Synthesis of nylon-6 triblock copolymers with bifunctional polymeric activators

Petrov, Petar; Gancheva, Valeria; Philipova, Tz.; Velichkova, R.; Mateva, R.

doi:10.1002/1099-0518(20001115)38:22<4154::aid-pola160>3.0.co;2-x

Cited by 20 publications

(6 citation statements)

References 17 publications

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“…The reaction of polymerization was carried in bulk at 140, 160, or 180 • C with an ampoule technique. 18 The functionalized polyester, dried monomer CLA, and the ampoules were added to a glass reactor in a nitrogen atmosphere and were melted at 100 • C with continuous stirring for 20 min, which is a requisite condition for the in situ formation of MAs. The reaction temperature was increased to 135-140 • C, and the initiator (NaCL) was added under vigorous stirring; whereas the polymeric mixture was forced into ampoules with N 2 .…”

Section: Synthesis Of P[(cla)-co-(clo)] and P[(cla)-co-(vlo)] Copolymersmentioning

confidence: 99%

Synthesis and characterization of poly(ε‐caprolactones) and poly(δ‐valerolactone): Macroactivators for obtaining poly(esteramides)

Toncheva

Mateva

2007

Adv Polym Technol

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Two new families of biodegradable poly[(ε-caprolactam)-co-(ε-caprolactone)] and poly[(ε-caprolactam)-co-(δ-valerolactone)] copolymers were synthesized via anionic polymerization. The polymerization was activated with macroactivators (MAs) based on telechelic poly(ε-caprolactones) (PCLOs) and poly(δ-valerolactone) (PVLO) polyols. The molecular weights of the polyesters were varied to obtain a large diversity of copolymer structures and properties. The MAs were prepared by reaction of reactive hydroxyl end-groups of PCLO polyols or hydroxyl-carboxyl end-groups PVLO polyol with isophorone diisocyanate (IF). The diisocyanate-end-capped poly(lactones) were additionally blocked in situ with ε-caprolactam to receive corresponding carbamoyllactam derivates. Analyses of the isolated products by FTIR, 1 H NMR spectroscopy, and size exclusion chromatography indicated that nearly quantitative

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Section: Synthesis Of P[(cla)-co-(clo)] and P[(cla)-co-(vlo)] Copolymersmentioning

confidence: 99%

Synthesis and characterization of poly(ε‐caprolactones) and poly(δ‐valerolactone): Macroactivators for obtaining poly(esteramides)

Toncheva

Mateva

2007

Adv Polym Technol

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“…Many efforts have been made to use the prepolymers or small molecules with functional groups reacting with the -caprolactam (CL) monomer for the second technique, and then polymerize to form the copolymer, which acts as compatibilizers. For example, amine-or hydroxy-terminated prepolymers, which are usually liquid and modified by diisocyanate or blocked by dicaprolactam, have been incorporated into CL during in situ polymerization [22][23][24][25][26].…”

Section: Introductionmentioning

confidence: 99%

Preparation and characterization of thermoplastic polyurethane elastomer and polyamide 6 blends by in situ anionic ring‐opening polymerization of ϵ‐caprolactam

Hou

Liu

Yang

2006

Polymer Engineering & Sci

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The blends of thermoplastic polyether-based urethane elastomer (TPEU) and monomer casting polyamide 6 (MCPA6) were prepared using -caprolactam (CL) as a reactive solvent, and CL sodium as a catalyst at various TPEU contents (2.5-15 phr by weight). In situ anionic ring-opening polymerization and in situ compatibilization of TPEU/MCPA6 blends were realized in one step. The dissociated TPEU chains acted as macroactivator to initiate MCPA6 chain growth from the TPEU chains. The formed block copolymers (TPEU-co-MCPA6), which have been confirmed by Fourier transform infrared spectroscopy and 1 H-NMR analysis, improved the compatibility between TPEU and MCPA6. In addition, both differential scanning calorimetry and dynamic mechanical analysis studies revealed that the crystallinity temperature, melting temperature, the degree of crystallization, and the glass-transition temperature of MCPA6 component remarkably shifted to a low temperature with increasing TPEU content. Mechanical properties demonstrated that the impact strength and the elongation-atbreak of the blends significantly increased with the content of TPEU, whereas a progressive decrease occurred in tensile strength, flexural strength, and flexural modulus. WAXD spectra showed that only ␣-form crystal of PA6 component existed in the TPEU/MCPA6 blends. Furthermore, scanning electron microscopes (SEM) of the cryo-fractured surfaces confirmed a substantially improved compatibility, and reflected a seemly single-phase morphology. POLYM. ENG. SCI., 46: 1196 -1203, 2006.

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“…Transamidation (or an interchange reaction) and branching/ crosslinking, both known to occur in the anionic polymerization of caprolactam, is most favorable when reaction temperatures exceed 180 C and near full monomer conversion. 5,16,17 At the end of the polymerization there remains anionic species with little monomer to propagate, leading to a variety of reactions that result in transamidation and branching. The caprolactam anion can react with backbone amides via transamidation forming n-acyl species which can further react.…”

Section: Pa-12t Macrocoinitiatormentioning

confidence: 99%

“…This approach is advantageous because the macroinitiator can be synthesized by other polymerization methods, thereby making a wide variety of PA-6 block copolymers available. Examples in the literature of such macroinitiators include polybutadiene, 3,4 polytetrahydrofuran, 5 polyisoprene, 6 polyethylene oxide-polyisoprene, 7 polyimides, 8 polysiloxanes, 9 and poly(butadiene-co-acrylonitrile). 10 Here, it is essential that the McI has terminal N-acylcaprolactam functionalities, usually requiring an extra derivitization step in the synthetic scheme.…”

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confidence: 99%

One‐pot synthesis of polyamide 12,T–polyamide‐6 block copolymers

Novitsky

Mathias

2011

J. Polym. Sci. A Polym. Chem.

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Polyamide 12,T-polyamide-6 (PA-12,T-PA-6) block copolymers were synthesized by anionic polymerization of caprolactam using a PA-12,T macrocoinitiator (McI). PA-12,T McI and its precursors are soluble in molten caprolactam allowing for both the McI step-growth polymerization and anionic polymerization to be performed in one-pot. It was found that the competing reaction rates of caprolactam ring-opening polymerization and McI transamidation are both deterred by a common ion effect using CaCl 2 and soluble materials were obtained using >1 mol % CaCl 2 . Without CaCl 2 , the reaction mixture solidifies in less than 30 s and produces crosslinked materials. To understand this effect, PA-12,T McI reactions with caprolactam were performed with 1-10 mol % CaCl 2 , and polymer structures were characterized using 13 C NMR and dilute solution viscometry. These data were then correlated with unique thermal properties and swelling behavior of the block copolymers.

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Synthesis of nylon-6 triblock copolymers with bifunctional polymeric activators

Cited by 20 publications

References 17 publications

Synthesis and characterization of poly(ε‐caprolactones) and poly(δ‐valerolactone): Macroactivators for obtaining poly(esteramides)

Synthesis and characterization of poly(ε‐caprolactones) and poly(δ‐valerolactone): Macroactivators for obtaining poly(esteramides)

Preparation and characterization of thermoplastic polyurethane elastomer and polyamide 6 blends by in situ anionic ring‐opening polymerization of ϵ‐caprolactam

One‐pot synthesis of polyamide 12,T–polyamide‐6 block copolymers

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