Polymerisation Catalysis Calculating Molecular Weights and Related Terms There are several ways of measuring the average

molecular weight of a polymer, it is possible to calculate the number average molecular weight and weight average molecular weight.
Equation 1 - Calculating the number average molecular weight

Equation 2 - Calculating the weight average molecular weight

The polydispersity index (PDI) is related to both of these terms, ideally this value would be equal to 1 as this would represent entirely uniform chain length, i.e. each catalyst displays perfect specificity and forms chains of the exact same length.
Equation 3 - Calculating the PDI

Mn is always less than Mw and so PDI values are larger than 1, ca. >5 for heterogeneous catalysts (multiple active sites leads to different rates of reaction and termination) and <2 for homogeneous catalysts (well-defined active catalyst site limits different active sites with the intention of there being only one). Using a non-degrading catalyst a polymer with a PDI of 1.05 is achievable, however, that does that indicate how useful it is. Here the chain length is directly related to the time given for the reaction to occur, allowing for the successful formation of a uniform, directly chosen length of polymer chain. Polymers with this low a PDI are often very brittle and crystalline and have very little purpose. For this reason a mix of homogeneous and heterogeneous catalyst is often employed to provide a suitably malleable and manageable polymer. Catalyst Activity and Lifetime Catalyst activity is defined in units of kgpolymer molcatalyst-1 h-1 bar-1 with <1 being considered a very low activity and >1000 considered very high. Catalyst activity may be a misleading figure though. There is no standard reaction time for polymerisation and so without accounting for time it is possible to make a catalyst appear much more efficient than it actually is. It is also possible that the catalyst will degrade under exothermic reaction conditions, as is often the case with group III and lanthanide catalysts, and so temperature is also an important variable.

Olefin Polymerisation

Figure 1 - A general description of olefin polymerisation

The properties of a polymer depend on; molecular weight and the distribution or range of molecular weights (the polydispersity index, PDI) the distribution and nature of chain branches (R/R H) either through polymer reincorporation, chain isomerisation or additional co-monomer in -olefins the control of relative stereochemistry at the chiral carbon, i.e. the tacticity modification post-polymerisation, e.g. end-group functionalization

The need to control and select these characteristics in order to achieve polymers with different uses and properties has led to the development of several types of catalyst, including; Phillips heterogeneous, solid supported chromium ions or complexes, there is often confusion or lack of clarity over the number of chromium oxidation states involved which can cause irregular behaviour Ziegler-Natta solid supported titanium compounds used in conjunction with organoaluminium co-catalysts Single-site catalysts consisting of a single molecule or metal complex, these behave homogenously despite not strictly being so. They are high specificity, and often provide a low range of molecular weights (cf. to Phillips and Ziegler-Natta catalysts this is definitely true) due to the uniform rate of polymerisation. They are also more likely to distribute monomers, i.e. build regular units in systems with competing monomer units, e.g. ethylene and hexane

The last of these three is the most commonly used in industry for many reasons, some of which are described above. On an industrial scale these catalysts are solid supported, most often in pores of silica or MgCl2, and are bound only by adsorption they retain their identity as a complex hence the ability to act as a homogeneously catalyst. As the polymer forms and the chain gets larger the solid support begins to fragment, this reveals more pores and in turn more active catalyst and so this process continues until the reaction is complete, the catalyst has been incorporated into the polymer and the solid support has degraded into much smaller beads. If the catalysts were to be used in solution they would cling to the reactor walls, increasing downtime, and so this solid supported method which maintains homogeneous behaviour of the catalyst also has economic advantages. The most frequently used single-site catalysts are the metallocenes. Metallocene Catalysts These are essentially homogeneous versions of the Ziegler-Natta catalyst, they consist of an early transition metal in a high oxidation state (i.e. Ti(IV), Zr(IV), Hf(IV), though catalysts based on

scandium, yttrium and lanthanides are known) made net neutral with 2 cyclopentadiene ligands and 2 chloro- or alkyl ligands in the cis isomer. Early transition metals are used in a high oxidation state as this reduces the interaction with the methyl ligands, they are small d0 atoms and so bonding with the methyl group is minimal so the cationic active catalyst can be made, analysed and reacted in situ. The proposed mechanism is;

Figure 2 - Proposed mechanistic cycle for olefin polymerisation

The four steps are as follows; Initiation formation of the cationic alkyl complex (note the empty coordination site drawn is unlikely to exist as a tetrahedral species, there is likely to be a concerted exchange or a fluxion in geometry)

In a laboratory the metal bis-chloride is first converted to the metal bis-alkyl with an aluminium alkyl, which is then able to extract a methyl and activate the catalyst. In an industrial setting methylaluminoxane (MAOFigure 3 - Methylaluminoxane (MAO)) (Figure 3) is instead used, the preparation involves partial hydrolysis of AlMe3 (which is very air sensitive).

