Francesco Ciardelli

• Professor Emeritus
• Professor Emeritus at University of Pisa

The elastic response of chromium-tanned leather was successfully improved by treatment with XSBR, a carboxylated styrene-butadiene copolymer. The carboxylic groups pending from a styrene-butadiene rubber (SBR) backbone were found to promote penetration of the aqueous polymer dispersion into the fibrous tanned leather and participated in pH-reversib...

In recent years, there has been increasing interest in developing novel materials based on natural biopolymers as a renewable alternative to petroleum-based plastics. The availability of proteins derived from agricultural by-products, along with their favourable properties, has fostered a renewed interest in protein-based materials, promoting resea...

In recent years there has been an increasing interest in developing novel materials based on natural biopolymers as a renewable alternative of petroleum-based plastics. The availability of proteins derived from agricultural by-products, along with their favourable properties, has fostered a renewed interest in protein-based materials, promoting res...

Partially fluorinated coating materials were prepared by homo-and copolymerization of different acrylic derivatives with some of thè side chain hydrogen atoms substituted by fluorine. Also samples having thè same Chemical composition but different molecular weight characteristics were obtained. The Chemical and photochemical stability of thè above...

One promising way to improve the efficiency of borehole heat exchangers (BHEs) in shallow geothermal applications is to enhance the thermal properties of the materials involved in its construction. Early attempts, such as using metal tubes in the 1980s or the utilization of thin–foil hoses, did not succeed in being adopted by the market for diverse...

The preparation process and the final properties of new thermoplastic lead-free medium voltage (MV) insulation compounds based on the thermoplastic vulcanized (TPV) technology are reported and discussed at molecular level. The TPV MV insulation compounds were prepared starting from a peroxide curable lead free MV insulation, which is the actual mar...

This chapter deals with the preparation of products from material based on plastic polymers from fossil origin (Bruckner et al. 2001). The production route of traditional plastic polymers starts from available monomers, followed by the reaction for converting them into polymers and successive processing to obtain objects. This synthetic description...

Under the pressure of the social requirement for a more natural style of life, many commercial products were rendered more attractive with a more or less valid superficial coverage of bio-related aspect; these products are often mixed without any scientific rule with environmentally friendly products with misleading information of the users. The ai...

Plastic polymers have benefited the human society and heavily contributed to our improved style of life from several viewpoints. Indeed, the easy processable, light and low-cost structural plastics and the possibility of combining in them functional and thermomechanical properties have allowed a rapid growth for easy and large-scale production with...

The society concern for the environmental compatibility of man-made products has been growing in the past few decades and evolved in many directions, with an evident predominance of emotion on technical rationality. These last aspects are clearly justified in the main part of population under the pressure of overwhelming information by mass media w...

This chapter deals with the preparation of products from material based on plastic polymers from fossil origin. The production route of traditional plastic polymers starts from available monomers, followed by reaction for converting them into polymers and successive processing to obtain objects. This synthetic description is considered necessary fo...

Plastics were investigated based on homopolymers, which are polymers consisting of macromolecules characterized by the uniform chemical structure along the main chain, the successive investigation and related discovery demonstrated that the plastics’ behaviour could be reached with more complex systems in terms of molecular structure and compositio...

This chapter following the general introduction is devoted to provide the reader with the basic concepts related to the understanding of the fundamental necessary properties of a polymeric material to perform as a plastic material and then to be used in the corresponding applications. The main objective of this chapter is to highlight the structura...

The book describes the development and commercialization of materials with viscoelastic properties, placing particular emphasis on the scientific and technological differences between plastics and bioplastics. The authors explain how to handle each of the two types of materials and determine the comparative environmental impact of the material life...

Post-consumer poly(ethylene therephthalate) (PET) obtained from milled water bottles was chemically degraded by glycolysis, using suitable amounts of diethylene glycol (DEG) and Ca/Zn stearate as catalyst system. The process was carried out by employing a melt mixer as the chemical reactor, which is the facility generally used for plastic compoundi...

