Other polymerization techniques

By
Dr. Ajaya Kumar Behera
Asst. Prof., Dept. of Chemistry, U.U.
 Meta-thesis polymerization
It is of two types
Olefin Metathesis
Vinyl polymers don't often have double bonds in the polymer backbones (unless one monomer is butadiene, maybe). Now
we're going to talk about taking monomers with double bonds, and using them to make polymers with double bonds in the
backbone chain, without loss of the double bonds. We call these polymers polyalkenamers. One way to make polyalkenamers
to use a nifty reaction called "olefin metathesis."

Olefin is an old fashioned word, kind of like betwixt or forsooth. An olefin is the same thing as an alkene; that is, a molecule
with a carbon-carbon double bond. Olefin metathesis is (of course) a reaction involving olefins. Two olefins, to be exact. It
seems counter-intuitive but here's what they do: the double bond carbons change partners, to form two new olefins, just like in
the little picture here:
Acyclic Diene Metathesis Polymerization

The two different polymerizations are called ring opening metathesis polymerization, or ROMP, and acyclic diene metathesis
polymerization, or ADMET. We'll talk about ADMET first because it's simpler, even though ROMP has been more thoroughly
researched. In ADMET we start with an acyclic diene (surprise, surprise) such as 1,5-hexadiene, and end up with a polymer with
double bonds in the backbone chain at regular repeat sequences.

There's also the by-product, ethylene gas. Loss of ethylene helps drive the reaction to high molecular weight polymer (think:
thermodynamics). How does metathesis make this possible? I'll show you how, using the example of two molecules of 1,5-
hexadiene reacting together:
let's start with the first step, although it's actually the second one. The first involves formation of the metal complex that actually
does the initiation step. Anyway, click below to see the metal carbene (carbon double bond to the metal catalyst) approach and
bond to the terminal alkene (vinyl).

And the third step with new complex formation

Metathesis Polymerization #2:

We can get polymers from cyclic olefins, too. Look at the picture below, and you see that a cyclic olefin, cyclopentene in this
case, is used to make a polymer which doesn't have cyclic structures in its backbone.
 Ring-opening polymerization
In polymer chemistry, ring-opening polymerization (ROP) is a form of chain-growth polymerization, in which the terminus
of a polymer chain attacks cyclic monomers to form a longer polymer (see figure). The reactive center can be radical, anionic
or cationic. Some cyclic monomers such as norbornene or cyclooctadiene can be polymerized to high molecular weight
polymers by using metal catalysts. ROP is a versatile method for the synthesis of biopolymers. Ring-opening of cyclic
monomers is often driven by the relief of bond-angle strain. Thus, as is the case for other types of polymerization, the
enthalpy change in ring-opening is negative.
Cyclic monomers that are amenable to ROP include epoxides, cyclic trisiloxanes, some lactones, lactides, cyclic carbonates,
and amino acid N-carboxyanhydrides. Many strained cycloalkenes, e.g norbornene, are suitable monomers via ring-opening
metathesis polymerization.

Ring-opening polymerization can proceed via radical, anionic, or cationic polymerization as described below.[13] Additionally,
radical ROP is useful in producing polymers with functional groups incorporated in the backbone chain that cannot otherwise
be synthesized via conventional chain-growth polymerization of vinyl monomers. For instance, radical ROP can produce
polymers with ethers, esters, amides, and carbonates as functional groups along the main chain
Anionic ring-opening polymerizations (AROP) are involve
nucleophilic reagents as initiators. Monomers with a three-member
ring structure - such as epoxides, aziridines, and episulfides -
undergo anionic ROP.
A typical example of anionic ROP is that of ε-caprolactone, initiated
by an alkoxide
Cationic initiators and intermediates characterize cationic ring-
opening polymerization (CROP). Examples of cyclic monomers
that polymerize through this mechanism include lactones, The general mechanism for anionic ring-opening polymerization. Polarized
functional group is represented by X-Y, where the atom X (usually a carbon atom)
lactams, amines, and ethers. CROP proceeds through an SN1 or becomes electron deficient due to the highly electron-withdrawing nature of Y
SN2 propagation, chain-growth process. The mechanism is (usually an oxygen, nitrogen, sulfur, etc.). The nucleophile will attack atom X,
affected by the stability of the resulting cationic species. For thus releasing Y-. The newly formed nucleophile will then attack the atom X in
another monomer molecule, and the sequence would repeat until the polymer is
example, if the atom bearing the positive charge is stabilized by formed
electron-donating groups, polymerization will proceed by the
SN1 mechanism. The cationic species is a heteroatom and the
chain grows by the addition of cyclic monomers thereby
opening the ring system. The monomers can be activated by
Bronsted acids, carbenium ions, onium ions, and metal cations.

