Synthesis of β-Myrcene-Based Polymers and Styrene Block and Statistical Copolymers by SG1 Nitroxide-Mediated Controlled Radical Polymerization

Métafiot, Adrien; Kanawati, Yara; Gérard, Jean‐François; Defoort, Brigitte; Marić, Milan

doi:10.1021/acs.macromol.6b02675

Cited by 58 publications

(79 citation statements)

References 112 publications

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“…On the other hand, all poly(S-co-Fa) samples were white powders. The catalyst productivity decreased with an increase of the cases of styrene/β-myrcene and styrene/farnesene copolymerization, respectively, entries 4-10 and entries [13][14][15][16][17]; this is consistent with the fact that 1 is poorly active towards β-myrcene and farnesene homopolymerization (entries 1-2 and 11-12). On the other hand, as the [terpene] 0 /[St] 0 feed ratio was raised, the terpene content in the resulting copolymers increased as expected; thus, a wide range of compositions was obtained (My content = 5.6-30.8 mol % and Fa content = 1.5-9.8 mol %).…”

Section: Copolymerizations Of Styrene With β-Myrcene and Farnesenesupporting

confidence: 71%

“…Syndioselective copolymerization of styrene with small amounts of a second monomer is one of the most common ways to tune the properties of sPS, and thus to improve its processability [9][10][11]. A few examples of styrene-myrcene polymers have already been reported, mostly via anionic or radical copolymerizations [12][13][14]. To our knowledge, only one paper has addressed the coordination copolymerization of styrene with β-myrcene (My) in the presence of the ternary system Cp * La(BH 4 ) 2 (THF) 2 /nBuEtMg/AliBu 3 , affording poly(S-co-1,4-trans-My) containing high amounts of myrcene (66-96 mol %) [15].…”

Section: Introductionmentioning

confidence: 99%

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Stereoselective Copolymerization of Styrene with Terpenes Catalyzed by an Ansa-Lanthanidocene Catalyst: Access to New Syndiotactic Polystyrene-Based Materials

et al. 2017

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Abstract:The copolymerization of bio-renewable β-myrcene or β-farnesene with styrene was examined using an ansa-neodymocene catalyst, affording two series of copolymers with high styrene content and unprecedented syndioregularity of the polystyrene sequences. The incorporation of terpene in the copolymers ranged from 5.6 to 30.8 mol % (β-myrcene) and from 2.5 to 9.8 mol % (β-farnesene), respectively. NMR spectroscopy and DSC analyses suggested that the microstructure of the copolymers consists of 1,4-and 3,4-poly(terpene) units randomly distributed along syndiotactic polystyrene chains. The thermal properties of the copolymers are strongly dependent on the terpene content, which is easily controlled by the initial feed. The terpolymerization of styrene with β-myrcene in the presence of ethylene was also examined.

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Section: Copolymerizations Of Styrene With β-Myrcene and Farnesenesupporting

confidence: 71%

Section: Introductionmentioning

confidence: 99%

Stereoselective Copolymerization of Styrene with Terpenes Catalyzed by an Ansa-Lanthanidocene Catalyst: Access to New Syndiotactic Polystyrene-Based Materials

et al. 2017

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“…Myrcene has been copolymerized with monomers typically used for thermoplastics like α‐methyl‐ p ‐methylstyrene and poly(lactic acid) by anionic polymerization, and more recently copolymerized with GMA and styrene by NMP . Far has been homopolymerized by ionic polymerization, but polymerization by RDRP has not yet been reported.…”

Section: Introductionmentioning

confidence: 99%

Nitroxide‐Mediated Polymerization of Bio‐Based Farnesene with a Functionalized Methacrylate

