Combining Ring‐Opening Metathesis Polymerization and Thiol‐Ene Coupling Chemistries: Facile Access to Novel Functional Linear and Nonlinear Macromolecules

Lowe, Andrew B.; Liu, Meina; Hensbergen, Johannes A. van; Burford, R. P.

doi:10.1002/marc.201300744

Cited by 31 publications

(26 citation statements)

References 86 publications

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“…Recently, we have been interested in the synthesis of novel functional ROMP‐active exo ‐7‐oxanorbornene monomers and have detailed the synthesis and (co)polymerization of a series of novel thioether‐based substrates (obtained via facile thiol‐Michael coupling) to give both linear and nonlinear macromolecules (hyperbranched and dendritic species) . Additionally, we have investigated the chemical modification of ROMP‐polymer backbones via radical thiol‐ene chemical modification and extended these general synthetic approaches to include examples of monomers and materials obtained via ADMET polymerization .…”

Section: Resultsmentioning

confidence: 99%

ROMP synthesis of novel thermo‐, pH‐, and salt‐responsive (co)polymers containing the morpholino functional group

Hensbergen

Ganda

Roth

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

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We report the ring-opening metathesis polymerization (ROMP) synthesis of novel (co)polymers containing the multiresponsive morpholino functional group [(3aR,7aS)22-(2-morpholinoethyl)23a,4,7,7a-tetrahydro-1H24,7-epoxyisoindole-1,3(2H)-dione (M1)]. All (co)polymers were prepared with the Grubbs' first generation initiator, RuCl 2 (PCy 3 ) 2 CHPh, in CH 2 Cl 2 or CH 2 Cl 2 /2,2,2-trifluoroethanol solvent mixtures. M1 homopolymers exhibit a pH dependent aqueous solubility being fully soluble below pH 5.0 and above pH 6.0. At these intermediate values, the polymers exhibit molecular weight (MW) independent inverse temperature dependent solubility with measured cloud points (T CP ) of 86 C at pH 5.0 and 79 C at pH 6.0. In the case of the lowest MW homopolymer (absolute MW of 9950 g/ mol), there was a clear dependence of the T CP on the homopolymer solution concentration and varied over the range 78-88 C. The T CP could be further tuned via the preparation of novel AB statistical copolymers. Incorporation of a permanently cationic comonomer as a more hydrophilic species resulted in an increase of the T CP at low incorporations (up to 10 mol %) and the complete disappearance of any temperature dependent solubility at 20 mol %. In a complementary approach, the T CP could also be lowered by the preparation of statistical copolymers of M1 with a more hydrophobic comonomer. Finally, we note that M1 homopolymers are also responsive to Na 2 SO 4 and could be readily salted-out of an aqueous solution salt at a [Na 2 SO 4 ] of 2.0 M giving a third trigger for controlling aqueous solubility. These copolymers represent examples of new multiresponsive materials and demonstrate the effectiveness of ROMP as a synthetic tool for the preparation of new and interesting materials.

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Section: Resultsmentioning

confidence: 99%

ROMP synthesis of novel thermo‐, pH‐, and salt‐responsive (co)polymers containing the morpholino functional group

Hensbergen

Ganda

Roth

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

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“…Here, we have taken inspiration from work that has utilized norbornene and internal double bonds produced from ROMP polymers and poly(butadienes) as functional handles using thiol‐ene chemistry; this is a new strategy in the development of a range of functional polyolefins. Our simple and versatile approach to develop functional polyethylenes is based on the preparation of polycyclooctene (P oct ) by ROMP of cyclooctene with Grubbs second generation catalyst.…”

Section: Methodsmentioning

confidence: 99%

Facile and versatile platform for the preparation of functional polyethylenes via thiol‐ene chemistry

