1. introduction to polymers
TRANSCRIPT
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1. Introduction to Polymers
Polymers in Everyday Life
Tooth Brush
Shaving blade
Shampoo
Lotions
Sun screens
Mascara
Cosmetics
Nail enamels
Polymers Everywhere
Definitions
Polymer: a substance whose molecules consist of
many (poly-) parts (meros, greek) or units.
Large molecular weight
Macromolecule
Plastic: a polymer-based material that can be
molded, cast, extruded, drawn, or laminated into
objects, films, or filaments.
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Multimer
Oligomers and Polymers
Monomer, Dimer, Trimer
Oligomer
(N = 30-200)
Polymer
(N = >200)
Molecular weight: heterogeneous average
Polyhuman. Poly(red man)
Crosslinked gel (1940s)
Linear polymers (1930s)
Synthetic Polymers
Homopolymer, block copolymer
Branched polymers (1960s)
Dendrimers (1980s)N
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Books on Polymers/Plastics
Polymers/Plastics: Synthetic, artificial, cheap,
non-genuine, low-class
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Sabrina (1954)
One word. Just one word:Plastics. Theres a great
future in plastics.
The Graduate (1967)
Polymer Stuff C CH
H
C
H
C
H
HCH3
Polyisoprene 1839Natural Rubber
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Giant molecules. Essential materials for everyday living and problemsolving. Raymond B. Seymour & Charles E. Carraher.John Wiley & Sons, Inc., 1990, pp. 117-119.
The first thermoplastic. The first flexible photographic films for still and m otion pictures
1866Celluloid
TM
Cellophane & Rayon
Rayon: artificial silk. (1891)
Regenerated man-made fibers of cellulose from
cuprammonium cellulose, viscose (cellulose xanthate), or
cellulose acetate.
Study on silkworm by Louis Marie Hilaire Bernigaut,Paris: Silkworm secretes a liquid from a narrow orifice
that hardens upon exposure to air (silk).
Idea: Pass a liquid that has s imilar characteristics to silk
before being secreted through a man-made apparatus to
form fibers that can spun and feel like silk.
Cellulose is dissolved in alkali and carbon disulfide to make a solution calledviscose.
Wash viscose in a bath of dilute sulfuric acid and sodium sulfate to reconvert into cellulose.
(Plasticizer Glycerin)
Cellophane = cellulose and diaphane ("transparent)
Plastics The Beginning of the Synthetic Polymers:Ivory replacement in 1866
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The Polymer History:
1907. Bakelite
Phenol-formaldehyde resin.
The first completely
man-made substance.
The first thermoset plastic.
Urea-formaldehyde Resin (1929)
Beginning of Synthetic Polymers
1907Bakelite
Giant Molecules. Essential Materials for Everyday Living AndProblem Solving. Raymond B. SEYMOUR & CHARLES E.Carraher. John Wiley & Sons, Inc., 1990, pp. 43-44.
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Poly(vinyl alcohol) 1924CH2 CH
OH n
http://www.wacker.com/cms/en/wacker_group/wacker_facts/history/history.jsp
http://www.azom.com/article.aspx?ArticleID=266
Poly(vinyl alcohol) has been available since around 1924, when its
synthesis via the saponification of poly(vinyl acetate) was firstdescribed by Herman and Haehnel. In the early years, the principalapplication for PVOH was in textile sizing. Today, much of the PVOH
produced is used as a protective colloid in the manufacture of polymeremulsions. It is also found in many other applications, including the
binding of pigments and fibres, dip coated articles, protectivestrippable coatings, the production of detergents and cleansing agents,
adhesives, emulsion paints and solution cast film.All of these applications involve the use of the polymer in solution,since the thermal degradation characteristics of PVOH limit its ability
to be used as a conventional thermoplastic. UnplasticisedPVOH
thermally degrades at temperatures of about 150C, with the release ofwater and the formation of conjugated double bonds. As the crystalline
melting point of PVOH ranges from 180C to 240C, its use as athermoplastic, processable on conventional thermoplastic processingequipment, is limited unless it can be plasticisedto such an extent thatthermal dehydration is avoided. In practice, the amount of plasticiser
necessary to achieve this is so high that many of the useful propertiesof PVOH are sacrificed.
C C
H
H
H
Cl
Poly(vinyl Chloride)
1927
Vinyl Polymerization
C C
H
H
C
H
C
H
HCl
Polychloroprene
= Poly(2-chloro-1,3-butadiene)]
(Trade name: Neoprene) 1931
Synthetic Rubber
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Workers cover the ski slopes on the Pitztal
Glacier in Austria with an innovative white
fleece in an effort to protect the mountain
from glacier melting.
