Buku Diktat

(Untuk keperluan pengajaran)

KIMIA POLIMER
(POLYMER CHEMISTRY)

Disusun oleh
Ir. Roosmariharso, MBA
POLITEKNIK STMI JAKARTA
2015

Daftar Isi

I. Polymer Definitions & Classification

II. Polymer Synthesis
III. Polymer Structure
IV. Molecular Weight Definitions & Distribution
V. Polymer Morphology
VI. Viscocity
VII.Polymer Properties
VIII.Polymer Rheology
IX. Polymer Additives

I.Polymer Definition & Classification

Polymers: Introduction
Polymer: High molecular weight molecule made
up of a small repeat unit (monomer).
A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A

Monomer: Low molecular weight compound that

can be connected together to give a poymer
Oligomer: Short polymer chain
Copolymer: polymer made up of 2 or more
monomers
Random copolymer: A-B-B-A-A-B-A-B-A-B-B-B-A-A-B
Alternating copolymer: A-B-A-B-A-B-A-B-A-B-A-B-A-B
Block copolymer: A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B

IUPAC Definition

A polymer is a substance composed

of molecules characterized by the
multiple repetition of one or more
species of atoms or groups of atoms
(constitutional repeating units)
linked to each other in amounts
sufficient to provide a set of
properties that do not vary
markedly with the addition of one or
a few of the constitutional repeating
units.

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 :

Acoording to name of functionalgroup in the
polymer backbone

Nomenclature

Trade name : The commercial names by manufacturer Teflon, Nyl

Abbreviation name : PVC, PET

omplex and Network polymer : Phenol-formaldehyde polymer

Vinyl polymer : Polyolefin

Common Polymers
Polymers are common in nature.
Wood, rubber, cotton, silk, proteins,
enzymes, and cellulose are all
examples of polymers
A wide variety of synthetic polymers
have been produced, largely from
petroleum based raw materials.
These include polyurethane, teflon,
polyethylene, polystyrene, and nylon.

Common Polymers

Common Polyolefins
Monomer
Ethylene
CH3
Propylene
Ph
Styrene

Polymer
Polyethylene

Polypropylene

Polystyrene

CH3

H3C

Vinyl Chloride
F2C CF2
Tetrafluoroethylene

CH3

CH3 CH3 CH3 CH3 CH3 CH3 CH3

Ph

Ph

Ph

Ph

Cl
Poly(vinyl chloride)

Repeat unit

Cl

F3C
Poly(tetrafluoroethylene): Teflon

Cl
F2
C

C
F2

Cl
F2
C

C
F2

Cl
F2
C

C
F2

CH3

Ph

F2
C

Ph

Ph
CH3

Cl

C
nF
2

Cl
F2
C

C
F2

Cl
F2
C

C
F2

CF3

Polyesters, Amides, and

Urethanes
Monomer
Polymer
HO2C

CO2H

Terephthalic
acid
O

OH

HO
Ethylene
glycol

Poly(ethylene terephthalate

HO

Nylon 6,6

O
CO2H H2N

HO2C

NH2

1,4-Diamino
benzene

Terephthalic
acid
H2
C

OCN

NCO

4,4-diisocyantophenylmethane
O
HO

H
N

H2
C

Kevlar

HO

Ester
O

NH2
OH H2N
4
1,6-Diaminohexane

H2 H2
O C C O H

HO

HO
4
Adipic Acid

O
4

N
H

N
4
H
Amide
O

H
N

H
n

H
N H
n

OH
HO
Spandex
Ethylene
glycol
O
H2 H2
H
N
O C C O H
n

Urethane linkage

Natural Polymers

Polymer

Monomer

Isoprene
H OH
HO
HO

Polyisoprene:
Natural rubber

HO

H OH
H

OH
H
H
-D-glucose

OH

Poly(-D-glycoside):
cellulose

Polyamino acid:
protein

R
Amino Acid

O P O
O

O
O

H3N

OH
Nucleotide
Base = C, G, T, A

Base
oligonucleic acid
DNA

OH

OH
H

H
N

R1
DNA

HO

O
HO

O
H3N

Rn+1

H
N
n

OH
Rn+2

O
O P O

O
O

DNA

Base

Plastics Recycling Codea

Plastic

Number

Letters

PETEb

Poly(ethylene terephthalate)

HDPE

High-density polyethylene

V or PVC

LDPE

PP

Polypropylene

PS

Polystyrene

OTHER

Poly(vinyl chloride)
Low-density polyethylene

Others or mixed plastics

Adopted by the Society of the Plastics lndustry (SPI).