Figure 3 - Methylaluminoxane (MAO)

The structure of MAO is ill-defined, consisting of highly varied oligomers. Typically MAO is used in a ratio of over 200:1 with pre-catalyst, however, it has the added benefit of removing water from the

reaction. There are then three methods for forming the active catalyst; 1. Oxidative M-C cleavage

2. Protonation

3. Abstraction

This is the most commonly used. Anions must be chosen carefully as some typical cations are capable of deactivating the catalyst, some coordinate with the metal, while perfloro anions (BF4-, PF5-) can undergo Fabstraction and [BPh4-] can either -coordinate or undergo phenyl abstraction. Perfluorophenylborate anions are very weakly coordinating and less prone to extraction than alkyl derivates, examples of these include B(C6F5)3, [B(C6F5)4]- and [MeB(C6F5)3]-. The latter of these sometimes displays a B-MeM interaction;

Figure 4 - Illustration of a B-Me--M interaction

This coordination, which disables the catalyst, can be determined by 19F NMR with a change in the difference between the meta and para 19F resonances (ca. 2.6 ppm to > 3 ppm) indicative of a B-MeM interaction. Another common feature that enhances characterisation is that of agostic interactions. Since these species are d0 it is difficult to achieve an 18e- configuration and as a result these interactions are common, particularly for organometallic complexes and occasionally for C-H and -Si-H bonds. These interactions can be determined by gated coupled (decoupled) 13 C NMR, here the decoupler is on during the relaxation delay and off during acquisition, ensuring a good signal to noise ratio without sabotaging the 13C NMR which depends on decoupling. The indication of an agostic interaction is a shift in the 1J(CH) coupling constant from ca. 125 Hz to ca. 200 Hz, or using 29Si NMR a shift from ca. -5 to 5 ppm to ca. -20 ppm.

These systems are air and water sensitive, again due to the high oxidation state, assuming no ligand degradation they will form bridging oxo-compounds, deactivating the catalyst. Suitable solvents for this reaction include chlorobenzene and bromobenzene, coordinating solvents (e.g. THF, pyridine, ethers) are semi-innocent and may be used while protic solvents (e.g. CHCl3, DMSO) are non-innocent (they are liable to decomposition and deactivate the catalyst) and aliphatic hydrocarbons are non-solvating. Propagation addition of the olefin and extension of the polymer chain

The mechanism for propagation, suggested by Brookhart and Green, is;

Figure 5 - Brookhart-Green mechanism

This mechanism stresses the importance of agostic interactions as they are necessary for holding the methyl group in position for insertion, this interaction increases the electron density at the metal, in turn improving the lability of the methyl group. The d0 configuration means that back-bonding into the * of the olefin is weak, so much so that the olefin complex cannot be isolated. Proof of olefin insertion was demonstrated by Eisch et al 1;

J. J. Eisch et al., J. Am. Chem. Soc., 1985, 107, 7219.

Figure 6 - Crystal structure showing the agostic interaction

This is then unable to further interact as the species stearically prevents more substrate from approaching the metal, this complex was then isolated as crystals (Figure 6). Termination the processes that halt propagation, e.g. the release of the polymer chain during reformation of the active catalyst

Figure 7 - The termination process

Where the R group is the polymer chain, once released a new olefin may approach and the process begin anew. Chain transfer transfer of the polymer chain to the aluminium co-catalyst, often due to residual AlMe3 found in MAO

Figure 8 - Chain transfer

Polymer Characterisation The two techniques used most often are mass spectrometry and gel permeation chromatography (GPC). Mass spectrometry will indicate which masses are present without providing information on the abundance of each (a larger peak indicates a better flying capability, not a greater amount). GPC, a form of size exclusion chromatography, indicates the relative abundance of each molecular weight by retention time (calibrated against polystyrene standards). Distortions in the chromatogram peaks, e.g. shoulders, suggest different forms of catalyst (i.e. 4 shoulders would infer 4 forms of active catalyst), and so GPC offers more information that mass spectrometry.

Stereospecific Olefin Polymerisation For all but the simplest of -olefins there is a chiral carbon with an R group attached, relative orientation of these R groups in the polymer chain controls the properties of the polymer and so control of this orientation, or tacticity, is necessary when designing catalysts. The different types of tacticity are isotactic (Figure 9), syndiotactic (Figure 10) and atactic (Figure 11).

Figure 9 - Isotactic orientation (regular)

Isotacticity is very difficult to achieve and most isotactic polymers are in fact very slightly atactic. A chain may be hemiisotactic if every other repeat unit has randomised insertion.

