Ti-Catalyzed Living Radical Polymerization of Styrene Initiated by

Chapter 10

Ti-Catalyzed Living Radical Polymerization of Styrene Initiated by Epoxide Radical Ring Opening

Downloaded by CORNELL UNIV on August 10, 2012 | http://pubs.acs.org Publication Date: September 7, 2006 | doi: 10.1021/bk-2006-0944.ch010

Alexandru D. Asandei, Isaac W. Moran, Gobinda Saha, and Yanhui Chen Department of Chemistry and Institute of Materials Science, Polymer Program, University of Connecticut, 97 North Eagleville Road, Storrs,CT 06269-3136

The steric and electronic ligand effects in the Ti-catalyzed living radical polymerization (LRP) of styrene initiated by epoxide radical ring opening (RRO) was investigated in a series of Ti(III) complexes (L TiX ) derived in situ from Zn reduction of commercially available Ti(IV) precursors. Based on the ability to perform initiation by epoxide RRO and mediate LRP via reversible C-Ti bond formation, these catalysts ranked: L = metallocene (η -RCp: R = H ~ Et ~ Pr ~ Bu > Ind >> Cp*) >> O-ligands (alkoxides > bisketonates) >> Ν ligands (Tp > Pc), while X = Cl > Br >> F ~ Me and L T i C l > L TiCl . The inexpensive Cp TiCl was one of the most active species. n

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© 2006 American Chemical Society

In Controlled/Living Radical Polymerization; Matyjaszewski, K.; ACS Symposium Series; American Chemical Society: Washington, DC, 2006.

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Introduction Over the last decade, convenient molecular weight (M ) and polydispersity (M /M ) control and relative robustness vs. ionic procedures have enabled living radical polymerization (LRP) to become a fundamental tool in modern polymer chemistry. Consequently, the wide applications of LRP to complex macromolecular synthesis have prompted extensive efforts in the development of novel initiators and catalytic systems. Detailed investigations have demonstrated that M„ and M / M can be controlled by reversible termination of growing chains with persistent radicals or degenerative transfer (DT) agents (7). Mechanistically, LRP occurs by atom transfer (ATRP), dissociation-combination (DC) or degenerative transfer (DT) (/). ATRP is catalyzed by late transition metal (Cu, Ru, Ni, Fe, Mo etc) (1,2) halides in conjunction with ligands and additives. DC is mediated by organic (nitroxides) (3) or organometallic (Co, Mo) (4) persistent radicals, while DT employs sulfiir-based reversible additionfragmentation (RAFT) (7) agents as well as iodine (J), Te or Sb derivatives (6). Living radical polymerizations are typically initiated from activated halides or thermal systems (la,b). However, the restricted selection of initiator types may limit the direct use of polymer chains as macromolecular building blocks. Therefore, the polymer synthesis toolbox would be greatly enhanced by the availability of a wider initiator assortment that provide access to new functional chain ends, while the development of new catalysts for simultaneous one-pot living polymerizations of dissimilar monomers would be highly desirable in the synthesis of complex monodisperse polymeric architectures. Recently, apart from their applications in α-olefm coordination polymerizations and organometallic reactions (7), early transition metal complexes have become increasingly employed in radical organic chemistry (8). One of the most successful examples, the soluble paramagnetic Cp Ti(III)Cl complex (P), is inexpensively synthesized in situ by the Zn reduction of Cp Ti(IV)Cl (70). The lime-green Cp TiCl (10b) is a very mild one electron transfer agent and catalyzes a variety of radical reactions (77) including the radical ring opening (RRO) of epoxides (72). We have recently introduced the Cp TiCl-catalyzed LRP of styrene initiated by epoxide RRO as a novel initiation and respectively catalysis methodology for LRP (75). Furthermore, we have also demonstrated that Ti alkoxides generated in-situ by epoxide RRO are efficient catalysts for the living ring opening polymerization of cyclic esters (14). Therefore, epoxides and titanium complexes represent potent new classes of initiators and respectively catalysts for both radical and ring opening polymerizations. In addition, as fundamental motifs in organic and polymer chemistry, they have the advantage of inexpensive commercial availability with wide structural diversity. n

