CH CH CH CH Side-Chain Extension Reaction CH CH CH CH
CH CH CH CH Side-Chain Extension Reaction CH CH CH CH
CH CH CH CH Side-Chain Extension Reaction CH CH CH CH
Polymers
A large molecule consisting of repeating smaller structural units (called monmrt units)
Polymerization
The sequence of repetitive reactions between a monomer unit and the growing
macromolecule or polymer chain
ie.
CH2=CH2
[-CH2-CH2-]n
a monomer unit
polymerization
polymer
Only one type of monomer molecule is used to make a polymer, with repeating units of
this one monomer
Copolymer Polymer formed by the combination of 2 or more different monomer molecules; The
sequence arrangement of these units can vary in four different ways.
1)
2)
3)
Block copolymer a sequence where there are repeating blocks of identical monomer units.
-A-A-A-A-B-B-B-B-A-A-A-A-B-B-B-B-
4)
Graft copolymer a chain which have side-chains from which to create extensions to
another polymer chain.
CH2 CH
CH2 CH CH2 CH
CH2 CH
side-chain extension
reaction
n
polystyrene chain
OCH3 O
OCH3
n
Polymer
Commercial Use
ethylene
CH2=CH2
-[-CH2CH2-]npolyethylene
vinyl chloride
CH2=CH-Cl
tetrafluoroethylene
CF2=CF2
ethylene glycol
HO-CH2CH2-OH
Cl
CH2 CH
poly(vinyl chloride)
(PVC)
-[-CF2CF2-]npoly(tetrafluoroethylene)
(Teflon)
poly(ethyleneglycol)
(PEG)
(-CH2CH2-O)-
acrylonitrile
CH2=CH-CN
terephthalic acid
O
HO C
O
C OH
CN
CH2 CH
inert, non-stickcaoting
used in carpets to make
them stain resistant
emulsifying and thickening
agent
(non edible) in shampoos,
lubricant oils, antifreeze
used to make a co-polymer
with PMMA
(polymethylmethacrylate) in
acrylic fibres for clothing
poly(acrylonitrile)
Orlon, Acrilan
O
C
O
C O CH2 CH2 O
poly(ethylene terephthalate)
(PET
Physical properties
The structure of the monomer will confer unique structural and physical characteristics
in the polymer at different temperatures.
Some polymer chains can pack or arrange/order themselves in a highly organized
manner, resulting in highly crystalline material. For example linear polyethylene
Some polymer chains have branching on the chain and cannot order themselves in a
crystalline lattice and often said to be amorphous solids. For example rubber
(polyisoprene)
Most polymers are semi-crystalline, where some regions are highly ordered and
crystalline, while other regions are not and have amorphous properties.
Intermolecular forces that increase the melting point of a polymer are:
a) structural regularity in polymer chain
b) bond rigidity
c) close-packing ability
d) strong inter-chain attractive forces (eg. H-bonding)
Examples
Polymer
O
C
O
C O R O
R-Goup
n
CH2 CH2
Physical Poperty
solid
Melting point 265C
a terephthalate-based
poyester
CH2 CH
CH3
CH2 CH CH2
CH3
CH3
CH2 C CH2
CH3
H3C
O
C
O
C O R O
CH3
O
C
O
C O R O
not crystalline
not crystalline
solid
Melting point 140C
solid
Melting point 170C
CH2 CH2
CH2 CH2
solid
Melting point 70C
CH3
CH 2 CH
n
C O
O
CH 3
poly(methacrylate)
CH3
CH2 C
n
C O
O
CH3
hard plastic
Melting point 200C
poly(methyl
methacrylate)
CH2 CH
n
C O
OH
solid
absorbs water
used in diapers
poly(acrylic acid)
CH2 CH
n
C O
NH2
polyacrylamide
soft plastic
used in making
soft contact lenses
Polymers
Free radical Polymerization
Initiation -usually by homolysis of an initiator molecule for example benzoyl peroxide.