Polyethylene
Cost: $12 million per square mile
1933
http://www.wired.com/wired/archive/11.09/navy_pr.html
LANDINGS
VERSION 1.0 When a 50,000-pound fighter lands on theReagan at 150 mph, a hookbolted to the jet's tail catches one of threepolystyrene cables on the deck, yanking the
aircraft to a halt in 350 feet. The brute force of those arresting wires wears down
fighters and could break lightweight drones.UPGRADE Engineers are developing a system that will ID incoming aircraft and
automatically adjust cable tension for a smoother landing.
Polystyrene 1937
C C
H
H
CH3
C O
OCH 3
C C
H
H
CH3
C O
OCH 2 CH 2OHPoly(hydroxyethyl Methacrylate)
Contact Lens Poly(methyl Methacrylate)1931
(Plexiglas, Lucite)1936
1960
Contact Lens
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C C
F
F
F
F
Poly(tetrafluoro ethylene)During World War II, designers of the atomic bomb utilized Teflon to
manufacture gaskets and linings that could resist the bomb's corrosiveuranium hexafluorides.
1938 Nylon
Nylon 6-10
Condensation Polymerization
(Step-reaction Polymerization)
H2N (CH 2 )6 NH 2
Cl C
O
(CH 2)8 C
O
Cl
C C
Cl
Cl Cl
Cl
N
Hexamethylenediamine in water
(CH 2)6
+
N
Sebacoyl chloride in tetrachloroethylene
H
C
O
(CH 2)8 C
OH
x
Need For New Tough Plastic.
Synthesis of nylon based on Staudingers theory on
polymeric nature of plastics.
Nylon
1939
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Tradenames:
Dacron
Vycron (Fibers)
Mylar (Films)
Applications:Biomaterials
Film
Recording Tapes
Bottles
Poly(ethylene Terephthalate)
1941
Si O
CH3
CH3
Silicone Rubber
1943
Silicone Rubber
C C
H
H
H
Cl
OCN R NCO
HO R' OHO C
O
N
H
R N C
O
O R'
H
n
+
Polyurethane 1943
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Velcro
1955
Nylon, Polyesters, Teflon
1957
Polycarbonate
Carbon Fiber
Polyacrylonitrile (PAN)
(1) Polymerization of acrylonitrile to PAN
(2) Cyclization during low temperature process
(3) High temperature oxidative treatment of carbonization (hydrogen is removed)
(4) Process of graphitization: nitrogen is removed and chains are joined into graphite planes
(http://en.wikipedia.org/wiki/Carbon_%28fiber%29)
1958Carbon fiber reinforced plastic
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Hydrogen bonding and van der Waals forces
Gossamer Albatross crossed the English Channel in 1979.
It was constructed frpm a variety of plastics, includingKevlar film, Teflon, Delron, acetral resin, molded
polystyrene, and carbon-reinforced polymer (E.I.; DuPont).
Kevlar (Poly(p-phenylene terephthalamide)
Stephanie Kwolek
1964
C C
H
H
H
COOH
Poly(acrylic acid)
Poly(acrylic acid) as a super-absorbent (SAP) was patented in 1966 by Gene
Harper of Dow Chemical and Carlyle Harmon of Johnson & Johnson.
It was first used in diapers in 1982 in Japan.http://toxipedia.org/display/toxipedia/Polyacrylic+Acid
Patented in 1966 Polyacrylamide
C C
H
H
H
CON H2
Additional Evidence That Potato Chips
Should Be Eaten Only In Moderation
ScienceDaily (Feb. 26, 2009) A newstudy published in the March 2009
American Journal of Clinical Nutritionby
Marek Naruszewicz and colleagues from
Poland suggests that acrylamide from
foods may increase the risk of heart
disease. Acrylamide has been linked
previously to nervous system disorders and
possibly to cancer.
http://www.sciencedaily.com/releases/2009/02/090213161040.htm
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No charge.
Poor water solubility.
The ability to form
intermolecular hydrogen
bonding.
Poly(acrylic acid)
in acid formCH2
HC
CO
O
H
CH CH2
CO N
CH3
CH3
CH2HC
CO
O
H
CH CH2
CO N
H
H
CH2HC
CO O
CH2
N
N
O
H
H
O
INTER- AND INTRAMOLECULAR HYDROGEN
BONDING POLYMERS
N
N
n
O
O
nn
n
H2C
(A)
OC
OCH
CH2
n
(B)
n
Intermolecular Hydrogen Bonding
Strong Adhesive
CH2 CH
NO
n
O
OR
OR
CH2OR
O
OR
OR
CH2OR
O O
R
RO
n
R =H or CH2CHCH3
OH
HydroTac Result of a failure of making high
strength polymeric adhesive
Post-it
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Surlyn is the random copolymer poly(ethylene-co-methacrylic
acid). The incorporation of methacrylic acid is typically low
(< 15mol. %). Some or all of the methacrylic acid units can be
neutralized with a suitable cation, commonly Na+ or Zn+2.
