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. 2023 May 31;145(23):12459–12464. doi: 10.1021/jacs.3c03978

cis-Selective Acyclic Diene Metathesis Polymerization of α,ω-Dienes

Samuel J Kempel †, Ting-Wei Hsu †, Jake L Nicholson †, Quentin Michaudel †,§,*
PMCID: PMC10330887  NIHMSID: NIHMS1906311  PMID: 37255463

Abstract

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The cis/trans stereochemistry of repeating alkenes in polymers provides a powerful handle to modulate the thermal and mechanical properties of these soft materials, but synthetic methods to precisely dictate this parameter remain scarce. We report herein a cis-selective acyclic diene metathesis (ADMET) polymerization of readily available α,ω-diene monomers with high functional group tolerance. Identification of a highly stereoselective cyclometalated Ru catalyst allowed the synthesis of a broad array of polymers with cis contents up to 99%. This platform was leveraged to study the impact of the cis geometry on the thermal and mechanical properties of polyalkenamers, including an ABA triblock copolymer synthesized via extension of a cis-rich telechelic polyoctenamer with d,l-lactide. These results suggest that cis-selective ADMET affords an efficient strategy to tune the properties of a variety of polymers.

The development of stereoselective methods to access olefin-containing macromolecules with precise geometries remains a grand synthetic challenge despite the documented dependence of the properties of such soft materials on cis/trans stereochemistry.1 For example, cis-polyisoprene (PI) is an elastic soft material, while trans-PI is a hard, brittle material.2 Homogeneous and heterogeneous catalysts have been developed for the coordination–insertion polymerization of 1,3-dienes with selective formation of either trans or cis linkages, but these catalytic systems are notoriously intolerant to polar functional groups and can lead to the formation of vinyl defects through competitive 1,2-insertions.3 Recently, several elegant approaches have been implemented to deliver polymers with predictable cis/trans contents either through thiol–yne click chemistry4−6 or via a metal-free ring-opening metathesis polymerization (ROMP) mediated by light.7 However, the scope of these processes is limited, and high cis contents are generally more challenging to access because of thermodynamic penalties. Monomers containing a spectator cis-olefin have been used to circumvent this issue,8−10 but undesired isomerization can erode the stereochemistry of the macromolecules.11,12

Polymerizations based on olefin metathesis, such as acyclic diene metathesis (ADMET)13,14 and ROMP,15 represent a promising and versatile strategy to access a diverse pool of stereodefined polyalkenamers because of the robustness, functional-group tolerance, and structural diversity of metathesis catalysts.16,17 Specifically designed W or Mo alkylidenes were found to overcome the thermodynamic preference of ROMP and to deliver high cis selectivity mostly with nonpolar monomers via kinetic control.18,19 The recent development of Z-selective20−25 and stereoretentive26−28 Ru catalysts has allowed the expansion of the scope of cis-selective ROMP processes.29−32 Interestingly, while ADMET is a powerful tool for the precise synthesis of polymers,33,34 control over the stereochemistry of the repeating alkenes has long escaped this versatile polymerization.

ADMET typically delivers polymers with a predominance of trans alkenes with Grubbs and Hoveyda–Grubbs dichloro Ru catalysts (Scheme 1a).13,14 We recently leveraged the exquisite stereoretention afforded by dithiolate Ru catalysts to produce a variety of all-cis polyalkenamers using cis,cis-diene monomers (Scheme 1b).35 However, this method required the synthesis of monomers with preinstalled cis,cis stereochemistry and utilized air-sensitive Ru carbenes.36

Scheme 1. Typical ADMET versus Stereoretentive and cis-Selective Processes.

Scheme 1

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Herein, we report a cis-selective ADMET process capitalizing on robust cyclometalated Ru–carbenes (Scheme 1c), which afforded a broad array of polyalkenamers with cis content up to >99% from readily accessible α,ω-dienes containing various functional groups. This diversity-oriented polymerization allowed the study of the influence of olefin stereochemistry over the thermal properties of these materials. Finally, an ABA triblock copolymer was prepared to demonstrate that mechanical properties can be modulated through modification of the stereochemistry of the middle block.

