History History: First there were Bio

History: First there were Bio-Polymers
History
Animal Hides (Proteins): Fiber & Films
Ligaments (Collagen): Hinges
Silk Fibers (Protein): Fibers
Plant Fibers (Cellulose): Fibers
Yucca-fiber sandals
Bison-Hide teepee
Structural Materials: High Modulus & Strong
Wood (Cellulose & Lignin): S
Antlers (Keratin): Tools, jewelry & weapons
Horn (Keratin): Tools, jewelry & weapons
Tusks (enamel & dentin): Tools, jewelry & weapons
Ivory lunar cycle charts
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History
1839
1862
1868
1885
1909
1922
1927
1928
1930
1931
1935
1936
1937
1938
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History
Vulcanized rubber (C. Goodyear)
Celluloid (Parkes)
Nitrocellulose 합성 (J.W. Hyatt)
Rayon, Cellopane
phenol-formaldehyde resin (L.H. Baekeland)
(1910 한일합병/을사보호조약)
(1919 김성수, 국민 모금 경성방직 설립, 무명 옷감 제조)
Polymer by H. Staudinger
Cellulose actate, Poly(vinyl chloride)
Buna S (butadiene-styrene rubber (Bayer Co.)
Poly(methyl methacrylate)(O. Rohm).
Polystyrene.
Neoprene (DuPont Co. W. H. Carothers)
Nylon 66 (W.H. Carothers).
PAN, SAN, Poly(vinyl acetate)
Polyethylene (O. Bayer).
Nylon 6, Epoxy resin, LDPE
1941
1942
1948
1950
1952
1953
1954
1955
1956
1957
1964
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PET (J.R. Whinfield와 J.T. Dickinson).
PAN (commercialized by DuPont).
(1945 제2차세계대전 종전/대한민국 독립)
(1943 국제고무 "말표" 고무신 생산)
(1947 한국나이롱 나일론 66 방적)
ABS resin.
한국전쟁 발발/ 자동차 타이어의 노화 원인이 오존인 것
을 밝혀내고 antiozonant의 개발 시작
Catalyst for PE under low pressure (by K. Ziegler).
Nobel Prize winning of Hermann Staudinger
(Work on macromolecules)
Polyurethane
Stereoregular polymer using Ziegler-Natta Catalyst(G. Natta)
Acetal
Polypropylene, Polycarbonate
Ionnmer, Polyimide
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History
History
Rubber :
▶ Nitrocellulose :
- by Christian Schoenberg, Swiss Chemist, 1840’s
- Applications : guncotton(면화약), film
→ Vulcunization of natural rubber by Charles Goodyear, 1839
Poly-cis-isoprene
Sulfur
crosslinking
S
S
Vulcunization
S
S
S
Nitrocellulose was perceived as
a possible "smokeless powder"
and a propellant for artillery
shells thus it received the name
of guncotton.
S
Enabled commercialization of natural rubber
 1942 합성고무 프로젝트 (WWII)
“우리가 대규모의 새로운 고무 공급이 이루어지지 않으면 전쟁노력과 국내경제도 모두 붕괴될 것이다.”
– Baruch 위원회 보고서, 1942 (전선, 타이어 등의 수요 급증)
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History
History
▶ Polystyrene :
- by Eduard Simon, 1839
- Applications : ; packaging (Styrofoam)
▶ Celluloid :The first man-made plastic
- by Alexander Parkes, 1862, London
International fair
- Parkesine: made from cellulosics materials,
can be molded by heating
- Applications : Buttons, Cobs, Pens, Billiards
balls
cf. J. Hyatt (1869, USA)
▶ Poly(vnylchloride) (PVC) :
- by Eugen Baumann, 1872
- Applications : pipe, toys, floor
▶ Rayon :
- first man-made fibers, regenerated cellulose
- applications : textiles, tire cord, cellophane,
▶ Cellophane : Celluloid Photographic Film
- by George Eastman – 1885
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68
History
History
▶ Bakelite : first totally synthetic plastics
(Thermoset resin; formaldehyde resin)
Wallace Hume Carothers
- 1929 : Concepts of Addition and Condensation polymers
- Neoprene : First Synthetic Rubber
- Polyester
- Nylon (Polyamide)
- by Leo Bakeland, 1907
- applications : replaced rubber for insulation in electrics
▶ Nylon : Nihil(허무)+Dupont
- by Wallace H Carothers, 1830년대
- Applications : packaging and stocking
Extract from "Fortune Magazine" about nylon circa 1938: "nylon breaks the basic elements like
nitrogen and carbon out of coal, air and water to create a completely new molecular structure
of its own. It flouts Solomon. It is an entirely new arrangement of matter under the sun, and
the first completely new synthetic fiber made by man.
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History
DuPont touted its new fiber as being "as strong as steel, as fine as a
spider's web," and first announced and demonstrated nylon and nylon
stockings to the American public at the 1939 New York World's Fair.
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History
Applications of Nylon
O
▶ Polyester :
- by Dupont, Dacron® cf. Terylene ® (by ICI)
- Applications : Leisure wear
OH
OMe
MeO
O
HO
O
O
O
O
O
O
O
O
O
O
O
▶ Teflon
- by Roy Plunke, 1938
- Applications : Artillery shell cover
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72
History
History
▶ Polyethylene (PE):
- by E.W. Fawcett & R.O. Gibson, 1933
- Applications : First used for underwater cable coatings and insulation for radar
now, most versatile plastic
LDPE, 1939
▶ Acrylics
▶ Spandex
▶ High performance Textiles: Aramid (ex. Kevlar)
▶
▶
▶
▶
HDPE, Ziggler-Natta catalyst, 1943
Polymer Blend
Compoiste: ex. Fiber-reinforeced plastics, FRP섬유강화복합재료)
Nanocomposite
High performance & Novel functionality
▶ Polypropylene (PP):
- by Guilier Natta, 1957
- Applications : packaging film, tape, fiber,
pipe, toy, and miscellaneous
Ziegler & Natta:
(Cowinner of Nobel Prize, 1963)
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Applications : Part of an automobile
Boby
ABS (bumper)
All for Saturn
Wiper
Polyisoprene
Applications : electronics
Interior
Nylon, PP (carpet)
PET, leather (seats)
SBS (dashboard)
Headlight can
Polycarbonate
Air filter
Cellulose,
polyisoprene
Hose
Polyisoprene
Tire
SBS, Polyisoprene,
Polyisobutene, Kevlar
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Housings
Speakers
Polystyrene, ABS
Cellulose, PP, PVDF
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Applications : electronics
Applications : electronics
Epoxy, Polyimide (packaging)
PHS (photoresist)
Polyimide, silicon polymer
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Applications
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Applications: Flexible display
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Applications:
Applications:
Tyvek
- a brand of flashspun high-density polyethylene fibers, a synthetic material;
commercialized by DuPont.
- very strong; difficult to tear but can easily be cut with scissors or a knife.
Water vapor can pass through Tyvek (highly breathable), but not liquid water.
- Applications : envelopes, car covers, air and water intrusion
barriers(housewrap) under house siding, labels, coveralls, wristbands,
mycology, and graphics.
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Applications:
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Applications:
An artificial organ
is a man-made device that is implanted or
integrated into a human to replace a
natural organ, for the purpose of restoring
a specific function or a group of related
functions so the patient may return to as
normal a life as possible.
MOTO W233 Renew
Blue Earth
Ex. Heart, bone, skin, blood vessel, joint
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Recycling symbols
O
O
* O
O
Sustainable Development
O
n *
*
Poly(ethylene terephthalate) or PETE
“ that meets the needs of the present without compromising the ability of future generations to meet their own needs” *
n
Me
poly(propylene)
(Brundtland Commission, 1987)
*
n
*
high density polyethylene
*
since the 1980s sustainability has
been used more in the sense of
human sustainability on planet Earth
and this has resulted in the most
widely quoted definition of
sustainability as a part of the
concept sustainable development
*
n
polystyrene
*
n
*
Cl
polyvinyl chloride
the relationship between the
three pillars of sustainability
suggesting
that both economy and society
are constrained by
environmental limits
Not recyclable
*
*
n
low density polyethylene
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Renewable sources of energy : Green sources
The world is gradually running short of oil
Bio-diesel
a vegetable oil- or animal fat-based diesel fuel consisting of long-chain alkyl
(methyl, propyl or ethyl) esters. Biodiesel is typically made by chemically reacting
lipids (e.g., vegetable oil, animal fat) with an alcohol producing fatty acid esters.
Bus run by biodiesel
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Wind power plant
Synthetic Materials from Petroleum
Solar power
Tidal power
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Greenhouse Effect
Environmental Demands

