Stereochemistry of Polymers
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Introduction
• The properties of a polymer are strongly influenced by its
molecular microstructure.
• Molecular microstructure:
I. The geometric and configurational arrangements of the
atoms in the repeat unit
II. The distribution of these different spatial arrangements for
the repeat units along the chain
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Tacticity of Polymers
• Chiral is the term used to describe objects which are non-
superimposable on their mirror image (e.g. human hands and
feet).
• The simplest chiral molecules
have an sp3-hybridized carbon
atom to which four different
groups are attached, which makes
the carbon atom asymmetric.
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• For polymers prepared from monomers of the general
structure CH 2=CXY, where X and Y are two different
substituent groups, there are two distinct configurational
arrangements of the repeat unit
• These two stereoisomers of the repeat unit cannot be
interchanged by bond rotation and exist because the
substituted sp3-hybridized carbon atom is asymmetric.
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• The existence of two isomeric forms of the repeat unit, and in
particular their distribution along the polymer chain, are of
great significance.
• Three stereochemical forms:
i. Isotactic polymers, all the repeat units have the same
configuration.
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ii. Syndiotactic polymers the configuration alternates from
one repeat unit to the next.
iii. Atactic polymers have an irregular or random placement
of the two configurations
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Tacticity of polypropylene PP (X = H, Y = CH 3):
• The commercial PP is essentially isotactic and due to its regular
structure is crystalline (~65%). It is the crystalline regions that
give rise to the good mechanical properties of commercial
polypropylene.
• In contrast, atactic polypropylene is unable to crystallize
because of its irregular structure and is a soft, wax-like
amorphous material which has no useful mechanical
properties.
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• Steric and/or electronic repulsion between similar substituent
groups results in a slight preference for syndiotactic rather than
isotactic placements.
• By reducing the reaction temperature, highly syndiotactic
polymers can be formed by ionic polymerization in a polar
solvent at low temperature (e.g. anionic polymerization of
methyl methacrylate initiated by 9-fluorenyllithium at −78 °C
in tetrahydrofuran).
• The relatively high temperatures normally employed for radical
polymerizations result in the formation of essentially atactic
polymers which, as a consequence of their irregular
microstructure, do not crystallize.
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• Highly isotactic polymers can be prepared by ionic
polymerization if there is strong coordination of the
counter-ion with the terminal units in the polymer chain and
with the incoming molecule of monomer.
• The complications of tacticity are absent in polymers prepared
from monomers of the type CH2=CX2 because they contain
no asymmetric backbone carbon atoms and therefore must be
stereoregular.
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Geometric Isomerism in Polymers
prepared from conjugated dienes
• The general structure of (1,3-dienes) CH2=CR─CH=CH2
• There are four basic modes for addition of such 1,3-dienes to
a growing polymer chain and these are shown in the next slide
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(for butadiene there are only three modes because the 1,2- and 3,4-
additions are identical since R = H).
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• Polyisoprene:
i. trans-1,4-polyisoprene, and due to their regular
structure are able to crystallize, which causes
them to be hard, rigid materials.
ii. natural rubber is cis-1,4-polyisoprene, which has
a less symmetrical structure that does not allow
easy crystallization under normal conditions and
so is an amorphous rubbery material.
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Molecular microstructures of butadiene and isoprene
homopolymers prepared using various polymerization conditions
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• Anionic polymerization in a non-polar solvent using Li+ as the
counter-ion leads to formation of polymers with high
proportions of cis-1,4 repeat units.
• Under these conditions, as the monomer adds to the growing
chain, it is held in the cisoid conformation by strong
coordination to the small Li+ counter-ion
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Ziegler–Natta coordination polymerization
• Coordination polymerisation is a form of polymerization
that is catalyzed by transition metal salts and complexes.
• The use of ionic polymerizations for preparation of highly
stereoregular polymers is restricted to specific monomers, in
particular polar monomers.
• This method require stronger coordination than can be
achieved with the counterions used in ionic polymerizations
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Stereochemistry and PE:
• Ziegler reported the preparation of linear polyethylene by
polymerization of ethylene using catalysts prepared from
aluminium alkyl compounds and transition metal halides.
• Natta quickly recognized, and pursued, the potential of this
new type of polymerization for the preparation of
stereoregular polymers. By slightly modifying the catalysts used
in Ziegler’s work, he was able to prepare highly isotactic linear
crystalline polymers from non-polar α-olefins (e.g. propylene).
• The enormous academic and industrial importance of these
discoveries was recognized in 1963 by the joint award to
Ziegler and Natta of the Nobel Prize for Chemistry.
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Ziegler–Natta Catalysts
• Ziegler–Natta catalysts involves reacting compounds
(commonly halides) of groups IV–VIII transition metals (e.g.
