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polymer chemistry Polymer chemistry is a sub-discipline of chemistry that focuses on the structures of chemicals, chemical synthesis, and chemical and physical properties of polymers and macromolecules. The principles and methods used within polymer chemistry ar ...
, living polymerization is a form of chain growth polymerization where the ability of a growing
polymer chain A polymer (; Greek '' poly-'', "many" + ''-mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
to terminate has been removed. This can be accomplished in a variety of ways. Chain termination and chain transfer reactions are absent and the rate of chain initiation is also much larger than the rate of
chain propagation Chain propagation (sometimes referred to as propagation) is a process in which a reactive intermediate is continuously regenerated during the course of a chemical chain reaction. For example, in the chlorination of methane, there is a two-step ...
. The result is that the polymer chains grow at a more constant rate than seen in traditional chain
polymerization In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many f ...
and their lengths remain very similar (i.e. they have a very low polydispersity index). Living polymerization is a popular method for synthesizing block copolymers since the polymer can be synthesized in stages, each stage containing a different
monomer In chemistry, a monomer ( ; '' mono-'', "one" + '' -mer'', "part") is a molecule that can react together with other monomer molecules to form a larger polymer chain or three-dimensional network in a process called polymerization. Classification ...
. Additional advantages are predetermined molar mass and control over end-groups. Living polymerization is desirable because it offers precision and control in macromolecular synthesis. This is important since many of the novel/useful properties of polymers result from their microstructure and molecular weight. Since
molecular weight A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bio ...
and dispersity are less controlled in non-living polymerizations, this method is more desirable for materials design In many cases, living polymerization reactions are confused or thought to be synonymous with controlled polymerizations. While these polymerization reactions are very similar, there is a distinction between the definitions of these two reactions. While living polymerizations are defined as polymerization reactions where termination or chain transfer is eliminated, controlled polymerization reactions are reactions where termination is suppressed, but not eliminated, through the introduction of a dormant state of the polymer. However, this distinction is still up for debate in the literature. The main living polymerization techniques are: * Living anionic polymerization * Living cationic polymerization * Living
ring-opening metathesis polymerization Ring-opening metathesis polymerization (ROMP) is a type of olefin metathesis chain-growth polymerization. The driving force of the reaction is relief of ring strain in cyclic olefins (e.g. norbornene or cyclopentene). A variety of heterogeneous ...
* Living free radical polymerization * Living chain-growth polycondensations


History

Living polymerization was demonstrated by Michael Szwarc in 1956 in the anionic polymerization of styrene with an
alkali metal The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...
/
naphthalene Naphthalene is an organic compound with formula . It is the simplest polycyclic aromatic hydrocarbon, and is a white crystalline solid with a characteristic odor that is detectable at concentrations as low as 0.08  ppm by mass. As an aromat ...
system in
tetrahydrofuran Tetrahydrofuran (THF), or oxolane, is an organic compound with the formula (CH2)4O. The compound is classified as heterocyclic compound, specifically a cyclic ether. It is a colorless, water- miscible organic liquid with low viscosity. It is ...
(THF). Szwarc showed that electron transfer occurred from radical anion of
naphthalene Naphthalene is an organic compound with formula . It is the simplest polycyclic aromatic hydrocarbon, and is a white crystalline solid with a characteristic odor that is detectable at concentrations as low as 0.08  ppm by mass. As an aromat ...
to styrene. The initial radical anion of styrene converts to a
dianion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by con ...
(or equivalently disodio-) species, which rapidly added styrene to form a "two – ended living polymer." An important aspect of his work, Szwarc employed the
aprotic solvent A polar aprotic solvent is a solvent that lacks an acidic proton and is polar. Such solvents lack hydroxyl and amine In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Am ...
tetrahydrofuran Tetrahydrofuran (THF), or oxolane, is an organic compound with the formula (CH2)4O. The compound is classified as heterocyclic compound, specifically a cyclic ether. It is a colorless, water- miscible organic liquid with low viscosity. It is ...
, which dissolves but is otherwise unreactive toward the organometallic intermediates. After initial addition of monomer to the initiator system, the
viscosity The viscosity of a fluid is a measure of its resistance to deformation at a given rate. For liquids, it corresponds to the informal concept of "thickness": for example, syrup has a higher viscosity than water. Viscosity quantifies the int ...
increased (due to increased polymer chain growth), but eventually cease after depletion of monomer concentration. However, he found that addition of ''more'' monomer caused an increase in viscosity, indicating growth of the polymer chain, and thus concluded that the polymer chains had never been terminated. This was a major step in polymer chemistry, since control over when the polymer was quenched, or terminated, was generally not a controlled step. With this discovery, the list of potential applications expanded dramatically. Today, living polymerizations are used widely in the production of many types of polymers or plastics. The approach offers control of the chemical makeup of the polymer and, thus, the structural and electronic properties of the material. This level of control rarely exists in non-living polymerization reactions.


