Homologous Poly(isobutylene)s: Poly(isobutylene)/High-Density Poly(ethylene) Hybrid Polymers

Binder, Wolfgang H.; Kurzhals, Steffen; Pulamagatta, Bhanuprathap; Decker, Ulrich; Pawar, Gajanan M.; Wang, Dongren; Kühnel, Christa; Buchmeiser, Michael R.

doi:10.1021/ma801465r

Cited by 47 publications

(51 citation statements)

References 44 publications

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“…Materials : All reagents were purchased from Sigma‐Aldrich and used without further purification. Endo,exo[2.2.1] bicyclo‐2‐ene‐5,6‐dicarboxylic acid dimethylester (monomer A ) and exo‐ N ‐(4,4,5,5,6,6,7,7,7‐nonafluoroheptyl)‐10‐oxa‐4‐azatricyclodec‐8‐ene‐3,5‐dione (monomer D ) were synthesized according to methods reported elsewhere 32–34 . A m D n BCPs were synthesized by sequential ring opening metathesis polymerization of monomer A and subsequently of monomer D using Grubbs 1st generation catalyst [RuCl 2 (PCy 3 ) 2 (CHPh)] in dry CH 2 Cl 2 under argon atmosphere at room temperature.…”

Section: Methodsmentioning

confidence: 99%

Block Copolymer Nanotubes by Melt‐infiltration of Nanoporous Aluminum Oxide

et al. 2010

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The use of shape-defi ning hard templates containing arrays of cylindrical nanopores, such as self-ordered nanoporous anodic aluminum oxide (AAO), [ 1 , 2 ] is a well-established synthetic approach to one-dimensional (1D) nanostructures. [ 3 ] However, generating specifi c functionalities requires control over mesoscopic structure formation processes occurring in the confi ned geometry of nanorods or nanotube walls, such as crystallization and phase separation. [ 4 ] The self-assembly of block copolymers (BCPs) in nanopores having hard confi ning pore walls has been considered as an attractive access to 1D nanostructures exhibiting mesoscopic fi ne structures as a second hierarchical structure level. Their nanoscopic domain structures could be converted into polymeric scaffolds containing mesoporous structures by post-infi ltration process steps including selective degradation of one of the blocks [ 5 ] or selective swelling of one of the components. [ 6 , 7 ] Since nanotubes can be exploited as nanoscopic containers, pipelines or separation media, it is highly desirable to fabricate tubular nanostructures, the walls of which consist of microphase-separated BCPs. Hence, potential functionalities of nanotubes and of BCPs could be combined. Thus, for example, nanotubes with walls composed of multiple concentric layers having different properties could be accessible in this way. Catalytic systems, micro reactorscharge storage systems, pipelines or sensors consisting of hallow/tubular nanostructures with multilayered walls may show superior properties as compared to device architectures based on corresponding soilid rodlike nanostructures. [ 8 ] BCP nanotubes inside nanoporous hard templates were produced previously by solution-infi ltration of BCPs dissolved in organic solvents. [ 9 , 10 ] In this case, the adsorption kinetics depends on a multitude of parameters including temperature and thermodynamic quality of the solvent. Most importantly, the evaporation of the solvent required for solidifi cation of the BCP is a non-equilibrium process diffi cult to control in a satisfactory manner, which involves additional migration of polymer from the supernatant solution into the pores, separation into solventrich and polymer-rich phases, occurrence of hydro dynamic instabilities and surface reconstruction processes, as well as uncontrolled development of ill-defi ned gradient structures. In contrast, the melt infi ltration of block copolymers has always yielded solid nanorods via a capillary fi lling mechanism. [11][12][13][14] Here we demonstrate that during melt infi ltration of microphase-separated BCPs having a fl uorinated block into AAO hard templates precursor fi lms form, the solidifi cation of which yields exclusively tubular BCP nanostructures. Terminal fl ow of the BCPs is not a prerequisite for precursor fi lm formation if the surface energy of the newly formed BCP/air interface is low enough, thus providing access to tubular BCP nanostructures with walls having mesoscopic fi ne structures such as concentri...