Xiao

Bennett

Connal

2015

J. Polym. Sci. Part A: Polym. Chem.

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Polyethylene (PE) is the most used commodity polymer today. The reason PE has found widespread use in a range applications is due to the unique and tuneable properties available by tuning the molecular weight, the degree of branching, and choice of comonomers made by Ziegler-Natta or metallocene chemistry.1 The common industrial techniques used to make PEs have limited versatility to prepare functional PEs with, especially with polar comonomers. However, the range of applications could be increased further with the ability to prepare functional polyolefins.A range of techniques have been developed to prepare functional PE polymers. 3 The Wagner group has developed a number of strategies using acyclic diene metathesis (ADMET) polymerizations. [4][5][6][7][8] Recently, Hillmyer and coworkers 9 developed a two-step synthesis using ring-opening metathesis polymerization (ROMP) of acetoxy functional cyclooctene to produce stereo regular functional polyolefins. A range of functional groups have been incorporated into PE's structure including: phosphonic ester and phosphonic acid, 10 carboxylic acid, 11 amino, 12 alcholol, 13 methylimidazolium bromide. 6Most of the strategies developed require functionalization of monomers. Herein, we describe a versatile platform synthesis whereby the one polymer platform can be functionalized with a number of polar or nonpolar groups.Here, we have taken inspiration from work that has utilized norbornene 14 and internal double bonds produced from ROMP polymers [15][16][17] and poly(butadienes) 18 as functional handles using thiol-ene chemistry; this is a new strategy in the development of a range of functional polyolefins. Our simple and versatile approach to develop functional polyethylenes is based on the preparation of polycyclooctene (P oct ) by ROMP of cyclooctene with Grubbs second generation catalyst. Subsequent functionalization reactions of the internal alkene bond can be achieved with a range of thiol functional molecules, via photoactivated thiol-ene click chemistry to prepare a range of functional PEs,19,20 providing a unique and versatile technique to functionalize PEs.ROMP polymerizations of cyclooctene were performed for 1 h in dichloromethane at 30 C, resulting in a library of polymers with M n ranging from 7 to 165 kDa and typical dispersity index of about 1.6, see Supporting Information Table S1 for details. These versatile platform polymers were used to demonstrate facile functionalization strategies using thiol-ene photochemistry, with a wide range of thiols (Scheme 1). The thiol-ene photoinitiated reactions were performed in appropriate solvents with an excess amount of thiol-containing small molecules (2-5 equivalents per double bond). 2,2-Dimethoxy-2-phenylacetophenone (DMPA) was used as a photoinitiator and irradiated with UV (365 nm) light for 6 h.

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“…(10) preparation of stereoregular polymers via ROMP [37]; (11) preparation of self-assembled supramolecular polymers [38]; (12) combining ROMP and thiol-ene coupling chemistry for preparation of linear and nonlinear macromolecules [39]; (13) synthesis of cyclo-polyolefins through ring expanding metathesis polymerization [40]; (14) precision polymers through ADMET polymerization [41,42]; (15) systematic studies of morphological changes of ADMET-derived precision polyethylene [43]; (16) concurrent cross metathesis and enzymatic oxidation reactions [44]; (17) rhenium oxide based olefin metathesis [45]; and (18) olefin metathesis over molybdenum-exchanged zeolites [46]. Additional reviews in languages other than English include: (1) olefin metathesis in complex synthesis [47]; (2) Z-selective olefin metathesis catalysts and their applications [48]; (3) modification of biodiesel using olefin metathesis [49]; (4) cyclic aminocarbene complexes (Bertrand carbene complexes) in olefin metathesis reactions [50]: (5) progress in ROMP of dicyclopentadiene [51]; and (6) the role MgO in WO 3 / SiO 2 catalyzed olefin metathesis [52].…”

Section: A Review Articles Highlights and Commentsmentioning

confidence: 99%

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

Herndon

2016

Coordination Chemistry Reviews

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Combining Ring‐Opening Metathesis Polymerization and Thiol‐Ene Coupling Chemistries: Facile Access to Novel Functional Linear and Nonlinear Macromolecules

Cited by 31 publications

References 86 publications

ROMP synthesis of novel thermo‐, pH‐, and salt‐responsive (co)polymers containing the morpholino functional group

ROMP synthesis of novel thermo‐, pH‐, and salt‐responsive (co)polymers containing the morpholino functional group

Facile and versatile platform for the preparation of functional polyethylenes via thiol‐ene chemistry

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

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