Front Cover: Processing of PLA/PBAT compostable blends with dicumyl peroxide gives chain-branching and crosslinking, thus providing a simple and economically affordable strategy to finely modulate the thermo-mechanical properties of the commercial material. Further details can be found in the article by F. Signori,* A. Boggioni, M. C. Righetti, C....

In this work, different amines (bifunctional, as diazabicyclo[2.2.2]octane (Dabco) and monofunctional, as N-methylimidazole or trimethylamine) were utilized for the amination of benzyl chloride-grafted polystyrene-b-poly(butadiene)-bpolystyrene triblock copolymers (SBS-g-VBC). The use of Dabco solutions in mixture with variable amounts of monoamine...

A sustainable procedure for recycling powdered rubber coming from scrap tires (ground tire rubber [GTR]) is proposed as based on the dispersion in polyketone (PK) matrix, obtained in situ by CO/ethylene copolymerization. Three types of catalysts are used operative in solvents of different polarities. The catalyst productivity and the hybrids morpho...

Aiming at the tuning of thermo-mechanical features by chemical cross-linking, a biopolyester commercial blend based on poly(lactic acid) (PLA) with poly(butylene adipate-co-terephthalate)(PBAT) (ecovio®T2280, BASF) was processed in Brabender in the presence of dicumyl peroxide (DCP, 0–0.2 wt.-%). The effect of DCP addition was investigated and rati...

The title complex (1) has been prepared by reaction of ZrCl4 with l,2,3,4-(tetraphenyl)-cyclopenta-l,3-dienyl lithium (2). The phenyl substituents on the metallocene ligands exert both steric and electronic effects on the active site obtained by activation of 1 with MAO. Thus this catalytic system shows lower polymerization activity than in case of...

Previously prepared (J. Mol. Catalysis 11, 353 (1981)) polystyrene/ruthenium systems have been examined by EXAFS, TEM, IR and Raman spectroscopy. A structure based on small metal clusters bound to the polymer by single ruthenium-arene binding is proposed. The general validity of the approach has been confirmed by preparing a similar product when st...

Novel hybrid materials composed by a high density polyethylene (HDPE) matrix and powdered rubber coming from scrap tyres (ground tyre rubber [GTR]) were prepared. Two methods were followed: ethylene was polymerized by a metallocene catalyst (Cp2ZrCl2/methylaluminoxane) in the presence of a toluene dispersion of the filler (in-situ polymerization);...

Polyolefin-based materials are increasingly being used in many industrial applications for packaging, automotive and construction materials. The recent developments of research have been aimed at making these materials, often complex, being mixtures, block copolymers, micro- and nanocomposites with inorganic and organic fillers, more efficient and...

In this work, different amines (bifunctional, as diazabicyclo[2.2.2]octane (Dabco) and monofunctional, as N-methylimidazole or trimethylamine) were utilized for the amination of benzyl chloride-grafted polystyrene-b-poly(butadiene)-bpolystyrene triblock copolymers (SBS-g-VBC). The use of Dabco solutions in mixture with variable amounts of monoamine...

Poly(vinyl chloride) (PVC)/layered double hydroxide (LDH) composites and PVC/poly(methyl methacrylate) (PMMA)/LDH composites were prepared via solution intercalation into PVC using both unmodified and organo-modified LDHs and variable-molecular-weight PMMA as additional components. The LDH dispersion was investigated using X-ray diffraction analysi...

Glycogen, a natural hyperbranched polymer of glucose characterized by a substantially spherical macromolecular structure, was oxidized by periodate to obtain reactive intermediates for the preparation of nanostructured materials. The reaction was carried out at room temperature in water, methanol, isopropanol or N,N-dimethylformamide as solvents. T...

Molecularly designed materials based on macromols. and org. dyes offer unique opportunities in connection with the possibility of prepg. optically responsive smart' materials. Indeed macromols. are able to transmit and amplify small signals reaching sites at interacting distance through the involvement of the whole chain. The corresponding material...