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Section: Methodsmentioning

confidence: 99%

Block Copolymer Nanotubes by Melt‐infiltration of Nanoporous Aluminum Oxide

et al. 2010

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“…7 Shortly after this, Faust and Kennedy et al reported the first living carbocationic polymerization of isobutylene (IB); 8 this breakthrough led to the preparation of well-defined hydroxy-/amino-telechelic PIBs with low dispersity. 13 More recently, Binder et al synthesized poly(homo-isobutylene) from 3,3-dimethylcyclopropene utilizing a similar strategy, 14 and this pseudo-PEIB had a moderate dispersity (1.9-3.9) and a melting temperature (T m ) of 108°C. 9,10 In addition, poly(styrene)-b-poly(iso-butylene)-b-poly(styrene) (SIBS) block polymers have been used as polymeric coatings in a drug-eluting coronary stents.…”

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confidence: 99%

Hydroxy-telechelic poly(ethylene-co-isobutylene) as a soft segment for thermoplastic polyurethanes

Wang

2015

Polym. Chem.

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Facile preparation of linear amorphous hydroxy-telechelic poly-(ethylene-co-isobutylene) (PEIB) was enabled by ROMP of a new monomer, (Z)-5,5-dimethylcyclooct-1-ene (Me 2 COE). Control of the equivalent isobutylene content and the resulting thermal properties was accomplished via copolymerization with COE. The applicability as a prepolymer was demonstrated by the synthesis of a tough, elastic and free-standing polyurethane film. cyclooctadiene (1,5-COD), as shown in Scheme 1. tert-Butyl Scheme 1 Synthesis of the monomer Me 2 COE 5. † Electronic supplementary information (ESI) available. See Scheme 2 Synthesis of hydroxy-telechelic PEIBs PH(Me 2 COE)-OH 7 and PH(COE-s-Me 2 COE)-OH 9: ROMP, hydrogenation and hydrolysis. CommunicationPolymer ChemistryPolym. Chem. This journal is

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“…A chemical shift difference of about 1 ppm is expected for cis vs. trans olefins in ROMP polymers (such as polyDCMNBD7b). In a recent report, polyMPCP obtained with a ruthenium-based initiator was assigned to have the trans configuration on the basis of an absorption at ~980 cm −1 and an olefinic 13 CNMR resonance at 136 ppm 21. Therefore the structures of polyMPCP 1 and polyMPCP 3a are assigned as cis , while polyMPCP 2a is assigned to be trans .…”

Section: Resultsmentioning

confidence: 99%

Z-Selective and Syndioselective Ring-Opening Metathesis Polymerization (ROMP) Initiated by Monoaryloxidepyrrolide (MAP) Catalysts

et al. 2010

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We report the Z-selective and syndioselective polymerization of 2,3-bis(trifluoromethyl)bicyclo[2.2.1]hepta-2,5-diene (NBDF6) and 3-methyl-3-phenylcyclopropene (MPCP) by monoaryloxide monopyrrolide imido alkylidene (MAP) catalysts of Mo. The mechanism of polymerization with syn-Mo(NAd)(CHCMe 2 Ph)(Pyr)(OHIPT) (1; Ad = 1-adamantyl, OHIPT = O-2,6-(2,4,6-i-Pr 3 C 6 H 2 ) 2 C 6 H 3 ) as the initiator is proposed to consist of addition of monomer to the syn initiator to yield a syn first insertion product and propagation via syn insertion products. In contrast, the mechanism of polymerization with syn-Mo(NAr) (CHCMe 2 Ph)(Pyr)(OTPP) (4; Ar = 2,6-i-Pr 2 C 6 H 3 , OTPP = 2,3,5,6-Ph 4 C 6 H) as the initiator at −78°C consists of addition of monomer to the syn initiator to yield an anti first insertion product and propagation via anti insertion products. Polymerizations of NBDF6 and MPCP at room temperature initiated by 4 led to polymers without a regular structure. We propose that the syndiotacticity of cis polymers is the consequence of the required inversion at the metal center with each insertion of monomer, i.e., stereogenic metal control of the polymer structure. We also propose that the two mechanisms for forming cis,syndiotactic polymers arise as a consequence of the relative steric bulk of the imido and phenoxide ligands.

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Homologous Poly(isobutylene)s: Poly(isobutylene)/High-Density Poly(ethylene) Hybrid Polymers

Cited by 47 publications

References 44 publications

Block Copolymer Nanotubes by Melt‐infiltration of Nanoporous Aluminum Oxide

Block Copolymer Nanotubes by Melt‐infiltration of Nanoporous Aluminum Oxide

Hydroxy-telechelic poly(ethylene-co-isobutylene) as a soft segment for thermoplastic polyurethanes

Z-Selective and Syndioselective Ring-Opening Metathesis Polymerization (ROMP) Initiated by Monoaryloxidepyrrolide (MAP) Catalysts

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