ADMET is a polycondensation involving iterative cross-metathesis reactions between α,ω-dienes (Scheme 2). To drive this fully reversible process toward high molar masses, continuous removal of ethylene is required. We hypothesized that using catalysts allowing kinetic control, including cyclometalated Ru-3(21,37) or dithiolate Ru-4(38) (Table 1), would thwart the thermodynamic selectivity and lead to a cis-selective ADMET if a robust catalyst capable of maintaining high cis selectivity over time could be identified. Carbonate monomer 1a was selected at the onset of the investigation to favor ADMET over the competing ring-closing metathesis. As a benchmark, monomer 1a was exposed to typical ADMET conditions using dichloro Ru-1 and Ru-2. Upon reaction with Ru-1 at 80 °C in 1,2,4-trichlorobenzene (TCB) under vacuum (100 mTorr), polymer P1a was formed with only 14% cis double bonds (Table 1, entry 1). Polymerization with Ru-2 delivered P1a with a similarly low cis content (9%) (Table 1, entry 2). Surprisingly, commercially available cis-selective catalyst Ru-3a only marginally improved the cis content to 18% (Table 1, entry 3). On the basis of the unique geometry of the ruthenacycle imparted by the nitrato and adamantane ligand,24,39 we hypothesized that increasing the steric hindrance of the aryl substituent of the N-heterocyclic carbene (NHC) (DIPP vs Mes) might improve the stereoselectivity. Pleasingly, switching to Ru-3b, which was first reported by Grubbs and coworkers,23 more than doubled the cis selectivity to 38% (Table 1, entry 4). To further favor kinetic control and minimize potential unselective secondary metathesis events, the reaction temperature was lowered to 40 °C, which led to 97% cis content (Table 1, entry 5). Decreasing the temperature further to 23 °C led to the isolation of an all-cisP1a (>99% cis) within the limit of detection of 1H NMR (Table 1, entry 6). While a decrease in molar masses was observed at lower temperature, respectable degrees of polymerization (DP = ∼50–70) and molar masses (Mn = 9.8 and 13.5 kg/mol) were obtained for P1a exhibiting 97–99% cis-alkenes (Table 1, entries 5 and 6).

Scheme 2. Development of a cis-Selective ADMET Process through Kinetic Control.

Scheme 2

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Table 1. Optimization of cis-Selective ADMETa.

graphic file with name ja3c03978_0005.jpg

entry catalyst T (°C) Mn (kg/mol)b Đ cis (%)c
1 Ru-1 80 27.9 1.75 14
2 Ru-2 80 25.6 1.89 9
3 Ru-3a 80 17.7 1.73 18
4 Ru-3b 80 28.7 2.99 38
5 Ru-3b 40 13.5 1.75 97
6 Ru-3b 23 9.8 1.67 99
7d Ru-3b 23 9.9 1.47 99
8d Ru-3a 23 11.2 1.61 80
9d Ru-3c 23 6.8 1.52 89
10d,e Ru-4 23 — — —
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a

sNHC = saturated NHC; uNHC = unsaturated NHC; DIPP = 2,6-diisopropylphenyl; Mes = 2,4,6-trimethylphenyl.

b

Determined through size exclusion chromatography (SEC) in THF against polystyrene standards.

c

Determined via 1H NMR analysis.

d

Reaction performed at a concentration of 5 M.

e

Reacted for 4 h instead of 16 h.

Performing the polymerization at higher concentration (C = 5 M) did not increase Mn (Table 1, entry 7), while attempts to run the reaction in the bulk only delivered small oligomers (Table S1). The importance of the DIPP substituent on cis selectivity was further demonstrated by using Ru-3a in the optimal reaction conditions, which resulted in only 80% cis-P1a (Table 1, entry 8). Unsaturated variant Ru-3c,37 showcased slightly lower stereoselectivity (89% cis) and molar masses (6.8 kg/mol) (Table 1, entry 9). Finally, stereoretentive catalyst Ru-4 led to unproductive ADMET presumably because of the rapid degradation of the unstable dithiolate Ru methylidene intermediate (Table 1, entry 10).35,36 Further investigation into the solvent concentration, temperature, time, and catalyst loading did not produce polymers with higher molar masses (Table S1).

