Shanghai Jiao Tong University

School of Materials Science and Engineering

Smart Polymeric Materials F050524
Prof. Chuanliang FENG
Julio Csar Gonzlez L. ID 116050990008

Polymer Properties

Nomenclature

In spite of existence systematic IUPAC for polymers, common

naming system have been still accepted.

Further to common nomenclature, polymer is named according to its

source, that is the monomers used in their synthesis and the generic
term adopted is poly(monomer). The prefix poly is added before
the name of the monomer to form a single word. e.g., polyethylene.

Nevertheless, when the monomer has a multiword name, the name

of the monomer after the prefix will be enclosed in parenthesis, e.g.,
poly(vinyl chloride).

The nomenclature of random copolymers involve the names of the

monomers divided by the interfix, e.g., poly(styrene-co-methyl
methacrylate).

In the case of alternating and block copolymers, the interfix are alt
and b or block respectively. e.g., poly(styrene-alt-malei
anhydride) , poly(styrene-b-butadiene-b-styrene).

Molecular weight

Molecular weight is a dimensionless quantity that depicts the sum of

the atomic weights in the molecular formula. Polymers, unlike
organic and inorganic compounds, do not have a specific molecular
weight. The average length of a linear polymer is rendered by the
degree of polymerization or the number of repeat units in the chain.

Difference between Mw and Mn

The weight average molecular weight Mw is the result by dividing

the chains into size ranges and determining the fraction of chains
having molecular weights with that range.

Wi The weight fraction of the polymer having chains within th at range

W M i i
Wi weight of a molecule or oligomer i
MW i
W M
W
i i
i i Mi molecular weight of a molecule or oligomer
i
i

The number average molecular weight Mn is based on the number

fraction, rather than the weight fraction of the chains within each
size range. It is frequently smaller than the weight average
molecular weight Mw
W i
N i the fraction of the total number of chains within each range
Mn i
Ni M i Wi weight of a molecule or oligomer i
W / M
i
i i i
Mi molecular weight of a molecule or oligomer

Polydispersity

Polydispersity index is a measure of the breath of the molecular

weight distribution. In other words, describe the degree of non-
uniformity of a distribution. It is defined like ratio Mw / Mn.

What is Tg?

Tg depicts glass-transition temperature. This is an important

temperature since marks the beginning of movements of large
segments of the polymer chain due to available thermal energy (RT
energy units/mol). Typically, Tg is about 0.5 to 0.75 times the
absolute.
What are polymer structure unit, monomer unit ( ),
repeating unit ( ), chain element ( )? What is
relationship between them?

Structure unit are defined as atoms that constitute the backbone of a

polymer chain come in a regular order, and this order repeats itself
all along the length of the chain. Whereas the repeating unit of a
linear polymer is a small represent of the macromolecule such that
linking together these units one after another gives rise to the
formula of the whole molecule. A repeating unit can be made up by
different structures unit.

Finally, Monomer units are simple organic molecules from which

the polymer molecule is made.

Free radical polymerization

Free radical polymerization consists on a chain reaction which

involves the reaction between monomer and free radical, its mainly
three steps are: initiation, propagation, and termination, taking place
in sequence.

In the case of ethylene, the chain initiation is started by free radicals,

R, generated by reaction between some of the ethylene and the
oxygen initiator. Afterwards, each time a free radical hits an ethylene
molecule a new longer free radical is formed. This step is called
chain propagation.
CH 2 CH 2 R * RCH 2 CH 2 *
RCH 2 CH 2 * CH 2 CH 2 RCH 2 CH 2 CH 2 CH 2 * to be continued

Finally, two free radicals hit each other producing a final molecule.
The process stops here because there are not free radicals are
formed. (Chain termination)
 R CH 2 m * * CH 2 n R R CH 2 m CH 2 n R

The kinetics of ethylene can be described according the following:

The initiation:
I 2R *
d
R * 2 K d I
dt
Where R* is free radical, I initiator and Kd is rate constant. Whether
there is not wastage of the primary radicals by side reactions, the
rate of chain and radical Ri generation will be the same.