CROP can be a living polymerization and can be terminated by nucleophilic reagents such as phenoxy anions, phosphines, or
polyanions. When the amount of monomers becomes depleted, termination can occur intra or intermolecularly. The active end
can "backbite" the chain, forming a macrocycle. Alkyl chain transfer is also possible, where the active end is quenched by
transferring an alkyl chain to another polymer.
 In situ polymerization
In polymer chemistry, in situ polymerization is a preparation method that occurs "in the polymerization mixture" and is used to
develop polymer nanocomposites from nanoparticles. There are numerous unstable oligomers (molecules) which must be
synthesized in situ (i.e. in the reaction mixture but cannot be isolated on their own) for use in various processes. The in situ
polymerization process consists of an initiation step followed by a series of polymerization steps, which results in the formation
of a hybrid between polymer molecules and nanoparticles. Nanoparticles are initially spread out in a liquid monomer or a
precursor of relatively low molecular weight. Upon the formation of a homogenous mixture, initiation of the polymerization
reaction is carried out by addition of an adequate initiator, which is exposed to a source of heat, radiation, etc. After the
polymerization mechanism is completed, a nanocomposite is produced, which consists of polymer molecules bound to
nanoparticles.

Urea-formaldehyde (UF) and melamine formaldehyde (MF) encapsulation systems are other examples that utilize in situ
polymerization. In such type of in situ polymerization a chemical encapsulation technique is involved very similar to interfacial
coating. The distinguishing characteristic of in situ polymerization is that no reactants are included in the core material. All
polymerization occurs in the continuous phase, rather than on both sides of the interface between the continuous phase and the
core material. In situ polymerization of such formaldehyde systems usually involves the emulsification of an oil-phase in water.
 Then, water-soluble urea/melamine formaldehyde resin monomers are added, which are allowed to disperse. The initiation step
occurs when acid is added to lower the pH of the mixture. Crosslinking of the resins completes the polymerization process and
results in a shell of polymer-encapsulated oil droplets.
Applications
Recent improvements in the in situ polymerization process have led to the production of polymer-carbon nanotube composites
with enhanced mechanical properties. With regards to their energy-related applications, carbon nanotubes have been used to
make electrodes, with one specific example being the CNT/PMMA composite electrode.[5][6] In situ polymerization has been
studied to streamline the construction process of such electrodes.[5][6] Huang, Vanhaecke, and Chen found that in situ
polymerization can potentially produce composites of conductive CNTs on a grand scale.[6] Some aspects of in situ
polymerization that can help achieve this feat are that it is cost effective with regards to operation, requires minimal sample,
has high sensitivity, and offers many promising environmental and bioanlaytical applications.
Advantages and Disadvantages
There are several advantages of the in situ polymerization process, which include the use of cost-effective materials, being easy
to automate, and the ability to integrate with many other heating and curing methods. Some downsides of this preparation
method, however, include limited availability of usable materials, a short time period to execute the polymerization process, and
expensive equipment is required.
Advantages of In Situ Polymerization Using CNT
In situ polymerization offers several advantages in the preparation of polymer grafted nanotubes compared to other methods.
First and foremost, it allows polymer macromolecules to attach to CNT walls. Additionally, the resulting composite is
miscible with most types of polymers.[4] Unlike solution or melt processing, in situ polymerization can prepare insoluble and
thermally unstable polymers. Lastly, in situ polymerization can achieve stronger covalent interactions between polymer and
CNTs earlier in the process.

Plasma polymerization
Plasma polymerization (or glow discharge polymerization) uses plasma sources to generate a gas discharge that provides
energy to activate or fragment gaseous or liquid monomer, often containing a vinyl group, in order to initiate polymerization.
Polymers formed from this technique are generally highly branched and highly cross-linked, and adhere to solid surfaces
well. The biggest advantage to this process is that polymers can be directly attached to a desired surface while the chains are
growing, which reduces steps necessary for other coating processes such as grafting. This is very useful for pinhole-free
coatings of 100 picometers to 1 micrometre thickness with solvent insoluble polymers.
 Basic operating mechanism
Glow discharge
Plasma consists of a mixture of electrons, ions, radicals, neutrals and photons.
Some of these species are in local thermodynamic equilibrium, while others are
not. Even for simple gases like argon this mixture can be complex. For plasmas
of organic monomers, the complexity can rapidly increase as some components
of the plasma fragment, while others interact and form larger species. Glow
discharge is a technique in polymerization which forms free electrons which
gain energy from an electric field, and then lose energy through collisions with
neutral molecules in the gas phase. This leads to many chemically reactive
species, which then lead to a plasma polymerization reaction.[6] The electric
discharge process for plasma polymerization is the "low-temperature plasma"
method, because higher temperatures cause degradation. These plasmas are
formed by a direct current, alternating current or radio frequency generator
Common monomers/polymers
Monomers
As can be seen in the monomer table, many simple monomers are readily polymerized by this method, but most must be
smaller ionizable species because they have to be able to go into the plasma state. Though monomers with multiple bonds
polymerize readily, it is not a necessary requirement, as ethane, silicones and many others polymerize also. There are also other
stipulations that exist. Yasuda et al. studied 28 monomers and found that those containing aromatic groups, silicon, olefinic
group or nitrogen (NH, NH2, CN) were readily polymerizable, while those containing oxygen, halides, aliphatic hydrocarbons
and cyclic hydrocarbons were decomposed more readily. The latter compounds have more ablation or side reactions present,
which inhibit stable polymer formation. It is also possible to incorporate N2, H2O, and CO into copolymers of styrene.