Methyl methacrylate and styrene copolymers containing pendant benzil groups, such as 1-[4-(2-methacroyloxyethoxy)phenyl]-2-phenyl-1,2-ethanedione-co-methyl metacrylate (BzMA/MMA), 1-[4-(2-methacroyloxyethoxy)phenyl]-2-phenyl-1,2-ethanedione-co-styrene (BzMA/S), and 1-phenyl-2-(4-propenoylphenyl)-1,2-ethanedione-co-styrene (PCOCO/S), were prepared a...

The detection of mechanical stress in polymeric materials through optical variations has attracted considerable interest over the past ten years. In this tutorial review, the current state of knowledge concerning the preparation of polymers with mechanochromic features is summarized. Two types of procedures are illustrated and thoroughly discussed...

The 4-(1-naphthoate)-2,2,6,6-tetramethylpiperidine-1-oxyl (NfO-TEMPO) has been synthesized and successfully grafted in the melt onto a random poly(ethylene-co-1-ottene) copolymer. Functionalized polyolefins have been prepared by coupling reaction between NfO-TEMPO free radicals and macroradicals which have been formed by H-abstraction induced by th...

Poly(ethylene terephthalate) (PET) / poly(ethylene) (PE) granules coming from a post-industrial packaging stream were directed to new applications. The collected material was first characterized through selective extractions followed by infrared analysis. After the characterization work the presence of poly(ethylene-co-vinyl acetate) (EVA) copolyme...

New biodegradable compounds having high renewable resources starting materials content were developed and formulated at Lab, pilot and industrial level. Pipes were prepared using the here developed compounds, and perfectly mimic the mechanical behavior as well as the chemical resistance of the currently used polyethylene based materials. This work...

Mol. optical brighteners incorporated into filmable polymers to a very low extent from 0.05 to 0.5 wt.% by melt-processing, provide materials which show a well-defined excimer emission by increasing dye concn. flanked by a characteristic change of the luminescent properties of the films. Then, the original color of the film, provided by the radiati...

Maleic anhydride (MAH), trans cinnamic acid (AcCin) and ethyl cinnamate (EtCin) were radically graft onto poly(butylene succinate-co-adipate) (PBSA). Samples were prepared in Brabender at 175 °C by addition of increasing amounts of MAH, AcCin, EtCin and their combinations, i.e. MAH/AcCin and MAH/EtCin, setting DCP content in the 0.2–0.6 wt% range....

In this work, the functionalization of polystyrene-b-poly(butadiene)-b-polystyrene triblock copolymer (SBS) with vinylbenzyl chloride and benzoyl peroxide (BPO) or alpha ,alpha '-azo-bis-isobutyronitrile (AIBN) as free radical initiators was reported. The functionalization degree (FD), calcd. by 1H NMR spectroscopy and confirmed by elemental anal.,...

In this work the effect of nanofiller on nonisothermal crystallization behavior of composites based on polypropylene (PP) was investigated by differential scanning calorimetry. The materials were prepared by melt mixing. Both an alkyl sulfonate salt modified layered double hydroxide (LDH) and an unmodified LDH were used as nanofillers and both PP a...

Gelatin reactivity with isocyanate was studied by using the easy detectable 1-naphthyl-isocyanate (NphI). Four different NphI/gelatin feed ratios were investigated with NphI molar amount ranging between 1/10 and 1/1 with respect to the possible reactive groups of gelatin. The reactions were carried out at 45°C in DMSO as solvent, under nitrogen atm...

The transesterification during the melt blending of polylactide (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) was investigated in presence of Ti(OBu)4 as a catalyst. Both the effect of catalyst concentration and reaction duration was considered. The process was studied by analyzing the molecular weight of the polyesters by size exclusion...

Partially hydrophilic polymers have been prepared by free-radical copolymerization of trans-4-acryloyloxyazobenzene with N-tert-butylacrylamide and N-isopropylacrylamide. A turbidimetric method has been adapted to investigate the dependence of the polymer hydrophilic–hydrophobic balance on chemical composition and extent of photoisomerization of si...

Nitroxyl radicals were used as functionalizing agents during the free radical postreactor modification process of polyolefins carried out in the melt. The 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (HO-TEMPO) and the 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (BzO-TEMPO) free radicals were successfully grafted onto a polyethylene-based m...