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When plastics made from petroleum are burned, they release the
carbon dioxide contained in the petroleum into the atmosphere,
leading to global warming.
- Visible energy from the sun passes
through the glass and heats the
ground
- Infra-red heat energy from the
ground is partly reflected by the
glass, and some is trapped inside
the greenhouse
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Greenhouse Effect
Greenhouse Effect
- The Greenhouse Effect is a warming of the Earth’s surface and the lower
atmosphere.
- greenhouse effect make life on Earth possible – and could destroy life as
we know it.
- Greenhouse gases : Water vapor, 36-70%, Carbon dioxide, 9-26%,
methane, 4-9%, ozone, 3-7%
- Thermal radiation from a planetary surface is absorbed by atmospheric
greenhouse gases, and is re-radiated in all directions.
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Carbon footprint
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Carbon footprint
Atmosphere
Biogenic CO2
- For the typical household, there are five main sources of emissions:
CO2
- Almost everything we do involves burning fossil fuels at some point, either
directly or indirectly.
Atmosphere
Biomass
Carbon
- The natural ecosystem has ways to absorb the
increase in CO2 via natural carbon ‘sinks’ such as
trees and the ocean, but these natural balances are
unable to keep pace with the amount of carbon we are
emitting into the atmosphere(one-way process).
Non-biogenic CO2
- The total sets of greenhouse gas(GHG)(CO2, CH4) emissions caused by an
organization, event, product or person.
Fossil Fuel
- Since part of this re-radiation is back towards the surface and the lower
atmosphere, it results in an elevation of the average surface
temperature(14◦C) above what it would be in the absence of the gases (-19◦C)
- By having a big carbon footprint, you are contributing
to global warming.
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Carbon footprint
Climate Change
global warming will lead to some serious problems in the next few years:
Earth’s climate is warming and human activities
are primarily responsible (>90% certainty)
- increasing the spread
of disease,
- more extreme weather
events such as
hurricanes and
tornados,
- an increase in
droughts and deadly
heatwaves,
- increased animal
extinctions,
280 to 430ppm concentration between 1850 and 2000 (0.5‐0.8oC increase)
550ppm likely by 2035 with
77‐99% chance of 2oC increase
50% chance of 5oC increase
all of which will then
lead to severe
economic
consequences.
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Certified Emission Reduction
Kyoto Protocol
Certified Emission Reduction
Clean Development Mechanism (CDM)
The Demand:
Kyoto Projects
EU ETS Allowances
2012
AVG: 1990 - 5.2%
2008
The industrialised countries commit themselves
to reduce their collective GHG emissions by at
least 5% below 1990 emission levels
1990:
Base Year
GHG Emissions ton/ year
38 Developed Countries and Economies in Transition (Annex I
countries) took on reduction commitments in 1997
First Commitment
Period: 2008-2012
Annex I
Country
(Developed
Nations)
commit themselves to
reduce their
collective GHG
emissions by at
least 5% below
1990 emission
levels
Non-Annex I Country
Funding
Technology
Projects to reduce GHG
emissions
*Certified Emission
Reduction (CER)
*CER : a type of emissions unit (or carbon
credits) issued by the CDM Executive Board
for emission reductions achieved by CDM
projects
Emission reduction compared
to an existing baseline
- Contribute to sustainable development
- Facilitate technology transfer
- Improve financial returns
Certified Emission Reduction
Certified Emission Reduction (CER)
► CO2 neutral
having a net zero carbon footprint, refers to achieving net zero
carbon emissions by balancing a measured amount of carbon
released with an equivalent amount sequestered or offset, or
buying enough carbon credits to make up the difference
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Certified Emission Reduction
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Materials from Natural Resources
► CO2 neutral
 Biomaterials are from
renewable resources.
They are also biodegradable,
meaning that the material
returns to its natural state when
buried in the ground.