Surlyn: Distance
Polyurethane: Spin
Surlyn
Golf
C C
H
H
H
C
H
C
H
H
C C
H
H
C
H
C
H
HCH3
Polyisoprene
(Natural Rubber)
Polybutadiene
(Synthetic Rubber)
Polymer molding
http://www.gizmag.com/go/3062/
Body Armor
Computer Display
Artificial Muscle
Smart Fabric:Sense and seal out
chemical and
biological weapons
Polymeric Soldier of the Future
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Polyester Fiber Coolmax Polymeric Body Parts
Polyacrylonitrile hydrogels Colorful Polymers
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http://www.lightblocks.com/
LightBlocks
Electrifying Plastics Organic light-emitting diode
Tris(8-hydroxyquinolinato)
aluminium
Poly(p-phenylene vinylene)
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http://www.aerogel.org/?p=71
Polymer Aerogel
Organic RF Polymer aerogels are made of resorcinol-formaldehyde polymer
http://www.aerogel.org/?p=3
The specially engineered, highly flexible fabric called LZR PULSE is
ultrasonically welded so as to appear seamless.
http://www.speedousa.com/technology/index.jsp
Speedo LZR Racer
Natural Polymers
Nucleic acids
Proteins
Polysaccharides
Natural vs. Synthetic
Are all natural polymers safe?
DNA
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DNA Protein
http://apbrwww5.apsu.edu/thompsonj/Anatomy%20&%20Physiology/2010/2010%20Exam%20Reviews/Exam%201%20
Review/Ch02%20Protiens%20and%20Enzymes.htm
Cheese is made from milk that has been curdled by the addition of acids and an enzyme from the
stomach of calves called rennet. The acid can be from almost any food source, but for the most part
it is produced by bacteria that convert the milk sugar lactose into lactic acid. Yogurt is also
produced this way.
Cheese can be made without rennet, but the enzyme makes the curds stronger and more
rubbery. Rennet allows the milk to curdle with less acid, which in turn allows flavor producing
bacteria to colonize the curd. Cheeses made with rennet will melt easily, while cheeses made with
acid alone remain intact at high temperatures.
The curds are salted, and moisture pressed out, so the product will not be as easily attacked by
bacteria as raw milk would. Thus cheese making is a way of preserving milk.
(http://kitchenscience.sci-toys.com/protein)
Protein Aggregation by Acid
N C
R
C
H
H O
Peptide bondGelatin
Ballistics Gel for Bullet Tests
10% Gelatin gel (250 Bloom):
The density and viscosity of human
and animal muscle tissue.
Bloom: The weight (in grams) needed
by a probe (normally with a diameter
of 0.5 inch) to deflect the surface of the
gel 4 mm without breaking it.
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http://commons.wikimedia.org/wiki/File:AlphaHelixBALL.png
Alpha Helix Beta Pleated Sheet
http://commons.wikimedia.org/wiki/File:BetaPleatedSheetProtein.png http://iverson.cm.utexas.edu/courses/310N/POTDSp06/POTD2-26-10.html
Hydrogen Bonding Microtubules, Microfilaments
http://micro.magnet.fsu.edu/cells/microfilaments/microfilaments.html http://www.phschool.com/science/biology_place/biocoach/cells/cytoreview.html
http://www.freethought-forum.com/forum/showthread.php?t=11575&garpg=19 http://en.wikipedia.org/wiki/Cytoskeleton
The eukaryotic cytoskeleton. Actin filaments are shown in red,microtubules in green, and the nuclei are in blue.
Polysaccharides
O
OH
OH
CH 2OH
O O
O
OH
OH
CH 2OH
O
OC 2H5
OH
CH 2OC 2 H5
O O
O
OC 2H5
OH
CH 2OC 2 H5
O
OCH 2COOH
OH
CH 2OCH 2 COOH
O
H
O
O
OCH 2COOH
OH
CH 2OCH 2 COOH
Cellulose Ethylcellulose
Carboxymethylcellulose
O
OHOH
COOH
O O
O
OHOH
COOH
Alginic acid
O
NH2
OH
CH 2OH
O O
O
NH2
OH
CH 2OH
Chitosan
O
OH
OH
COO -
O O
O
NH
CH 2OH
OH
C O
CH 3Hyaluronic acid
Agarose: Gel eelectrophoresis for DNA sequencing
http://www.sumanasinc.com/webcontent/animations/content/gelelectrophoresis.html
There have been 297 post-conviction DNA exonerations in the United States.
The first DNA exoneration took place in 1989. Exonerations have been won in 36 states; since 2000,there have been 230 exonerations.
