Philippe Zinck

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• Professor
• Professor (Full) at University of Lille

Traditional computational methods simulate the microstructure of polymer chains from input reaction conditions, but a need exists for predicting optimum reaction conditions in a computationally demanding multivariable space leading to the synthesis of predesigned microstructures and architectures. Herein, the intelligent Monte Carlo (IMC) approach,...

The chain shuttling ring-opening copolymerization of l-lactide with ε-caprolactone has been achieved using two aluminum catalysts presenting different selectivities and benzyl alcohol as chain transfer agent. A newly synthesized aminobisphenolate supported aluminum complex affords the synthesis of lactone rich poly(l-lactide-co-lactone) statistical...

Surface modification of cellulose nanocrystals (CNC) by organocatalysed grafting through ring-opening polymerization (ROP) of trimethylene carbonate was investigated. Organocatalysts including an amidine (DBU), a guanidine (TBD), an amino-pyridine (DMAP) and a phosphazene (BEMP) were successfully assessed for this purpose, with performances in the...

Isoprene chain shuttling polymerisation between the 1,4-trans regulating Cp*La(BH4)2(THF)2/MgⁿBuEt (Cp* = C5Me5) and the 1,4-cis regulating NdCl3(THF)2/AlR3 (R = Et or ⁱBu) systems provides access to stereoblock polyisoprene. Under selected experimental conditions, the trans segments are semi-crystalline, leading to a thermoplastic elastomer-like m...

A lanthanide half-sandwich complex and a ansa lanthanidocene have been assessed for isoprene-styrene chain shuttling copolymerization with n-butylethylmagnesium (BEM). In the presence of 1 equiv BEM, a fully amorphous multiblock microstructure of soft and hard segments is achieved. The microstructure consists of poly(isoprene-co-styrene) blocks, wi...

Microplastic pollution in aquatic environments has emerged as a significant environmental concern, posing risks to ecosystems and human health. Urban stormwater runoff has been identified as a major source of microplastics, with microplastic concentrations reaching up to six times higher than those in wastewater treatment plant effluents. Given the...

This study compares the toxicity and pollutant vector roles of polar polylactic acid (PLA) bio- microplastics (bio-MPs) with apolar low-density polyethylene (LDPE) microplastics (MPs), both individually and in combination with methylmercury (MeHg) in Daphnia magna. PLA bio-MPs with MeHg significantly reduced survival rates and reproductive success....

This study compared the toxicological effects of environmentally relevant microplastics (MPs) on the marine rotifer Brachionus plicatilis, focusing on MPs derived from various sources, including fossil fuel-based low-density polyethylene, bio-based polylactic acid (PLA), biodegradable poly(butylene adipate-co-terephthalate), and a novel PLA modifie...

The escalating production and improper disposal of petrochemical-based plastics have led to a global pollution issue, with microplastics (MPs) posing significant ecological threats. Biobased and biodegradable plastics are believed to offer a potential solution to mitigate plastic pollution. However, their environmental fate and toxicity remain poor...

Mercury is a hazardous heavy metal that is distributed worldwide in aquatic ecosystems. Methylmercury (MeHg) poses significant toxicity risks to aquatic organisms, primarily through bioaccumulation and biomagnification, due to its strong affinity for protein thiol groups, which results in negative effects even at low concentrations. MeHg exposure c...

Bioplastics such as polylactic acid are actually promoted as eco-friendly alternatives to fossil fuel-derived plastics, yet bioplastic toxicity remains poorly known. Here we studied the acute and multigenerational effects of polylactic acid microplastics on the copepod Eurytemora affinis, a bioindicator species of zooplankton. Results on acute toxi...

A new hybrid catalyst consisting of cobalt nanoparticles immobilized onto cellulose was developed. The cellulosic matrix is derived from date palm biomass waste, which was oxidized by sodium periodate to yield dialdehyde and was further derivatized by grafting orthoaminophenol as a metal ion complexing agent. The new hybrid catalyst was characteriz...

The extensive use of plastics has led to a significant increase in global plastic production, which has steadily increased from 1.7 million tons in 1950 to over 400 million tons in 2022. Approximately 60% of all plastic ever produced ultimately finds its way to landfills and oceans. In these environments, plastics have the potential to fragment int...

Chain shuttling copolymerisation (CSP) is a synthetic strategy allowing the one-pot, one-step formation of block copolymers. Initially developed in the frame of coordinative polymerisation of olefins and conjugated dienes, it...