ET is the more widely accepted abbreviation.

Polymer Recycling Codes

Common household polymers

Polymers
The number code indicates the polymer
type

Polymers
Types of synthetic and natural polymers.

What is a Polymer?

Poly

mer
many

repeat unit

repeat
unit

repeat
unit

repeat
unit

H H H H H H
C C C C C C
H H H H H H

H H H H H H
C C C C C C
H Cl H Cl H Cl

Polyethylene (PE)

Poly(vinyl chloride) (PVC)

H
C
H

H H
C C
CH3 H

H H
C C
CH3 H

H
C
CH3

Polypropylene (PP)

Adapted from Fig. 14.2, Callister & Rethwisch 8e.

17

Polymers
Polymer : Materials are made up of many (poly) identical chemical units
(mers) that are joined together to construct giant molecules.
Plastics - deformable, composed of polymers plus additives. E.g. a variety
of films, coatings, fibers, adhesives, and foams. Most are distinguished by
their chemical form and composition.
The properties of polymers is related to their structures, which in turn,
depend upon the chemical composition. Many of these molecules contain
backbones of carbon atoms, they are usually called "organic" molecules
and the chemistry of their formation is taught as organic chemistry.
The most common types of polymers are lightweight, disposable, materials
for use at low temperatures. Many of these are recyclable. But polymers are
also used in textile fibers, non-stick or chemically resistant coatings,
adhesive fastenings, bulletproof windows and vests, and so on.

Polymers
Polymer : Materials are made up of many (poly)
identical chemical units (mers) that are joined together
2
to
construct
giant
Carbon
1s22s
2p2 molecules.
It has four electrons in its outermost shell, and needs four more to
make a complete stable orbital. It does this by forming covalent
bonds, up to 4 of which can be formed.
The bonds can be either single bonds, ie one electron donated by
each participating element, or double bonds (2 e- from each), or
triple bonds (3 from each)
2
2

X4

C
X4

X1

X4

X1

X4

Xi can be any entity ex H, O, another C, or even a similar monomer

Polymers many repeating units

X2
X4

C
X4

X2
X1

X4

X1

X4

C C C C C
And so on if the bonds can keep getting formed, entire string-like
structures (strands, or chains) of the repeating units are created. C
is the most common element in polymers. Occasionally, Si may

Polymers
Large molecules built up by repetitive bonding

together of monomers

21

Drawing Polymers
Indicate repeating unit in parentheses

22

Polymer Composition
Most polymers are hydrocarbons
i.e., made up of H and C
Saturated hydrocarbons
Each carbon singly bonded to four other
atoms
Example:
Ethane, C2H6
H

H
C

H
C
H

23

Hydrocarbon Molecules
Unsaturated: Double and triple bonds
CnH2n
eg.,

Ethylene
CH2=CH2
C2 H 4

CnH2n-2
Acethylene
CHCH
C2 H 2

24

Unsaturated Hydrocarbons

Double & triple bonds relatively reactive can form new

bonds
Double bond ethylene or ethene - CnH2n

H
C C

H C C H

Hydrocarbon Molecules
Saturated: single bonds
eg., CH4,C2H6, C3H8
CnH2n+2
Isomerism: n-butane
Straight chain

26

Isobutane
Branched chain

Isomerism
Isomerism
two compounds with same chemical formula
can have quite different structures
for example: C8H18
normal-octane
H H H H H H H H
H C C C C C C C C H

= H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3

H H H H H H H H

H3C ( CH2 ) CH3

6

CH3
H C CH CH2 CH CH3

3
2,4-dimethylhexane

CH2
CH3
27

Hydrocarbon Molecules

R-COOH

R-CHO

R-C

H5
Source: William Callister 7th edition, chapter 14, page 493, table 14.2
28

Polymer Molecules
Gigantic: Macromolecules
Monomer: One unit
Polymer Many units
eg., one unit

29

Polymer Molecules continue

PTFE: TEFLON
Polytetrafluoro ethylene

Mer

30

Polymer Molecules continue

PVC: Vinyl
Polyvinyl chloride
Mer
Polypropylene:

Mer
31

Polymer molecules
Homopolymer:

Repeating units of the chain are of the

same type

Co-polymer: Two or more different mer units.