The grafting of polar monomers to polyolefin backbones carried out in the melt in the presence of peroxides is accompanied by a restructuring of the pristine macromolecule architecture depending on reaction conditions and original polyolefin structure. In the case of polypropylene (PP), side reactions, mainly degradation, are often controlled by th...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

A series of polypropylene (PP)/organoclay nanocomposites with varied concentrations of clay, from 1 to 7 wt%, was successfully prepared via melt intercalation using a PP functionalized with maleic anhydride as compatibilizer. The morphology/property relationships of the nanocomposites were investigated by XRD, TGA and DSC analyses. Two distinct gro...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

In this work, a new thermal stimuli sensitive multiphase polymer system consisting of a bio-related mixt. of poly(lactic acid) (PLA, 85 wt%) and poly(1,4-butylene succinate) (PBS, 15 wt%) was prepd. by the controlled incorporation of moderate amts. (<0.2 wt%) of 4,4'-bis(2-benzoxazolyl)stilbene (BBS, a food-grade dye). Films obtained from the blend...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Although the improvement of tensile Modulus and thermal stability due to the addition of innovative organoclays to PLA were negligible, our investigation allowed to evidence that the preliminary preparation of an inorganic rich composite through in situ polymerization of lactyde gave a final morphology improved with respect to that achieved by simp...

The blending of PET from post‐consumer packaging products with polyolefins can provide toughened materials. PET and polyolefins are immiscible polymers and to the above purpose, different method of reactive compatibilization are investigated to achieve a fine dispersion of polyolefin domains into a PET matrix. The use of a functionalized polyolefin...

Chitosan was converted to its –NH2-protected derivative by reacting with phthalic anhydride and then selectively functionalized with an azido group in C-6 position. Two different procedures were employed. The first was a “one-pot” procedure and the second was a two steps reaction through the tosylated intermediate. Both methods resulted in an effec...

We studied relaxation dynamics of poly(ethylene-co-propylene) grafted diethylmaleate/montmorillonite nanocomposites at different clay loading, as well as of residue samples obtained through an extraction procedure performed on the nanocomposite. The modification of the relaxation properties, i.e. relaxation time and dielectric strength, of structur...

A derivative of 2-methylindole, 3-[2-(4-nitrophenyl)ethenyl]-1-allyl-2-methylindole, NPEMI-A, is studied for its photoconductivity and photorefractivity behaviour. Its blends with the organic polymer poly-(2,3-dimethyl-N-vinylindole), PVDMI, are also investigated. Due to the expected and devised mutual solubility of the two components of the blends...

IntroductionOrganic Chromophores as the Dispersed PhaseMetal Nanostructures as the Dispersed PhaseConclusions AcknowledgmentsReferences

The recovery of poly(ethylene terephthalate) from post-consumer packaging products, such as beverage bottles, allowed to obtain flakes with a purity level suitable for reprocessing. Among many possibilities, the blending with polyolefins can provide toughened materials but, as poly(ethylene terephthalate) and polyolefins are immiscible, different m...

A derivative of 2-methylindole, 3-[2-(4-nitrophenyl)ethenyl]-1-allyl-2-methylindole, NPEMI-A, has been studied for its photoconductivity and photorefractivity behaviour. The neat material was studied together with its blends with the organic polymer poly-(2,3-dimethyl-N-vinylindole), PVDMI. It was possible to carry out measurements with the content...

The functionalisation of a low molecular weight, liquid 1,2‐polybutadiene (PBL) was performed by the addition of either N ‐acetyl‐ L ‐cysteine or its methyl ester through the thiol‐ene radical reaction. The functionalisation runs were carried out in 1,4‐dioxane solution and in the presence of a free radical initiator (2,2′‐azobisisobutyrronitrile,...

Polypropylene (PP) was modified by radical grafting of acrylic acid (AA) in the melt by using dicumyl peroxide (DCP) as initiator. To reach a high grafting degree (GD) without substantially modifying PP-chain structure, a few runs were carried out by employing butyl 3-(2-furanyl)propenoate (BFA), which is a coagent able to preserve the molecular we...

