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Polymer Chemistry

MBM 471
Lecture 1: Introduction

Faculty Asst. Prof. İlke Anaç (e-mail:ilkeanac@gyte.edu.tr)


Room: 212
Content-1
Introduction: Basic concepts and definitions, classification of
polymers, nomeculature of polymers, molecular weight and its
distribution

Polymerization mechanisms: Chain polymerization
-Free radical polymerization
-Cationic polymerization
- Anionic polymerization

Step- growth polymerization, ring-opening polymerization,


coordination polymerization

Chemical bonding and polymer structure, polymer molecular weight

Thermal transitions in polymers

Polymer modification: Copolymerization, post polymerization


reactions and functional polymers
Content-2
Polymer additives and reinforcements

Polymerization techniques

Polymer processing: an overview of processing


techniques for thermoplastics and thermosets

Solution properties of polymers

Mechanical properties of polymers Assesment


Polymer viscoelasticity Midterm- %35 (18 November)

Final: %50

Quiz- %10 (4 quiz)

Attendence % 5
Textbook
• Textbook: Polymer Science and Technology, Robert O Ebewele
(CRC press, New York,2000)

Additional Books: Introduction to Polymers, R.J. Young and P. A.
Lowell (Stanley Thornes, 2nd edition)
• Polymer Science & Technology, Joel R. Fried, Prentice Hall, 2nd
edition
• Polymer Kimyası, Prof. Dr. Mehmet Saçak, Gazi Yayınevi, 5. baskı
• Polymer Teknolojisi, Prof. Dr. Mehmet Saçak, Gazi Yayınevi, 5.
baskı
Historical Background
Ages ago - Natural Fibers Ex. Wool, silk, cotton

In 1736, Charles Marie de La


Condamine introduced the para
rubber tree (natural rubber).

Hevea brasiliensis

Natural (hevea) rubber known as “Crying tree” Latex Coating


polyisoprene in its synthetic form. (para rubber)
Historical Background
1839-Charles Goodyear
Vulcanization: Transformation of sticky natural rubber to a useful
elastomer for tire use

S8

1843-Charles Goodyear Ebonite High % vulcanization


(1st synthetic plastic made from natural rubber)

Fountain pen bodies smoking pipe mouthpiece bowling balls


Synthetic Polymers Started
1847 “Cellulose nitrate”

cellulose cellulose nitrate

1860s -Parkes (Electrical industry) and Hyatt (Billiard balls)

“Celluloid” (1st artificial thermoplastic)

Cellulose nitrate+ Camphor (as plasticizer)


1907-Leo Baekeland “Bakelite”
(thermosetting phenol-formaldehyde resin)

Bakelite letter opener


Bakelite radio

On further heating with HCHO, novalac undergoes cross-linking to an infusible solid called bakelite. It is hard scratch and water resistant.

Bakelite distributor rotor


Bakelite telephone 1st truly synthetic plastic
Nobel Prize-Chemistry 1953 for “his discoveries in the field of macromolecular chemistry”

1920 “Macromolecular Hypothesis”


Demonstrations of both synthetic and natural polymers

Polymer is a giant molecule

long chains of short repeating


molecular units linked by covalent bonds

Hermann Staudinger

A chain of paper clips (above) is a good


model for a polymer such as polylactic acid (below).
Between 1925-1950
Phenomenal growth in the number of polymeric products that achieved commercial use

1950`s acetal and polycarbonates (automotive and appliance parts)


1960s-1970s- thermoplastic polyesters (exterior automotive parts, bottles), high barrier nitrile resins and
high temperature plastics including materials such as polyphenylene sulfide, polyether sulfone.
Definitions
Polymer science is relatively a new branch of science . It deals with chemistry
physics and mechanical properties of macromolecule .

Polymer –is a large molecule consisting of a number of repeating


units with molecular weight typically several thousand or higher

Polymers are made up of many Monomers


Many units One units

Repeating unit – is the fundamental recurring unit of a polymer

Monomer - is the smaller molecule(s) that are used to prepare a


polymer

Oligomer –is a molecule consisting of reaction of several repeat


units of a monomer but not large enough to be consider a polymer
(dimer , trimer, tetramer, . . .)

Degree of polymerization (DP)- number of repeating units


1 2

Nylon 6,6
POLYETHYLENE

Zig-zag conformation
Substituent groups such as –CH3, -OCOCH3, CN, Cl or –Ph that are attached
to the main chain of the skeletal atoms are known as pendant groups. Their
structure and chemical nature can offer unique properties on polymer.
Classification of Polymers

A. Classification by Origin

• Natural Polymers
-Biological Origin - enzymes, nucleic acids, proteins
-Plant Origin – cellulose, starch, natural rubber
•Synthetic Polymers
- Fibers
- Elastomers
- Plastics
-Adhesives
3.Classification by Polymerization Mechanism

Classification of polymers to be suggested by Carothers

Addition polymers are produced by reactions in which monomers are added


one after another to a rapidly growing chain. Most important addition polymers
are polymerized from ethylene based polymers.