More than 390 million tons of fossil fuel plastics have been produced in 2022, and plastic pollution has become a major health issue for humans and ecosytems. Fossil fuel plastics are commonly recalcitrant, thus accumulating in the environment. Fossil fuel plastics also contains toxic chemicals that leach out to waters and are ingested by living or...

Global pollution by plastics derived from petroleum has fostered the development of carbon–neutral, biodegradable bioplastics synthesized from renewable resources such as modern biomass, yet knowledge on the impact of bioplastics on ecosystems is limited. Here we review the polylactic acid plastic with focus on synthesis, biodegradability tuning, e...

Organocatalysts for polymerization have known a huge interest over the last two decades. Among them, heterocyclic nitrogen bases are widely used to catalyse the ring-opening polymerization (ROP) of heterocycles such as cyclic carbonates. We have investigated the ring-opening polymerization of trimethylene carbonate (TMC) catalysed by DMAP (4-dimeth...

Organocatalysis for polymer chemistry has become a subject of significant interest in the last two decades. In this contribution, we have studied the evolution of the microstructure of poly(L-lactide) in solution in toluene at 105 °C in the presence of various organocatalysts. Weak bases such as triethylamine and DMAP (4-dimethylaminopyridine) lead...

A green method for the production of cobalt/(TEMPO-Cell) aerogel heterogeneous catalyst was developed. The preparation implied the reduction of CoSO4 by NaBH4 in TEMPO-Cell water dispersion in ambient conditions. The formation of Cobalt particles is due to the presence of “TEMPO-CELL” which screens the Co²⁺ ions and prevents their combination with...

Cyclodextrins (CDs) are cyclic oligosaccharides used in many fields. Grafting polymers onto CDs enables new structures and applications to be obtained. Polylactide (PLA) is a biobased, biocompatible aliphatic polyester that can be grafted onto CDs by -OH-initiated ring-opening polymerization. Using 4-dimethylaminopyridine (DMAP) as an organocatalys...

Controlled polymerization techniques make possible fabrication of polymers with desired molecular weights, narrow dispersity, and also tailor-making of advanced hybrid materials. Thiol-Lactam Initiated Radical Polymerization (TLIRP) was introduced in 2002 and developed during the last two decades. The thiol/lactam combination enables one to generat...

La présente invention concerne une résine polyester biosourcée comprenant un mélange de diols et de polyacides, son procédé de préparation ainsi qu’une composition filmogène et un vernis à ongles comprenant ladite résine. La résine polyester peut notamment être utile en tant que liant dans un vernis à ongles.

Recent progress in macromolecular reaction engineering has enabled the synthesis of sequence‐controlled polymers. The advent of olefin block copolymers (OBCs) via chain shuttling polymerization of ethylene with α‐olefins has opened new horizons for the synthesis of polyolefins having a dual character of thermoplastics and elastomers. Nevertheless,...

Starch based materials are attractive bio-based alternative to fully synthetic polymers. Native starch has however limited thermoprocessability and properties and must be modified. In order to improve the properties of starch-graft-poly(butyl-acrylate-co-styrene) copolymers via a process as green as possible, we report herein a new method for the d...

Research toward bio-based polymers is an expanding field due to environmental concerns. A library of new aliphatic diol-diamide monomers with different chain lengths between the two amido groups was synthesized from sustainable levulinic acid and various linear aliphatic diamines (C2–C10). The monomers were prepared by diacylation of the diamines f...

Polyesters are thermoplastic and thermosetting polymers which find applications in very wide areas of daily life and in particular in packaging, textiles and biomedical. The most produced polyester is PET due to its use for the production of bottles and for textiles. Many biobased and biodegradable and / or compostable thermoplastic polyesters can...

Among the various catalysts that can be used for polycondensation reactions, enzymes have been gaining interest for three decades, offering a green and eco-friendly platform towards the sustainable design of renewable polyesters. However, limitations imposed by their delicate nature, render them less addressed. As a case study, we compare herein bu...

The surface initiated ring opening polymerization (SI-ROP) of cellulose nanofibers (CNF) with rac-Lactide under mild conditions using N,N-dimethyl aminopyridine (DMAP) was investigated. The influence of catalyst amount, monomer-to-initiator (cellulose surface –OH groups) ratio, temperature, and cellulose preconditioning (lyophilization vs solvent e...