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As the Ti complex is involved in both initiation and reversible termination steps, the catalyst ability to efficiently perform both epoxide RRO and reversible chain endcapping determines the polymerization livingness. Accordingly, the Ti reactivity can be fine-tuned by manipulation of steric and electronic ligand effects. However, while Ti complexes were thoroughly studied in Ziegler-Natta and metallocene polymerizations (75), understanding of ligand effects in Ticatalyzed radical reactions is limited (8,16,17). Thus, towards the rational design of multifunctional catalytic systems for living radical, ring opening and coordination polymerizations, we have started to investigate the effect of Ti ligands and reaction conditions in the LRP of styrene initiated by epoxide RRO and catalyzed by Ti(III) complexes derived from Zn reduction of structurally diverse, commercially available Ti(IV) precursors (18). Herein we present investigations of a series of 19 Ti complexes (Chart 1) with nitrogen (PcTiCl , TpTiCl ) and oxygen ligands ((dpm) Ti, (dpm) TiCl , CPrOVTiCfe, CPrO) TiCl)) as well as r| -cyclopentadienyl (Cp) half-sandwich (LTiCl , L = Cp, Cp*, Ind) and sandwich metallocenes (L TiCl , L = Cp, EtCp, 'PrCp, *BuCp, Cp*, Ind; Cp TiX , X = F, CI, Br, CO and *ΒηΟρ ΤίΜβ ). Some of these complexes were successful in stereospecific styrene coordination polymerization using MAO but were not investigated for either epoxide RRO or LRP. 2

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Chart 1. Structures of the L„TiX precursors. m


128

Experimental Materials. Bis(cyclopentadienyl)titanium dichloride (Cp TiCl , 97 %, recrystallized from CH C1 ), cyclopentadienyltitanium trichloride (CpTiCl , 99%), chlorotitanium triisopropoxide (CPrO^TiCl, 98%), bis(Wylcyclopentadienyl)titanium dichloride ( BuCp TiCl ) (all from Acros); bis(cyclopentadienyl) titanium dibromide (Cp TiBr , Pfaltz & Bauer); dichlorotitanium diisopropoxide (CPrOfcTiCt, 95+%, TCI) bis(ethylcyclopentadienyl)titanium (IV) dichloride (EtCp TiCl , 98%), bis( propylcyclopentadienyl)titanium dichloride ('PiCjhTiCfe, 98%), dimethylbisObutylcyclopentadienyOtitanium (IV) ( BuCp TiMe , 98%), bis(pentamethylcyclopentadienyl)titanium dichloride (Cp* TiCl , 99%), trichloro(pentamethylcyclopentadienyl)titanium(IV) (Cp*TiCl , 98%), indenyltitanium trichloride (IndTiCl , 99%), tris(2,2,6,6-tetramethyl-3,5heptanedionato)titanium (III) ((dpm) Ti, 99%), hydrotris(pyrazol-lylborato)trichlorotitanium (IV) (TpTiCl , 95%), bis(cyclopentadienyl) dicarbonyl titanium (II) (Cp Ti(CO) , 98%) (all from Strem); dichlorobis(2,2,6,6-tetramethyl-3,5-heptanedionato)titaniu^^ ((dpm) TiCl , 97%), dichlorobis(indenyl)titanium(IV) (Ind TiCl ), titanium(IV) phthalocyanine dichloride (PcTiCl , 95%), Zn (nanosize, d = 35 nm) 99+ %), glycidyl 4methoxyphenyl ether (GME, 99%), and 1,4-butanediol diglycidyl ether (BDGE, 95%), (all from Aldrich) were used as received. Bis(cyclopentadienyl)titanium difluoride was prepared (19). 1,4-dioxane (99.7 %, Fisher) was distilled from a blue solution of Nafàenzophenone. Styrene (99+ %, Fluka), was dried over CaH (93%, Acros), filtered, and passed through an acidic A1 0 column. 2