•Initiation
•Propagation
Unsaturated (C-C double bond)
(ethylene based monomers) •Termination

Ring opening polymerization

Polyoxymethylene

Trioxane
2.Classification by Polymerization Mechanism

Condensation polymers are obtained by random reaction of two molecules.


A molecule participating in a condensation reaction may be a monomer, oligomer, or high molecular
weight intermediate each having complementary functional end units, such as carboxylic acid or
hydroxyl groups. Typically condensation polymerizations occur by the liberation of a small molecule in
the form of gas, water, or salt.

More recently, another classification scheme based on polymerization kinetics has been adopted
over the more traditional addition and condensation categories.

• Step growth
• Chain growth
3.Classification by Polymer Structure

Classification by Chain structure (molecular architecture)


The architecture of the polymer is often physically determined by the functionality of the monomers
from which it is formed. This property of a monomer is defined as the number of reaction sites at which
may form chemical covalent bonds.

bifunctional

bifunctional bifunctional
3.Classification by Polymer Structure

Classification by Chain structure (molecular architecture)


The basic functionality required for forming even a linear chain is two
(a) linear bonding sites.

(b) branch Higher functionality yields branched or even crosslinked or networked


polymer chains.

Branched polymers have side chains, or branches, of significant


points (known as junction points), are characterized in terms of the
number and size of the branches

(c) network Network polymers have three dimensional structures in which each
chain is connected to all others by a sequence of junction points and
other chains. Such polymers are said to be crosslinked and
characterized by their crosslink density, or degree of crosslinking,
which is related to the number of junction points per unit volume

Non linear polymers may be formed by polymerization, or can be prepared by linking together (ex.
crosslinking) pre-existing chains.
2.Classification by Polymer Structure

Classification by Chain structure (molecular architecture)

(d) ladder polymer

Ladder polymers constitute a group of polymer with a regular sequence of crosslinks.

diacetylene
2.Classification by Polymer Structure

Classification by Chain structure (molecular architecture)

(g) dendrimer

Dendrimers are repeatedly branched, roughly


spherical large molecules.
4.Classification by Polymer Structure

Classification by Monomer Composition


A. Homopolymer -contain only one type of repeat unit (A))

B. Copolymer -contain two different repeating units (AB)


If there are three chemically different repeating unit, it is then called terpolymer

Poly(styrene-co-acrylonitrile) (SAN)
Type of Copolymers
Random copolymer : -A-B-B-A-B-A-A-B-
-two or more different repeating unit are distributed randomly

Alternating copolymer : -A-B-A-B-A-B-A-B-


-are made of alternating sequences of the different monomers

Block copolymer : -A-A-A-A-B-B-B-B-


-long sequences of a monomer are followed by long sequences of
another monomer

B-B-B-B-B-

Graft copolymer : -A-A-A-A-A-A-A-A-


-Consist of a chain made from one type of monomers with branches
of another type
5.Classification by Thermal Behavior

A thermoset is a polymer that, when heated, undergoes a chemical change to produce a


cross-linked, solid polymer.( Ex: urea-formaldehyde, phenol-formaldehyde, epoxies)

Thermoplastic polymers soften and flow under the action of heat and pressure. Upon
cooling, the polymer hardens and assumes the shape of the mold (container).
(Ex: polyethylene, polystyrene, and nylon)
6.Classification by Preparative Technique

A) Bulk polymerization-only the monomer (and possibly catalyst and initiator, but no solvent) is
fed into the reactor. The monomer undergoes polymerization, at the end of which a (nearly) solid
mass is removed as the polymer product.

B) Solution Polymerization- involves polymerization of a monomer in a solvent in which both


the monomer (reactant) and polymer (product) are soluble

C) Suspension Polymerization- refers to polymerization in an aqueous medium with the


monomer as the dispersed phase. Consequently, the polymer resulting from such a system forms
a solid dispersed phase.