Benzoyl peroxide
O
Ph
O
O
heat
Ph
homolysis
O
2
Ph
-bond
cleavage
Ph
+ CO2
Radical chain
polymerization
initiating
species
phenyl -- Ph
CH
H2C
Propagation steps:
Ph
In
H2C
In
Ph
styrene
benzylic radical
Ph
Ph
H2C
In
Ph
H2C
etc.
Ph
n
polystyrene
Ph
Chain termination:
Radical combination:
In
Ph
Ph
Ph
Ph
Ph
Ph
Ph
H-atom transfer
Ph
Ph
Ph
In
Ph
In
H
n
Ph
In
In
In
Ph
Ph
H
n H
Ph
H
Ph
In
In
n
In
H H
R
In
H
n
+
n
Branched chain
poly mer f ormation
n
R
m
R
CH 2
H2 C
CH 2
CH 2
CH 3
H2 C
C
H2
CH 2
C
H2
CH2=CH2
CH 2
CH
CH 2
CH 2
n
H2 C
4-carbon
branch
CH 2
H2 C
CH 3
H2C CHCl
CF2
vinylidine fluoride
Cl
plastics, plexiglas
CH2 CH
4-vinylpyridine
O
methyl methacrylate
PVC polymer
photoresists for
microelectronics
thickeners adhesives
sporting goods
HO
acrylic acid
O
t-BOC styrene
O
O
O
O
(CH2)6 O
CN
CH2
soft contact
lenses
CH2
OH
Interpenetrating polymer
There are many compounds that have been developed containing more than
one polymerizable vinyl group. As you can expect with two reactive sites on one
monomer at some point crosslinking will occur. Interpenetrating polymer
networks or IPNs are combinations of two or more polymers in network form. At
least one of the polymers is synthesized and/or crosslinked in the presence of
another. As such, IPNs share some of the advantages of both polymer blends
and network polymers. One of the earliest commercial IPNs used in the
automotive industry consists of polypropylene and ethylene-propylene-diene
terpolymer (EPDM). Potential applications include toughened plastics, ionexchange resins, pressure sensitive adhesives, soft contact lenses, preparation
of novel membrane systems and sound- and vibration-damping material.
Given below is an example of the formation of an IPN. First formed is the
crosslinked poly(ethyl acrylate) (PEA) network by free radical polymerization.
Then the monomers styrene and divinylbenzene are added (this is called
swollen, i.e. the polymer is swollen with the monmers) and then polymerized to
form a crosslinked interpenetrating polystyrene (PS) network.
CH
C
CH2
O
O(CH2CH2OCH2CH2O CH
C
OCH2CH3
ethyl acrylate
CH2 )2
O
OCH2CH3
tetraethylene glycol dimethacrylate
CH
+
CH2
CH
styrene
PEA network
CH2
AIBN
heat
+
CH
PEA network
AIBN
heat
CH2
divinylbenzene
PEA-PS IPN
HC
CH2 In HC CH2 In
HC CH2 CH CH2CH CH2
Ph
Ph
Ph
Cross linking:
CH
CH2
CH CH2
CH CH2
F
Lewis acid
(electron deficient)
H
O
H
Lewis base
(electron rich)
Initiation
F
F
H
B
H2 C
H
CH 3
F
CH 3
B
F
CH 3
H
O
H3 C
CH 3
CH 3
Propagation
CH 3
H3 C
CH 3
H3 C
H2 C
CH 3
H3 C
CH 3
H2 C
CH 3
CH 3
CH2
etc.
CH 3
H3 C
Chain Termination
Protontransfertocatalyst
CH 3
CH2
CH 3
CH2
CH 3
CH 3
CH 3
H
O
F
F
CH2
CH 2
CH2
CH 3
CH 3
terminatedchain
+
F
H
O
H
F
F
CH 3
CH2
CH 3
CH 3
CH 3
CH 3
H2 C
CH2
CH 2
CH2
CH 3
CH 3
CH 3
terminated chain
+
CH 3
H3 C
CH 3
Chain transfer to monomer results in short polymer chains (approx. molecular weight = 2,000 -3000) when the
polymerization is carried out at room temperature
Such polymers find some use as additives to lubricating oils but are not useful as plastics or rubber
Much longer chain polymers can be produced by using low temperature (-90o C).