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Techniques. 'H-NMR (500 MHz) spectra were recorded on a Bruker DRX500 at 24 °C in CDC1 (Aldrich; 0.03% v/v TMS as internal standard). GPC analyses were performed on a Waters 150-C Plus gel permeation chrQmatograph equipped with a Waters 410 differential refractometer, a Waters 2487 dual wavelength absorbance UV-VIS detector set at 254 nm, a Polymer Laboratories PL-ELS 1000 evaporative light scattering (ELS) detector and with a Jordi Flash Gel (lxlO Â, 2 χ 10 Â, lxlO Â) column setup with THF as eluent at 3 mL/min at 34 °C. Number-average (M ) and weight-average molecular weights (M ) were determined from polystyrene calibration plots. 3

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Polymerizations. Catalyst (Cp TiCl , 86.9 mg, 0.35 mmol), Zn (45.6 mg, 0.70 mmol) and dioxane (0.5 mL containing -10 mg CaH , as trace water scavenger) were added to a 25-mL Schlenk tube. The tube was degassed by several freeze pump thaw cycles, filled with Ar, and the reduction was carried out at it. The characteristic lime-green Cp Ti(III)Cl color was observed in under 5 min. The tube was then cooled to -78 °C and a mixture of styrene (0.5 mL, 2

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4.36 mmol) and BDGE (16.8 μι, 0.087 mmol) was injected and the tube was redegassed and heated at 90 °C. Samples taken under Ar were used for conversion and molecular weight determination by NMR and respectively by GPC.


Results and Discussion The proposed mechanism of the Ti-catalyzed LRP of styrene initiated by epoxide RRO is outlined in Scheme 2. The Ti(ffl) species were generated in situ by Zn reduction (Ar, dioxane, rt) of the Ti(IV) precursor (eq. 1). As Zn is a heterogeneous component, a Zn/Ti = 2/1 ratio was typically employed. The occurrence of the reduction was easily recognized by the characteristic green/blue color of the Ti(III) complexes. With very few exceptions (20), the reduction potentials in this Ti series are not available, but it is likely that Zn was not reductive enough for Cp *TiCl , Cp TiF , Cp TiC0 and 'BuCp TiMe which did not undergo a color change even in more polar solvents at higher temperatures and led to very little polymer formation. In all other cases, injection of excess epoxide into Ti(III) solutions rapidly recovered of the original Ti(IV) color indicating the occurrence of epoxide RRO. 2

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Scheme 1. Ti-catalyzed styrene LRP initiated by epoxide RRO (L = ligand, X = halide).


130 Epoxides are unique initiators as their Ti-catalyzed RRO occurs with the formation of a pair of very reactive primary and secondary constitutionally βtitanoxy radicals derived from RRO regioselectivity (17) (eqs. 2,3). Interestingly, these species possess the same thermodynamic stabilization as the corresponding alkyl radicals (21). In this study, the polymerizations were initiated from 1,4-butanediol diglycidyl ether (BDGE) a diepoxide that provided the best results in our earlier experiments with Cp TiCl (13). Addition of the epoxide derived radicals to styrene initiates the polymerization (eq. 4) which proceeds in a living fashion, mediated by the reversible end-capping of the propagating chain end with a second equivalent of Ti(III). The reversible C-Ti bond homolysis most likely occurs via a combination of the DC and DT mechanisms (eqs. 5, 6) (13). Thus, one Ti equivalent is required for the epoxide RRO and another one for the polymerization control. The conversion dependence of M and M / M for these Ti-catalyzed styrene polymerizations is presented in Figures 1-4 while a comparison of the results at similar conversions is summarized in Table I. In the case of N-ligands (exp. 1, 2) no polymerization was observed for the poorly soluble PcTiCl (22) while the TpTiCl scorpionate derivative (23) formed an insoluble purple precipitate typically associated with over-reduction (23b,c), and thus provided a broad, poorly controlled polymerization (vide infra). Four different complexes with O-ligands were subsequently studied (exp 37). Ti alkoxides were previously used as additives for Ru (2b) and Mo (24) catalyzed radical polymerizations as well as in various organic reactions (7). Such compounds are relatively inexpensive and moreover, while other transition metal catalyzed processes are strongly colored, they are typically colorless and expected to generate white polymer. However, due to the limited steric accessibility of the metal centers (25), both Ti bisketonates performed rather poorly. Thus, no polymer was obtained from (dpm) Ti while an uncontrolled free radical polymerization (FRP) was observed for (dpm) TiCl . However, a clear improvement was observed (Figure 1) for both ( PrO) TiCl and ( PrO) TiCl which were the first catalysts in this series to display a linear dependence of M on conversion. The broad M / M values and low initiator efficiencies (IE) are a consequence of the slow RRO initiation due to the strong lone pair donation of the alkoxide ligands. This effect reduces the Ti oxophilicity (7b), thus decreasing the rate and yield of the epoxide-RRO. The better control afforded by ( PrO) TiCl vs. ( PrO) TiCl is related to the increased steric demand of the three PrO ligands which may weaken the C-Ti bond enough to allow for a more efficient reversible termination. Interestingly, the BDGE-initiated polymerizations slowly gelled at higher conversions but the polymer dissolved immediately upon addition of a drop of dilute HC1. In addition, polymerizations initiatedfrommonofunctional epoxides