The organocatalytic sequential block polymerization between a cyclic ester and a vinyl monomer is reported for the first time. The new block copolymer self-assembles into nanostructures leading to a thermoplastic elastomer-like material.

The epimerization of polylactide is reported in the presence of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) at 105 °C in toluene. The extent of the reaction depends on the amount of TBD introduced and the reaction time. Up to ca. 46% D units can be formed starting from poly(l-lactide) in the presence of 5 mol% TBD. The epimerization rate is slightly...

A one‐pot synthesis of 2,5‐disubstituted furans from γ‐ketoacids is reported. In situ formation of allenoates by action of chloroformate on carboxylic acid following by enolization of ketone affords furan derivatives by cyclization. The reaction was extended to a wide scope of ketoacids and phosphonium salts. This methodology was applied on levulin...

La présente invention concerne une résine thermoplastique comprenant une matière amylacée sur laquelle sont greffés des greffons G1 comprenant chacun au moins une unité de répétition issue de la polymérisation d'au moins un monomère A1 comprenant une double liaison carbone-carbone (C=C), et des greffons G2 comprenant chacun au moins une unité de ré...

Organocatalysts are assessed for the insertion of isosorbide, a rigid, biobased diol monomer, into poly(ethylene terephthalate). A sulfonic acid (p‐toluenesulfonic acid—APTS), an amidine base (1,8‐diazabicyclo [5.4.0] undec‐7‐ene—DBU) and a guanidine base (1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene—TBD) successfully catalyze the polymerization. The reacti...

Environmental regulation and depletion of fossil resources are boosting the search for new polymeric materials produced from biomass. Here, the synthesis of a new diester bearing a pendant lactam unit from methyl levulinate and aspartic acid is reported. The palladium‐catalyzed reductive amination/cyclization sequence was carefully optimized to aff...

The human nail, like any biological material, is not readily available in large amounts and shows some variability from one individual to another. Replacing it by synthetic models is of great interest to perform reproducible and reliable tests in order to assess drug diffusion or nail lacquer adhesion for example. Keratin films, produced at the lab...

Nowadays, polymer reaction engineers seek robust and effective tools to synthesize complex macromolecules with well-defined and desirable microstructural and architectural characteristics. Over the past few decades, several promising approaches, such as controlled living (co)polymerization systems and chain-shuttling reactions have been proposed an...

Dextrin/starch-graft-poly(butyl acrylate-co-styrene) copolymers have been synthesized by radical graft copolymerization and their structure and mechanical properties are reported. High molecular weight grafted chains formation is favored, leading to a low degree of substitution of starch hydroxyl groups. Wide-Angle-X-ray Scattering (WAXS) analysis...

In this work, we aimed to understand the biological activity and the mechanism of action of three polymer-‘ruthenium-cyclopentadienyl’ conjugates (RuPMC) and a low molecular weight parental compound (Ru1) in cancer cells. Several biological assays were performed in ovarian (A2780) and breast (MCF7, MDA-MB-231) human cancer derived cell lines as wel...

End-functionalized 1,4-trans-polydienes (isoprene, myrcene) were prepared by means of a neodymium mediated continuous polymerization-functionalization process. A chain transfer stage was essential to get a high level of functionalization of the polymer. The living 1,4-trans stereoregular polymer chain was reacted with benzophenone to afford up to 9...

La présente invention concerne un procédé utile pour la fonctionnalisation terminale de chaînes polydiènes stéréo-régulières trans-1,4 et obtenues par polymérisation par catalyse de coordination d'au moins un monomère diénique conjugué. Elle concerne également un polydiène possédant un taux d'enchaînement trans-1,4 d'au moins 85%, de préférence d'a...

Four novel biobased monomers (i.e. two diesters and two hydroxyesters) bearing a tertiary amine in their backbone have been synthesized from the sustainable methyl levulinate and amino-alcohols/amino-esters derived from natural amino acids. Their homopolymerization/copolymerization with diols leads to six poly(amine-co-ester)s with various microstr...

The insertion of rigid monomers such as isosorbide into poly(ethylene terephthalate) (PET) allows for the access of polymers with improved properties, notably in terms of thermal stability. This biobased monomer is however poorly reactive, and harsh reaction conditions lead to color concerns regarding the resulting polymer. This has motivated the d...

The identification of the mode of action of a drug is mandatory for the development of clinically effective chemotherapeutics. Ruthenium complexes hold potential as alternatives to platinum drugs in cancer chemotherapy. In spite of their great importance, their mechanisms of action have not yet been fully elucidated. Inspired by platinum-based drug...