Fast rate of initiation: low polydispersity

One of the key characteristics of a living polymerization is that the chain termination and transfer reactions are essentially eliminated from the four elementary reactions of
chain-growth polymerization Chain-growth polymerization ( AE) or chain-growth polymerisation ( BE) is a polymerization technique where unsaturated monomer molecules add onto the active site on a growing polymer chain one at a time. There are a limited number of these acti ...
leaving only
initiation Initiation is a rite of passage marking entrance or acceptance into a group or society. It could also be a formal admission to adulthood in a community or one of its formal components. In an extended sense, it can also signify a transformation ...
and (chain) propagation reactions. A key characteristic of living polymerization is that the rate of initiation (meaning the dormant chemical species generates the active chain propagating species) is much faster than the rate of chain propagation. Thus all of the chains grow at the same rate (the rate of propagation). The high rate of initiation (together with absence of termination) results in low (or narrow) polydispersity index (PDI), an indication of the broadness in the distribution of polymer chains
Living polymers
The extended lifetime of the propagating chain allowing for co-block polymer formation and end group functionalization to be performed on the living chain. These factors also allow predictable molecular weights, expressed as the number average molecular weight (Mn). For an ideal living system, assuming efficiency for generating active species is 100%, where each initiator generates only one active species the Kinetic chain length (average number of monomers the active species reacts with during its lifetime) at a given time can be estimated by knowing the concentration of monomer remaining. The number average molecular weight, Mn, increases linearly with percent conversion during a living polymerization :\ v = \frac


Techniques


Living anionic polymerization

As early as 1936,
Karl Ziegler Karl Waldemar Ziegler (26 November 1898 – 12 August 1973) was a German chemist who won the Nobel Prize in Chemistry in 1963, with Giulio Natta, for work on polymers. The Nobel Committee recognized his "excellent work on organometallic compound ...
proposed that anionic polymerization of styrene and butadiene by consecutive addition of monomer to an alkyl lithium initiator occurred without chain transfer or termination. Twenty years later, living polymerization was demonstrated by Szwarc through the anionic polymerization of styrene in
THF Tetrahydrofuran (THF), or oxolane, is an organic compound with the formula (CH2)4O. The compound is classified as heterocyclic compound, specifically a cyclic ether. It is a colorless, water-miscible organic liquid with low viscosity. It is ma ...
using sodium naphthalene as an initiator. The naphthalene anion initiates polymerization by reducing styrene to its radical anion, which dimerizes to the dilithiodiphenylbutane, which then initiates the polymerization. These experiments relied on Szwarc's ability to control the levels of impurities which would destroy the highly reactive organometallic intermediates.


