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 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

g. 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 Polymer
CH3
H3C
Polyethylene n
Ethylene Repeat unit

CH3
CH3 n
Polypropylene CH3 CH3 CH3 CH3 CH3 CH3 CH3
Propylene

CH3
Ph n
Polystyrene Ph Ph Ph Ph Ph Ph Ph
Styrene

CH3
Cl n
Poly(vinyl chloride) Cl Cl Cl Cl Cl Cl Cl
Vinyl Chloride
F2 F2 F2 F2 F2 F2
F2C CF2 C C C C C C CF3
F3C C C C C C C
F2 F2 F2 nF F2 F2
Tetrafluoroethylene Poly(tetrafluoroethylene): Teflon 2
 Polyesters, Amides, and Urethanes
Monomer Polymer
O O
H2 H2
HO2C CO2H OH HO O C C O H
HO
Ethylene Poly(ethylene terephthalate n
Terephthalic
acid glycol Ester

O O O O
H
HO 4
OH H2N 4
NH2 HO N 4 N
4
Adipic Acid 1,6-Diaminohexane Nylon 6,6 H H n
Amide
O O
H H
HO2C CO2H H2N NH2 HO N N H
Kevlar n
Terephthalic 1,4-Diamino
acid benzene
H2
OCN C NCO OH
HO
Ethylene Spandex
4,4-diisocyantophenylmethane
glycol
O O
H H2 H H2 H2
HO N C N O C C O H Urethane linkage
n
 Natural Polymers
Monomer Polymer

Isoprene Polyisoprene:
Natural rubber n
H OH H OH
HO H HO
HO O
HO OH HO OH
H OH Poly(-D-glycoside): H OH
H H cellulose H H n

-D-glucose
O O O O
H H
H3N H3N N N OH
O Polyamino acid:
protein R1 Rn+1 n Rn+2
R
Amino Acid
O O
DNA
O P O Base O P O
O Base
O O O
oligonucleic acid
OH DNA
O
Nucleotide DNA
Base = C, G, T, A
 Plastics Recycling Codea

Number Letters Plastic

1 PETEb Poly(ethylene terephthalate)

2 HDPE
3 V or PVC
4 LDPE
5 PP
6 PS
7 OTHER
High-density polyethylene
Poly(vinyl chloride)
Low-density polyethylene
Polypropylene
Polystyrene
Others or mixed plastics

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

bPET 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 repeat repeat

unit unit unit
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Poly(vinyl chloride) (PVC) Polypropylene (PP)
Adapted from Fig. 14.2, Callister & Rethwisch 8e.

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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 to construct giant molecules.
Carbon 1s22s22p2
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)
X2 X2

X4 C X1 X4 C X1

X4 X4
Xi can be any entity ex H, O, another C, or even a similar monomer
Polymers many repeating units
X2 X2

X4 C X1 + X4 C X1 +

X4 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 also participate in such bonding.
 Polymers
Large molecules built up by repetitive bonding together of
monomers

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 Drawing Polymers
Indicate repeating unit in parentheses

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 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
H
C C

H H
H

23
Hydrocarbon Molecules

Unsaturated: Double and triple bonds

CnH2n CnH2n-2

eg., Ethylene Acethylene

CH2=CH2 CHCH

C2 H 4 C2 H 2

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 Unsaturated Hydrocarbons
Double & triple bonds relatively reactive can form new bonds
Double bond ethylene or ethene - CnH2n

H H
C C
H H
4-bonds, but only 3 atoms bound to Cs

Triple bond acetylene or ethyne - CnH2n-2

H C C H
Hydrocarbon Molecules

Saturated: single bonds

eg., CH4,C2H6, C3H8

CnH2n+2

Isomerism: n-butane Isobutane

Straight chain Branched chain

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 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
2,4-dimethylhexane CH3
H3C CH CH2 CH CH3
CH2
CH3
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Hydrocarbon Molecules

R-COOH

R-CHO

R-C 6 H 5

Source: William Callister 7th edition, chapter 14, page 493, table 14.2
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Polymer Molecules

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

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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.

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 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

Trifunctional: Three (3) active bonds

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

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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

backbone

side-group

a) & b) 3 dimensional models,

c) Is a simpler 2-D representation
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

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

Polymers

Thermoplastics Elastomers Thermosets

Crystalline Amorphous
 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 untangle but not deform permanently
(like the thermoplastics).
Of all the materials, polymers are perhaps the most versatile, not only because the
properties can be drastically modified 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 INDISPENSIBLE to life
as we know it
 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%.

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 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.

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 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

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 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!!
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 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
three-dimensional space
model, and (c) a simple two-
dimensional model.

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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.

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 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.

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 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

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 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

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 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

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 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.

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Industrial Polymers

a. The world consumption of synthetic polymers

: 150 million metric tons per year.

1) Plastics : 56%
2) Fibers : 18%
3) Synthetic rubber : 11%
4) 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

Low-density polyethylene LDPE Packaging film, wire and cable insulation,

toys, flexible bottles housewares, coatings

High-density HDPE Bottles, drums, pipe, conduit, sheet, film,

Polyethylene wire and cable insulation
PP Automobile and appliance parts, furniture,
Polypropylene
cordage, webbing, carpeting, film packaging

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 Abbreviation

Acetala POM
Polyamideb
Polyamideimide PAI
Polyarylate
Polybenzimidazole PBI
Poltcarbonate PC
Polyeseterc
Polyetheretherketone PEEK
Polyetherimide PEI
Polyimide PI
Poly(phenylene oxide) PPO
Poly(phenylene sulfide) PPS
Polysulfoned
 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-formaldehyde MF 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 rayon Cellulose acetate
Viscose rayon Regenerated cellulose
Noncellulosic
Polyester Principally poly(ethylene terephthalate)
Nylon Includes nylon 66, nylon 6, and a variety of other aliphatic and
aromatic polyamides
Olefin Includes polypropylene and copolymers of vinyl chloride, with
lesser amounts of acrylonitrile, vinyl acetate, or vinylidene
chloride (copolymers consisting of more than 85% vinyl
chloride are called vinyon fibers)
Acrylic Contain at least 80% acrylonitrile; included are modacrylic fibers
comprising acrylonitrile and about 20% vinyl chloride or
vinylidene chloride
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 on

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;

propylene made up principally of ethylene and propylene units with small amounts
of a diene to provide unsaturation

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

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