Synthesis and characterization of chiral poly(<i><scp>l</scp></i>‐lactide‐<i>b</i>‐hexyl isocyanate) macromonomers with norbornenyl end groups and their homopolymerization through ring opening metathesis polymerization to afford polymer brushes

Choinopoulos, Ιoannis; Koïnis, Spyros; Pitsikalis, Marinos

doi:10.1002/pola.28471

Cited by 14 publications

(38 citation statements)

References 15 publications

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“…The synthesized complexes were used as initiators either to polymerize enantiomeric l ‐lactide or racemic rac ‐lactide. A significant issue of the use of alkoxy half‐titanocene initiators was the incorporation of the alkoxy substituent of the complex at the end of the growing polymeric chain . As was assumed, this characteristic applied to titanocene alkoxides as well.…”

Section: Resultsmentioning

confidence: 99%

“…This diblock copolymer exhibits unique optical properties, as both blocks possess helical conformations. The poly(hexyl isocyanate) block is a dynamic helix sensitive to temperature changes, while the poly( l ‐lactide) block retains its conformation, a fact that may lead to high technology applications …”

Section: Resultsmentioning

confidence: 99%

“…We have also shown that poly( l ‐lactide‐ b ‐hexyl isocyanate) bearing a functional end group can be easily prepared employing a half‐titanocene complex. The study of the optical properties of this diblock copolymer revealed that the left‐handed helical poly( l ‐lactide) block induces the formation of only the right‐handed poly(hexyl isocyanate) helix …”

Section: Introductionmentioning

confidence: 99%

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Employing (half‐)titanocene complexes as initiators for the synthesis of end‐functionalized polylactides by coordination polymerization

Patias

Choinopoulos

Koïnis

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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Seven (half‐)titanocene alkoxide complexes, [Cp2TiCl(OEt)], [Cp2TiCl(O‐2‐Bu)], [Cp2TiCl(OCH2CF2CF2H)], [CpTiCl2(OEt)], [CpTiCl2(O‐(S)‐2‐Bu)], [CpTiCl2(OCH2CF3)], and [Cp2TiCl(OCH2CF3)], were synthesized and employed in lactide coordination polymerization. These organotitanium (IV) compounds proved to be very efficient initiators for the ring‐opening polymerization of enantiomeric l‐lactide and racemic mixture of rac‐lactide, leading to end‐functionalized polymers. Kinetic studies illustrated that these compounds produce well‐defined polymers in a controlled manner. This was further demonstrated by synthesizing poly(l‐lactide‐b‐hexyl isocyanate) diblock copolymer. The effect of the alkoxy end groups on the thermal behavior of the polymers was also studied by thermogravimetric analysis and differential scanning calorimetry. The polymers were characterized using size exclusion chromatography and proton nuclear magnetic resonance spectroscopy. The optical properties of the diblock copolymer were also investigated. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2192–2202

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Employing (half‐)titanocene complexes as initiators for the synthesis of end‐functionalized polylactides by coordination polymerization

Patias

Choinopoulos

Koïnis

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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“…The less stoichiometric carbodiimide is used to react with all of the carboxylic acid present. There is a possibility that in some instances rapid loss of carbodiimide func# onality in excess may be due to self-condensa# on, similar in the case of polyisocyanates [35]. Polycarbodiimides have prac!…”

Section: Pot-lifementioning

confidence: 99%

“…Xiaoyan and Zhiwen [37] have synthesized a new cross-linker for microcapsule by interfacial polymeriza! on using hydrophobic carbodiimide cross-linker ( Figure 11) for high tensile strength [35]. The reac!…”

