PART 1 – Macromolecular Architecture

João F. Mano
Universidade de Aveiro
Macromolecule:
“small mass” (molecula) + “large” (makros)
- Simply indicates that it is a molecule of high relative molecular mass.
- No information about the structure.

E.g. enzymes are, for example, macromolecules that are composed by

hundreds or thousands of a-aminoacid units, -NH-CHR-CO- with up to 20
different substituents R. The a-aminoacids are arranged in a non-repetitive
sequence such as ser-his-cys-met-glu-leu-lys…
Macromolecules in the living world
Natural Macromolecules and their building blocks

nucleotide
DNA

aminoacid
protein

monosaccharide

polysaccharide
Concept of Polymer (“Polímero”)
The term “polymer” does imply a multiple repetition: Many (poly) parts (meros). In
synthetic polymers one structure, termed a constitutional repeating unit (CRU), can be
considered as producing the polymer molecules by its replication. Each CRU is joined to its
neighbours by covalent bonds which are part of the backbone, defined as the minimum set
of bonds and intervening atoms which extend continuously from end to end of the polymer
molecules.

Polímeros (do grego poli, “muitas”, e meros, “partes”)

são macromoléculas formadas através da ligação de 1000 a 1 000 000
várias unidades de moléculas pequenas, produzidas monomers per chain
através de um processo chamado polimerização, no
qual moléculas simples, os monómeros, reagem
quimicamente entre si.

Poli - many

Plastic:
A plastic is a polymer with additives. Additives are Mono - one
introduced to increase the performance of the Meros - units
materials (colour, mechanical strength,
transparency...)
CONCEITO DE POLÍMERO

Na cadeia de polímero, a ligação química é forte ao

longo das unidades repetitivas;

As interações entre as macromoléculas vizinhas são

fracas, do tipo Van der Waals ou pontes de hidrogénio
 Classification of macromolecules

Macromoléculas

naturais (biopolímeros) sintéticos

(polímeros)

Proteínas Polissacarídeos Polinucleótidos Latex

Outros: lignina, “lípidos”, poliésteres...
Elastómeros Termoplásticos Termoendurecíveis
Combinações: glicoproteínas
propriedades

Semi-cristalinos Amorfos
estrutura
Name and structure of common polymers
Designação Estrutura Nome Comum sigla

poli(metileno) ( CH2CH2 )n polietileno PE

( CH CH2 )n
poli(propileno) polipropileno PP
CH3

CH3

(C CH2 )n
poli(1,1 di-metiletileno) poliisobutileno

CH3

(C CHCH2 CH2 )n
poli(1-metilbutileno) Poli(isopreno)
CH3

poli(1-butileno) ( CH CHCH2 CH2 )n polibutadieno

( CH CH2)n

poli(1-feniletileno) poliestireno PS
Designação Estrutura Nome Comum

( CH CH2)n
poli(acrilonitrilo) poliacrilonitrilo PAN
CN

( CH CH2 )n
poli(1-hidroxietileno) poli(álcool vinílico) PVA
OH

( CH CH2 )n
poli(1-cloroetileno) poli(cloreto de vinilo) PVC
CI

( CH CH2 )n
poli(1-acetoxietileno) poli(acetato de vinilo)
OOCCH3

poli(1,1 difluoretileno) (C CH2 )n Poli(fluoreto de vinilo)

F
Designação Estrutura Nome Comum Nome
comercial
( CH CH2 )n
poli(1-metoxicarbonil
poli(acrilato de metilo)
etileno) COOCH3

CH3
poli(1-metoxicarbonil- (C CH2 )n
poli(metacrilato de
-1-metiletileno) metilo) acrílico
COOCH3

poli(oximetileno) ( OCH2 )n poliformaldeído

poli(óxido de etileno)
poli(oxietileno) ( OCH2CH2 )n ou
polietileno glicol

poli(oxifenileno) (O )n poli(óxido de fenilo)

poli(tereftalato de
(OCH2CH2OOC CO)n Terylene (ou PET)
etileno)
poli(hexametileno- (NH(CH2)6NHCO(CH2)4CO)n Nylon-6,6
adipamida)

F F

poli(difluormetileno) (C C )n poli(tetrafluoretileno) teflon

F F
 Polymer synthesis: synthetic versus natural

SYNTHETIC
polymerization

different properties
Polymer 1
monomers

Polymer 2
Polymer 3
Polymer 4

NATURAL

different properties
rational assembly

Polymer 1
monomers

Polymer 2
Polymer 3
Polymer 4
 Natural based polymers
polycationic
polysaccharides ( )n
laminarin chitin
neutral

chitosan
starch levan
dextran

hyaluronic acid
polyanionic

carragenan
(k, i, l)
alginate sulfated
carboxylated gellan gum chondroitin sulfate ulvan

fucoidan

proteins
silk fibroin polyesters

collagen fibronectin poly(hydroxybutyrate)

J.F. Mano +, J.R.Soc.Interface ‘07

COMMON PLASTICS
Macromoléculas versus moléculas de baixo
peso molecular

1- As macromoléculas apresentam grande capacidade de apresentar

muitos arranjos conformacionais [distribuição dos átomos no espaço
apenas por rotações de ligações covalentes]

1- Macromolecules have a great capacity to present many

conformational arrangements [distribution of atoms in space only by
rotations of covalent bonds]
Arranjos espaciais em polímeros
 CONFORMAÇÕES
Quando os átomos de carbono se organizam numa cadeia macromolecular
mantêm entre si ângulos espaciais de 109.5º, que são característicos da
geometria tetraédrica do carbono tetravalente; cada átomo individual na
cadeia pode rodar livremente em torno da ligação C-C