32

All the same monomer

Monomers all
same type (A)
A+A+A+A
-A-A-A-A eg poly(ethene)
polychloroethene
PVC

Different monomers
Monomers of two
different types A
+B
A+B+A+B
-A-B-A-B eg polyamides
polyesters

Co-polymers
Co polymers are made from than one
monomer
Many natural polymers are
copolymers. For example, proteins
are condensation polymers formed by
joining as many as 20 different
amino acids

Copolymers
Copolymers are like polymer alloys.
Different mers are joined to form a
mixture in the backbone, eg. ABS.
they can be tailored to obtain
specific properties.

Polymer molecules continue

Bifunctional:

Two (2) active bonds

Three (3) active bonds

Trifunctional:

37

Chemistry and Structure of

Polyethylene
Adapted from Fig.
14.1, Callister &
Rethwisch 8e.

Note: polyethylene is a long-chain hydrocarbon

- paraffin wax for candles is short polyethylene
38

Bulk or Commodity Polymers

39

Bulk or Commodity Polymers (cont)

40

Bulk or Commodity Polymers (cont)

41

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

Illustration

backbon
e

side-group

a) & b) 3 dimensional
models,

c) Is a simpler 2-D

Chain Conformations

Ancient Polymers
Originally natural polymers were used
Wood Rubber
Cotton Wool
Leather Silk

Oldest known uses

Rubber balls used by Incas
Noah used pitch (a natural polymer)
for the ark
44

Polymer Classification
Polymers are commonly classified based
on their underlying molecular structure.
Polymers

Thermoplastics
Crystalline Amorphous

Elastomers

Thermosets

Classes of Polymers
Thermoplastics:
Consist of flexible linear molecular chains
that are tangled together like a plate of
spaghetti or bucket of worms. They
soften when heated.
Thermosets:
Remain rigid when heated & usually
consist of a highly cross-linked, 3D
network.
Elastomers:
Consist of linear polymer chains that are
lightly cross-linked. Stretching an
elastomer causes chains to partially
Of all
the materials,
polymers
are perhaps the most versatile,
untangle
but not deform
permanently
not only
because
the properties can be drastically modified
(like the
thermoplastics).
by simple chemistry, but the behavior is also dependent on
the architecture of the chains themselves.
From proteins to bullet-proof jackets to bottles, polymers are

Section
Classification of Polymers
Linear polymer - Any polymer in which molecules
are in the form of spaghetti-like chains.
Thermoplastics - Linear or branched polymers in
which chains of molecules are not interconnected to
one another.
Thermosetting polymers - Polymers that are heavily
cross-linked to produce a strong three dimensional
network structure.
Elastomers - These are polymers (thermoplastics or
lightly cross-linked thermosets) that have an elastic
deformation > 200%.

47

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under
license.

Figure 15.1 Schematic showing linear and branched polymers. Note that branching can occur in any type of polymer (e.g.,
thermoplastics, thermosets, and elastomers). (a) Linear unbranched polymer: notice chains are not straight lines and not connected.
Different polymer chains are shown using different shades and design to show clearly that each chain is not connected to another. (b)
Linear branched polymer: chains are not connected, however they have branches. (c) Thermoset polymer without branching: chains
are connected to one another by covalent bonds but they do not have branches. Joining points are highlighted with solid circles, (d)
Thermoset polymer that has branches and chains that are interconnected via covalent bonds. Different chains and branches are shown
in different shades for better contrast. Places where chains are actually chemically bonded are shown with filled circles.

48

Types of Polymers
Polymer Classifications
Thermoset: cross-linked polymer that cannot be melted
(tires, rubber bands)
Thermoplastic: Meltable plastic
Elastomers: Polymers that stretch and then return to
their original form: often thermoset polymers
Thermoplastic elastomers: Elastic polymers that can be
melted (soles of tennis shoes)
Polymer Families
Polyolefins: made from olefin (alkene) monomers
Polyesters, Amides, Urethanes, etc.: monomers linked
by ester, amide, urethane or other functional groups
Natural Polymers: Polysaccharides, DNA, proteins

Types of Polymers

50

Main Categories of
Polymers:
Plastics:
Thermoplastics can be remelted:
Engineered Thermoplastics
Commodity Thermoplastics

Thermosetting Plastics can not be

remelted
Engineered Thermosets
Commodity Thermosets

Elastomers:
Thermosets and thermoplastic!!
51

Thermoplastics
Often referred to as just Plastics are linear or
branched polymers which soften upon heating.
They can be moulded (and remoulded) into
virtually any shape
injection moulding, extrusion

and constitute the largest portions of the polymers

used in industry
Thermoplastics never achieve 100% crystallinity,
but instead are semicrystalline with both
crystalline and amorphous domains.

