own needs

    1990

  • RoHS: Pb, Cd, Cr(VI), Hg, PBB, PBDE

    REACHRegistration/Evaluation/

    Authorization/Restriction of Chemicals

    SusChem: a technological platform for EU R&D on sustainable chemistry

    http://www.suschem.org

  • Green Chemistry

    The design of chemical products and processes that reduce or eliminate the use and generation of hazardous substances.

    Anastas et al.

  • Minimize risk by minimize hazard

    x

  • The 12 Principles of Green ChemistryThe 12 Principles of Green Chemistry Prevention Atom Economy Less Hazardous Chemical Synthesis

    Designing Safer Chemicals Safer Solvents and Auxiliaries

    Design for Energy Efficiency

  • Use of Renewable Feedstocks:

    Reduce Derivatives Catalysis Design for Degradation Real-time Analysis for Pollution Prevention

    Inherently Safer Chemistry for Accident Prevention

  • Stricter rulesConsumer Cost down

  • % Yield = 100 x (/)

    => 11

    5515g

    900g800g

  • Atom Economy

    % Atom Economy =100 x (/)

    % Yield =100 x (/)

  • Atom Economy

    Atom economic reactions

    Rearrangement Addition Diels-Alder Other concerted

    reactions

    Atom un-economic reactions

    Substitution Elimination Wittig Grignard

  • % Atom Economy =100 x (/)

  • Friedel-Crafts acylation showing a typical starting materials/products/waste balance

    Clark, J. H. Green Chemistry 1999, 1, 1

  • Catalysis ()

    Homogeneous catalysisHomogeneous catalysis Heterogeneous catalysisHeterogeneous catalysis BiocatalysisBiocatalysis PhotocatalysisPhotocatalysis

    Fast reaction due to correct catalyst orientation

    High degree of selectivity; possible for asymmetric synthesis

    Water soluble; opportunity for aqueous-phase reactions

    Naturally occurring; non-toxic, low hazard

    Energy-efficient reactions under moderate conditions of pH, temperature

    Possibility for carrying out sequential one-pot synthesis

    Activation of semiconductors by light

    Good potential for waste treatment and pollution clean-up

    CCxxHHyyClCl + O+ O22 COCO22 + H+ H22O + O + HClHCl

  • OHO2C

    CO2H

    O OH

    HO2CCO2H

    OHOH

    OH OHOH

    OHOHO

    CO2H

    Hi-Al2O3

    370-800 psi

    Co-O2

    120-140 psi HNO3

    adipic acid

    E. coli E. coli

    Pt, H250 psi

    Route 1

    Route 2

    Route 2

    Nylon adipic acid

  • methanolwater or ethanolwater mixtures are environmentally favourablecompared to pure alcohol or propanolwater mixtures.

  • dipole

  • Mike Lancaster, Green Chemistry: An Introductory Text

  • Challenges Science 2002, 297, 807

    Alternative feedstocksMove from petroleum to renewable or biologically derived sources

    Petroleum chemistry => need oxidation chemistry Sugar => need reduction chemistry

    CO2 => need new catalysts (already have examples of incorporating CO2 into polymer and to make formic acid)

    Alternative solventsNo solvent (neat solution; grinding)Supercritical CO2, ionic liquid

    Alternative synthetic pathwaysNew catalystsMove to biocatalysts (no toxic metals; intrinsically safer)Research into reuse and recycling catalysts still in infancy

  • The 2006 Impact Factor (4.192) has risen by a massive 29% over the 2005 value.

    Green Chemistry Journal general text search with China146 hits (Oct. 29, 2007); with Taiwan 15 hits

  • http://www.sinica.edu.tw/chem/gc

  • -- a laymans report

    Make a greener choice

  • Guest editor of Acc. Chem. Res. 2002, 35(9).

    Chemist

    Molecular designer

    Istvn T. Horvth

    Chemist vs. fashion designer

  • Sustainable Chemistry and Green Chemistry Who should care about it ?

    Today, most students who want to change the world end up being activists. "How many 18-year-olds who care about the planet say, 'I'm going to go be a chemist'?"But now they can go to the lab and invent something that can save the world."

    USA Today 11/22/2004 by Elizabeth Weise

    John C. Warner of the University of Massachusetts-Lowell, which hosts the nation's only doctoral program in green chemistry

    C&EN 2/26/2007 by Stephen K. Ritter

    Warner is working with a group of scientists to take culled potatoes from Maine processors and use the starch to make polylactic acid, a biopolymer used to make food wrappers and clothing.

  • References

    Lancaster, M. Green Chemistry An Introductory Text; Royal Society of Chemistry: Cambridge, 2002.

    Clark, J. H. Green Chemistry 1999, 1, 1. Poliakoff, M.; Fitzpatrick, J. M.; Farren, T. R.; Anastas, P. T.

    Science 2002, 297, 807. Anastas, P. T.; Kirchhoff, M. M. Acc. Chem. Res. 2002, 35, 686. Green Chemistry: Background, Key Concepts and Principles

    http://www.grc.uri.edu/programs/2006/green.htm Green Chemistry: Pollution Prevention by Design

    http://www.zerowaste/org/publications/gc_pres/index.html Green Chemistry School Lectures

    http://www.chemsoc.org/pdf/GCN/schoolslecture05.pdf

  • Treat the earth well. It was not given to you by your parents. It is loaned to you by your children.

    Kenyan Proverb

    Creativity can solve almost any problem. The creative act, the defeat of habit by originality, overcomes everything.

  • 2007.4.

  • 35%

    (CH3CO)2O

    AlCl3

    O

    ClCH2CO2C2H5

    NaOC2H5

    O CHCO2C2H5

    H+

    H2O

    H2NOH

    CH=NOHCHO

    CN CO2H

    Ibuprofen

    Ibuprofen

    3580(99)

  • 80%

    (CH3CO)2O

    HF

    O

    H2

    catalyst

    OH

    CO, Pd

    CO2H

    Ibuprofen

  • Green Chemistry