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Biocomposites and
Automobiles
Fiber Reinforced Composites (FRP)
Fibers :
Matrix :
FRP
• Biocomposites
• Carbon fibers
• Petroleum‐based polymers
• Aramid fibers
• Metals
• Biofibers
(cellulose, protein, …)
• Ceramics
+
• Glass fibers
• Biopolymers
(starch, PLA, …)
•
•
•
•
•
•
•
•Growing at 9.9% per year
•Substituting glass fiber Reduced weight
Increased flexibility
Greater moldability
Less expensive
Sound insulation
Renewable resource
Self-healing properties
•The current Benz A‐Class has 26 components containing renewable raw materials such as abaca, flax, and hemp.
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Building Materials : ex. Hemp
‐ Extremely high thermal resistance , acoustic properties ‐ It has an ability to absorb & release moisture without effecting thermal performance. ‐ It is not affected by mould growth or insect attack as the fiber does not contain proteins.
‐ It does not cause irritation.
‐ Lightweight, easy to handle
Packaging Materials
Bioplastics
► biodegradable and recyclable
► CO2 neutral

Biodegradable replacements for plastic bags of all kinds

Add fiber to recycled paper to extend life

After their initial use they can be reused as bags for
organic waste and then be composted. .
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Polymers vs. Macromolecules


Polymers vs. Macromolecules
A macromolecule is a very large molecule commonly created by polymerization
of smaller subunits.
In biochemistry, the term is applied to the three conventional biopolymers
(nucleic acids, proteins and carbohydrates), as well as non-polymeric molecules
with large molecular mass such as lipids and macrocycles.
Which macromolecule is not a polymer?
Answer:
Lipids are macromolecules that aren't polymers, as their structure
does not consist of a repeating chain of monomers.
a polypeptide macromolecule
A protein is an example of a macromolecule.
Each amino acid in the chain (the monomers)
can be different and the macromolecule has a
definitive shape that is controlled by the
monomers in it.
Unlike plastic where the monomers are all the
same. Every amino acid has the same
backbone N-C-C=O but has different "R" groups
on it depending on it function.
Hexameric Palladium(II)
Terpyridyl
Metallomacrocycles
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Polymers vs. Macromolecules
Polymers vs. Macromolecules
Dendrimers : repetitively branched molecules
DNA
a polyphenylene dendrimer macromolecule
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