ângulo de valência

A possibilidade de rotação livre dá origem a inúmeras posições espaciais de

uma macromolécula (conformações); as posições preferenciais são
determinadas pela polaridade, flexibilidade e regularidade das unidades
repetitivas que constituem a cadeia
Chain conformations
“Free” rotation

Fixed (chemical bonds)

In this case all carbons are in the plain: f=0 (trans conformation)
 C1 C4 Planar cis H
H
(a)
H H
- 1 CH
C1 C4 distance = 2.6A
4-carbon conformations
3
3
36 2 Chapter
2
2
C2 C3 4CH3
H H H H
3

CH3 -- CH2 -- CH2 -- CH3 CH3

- C4
Planar trans
C1 C4 distance = 3.9A
Newman
4
projections: n-butane
C1 C2 C3 C4 Figure 2.1 Conformations produced by rotation about C2 -C3 bond of n-butane m
CH3 sp3 hybridized, is tertrahedral with bond angles
atom in this molecule, being CHof3 109
CH3
conformation, corresponding to the closest approach of the two bulky methyl group
Conversely, the planar trans conformation, where the bulkyHgroups
3C are farthest apa
H
(After(b)
C1 C4 Planar cis Young and Lovell, 1990.)
H

-
C1 C4 distance = 2.6A H
H
H
H
H
H

C2 C3 Figure 2.2 Newman1 and “saw horse” projections for n-butane. (a) A staggered st
CH 3
angle of bond rotation Φ " 0 and (b) an eclipsed state (planar cis) with Φ " 180! .
H
H H 1 CH H
(a) 3
3
2 2
4CH3
Planar trans H H H H
C4
-
C1 C4 distance = 3.9A
3

CH3
4

Figure 2.1 Conformations produced by rotation about C2 -C3 bond of n-butane CH3 molecule. Each carbon
CH3
CH
atom in this molecule, being sp3 hybridized, is tertrahedral with bond angles
3
of 109.50! . TheH planar cis
3C
H
conformation, corresponding to the closest approach of the two(b)bulky methyl groups, is the least stable.
H
Conversely, the planar trans conformation, where the bulky groups are farthest Hapart, is the Hmost stable.
H H H
(After Young and Lovell, 1990.) H

Figure 2.2 Newman and “saw horse” projections for n-butane. (a) A staggered sta
angle of bond rotation Φ " 0 and (b) an eclipsed state (planar cis) with Φ " 180! .
Newman projection of polyethylene
+180º
-180º
Cis Cis (cis)
(cis) Butane-like approach

De

This diagram just reflect the energy

landscape considering a series of 4
carbons.
rmations are shown as Newman projections in Fig.
ns that -give +rise to the maxima in Fig. 2.3. The highe
g g
e restrictions on the molecular conformation.
De C
above ttype of steric interactionstoccur at a local le
onformation about a given chain segment being, h
C g
t
out the segments on either g side Cto which it is directl
C
ictions influence the local C chain conformations all
pe and size.
nteractions, as shown
... Relative ditribution of the above, are important
different conformations along in determ
the chain will conformations
of different depend on the energy in variation
a along f and
polymer chain. Thu
temperature. Thus the ratio of the number of trans (nt ) to

ng !nt " 2 exp"$%Ε!kT #

e (ngauche
g ) states is isgiven
(ng) states given by:by
Macromoléculas versus moléculas de baixo
peso molecular

2- As macromoléculas podem apresentar diferentes massas moleculares,

e um conjunto de macromoléculas é normalmente descrito por uma
distribuição de massas moleculares.

2- Macromolecules can have different molecular masses, and a set of

macromolecules is usually described by a molecular mass distribution.
 nw
m
Distribution of Molecular Weight nw
Mw
m
where m is the mer molecular weight. Show Figures 4.3 and 4.4.

where m is the mer molecular weight. Show Figures 4.3 and 4.4.

Number average molecular weight

Average Molecular Weight Potência de Mi=1

Potência de Mi entre 1
e 2 (ver mais tarde eq.
Mark–Houwink )

Potência de Mi=2

Média em número Média em peso

2
Massa åi N i M i å mM å NM
molecular < M n >= < M w >= i i i = i i i
åi N i åi mi åi Ni Mi
Grau de åNX ånX åi mi X i åi ci X i
< X n >= i i i = i i i < X w >= =
polimerização åi i
m åi ci
åi N i åi ni
MASSA MOLECULAR

è Dependendo do método experimental que se utiliza, a massa molecular

média obtida pode ser em número, em peso, ou mesmo noutra
quantidade distinta.

è Uma relação de interesse entre as massas moleculares médias é o

índice de heterogeneidade ou polidispersividade, PI

PI = Mw / Mn

è Quando a distribuição de massas moleculares é muito apertada em

torno do valor médio, PI é próximo da unidade; quando a dispersão
aumenta, PI aumenta para valores de 2 a 3.

Para proteínas, PI=1

Molecular Weight: effect on the mechanical properties

A gama de massas moleculares

escolhida é um compromisso
entre as propriedades finais
óptimas e a possibilidade de
processamento do fundido. A
maioria dos polímeros usados
comercialmente apresenta uma
gama de massas moleculares
entre 20 000 e 200 000 g/mol.
 Molecular weigth -(CH2-CH2)-
parafin Ultra-high MW PE
Low-density PE

High-density PE
Experimental determination of molecular masses in
polymers

- Simple experiment: viscometry.