Living α-olefin polymerization

α-olefins can be polymerized through an anionic coordination polymerization in which the metal center of the catalyst is considered the counter cation for the anionic end of the alkyl chain (through a M-R coordination). Ziegler-Natta initiators were developed in the mid-1950s and are heterogeneous initiators used in the polymerization of alpha-olefins. Not only were these initiators the first to achieve relatively high molecular weight poly(1-alkenes) (currently the most widely produced thermoplastic in the world PE(
Polyethylene Polyethylene or polythene (abbreviated PE; IUPAC name polyethene or poly(methylene)) is the most commonly produced plastic. It is a polymer, primarily used for packaging ( plastic bags, plastic films, geomembranes and containers including b ...
) and PP (
Polypropylene Polypropylene (PP), also known as polypropene, is a thermoplastic polymer used in a wide variety of applications. It is produced via chain-growth polymerization from the monomer propylene. Polypropylene belongs to the group of polyolefins a ...
) but the initiators were also capable of stereoselective polymerizations which is attributed to the chiral
Crystal structure In crystallography, crystal structure is a description of the ordered arrangement of atoms, ions or molecules in a crystalline material. Ordered structures occur from the intrinsic nature of the constituent particles to form symmetric pattern ...
of the heterogeneous initiator. Due to the importance of this discovery Ziegler and Natta were presented with th
1963 Nobel Prize in chemistry
Although the active species formed from the Ziegler-Natta initiator generally have long lifetimes (on the scale of hours or longer) the lifetimes of the propagating chains are shortened due to several chain transfer pathways (
Beta-Hydride elimination β-Hydride elimination is a reaction in which an alkyl group bonded to a metal centre is converted into the corresponding metal-bonded hydride and an alkene. The alkyl must have hydrogens on the β-carbon. For instance butyl groups can undergo th ...
and transfer to the co-initiator) and as a result are not considered living. Metallocene initiators are considered as a type of Ziegler-Natta initiators due to the use of the two-component system consisting of a
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that can ...
and a group I-III metal co-initiator (for example methylalumoxane (MAO) or other alkyl aluminum compounds). The metallocene initiators form homogeneous single site
catalyst Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
s that were initially developed to study the impact that the catalyst structure had on the resulting polymers structure/properties; which was difficult for multi-site heterogeneous Ziegler-Natta initiators. Owing to the discrete single site on the metallocene catalyst researchers were able to tune and relate how the ancillary ligand (those not directly involved in the chemical transformations) structure and the symmetry about the chiral metal center affect the microstructure of the polymer. However, due to chain breaking reactions (mainly Beta-Hydride elimination) very few metallocene based polymerizations are known. By tuning the steric bulk and electronic properties of the ancillary ligands and their
substituent A substituent is one or a group of atoms that replaces (one or more) atoms, thereby becoming a moiety in the resultant (new) molecule. (In organic chemistry and biochemistry, the terms ''substituent'' and ''functional group'', as well as '' side ...
s a class of initiators known as chelate initiators (or post-metallocene initiators) have been successfully used for
stereospecific In chemistry, stereospecificity is the property of a reaction mechanism that leads to different stereoisomeric reaction products from different stereoisomeric reactants, or which operates on only one (or a subset) of the stereoisomers."Overlap Con ...
living polymerizations of alpha-olefins. The chelate initiators have a high potential for living polymerizations because the ancillary ligands can be designed to discourage or inhibit chain termination pathways. Chelate initiators can be further broken down based on the ancillary ligands; ansa-cyclopentyadienyl-amido initiators, alpha-diimine chelates and phenoxy-imine chelates. *Ansa-cyclopentadienyl-amido (CpA) initiators CpA initiators have one
cyclopentadienyl Cyclopentadienyl can refer to * Cyclopentadienyl anion, or cyclopentadienide, ** Cyclopentadienyl ligand * Cyclopentadienyl radical, • * Cyclopentadienyl cation, See also * Pentadienyl {{Chemistry index ...
substituent and one or more nitrogen substituents coordinated to the metal center (generally a Zr or Ti) (Odian). The dimethyl(pentamethylcyclopentyl)zirconium acetamidinate in figure___ has been used for a stereospecific living polymerization of 1-hexene at −10 °C. The resulting poly(1-hexene) was
isotactic Tacticity (from el, τακτικός, taktikos, "relating to arrangement or order") is the relative stereochemistry of adjacent chiral centers within a macromolecule. The practical significance of tacticity rests on the effects on the physical p ...
(stereochemistry is the same between adjacent repeat units) confirmed by 13C-NMR. The multiple trials demonstrated a controllable and predictable (from catalyst to
monomer In chemistry, a monomer ( ; '' mono-'', "one" + '' -mer'', "part") is a molecule that can react together with other monomer molecules to form a larger polymer chain or three-dimensional network in a process called polymerization. Classification ...
ratio) Mn with low Đ. The polymerization was further confirmed to be living by sequentially adding 2 portions of the monomer, the second portion was added after the first portion was already polymerized, and monitoring the Đ and Mn of the chain. The resulting polymer chains complied with the predicted Mn (with the total monomer concentration = portion 1 +2) and showed low Đ suggesting the chains were still active, or living, as the second portion of monomer was added (5). *α-diimine chelate initiators α-diimine chelate initiators are characterized by having a
diimine Diimines are organic compounds containing two imine (RCH=NR') groups. Common derivatives are 1,2-diketones and 1,3-diimines. These compounds are used as ligands and as precursors to heterocycles. Diimines are prepared by condensation reactio ...
chelating ancillary ligand structure and which is generally coordinated to a late transition (i.e. Ni and Pd) metal center. Brookhart et al. did extensive work with this class of catalysts and reported living polymerization for α-olefins and demonstrated living α-olefin carbon monoxide alternating copolymers.


