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  • Synthetic Polymers – Preparation and Properties. Prof. Attilio Citterio

    Dipartimento CMIC “Giulio Natta”

    http://iscamapweb.chem.polimi.it/citterio/education/course-topics/

    School of Industrial and Information Engineering

    Course 096125 (095857)

    Introduction to Green and Sustainable Chemistry

    http://iscamapweb.chem.polimi.it/citterio/education/course-topics/

  • Attilio Citterio

    Materials: Intensity of Use.

    Polymers growth

    is twice the one of

    other materials.

    80

    100

    120

    140

    160

    180

    200

    220

    1990 1992 1994 1996 1998 2000 2002 2004 2006

    Year

    R e

    la ti

    v e

    G ro

    w th

    Aluminum

    Steel

    Paper

    Glass

    Concrete

    GDP

    Polymers

    Source: UBS Warburg

  • Attilio Citterio

    Plastics

    1) Commodity plastics

    LDPE, HDPE, PP, PVC, PS

    2) Engineering plastics

    Acetal, Polyamide, Polyamideimide, Polyacrylate,

    Polybenzimidazole, etc.

    3) Thermosetting plastics

    Phenol-formaldehyde, Urea-formaldehyde,

    Unsaturated polyester, Epoxy,

    Melamine-formaldehyde

    4) Functional plastics

    Optics, Biomaterial, etc.

  • Attilio Citterio

    Six Polymers Have Around ~75% Share

    0

    2

    4

    6

    8

    10

    12

    MT

    Distribution of European (EU28+NO/CH) plastics converter demand by resin type in 2016.

    http://www.google.at/imgres?imgurl=http://de.academic.ru/pictures/dewiki/69/Envase_de_yogur.jpg&imgrefurl=http://de.academic.ru/dic.nsf/dewiki/1121293&usg=__PJFaQcGTAmp_Hm62OHbY87mz6VY=&h=1944&w=2592&sz=704&hl=de&start=85&zoom=1&tbnid=oCmTBzGuDd8OXM:&tbnh=158&tbnw=211&ei=e7MwTaDUL8GfOtOs1KwK&prev=/images?q=joghurtbecher&um=1&hl=de&gbv=2&biw=1260&bih=837&tbs=isch:1&um=1&itbs=1&iact=hc&vpx=969&vpy=548&dur=5141&hovh=194&hovw=259&tx=122&ty=177&oei=XbMwTf7wBomztAaV0Ln_CQ&esq=5&page=4&ndsp=22&ved=1t:429,r:21,s:85

  • Attilio Citterio

    Polymers Price as Function of Sale Volume.

    Source Biomer-UrsJ. Haenggi

    100

    1000

    10000

    100000

    0,1 1 10 100 1000 10000 100000

    P ri

    c e i

    n E

    u ro

    p e (

    € /t

    o n

    )

    Sales in Europe (ktons)

    PEEK

    LCP

    PSU

    POM

    PBT

    PET

    PS

    PC

    PA

    PMMA PE-HD PE-LD

    PPPVC

  • Attilio Citterio

    World and EU plastics production data (2017).

    Includes plastic materials (thermoplastics and polyurethanes) and other plastics

    (thermosets, adhesives, coatings and sealants). Does not include: PET fibers, PA fibers,

    PP fibers and polyacryls-fibers.

    Source: PlasticsEurope (PEMRG) / Conversio Market & Strategy GmbH

  • Attilio Citterio

    World Plastics Production (2011).

    Fig. 3 - World Plastic Material Production 2011

    w/ o Other Plastics (-45 Mtonne)

    Source: Plastic Europe Market Research Group (PEMRG)

    Fig. 2 - World Plastic Material Production 1950-2011

    Includes Thermoplastics, Polyurethanes, Thermosets, Elastomers, Adhesives,

    Coatings and Sealants and PP-Fibers. Not included PET, PA and Polyacrylic Fibers

    Source: Plastic Europe Market Research Group (PEMRG)

  • Attilio Citterio

    Distribution of Global Plastic Materials Production.

    China is the largest producer of plastic materials*, followed by Europe and NAFTA.

    World production of plastic materials in 2016: 280 million tonnes. (*Plastic materials: only

    thermoplastics and polyurethanes)

    Source: PlasticsEurope (PEMRG) / Conversio Market & Strategy GmbH

  • Attilio Citterio

    European Plastics Demand by Segment (weight %).

    Packaging; 38%

    other household;

    22%

    Building & construction

    ; 17,6%

    Electrical & electronic;

    7,3%

    Automotive; 7,0%

    Big Industry;

    5,2%

    Agriculture; 2,5%

    Total: 38.123.000 ton. (2002)

    Automotive

    8.3% Electrical &

    Electronic

    5.4%

    Others

    26.4%

    Packaging

    39.4%

    Building &

    Construction

    20.5%

    Total: 58.000.000 ton. (2011)

  • Attilio Citterio

    Plastics Converter Demand Main Market Sectors.