The grafting of a lanthanum trisbenzyl derivative onto dehydroxylated silica affords a mixture of [(≡SiO)2La(CH2Ph)(THF)n] and [(≡SiO)La(CH2Ph)2(THF)m] surface sites, in respective proportions of 80 and 20%, as evidenced from mass balance analyses, IR and ¹H, ¹³C and ²⁹Si 1D and 2D solid-state NMR spectroscopy. Significant transfer of alkyl groups...

Correction for ‘Isoprene chain shuttling polymerisation between cis and trans regulating catalysts: straightforward access to a new material’ by Y. Phuphuak et al., Chem. Commun., 2017, 53, 5330–5333.

Mole cular landscap e of ole fi n block cop olymers (OBCs) was patterned by hybrid izing capabi lities of Kineti c Monte Carlo (KM C) an d Art ifi cial Neural Network (ANN) stochastic mod eling approaches to explore comp lexit ies with chain shuttl ing copolymerization of ethylene wi th a -ole fi ns. Theoretical data on chai n mi crostructure were obt...

Research toward bio-based and biodegradable polymers has received a lot of attention these last years, due to environmental concerns and the need to replace fossil resources. Starch is in this frame an interesting starting material due to its abundance and low cost. Native starch displays however poor mechanical properties and is highly hydrophilic...

A series of vanadium complexes bearing dianionic tetradentate amine-bisphenolate [ONNO] ligands, V([double bond, length as m-dash]O)X[ONNO(Me)] (X = Cl (1); O(i)Pr (2)), VCl2[ONNO(Me)] (3) and V(O(i)Pr)2[ONNO(R)] (R = Me (4), (t)Bu (5), Cl (6)), displaying various electronic and steric properties have been prepared. The molecular structures of two...

Nucleobase-functionalized polymers are widely used in the fields of supramolecular chemistry and self-assembly , and their development for biomedical applications is also an area of interest. They are usually synthesized by tedious multistep procedures. In this study, we assess adenine as an organoinitiator/ organocatalyst for the ring-opening poly...

Mg(n-Bu){η2-HC[C(Me)NMes]2} (2) (Mes=mesityl, 2,4,6-Me3C6H2), a new β-diketiminate-supported magnesium alkyl, has been synthesized and structurally characterized. The X-ray analysis of the lanthanum half-sandwich complex Cp*La(BH4)2(THF)2 (1) (Cp*=pentamethylcyclopentadienyl; THF=tetrahydrofuran) is also reported. Complex 2 has been assessed as bot...

Chain shuttling copolymerization (CSP) is a modern polymerization technique that allows in a one-step procedure the access to multiblock microstructures of statistical copolymer blocks of different composition, providing notably new thermoplastic elastomers. The process involves the shuttle of a growing copolymeric chain between two catalysts showi...

New bis(phenolate)amine-supported neodymium borohydride complexes and their previously reported samarium analogues were tested as catalysts for the polymerisation of styrene and isoprene. Reaction of Na2O2NL (L = py, OMe, NMe2) with Nd(BH4)3(THF)3 afforded the borohydride complexes Nd(O2NL)(BH4)(THF) (L = py (1-Nd), OMe (2-Nd), NMe2 (3-Nd)). Comple...

(R)-(+)-binaphathyl-diyl hydrogen phosphate (BNPH)/ diazabicyclo[5.4.0]undec-7-ene (DBU) and (1R)-(−)−10-camphorsulfonic acid (CSA)/4-dimethylaminopyridine (DMAP) acid–base salts were synthesized and assessed for the ring-opening polymerization of rac-lactide. They were found to be inactive toward the polymerization in the presence of a protic init...

The functionalization of carbohydrates with aliphatic biocompatible and biodegradable polyesters such as polylactides and polylactones leads to a great variety of structures useful for applications in the fields of medicine, biotechnology and materials science notably. One of the preferred strategies for this purpose is the carbohydrate initiated r...

The polymerization of -caprolactone has been assessed in water using various Brönsted acids as catalysts. The reaction was found to be quantitative at 100°C, leading to number-average molecular weights up to 5000 g/mol. The Brönsted acid catalyzed polymerization of -caprolactone in water was further conducted in the presence of water-soluble poly...