Plasma polymers can be thought of as a type of graft polymers since they are grown off of a substrate. These polymers are
known to form nearly uniform surface deposition, which is one of their desirable properties. Polymers formed from this process
often cross-link and form branches due to the multiple propagating species present in the plasma. This often leads to very
insoluble polymers, which gives an advantage to this process, since hyperbranched polymers can be deposited directly without
solvent.
Polymers
Common polymers include: polythiophene, polyhexafluoropropylene, polytetramethyltin, polyhexamethyldisiloxane,
polytetramethyldisiloxane, polypyridine, polyfuran, and poly-2-methyloxazoline.
They are : polystyrene, polymethyl styrene, polycyclopentadiene, polyacrylate, polyethyl acrylate, polymethyl methacrylate,
polyvinyl acetate, polyisoprene, polyisobutene, and polyethylene.
Nearly all polymers created by this method have excellent appearance, are clear, and are significantly cross-linked. Linear
polymers are not formed readily by plasma polymerization methods based on propagating species. Many other polymers could
be formed by this method.
General characteristics of plasma polymers

The properties of plasma polymers differ greatly from those of conventional polymers. While both types are dependent on the
chemical properties of the monomer, the properties of plasma polymers depend more greatly on the design of the reactor and the
chemical and physical characteristics of the substrate on which the plasma polymer is deposited.[7] The location within the
reactor where the deposition occurs also has an effect on the resultant polymer's properties. In fact, by using plasma
polymerization with a single monomer and varying the reactor, substrate, etc. a variety of polymers, each having different
physical and chemical properties, can be prepared.[7] The large dependence of the polymer features on these factors make it
difficult to assign a set of basic characteristics, but a few common properties that set plasma polymers apart from conventional
polymers do exist.
The most significant difference between conventional polymers and plasma polymers is that plasma polymers do not contain
regular repeating units. Due to the number of different propagating species present at any one time as discussed above, the
resultant polymer chains are highly branched and are randomly terminated with a high degree of cross-linking.
All plasma polymers contain free radicals as well. Plasma polymers also contain an internal stress.
The degree of curling is dependent on the monomer as well as the conditions of the plasma polymerization. Most plasma
polymers are insoluble and infusible. These properties are due to the large amount of cross-linking in the polymers, previously
discussed. Consequently, the kinetic path length for these polymers must be sufficiently long, so these properties can be
controlled to a point.
The permeabilities of plasma polymers also differ greatly from those of conventional polymers. Because of the absence of
large-scale segmental mobility and the high degree of cross-linking within the polymers, the permeation of small molecules
does not strictly follow the typical mechanisms of "solution-diffusion" or molecular-level sieve for such small permeants.
Really the permeability characteristics of plasma polymers falls between these two ideal cases.
A final common characteristic of plasma polymers is the adhesion ability. The specifics of the adhesion ability for a given
plasma polymer, such the surface layer, again are particular for a given plasma polymer and few generalizations can be made. as
thickness and characteristics of
Advantages
 The most significant advantage of plasma polymerization is its ability to produce polymer films of organic compounds that
do not polymerize under normal chemical polymerization conditions.
 Nearly all monomers, even saturated hydrocarbons and organic compounds without a polymerizable structure such as a
double bond, can be polymerized with this technique
 A second advantage is the ease of application of the polymers as coatings versus conventional coating processes. While
coating a substrate with conventional polymers requires a number of steps, plasma polymerization accomplishes all these in
essentially a single step.
 This leads to a cleaner and 'greener' synthesis and coating process, since no solvent is needed during the polymer preparation
and no cleaning of the resultant polymer is needed either.
 Another 'green' aspect of the synthesis is that no initiator is needed for the polymer preparation since reusable electrodes
cause the reaction to proceed. The resultant polymer coatings also have a number of advantages over typical coatings.
 These advantages include being nearly pinhole-free, highly dense, and that the thickness of the coating can easily be varied.
Disadvantages
 The most significant disadvantage is the high cost of the process. A vacuum system is required for the polymerization,
significantly increasing the set up price
 Another disadvantage is due to the complexity of plasma processes. Because of the complexity it is not easy to achieve a
good control over the chemical composition of the surface after modification.
 The influence of process parameters on the chemical composition of the resultant polymer means it can take a long time to
determine the optimal conditions.
 The complexity of the process also makes it impossible to theorize what the resultant polymer will look like, unlike
conventional polymers which can be easily determined based on the monomer.
 Applications
 Plasma-polymerized films have also found electrical applications.
 Given that plasma polymers frequently contain many polar groups, which form when the radicals react with oxygen in air
during the polymerization process, the plasma polymers were expected to be good dielectric materials in thin film form.
Studies have shown that the plasma polymers generally do in fact have a higher dielectric property.
 Some plasma polymers have been applied as chemical sensory devices due to their electrical properties.
 Plasma polymers have been studied as chemical sensory devices for humidity, propane, and carbon dioxide amongst others.
Thus far issues with instability against aging and humidity have limited their commercial applications.
 The application of plasma polymers as coatings has also been studied.
 The use of plasma polymers to coat plastic lenses is increasing in popularity.
 Plasma polymers formed from tetramethoxysilane have been studied as protective coatings and have shown to increase the
hardness of polyethylene and polycarbonate.
 Plasma polymer surfaces with tunable wettability and reversibly switchable pH-responsiveness have shown the promising
prospects due to their unique property in applications, such as drug delivery, biomaterial engineering, oil/water separation
processes, sensors, and biofuel cells
 Chain-transfer polymerization
Chain transfer is a polymerization reaction by which the activity of a growing polymer chain is transferred to another molecule.