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Ca+ +
C h e l a t i n ga g e n t
Calcium ion
O
OHOH
COOH
O O
O
OHOH
COOH
Alginic Acid Dietary Fibers
Dietary fiber is a relatively broad term that includes manyplant components that share the characteristics of beingindigestible . This means that dietary fiber is not digested, absorbed by the body , or used for energy. There are two main
sources of dietary fibersoluble fiber and insoluble fiber. *Note many plant sources include both soluble and insolublefiber.
Insoluble fiber does not dissolve in water and does not get broken down by bacteria in the intestine. Instead, it essentially
absorbs water to help to increase bulk and to soften stool.
Soluble Fiber differs from insoluble fiber in that it dissolves in water and additionally is broken down by bacteria in theintestine. Soluble fiber helps prevent cholesterol from being absorbed by the intestines and is thought to help minimize the
rise in blood sugar following a meal.
http://www.jarretmorrow.com/dietary-fiber-cheat-sheet/
Plant substances that are indigestible
in the digestive system.
20-35 g/day/adult
(American Dietetic Association)
O
NH2
OH
CH 2OH
O O
O
NH2
OH
CH 2OH
The U.S. military became HemCon's first and biggest customer. "The military
has already paid for 21,000 bandages and th ey are being used in Iraq," said SueVan Brocklin, spokeswoman for HemCon. "The HemCon bandage is also
approved for use by paramedics, firefighters and hospitals."
Made from chitosan, a shrimp-based product, the bandage is designed to halt
severe bleeding fast. But the four-inch by four-inch patch doesn't come cheap,
costing about $130 a piece.
Van Brocklin said demand for the bandage has risen rapidly since it won FDA
clearance and the company does have plan to bring the HemCon bandage to the
consumer market.
"The cost and the size is a factor right now," said Brocklin. "But eventually as
the cost comes down we are hoping to move it to civilian u se. The bandage will
probably be smaller and come as a part of a first-aid kit available in drug stores.
http://money.cnn.com/2003/04/09/news/companies/war_fads/index.htm
Chitosan: Hemorrhage control bandage Starch
Bread:
Soft
Hard
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Guar Gum Industrial applicationsPharmaceutical industry as binder or as disintegrator in
tablets; main ingredient in some bulk-forming laxatives
Cosmetics and toiletries industries thickener in toothpastes,
conditioner in shampoos
Hydroseeding formation of seed-bearing "guar tack"Medical institutions, especially nursing homes - used to
thicken liquids and foods for patients with dysphagia
Fire retardant industry - as a thickener in Phos-Chek
Food applications
The largest market for guar gum is in the food industry.
Xanthan gum and guar gum are the most frequently used gums
in gluten-free recipes and gluten-free products.
Applications include:
In baked goods, it increases dough yield, gives greater
resiliency, and improves texture and shelf life; in pastry
fillings, it prevents "weeping" (syneresis) of the water in the
filling, keeping the pastry crust crisp.
In dairy products, it thickens milk, yogurt, kefir, and liquidcheese products, and helps maintain homogeneity and textu re
of ice creams and sherbets
For meat, it functions as a binder.
In condiments, it improves the stability and appearance of
salad dressings, barbecue sauces, relishes, ketchups and others.
It is also used in dry soups, instant oatmeal, sweet desserts,
canned fish in sauce, frozen food items and animal feed.
http://en.wikipedia.org/wiki/Guar_gum
Xanthan Gum
Pectin Pectic Acid
Pectic acid, also known as polygalacturonic acid
is a water insoluble, transparent gelatinous acid
existing in ripe fruit and some vegetables. It is a
product of pectin degradation in plants, and is
produced via the interaction between pectinaseand pectin (the latter being common in th e wine-
making industry).
http://en.wikipedia.org/wiki/Pectic_acid
Pectin is a complex polysaccharide consisting mainly
of esterified D-galacturonic acid resides in an alpha-
(1-4) chain. The acid groups along the chain arelargely esterifed with methoxy groups in the natural
product. There can also be acetyl groups present on
the free hydroxy groups. The galacturonic acid main
chain also has the occasional rhamnose group present
which disrupts the chain helix formation.
http://www.cybercolloids.net/library/pectin/introduction-pectin-structure
http://www.scientificpsychic.com/fitness/carbohydrates2.html
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Emergence of Synthetic Polymers
Year 1960 - present
1. Large scale operations.
2. Applications in daily lives, transportation,
communications, education, & leisure.
3. Polymer composites
4. Polymers as biomaterials.
5. Functional polymers
Polymers with bioactivity6. Smart polymers and hydrogels
7. Biodegradable polymers
Foundation of Polymer Science
Polymers are indispensable in our daily life and in the
biomedical and pharmaceutical systems.
Understanding relationshipsbetween chemical structure
and (molecular and bulk) properties of polymers.
Polymercharacterization
Use the relationships to design new materials with
predictable properties, and to mimic natural substances
without need to duplicate their structures in detail.