The coordinative chain transfer co- and ter-polymerizations of myrcene, isoprene and styrene have been achieved using Cp*La(BH4)2(THF)2 (Cp* = pentamethylcyclopentadienyl) combined with magnesium dialkyl and aluminum dialkyl. New highly stereoregular poly(myrcene-co-styrene), poly(myrcene-co-isoprene), and poly(myrcene-co-isoprene-co-styrene) copol...

The microstructural analysis of 1,4-cis- and 1,4-trans-polymyrcene was conducted by means of thorough investigations at a very high field NMR (21.1T, 900 MHz). A set of 1D and 2D experiments helped to entirely assign the resonances of the spectra for both stereoisomers. A simple method to distinguish between each stereoisomer by NMR spectroscopy is...

The combination of a neodymium borohydride, Nd(BH4)3(THF)3 (1) or Cp*Nd(BH4)2(THF)x (2), with MgnBuEt (BEM), affords an efficient and highly selective (up to 96.7% 1,4-trans) catalyst for butadiene polymerization. In the presence of excesses of Mg co-catalyst, polymer chain transfer takes place between neodymium and magnesium, and significant amoun...

The development of the first star-structured poly(l-lactides) (s-PLLAs) with dual functionality as both nucleating agent and plasticizer in polylactide (PLA) blends is described. Mechanisms controlling this functionality are deduced. Blends of PLA containing s-PLLAs show significant improvements in thermal and mechanical properties. The s-PLLAs are...

This chapter describes a large spectrum of opportunities offered by controlled polymer chain transfer between pre-catalyst and co-catalyst in polymerization catalysis, also called CCTP, with rare earths based catalysts. Among them, borohydride derivatives, which are very prolific in this regard, are emphasized. Examples are cited in homo- and co-po...

d-glucose end-capped polylactide ruthenium cyclopentadienyl complex (RuPMC) was newly synthesized by a straightforward method. RuPMC was tested against human MCF7 and MDAMB231 breast and A2780 ovarian adenocarcinoma revealing IC50 values in the micromolar range. A pH dependent hydrolysis is advanced by preliminary UV-visible spectroscopy. Cellular...

Binaphthyl-diyl hydrogen phosphate has been assessed for the first time as a catalyst for the ring-opening polymerization of epsilon-caprolactone and delta-valerolactone. In the presence of benzyl alcohol as co-initiator at 40-60°C, the polymerization is quantitative and controlled both in terms of dispersity and of number-average molecular weight...

Narrow molecular weight distributions are obtained, and the macromolecular chains are end-capped with the chain transfer metal, enabling further functionalization based on the chemistry of the main group metal. CCTP and CCG reactions thus afford a controlled polymerization in the absence of termination pathways other than chain transfer to the CTA...

Polymerization of β-myrcene with neodymium borohydride-based coordination catalysts is very efficient, affording poly-β-myrcene (polymyrcene, PMy) with high selectivity. With stoichiometric amounts of n-butylethyl magnesium (BEM) as co-catalyst, good control over macromolecular data along with cis-stereoselectivity up to 98.5%, are obtained. In the...

The discrete phenolate Nd(2,6-di-tert-butyl-OC6H3)3 has been assessed as pre-catalyst for the polymerization of isoprene using various aluminum based co-catalysts. In combination with MAO and MMAO in toluene, the reaction is quantitative in 1 h at 60 °C, yielding activities comparable to neodymium versatate and isopropylate in similar conditions. I...

Aliphatic polyesters and cyclodextrins are widely used for biomedical applications, due to their biocompatible and biodegradable character, and to the possibility to host molecules of pharmaceutical interest for the latter. Cyclodextrins have been used as initiators or co-initiators for the ring-opening polymerization of cyclic esters these last ye...

The precipitation polymerization of epsilon-caprolactone has been assessed in water using various commercial metal triflates as catalysts. The reaction is quantitative at 70 and 100 A degrees C, leading to number-average molecular weights up to 5,400 g/mol and dispersities around 1.5-2.0. A polycondensation mechanism operating from in situ generate...

Polymerization of b-myrcene with neodymium borohydride- based coordination catalysts is very efficient, affording polyb- myrcene (polymyrcene, PMy) with high selectivity. With stoichiometric amounts of n-butylethyl magnesium (BEM) as co-catalyst, good control over macromolecular data along with cis-stereoselectivity up to 98.5%, are obtained. In th...