-the activation energy for chain transfer to monomer reactions is higher than that for chain propagation;
therefore, lowering the temperature slows down the chain terminating step more so than the propagation step
These longer chain polymers are still too soft and pliable for use as rubber because the polymer chains move
fairly easily relative to one another
The polymers can be made tougher and more rigid by decreasing the ability of polymer chains to move
relative to one another by forming covalent bond between polymer chains
The polymer chain crosslinking of rubber is called vulcanization. In order to create polymer crosslinks,
potentially reactive sites for covalent bond formation have to be introduced along the polymer chain. This is
done by adding a small amount (approx. 1- 5%) of a second monomer (often isoprene) when polymerization
is carried out. The resultant co-polymer has vinyl (alkene) groups at some positions along the polymer chains
SH
mercaptobenzothiazole
(MBT)
Vulcanization
CH 3
CH 3
C H2
CH 3
CH 3
CH 3
C H2
C H2
C H2
CH 3
CH 3
H2 C
C H2
CH 3
H2 C
CH 3
H2 C
CH 3
C H2
CH 3
CH 3
CH 3
CH 2
C H2
C H2
CH 3
CH 3
CH 3
CH 3
C H2
C H2
CH 3
CH 3
Sx
heat
CH 3
C H2
CH 2
n
S
CH 3
CH 3
CH 3
C H2
CH 3
CH 3
H2 C
CH 3
m
x > 1 (polysulfide crosslink)
N
SH
mercaptobenzothiazole
(MBT)
S
S
Sx
a hypothetical intermediate
acelerated vulcanization
CH 3
Condensation Polymerization
Involves the condensation of two different bifunctional monomers, resulting in the
elimination of a small stable molecule (H2O, HCl, ROH). It essentially involves a
nucleophilic acyl substitution by one nucleophilic monomer on the electrophilic monomer.
Examples:
1)
O
O
n HO C (CH2)4 C OH + nH2N (CH2)6 NH2
hexanedioic acid
(adipic acid)
1,6-hexanediamine
O
O
HN (CH2)6 NH C (CH2)4 C
+ 2n H2O
n
Nylon 6,6
6 carbons in diamine
6 carbons in the acid
vaporized
which drives
the reaction
Mechanism
O
HO
O
(CH2)4
OH
H2N
(CH2)6
NH2
HO
O
(CH2)4
C
H2N
+
OH
(CH2)6 NH2
amide linkage
O
HO
O
(CH2)4
HN
HO
(CH2)6 NH2
O
(CH2)6
NH2
HO
O
(CH2)4
O
HN
(CH2)6
NH
(CH2)4
C
HN
+ H2O
H2N
O
(CH2)4
C
n
OH
+ H
O H
(CH2)6 NH2
2)
HO
OH
+ n HO CH 2 CH 2 OH
C
O
ethylene glycol
Naphthalene dicarboxylate
O
C
O
Mechanism:
HO
R1 C
C
O
O CH 2 CH 2
+ 2n H2O
n
poly(ethylenenaphthalate)
O
OH
HO
R2 OH
HO
O
R1
OH
HO R2 OH
+
ether linkage
H2O + HO
R1 C
R2 OH
HO
R1 C
HO
O
HO
R2 OH
HO
O
O
R2 O
O
R1
O
R1
OH
+ H
O H
R2
OH
3)
n HO
O
O C O
OH + n
NaOH
diphenyl carbonate
Bisphenol A
CH3
C
CH3
O
O C
+ 2n HO
n
or
CH3
C
CH3
n HO
OH + n
Cl
O
C
NaOH
CH3
C
CH3
Cl
O
O C
+ 2n HCl
n
phosgene
Bisphenol A
O
HO
OH
R
O
H
HO R O C
+
Cl
-HCl
HO R O C O R OH
Cl
Cl
O
HO R O C
Cl
O H
Cl
HO R OH
Cl
O
-HCl
O
HO R O C O R OH
Cl
C
etc
Cl
O
C O
O
n
OH
+ n HO
OH
heat
O
O
O
O
C O
O
O
n
Addition reactions
1)
Poly(urethane) Synthesis
Polyurethanes are the most well known polymers used to make foams like foam cushions. Polyurethanes can also
be used as in paints, synthetic fibers, and they can also be used as adhesives.