- More expensive: gel permeation (or size
exclusion) chromatography (GPC).
 Viscometry
Versatile but not absolute (need some form of calibration)
Basic measurement: time (t) for a specific volume of a solution of
polymer flow down a length of capillary tubing: t is proportional
to the coefficient of viscosity of the solution.

where t0 and ρ0 are the elution time and density of

the pure liquid, and ηr is the relative viscosity.

When the solution is very diluted Ubbelohde

viscometer
The so-called specific viscosity is:

Dimentions of h: Pascalxsecond
 Usually sp is a quantity between
is called the reduced viscosity (where c is the the mass concentration
Theincreases
of the polymer in solutions). It usually specific viscosity, dividedofby
with increasing c the c
(greater chain entanglement). The zero valueconcentration,
extrapolatedyields the intrinsic
to infinite
dilution, known as the intrinsic viscosity, [η]:

In general, the Huggins Equation is an empiricalFor dilute solutions,

equation usedwhere the relativ
to relate
the to
the reduced viscosity of a dilute polymer solution following algebraic expansion
the concentration of the is u
polymer in solution. The Huggins equation states

[η]2 c dividing ln rel by c and extrapola

ηsp ⁄ c = [η] + kHThen,
the intrinsic viscosity:
where kH is a constant for a series of polymers in a given solvent.

We may construct another expansion based Noteon that

the relative viscosity,
the natural in of
logarithm rel is
dilute solutions where the specific viscosity is much less term
itself. The than (ln
1. )/c is called the
rel rel

Using the expression for the specific viscosity in the Huggins equation above:
Giving rise to the Kremer equation:

ln(ηr) ⁄ c = [η] - kK[η]2 c

where kK is the Kraemer constant. In the Kraemer plot, (ln ηr)/c vs c, [η] is the
intercept, and the slope should be -kK[η]2. It is frequent to display the [η]
determination in a dual Huggins–Kraemer plot, where kH-kK=0.5.

ηsp ⁄ c

Reduced and inherent viscosity-

concentration curve for a polymer in
a given solvent.

ln(ηr) ⁄ c
 The Mark–Houwink equation, gives a relation between intrinsic
viscosity and molecular weight: Viscometry yield a viscosity
3.8.2 The Equivalent Sphere Model average molecular weight:

In assuming a dilute dispersion vof uniform, rigid, noninteracting spheres, Einstein

(69,70) derived an equation expressing the increase in viscosity of the
dispersion,….., and derivation by Flory, etc. [Procedures skipped. See text book]
The values of the Mark–Houwink parameters, a and K, depend on the
particular polymer-system. a=0.8 for good solvents. For most flexible
polymers 0.5<a<0.8 and for semi-flexible polymers a>0.8.

17
 Determining the Mark–Houwink constants
If the Mark-Houwink constants are not known from literature, they have to be
determined experimentally by plotting the logarithm of the intrinsic viscosity as a
function of the logarithmic molar mass. The intersection with the y-axis of a linear fit of
data gives the constant log K, the slope of the curve gives the constant a. Note that for
this experiments we will need to have standards of the specific polymer with well known
molecular weights.

https://wiki.anton-paar.com/en/intrinsic-viscosity-determination/
 Gel permeation chromatography (GPC)
The key phenomenon is that individual polymer molecules explore the pore systems of
the columns to the extent allowed by their size and hence relative molecular mass.
The eluent (mobile phase) should be a good solvent for the polymer, should permit
Stationary Phase high detector response from the polymer and should wet the packing surface.
gel particles

pore size: 5nm - 100 µm

column
Insoluble gels often composed
by cross-linked polystyrene with
the shape of semirigid beads
Usually refractive index, UV-IR
absorption or light scattering

Ou Volume de eluição
Polymer Molecular Weights 203
Typical GPC curves for narrow MW polymers
Gel permeation chromatography elution
Increasing molecular curves for polymer standards having very
Amount of polymer

Weight narrow molecular weight distribution.

204
(After Rudin, 1982.)

100
in eluant

Standard molecular weight, Ms x 10 4

Figure 4.20 Gel permeation
40
chromatography elution curves
for polymer standards having
very 10narrow molecular weight

4
distribution. (After Rudin,
Elution volume 1982.)

For polystyrene, for example, anionically polymerized

1
samples of narrow molecular weight distributions with
that monodisperse or very narrow distribution samples of most polymers are not generally avail-
polydispersity index less than 1.15 are commercially
able. However, such samples are available for a few specific
available in a wide range of molecular weights (103 to
polymers. For 0.4
polystyrene, for exam-
ple, anionically polymerized samples of narrow molecular weight distributions (MWD) with poly-
106). Using
dispersity such
index lessnarrow MWD
than 1.15 are samples, a polystyrene
commercially available in a wide range of molecular weights
(10 to 10 ). Using such narrow MWD samples, avolume
calibration
3 6 of molecular weight versus elution 0.1 of molecular weight
100 140 180
polystyrene calibration
can beelution
versus easilyvolume
obtained
canfor
be the given
easily GPC for
obtained column (or GPC column (or
the given columns) and the
columns)
given GPC and the given
solvent. GPC solvent.
A problem Peak elution
that would then remain is to establish a relationship partic-Ve (cm3)
volume,
for the
ular GPC column between the elution volume and molecular weight of some chemically different
A typical polystyrene standard calibration
polymer. We now consider these two steps in sequence.
curve (Ms versus Ve) for GPC
GPC - Universal Calibration Curve
É possível mostrar-se que [η]M depende do volume
hidrodinâmico de uma cadeia macromolecular (num
modelo de esfera equivalente), que é o parâmetro
associado à capacidade de permeação das cadeias
pelos poros das partículas na coluna de GPC.
 !Η"M characteristics; that is,
that is,

