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.

New aromatic diamines containing a multiring flexible skeleton for the synthesis of thermally stable polyimides

Abstract Multi-ring aromatic diamines bearing a long alkyl chain (C 6 , C 8 or C 16 ) were obtained from the corresponding dinitro compounds synthesized by a Friedel–Crafts alkylation of substituted mesitylenes by paranitrobenzyl chloride. The bismaleimide synthesized from the diamine bearing a C 16 chain formed a thermostable polyimide.

Mono(cyclooctatetraenyl)samarium Complexes: the Return of the Normally “Inaccessible” Bis(trimethylsilyl)amido Derivative

Lanthanides benzimidinates: initiators or real catalysts for theɛ-caprolactone polymerization

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 as single component homogeneous catalysts for isoprenehex—1-ene co-polymerisation

Abstract Bisallylansalanthanide complexes act as single component catalysts of diene polymerisation; from an equimolar mixture of isoprene and hex-1-ene, a co-polymer hex-1-ene/isoprene = 1:10 is obtained, this copolymer is essentially formed of 1,4- trans polyisoprene blocks separated by only one inserted hexyl group.

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.

Anionic Monosubstituted Cyclopentadienylsamarium Derivatives: Catalysts for a Stereospecific Isoprene Polymerization

New alkyl and allyl complexes 1–3 {1: [Cp′2Sm(C3H5)]n, Cp′ = Me3CC5H4; 2: [Me4C2(C5H4)2]Sm(C3H5)2Li(dme),dme = (CH3OCH2CH2OCH3); 3: Cp′2SmMe2Li(dioxane)} were synthesized from (Cp′2SmCl)2and from the magnesium derivative [Me4C2(C5H4)2]SmCl · MgCl2(THF)4 (4). The ansa anionic complex 2 exhibited good activity for the stereospecific 1,4-trans polymerization of isoprene, whereas the neutral derivative 1 was inactive. In the same way, the anionic complex [Cp′2SmMe2]Li(dioxane) (3) was found to be an ethylene polymerization catalyst of very short lifetime. The lack of reactivity of 1 is related to the associated structure of this coordinatively unsaturated complex: this fact was established by t…

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.

UraniumIV and uranyle salts, efficient and reusable catalysts for acylation of aromatic compounds

Abstract Uranium tetrachloride, uranyle chloride, fluoride and also nitrate or acetate are very efficient homogeneous catalysts for the Friedel–Crafts acylation of aromatic compounds. With uranyle salts, the reaction, carried under dry air, is highly specific and the mono- or bisacylation products are obtained in high yield. Uranyle catalyst can be quantitatively recovered and reused and the organic products are obtained free of uranium.

Synthesis of new soluble polybenzyls by Friedel-Crafts reactions

Soluble polybenzyls were prepared by a catalytic electrophilic Friedel-Crafts type polycondensation between α,α'-dichloro-p-xylene and substituted (by an alkyl or an alkoxy side-chain) mesitylene. The influence of the length of the side-chain on the solubility of the polymer was examined. The polymers were found to be soluble in common organic solvents. Polymer characterizations were made by 13 C nuclear magnetic resonance spectroscopy (NMR), size exclusion chromatography (SEC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and elemental analysis.

Lanthanide bis(trifluoromethylsulfonyl)amides vs. trifluoromethylsulfonates as catalysts for Friedel–Crafts acylations

Abstract The use of catalytic amounts: 1 mol% or less of perfluoroalkyl lanthanide salts as homogeneous catalysts for Friedel–Crafts acylations in non-hazardous solvents is thereafter investigated. Lanthanide bis(trifluoromethylsulfonyl)amides are better catalysts than the triflate analogues towards the acetylation of activated aromatic rings.

Catalytic activity of rare-earth-supported catalysts in Friedel–Crafts acylations

Abstract Friedel–Crafts acylations are catalysed by rare-earth-supported catalysts. The preparation, characterization and performance of these solid catalysts in a test acylation reaction and in a variety of syntheses of aromatic ketones are reported. In contrast to the reactions using AlCl3, the experimental conditions are non-polluting and the final work-up does not require any aqueous treatment.

Friedel-Crafts catalytic alkylations using rare earth-based mineral supports

Abstract Rare earth halides supported on mineral supports (K10 montmorillonite and silica) were investigated as catalysts for Friedel-Crafts alkylations. This project concerns the replacement of the widely used Lewis acid AlCl3 in Friedel-Crafts reactions by environmentally friendly catalysts in that they circumvent the production of aluminum waste. The catalytic activity of these heterogeneous catalysts was established in a series of alkylations of aromatic compounds.

Early lanthanide organometallic hydrides: electronic and steric control of the stability

Abstract Steric and electronic effects on the stability of early lanthanide, neodymium and samarium, organometallic hydrides are discussed. The instability of (tmp)2SmH (tmp=tetramethylphospholyl) is attributed to electronic factors and the low stability of (tBuC5H4)2SmH is related to steric reasons. The analogous neodymium hydride (tBuC5H4)2NdH, could not be obtained, whereas the more hindered triethylborohydride was formed. Access to bisphospholyl bridged heterobimetallic ruthenium–lanthanide hydrides is also related to the size of the lanthanide atom. The bimetallic structures are accessible for lanthanides of ionic radii smaller than 1 A. The role of organometallic hydrides versus alkyl…

Catalytic activity of solvated and unsolvated lanthanide halides in Friedel–Crafts acylations

Abstract Anhydrous lanthanide halides — chlorides and bromides — can act as homogeneous catalysts of Friedel–Crafts acylations. The catalytic activity is related to the solubility of these anhydrous salts. More soluble THF or dioxane (Diox.) neodymium and samarium adducts are more active catalysts.