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131 Table I. Styrene Polymerizations Catalyzed by Ti Complexes. Exp. [StJ/[BDGE]/ ÎL TiXJ/iZnl 1 50/1/4/8 2 50/1/4/8 3 50/1/4/8 4 50/1/4/8 5 50/1/4/8 6 50/1/4/8 50/1/4/3" 7

L TiX n

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PcTiCl TpTiCl (dpm) Ti (dpm) TiCl 0PrO) TiCl ('PrO^TiCl ('PrO) TiCl 2

3

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8 9 10

50/1/4/8 50/1/4/8 50/1/4/8

Cp*TiCl Cp*TiCl IndTiCl

11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28

50/1/4/8 50/1/2/4 50/1/1/2

CpTiCl CpTiCl CpTiCl Cp* TiCl Ind TiCl Ind TiCl EtCp TiCl 'PrCp TiCl 'BuCp TiCl Cp TiBr Cp TiCl Cp TiCl Cp TiCl Cp TiCl Cp TiCl Cp TiF 'BuCp TiMe Cp Ti(CO)

50/1/4/8 50/1/4/8 50/1/4/8 50/1/4/8 50/1/4/8 50/1/4/8 50/1/4/8 50/1/4/8 50/1/4/2 50/1/4/4 50/1/4/8 50/1/4/8 50/1/4/8 50/1/4/8 50/1/4/8

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90 90 90 90 90 130

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1.53 1.54 1.66 1.42

V"" Wxmin" NA 3.50 NA 5.50 33.1 61.1 48.3

1.65 1.66

3.00 39.0

N/A 0.16

1.26 1.23 1.91 1.51

28.6 29.1 33.3 79.3

0.22 0.24 0.06 0.46

1.30 17.6 11.8 72.5 91.1 54.6 18.0 68.6

N/A 0.38

9.9 10.2 4.5

1.54 1.23 1.12 1.13 1.10 1.10 1.21 1.17

7.1 2.9 10.9 7.4 N/A

2.11 1.63 1.58 1.22 N/A

9.60 30.5 128.0 120.0 N/A

N/A N/A

N/A N/A

N/A N/A

Τ M xl0 °C 90 NA 49.8 90 90 NA 90 6.4 90 180 90 18.3 25.6 90 10.2 90 18.8 110 90 14.3 90 14.5 47 90 21.7 90 4.9 90 90 6.8 70 4.8 90 4.7 2.4 90 n

n

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110 90 90 90

3a

M /M„ w

NA 2.83 NA

a

a

At 50% Conv. Calculated as the slope of the kinetic plots. IE = M /M with M = MW + [St] /[Initiator] *MW *conv. G M E as initiator. C