log #!Η"x Mx $ " log #!Η"s Ms $

Obtaining M from the calibration curve
log #!Η" x Mx $ of #!Η"sat s$
(4.108)
- The product [η]M is a direct function of the hydrodynamic volume "thelog
solute Minfinite
dilution.
and s indicate
- GPC the unknown
separations have shownpolymer (i.e., polymer
that polymers appear in with unknown
the eluate molecular
in inverse
Chapter 4order of their
rdhydrodynamic whereinthe
volumes
polymer, respectively. thesubscripts
particular
If x and s indicate
solvente.
each intrinsic viscositytheterm
unknown
in Eq.polymer
(4.108)(i.e.,
is polym
- Therefore,[Eq. weight) and the that
two different standard polymer, respectively. If eacha given
intrinsic visco
expression (4.92)],polymers
one obtainsappear
for theat the
twosame elution at
polymers volume
equalin elution solvent
and particular GPCreplaced
column atbya its
given
MHStemperature
expressionhave[Eq.
the same hydrodynamic
(4.92)], one obtainsvolumes
for theandtwo
hence the same [η]M.
volumes:

log #Kx Mxax #1 $ " log #Ks Msas #1 $

log #!Η"x Mx $ " log #!Η"s Ms $ log #Kx Mxax #1 $ "(4.108)#Ks Msas #1 $
Mark–Houwink equation

log(4.109)
es x and s are for the unknow polymer and strandard
Solving for log Mx gives

Mx " % If each & logintrinsic log Mx s " % & log

dicate the unknown polymer (i.e., polymer with unknown molecular
1 Ks 1 # as 1 Ks 1 # as
mer,
logrespectively. # viscosity log M term in Eq. (4.108) is
(4.110)
# log M
1 # ax Kx 1 # ax 1 # a K 1 # a

volume 'Vcurve ( thatfor Mx . T

on [Eq. (4.92)], one obtains for the two polymers at equal x x
elution x
This equation describes the elution volume calibration curve for Mx. The elution
s the elution volume This calibration curve for
equation describes theM x . Thevolume
elution elutioncalibration
volume that corresponds to a GPC peak in the unknown polymer is used to eobtain a

#Kx M $ # $curve
peak in of
value thelogM
unknown corresponds
from a polymer to aisstandard
polystyrene GPC
usedpeak in the
tocurve
obtainthataunknown
value
has been polymer
ofobtained
log Ms in isthe
from usedtheto obtain
same
ax #1s as #1
log
urve (Fig.
column 4.21)
and
x "
that
solvent, log
polystyrene
has
and been
Mx K
iss M
standard
obtained
then (Fig.
in the
s calculated same
from 4.21)
the that has
column
equation. and (4.109)
been obtained
solvent, andin the sam
from Eq. (4.110). is then calculated
M Alternatively, from Eq. values(4.110).ofAlternatively, a number of
Wex need to know Ks, aas, number
Kx and ax. of
If not, we need Vtoe determine
can be chosen
[η] and
urve for the polymer anddirectly
use aunder
new the
calibration
study cancurve
universal forcurve.
the polymer
be constructed
standard usingunder study curve
a standard can be constru
 Isomerisms / Configurations in Polymers
The same monomer can lead to polymers with different molecular arrangements.

Ä Isomerismo de Constituição (constitutional isomerism)

Involve constitutional variations of a molecule.
Check polymer synthesis class: during polymerization, the monomer in principle can be
joined by head-to-tail (predominant) or head-to-head/tail-to-tail addition, resulting into
different polymeric organizations.

CH2=CHR

In poly(vinyl chloride) (R=Cl), poly(ethyl methacrylate), (R=COOCH3), and polystyrene (R= C6H5):
head to tail.
Some polymer, e.g. poly(vinyl fluoride (R=F), have a significant number of units incorporated
“backwards” into the chain, giving head to head and tail to tail placements.
 andposition
bond (b) polyisoprene
as well.? How many constitutional isomers can form in the polymerization of (a) polybu
andAnswer:
(b) polyisoprene ?
Polymers of dienes - hydrocarbons containing
The conjugated diene butadiene
Answer: twoto produce
can polymerize carbon-carbon
1,4 and 1,2 productsdouble bonds
(Rudin, 1982):
H polymerize
The conjugated diene butadiene can H to produce 1,4 and 1,2 products (Rudin, 1982):
C C
H
H Hn
CH
C C
H H CH2 n
H2C C C CH2 H CH
1 2 3 4
H H CH2
From butadiene: H2C C C CH2
1 2 3 4 CH2 C
H H
C CH2
n
H H
Thus, there are three possible constitutional
CH2 isomers
C C and,CH2in addition, there is the possibility of mixed struc-
n
tures. Note that there is no 3,4-polybutadiene because it is identical with 1,2-polybutadiene. This is not the
case with 2-substituted conjugated butadienes like isoprene and chloroprene. Thus, as shown below, there
are six possible constitutional isomers of isoprene or chloroprene, to say nothing of the potential for mixed
Thus, there (Rudin,
structures are three possible
1982) : constitutional isomers and, in addition, there is the possibility of mixed
tures. Note that there is no 3,4-polybutadiene
R because it is identical with 1,2-polybutadiene. This is
head-to-head
case with 2-substituted conjugated butadienes
CH2 C like isoprene and chloroprene. Thus, as shown below
n
are six possible constitutional isomersHofCisoprene
CH2 or chloroprene, to say nothing of the potential for
head-to-tail
structures (Rudin, 1982) : 1,2 polymer
R head-to-head
CH2 C
H H n
head-to-head
head-to-tail
1 2 H C CH
From isoprene/ CH2 C C CH2 CH2 C n
1,2C polymer
2
3 4 R head-to-tail
chloroprene: R
CH2
Isoprene: R=CH3 3,4 polymer
Chloroprene:
H R=Cl H
1 2 R H head-to-head
CH2 C C CH2 CH2 C head-to-head
CH2 C C CHn2
3 4 C R n head-to-tail
head-to-tail
R 1,4 polymer
 Ä Configurational Isomerism

