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 61

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 63

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 64

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) 66

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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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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. 69

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

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▶ 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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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) 74

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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 77

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. 81

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. 95

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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. 97

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. 105

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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 111

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Polymers vs. Macromolecules

Polymers vs. Macromolecules Dendrimers : repetitively branched molecules

DNA

a polyphenylene dendrimer macromolecule

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