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1

Init. Effic. NA 0.12 NA NA 0.02 0.14 0.12

c

0.57 0.56 0.64 0.34 0.27 0.63 0.39 0.83 0.28 0.30 N/A N/A N/A

132 (GME) did not form gels and provided M / M = 1.4, the narrowest in the alkoxide series. However, further optimization efforts met with limited success. We attribute this behavior to the facile ligand exchange process of Ti alkoxides (7,26)· This is consistent with the slow O-Ti-0 inorganic crosslinking from BDGE but also indicates an underlying limitation of Ti alkoxides in LRP. A comparison of four piano-stool trichloro half-sandwich metallocene and scorpionate Ti complexes (LTiCl L = Cp, Cp*, Ind and Tp, exp 2, 8-13), is provided in Figure 2. As described above, potential over-reduction of TpTiCl leads to a poor polymerization performance. By contrast, the strong electron releasing effect of Cp* (20,27,28) increases the reduction potential, stabilizes the higher oxidation state and renders the Zn reduction difficult. Consequently, after epoxide RRO, Cp*Ti(III)Cl traps the growing chain with a relatively strong TiC bond. Thus, at 90 °C, the dissociation equilibrium is strongly shifted towards the dormant species and a very slow, poorly controlled process is observed. w

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Conversion

Figure 1. Ligand and initiator effect in Ti-alkoxide catalyzed styrene polymerizations initiated by epoxides: conversion dependence of M and MJM [St]/[BDGE]/[L TiX„J/[Zn] = 50/1/4/8, 90 °C (PrO) TiCl (M), (dpm) TiCl (·), (PrO) TiCl «); [St]/[GME]/[(PrO) TiCl]/[Zn] = 50/1/4/3, (>). n

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133 However, increasing the temperature to 110 °C increases the dissociation rate, and consequently, a linear dependence of M on conversion emerges, with a PDI of about 1.6. By contrast, both Ind and Cp which are very close in electronic effects (29) and have identical reduction potentials (20c) are readily reduced by Zn and catalyze the LRP of styrene with very similar values of the rates (k - 3 χ 10 min ), IE (0.2) and M / M (1.25). Most likely, in the dormant species, the Ind ring points away from the polystyrene chain end, thus providing a steric effect comparable to Cp. Thus, a comparison of these catalysts (Figure 2) reveals a Cp - Ind » Cp* » Tp ligand trend and indicates that electronic effects may be more important than steric considerations in the LTiCl group. As described above, two Ti equivalents are required per epoxide group: one opens the epoxide, while the second mediates reversible termination. This is further demonstrated (Figure 2, exp 11-13) by the effect of the BDGE/CpTi(III)Cl ratio. n

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Figure 2. Effect of ligand, epoxide/Ti(III) ratio, and temperature in the LTiCl catalyzed styrene polymerization initiatedfromepoxides: dependence of M„ and MJM on conversion. [St]/[BDGEJ/[LTiCl J/[Zn] = 50/1/4/8; Τ = 90 °Cfor CpTiCl (7), Cp*TiCl (O), IndTiCl (A), TpTiCl (M), and T=110°Cfor Cp*TiCl (·). [St]/[BDGE]/[CpTiCl ]/[Zn] = 50/1/1/2 (A), 50/1/2/4 (A), T= 90 °C 3