Ä Isomerismo Geométrico ex: polimerização de dienos

Monómero: CH2=CH-CH=CH2
1 2 3 4

polybutadiene
(1) (4)
(CH2 (2) (3) CH2 ) ( CH2 H
C C C C
H H H CH2 )
cis trans

-As estrutura trans tem mais tendência a cristalizar: polímeros mais rígido /
menos flexível
Isomeria óptica

(centros quirais)

Br H H
quiralidade C
Br
C
ex: isómeros ópticos do C(CH3)ClBrH Cl
CH3 CH3 Cl

H
centros pseudo-quirais em polímeros CH2 C *
R

H
poli(óxido de propileno) [c/ act. óptica] O CH2 C*
R
Ä Stereoisomerism

-CH2-CHR-
Mesmo estereoisómero ao longo da cadeia

=>
Poly(cloreto de vinilo) [poly(vinyl chloride)]

Views of computer-generated chains of eight repeating units (octamer) of vinyl

chloride. These views are looking down on the chain with the chlorine atoms
(large spheres) sitting at the base of each chain. Small light gray spheres
represent hydrogen atoms while larger dark gray spheres identify the carbon
atoms.

Exercise: classify A and B as atatic, isotatic or syndiotatic.

Why is this important?
• Tacticity affects the physical properties
– Atactic polymers will generally be amorphous, soft, flexible
materials
– Isotactic and syndiotactic polymers will be more
crystalline, thus harder and less flexible [differences occurs
between isotatic and syndiotectic polymers in terms of
crystalline structure and melting points]
• Polypropylene (PP) is a good example
– Atactic PP is a low melting, gooey material.
– Isotactic PP is high melting (176º), crystalline, tough
material that is industrially useful.
– Syndiotactic PP has similar properties, but is very clear. It is
harder to synthesize.
Chain structure
Branched chains
Cadeias ramificadas
Linear chains
Cadeias lineares

Crosslinked chains
Cadeias reticuladas 3D-networks
Rede 3-D
Branched polymers

• Side-branch chains are connected to the main

chains
• Branches result usually from side reactions during
synthesis
• Chain packing efficiency is reduced (lower
polymer density)
Polietylene
Grau de Temp. de
ramificação
densidade fusão
CH3/100C g/cm3 ºC

LDPE
2-7 0.915-0.94 100-129
PE de baixa densidade

High pressure free radical polymerization

HDPE
0.1-2 0.94-0.97 108-129
PE de alta densidade
Low T,P, using Ziegler-Natta and metallocene catalysts or
activated chromium oxide (Phillips catalyst)

LLDPE 2-6 0.91-0.94 99-108

PE de baixa densidade
linear
Made by copolymerization of ethylene with longer-
chain olefins (butene, hexene, or octene)
Linear low density PE versus LDPE and HDPE

LLDPE has higher tensile strength and higher impact and puncture resistance than
does LDPE. It is very flexible and elongates under stress. It can be used to make
thinner films, with better environmental stress cracking resistance.
Branched natural macromolecules
The type of branching can strongly influence polymer properties. Examples include natural polysaccharides,
which occur after enzymatic polymerization of glucose, forming different types of branching.
In glycogen the glucose units are arranged in a tree-like branched structure with a branching point every 8–
12 glucose units. Glycogen is an energy supplier for animal cells and is the product of an enzymatic
decomposition of starch.
Starch is composed of amylose and amylopectin, which are
also formed of glucose units, but while amylose possesses linear
or very slightly branched chains, in amylopectin branching
occurs every 25 units.
nds
c bo ds
idi n
cos c bo
ly i
g sid
4 co
-1, ly
α
, 6g
1
α-
Brush-like macromolecules
Linear brush-like molecular architectures are well-known
in biology where they are responsible for various functions
including mucociliary clearance of lung airways and
mechanical performance of articular cartilage.
Brush-like macromolecules in the extracellular matrix:
PROTEOGLYCANS

Proteoglycans are a combination of

proteins and glycosaminoglycans*.
They exhibit a net negative charge
that attracts positively charged
sodium ions (Na+), which attracts
water molecules via osmosis,
keeping the ECM and resident cells
highly hydrated. They are therefore
useful to the body as a lubricant or proteoglycan monomer
as a shock absorber.
Proteoglycans may also help to trap
and store growth factors within the
ECM.

* Glycosaminoglycans (GAGs) are large linear polysaccharides constructed of repeating

disaccharide units with the primary configurations containing an amino sugar (either
GlcNAc or GalNAc) and an uronic acid (either glucuronic acid and/or iduronic acid).
Polymer brushes

Physisorption

M M
M M

Preparation of polymer brushes by B M

“physisorption”, “grafting to” and *
I I I I
“grafting from”. A A A A

“Grafting to” “Grafting from”

B. Zhao, W.J. Brittain / Prog. Polym. Sci. 25 (2000) 677–710

Fig. 9. Preparation of polymer brushes by “physisorption”, “grafting to” and “g
Smart polymer brushes in biomedicine:
Temperature responsive platforms for cell culture

N. Idota, 2012
doi:10.1088/1468-6996/13/6/064206

(more on Module 6) !!!

