Copolymerization of Ethylene with 1-Butene and Norbornene to Higher Molecular Weight Copolymers in Aqueous Emulsion

Abstract

Ethylene/norbornene and ethylene/1-butene copolymerization with nickel(II) salicylaldiminato complexes [{κ2-N,O-6-C(H)N(2,6-R2C6H3)-2,4-R‘2C6H2O}NiMe(pyridine)] (1a, R = 3,5-Me2C6H3, R‘ = I; 1b, R,R‘ = 3,5-(F3C)2C6H3; 1c, R = 3,5-(F3C)2C6H3, R‘ = I; 2, R = iPr, R‘ = I) were studied in toluene as a reaction medium and in emulsion, the latter affording polymer dispersions. High molecular weight copolymers (M n > 104 g mol-1) are formed. Incorporation of ethylene is much preferred over butene incorporation, X Bu/x Bu ∼0.05 under typical reaction conditions, by comparison incorporation of the strained olefin norbornene is higher, X NB/x NB ∼0.25 (X = comonomer mole fraction in polymer; x = comonomer mole fraction in reaction mixture). Dispersions contained copolymers with up to 6 mol % comonomer (12 wt % for 1-butene; 20 wt % for norbornene). Incorporation of a few mol % of norbornene strongly decreases polymer crystallinity, which enhances the film forming properties of dispersions. Microstructure analysis by 13C NMR shows that butene is incorporated in a 1,2-, 1,3- and 1,4-fashion. Whether 1,2- or 1,3-incorporation is predominant depends on the catalyst (nature of R).

Catalytic Ethylene Polymerisation in Carbon Dioxide as a Reaction Medium with Soluble Nickel(II) Catalysts

“…For 6 c and 6 e, which have also been studied in toluene as a reaction medium, the overall properties of the polyethylenes obtained in scCO 2 and in toluene are similar (toluene; 40 bar ethylene pressure; 50 8C polymerisation temperature; 6 c: M w = 4.6 10 4 g mol À1 ; M w /M n = 2.3; T m = 111 8C; 45 % crystallinity; [26] 6 e: M w = 1.0 10 5 g mol À1 ; M w /M n = 5.1; T m = 123 8C; 50 % crystallinity [22] ). Comparing the polymers prepared in scCO 2 with the different catalyst precursors, branching and thus crystallinity can be varied over a substantial range through the substitution pattern of the salicylaldimine ligand (Table 1).…”

“…Employing aldehyde 4' [26] substituted with 3,5-(CF 3 ) 2 -A C H T U N G T R E N N U N G (C 6 H 3 ) groups introduces a higher number of fluorinated groups to the ligand backbone, [27] and can also render the salicylaldimine ligand more electron withdrawing. Condensation with different anilines afforded salicylaldimines 5 c and 5 d. Efforts to prepare a ligand containing para-R F -substituted aryl groups in the aldehyde moiety, through Suzuki coupling of 1 and 4, failed.…”

“…[NiA C H T U N G T R E N N U N G (tmeda)(Me) 2 ] was supplied by MCat (Konstanz). 4-(Trifluoromethyl)phenylboronic acid [39] (2'), 6-C(H)=O-2,4-{3,5-(F 3 C) 2 C 6 H 3 } 2 C 6 H 2 OH (4'), [26] and 6-C(…”

“…, [26] and complexes 6 c [26] and 6 e [22] were prepared according to known procedures. Perfluorinated surfactants FLUOWET NMQ and Fluowet PL80 were provided by Clariant GmbH.…”

From polymeric particles to multifunctional nanocapsules for biomedical applications using the miniemulsion process

“…Therefore, other types of polymerizations can also be carried out in miniemulsion: the anionic polymerization in nonaqueous miniemulsions leads to polyamide nanoparticles, 21 and in aqueous phase, polybutylcyanoacrylate (PBCA) nanoparticles can be synthesized. 22 The cationic polymerization allows the formation of poly-p-methoxystyreneparticles, 23,24 the catalytic polymerization enables the synthesis of polyolefine 25,26 or polyketone particles, 27 the ring-opening metathesis polymerization leads to polynorbonene nanoparticles, 28,29 and the step-growth acylic diene metathesis (ADMET) polymerization to oligo(phenylene vinylenes) particles. 30 The polyaddition in miniemulsion allows the formation of polyepoxides 31 or polyurethanes (PUs) particles.…”