Living cationic polymerization

Monomers for living cationic polymerization are electron-rich alkenes such as vinyl ethers,
isobutylene Isobutylene (or 2-methylpropene) is a hydrocarbon with the chemical formula . It is a four-carbon branched alkene (olefin), one of the four isomers of butylene. It is a colorless flammable gas, and is of considerable industrial value. Producti ...
, styrene, and N-vinylcarbazole. The initiators are binary systems consisting of an electrophile and a Lewis acid. The method was developed around 1980 with contributions from Higashimura, Sawamoto and Kennedy. Typically, generating a stable carbocation for a prolonged period of time is difficult, due to the possibility for the cation to be quenched by a β-protons attached to another monomer in the backbone, or in a free monomer. Therefore, a different approach is taken In this example, the carbocation is generated by the addition of a Lewis acid (co-initiator, along with the halogen "X" already on the polymer – see figure), which ultimately generates the carbocation in a weak equilibrium. This equilibrium heavily favors the dormant state, thus leaving little time for permanent quenching or termination by other pathways. In addition, a weak nucleophile (Nu:) can also added to reduce the concentration of active species even further, thus keeping the polymer "living". However, it is important to note that by definition, the polymers described in this example are not technically living due to the introduction of a dormant state, as termination has only been decreased, not eliminated (though this topic is still up for debate). But, they do operate similarly, and are used in similar applications to those of true living polymerizations.