 Hyperbranched macromolecules

Chem. Soc. Rev., 2015,44, 4131-4144

Dendrimers
Schematic are three-dimensional,
overview nanosized,
of the sub-classes of theoften radially
family symmetricpolymers.
of dendritic molecules with a well-
defined and monodisperse architecture. Dendrimers consist of tree-like branches (dendrons)
built around a core unit. Their size is measured in generations (G), based on the layer-bylayer
structure by which they are synthesized
 Knotted polymers
structure consisting of multiple intramolecular cyclization units within a single polymer
chain (Wenxin Wang, JACS 2011)

Synthesis

Single chain cyclized polymers consist of multiple cyclized rings which afford them some unique properties,
including high density, low intrinsic viscosity, low translational friction coefficients, high glass transition
temperatures and excellent elasticity of the formed network. In particular, an abundance of internal space
makes the single chain cyclized polymers ideal candidates as efficient cargo-carriers.
Crosslinked polymers / Polímeros reticulados

• Crosslinked Polymers
– Adjacent linear chains are joined at various
positions by covalent bonds
– Achieved during synthesis or after synthesis
(sometimes called curing - or in the case of
rubbers - vulcanization
 N N N CH2 N CH2 N

Thermosets (“termoendurecíveis”) H2N C

N
C NH2
C O
N CH2 N CH2
C O
N CH2 N

M ela m in e C O C O
A thermosetting plastic is a polymer that can NbeCHcaused N CH toCHundergo
N N cross-linking to
2 2 2

produce a network polymer, called a thermoset polymer. Quite commonly,

N etw ork p olym er (U F )

thermosetting resins are prepared,

Figure 1.10 Theby intent,
two important inof amino-resins
classes only partially are the productspolymerized states
of condensation reactions of urea
and melamine with formaldehyde. Reactions for the formation of urea formaldehyde amino-resins (UF) are
(prepolymers), so that they can
shown.be deformed
Preparation in a heated
of melamine-formaldehyde mold
resins (not and
shown) is similar.then hardened by

curing (crosslinking). O CH 3

CH2 CH CH 2 Cl + HO C OH

E p ich lo ro h y d rin CH3

a q. N a O H B is p h en o l-A

O CH3 OH
CH2 CH CH2 O C O CH2 CH CH2 O
O
CH3
E p o xy res in in term ed ia te

H3C C CH3

CH2 CH CH2 O

C u rin g o f a n ep o x y res in

CH2 CH CH2 + H2N R NH2

E p o x y en d g ro u p D ia m in e Figure 1.11 Epoxy

H2C CH CH2 monomers and polymer and
OH curing of epoxy resins.
CH2 CH CH2 N
Polyamines such as diethyl-
OH R
enetriamine, (H2 NC2 H4 NH-
N CH2 CH CH2 C2 H4 NH2 ), are widely used for
CH2 CH CH2 OH the production of network
OH polymers by room tempera-
ture curing.
N etw o rk p olym er
composites
Rubbers (“soft” thermosets)

• Natural rubber is too soft and chemically reactive to make a useful

material.
• By vulcanizing the rubber (crosslinking the polymer chains) useful
materials are made.
• Rubber is usually cross-linked with sulfur.
• Cross-linked rubber is stiffer, more elastic and less susceptible to
chemical reaction.
rubbers

Charles Goodyear
(1800-1860)
Sulfur bonds in biology: disulfide bridges
In biology, disulfide bridges formed between thiol groups in two cysteine
residues are an important component of the secondary and tertiary
structure of proteins.

The disulfide bonds are strong, with a

typical bond dissociation energy of 60 kcal/mol,
about 40% weaker than C−C and C−H bonds: the
disulfide bond is often the "weak link" in many
molecules. Reflecting the polarizability of
divalent sulfur, the S−S bond is susceptible to
scission by polar reagents, both electrophiles and
especially nucleophiles

The most important aspect of disulfide bonds is their cleavage, which occurs via
reduction. A variety of reductants can be used. In biochemistry, thiols such as β-
mercaptoethanol (β-ME) or dithiothreitol (DTT) serve as reductants;
Disulfide bridges in curly hair
Hairs are made of keratin molecules,
which form a helical structure. Pairs of
those then coil about each other in a left-
hand coiled-coil structure. These are then
attracted to another coiled coil so two
keratin helices will stick together. These
four-chain structures then associates
with another four-chain structure to form
the hair filament at the lowest scale, and
disulfide bonds between cysteins play an
important role in such stabilization. The
more interactions between filaments, the
more tightly coiled the coiled-coil
becomes. Hence, curly hair has more
interactions than straight hair.
How hairs are curled artificially via perming?

Manipulating disulfide bonds in hair is the basis for the permanent

wave in hairstyling. Reagents that affect the making and breaking of
S−S bonds are key, e.g., ammonium thioglycolate.
Supramolecular polymers
Supramolecular polymers can be defined as polymeric systems that extend
beyond the molecule and utilize noncovalent interactions to direct
their self-assembly, to control their conformations. Due to the reversibility
of noncovalent interactions, these materials are capable of undergoing self-
healing and adaptation processes, which afford supramolecular polymers a
major advantage over conventional, covalently bonded polymers.