Thermoplastics (80%)

No cross links between chains.

Can change shape.
Can be remoulded.

Thermoplastics
The crystalline phases of such polymers are
characterized by their melting temperature
(Tm).
Many thermoplastics are completely amorphous
and incapable of crystallization, these amorphous
polymers (and amorphous phases of
semicrystalline polymers) are characterized by
their glass transition temperature (Tg).
the temperature at which they transform abruptly
from the glassy state (hard) to the rubbery state
(soft).

Thermoplastics
Glass transition temperature (Tg)
This transition corresponds to the
onset of chain motion
below the Tg the polymer chains are
unable to move and are frozen in
position.

Both Tg and Tm increase with increasing

chain stiffness and increasing forces of
intermolecular attraction

56

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

Figure 15.2 Three ways

to represent the
structure of
polyethylene: (a) a solid
three-dimensional
model, (b) a threedimensional space
model, and (c) a simple
two-dimensional model.

57

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

Figure 15.3 Two ways to represent the benzene ring. In this case,
the benzene ring is shown attached to a pair of carbon atoms,
producing styrene.
58

Commodity Thermoplastics
Commodity: Polyethylene (PE), Polystyrene
(PS), Polypropylene (PP), Polyvinyl Chloride
(PVC or vinyl) 80% of all thermoplastics!!
Also, Styrene Acrylonitrile (SAN) the
copolymer we tested in lab
Flows at elevated temperatures.
Has a glass transition temperature.
Long polymer chains
Can be remelted and recycled.
59

Engineering Thermoplastics
Engineering Plastics: Polycarbonate
(PC), Acrylonitrile-butadiene-styrene
(ABS), Polyamide (Nylons, PA)
Engineered plastics account for
about 10% of all plastic usage.
Generally have higher tensile
strength and elongation than
commodity plastics
60

Thermosets
Thermosets - normally rigid materials network polymers in which chain motion
is greatly restricted by a high degree of
crosslinking
As with elastomers, they are intractable
once formed and degrade rather than
melt upon the application of heat.

Thermosets

Cross-linking formed by
covalent bonds.
Bonds prevent chains moving
relative to each other.

Thermosetting Plastics
Polyurethane, Phenolics, silicones,
ureas
Tend to be strong but brittle
Molecules cross-linked
Can not be remelted or reprocessed

63

Elastomers
Elastomers - crosslinked rubbery
polymers - rubber networks - that can be
easily stretched to high extensions (3x to
10x original dimensions)
the rubbery polymer chains become
extended upon deformation but are
prevented from permanent flow by
crosslinking, and driven by entropy, spring
back to their original positions on removal
of the stress.

Elastomers
Butyl, natural rubber (polyisoprene),
EPDM, neoprene, nitrile, etc..
Characterized by high deformation
(extremely flexible) generally
greater than 100%.
Almost all are thermosetting with
exception of TPEs

65

Biodegradable Polymers
These polymers can be broken into small segments by
enzyme-catalyzed reactions

Design/Materials Selection for Polymer

Components
Design the type of polymer material you might select for
the following applications: a surgeons glove, a beverage
container and a pulley.
Example
The glove must be capable of stretching a great deal
in order to slip onto the surgeons hand. This
requirement describes an elastomer.
A thermoplastic such as polyethylene terephthalate
(PET) will have the necessary formability and ductility
needed for this application.
A relatively strong, rigid, hard material is required to
prevent wear, so a thermosetting polymer might be
most appropriate.
67

Industrial Polymers
a. The world consumption of synthetic polymers
: 150 million metric tons per year.

1)
2)
3)
4)

Plastics : 56%
Fibers : 18%
Synthetic rubber : 11%
Coating and Adhesives : 15%

b.Styrene-butadiene copolymer

Synthetic rubber, PET

Fiber

(polyester)
Latex paint

Plastic (bottle)

Plastics
1) Commodity plastics
LDPE, HDPE, PP, PVC, PS cf) Table 1.4
2) Engineering plastics

Acetal,
Polyamide,
Polyamideimide,
Polyarylate,
Polybenzimidazole, etc. cf) Table 1.5
3) Thermosetting plastics
Phenol-formaldehyde, Urea-formaldehyde,
Unsaturated polyester, Epoxy,
Melamine-formaldehyde
cf) Table 1.6
4) Functional plastics
Optics, Biomaterial, etc.