Ri K i R * CH 2 CH 2 2 K d I

The rate of propagation will be described by the expression

R p K P CH 2 CH 2 RCH 2 CH 2 *

Finally, the termination of chain radicals can also take a place by a

combination of coupling and disproportionation. Therefore, its rate
Rt will be:
Rtc 2 K tc RCH 2 CH 2 * ; Rtd 2 K td RCH 2 CH 2 *
2 2

The overall process of termination

Rtotal termination 2 K td K tc RCH 2 CH 2 *
2

Ionic polymerization

It is a mechanism of polymerization which the growing chain end

carbon bears a negative charge (carbanion) or a positive charge
(carbonium ion). In the first case, the polymerization is called
anionic polymerization and in the latter case as cationic
polymerization.

Basic principle of coordination polymerization of polypropylene

According to electronic configuration of titanium, it has to fill its
orbitals. Consequently, a propylene molecule appears and two
electrons in the system of carbon double bond. Those electrons are
used to take over the empty orbitals. Afterwards, a bond between
carbon and titanium is formed. The pair of electrons is going to
move to form a bond between the radical R and methyl substituted
carbon of propylene monomer. Finally, titanium returns to its initial
state with an empty orbital in order to take another monomer.

The similar phenomena between ionic polymerization and free

radical polymerization

Both ionic and free radical polymerization requires of mechanism of

chain reaction. They share same kind of inhibitor (benzoquinone)

The difference between ionic polymerization and free radical

polymerization

Free radical polymerization Ionic polymerization

Type of initiator is easy to
produce
The monomer structure consist
on Vinyl monomers with weak
electron-donating absorption
Conjugated olefins
The solvent chain transfer, will
reduce the molecular weight and
cage effect, decrease the
efficiency of the initiator f
Employing reactive ion prone
substance as an initiator
High selectivity of monomers.
The polarity of the solvent and
the solvation ability, of activity
has a great influence on the
shape both ion pairs and free.

Reaction temperature depends Activation energy is small. In

on the decomposition order to prevent the chain
temperature of the initiator 50 transfer, rearrangement, etc.
80
Polymerization mechanism is Polymerization mechanism is
mostly double-terminated. not double-terminated.

The formation procedure of carbocations or carbanion

Lewis acid induces formation of carbocation that propagates when

reacting with olefin. For example, in cationic polymerization, Vinyl
monomer must be substituted to stabilize carbocation.

The basic concept of coordination polymerization

It is a form of addition polymerization which monomer adds to a

growing macromolecule through an organometallic active center
(transition metal).

Consider a polymer sample comprising 10mol of polymer

molecules having molecular weight of 104 and 5mol of polymer
molecules having molecular weight of 105. Please calculate its
molecular weight, Mw and Mn. How about polydispersity?
Please calculate the value.
W M i i N Mi i
2

2
10 10 4 5.10 5 2

MW i
i
85000
W i N Mi i
10 10 4 5.10 5
i i
 W i N M i i

10 10 4 5 10 5
Mn i
i
40000
W / M
i
i i N i
i 10 5

M W 85000
Polydisper sity 2,125
M n 40000

Therefore, the distribution of molecular weight is narrow.

Name of polymers

CH CH 2 n Poly(phenyl ethylene)
Poly(1-phenylethylene) (IUPAC)

CH3 Poly(methyl methacrylate)

C CH 2 n Poly[1-(methoxycarbonyl)-1-methyl
COOCH3 ethylene ] (IUPAC)

NH(CH 2)6NHCO(CH 2)4CO n Poly(Hexane-1,6diamine-alt-adipic

acid)
Poly(iminohexamethylene imino
adipoyl) (IUPAC)

References

Morton R., Rane S.(2005) Polydispersity Index: How Accurately

Does It Measure the Breadth of the Molecular Weight Distribution?
Chem. Mater, 17 (4), pp 926926

Chanda M.(2013) Introduction to polymer science and chemistry. A

problem solving-approach. CRS Press, 730 p.

Online Resources
http://www.chemguide.co.uk/mechanisms/freerad/polymtt.html

http://chemed.chem.purdue.edu/genchem/topicreview/bp/1polymer/r
eactions.html

http://tecnologiadelosplasticos.blogspot.ae/2013/09/nomenclatura-
iupac.html