Ti, V, Cr, Zr) with organometallic compounds (e.g. alkyls, aryls
or hydrides) of groups I–III metals (e.g. Al, Mg, Li).
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• The catalysts which are useful for preparation of isotactic
polymers are heterogeneous.
• Ziegler–Natta catalysts that are soluble in the solvent in which
they are prepared (i.e. homogeneous) are of limited use
because in general they do not provide stereochemical control.
Exceptions:
i. Syndiotactic polypropylene can be prepared at low
temperatures (e.g. −78 °C) using soluble catalysts based
upon vanadium compounds (e.g. VCl4 + AlEt3).
ii. Benzyl derivatives of Ti and Zr have yielded isotactic
polypropylene but are of low activity.
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Heterogeneous
Ziegler–Natta catalysts
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Propagation: monomer insertion at group i–iii metal–
carbon bonds
• This proposed mechanism is a bimetallic mechanism
• An example is the mechanism proposed by Natta in which the
active site is an electron-deficient bridge complex formed by
reaction between a surface Ti atom and AlR3. Propagation may
be represented by
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• The proposed mechanism involves:
a. initial coordination of monomer to the Ti atom.
b. followed by cleavage of the Ti–C bridging bond and
polarization of the monomer in a six-membered cyclic
transition state.
c. The molecule of monomer then inserts into the Al–C bond
and the bridge reforms.
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Propagation: monomer insertion at transition metal–carbon
bonds
• A monometallic mechanism is the most widely accepted
mechanism in which propagation occurs by insertion of
monomer at transition metal–carbon bonds.
• They recognized that for electrical neutrality in α-TiCl3 crystals
the octahedrally coordinated surface Ti atoms must have Cl
vacancies (i.e. empty d-orbitals) and proposed that the active
sites are surface Ti atoms which have been alkylated by
reaction with AlR3.
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• The overall propagation reaction is represented by
• Details of the mechanism:
a. Coordination of the monomer at the vacant d-orbital.
b. Insertion of the monomer into the Ti–C bond via a cyclic
transition state and migration of the chain
“Since this requires the least movement of atoms. The
polymer chain then migrates back to its original position thus
preserving the stereochemical constraints associated with the
specific nature of the original active site at the catalyst
surface”
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• Termination of chain growth:
• Although there is no inherent termination reaction, several
types of transfer reaction are possible and these terminate the
growth of a propagating chain.
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T is a molecular fragment bonded to an active hydrogen atom.
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Metallocene Coordination
Polymerization
• Metallocenes are organometallic sandwich compounds of a
transition metal (Mt) with two cyclopentadienyl (Cp) anions
• The simplest metallocenes have the general structure Cp2Mt
• Examples:
ferrocene, where Mt = Fe and titanocene, where Mt = Ti
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• Metallocene derivatives are common and have additional
groups attached to the metal in a higher oxidation state and/or
the cyclopentadienyl ring (e.g. zirconocene dichloride
Cp2ZrCl2).
• Metallocene derivatives were first investigated as catalysts for
olefin polymerization during the period when Ziegler–Natta
polymerization was being developed, because they are soluble
(i.e. homogeneous catalysts) and easier to study.
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Metallocene Catalysts
• Titanocene and zirconocene derivatives have received most
attention as catalysts for effecting polymerization of olefins.
• The most important metallocene catalysts are based upon
zirconocene dichloride derivatives which are activated by
reaction with methylaluminoxane (MAO).
• MAO is formed by controlled hydrolysis of
trimethylaluminium and, although it is known to be oligomeric,
its precise structure has proven difficult to elucidate.
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• MAO is represented most commonly as a linear oligomer
where x ≈ 3–20.
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Mechanism of Polymerization with Zirconocene:
MAO Catalysts
• The catalyst sites are formed from zirconocene dichlorides by
methylation on reaction with MAO
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• MAO reacts further to activate the catalyst site by formation
of an ion pair that can exist as a solvent-separated ion pair
with strong coordination (and Covalent character)
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• Propagation proceeds by coordination of monomer to the
activated Zr atom, followed by insertion of monomer into the
Zr–C bond.
• Propagation is regioselective, with monomer molecules almost
always being inserted such that the methylene carbon atom
from the monomer is bonded to the Zr atom.
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• The mechanism involves:
i. An initial displacement of the counter-ion by coordinated
monomer
ii. Followed by monomer insertion through migration of the
existing chain because this minimizes the atomic movements
necessary for insertion
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Summary
• A metallocene is a positively charged metal ion
sandwiched between two negatively charged
cyclopentadienyl anions.
• Metallocene polymerization is also good for making
polymers of very specific tacticities.
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