Arylzinc Complexes as New Initiator Systems for the Production of Isobutene Copolymers with High Isoprene Content

Garratt, Shaun; Guerrero, Antonio; Hughes, David L.; Bochmann, Manfred

doi:10.1002/anie.200353787

Cited by 37 publications

(26 citation statements)

References 54 publications

(11 reference statements)

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“…2 mol‐% IP incorporation was obtained for this initiator system. Zinc‐based initiators are evidently less affected by higher IP concentrations than Et 2 AlCl/ t BuCl for example; indeed we have shown earlier that another zinc initiator, Zn(C 6 F 5 ) 2 (toluene)/ t BuCl, is capable of producing high molecular weight linear copolymers with nearly 15 mol‐% IP 24…”

Section: Resultsmentioning

confidence: 81%

“…We have recently reported zinc‐based initiator systems for isobutene (IB) polymerizations and shown that mixtures of Zn(C 6 F 5 ) 2 (toluene) and alkyl halides give isoprene (IP)‐rich high molecular weight IB copolymers at −78 to −35 °C 24. Another zinc initiator, EtZnCl/ t BuCl, homopolymerizes IB at room temperature to give the so‐called ‘highly reactive’ PIBs with $\overline M _{\rm n}$ values of 10 000–28 000 g · mol −1 and up to 92% terminal CC bonds 25.…”

Section: Introductionmentioning

confidence: 99%

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Alkyl Zinc Chlorides as New Initiators for the Polymerization and Copolymerization of Isobutene

Guerrero

Kulbaba

Bochmann

2008

Macro Chemistry & Physics

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Mixtures of RZnCl and tBuCl (R = Et) initiate the polymerization of isobutene in the temperature range of (- 35) - (+ 35) degrees C. The order of addition of the reagents is important for effective polymerization. Increasing the solubility of the zinc reagent (R = n-octyl) and use of cumyl chloride as co-initiator provides a system that is active from (-90) - (+35) degrees C. The molecular weights show a remarkably small temperature dependence, E-DP = -3.3 KJ.mol(-1), compared to E-DP = -23 kJ.mol(-1) in classical systems (AlCl3, EtAICl(2)). The molecular weights increase with decrease in zinc concentration and are consistently higher for n-octyl zinc chloride, as expected for a bulkier, less coordinating counteranion polymerizations are not retarded by isoprene addition; homopolymers and copolymers show essentially identical conversions and molecular weights

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Section: Resultsmentioning

confidence: 81%

Section: Introductionmentioning

confidence: 99%

Alkyl Zinc Chlorides as New Initiators for the Polymerization and Copolymerization of Isobutene

Guerrero

Kulbaba

Bochmann

2008

Macro Chemistry & Physics

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“…It was reported that the low‐level unsaturated units between long polyisobutylene segments will bring about the excellent gas barrier and good flex properties of BIIR . However, only a few experimental studies on altering the copolymer composition of IIR rather than BIIR have been reported . For example, Garratt et al developed an initiating system for preparing IIR with high isoprene content and confirmed the high efficiency of the system .…”

Section: Introductionmentioning

confidence: 99%

“…However, only a few experimental studies on altering the copolymer composition of IIR rather than BIIR have been reported . For example, Garratt et al developed an initiating system for preparing IIR with high isoprene content and confirmed the high efficiency of the system . McInenly et al successfully prepared a high isoprene content IIR and found that the T g increased with increasing isoprene content .…”

Section: Introductionmentioning

confidence: 99%

The Relationship between Specific Structure and Gas Permeability of Bromobutyl Rubber: A Combination of Experiments and Molecular Simulations

Cai

You

Zhao

et al. 2019

Macro Theory & Simulations

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The relationship between the specific structure and gas permeability of brominated poly(isobutylene‐co‐isoprene) rubber (BIIR) is investigated by a combination method of both experiments and molecular simulation. It is found that the various content of secondary allyl bromide isoprene (SABI) units exert an effect on transport behavior, including both diffusion and solution behavior of small molecule in BIIR, glass transition temperature, and vulcanization characteristics. The results show that a minimum value of permeability coefficient exists with the increase of SABI content. Moreover, more SABI in BIIR will lead to a rise in glass transition temperature and curing rate. It means that the gas permeability of BIIR can be further improved by adjusting composition of the copolymer BIIR. Meanwhile, this research may also provide useful information for understanding the penetration mechanism of oxygen in the BIIR matrix and supply a theoretical tool for designing high air tightness rubber materials.

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“…The saturated hydrocarbon backbone is responsible for many advantageous properties of PIB, but it also limits the ability to modify and tune the properties of the polymer. Thus, many applications of PIB have involved the introduction of chemical functionalities to the PIB backbone or termini, or the incorporation of PIB into block copolymers . For example, IB can be copolymerized with small amounts (i.e.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and properties of bromide‐ functionalized poly(isobutylene‐co‐p‐ methylstyrene) random copolymer

Xie

Chang

et al. 2016

Polymer International

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Poly(isobutylene-co-p-methylstyrene) (IB/p-MS) random copolymer is a new generation of polyisobutylene-based elastomers. The cationic copolymerization of IB with p-MS was thoroughly examined by using 2-chloro-2,4,4-trimethylpentane/ ethylaluminiumsesquichloride/electron donor as initiating system. IB/p-MS random copolymers with high molecular weight were obtained at elevated temperature through the addition of ethyl acetate; the reaction proceeded in a mildly exothermic manner. Although the reactivity ratios of comonomer pairs differ by close to an order of magnitude, p-MS was uniformly distributed in the chains. IB/p-MS random copolymer can be brominated by adding molecular bromine into the copolymer solution, thereby yielding a completely saturated polymer backbone with a chemically reactive site. The types and selection of appropriate vulcanization systems for bromide-functionalized IB/p-MS random copolymers are also discussed.

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Arylzinc Complexes as New Initiator Systems for the Production of Isobutene Copolymers with High Isoprene Content

Abstract: The initiator system [Zn(C6F5)2]/tBuCl for isobutene/isoprene copolymerizations (see scheme) gave products with high molecular weights, significantly increased isoprene incorporation, and minimal cross-linking

Cited by 37 publications

References 54 publications

Alkyl Zinc Chlorides as New Initiators for the Polymerization and Copolymerization of Isobutene

Alkyl Zinc Chlorides as New Initiators for the Polymerization and Copolymerization of Isobutene

The Relationship between Specific Structure and Gas Permeability of Bromobutyl Rubber: A Combination of Experiments and Molecular Simulations

Synthesis and properties of bromide‐ functionalized poly(isobutylene‐co‐p‐ methylstyrene) random copolymer

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