Figure 10 - Syndiotactic orientation (alternating)

Figure 11 - Atactic orientation (random)

These polymers are, despite containing a large number of chiral carbons, not optically active as they possess symmetry however poly(-olefins) do display optical rotation. In solution the polymer chains form helices, and for polymers longer than poly(propylene) this helix is unable to unwind. This does mean that optical activity is not a method for measuring the tacticity of a polymer as it is due to the size of the polymer chain and not the orientation of the individual chiral centres. To determine the tacticity of a polymer 13C NMR (Figure 13) is utilised. By locating and identifying the peaks associated with certain pentads the orientation of monomer units can be determined. The length of chain with five R groups (Figure 12), which forms the pentad, can be described by the relationship between neighbouring R groups using the letters r and m, where r represents a rac relationship and m a meso relationship. These relationships effect the shift of the observed peaks

Figure 12 - Example pentads with m/r notation

If a pentad is symmetrical it will have the same description as its mirror image (i.e. rmmr will rotate around the central carbon to give rmmr). The most indicative resonance in the 13C NMR is that of the first carbon in the polymer R-group, C3.

Figure 13 - An example C NMR of poly(1-hexene) with pentads (in m/r notation) identified

13

Stereocontrol in polymerisation is achieved either with chain end control, where the growing polymer chain determines the stereochemistry, or by enantiomorphic site control at the ligand using a chiral catalyst. In chain end control any erroneous insertion (i.e. any insertion of a wrongly orientated molecule) will propagate throughout the polymer, whereas with enantiomorphic site control an error will not propagate as the catalyst still prefers a certain configuration upon the next addition of monomer unit to the complex. In the polymerisation of -olefins there is a preference for the R-group to be at as great a distance as possible from the growing polymer chain (Figure 14). There are, however, other factors to consider;
2

T. Asakura, M. Demura and Y. Nishiyama, Macromolecules 1991, 24, 2334.

in a metallocene catalyst the polymer chain is able to move side to side, and so the chirality of both sites (the cis coordination sites of the metal) must be considered for full stereocontrol. A rotation of the cyclopentadienyl rings will also remove selectivity

Figure 14 - Illustration of the preferred, stearically controlled, orientation of an incoming monomer unit

The solution is to link the two rings, creating an ansa-metallocene (Figure 15).

Figure 15 - An example of an ansa-metallocene

The chirality of the polymer is then dependent on the chirality of the metallocene catalyst and the active catalyst species, according to Ewens symmetry rules.

Figure 16 - The result of different chiralities, based on symmetry, of metallocenes. The C2V and Cs (achiral) symmetries provide atactic polymer, the C2 symmetry provides isotactic polymer, the Cs (prochiral) provides syndiotactic polymer and the C1 symmetry gives hemi-isotactic polymer.

Post-Metallocene Catalysts Although metallocene catalysts are almost ideal they are very difficult to research, this is due to years of aggressive patent applications. Patents will often include several variations, including different metals or modified moieties, beyond the scope of the work actually performed. This leaves very few available systems for research.

This has led to work on post-metallocene catalysts, these use alternate supporting ligands and allow for more variability as well as a higher degree of control. The metals used in post-metallocene systems are the group III and IV metals, the lanthanides, vanadium, chromium, iron and nickel. Nickel provides the best catalysis however nickel allergies are quite common, and so polymers with embedded nickel catalyst are not desirable for large sections of industry. The first class of post-metallocene catalyst is the half-sandwich (Figure 17), using a single Cp ring held in a constrained geometry. These systems are considerably less effective than bis-Cp systems, however.

Figure 17 - Example 'half-sandwich' complexes

Group IV catalysts are often based on amido (NR2) ligands (Figure 18) in conjunction with cis-halides.

Figure 18 - Example amido complexes

Group III and lanthanide catalysts, usually in the +3 oxidation state, are adapted to different ligand types compared to group IV, however, they are also susceptible to several unique challenges. Particularly in the case of lanthanides a lot of the tuning can be achieved with the selection of the metal, however, as the lanthanides get smaller across the group the activity decreases as thermal stability increases and so a trade-off must be achieved. The redox stability of lanthanides are also important, europium and ytterbium have a very high 3rd ionisation energy (~2400 kJ mol-1) while cerium and gadolinium have very low 4th ionisation energies compared to other lanthanides, and so maintaining a 3+ oxidation state is also a challenge. Group III catalysts should be active without ionisation as they are isoelectronic with the active cationic group IV catalysts (Figure 19), however, using a similar system to bis-Cp, they have yet to materialise as a competitive alternative.

Figure 19 - Isoelectronic scandium and cationic titanium complexes

Homoleptic alkyl catalysts (Figure 20) using lanthanides have emerged as incredibly active catalysts for ethylene polymerisation with an increase at the metal ionic radii leading to an increase in activity (Figure 21).