Living ring-opening metathesis polymerization

Given the right reaction conditions
ring-opening metathesis polymerization Ring-opening metathesis polymerization (ROMP) is a type of olefin metathesis chain-growth polymerization. The driving force of the reaction is relief of ring strain in cyclic olefins (e.g. norbornene or cyclopentene). A variety of heterogeneous ...
(ROMP) can be rendered living. The first such systems were described by
Robert H. Grubbs Robert Howard Grubbs ForMemRS (February 27, 1942 – December 19, 2021) was an American chemist and the Victor and Elizabeth Atkins Professor of Chemistry at the California Institute of Technology in Pasadena, California. He was a co-recipient ...
in 1986 based on
norbornene Norbornene or norbornylene or norcamphene is a highly strained bridged cyclic hydrocarbon. It is a white solid with a pungent sour odor. The molecule consists of a cyclohexene ring with a methylene bridge between carbons 1 and 4. The molecule car ...
and Tebbe's reagent and in 1978 Grubbs together with Richard R. Schrock describing living polymerization with a
tungsten Tungsten, or wolfram, is a chemical element with the symbol W and atomic number 74. Tungsten is a rare metal found naturally on Earth almost exclusively as compounds with other elements. It was identified as a new element in 1781 and first isol ...
carbene complex. Generally, ROMP reactions involve the conversion of a cyclic olefin with significant ring-strain (>5 kcal/mol), such as cyclobutene, norbornene, cyclopentene, etc., to a polymer that also contains double bonds. The important thing to note about ring-opening metathesis polymerizations is that the double bond is usually maintained in the backbone, which can allow it to be considered "living" under the right conditions. For a ROMP reaction to be considered "living", several guidelines must be met: # Fast and complete initiation of the monomer. This means that the rate at which an initiating agent activates the monomer for polymerization, must happen very quickly. # How many monomers make up each polymer (the degree of polymerization) must be related linearly to the amount of monomer you started with. # The dispersity of the polymer must be < 1.5. In other words, the distribution of how long your polymer chains are in your reaction must be very low. With these guidelines in mind, it allows you to create a polymer that is well controlled both in content (what monomer you use) and properties of the polymer (which can be largely attributed to polymer chain length). It is important to note that living ring-opening polymerizations can be anionic ''or'' cationic. Because living polymers have had their termination ability removed, this means that once your monomer has been consumed, the addition of more monomer will result in the polymer chains continuing to grow until all of the additional monomer is consumed. This will continue until the metal catalyst at the end of the chain is intentionally removed by the addition of a quenching agent. As a result, it may potentially allow one to create a block or gradient copolymer fairly easily and accurately. This can lead to a high ability to tune the properties of the polymer to a desired application (electrical/ionic conduction, etc.)


"Living" free radical polymerization

Starting in the 1970s several new methods were discovered which allowed the development of living polymerization using free radical chemistry. These techniques involved catalytic chain transfer polymerization, iniferter mediated polymerization, stable free radical mediated polymerization (SFRP), atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer ( RAFT) polymerization, and iodine-transfer polymerization. In "living" radical polymerization (or controlled radical polymerization (CRP)) the chain breaking pathways are severely depressed when compared to conventional radical polymerization (RP) and CRP can display characteristics of a living polymerization. However, since chain termination is not absent, but only minimized, CRP technically does not meet the requirements imposed by IUPAC for a living polymerization (see introduction for IUPAC definition). This issue has been up for debate the view points of different researchers can be found in a special issue of the Journal of Polymer Science titled
Living or Controlled ?
The issue has not yet been resolved in the literature so it is often denoted as a "living" polymerization, quasi-living polymerization, pseudo-living and other terms to denote this issue. There are two general strategies employed in CRP to suppress chain breaking reactions and promote fast initiation relative to propagation. Both strategies are based on developing a dynamic equilibrium amongst an active propagating radical and a dormant species. The first strategy involves a reversible trapping mechanism in which the propagating radical undergoes an activation/deactivation (i.e. Atom-transfer radical-polymerization) process with a species X. The species X is a persistent radical, or a species that can generate a stable radical, that cannot terminate with itself or propagate but can only reversibly "terminate" with the propagating radical (from the propagating polymer chain) P*. P* is a radical species that can propagate (kp) and irreversibly terminate (kt) with another P*. X is normally a nitroxide (i.e.
TEMPO In musical terminology, tempo ( Italian, 'time'; plural ''tempos'', or ''tempi'' from the Italian plural) is the speed or pace of a given piece. In classical music, tempo is typically indicated with an instruction at the start of a piece (ofte ...
used in Nitroxide Mediated Radical Polymerization) or an organometallic species. The dormant species (Pn-X) can be activated to regenerate the active propagating species (P*) spontaneously, thermally, using a catalyst and optically. The second strategy is based on a degenerative transfer (DT) of the propagating radical between transfer agent that acts as a dormant species (i.e. Reversible addition−fragmentation chain-transfer polymerization). The DT based CRP's follow the conventional kinetics of radical polymerization, that is slow initiation and fast termination, but the transfer agent (Pm-X or Pn-X) is present in a much higher concentration compared to the radical initiator. The propagating radical species undergoes a thermally neutral exchange with the dormant transfer agent through atom transfer, group transfer or addition fragment chemistry.