Linear low d. polyethylene (LLDPE) films contg. different concns. of perylene (P) chromophores have been prepd. by soln.-casting and compression-molding. The light emission features of the films depend on P concn. and polymer films deformation. A well-defined band attributed to the formation of micro/nano-structured perylene chromophoric aggregates...

A careful insight into melt compounding procedure is proposed in order to achieve a better understanding and control of the dispersion and orientation mechanisms of organo-clay platelets into LDPE nanocomposites. The method involved is the preparation of a maleic anhydride grafted polyethylene master-batch containing 10 wt% organo-clay via twin-scr...

The possibility of employing materials based on post-consumer PET for injection moulded external and internal body parts in automotive and other applications requires passing mechanical properties, processability, weather resistance, surface stability. Different strategies pursued in our laboratory to improve the properties and broaden the applicat...

The photorefractivity of an indole derivative and of its polymer blends has been studied at room temperature. The indole derivative 3-[2-(4-nitrophenyl)ethenyl]-1-(2-ethylhexyl)-2-methylindole (NPEMI-E) is a typical low-molecular-weight glass-forming molecule having peculiar nonlinear optics characteristics. It is unconditionally soluble in the pho...

In this work we present controlled, low-damage nanotopographic surface modification of poly(ethylene terephthalate) (PET). High-resolution nanopatterning over macroscopic areas was performed by " low-temperature" hot embossing lithography (HEL). While for standard HEL the temperature is typically raised up to many tens of Celsius degrees above the...

This study was aimed at the modulation of poly(lactic acid) (PLA) properties by the addition of both a low-molecular-weight plasticizer, acetyl tributyl citrate (ATBC), and a biodegradable aliphatic–aromatic copolyester, poly(butylene adipate-co-terephthalate) (PBAT). PLA/PBAT, PLA/ATBC, and PLA/PBAT/ATBC mixtures with 10–35 wt % ATBC and/or PBAT w...

Relevant examples are described here concerning the light response of polypeptides bearing covalently bound photochromic groups in the side chains and the optical properties changes of nanocomposites from org. dyes aggregates dispersed in a thermoplastic matrix. The former system shows how the light induced structural changes in side chain chromoph...

Polymer nanocomposite films with unusual and anisotropic optical properties were obtained by the controlled in-situ generation of noble metal nanoparticles (NPS). Poly(vinyl alc.) (PVA) and poly(ethylene-co-vinylalc.) (EVAl) nanocomposites contg. gold and silver NPs were efficiently produced by a photoredn. or thermal process both operating directl...

Polyolefins are today the most used thermoplastic materials thanks to the high technology and sustainability of the polymerization process, their excellent thermomechanical properties and their good environmental compatibility, including easy recycling. In the last few decades much effort has been devoted worldwide to extend the applications of pol...

The extent of interphase interactions between polymer phase and inorganic particles is the driving force addressing the preparation/properties design in the field of the corresponding micro- and nanocomposites. In the case of preparation of nanocomposites based on polyolefins (POs) and inorganic compounds as potentially nanodispersed phase, the use...

Degeneration of intervertebral discs is the most common cause of back pain. The first phase of this degenerative process involves the nucleus pulposus. A rapid recovery of this structure can prevent further degradation of the annulus fibrosus. Guar Gum is an hydrophilic polysaccharide extracted from the seed endosperm of a plant. Through a cross-li...

PIB derivatives such as PIBSAs and the corresponding PIBSIs characterized by different contents of functional groups were prepared. They showed luminescence both in their neat form and in heptane solution when the amount of functional groups per polymer chain was higher than a critical value. This behavior is attributed to aggregation‐induced emiss...

The transesterification between poly(ethylene terephthalate) (PET) and dibutyl succinate functionalized polyethylene (POF) was studied by preparing blends in a discontinuous mixer in the presence of different Zn and Ti catalysts. In particular the catalytic activities of Zn(OOCCH3)2, Ti(OBu)4, ZnO and TiO(OCCH3)2 were compared. The mechanism of rea...