Figure 20 - Structure and synthesis of homoleptic alkyl catalyst

Figure 21 - Data showing the trend in ionic radii:activity

Another group of complexes used in ethylene polymerisation are amidinate complexes (Figure 22). Here the importance of balancing stability with activity can be observed (Figure 23) with activity peaking at yttrium (1.04 ). This peak is different for any given ligand system.
3

S. Arndt, T. P. Spaniol, and J. Okuda, Angew. Chem. Int. Ed., 2003, 42, 5075

Figure 22 - Synthesis of an amidinate complex

Figure 23 - Data for amidinate complexes of different metals

N3 donor ligands have also been reported (Figure 24).

Figure 24 - Example N3 donor catalysts

4

56

S. Bambirra, M. W. Bouwkamp, A. Meetsma, and B. Hessen, J. Am. Chem. Soc., 2004, 126, 9182.

Stereoselectivity using post-metallocenes is considerably understudied though some attempts have been made using trisoxalane ligands. Polylactic Acid There is a desire to move away from poly(-olefins) as the starting materials are derived from crude oil, a limited resource with negative ecological effects. Polymers based on biomass show some potential, being less reliant on hydrocarbon resources and biodegradable they have some preferable qualities, however, there remains debate about the efficiency and the amount of land required to grow the crops from which the monomers are then taken. Polylactic acid (PLA), from starch, is one of the most studied biomass polymers. Uses are limited as PLA has a low glass transition temperature, Tg, the temperature at which the polymer becomes brittle and likely to disintegrate.

Figure 25 - The polylactic acid cycle

For the ring opening polymerisation (ROP) step (Figure 26) a tin catalyst is, in industry, almost exclusively used. Tin is subject to safety regulations however, and although usage currently complies with these laws they are changeable, and so research must be done to identify replacement catalysts if PLA is to continue to be manufactured. Most research is done using d0 group II/III/IV metals, although aluminium is also used (Figure 27), in order to minimise discolouring.

S. Hajela, W. P. Schaefer, J. E. Bercaw, J. Organomet. Chem., 1997, 532, 45. S. C. Lawrence, B. D. Ward, S. R. Dubberley, C. M. Kozak, P. Mountford, Chem. Commun., 2003, 2880.

Figure 26 - Mechanism of ROP

Figure 27 - Examples of aluminium catalysts for PLA synthesis

Stereoselective Polymerisation of Lactic Acid and Tacticity There are 3 possible isomers of lactide when formed from lactic acid; D-lactide, L-lactide and mesolactide. Meso-lactide can be separated leaving D/L-lactide, or rac-lactide, to then be used in polymerisation.

Figure 28 - The different isomers of lactide

Unlike with -olefins the chiral carbon here is not at the point of insertion and tacticity is determined entirely by the chirality of the monomer. Enantiopure, (RR) or (SS), monomer will result in an isotactic polymer but is a far too expensive solution and so catalysts are chosen that will polymerise only one enantiomer in the racemic mixture, it is possible to use racemic catalysts to achieve a crystalline mixture of R-PLA and S-PLA.

A. D. Schwarz, Z. Chu, P. Mountford, Organometallics, 2010, 29, 1246.

Tacticity in PLA systems is slightly more complicated, heterotactic (alternating RR/SS monomer units) and atactic are still as before, but isotactic polymer may now, in order of decreasing control, be considered chiral (i.e. PLLA and PDLA formed as separate chains), diblock (i.e. all of one monomer is polymerised followed by the other) or multiblock (i.e. blocks of various length of each monomer are incorporated in turn).

Figure 29 - Different types of tacticity (atactic omitted) in polylactides

PLA is itself chiral and so tacticity can be determined by optical rotation however NMR, both `13C and homonuclear decoupled 1H modes (this prevents coupling of the methyl and methine protons allowing analysis of tetrad units that describe the tacticity present), is preferred. Similar to -olefins the NMR shift depends on the orientation of L and D units, with i describing an iso relationship and s a syndio relationship. The tacticity of PLA is often defined as the probability of meso (Pm) or racemic (Pr) enchainment. If Pr=Pm=0.5 the polymer is atactic, Pr=1 is heterotactic and Pm is isotactic. Metathesis From the Greek for transposition, metathesis describes a bimolecular reaction involving the exchange of chemical bonds between the two reactants, for example the metal halide/alkyl exchange using MeLi to generate an active catalyst for olefin polymerisation is described as a halide metathesis, similarly catalysts for PLA synthesis can be prepared by -bond metathesis. Ring opening metathesis polymerisation (ROMP) is a common approach to synthesising functionalised polymers, in particular olefinic groups that can be subsequently used in cross-linking. By using strained, cyclic olefins the reaction is thermodynamically preferable, for example the polymerisation of norbornene.

Figure 30 - Poly(norbornene) synthesis

Figure 31 - General mechanism for ROMP reactions