Living chain-growth polycondensations

Chain growth polycondensation polymerizations were initially developed under the premise that a change in substituent effects of the polymer, relative to the monomer, causes the polymers end group to be more reactive this has been referred to as "reactive intermediate polycondensation". The essential result is monomers preferentially react with the activated polymer end groups over reactions with other monomers. This preferred reactivity is the fundamental difference when categorizing a polymerization mechanism as chain-growth as opposed to step-growth in which the monomer and polymer chain end group have equal reactivity (the reactivity is uncontrolled). Several strategies were employed to minimize monomer-monomer reactions (or self-condensation) and polymerizations with low D and controllable Mn have been attained by this mechanism for small molecular weight polymers. However, for high molecular weight polymer chains (i.e. small initiator to monomer ratio) the Mn is not easily to controlled, for some monomers, since self-condensation between monomers occurred more frequently due to the low propagating species concentration.


Catalyst-transfer polycondensation

Catalyst transfer polycondensation (CTP) is a chain-growth polycondensation mechanism in which the monomers do not directly react with one another and instead the monomer will only react with the polymer end group through a catalyst-mediated mechanism. The general process consists of the catalyst activating the polymer end group followed by a reaction of the end group with a 2nd incoming monomer. The catalyst is then transferred to the elongated chain while activating the end group (as shown below). Catalyst transfer polycondensation allows for the living polymerization of π-conjugated polymers and was discovered by Tsutomu Yokozawa in 2004 and Richard McCullough. In CTP the propagation step is based on organic cross coupling reactions (i.e. Kumada coupling,
Sonogashira coupling The Sonogashira reaction is a cross-coupling reaction used in organic synthesis to form carbon–carbon bonds. It employs a palladium catalyst as well as copper co-catalyst to form a carbon–carbon bond between a terminal alkyne and an aryl or vi ...

Negishi coupling
top form carbon carbon bonds between difunctional monomers. When Yokozawa and McCullough independently discovered the polymerization using a metal catalyst to couple a
Grignard reagent A Grignard reagent or Grignard compound is a chemical compound with the general formula , where X is a halogen and R is an organic group, normally an alkyl or aryl. Two typical examples are methylmagnesium chloride and phenylmagnesium bromide . ...
with an organohalide making a new carbon-carbon bond. The mechanism below shows the formation of poly(3-alkylthiophene) using a Ni initiator (Ln can be 1,3-Bis(diphenylphosphino)propane (dppp)) and is similar to the conventional mechanism for Kumada coupling involving an oxidative addition, a
transmetalation Transmetalation (alt. spelling: transmetallation) is a type of organometallic reaction that involves the transfer of ligands from one metal to another. It has the general form: :M1–R + M2–R′ → M1–R′ + M2–R where R and R′ can be, but ...
and a reductive elimination step. However, there is a key difference, following reductive elimination in CTP, an associative complex is formed (which has been supported by intra-/intermolecular oxidative addition competition experiments) and the subsequent oxidative addition occurs between the metal center and the associated chain (an intramolecular pathway). Whereas in a coupling reaction the newly formed alkyl/aryl compound diffuses away and the subsequent oxidative addition occurs between an incoming Ar–Br bond and the metal center. The associative complex is essential to for polymerization to occur in a living fashion since it allows the metal to undergo a preferred intramolecular oxidative addition and remain with a single propagating chain (consistent with chain-growth mechanism), as opposed to an intermolecular oxidative addition with other monomers present in the solution (consistent with a step-growth, non-living, mechanism). The monomer scope of CTP has been increasing since its discovery and has included poly(phenylene)s, poly(fluorine)s, poly(selenophene)s and poly(pyrrole)s.