P• + XR' → PX + R'•
Chain transfer reactions reduce the average molecular weight of the final polymer. Chain transfer can be either introduced
deliberately into a polymerization (by use of a chain transfer agent) or it may be an unavoidable side-reaction with various
components of the polymerization. Chain transfer reactions occur in most forms of addition polymerization including radical
polymerization, ring-opening polymerization, coordination polymerization, and cationic polymerization, as well as anionic
polymerization.
Types
Chain transfer reactions are usually categorized by the nature of the molecule that reacts with the growing chain.
Transfer to chain transfer agent: Chain transfer agents have at least one weak chemical bond, which therefore facilitates the
chain transfer reaction. Common chain transfer agents include thiols, especially dodecyl mercaptan (DDM), and halocarbons
such as carbon tetrachloride. Chain transfer agents are sometimes called modifiers or regulators.
Transfer to monomer: Chain transfer to monomer may take place in which the growing polymer chain abstracts an atom from
unreacted monomer existing in the reaction medium. Because, by definition, polymerization reactions only take place in the
presence of monomer, chain transfer to monomer determines the theoretical maximum molecular weight that can be achieved
by a given monomer. Chain transfer to monomer is especially significant in cationic addition polymerization and ring-opening
polymerization.
Transfer to polymer: Chain transfer may take place with an already existing polymer chain, especially under conditions in
which much polymer is present. This often occurs at the end of a radical polymerization when almost all monomer has been
consumed. Branched polymers are formed as monomer adds to the new radical site which is located along the polymer
backbone. The properties of low-density polyethylene are critically determined by the amount of chain transfer to polymer
that takes place.

Transfer to solvent. In solution polymerization, the solvent can act as a chain transfer agent. Unless the solvent is chosen
to be inert, very low molecular weight polymers (oligomers) can result.
 Ziegler-Natta polymerization of ethylene
The Ziegler-Natta polymerization of ethylene. Ethylene gas is pumped under pressure into a reaction vessel, where it
polymerizes under the influence of a Ziegler-Natta catalyst in the presence of a solvent. A slurry of polyethylene, unreacted
ethylene monomer, catalyst, and solvent exit the reactor. Unreacted ethylene is separated and returned to the reactor, while the
catalyst is neutralized by an alcohol wash and filtered out. Excess solvent is recovered from a hot water bath and recycled, and a
dryer dehydrates the wet polyethylene to its final powder form.
 Unit -1
Importance of Polymers Basic concepts: Monomers, repeat units, degree of polymerization, Linear, branched and network
polymers. Classification of Polymers. Polymerization condensation, addition, radical chain-ionic and co-ordination and co-
polymerization. Polymerization conditions and polymer reactions. Polymerization in homogeneous and heterogeneous
systems.
Polymer Characterization
Polydispersion-average molecular weight concept. Number, weight and viscocity average molecular weights.
Polydispersity and molecular weight distribution. The practical significance of molecular weight. Measurement of
molecular weights. End-group, viscosity, light scattering, osmotic and ultracentrifugation methods. Analysis and testing of
polymers-chemical analysis of polymers, spectroscopic methods, X-ray diffraction study Microscopy. Thermal analysis and
physical testing-tensile strength. Fatigue, impact. Tear resistance. Hardness and abrasion resistance.