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134 As BDGE is a afunctional initiator, a BDGE/Ti = 1/4 ratio is theoretically necessary for a living process. Thus, a BDGE/Ti = 1/1 ratio is insufficient for LRP and leads to the irreversible consumption of all available Ti(III) by excess epoxide. Consequently, only a free radical polymerization is observed. Upon increasing the available Ti(III) to BDGE/Ti = 1/2, partial living features such as linear dependence of M on conversion are observed. However, the M / M is quite broad. Nonetheless, the correct stoichiometric ratio provides a clear LRP with a linear dependence of M on conversion and low polydispersity (Mw/Mn < 1.2). These results support the proposed requirement of 2 Ti(III) equivalents/epoxide. The results from the polymerizations mediated by L TiX -derived catalysts using an optimum (75) BDGE/Ti/Zn = 1/4/8 ratio are presented in Table 1 (exp 14-28) and in Figures 3, 4. No Zn reduction was observed for Cp TiF (29), BuCp TiMe , Cp Ti(CO) and Cp* TiCl , which with two Cp* strong electron donating groups is considered to already be a one electron reduced species (29). With these exceptions, the other RCp TiX metallocenes (exp 15-21) were the most successful of the series and provided a clean LRP of styrene with linear M vs. conversion plots, low M / M values (-1.15) and relatively similar kinetics. The observed ligand effects are the cumulative result of the ligand influence on both the epoxide RRO and on the chain end dissociation equilibrium. Inspection of the data in Figure 3 and Table 1 reveals that in the RCp TiCl series, these effects are subtle and not very large. Thus, although the bulkier BuCp (77) or Ind may lower the yield in the epoxide RRO (8,12,17) and reduce IE, the Cp monosubstitution pattern does not have an appreciable consequence on the polymerization. Indeed, RCp TiCl (R = H, Et, Pr, *Bu) have very similar polydispersity ( M / M < 1.2), IE (0.5-0.6) and rate (k = 0.4-0.5 h" ) values. Apparently, there is insufficient difference in the stereoelectronic ligand effect (7,29) to strongly affect the Ti-C dissociation equilibrium. The low sensitivity to the ligand nature is most likely a consequence of the radical mechanism and of the constant balance between the electronic and steric effects in this series. Thus, while the C-Ti bond homolysis tendency decreases with increasing ligand electron donation on going from Cp to BuCp, this trend is counterbalanced by the corresponding increase in the steric bulk of the ligand. Preliminary molecular modeling experiments indicate that in the dormant species, the Cp substituents are oriented away from the polystyrene chain, thus supporting a weaker steric influence. By contrast, much stronger steric effects are observed with similar species in MAO-coordination polymerization (75). This observation, in conjunction with the atactic nature of the polystyrene (73), lends additional support to the radical mechanism of these polymerizations. In the case of Ind TiCl , the stronger steric effect of the two Ind ligands (7) weakens the C-Ti bond and shifts the dissociation equilibrium towards the active species, causing broader M / M and a larger M intercept at lower conversions. n

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12000

Conversion Figure 3. Effect of ligand structure in the RCp TiCl -catalyzed polymerization of styrene initiated by epoxide radical ring opening: dependence ofM„ and MJM on conversion. [St]/[BDGE]/[RCp TiCl ]/[Zn] = 50/1/4/8. Bu TiCl (A), Ind TiCl (O), Cp TiBr (M), 'PrCpJiCh (V), Cp TiCl (Ύ) andEtCp TiCl (V), all at Τ = 90 °C. Ind TiCl (·) at 70 °C. 2

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Thus, as expected, lowering the temperature (exp. 15, 16) from 90 °C to 70 °C results in a simultaneous increase in IE from 0.33 to about 0.56, a decrease in M / M from 1.23 to 1.12 and a very low M intercept. In addition, indenyl ring slippage (7,30) may also affect the catalyst reactivity at higher temperatures. The effect of the halide or methyl substituents in Cp TiX is also presented in exp. 20, 21, 26-28 and Figure 3. While complexes with X = F, Me and CO ligands could not be reduced by Zn and did not yield polymerization, both Br and CI performed reasonably well, with better IE and M / M values for Cp TiCl . This is due to the weaker C-Ti chain end bond with Cp TiBr and the formation of a mixture a products from the Zn reduction of Cp TiBr (20e). The effect of temperature and Zn was further explored (Figure 4 and exp 2227) for Cp TiCl . A linear dependence of M on conversion occurs at all temperatures in the 90-130 °C range. w

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Conversion Figure 4. Effect of temperature and Ti(IV)/Zn ratio in the Cp TiCl 'Catalyzed styrene polymerization initiated by epoxide radical ring opening: dependence M andMJM on conversion. [St]/[BDGE]/[Cp TiCl ]/[Zn] = 50/1/4/8 at 130 °C (+), 110 °C (·), 90 °C (A) and [St]/[BDGE]/[Cp TiCl ]/[Zn] = 50/1/4/2 (A) and 50/1/4/4 (Δ) at 90 °C. 2