Notice that in the mechanism not only monomers react, but also dimers, trimers, and so on. This makes it a step
growth polymerization. Also, because no small molecule by-products are produced, it is called an addition
polymerization
n O C N
CH2
N C O + n HO CH2 CH2 OH
ethylene glycol
a di-isocyanate
O
C N
H
CH2
H 3O +
catlyst
In this reaction there
is not a loss of a small
molecule
O
N C O CH2 CH2 O
H
urethane
linkage
Mechanism
O C N
CH2
OH
N C O + HO
R2
R
R
+
N
O
C
catalyst
H
O
O H + HO
+
O
R2
N
H
C
+
R2
H
O
R2
-H+
R2
O
R
H
O R
+
H
etc
H
urethane linkage
Sometimes, instead of using a small diol like ethylene glycol, a polyglycol, one with a molecular weight of
about 2000 can be used. This produces a polymer within a polymer and polyurethane that looks something like
this:
Spandex
O
C N
H
CH2
O
N C O CH2 CH2 O
x
H
soft rubbery block
Polyurea
If a diamine is used instead of a diol in this reaction a polyurea is made
n O C N
CH2
a di-isocyanate
ethylene diamine
O
C N
H
O
N C N CH2 CH2 O
H
H
CH2
urea
linkage
O C N
CH2
N C O + H2N
R2
R
R
O
N
H
H+
O
R
catalyst
H
N
H
NH2
O H + H2N
+
O
R2
N
H
C
+
R2
H
N
R2
-H+
C N R
+
H H
R2
O
R
H
urea linkage
etc
3)
n H2N
O
C
O
C
+ n
NH 2
pH 4-7
N
H
H
H
formaldehyde
urea
O
N
H
N
H
Mechanism
H
+
O
C
H
O
H2N
+
H
NH2
H2N
n
Melamine - Formaldehyde resins
O+
N
N
NH2
-H2O
NH2
H2N
N
NH2
melamine
O
C
H
H
formaldehyde
N
H
+ n
NH2
CH2
C + C
NH2
N
H
H
H H
C
H2N
H
C
H
O
N
H
pH 4-7
etc
NH2
H
N
n
N
H
N
N
H
N
H
N
N
N
N H
N
H
n
cross-linked polyurea
O
C
OH
pH 4-7
OH
H
H
formaldehyde
a crossed polyol
HO
HO
phenol
HO
Mechanism
OH
O
H
+ H
O
H+
H
OH
O
+
OH
+
H O
H
HO
H
H
HO
OH
H
OH
HO
H
H
HO
H + H
H+
OH
HO
-H+
-H2O
OH
HO
OH
etc
HO
OH
H
H
CH 3
Cl
HO
OH
CH 3
epichlorohydrin
bisphenol-A
NaOH
50 - 100
Cl
CH 3
O
O
CH 3
Cl
O
Cl
H2C
HC
CH3
H2C
CH2 CH
CH2 Cl
CH3
O
H2C HC
CH3
H2 C
O
O
CH2 CH
CH2
CH 3
R
CH3
O
O
H2C HC
CH2 O
CH3
CH3
O
O
O
CH3
etc
CH2 CH
CH2 O
Epoxy glues often consist of two components which the user mixes just
before the desired "gluing " process. One component is the polymer shown
above. The other component is often ethylene diamine. Ethylene diamine
reacts with the epoxide "end" groups of the epoxy resin shown above to
effect ring opening to form amino alcohols. Each amino group can react with
two epoxide groups so that the resultant system is a network of cross-linked
polymers which have very strong adhesion properties. The process of
forming this network of cross-links is called "curing ".