    Total converter demand: 49.9 MT

    Source: PlasticsEurope (PEMRG) / Conversio Market & Strategy GmbH

    2016

  • Attilio Citterio

    European Plastics Demand by Country (kton/year).

    Source: PlasticsEurope Market Research Group (PEMRG)

    0

    1 0 0

    0

    2 0 0

    0

    3 0 0

    0

    4 0 0

    0

    5 0 0

    0

    6 0 0 0

    7 0 0

    0

    8 0 0

    0

    9 0 0

    0

    1 0 0

    0 0

    1 1 0

    0 0

    1 2 0

    0 0

    Austria

    Belgium & Lux.

    Bulgaria

    Cyprus/Malta

    Czech Republic

    Denmark

    Estonia

    Finland

    France

    Germany

    Greece

    Hungary

    Ireland

    Italy

    Latvia

    Lithuania

    Netherlands

    Poland

    Portugal

    Romania

    Slovakia

    Slovenia

    Spain

    Sweden

    United Kingdom

    Norvey

    Switzerland

    kton

    2002

    2010

  • Attilio Citterio

    Top Extra EU Trade Partners of Plastics in Value.

    Source: PlasticsEurope (PEMRG) / Conversio Market & Strategy GmbH

  • Attilio Citterio

    European plastics converter demand by

    segments and polymer types in 2016.

    39.9%

    19.7%

    10%

    6.2%

    20.9%

    Packaging

    Building &

    Construction

    Automotive

    Electrical &

    Electronic

    Agriculture

    Others

    3.3%

    Source: PlasticsEurope (PEMRG) / Conversio Market & Strategy GmbH

  • Attilio Citterio

    Production and Consumption of Plastics in Italy.

    kt

    0

    1000

    2000

    3000

    4000

    5000

    6000

    7000

    8000

    1997 1998 1999 2000 2001 2002 2003 2004 2005

    Production Import Export Final consumption

  • Attilio Citterio

    Plastics Uses in Italy by Segments (2010).

    House packaging

    40%

    Building & construction

    14%

    Industrial and commercial packaging

    12%

    Electrical & Electronic

    8%

    Automotive & transport

    7%

    Agriculture 6%

    Furniture; 5%

    Other household;

    4% Industry

    4%

  • Polymers: Synthetic Methods and

    Manufacturing.

  • Attilio Citterio

    What is a Polymer?

    C C C C C C

    HHHHHH

    HHHHHH

    Polyethylene (PE)

    ClCl Cl

    C C C C C C

    HHH

    HHHHHH

    Poly(vinyl chloride) (PVC)

    HH

    HHH H

    Polypropylene (PP)

    C C C C C C

    CH3

    HH

    CH3CH3H

    Only carbon chain backbone

    Poly mer many repeat unit (building blocks)

    repeat

    unit

    repeat

    unit

    repeat

    unit

    Polymer (from Greek terms = “poly” + “mer”) means several units and

    emphasizes what the polymer is: a long chain (macromolecule) of one,

    two or occasionally more units of small identical molecules bonded

    together. The term “Polymer” firstly used by Berzelius in 1833.

  • Attilio Citterio

    Structure of Polyethylene.

    Tetrahedral

    arrangement

    of -CH2- unit

    • Polyethylene is a long-chain hydrocarbon.

    • Top figure shows repeat unit and chain structures.

    • Other figure shows zigzag backbone 3D structure.

    H Repetitive Unit

    ―C―C―C―C―C―C―C―C―

    H―H―H―H―H―H―H―H

    H―H―H―H―H―H―H―H

    Repetitive Unit

    H

    C

  • Attilio Citterio

    Polymer Classification.

    Polymers consist of high molecular weight molecules, generally organic,

    known as macromolecules.

    Macromolecules originate by bonding a large number of small units,

    called monomers, to form very long chains.

    • Main synthetic polymers are old of ~100 years, some were

    discovered more recently ( proteins

    • coatings > nucleic acids

    • adhesives > polysaccharides ...

    • fibers

  • Attilio Citterio

    Definitions.

    A. According to the amount of repeating units

    monomer : one unit

    oligomer : few units

    polymer : many units (poly – several, mer – part)

    telechelic polymer : polymer containing reactive end group

    (tele = far, chele = claw)

    telechelic oligomer : oligomer containing reactive end group

    macromer (= macro monomer) : monomer containing long

    chain

  • Attilio Citterio

    Definitions (2).

    B. DP : Degree of polymerization

    The total numbe

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