Complex Branched Polyolefin Generated from Quasi-living Polymerization of 4-Methyl-1-pentene Catalyzed by α-Diimine Palladium Catalyst

Guo, Lihua; Gao, Haiyang; Li, Lin; Wu, Qing

doi:10.1002/macp.201100152

Cited by 24 publications

(13 citation statements)

References 32 publications

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“…Otherwise, 1,4-paired long branch units (1,4-B n ) or 1,4-paired long branches-onbranches unit, observed in the spectra of poly(4M1P) by a-diimine palladium catalysts, were not detected. 16,41 Starting from previous E-4M1P assignments, at low comonomer content, it is easy to identify, in Fig. 2b, the resonances corresponding to 4M1P units CH 3 (sc), CH(sc) and CH 2 (sc) at 21.18, 23.75, and 42.50 ppm, respectively (Scheme 3).…”

Section: Nmr Assignmentsmentioning

confidence: 78%

“…The absence of long comonomer sequences was also pointed out in the homopolymerization of 4M1P with Ni(II) and Pd(II) based catalysts, where this phenomenon was ascribed to the increased rate of chain-walking that was greater with respect to the rate of 4M1P insertion. 14,16 In the poly(E-co-4M1P) reaction, the rate of ethylene insertion seems to be generally greater than the rate of chain walking or 4M1P insertion.…”

Section: Mechanistic Explanationmentioning

confidence: 99%

“…1-hexene (1-Hex), and branched a-olens, i.e., 4-methyl-1-pentene (4M1P). [13][14][15][16][17][18][19][20][21][22][23][24][25] In this scenario, we recently rst reported a brief communication (Polym. Chem, 3,2012,1987) on the copolymerization of E with 4M1P catalyzed by [ArN]C(CH 3 )-(CH 3 )C]NAr]NiBr 2 with Ar ¼ 2,6-( i Pr) 2 C 6 H 3 (compound Ni-1) and diethylaluminium chloride (Et 2 AlCl).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Ethylene–4-methyl-1-pentene copolymers of complex chain architecture using α-diimine Ni(ii) catalysts: synthesis, 13C NMR assignment and understanding the chain-walking mechanism

et al. 2014

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Section: Nmr Assignmentsmentioning

confidence: 78%

Section: Mechanistic Explanationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Ethylene–4-methyl-1-pentene copolymers of complex chain architecture using α-diimine Ni(ii) catalysts: synthesis, 13C NMR assignment and understanding the chain-walking mechanism

et al. 2014

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“…The polymer with high molecular weight ( M n =51 000 and 15 600) and narrow molecular weight distribution ( M w / M n =1.28 and 1.10) was obtained in the polymerization at 0 or −20 °C (runs 3 and 4), indicating living character of the polymerization at those temperatures 16c…”

Section: Resultsmentioning

confidence: 98%

Olefin Polymerization Catalyzed by Double‐Decker Dipalladium Complexes: Low Branched Poly(α‐Olefin)s by Selective Insertion of the Monomer Molecule

Takano

Takeuchi

Osakada

2015

Chemistry A European J

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Dipalladium complexes of a cyclic bis(diimine) ligand with a double-decker structure catalyze polymerization of ethylene and α-olefins and copolymerization of ethylene with 1-hexene. The polymerization of 1-hexene yields a polymer that is mainly composed of the hexamethylene unit formed by 2,1-insertion of the monomer into the palladium-carbon bond, followed by chain-walking (6,1-insertion). The polymerization of 4-methyl-1-pentene proceeds by 2,1-insertion with a selectivity of 92-97 %, and affords the polymer with methyl and 2-methylhexyl branches. 2,1-Insertion occurs selectively in all of the polymerization reactions of α-olefins catalyzed by the dipalladium complexes. Ethylene polymerization with the catalyst at 100 °C lasts over 24 h, whereas the monopalladium-diimine catalyst loses its activity within 8 h at 60 °C. Polyethylene obtained by the dipalladium catalyst is less-branched and has a higher molecular weight compared to that of the monopalladium catalyst under the same conditions. Copolymerization of ethylene with 1-hexene affords solid products with melting points and molecular weights that vary depending on the polymerization time, suggesting formation of a block and/or gradient copolymer.

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“…[19][20][21][22][23][24][25][26][27][28] Since Brookhart's initial reports, 29 a-diimine nickel, palladium catalysts for olen polymerization have received much attention because they can produce polyolens with various types of branches and have a good polar group tolerance. [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45] Especially, the reduced oxophilicity of the palladium center gives the catalyst the ability to produce copolymers with a variety of polar-functionalized olens.…”

Section: Introductionmentioning

confidence: 99%

Substituent effects and activation mechanism of norbornene polymerization catalyzed by three-dimensional geometry α-diimine palladium complexes

Huo

Liu

et al. 2014

Polym. Chem.

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A series of three-dimensional geometry 9,10-dihydro-9,10-ethanoanthracene-11,12-diimine methyl palladium chloride complexes were synthesized and characterized. These three-dimensional geometry a-diimine palladium complexes exhibited high activities toward the homopolymerization of norbornene and copolymerization of norbornene with 5-norbornene-2-carboxylic acid methyl ester in the presence of B(C 6 F 5 ) 3 . It was observed that the palladium-halogen bond of the complexes could be effectively activated by B(C 6 F 5 ) 3 . The activation mechanism was clarified by the end group analysis of the polymer, which provided a new pathway for the activation of palladium complexes. Meanwhile, the palladium catalysts with a three-dimensional geometry on the backbone were found to show a good thermal stability and afford a high incorporation of the polar monomer in norbornene polymerization. Moreover, the a-diimine palladium complexes with a large steric hindrance or strongly electron-donating group on the aryl ring of ligands could achieve a higher reactivity.

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Complex Branched Polyolefin Generated from Quasi-living Polymerization of 4-Methyl-1-pentene Catalyzed by α-Diimine Palladium Catalyst

Cited by 24 publications

References 32 publications

Ethylene–4-methyl-1-pentene copolymers of complex chain architecture using α-diimine Ni(ii) catalysts: synthesis, 13C NMR assignment and understanding the chain-walking mechanism

Ethylene–4-methyl-1-pentene copolymers of complex chain architecture using α-diimine Ni(ii) catalysts: synthesis, 13C NMR assignment and understanding the chain-walking mechanism

Olefin Polymerization Catalyzed by Double‐Decker Dipalladium Complexes: Low Branched Poly(α‐Olefin)s by Selective Insertion of the Monomer Molecule

Substituent effects and activation mechanism of norbornene polymerization catalyzed by three-dimensional geometry α-diimine palladium complexes

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