Luk

Marić

2019

Macro Reaction Engineering

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polymers with controlled architectures. [11,12] Styrene-butadiene-styrene (SBS) and styrene-isoprene-styrene (SIS) triblock copolymers have long been commercialized too, such as the Kraton family of thermoplastic elastomers, which are made by anionic polymerization. [13,14] While many industrial applications use free radical polymerization, CRP precisely controls the molecular architecture of polymer chains, therefore making homopolymers, diblock and triblock copolymers with narrow molecular weight distributions (MWDs) and low dispersity. [15] Ionic polymerization is a truly "living" method, but it is intolerant to functional monomers and impurities. [16] CRP, more properly defined as reversible deactivation radical polymerization (RDRP), is a newer, more versatile technique to control the polymerization of free radicals. It utilizes activationdeactivation equilibrium or reversible chain transfer to suppress irreversible termination such that the propagating radical is primarily in its dormant state. [17] Amongst the several types of RDRP, atom transfer radical polymerization (ATRP) [18][19][20] and reversible additionfragmentation transfer (RAFT) [21][22][23] can polymerize a wide variety of functional monomers like vinyl esters and (meth) acrylates. This study will focus on nitroxide-mediated polymerization (NMP) as it is particularly adept for polymerization of styrene-diene systems. [24][25][26] NMP is able to polymerize functionalized styrene and acrylate monomers successfully, [27] however it is limited in its ability to maintain active chain ends in the polymerization of methacrylates. [28,29] It was discovered that the rate of dissociation (k d ) is very large because of steric stabilization of the propagating methacrylate radical, and the rate of combination (k c ) is very low due to steric hindrance provided by the bulky SG1-nitroxide (N-tert-butyl-N-[1-diethylphosphono-(2,2dimethylpropyl)] nitroxide). Consequently, the activationdeactivation equilibrium (K eq = k d /k c ) is high, resulting in termination by disproportionation. [30] To overcome this, small amounts of controlling comonomer like styrene or acrylonitrile can be added to effectively lower K eq . [28,31] Furthermore, the SG1-based nitroxide, BlocBuilder, can be modified with an N-succinimidyl ester group (N-succinimidyl modified commercial BlocBuilder [NHS-BB]) to better control the polymerization of methacrylates, [32] and successful polymerization of Nitroxide-Mediated Polymerization Farnesene (Far) is a bio-based terpene monomer that is similar in structure to commercially used dienes like butadiene and isoprene. Nitroxide-mediated polymerization (NMP) is adept for the polymerization of dienes, but not particularly effective at controlling the polymerization of methacrylates using commercial nitroxides. In this study, Far is statistically copolymerized with a functional methacrylate, glycidyl methacrylate (GMA), by NMP using N-succinimidyl modified commercial BlocBuilder (NHS-BB) initiator. Reactivity ratios are determined to be r Far = ...

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“…Early work by David presented emulsion copolymerization of styrene/methyl methacrylate and myrcene initiated by 2,2‐azobisisobutyronitrile, wherein a higher molecular weight (20 000 Da) but a lower conversion rate (5–13%) was obtained. In the last 3 years, additional works initiated by free radicals have been investigated . However, those studies revealed that free radical polymerization did not produce ideal results as they encountered issues such as longer reaction time (>15 h), uncontrollable microstructure, and unsatisfactory conversion rate (only up to 80%) .…”

Section: Introductionmentioning

confidence: 99%

Bio‐based β‐myrcene‐modified solution‐polymerized styrene–butadiene rubber for improving carbon black dispersion and wet skid resistance

Zhang

et al. 2019

J of Applied Polymer Sci

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β-Myrcene, a bio-based monoterpene derived from plants, was introduced to replace butadiene in the solution-polymerized styrene-butadiene rubber by using the conventional anionic copolymerization technique. The anionic copolymerization of β-myrcene was found to be stoichiometric and controllable. A series of solution-polymerized styrene-myrcene-butadiene rubber (S-SMBR) with 100% conversion, high-molecular weight (150 000-200 000 Da), low polydispersity, and uniform compositions was obtained. The glass transition temperature of S-SMBR exhibited imperceptible variation with different myrcene/butadiene ratios. Interestingly, the introduction of such a long nonpolar pendant group containing isopropylidene could greatly improve carbon black dispersibility in the rubber. Furthermore, the wet skid resistance of the rubber could be improved without impairing its low rolling resistance. The tensile strength of S-SMBR was found to be higher than that prepared by radical emulsion copolymerization. The S-SMBR prepared by anionic solution copolymerization is thus a promising material for tires to attain sustainable development. HIGHLIGHTS• A bio-based monomer was successfully introduced to replace diene part in SBR through anionic polymerization.• Carbon black dispersibility in the rubber was greatly improved.• The wet skid resistance of the rubber could be improved without impairing its low rolling resistance.• Robust tensile behaviors were obtained compared with the rubber prepared by radical emulsion polymerization.

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Synthesis of β-Myrcene-Based Polymers and Styrene Block and Statistical Copolymers by SG1 Nitroxide-Mediated Controlled Radical Polymerization

Abstract: International audienc

Cited by 58 publications

References 112 publications

Stereoselective Copolymerization of Styrene with Terpenes Catalyzed by an Ansa-Lanthanidocene Catalyst: Access to New Syndiotactic Polystyrene-Based Materials

Stereoselective Copolymerization of Styrene with Terpenes Catalyzed by an Ansa-Lanthanidocene Catalyst: Access to New Syndiotactic Polystyrene-Based Materials

Nitroxide‐Mediated Polymerization of Bio‐Based Farnesene with a Functionalized Methacrylate

Bio‐based β‐myrcene‐modified solution‐polymerized styrene–butadiene rubber for improving carbon black dispersion and wet skid resistance

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