OH
CH3
O
CH3
O
O
CH3
CH3
n
NH2
H2N
OH
OH
CH3
O
OH
CH3
O
O
CH3
CH3
N
N
HO
OH
O
O
H3C
H3C
CH3
OH
HO
H3C
H3C
CH3
O
O
HO
OH
CH3
CH3
Conducting Polymers
From the web site: Plastic polymers:
http://www.rsc.org/lap/educatio/eic/2003/higgins_may03.htm
Prior to the 1970s all synthetic polymers were insulated
Conjugated polyacetylene was one of the first conducting polymers
But hard to work with insoluble unstable, sensitive to oxygen.
Polythiophene and polyohenylevinylene less sensitive to oxygen
-- more stable long chain backbones could be attached to the polymers
to make them more soluble in non-polar solvents.
Why are they conducting? Large number of delocalized bonding
electrons allows movement along skeletal structure.
Conducting polymers (ICPs) have attracted much attention because of their potential applications in
organic light emitting diodes (OLEDs), printed circuits, chemical sensors, electronic switches,
rechargeable batteries, electrolytic capacitors, smart windows, EMI shielding and electrostatic charge
dissipation (ESD) coatings. In spite of the thousands of papers published and patents filed in this field,
the number of commercial applications of ICPs is still small. Poor long term stability and lack of
reasonable processing methods have been the major showstoppers to the commercialization of ICPs.
TDA's research on ICPs has focussed on improving the solvent processability of conducting polymers
with proven stability, including poly(3,4-ethylenedioxythiophene) (PEDOT) and polypyrrole.
Organic-Processable PEDOT:
Materials that combine electronic
conductivity with optical clarity are
sought for the fabrication of flat panel
displays and other electronic devices.
PEDOT has excellent transparency in the
visible region, good electrical
conductivity, and environmental
stability. Unfortunately PEDOT, like most
conducting polymers, is infusible and
insoluble and therefore difficult to
process in a thin-film form or in other
shapes. Lack of processability has been
a major impediment to the commercial
acceptance of this polymer. A water dispersion of PEDOT doped with
poly(styrenesulfonate) (PSS) is available from H.C. Starck under the trade name of
Baytron
Langmuir Trough
Amphiphilic Molecules (Soap)
connection between hydrophilic and
hydrophobic liquids
hydrophilic
hydrophobic
hydrophilic
Molecular Switch
One of the focuses of our research is the development of novel molecular
electronic devices. That is, devices made from a hybridization of conventional
semiconductor fabrication methods and self-assembling synthetic molecules
which have unique and useful electronic characteristics. We presently utilize a
break junction method for making two terminal electrical contact to single
molecule. We also have a method for making electrical contact to both sides of a
molecular SAM (self-Assembled Monolayer): the nanopore. Using these
measurement tools we have identified molecules which work well as insulators,
conductors, diodes, two-terminal switches and random access memory cells.
http://www.eng.yale.edu/reedlab/research/device/mol_devices.html#overview
Molecular Switch
The conduction path in a
conventional microelectronics
transistor
is turned on using an applied
voltage at the gate electrode.
Similarly, the conduction path
through a molecular switch is
turned on by an applied voltage.
The applied voltage is believed to
cause a conformational shift
which, in concert with the
charging of the molecule, opens
the conduction pathway.
NH2
O
S
CH3
O2N
http://www.eng.yale.edu/reedlab/research/device/mol_devices.html#overview
Illustration of an EAP-powered forceps. (a) forceps open; (b) forceps closes upon polarity reversal;
(c) and (d) lift action.
Upon the application of an electrical field across a moist EAP, which is held between metal electrodes
attached across a partial section of an EAP strip, bending of the EAP is induced. Positive counter
ions move towards the negative electrode (cathode), while negative ions that are fixed (or immobile)
to the polymer (e.g. SO3) experience an attractive force from the positive electrode (anode). At the
same time, water molecules in the EAP matrix diffuse towards the region of high positive ion
concentration (near the negative electrode) to equalize the charge distribution. As a result, the region
near the anode swells and the region near the cathode de-swells, leading to stresses which cause the
EAP strip to bend towards the positive anode.