Chem. Rev. 2001, 101, 12, 4071–4098

self-assembly

Schematic representation of a covalent polymer (a); and a supramolecular

polymer (b).
rview wires.wiley.com/n

Natural structures obtained by self-assembly

(a) (b)
Building block Hydrogen bonds

Phosphate
α-helix G C

Sugar + C Self-assembly T A

A T
C

Self-assembly Self-assembly Self-assembly T A

Base Nucleotide

50 nm
C
Hydrogen bonds Hydrogen bonds G

Hydrophobic interactions C G

R O R Ionic interactions
H
N OH P
H H TT - TT
H2N N O

stacking
O H
H H O H2N G C
O R O HO H O
N

N
OH
n N N N
Thymine (T) A T
O
N H
H
H
O
Adenine (A)
O
T A
HO N O
H H
O H N P

1-6 nm
2

N OH
H O
H NH
N
O N
O H

Building block
N

Secondary structure
O H
P

Tertiary structure
H

Quaternary structure
H H NH
2
O O
H O
Guanine (G)
Polypeptide H H
P

Cytosine (C)

2 nm

(c) Tobacco Musaic Virus (TMV)

(d) CH2-N(CH2)3 Hydrophobic interactions

Hydrophilic
headgroup
CH2

O Self-assembly
RNA
Two stacked discs made of 34 building block O P O

subunits O

H2C HC CH2 K+

300 nm
O O

C OC O
Channel

Double hydrophobic
CH2 CH2

2–4 nm
Protein Self-assembly CH2 CH2

alkyl chain
CH2 HC

CH2 CH

CH2
CH2
CH2
CH2
CH2
18 nm CH2
CH3

Building blocks
CH3
Membrane
Beginning of the helix Helical turns are
Receptor
formation threaded onto the RNA
Building block
Phospholipid Ca2+ Na+

RE Inspiration
2 | Examples offrom the nature: Examples of biological self-assembled structures showing the
biological self-assembled structures showing the building blocks and the relevant interactions involved in the
building
embly blocks
process. (a) Proteinand the(b)relevant
folding; ds-DNA; (c)interactions
tobacco mosaicinvolved
virus (TMV);inand
the
(d) self-assembly
cell membrane. process.
(a) Protein folding; (b) ds-DNA; (c) tobacco mosaic virus (TMV); and (d) cell membrane.
buted symmetrically despite their self-assembly The
A.C. Mendes et al., WIREs cytoplasmic
Nanomed membrane
Nanobiotechnol (Figure 2(d))
2013 (DOI: 10.1002/wnan.1238)
 Supramolecular Polymers 1987

Supramolecular polymers are composed by monomeric

repeating units held together with directional and
reversible (noncovalent) secondary interactions (e.g.
hydrogen bonds, p-p interactions, metal coordination).

Simple hydrogen bonds between neutral molecules are not

enough: either multiple hydrogen bonds with cooperativity Jean Marie Lehn (1939-)
must be used or hydrogen bonds should be supported by
additional forces like excluded volume interactions.
https://www.youtube.com/watch?v=9Kkl2SpNOFQ

https://www.youtube.com/watch?v=9Kkl2SpNOFQ
Supramolecular Polymers: UPy dimers
Figure 1.3 Schematic representation of (a) a covalent polymer and (b) a supramolecular polymer. (After
Brunsveld et al., 2001.)

2-ureido-4[1H]-pyrimidinone (UPy) are easily synthetized and they dimerize strongly

(constant >106 M-1 in CHCl3) by self-complementary quadrupole hydrogen bonding.

Figure 1.4 Synthesis of a monofunctional 2-ureido-4[1H]-pyrimidinone (UPy) (1) and dimerization of 1 in

solution forming a quadrupole hydrogen-bonded unit. (After Sijbesma et al., 1997.)

M. Chanda, Introduction to Polymer Science and Chemistry, 2nd Ed., CRC Press, 2013
Thus the electrophilic isocyanate group (–NCO) of ‘synthon’ (3 in Fig. 1.5) can be reacted with

Supramolecular Polymers based on UPy

common nucleophilic end groups (–OH or –NH2 ) of telechelic oligomers, resulting in supramolec-
ular polymers by chain extension (Fig. 1.6). Thus the material properties of telechelic polymers
have been shown to improve dramatically upon functionalization with synthon, and materials have
Preparation
been of (A) many
obtained that combine UPyofpossessing an isocyanate functional
(3) and (B) a difunctional
the mechanical properties of conventional group
macromolecules

UPy compound (4) which forms a supramolecular polymer by hydrogen bonding (5).

A
18

2
B 1 C

Figure 1.6 Schematic representation of the formation of supramolecular polymer (7) by chai
C: Schematic representation of the formation of
reactive telechelic oligomer with UPy. (From Folmer et al., 2000. With permission from John
Inc.)
supramolecular polymer (7) by chain extension
ofthereactive
with telechelic
low melt viscosity oligomer
of oligomers with
(Brunsveld et UPy.
al., 2001). In contrast to conve
Figure 1.5 Preparation of (a) UPy possessing an isocyanate functional group molecular-weight polymers,
(3) and (b) a difunctional UPysupramolecular (reversible) polymers with a high “virtua
weight show excellent processability
compound (4) which forms a supramolecular polymer by hydrogen bonding (cf. Fig. 1.4). (After Folmer et due to the strong temperature dependency of
al., 2000; Brunsveld et al., 2001.) cosity (Folmer et al., 2000). Moreover, hybrids between blocks of covalent macrom
supramolecular polymers can be easily made.
Supramolecular interactions in biology
One motivation behind supramolecular chemistry is the design of chemical
systems that mimic biological processes. For example, supramolecular host
molecules can be seen as receptor molecules that contain intramolecular
cavities into which guest molecules may bind, thereby forming an inclusion
complex reminiscent of protein-ligand complexes.
“host-guest”: hóspede-hospedeiro

Molecular recognition, which is the

process of biological macromolecules
interacting with each other or various
small molecules with a high specificity
and affinity to form a specific complex,
constitutes the basis of all processes in
living organisms.
Water-soluble host molecules in supramolecular chemistry
One motivation behind supramolecular chemistry is the design of chemical systems that mimic
biological processes. For example, supramolecular host molecules can be seen as receptor
molecules that contain intramolecular cavities into which guest molecules may bind, thereby
forming an inclusion complex reminiscent of protein-ligand complexes. Until now, numerous
types of natural and synthetic macrocyclic host molecules have been reported.