With these optimized conditions in hand, we investigated the scope of the polymerization (Table 2). Polycarbonate P1a, polysulfite P2a, and polyether P4a were all isolated with 99% cis content, while polyester P3a was formed with slightly diminished cis content (91% cis). Reducing the number of methylene spacers between the alkene and the functional group did not negatively affect the stereoselectivity (P1b–4b). Commercially available deca-1,9-diene (5) was transformed into all-cis polyoctenamer P5,40 the cis variant of industrially produced vestenamer.41 To further explore the functional group tolerance of the cis-selective ADMET, polysiloxanes, which are common in coatings, ceramics, and dynamic covalent networks,42,43 were targeted. Polysiloxanes P6a and P6b were isolated from monomers 6a and 6b with exquisite cis selectivity and Mn values up to 17.6 kg/mol. Halogenated monomers 7a,b and 8a,b were tolerated, albeit with a slight decrease in cis selectivity, which is nonetheless in stark contrast to the typical ADMET polymerization of 7a,b and 8a,b with dichloro Ru carbenes.44 These halogenated polymers might be amenable to postpolymerization functionalization for the precise synthesis of additional polymer classes.45,46 Interestingly, alcohol monomers 9a and 9b were polymerized with high cis selectivity (93 and 96%) but in lower molar masses, which was ascribed to potential poisoning of the Ru catalyst. Overall, all monomers could be purchased or synthesized without tedious purifications, which is a notable advantage of the cis-selective ADMET. Additionally, Ru-3b was not found to be sensitive to oxidative degradation in contrast to dithiolate Ru catalysts (e.g., Ru-4, Table S2).47

Table 2. Substrate Scope for cis-Selective ADMET.

graphic file with name ja3c03978_0006.jpg

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a

N2 purging instead of vacuum; C = 2 M instead of 5 M.

The development of a versatile cis-selective ADMET allowed us to probe the impact of cis/trans stereochemistry over the thermal properties of about 30 polyalkenamers. trans-Rich variants of P1–P8 (>70% trans) were synthesized using Ru-1 (Supporting Information) and compared with the cis-rich polymers synthesized with Ru-3b. The thermal stability of the polymers was tested through thermogravimetric analysis (TGA, Figure 1a). Interestingly, cis-rich polyalkenamers were found to have higher decomposition temperature (Td) values in almost all cases, with the exception of P5 and P6a. The increased thermal stability is especially marked for polyesters (ΔTd = 36 °C for P3b) and polycarbonates (ΔTd = 36 °C for P1a and 61 °C for P1b). The thermal properties were further investigated through differential scanning calorimetry (DSC). A general trend was also observed for the glass-transition temperature (Tg) values. All polyalkenamers with an observable Tg within the scanned temperature range exhibited a lower Tg for the cis congener relative to the trans one (Figure 1b). Finally, only a few polyalkenamers presented a melting transition (Figure 1c). While P5 was characterized by a melting temperature (Tm) in both cis-rich (Tm = 32 °C) and trans-rich forms (Tm = 24 °C), P1a, P3a, P4a, and P4b only had a Tm when trans linkages were predominant throughout the backbone. Semicrystallinity is known to increase with the trans content in poly(1,3-diene)s, but inconsistent trends have been observed between stereochemistry and semicrystallinity with other families, including polycarbonates8,35 and polynorbornene.7,48 ADMET offers a unique opportunity to generate libraries of both trans-rich and cis-rich polyalkenamers upon the choice of catalyst and to interrogate the complex relationship between precise molecular structure and material properties.

Figure 1.

Figure 1

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Bar graphs comparing the influence of stereochemistry on (a) Td (5% weight loss), (b) Tg, and (c) Tm.