Section: Pot-lifementioning

confidence: 99%

Polycarbodiimide and polyurethane cross-linkers for leather finishing

Ramkumar¹,

Murali²,

Preethi³

et al. 2017

LFJ

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ABSTRACT. This review focuses on polyurethane and carboxylic acid-carbodiimide cross-linked systems for leather fi nishes. Recently, these cross-links have become very popular in leather fi nishing. The cross-links in leather fi nishes improve the strength proper# es of the fi nished leather, the excess of cross-links causes bri$ leness. The mul# func# onal carbodiimide cross-linkers are useful for leather surface proper# es improvement. The carbodiimide groups are sensi# ve to hydrolysis; life # me of this func# onal group during polymeriza# on is enhanced. Water dispersible isocyanates, polyurethane copolymers and polyisocyanate cross-links have applica# ons in new technologies are discussed in this review. KEY WORDS: cross-linker, polycarbodiimide, diisocyanate, leather, polyurethane AGENŢI DE RETICULARE PE BAZĂ DE POLICARBODIIMIDĂ ŞI POLIEURETAN PENTRU FINISAREA PIELIIREZUMAT. Acest ar# col se concentrează asupra sistemelor de re# culare pe bază de poliuretan şi acid carboxilic-carbodiimidă pentru fi nisarea pielii. Recent, aceste # puri de re# culări au devenit foarte populare în fi nisarea pieilor. Re# cularea pielii la fi nisare îmbunătăţeşte proprietăţile de rezistenţă ale pieii fi nite, în # mp ce excesul de legături încrucişate determină fragilitate. Agenţii de re# culare mul# funcţionali carbodiimidici sunt u# li pentru îmbunătăţirea proprietăţilor de suprafaţă ale pielii. Grupările carbodiimidice sunt sensibile la hidroliză; durata de viaţă a acestui grup funcţional în # mpul polimerizării este sporită. Re# culările cu izocianaţii dispersabili în apă, copolimerii poliuretanici şi poliizocianaţi discutate în această lucrare au aplicaţii în tehnologii noi. CUVINTE CHEIE: agent de re# culare, policarbodiimidă, diizocianat, piele, poliuretan AGENTS DE RÉTICULATION POLYCARBODIIMIDE ET POLYURÉTHANE POUR LA FINITION DU CUIRRÉSUMÉ. Cet ar# cle met l'accent sur les systèmes de ré# cula# on à base de polyuréthane et de l'acide carboxylique-carbodiimide pour la fi ni# on du cuir. Récemment, ces types de ré# cula# ons sont devenus très populaires dans la fi ni# on du cuir. La ré# cula# on du cuir dans l'opéra# on de fi ni# on améliore les propriétés de résistance du cuir fi ni, tandis que la ré# cula# on excessive entraîne une fragilité. Les agents de ré# cula# on mul# fonc# onnels de carbodiimide sont u# les pour améliorer les propriétés de surface du cuir. Les groupes carbodiimide sont sensibles à l'hydrolyse; la durée de vie de ce groupe fonc# onnel pendant la polymérisa# on est augmentée. Les ré# cula# ons avec des isocyanates dispersables dans l'eau, des copolymères de polyuréthane et des polyisocyanates décrits dans cet ar# cle ont des applica# ons dans de nouvelles technologies. MOTS CLÉS: agent de ré# cula# on, polycarbodiimide, diisocyanate, cuir, polyuréthane

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Synthesis and characterization of statistical and block copolymers of n‐hexyl isocyanate and 2‐chloroethyl isocyanate via coordination polymerization

Mantzara,

Katara,

Panteli

et al. 2024

Journal of Polymer Science

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Statistical and block copolymers of n‐hexyl isocyanate (HIC) and 2‐chloroethyl isocyanate (ClEtIC) were synthesized via cοοrdination polymerization employing the half‐titanocene complex [(η5‐C5H5)((S)‐2‐Bu‐O)TiCl2] as initiator. The complex, bearing a chiral substituent, led to optically active products, as confirmed by circular dichroism measurements. The molecular characterization of all products was carried out by NMR and IR spectroscopy and size exclusion chromatography (SEC), while their thermal stability was investigated through differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and differential thermogravimetry (DTG). The reactivity ratios of the two monomers were determined using various graphical methods, as well as the COPOINT program, according to the terminal copolymerization model. Structural parameters, such as the dyad monomer sequences and the mean sequence lengths were calculated as well. In addition, the kinetics of the thermal degradation of the statistical copolymers was studied, and the activation energies of the thermal degradation were calculated employing the Kissinger, Ozawa–Flynn–Wall (OFW), and Kissinger–Akahira–Sunose (KAS) methods. The block copolymers were synthesized by sequential addition of monomers starting from the polymerization of HIC. Well‐defined products were obtained in a controlled way as revealed by SEC, IR, and NMR measurements.

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Synthesis and characterization of chiral poly(l‐lactide‐b‐hexyl isocyanate) macromonomers with norbornenyl end groups and their homopolymerization through ring opening metathesis polymerization to afford polymer brushes

Cited by 14 publications

References 15 publications

Employing (half‐)titanocene complexes as initiators for the synthesis of end‐functionalized polylactides by coordination polymerization

Employing (half‐)titanocene complexes as initiators for the synthesis of end‐functionalized polylactides by coordination polymerization

Polycarbodiimide and polyurethane cross-linkers for leather finishing

Synthesis and characterization of statistical and block copolymers of n‐hexyl isocyanate and 2‐chloroethyl isocyanate via coordination polymerization

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