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However, larger polydispersity ( M / M = 1.8) is observed at 130 °C. Upon decreasing temperature from 130 °C to 110 °C and finally to 90 °C, an increase in IE from 0.3 to 0.6 is observed. This is likely due to the thermal suppression of competing side reactions including termination, transfer and epoxide deoxygenation (12). Lower temperatures still provide living polymerizations but with lower rates. Consequently, an optimum in polydispersity and IE occurs at 90 °C. The effect of the amount of Zn is also described in Figure 4 and exp 2224. A Ti/Zn = 1/0.5 ratio (i.e. Ti/Zn = 4/2 for the difunctional BDGE epoxide) should theoretically suffice. Indeed, a linear dependence of M on conversion is already observed at this ratio. However, the polydispersity is large ( M / M = 2.1) most likely due to slow initiation. Thus, the metallic nature of Zn demands its use in a slight excess. Indeed, increasing the amount of Zn from Ti/Zn = 4/2 to 4/4 and 4/8 leads to a continuous decrease in polydispersity from 2.1 to 1.5 w

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137 and finally to below 1.2. This reflects the heterogeneous nature of Zn as well as its possible involvement (via fast Ti reduction) (31) in both the initiation and reversible termination. Consequently, the presence of excess Zn is critical for the quality of this polymerization.


Conclusions The present investigation of the ligand effect in the living radical polymerization of styrene initiated by epoxide radical ring opening and catalyzed by Ti(III) complexes reveal several trends which reflect the combined catalyst ability to perform both epoxide RRO and reversible Ti-C bond formation: First, îl -RCp > O-ligands » Ν ligands. Thus, cyclopentadienyls (Ti -RCp) are vastly superior to both oxygen and nitrogen homoleptic ligands and provide living radical polymerization of styrene with reasonably low M / M values. The N ligand complexes were either insoluble or with a mismatched reduction potential and thus performed very poorly (Tp > Pc). O-ligands (alkoxides > bisketonates) did provide a linear dependence of M on conversion but the fast ligand exchange and low yield in the radical ring opening initiation led to relatively broad polydispersity. The strong steric effect of the bisketonates ligands limited their use in the polymerization. Second, in the metallocene series, by contrast to the corresponding MAO-activated coordination processes, a relatively weak dependence of the polymerization on the nature of the Cp substituent was observed. Thus, for RCp, R = H ~ Et ~ *Pr ~ Bu > Ind » Cp*. This can be provisionally rationalized as the result of the Cp ligand substituents pointing away from the dormant polystyrene chain and of the balance between their electronic and steric effects. Third, sandwich titanocenes provided better living features than the half-sandwich derivatives (L TiCl > LTiCl , L = Cp, Ind) and similarly, CPrO) TiCl > (*ΡΓΟ) ΤΚ:1 . Thus, L T i C l > L„.,TiCl . In addition to the steric contribution, this trend qualitatively parallels the decrease in the Lewis acidity with decreasing the number of CI ligands and increasing the number of electron donating substituents. However, strong donors (Cp*) are also less performant. In addition, chlorine ligands allowed for better control than the bromine derivatives (CI > Br » F ~ Me). It is rewarding that the most promising catalysts are also the least expensive ones for both metallocenes (Cp TiCl ) and alkoxides ((0 Pr) TiCl). Furthermore, we anticipate that most Ti structures currently used in coordination polymerization may also be successful in living radical polymerization in conjunction with Zn, epoxides or other initiators. Investigations of epoxides and Ti complexes as multifunctional initiators and catalysts for LRP and ROP, as well as studies on bridging LRP and coordination polymerizations are currently in progress in our laboratory. 5

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138 Acknowledgements The the National Science Foundation (CHEM-0518247) and the Donors of the Petroleum Research Fund (PRF-G) administered by the American Chemical Society are gratefully acknowledged for financial support.

References


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Ti-Catalyzed Living Radical Polymerization of Styrene Initiated by

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