Commodity Plastic

Type

Abbreviation

Major Uses

ow-density polyethyleneLDPE Packaging film, wire and cable insulation,

toys, flexible bottles housewares, coating

High-density
Polyethylene

Polypropylene

HDPE Bottles, drums, pipe, conduit, sheet, film,

wire and cable insulation
PP Automobile and appliance parts, furniture,
cordage, webbing, carpeting, film packa

Poly(vinyl chloride)

PVC

Construction, rigid pipe, flooring, wire

and cable insulation, film and sheet

Polystyrene

PS

Packaging (foam and film), foam

insulation appliances, housewares, toys

Principal Engineering Plastics

Type
Acetala
Polyamideb
Polyamideimide
Polyarylate
Polybenzimidazole
Poltcarbonate
Polyeseterc
Polyetheretherketone
Polyetherimide
Polyimide
Poly(phenylene oxide)
Poly(phenylene sulfide)
Polysulfoned

Abbreviation
POM
PAI
PBI
PC
PEEK
PEI
PI
PPO
PPS

TABLE 1.6 Principal Thermosetting Plastics

Type

Abbreviation

Typical Uses

Phenol-formaldehyde PF
Electrical and electronic equipment,
automobile parts, utensil handles,
plywood adhesives, particle board
binder
Urea-formaldehyde UF
Similar to PF polymer; also
treatment of textiles, coatings
Unsaturated polyester UP
Construction, automobile parts, boat
hulls, marine accessories,
corrosion-resistant ducting, pipe,
tanks, etc., business equipment
Epoxy
Protective
coatings, adhesives,
electrical and electronics
applications, industrial flooring
highway paving materials,
composites
Melamine-formaldehydeMF
Similar to UF polymers; decorative
panels, counter and table tops,
dinnerware

Fibers
1) Cellulosic :
Acetate rayon, Viscose rayon
2) Noncellulosic :
Polyester, Nylon(Nylon6,6, Nylon6, etc)
Olefin
(PP, Copolymer(PVC 85%+PAN and others 15%;
vinyon))
3) Acrylic :

Contain at least 80% acrylonitrile

(PAN 80% + PVC and others 20%)

Rubber (Elastomers)
1) Natural rubber :
cis-polyisoprene
2) Synthetic rubber :
Styrene-butadiene, Polybutadiene,
Ethylene-propylene(EPDM), Polychloroprene,
Polyisoprene,
Nitrile, Butyl, Silicone, Urethane
3) Thermoplastic elastomer :

Styrene-butadiene block copolymer

(SB or SBS)

Principal Synthetic Fibers

Type

Description

Cellulosic
Acetate rayonCellulose acetate
Viscose rayonRegenerated cellulose
Noncellulosic
Polyester
Principally poly(ethylene terephthalate)
Nylon
Includes nylon 66, nylon 6, and a variety of other
aliphatic and
Olefin
aromatic polyamides
Includes polypropylene and copolymers of vinyl
chloride, with
lesser amounts of acrylonitrile, vinyl acetate, or
Acrylic
vinylidene
chloride (copolymers consisting of more than 85%
vinyl
chloride are called vinyon fibers)
Contain at least 80% acrylonitrile; included are

Coating and Adhesives

1) Coating :
Lacquer, Vanishes, Paint (Oil or Latex), Latex
2) Adhesives :
Solvent based, Hot melt, Pressure sensitive,
etc.

Acrylate, Epoxy, Urethane, Cyanoacrylate

Principal Types of Synthetic Rubber

Type

Description

Styrene-butadiene
Copolymer of the two monomers in various proportions depending
properties desired; called SBR for styrene-butadiene rubber
Polybutadiene
Consists almost entirely of the cis-1,4 polymer

Ethylene- Often abbreviated EPDM for ethylene-propylene-diene monomer;

propylenemade up principally of ethylene and propylene units with small am
of a diene to provide unsaturation

Polychloroprene
Principally the trans-1,4polymer, but also some cis-1,4 and 1,2 poly
also known as neoprene rubber

Polyisoprene
Mainly the cis-1,4 polymer; sometimes called synthetic natural rub
Nitrile
Copolymer of acrylonitrile and butadiene, mainly the latter
Butyl
Copolyner of isobutylene and isoprene, with only small amounts of
Latter
Silicone
Contains inorganic backbone of alternating oxygen and methylated
atoms; also called polysiloxane (Chap. 15)
Urethane Elastomers prepared by linking polyethers through urethane groups
(Chap. 13)