A random ethylene–propylene copolymer (EPM) functionalized with grafted diethylsuccinate groups was melt blended with increasing amount (to 20 wt%) of organophilic montmorillonite (OMMT) to prepare nanocomposites with different morphologies as evidenced by XRD and TEM analysis. All the nanocomposites were treated with boiling toluene that did not e...

Boehmite nanoparticles covered with a polymer shell enhancing the organophilicity of the surface were prepared by physical adsorption of a polyelectrolyte atom transfer radical polymerization (ATRP) macroinitiator followed by graft-polymerization of methyl methacrylate or 2-hydroxyethyl methacrylate. The presence of polymer chains adsorbed/grafted...

Boehmite nanoparticles covered with a polymer shell enhancing the organophilicity of the surface were prepared by physical adsorption of a polyelectrolyte atom transfer radical polymerization (ATRP) macroinitiator followed by graft-polymerization of methyl methacrylate or 2-hydroxyethyl methacrylate. The presence of polymer chains adsorbed/grafted...

PIB derivatives such as PIBSAs and the corresponding PIBSIs characterized by different contents of functional groups were prepared. They showed luminescence both in their neat form and in heptane solution when the amount of functional groups per polymer chain was higher than a critical value. This behavior is attributed to aggregation-induced emiss...

Abstract Polyisobutene (PIB) derivatives bearing polar functional groups and with molecular weight range of 500-5000 find various important technological applications in many fields. For example, polyisobutene succinic anhydrides (PIBSA) and their succinimides (PIBSI) derivatives are widely employed as detergent-dispersant additives in lubricants o...

Polyolefins are today the most used thermoplastic materials thanks to the high technology and sustainability of the polymerization process, their excellent thermomechanical properties and their good environmental compatibility, including easy recycling. In the last few decades much effort has been devoted worldwide to extend the applications of pol...

For several traditional applications, in particular those related to agriculture and fresh food packing, the use of a 100 % biodegradable plastics could represent a convenient alternative to polyolefin based materials. In this perspective, poly(lactic acid) (PLA), (a biodegradable linear aliphatic polyester), is receiving much attention thanks to i...

The formation of complex polyolefins based materials is described based on the combination of different transition metal catalysts in a single reactor (Reactor Blending). The paper describes how polymer properties can be controlled by selecting different homogeneous and heterogeneous catalyst and combining them in different ratio while at the same...

The chemical modification of isotactic polypropylene was performed by the free-radical-promoted grafting of 1,1,1-trimethylolpropane trimethacrylate (TMPTMA) in the presence of dicumyl peroxide (DCP) as the initiator. The reaction was carried out both in a batch internal mixer and in a corotating twin-screw extruder; the effects of the peroxide and...

Cover: 1,6‐Diisocyanatehexane promoting gelatin crosslinking was studied and exploited to prepare stable gelatin hydrogels supported on textiles. In the picture a gelatine IPN (inset) and the corresponding hydrogel prepared with cotton textile are shown. Further details can be found in the article by M. Bertoldo, * S. Bronco, T. Gragnoli, and F. Ci...

1,6‐Diisocyanatohexane and dimethyl sulfoxide were exploited as crosslinking agent and reaction solvent, respectively, for gelatin modification. Crosslinked samples were fractionated and analyzed by thermogravimetric analysis, infrared spectroscopy, acid and base titrations, and swelling measurements. The yield of crosslinking was found to increase...

Various diazo-compounds, 1,2,2,6,6-pentamethylpiperidin-4-yl diazoacetate (PMPDA), 2,2,6,6-tetramethylpiperidin-4-yl diazoacetate (TMPDA), methyl diazoacetate (MDA), 1,2,2,6,6-pentamethylpiperidin-4-yl 2-diazo-3-methyloxycarbonylpropionate (PMPMDS), 1,2,2,6,6-pentamethylpiperidin-4-yl 2-diazo-4-methyloxycarbonylbutanoate (PMPMDP), and one azide, me...

Properly designed organic chromophores based on functionalized terthiophenes by push–pull substituents and stilbene derivatives were efficiently incorporated into polyolefins (polyethylene (PE), polypropylene (PP) and their copolymers, even with polar functionalities) at various concentration (from 0.05 to 2 wt.%) either by casting from solvents or...