Coordinative chain transfer polymerization (CCTP) is a reversible group transfer polymerization involving a transition metal catalyst and a main group metal alkyl. CCTP affords well controlled polymerizations of olefins and conjugated dienes with catalyst economy and good potentialities for polymer end-functionalization. New concepts have recently...

The 4-dimethylaminopyridine (DMAP) catalyzed ring-opening polymerization of lactide using various carbohydrate initiators has been assessed for the functionalization of polylactide. Selectively protected glucose derivatives bearing a free primary alcohol (Glc-1r) and a free secondary alcohol (Glc-2r), glucose and cyclodextrin diol derivatives (Glc-...

The Cp*La(BH4)2(THF)2/n-butylethylmagnesium (BEM) catalytic system has been assessed for the coordinative chain transfer copolymerization of styrene and 1-hexene. Poly(styrene-co-hexene) statistical copolymers were obtained with number-average molecular weight up to 7600 g/mol, PDI around 1.4 and 1.5 and up to 23% hexene content. The occurence of c...

A series of ruthenium(II) complexes with the general formula [Ru(η5-C5H5) (η6-substituted arene)]+[PF6]- (substituted arene = 2-phenylpyridine (1), dibenzosuberone (2) and toluene (3)), in combination with isopropyl alcohol were used for the polymerization of ε-caprolactone. The polymerization was found to be quantitative and controlled, with PDI i...

A series of lanthanum and neodymium borohydrido complexes comprising the trisborohydrides Nd(BH4)3(THF)3 (1a) and La(BH4)3(THF)3 (1b) and the half-lanthanidocenes Cp*Nd(BH4)2(THF)2 (2a) (Cp* = C5Me5) and Cp*La(BH4)2(THF)2 (2b) has been assessed for the chain transfer copolymerization of isoprene and styrene. A transmetalation process is occurring e...

A method to evaluate the mean strength of brittle solids at short gauge length from experiments performed at higher gauge length is proposed for bimodal fracture behavior. The method based on additive Weibull bimodal distributions takes the evolution of the relative proportion of flaws along the gauge length into account via a gauge length dependen...

This article is devoted to the use of some concepts of organometallic chemistry for their application in homogeneous catalysis developed in our laboratory in Lille and presented in the Gecom-Concoord meeting in Albé. The first examples will deal with the use of bifunctional ligands, where it will be shown that designing an aminophosphine ligand all...

A series of lanthanum and neodymium complexes comprising the half-lanthanidocenes Cp*La(BH4)2(THF)2 (Cp* = C5Me5) (1) and Cp*Nd(BH4)2(THF)2 (2), the trisborohydrides La(BH4)3(THF)3 (3) and Nd(BH4)3(THF)3 (4), the trichlorides LaCl3(THF)3 (5) and NdCl3(THF)3 (6), the triisopropoxides La(OiPr)3 (7) and Nd(OiPr)3 (8), and the triaryloxide Nd(OC6H3-tBu...

The ability of various rare earth borohydride and chloride complexes / n-butylethylmagnesium (BEM) systems to operate styrene chain transfer polymerization in mild conditions has been assessed. Thirteen pre-catalysts have been considered: the rare earth trisborohydrides Ln(BH4)3(THF)x (x = 3, Ln= Nd (1), La (2), Sm (3), x=2, Ln = Y (4), Sc (5)), th...

Polyesters are widely used for biomedical applications such as drug delivery systems and resorbable implants. The degradation kinetic of these biopolymers can be tailored by the introduction of functional groups in their backbone, leading to a modification of their morphology and hydrophilicity. This is usually realized via long multistep reaction...

Syndiotactic polystyrene (sPS) is a promising material that has been commercialized and widely studied by the academic community. Several drawbacks can however restrict its practical use: its brittleness, in areas where mechanical properties are important, the lack of polar groups, for adhesion and compatibility with other polymers, and the need to...

Borohydrido‐halflanthanidocene/dialkylmagnesium combinations are found to be powerful catalytic systems for the chain transfer polymerization of isoprene and its copolymerization with styrene. A behavior close to a lanthanide catalyzed polyisoprene chain growth on magnesium is reported. Transmetalation is further shown to occur in the course of the...

We became aware, in the course of our on-going research, that the number-average molecular weight of poly(1,4-trans isoprene) determined by conventional gel permeation chromatography (GPC) in tetrahydrofuran (THF) using polystyrene standards differs from its true value by a factor 2. As far as we know, the Mark-Houwink coefficients of this polymer...