Diene/polar monomer copolymers, compatibilisers for polar/non-polar polymer blends. A controlled block copolymerisation with a single-site component samarocene initiator

A well-controlled two-step process, the polymerisation of isoprene or isoprene/hex-1-ene copolymerisation followed by e-caprolactone polymerisation, affords trans-polyisoprene or (trans-polyisoprene/hex-1-ene copolymer)–poly(e-caprolactone) diblocks of various lengths. The single component initiator is an allylsamarocene compound. An atomic force microscopy study shows that these copolymers are efficient compatibilisers for poly(e-caprolactone) and polyisoprene blends. Poly(e-caprolactone) chain growth from Sm–polyisoprene chain.

Highly trans-stereospecific Isoprene Polymerization by Neodymium Borohydrido Catalysts

Highly stereospecific polymerization of isoprene was achieved using borohydridoneodymium complexes. In combination with stoichiometric amounts of dialkylmagnesium, Nd(BH4)3(THF)3 (1) and Cp*‘Nd(BH4)2(THF)2 (2) (Cp*‘ = C5Me4nPr) afford very efficient catalysts. The activity reaches 37300 (g of polyisoprene/mol of Nd)/h. Half-lanthanidocene 2 gives rise to polyisoprene, 98.5% trans-regular, the highest content yet described for a homogeneous organometallic catalyst. NMR experiments argue for the formation of bimetallic Nd(μ-BH4)Mg active species.

Diene/olefin/polar monomer copolymerisation: unprecedented functional polymers from a rare earth catalyst

An ansasamarocene allyl system is an efficient initiator which polymerises 1,3-dienes, copolymerises dienes and long-chain α-olefins or α,ω-dienes to give functionalisable polymers. It also polymerises caprolactone and allows the controlled diblock copolymerisation of isoprene or isoprene/ α-olefin copolymer and caprolactone.

Organolanthanides, catalysts for specific olefin-diene copolymerization: access to new materials

Abstract Non-hindered ansa dicyclopentadienylallyl complexes of samarium, [(CMe2C5H4)2Sm(allyl)]n, and (CMe2C5H4)2Sm(allyl)L (L=THF or allylLi) polymerize isoprene without an aluminum cocatalyst. The polymerizations are highly stereospecific, affording nearly quantitatively 1–4 trans polyisoprene. In the presence of linear 1-olefins, copolymers are formed, with 6–10% of olefin inserted; the 1–4 trans structure of the polyisoprene chain is not altered, and only one olefin molecule is inserted between two polyisoprene fragments. In the common initiator of these three catalytic systems, the (CMe2C5H4)2Sm(allyl) moiety, only one vacant site would be available. As a consequence of the presence o…

New Viscoelastic Materials Obtained by Insertion of anα-Olefin in atrans-Polyisoprene Chain with a Single-Component Organolanthanide Catalyst

Copolymerisation of isoprene with C 6 -C 18 a-olefins by a single component organolanthanide catalyst affords poly(trans-1,4-isoprene) containing 6-10% of inserted olefin. The mechanical properties of highly crystalline transpolyisoprene are dratically modified after insertion of the alkyl chains, leading to quasi-amorphous viscoelastic materials.

Stereospecific Polymerization of Isoprene with Nd(BH4)3(THF)3/MgBu2 as Catalyst

The neodymium trisborohydride Nd(BH 4 ) 3 - (THF) 3 (THF = tetrahydrofuran) has been used as a catalyst precursor for isoprene polymerization for the first time. Associated to an excess of Al(Et) 3 , the resulting catalyst is moderately active, giving a mixture of cis- and trans- polymer. Addition of a stoichiometric amount of MgBu 2 to Nd(BH 4 ) 3 (THF) 3 affords a stereospecific catalyst providing trans-1,4-polyisoprene, more than 96% regular. That dual component Nd/Mg system also shows a better efficiency and good control of the molecular weights. A molecular structure is tentatively attributed to a bimetallic active species, based on 1 H NMR experiments.

Nouveaux complexes organométalliques monocyclopentadiényles de lanthanides

Non-hindered ansasamarocenes, versatile catalysts for diene/olefin/polar monomer copolymerisations. What is really the active species?

Abstract Catalytic systems containing an ansabiscyclopentadienyllanthanide core and lithium and/or magnesium salts are obtained by reaction of the chloride precursors with allyllithium. These allyl complexes lead to the same active species which polymerises 1,3-dienes, copolymerises 1,3-dienes and α-olefin or α,ω-dienes or allows the controlled diblock polyisoprene/polycaprolactone copolymerisation. The exact nature of this active species and of the allyl precursors is investigated here.

Organometallic early lanthanide clusters: syntheses and X-ray structures of new monocyclopentadienyl complexes.

The reaction of Ln(BH(4))(3)(THF)(3) or LnCl(3)(THF)(3) with 1 equiv of KCp*' ligand (Cp' = C(5)Me(4)n-Pr) afforded the new monocyclopentadienyl complexes Cp*'LnX(2)(THF)(n) (X = BH(4), Ln = Sm, n = 1, 1a, Ln = Nd, n = 2, 1b; X = Cl, Ln = Sm, n = 1, 3a) and [Cp*'LnX(2)](n') (X = BH(4), n' = 6, Ln = Sm, 2a, Ln = Nd, 2b; X = Cl, Ln = Nd, 4b). All these compounds were characterized by elemental analysis and (1)H NMR. Crystals of mixed borohydrido/chloro-bridged [Cp*'(6)Ln(6)(BH(4))(12-x))Cl(x)(THF)(n')] (x = 10, n' = 4, Ln = Sm, 2a', Ln = Nd, 2b'; x = 5, n = 2, Ln = Sm, 2a' ') were also isolated. Compounds 2a, 2b, 2a', 2b', and 2a'' were structurally characterized; they all exhibit a hexameric…