Polymers in Everyday Life

IPPH 363

Pharmaceutical Polymers

Tooth Brush Shaving blade Shampoo Lotions Sun screens Mascara Cosmetics Nail enamels

Professor Kinam Park (kpark@purdue.edu)

PURDUE
UNIVERSITY

Department of Biomedical Engineering Department of Pharmaceutics

Polymers Introduction to polymers

Polymer: a substance whose molecules consist of many (poly-) parts (meros, greek) or units. Plastic: a polymer-based material that can be molded, cast, extruded, drawn, or laminated into objects, films, or filaments.
Monomer, Dimer, Trimer Multimer Oligomer (N = 30-200)

Linear polymers (1930 s) (1930s)

Homopolymer block copolymer

Crosslinked gel (1940s) 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 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 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 N N N N N N N N N

Chain length: Not Uniform. Average Molecular Weight. (Different from proteins)

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Polyhuman. Poly(red human)

One word. Just one word: Plastics. Theres a great future in p plastics.

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H C CH 3 C

H C H

1839

C H

Polyisoprene

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Beginning of Polymers
1907. Bakelite Phenol-formaldehyde resin. The first completely man made man-made substance. The first thermoset plastic.

Urea-formaldehyde Resin (1929)

1907

Vinyl Polymerization

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Condensation Polymerization (Step-reaction Polymerization)

Nylon 6-10
H2N (CH 2 ) 6 + O Cl C (CH 2 ) 8 O C Cl Sebacoyl chloride in tetrachloroethylene Cl C Cl H N (CH 2 ) 6 H N O C (CH 2 ) 8 O C x Cl C Cl NH 2 Hexamethylenediamine in water

Need For New Tough Plastic. Synthesis of nylon based on Staudingers theory on polymeric nature of plastics.

H C H

CH 3 C C O

CH 3 C C O

Silicone Rubber

CH 3 Si O

Poly(methyl Methacrylate) Poly(hydroxyethyl Methacrylate)

C H

OCH 3

OCH 2 CH 2 OH

CH 3

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Silicone Rubber

Poly(vinyl chloride)
H C H H C Cl

Cohesive silicone gel implants, such as this one made by McGhan, a division of Inamed, are designed to avoid leaks.

Poly(tetrafluoro ethylene)

F C F

F C F

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Polyurethane

Poly(acrylic acid)

H C H

H C COOH

H C H

H C Cl

OCN n HO

R + R'

NCO OH O

O C

H N R

H N

O C O R'

CH2 CH OH

Poly(acrylic acid) in acid form

No charge. Poor water solubility. The ability to form intermolecular hydrogen bonding. Strong Adhesive

INTER- AND INTRAMOLECULAR HYDROGEN BONDING POLYMERS Intermolecular Hydrogen (A)

Bonding
CH2 O H O C CH CH2 n H C n C O H N H CH2 O H O C CH CH2 n H C C n O CH3 N CH3

(B) CH2 O H C
n

O CH2 N H O N N O O C H2 C O CH2 CH n

N H

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Kevlar (Poly(p-phenylene terephthalamide)

Stephanie Kwolek

Hydrogen bonding and van der Waals forces

Gossamer Albatross crossed the English Channel in 1979. It was constructed frpm a variety of plastics, including Kevlar film, Teflon, Delron, acetral resin, molded polystyrene, and carbon-reinforced polymer (E.I.; DuPont).

POLY(ETHYLENE TEREPHTHALATE) 1891. Rayon: artificial silk. Regenerated man-made fibers of cellulose from cuprammonium cellulose, viscose (cellulose xanthate), or cellulose xanthate) acetate. Sutdy 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 similar characteristics to silk before being secreted through a man-made apparatus to form fibers that can spun and feel like silk.

Tradenames: Dacron, Vycron (fibers) (fib ) Mylar (films) Applications: Biomaterials Film, Bottles Recording tapes

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Polyacrylamid e

H C H

H C CON H 2

Biodegradable Polymers

Agarose

Natural Polymers
Nucleic acids Proteins Polysaccharides

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Discovery of the DNA Structure (1953)

Protein

Gelatin

Peptide bond

H N H C R

O C

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Protein Folding

Introduction To Protein Structure Carl Branden & John Tooze, 1991

Introduction To Protein Structure Carl Branden & John Tooze,

Polysaccharides
CH 2 OH O OH OH O CH 2 OH O OH OH O

Alginic Acid
CH 2 OC 2 H 5 O OH OC 2 H 5 O CH 2 OC 2 H 5 O OH OC 2 H 5 O

++ Ca
Calcium ion

Cellulose
CH 2 OCH 2 COOH O OH O OCH 2 COOH CH 2 OCH 2 COOH O OH O

Ethylcellulose
COOH O OH OH O COOH O OH OH O

H
OCH 2 COOH

Ch e la t i n g a ge n t

Carboxymethylcellulose
CH 2 OH O OH NH 2 O CH 2 OH O OH NH 2 O

Alginic acid
COO O OH OH O OH NH C O CH 2 OH O O

COOH O OH OH O

COOH O OH OH O

Chitosan

Hyaluronic acid

CH 3

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Starch

Bread: Soft Hard

CH 2 OH O OH NH 2 O

CH 2 OH O OH NH 2 O

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Temperature-Sensitive Polymers & Hydrogels

Positive Thermosensitivity as T Solubility/Swelling g y Negative Thermosensitivity as T Solubility/Swelling

Hydrophobic interactions
H
CH3

CH2

C C N C O H H CH3

CH 2

C C N C O H H

H3C

H 2C

CH 2

Poly(N-isopropylacrylamide Poly(N-cyclopropylmethacrylamide

Competition between the two forces Covalent bond: (H-bonding & Hydrophobic interaction) ~ 5 eV ( 0.8 x 10-18 J) Temperature dependent interactions as T Hydrogen-bonding as T Hydrophobic interaction
Secondary interaction forces: ~ 0.1 eV Thermal fluctuation energy: ~ 0.03 eV ( 1 kT)

Competition between hydrogen bonding & hydrophobic interactions. Water-soluble at low temperature Water-insoluble at high temperature. Lower critical solution temperature: Temperature that induces polymer precipitation, i.e., phase separation.

Textbook Of Biochemistry With Clinical Correlations, Thomas M. Delvin, Ed., 5th Edn., 2002

Polymers: Hydrogels: Organogels:

Hydrophilic (Water-soluble) Hydrophobic (Water-insoluble) Network of hydrophilic polymers Network of hydrophobic polymers

Types of hydrogels

Chemical gel. gel Covalent crosslinking

Physical gel gel. Interpenetrating network Non-covalent crosslinking Covalent and/or Non-covalent crosslinking
++ Ca
Calcium ion

Ch e la t i n g a ge n t

Sodium alginate

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Polymers: Hydrogels: Organogels:

Hydrophilic (Water-soluble) Hydrophobic (Water-insoluble) Network of hydrophilic polymers Network of hydrophobic polymers

Smart Polymers & Hydrogels

Dissolution-Precipitation Swelling-Deswelling

Respond to small changes in environmental signals by large changes in physicochemical properties

Degradation Degradation

Ordinary Polymers & Hydrogels

Drug

Precipitation Shrunken state - Squeezing - Trapping

Crosslink

Dilution Swollen state - Opening - Absorbing

Sol-gel phase transition

Coil-Globule transition Shape transformation

Environmental Stimuli

Physical

Stimuli

Biological g

Chemical

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