A current challenge in
supramolecular chemistry is
the design of receptor
molecules, which efficiently
bind in water, because only
this environmentally benign
solvent allows biological
applications.

http://wernernau.user.jacobs-university.de/?page_id=219
Cyclodextrins
Cyclodextrins (CDs) are composed of 5 or more α-D-glucopyranoside units
linked 1->4. Because cyclodextrins are hydrophobic inside and hydrophilic
outside, they can form complexes with hydrophobic compounds (including
polymer chains).

side view
Cyclodextrins: preparation
Treatment of ordinary starch (eg, cornstarch) by enzymatic degradation in the presence of CD
glycosyl transferase (CGTase). This enzyme is produced by numerous microorganisms: Bacillus
macerans, Klebsiella oxytoca, Alkalophylic bacillus, Bacillus circulans...
Hydrophobic molecules / CDs complexes

Hydroxyls are the external surface (hydrophilic and hydrogen-bonding). The

carbon and hindered ether skeleton is internal (hydrophobic). A cyclodextrin
looks like a bonded hollow detergent micelle in water.

Based on the structure and properties

of drug molecule it can form 1:1 or 1:2
host-guest complexes.
Hydrophobic nature of the cyclodextrin cavity
Left: The relaxed structure of β-
cyclodextrin in water (79 water
molecules) from DFTB MD
simulations. The inside of β-
cyclodextrin is hydrophobic. It can
take a maximum of 7 water
molecules in equilibrium.
Right: The relaxed structure of β-
cyclodextrin plus binaphtyl guest
molecule in water (119 water
molecules): the water inside the
hydrophobic cavity of cyclodextrin
is easily displaced by an active
guest molecule like binaphtyl.
Molecular dynamics
simulation of curcumin/
Ɣ-cyclodextrin complex

curcumin

https://www.youtube.com/watch?v=cbWjtNVUHGY
 Supramolecular polymers using CDs

A B C

A. Miyawaki+, Chem.Commun. 2008

was found to form supramolecular polymers as well as 3-cinnamamide- -CD. To an aqueous solution
1 (40 mM) was added 1.5 M excess DMTMM and 1.5 M excess 1-adamanatanecarboxylic acid in
ueous solution, and was stirred for 1 day (Method 1). After removal of the insoluble materials by
ration, the filtrate was poured into acetone. The resulting precipitate was collected and washed with
etone.
Alternating supramolecular polymer of
3-AdC6NH-α-CD and 6-BocCiNH-β-CD
A. Aradai+, Aust. J. Chem. 2010
2
Supramolecular polymers: Examples including
host-guest interactions

Cartoon representation of the

formation of
supramolecular polymers based
on noncovalent interactions:
(a) multiple hydrogen bonding;
(b) metal coordination;
(c) π–π interaction;
(d) cucurbit[8]uril;
(e) β-cyclodextrins;
(f) pillar[5]arenes

Chem. Soc. Rev., 2012, 41, 1621-1636

REGULARIDADE QUÍMICA

Copolímero aleatório

Copolímero alternado

Copolímero de blocos

Copolímero de inserção
ou de enxerto

Copolímero com gradientes

de composição
Learning objectives:

• Distinguish between macromolecules and polymers.

• Identify the different classes of macromolecules.
• Recognize the structure of relevant polymers (e.g. PE, PP, PS, poly(butadiene), PTFE, PVC,
and PET)
• Understand the concept of conformations (in space and time) in polymeric chains, as a
consequence of “free” rotation along the backbone, and apprehend the steric restrictions
that will be on the basis of the energy landscape as a function of the torsion angles.
• Capture the concept of average level of polymerization, distribution of molecular weight
and polydispersity level. Distinguish between number average molecular weight and
weight average molecular weight.
• Recognize the relevance of molecular weight on the properties of macromolecules.
• Understand the principles of viscometry and gel permeation chromatography as
techniques to assess the molecular weight in macromolecules.
• Identify the distinct classes of isomerisms in polymers: sequence isomerism,
stereoisomerism (including the consequences in the physical properties), and structural
isomerism.
• Categorize the generic chain architectures in macromolecules (linear, branched, cross-
linked, 3D-networks), brush-like and hyperbranshed structures.
• Identify supramolecular polymers as non-covalently attached sequences of repeating
units.
• Classify the different copolymers taking into account the chain regularity.
Bibliography:

More relevant:
1- M. Chanda, Introduction to Polymer Science and Chemistry, 2nd Ed., CRC Press, 2013

2- P.C. Painter, M.M. Coleman, Fundamentals of Polymer Science, 2nd Edition, CRC Press
1997

3- Ian M. Campbell, Introduction pot synthetic Polymers, 2nd Edition, Oxford University
Press, 2000

4- L.H. Sperling, Introduction to Physical Polymer Science, 3rd Edition. Wiley-

Interscience, 2001.

Other sources:
F.W. Billmeyer, Texbook of Polymer Science, Wiley-Interscience, 1984

I.W. Hamley, Introduction to Soft Matter, John Wiley & Sons, 2007.