Living group-transfer polymerization

Group-transfer polymerization also has characteristics of living polymerization. It is applied to alkylated
methacrylate Methacrylates are derivatives of methacrylic acid. * Methyl methacrylate * Ethyl methacrylate * Butyl methacrylate * Hydroxyethyl methacrylate Hydroxyethylmethacrylate (also known as glycol methyacrylate) is the organic compound with the chemic ...
monomers and the initiator is a
silyl ketene acetal Silyl enol ethers in organic chemistry are a class of organic compounds that share a common functional group composed of an enolate bonded through its oxygen end to an organosilicon group. They are important intermediates in organic synthesis. ...
. New monomer adds to the initiator and to the active growing chain in a Michael reaction. With each addition of a monomer group the trimethylsilyl group is transferred to the end of the chain. The active chain-end is not ionic as in anionic or cationic polymerization but is covalent. The reaction can be catalysed by bifluorides and bioxyanions such as ''tris(dialkylamino)sulfonium bifluoride'' or ''tetrabutyl ammonium bibenzoate''. The method was discovered in 1983 by O.W. Webster and the name first suggested by
Barry Trost Barry M. Trost (born June 13, 1941, in Philadelphia) is an American chemist who is the Job and Gertrud Tamaki Professor Emeritus in the School of Humanities and Sciences at Stanford University. The Tsuji-Trost reaction and the Trost ligand are ...
.


Applications

Living polymerizations are used in the commercial synthesis of many polymers.


Copolymer synthesis and applications

Copolymer In polymer chemistry, a copolymer is a polymer derived from more than one species of monomer. The polymerization of monomers into copolymers is called copolymerization. Copolymers obtained from the copolymerization of two monomer species are ...
s are polymers consisting of multiple different monomer species, and can be arranged in various orders, three of which are seen in the figure below. While there exist others (alternating copolymers, graft copolymers, and stereoblock copolymers), these three are more common in the scientific literature. In addition, block copolymers can exist as many types, including triblock (A-B-A), alternating block (A-B-A-B-A-B), etc. Of these three types, block and gradient copolymers are commonly synthesized through living polymerizations, due to the ease of control living polymerization provides. Copolymers are highly desired due to the increased flexibility of properties a polymer can have compared to their homopolymer counterparts. The synthetic techniques used range from ROMP to generic anionic or cationic living polymerizations. Copolymers, due to their unique tunability of properties, can have a wide range of applications. One example (of many) is nano-scal
lithography
using block copolymers. One used frequently is a block copolymer made of polystyrene and poly(methyl methacrylate) (abbreviated PS-''b''-PMMA). This copolymer, upon proper thermal and processing conditions, can form cylinders on the order of a few tens of nanometers in diameter of PMMA, surrounded by a PS matrix. These cylinders can then be etched away under high exposure to UV light and acetic acid, leaving a porous PS matrix. The unique property of this material is that the size of the pores (or the size of the PMMA cylinders) can be easily tuned by the ratio of PS to PMMA in the synthesis of the copolymer. This can be easily tuned due to the easy control given by living polymerization reactions, thus making this technique highly desired for various nanoscale patterning of different materials for applications to catalysis, electronics, etc.


References


External links

* IUPAC Gold Bookbr>Definition

Living Ziegler-Natta Polymerization Article

Living polymers 50 years of evolution Article
{{DEFAULTSORT:Living Polymerization Polymerization reactions