Polyalkenamers are commonly incorporated into industrial block copolymers to obtain thermoplastic elastomers (TPE),1 but very few studies have investigated the effect of cis/trans configuration.49 We sought to build an ABA triblock copolymer using P5 as the middle block and poly(lactic acid) (PLA) as the end blocks. As a biosourced and biodegradable polymer, PLA is an attractive, yet brittle, material50 whose toughness can be improved by incorporation of a rubbery middle block.51 Building upon a polymerization–depolymerization ADMET strategy initially reported by Wagener and coworkers with Ru-1,52 telechelic P5cis-OAc was synthesized using monomer 5 in the presence of Ru-3b and acetate reagent 10 (Figure 2a). Optimized conditions provided quantitative capping of both chain ends, as shown by NMR. Subsequent basic hydrolysis cleanly delivered macromolecular diol P5cis-OH (Mn = 3.3 kg/mol, 99% cis) with no change in Mn compared with the acetoxy precursor. Meanwhile, P5trans-OH (Mn = 3.1 kg/mol, 89% trans) was prepared similarly using Ru-1. Chain extension of telechelic macroinitiators P5cis-OH and P5trans-OH using d,l-lactide (11) and triazabicyclodecene (TBD) as catalyst efficiently provided ABA triblock copolymers P11-b-P5-b-P11 with either a cis- or trans-rich middle P5 block but similar molar mass distributions. TGA and DSC analysis revealed interesting trends (Figure 2b). Both triblocks displayed higher Td values than that of homopolymer P11, with the cis triblock being highest (278 °C), which is consistent with our previous observations. Incorporation of a cis middle block also led to the starkest decrease in Tg (32 vs 44 °C for the trans and 49 °C for P11). Finally, only the trans triblock showcased crystallinity, which is in line with previous literature reports.51 Nanoindentation was subsequently used to determine the hardness (Figure S45) and reduced Young’s modulus (Er) of all three polymers from the unloading segments of the load–displacement curves (Figure S44) using the standard Oliver and Pharr analysis.53 As expected on the basis of prior studies,51 both triblock architectures had a decreased Er compared with P11 (4.7 GPa, Figure 2c). The cis triblock exhibited a lower Er (3.0 GPa) than the trans congener (3.4 GPa), which indicates that the stiffness of the rubbery block can be finely tuned as a function of its stereochemistry.

Figure 2.

Figure 2

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(a) Synthesis of cis triblock copolymer P11-b-P5cis-b-P11. (b) Thermal properties and (c) reduced Young’s modulus (Er) of cis/trans triblocks and homopolymer P11.

In summary, we have developed a cis-selective ADMET polymerization of readily available and inexpensive α,ω-dienes. Up to 99% cis selectivity was obtained for most monomers through exquisite kinetic control of the olefin metathesis process enabled by a robust cyclometalated Ru catalyst (Ru-3b) at room temperature. This diversity-oriented polymerization allowed us to compare the thermal properties of a variety of cis-rich polyalkenamers containing different polar functional groups with their trans-rich congeners. High cis content was found to correlate with increased thermal stability, a lower glass-transition temperature, and typically amorphous behavior. Moreover, an ABA triblock copolymer with PLA as end blocks and polyoctenamer as a rubbery middle segment was synthesized. Nanoindentation measurements revealed that the cis stereochemistry led to a greater decrease in stiffness when compared with the trans triblock. Overall, this study provides both insights in stereoselective catalysis for polymerization and a general method for the modulation of thermal and mechanical properties of soft materials, including TPE, via control of the cis/trans stereochemistry throughout the main chain.

Acknowledgments

This work was supported by Texas A&M University, and the NMR facility in the Department of Chemistry was used. Use of the Texas A&M University Materials Characterization Core Facility (RRID:SCR_022202) and Soft Matter Facility (RRID:SCR_022482), as well as the contributions of Dr. Wilson Serem and Dr. Peiran Wei, are acknowledged. The authors thank Umicore for the generous donation of metathesis catalysts Ru-3b and Ru-4. This work was supported by the National Institute of General Medical Sciences at the National Institutes of Health under Award Number R35GM138079. Preliminary catalyst screening was made possible by the support of the Petroleum Research Fund managed by the American Chemical Society under Grant Number 60540-DNI7.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.3c03978.

  • Detailed experimental procedures, spectroscopic characterization, and additional supporting data (PDF)

Author Contributions

‡ S.J.K. and T.-W.H. contributed equally to this study.

The authors declare no competing financial interest.

Supplementary Material

ja3c03978_si_001.pdf (13.9MB, pdf)

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