1. Introduction to Polymers

7/29/2019 1. Introduction to Polymers

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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

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

NN

N N N NN

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

NN

NNN

NN

N

N

N

N N

N

N

N

N

N

N

N

N

N

N N

N

N

N

N

N

N

N

N

N N

N

N

N

NN

N

N

N

N

N

N

NN

N

NN

N

N

N

N

N

N

N

N

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.

Documents

1. Introduction to Polymers