D) Emulsion Polymerization- is similar to suspension polymerization but the initiator is located


in the aqueous phase (continuous phase) in contrast to the monomer (dispersed phase) in
suspension polymerization.
Inorganic Polymers
Cl
CH3

N P
O Si
n
n
CH3
Cl

polydimethylsiloxane Poly(dichlorophosphazene)

Polyelectrolytes

CH3

H2 H H2
C C C C
n n
COOH COOH

Poly(acrylic acid) Poly(methacrylic acid)


MOLECULAR WEIGHT

The degree of polymerization represents one way of quantifying the molecular length or size of
a polymer. This can also be done by use of the term molecular weight (MW). By definition,

MW(Polymer) = DP × MW(Repeat Unit).

A number-average molecular weight Mn : divide


chains into series of size ranges and then determine the
number fraction Ni of each size range

Mn = ∑ Mi Ni / ∑ Ni
where Mi represents the mean molecular weight of the
size range i, and Ni is the fraction of total number of
chains within the corresponding size range

A weight average molecular weight Mw is based on


the weight fraction wi within the size range.

Mw = ∑ Mi Wi / ∑ Wi
Polydispersity Index (PDI)

A measure of the molecular-weight distribution is given by the ratios of molecular


weight averages.
For this purpose, the most commonly used ratio is Mw/Mn, which is called the
polydispersity index or PDI.

PDI= Mw/Mn

Mw/Mn = 1 monodisperse
Polymer sample consisting of molecules all of which have the same chain length.

Mw/ Mn > 1 polydisperse


Polymer consisting of molecules with the variety of chain length
Nomenclature

A. Types of Nomenclature

a. Source name : to be based on names of corresponding monomer

Polyethylene, Poly(vinyl chloride), Poly(ethylene oxide)

b. IUPAC name : to be based on CRU, systematic name

Poly(methylene), Poly(1-chloroethylene), Poly(oxyethylene)

c. Functional group name :


According to name of functional group in the polymer backbone

Polyamide, Polyester
Nomenclature

d. Trade name : The commercial names by manufacturer Teflon, Nylon

e. Abbreviation name : PVC, PET

f. Complex and Network polymer : Phenol-formaldehyde polymer


Vinyl polymers

A. Vinyl polymers
a. Source name : Polystyrene, Poly(acrylic acid),
Poly(α-methyl styrene), Poly(1-pentene)
b. IUPAC name : Poly(1-phenylethylene), Poly(1-carboxylatoethylene)
Poly(1-methyl-1-phenylethylene), Poly(1-propylethylene)
Polystyrene Poly(acrylic acid)

CH2CH CH2CH
CO2H

Poly(α-methylstyrene) Poly(1-pentene)
CH3
CH2C
CH2CH
CH2CH2CH3
Vinyl polymers

B. Diene monomers
CH 2CH CH 2CH CHCH 2

HC CH 2

1,2-addition 1,4-addition

Source name : 1,2-Poly(1,3-butadiene) 1,4-Poly(1,3-butadiene)

IUPAC name : Poly(1-vinylethylene) Poly(1-butene-1,4-diyl)


Vinyl copolymer

Type Connective Example

Unspecified -co- Poly[styrene-co-(methyl methacrylate)]

Statistical -stat- Poly(styrene-stat-butadiene)

Random -ran- Poly [ethyelene-ran-(vinylacetate)]

Alternating -alt- Poly[styrene-alt-(maleic anyhride)]

Block -block- Polystyrene-block-polybutadiene

Graft -graft- Polybutadiene-graft-polystyrene


* A statistical polymer is one in which the sequential distribution of the monomeric units obeys the statistical laws. In the case of random copolymer, the
probability of finding a given monomeric unit at any site in the chain is independent of the neighboring units in that position.
Polystyrene-block-polybutadiene

Polystyrene-graft-polybutadiene
* Representative Nomenclature of Nonvinyl Polymers

Monomer Polymer Source or IUPAC name


structure repeating unit Common Name

O
CH2CH2O Poly(ethylene oxide) Poly(oxyethylene)
H2C CH2

HOCH2CH2OH CH2CH2O Poly(ethylene glycol) Poly(oxyethylene)

O O

H2N(CH2)6NH2 NH(CH2)6NHC(CH2)8C

HO2C(CH2)8CO2H Poly(hexamethylene Poly(iminohexane-


sebacamide) or Nylon6,10 1,6-diyliminosebacoyl)
Abbreviations

Abbreviation Name

PVC Poly(vinyl chloride)


HDPE High-density polyethylene
LDPE Low-density polyethylene
PET Poly(ethylene terephthalate)
ABS Arcylonitrile-butadiene-styrene resin
PBT Poly(butylene terephthalate)
PE Polyethylene
PMMA Poly(methyl methacrylate)
PP Polypropylene
PS Polystyrene
PTFE Poly(tetrafluoroethylene)
PEO Poly(ethylene oxide)

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