Dual catalysis with an N-heterocyclic carbene and a Lewis acid: Thermally latent precatalyst for the polymerization of ε-caprolactam

So far, the earlier reported strong correlation between basicity of an N-heterocyclic carbene (NHC) and its reactivity in poly(ε-caprolactam) (PA6) synthesis resulted in a substantial limitation of applicable carbenes. Here, to overcome this issue, 1,3-dimethylimidazolium-2-carboxylate, an easily accessible, air and moisture-stable NHC, was applied as thermally latent initiator. In order to compensate for its low basicity, reactivity was enhanced by the addition of both a Lewis acid and an activator to ease the initial polymerization step. The resulting mixtures of ε-caprolactam, the CO₂-protected NHC, a Lewis acid and N-acylazepan-2-one constitute homogeneous, thermally fully latent “single-component” blends for the anionic polymerization-based synthesis of PA6. They can be stored both in the liquid and solid state for days and months, respectively, without any loss in activity. The role of the Lewis acid as well as technical implications of the prolonged pot-times are discussed.     

Anionic polymerization of ɛ-caprolactam in the presence of piperidine N-carboxamides

Piperidine N-carboxamides were shown to activate the anionic polymerization of ?-caprolactam. The activator structure affects properties of the resulting polycaproamide.     

Polymerization of lactams. 98: Influence of water on the non-activated polymerization of ε-caprolactam

The sensitivity of so-called non-activated polymerization of ε-caprolactam to the presence of water in the polymerization mixture has been studied. Polymerizations were initiated with 1 mol% sodium salt of ε-caprolactam, magnesium di(ε-caprolactamate) and/or ε-caprolactam magnesium bromide and were carried out at water concentration 0-1 mol% and in the temperature range of 190-230 °C. The influence of water content in the polymerization mixture on the polymerization rate and polymerization degree was evaluated. The studied initiators exhibited different sensitivity to the water added in the polymerization mixture and the role of water in the course of anionic polymerization of ε-caprolactam is discussed. Magnesium initiators are exceptional, they are capable to eliminate retardation effect of water on studied polymerization.     

Problems in low-temperature polymerization of lactams with MAlEt4–n (Lac)n as catalyst

The NaAl(Lac)₄-catalyzed polymerization of ε-caprolactam at the medium temperature range (70–150°C) was investigated. The initiation temperature was observed to decrease to about 100°C in the case of a high concentration (such as 2.0 mole-%) of catalyst. Moreover, in the prolonged polymerization of lactams with KAl(Lac)₂Et₂ catalyst, in the absence of initiator, the low activity of aluminum lactamate as initiator was observed. In connection with the polymerization of lactams with MAl(Lac)_nEt_4–n catalyst, the reactivity of MAlEt₄ (where M is Na or K) with N-acetyllactams was investigated. The results imply that no consumption of N-acyllactams by the reaction with MAl(Lac)_nEt_4–n occurs in the course of the low-temperature polymerization of lactams.     

Anionic polymerization of N-ethyl-2-vinylcarbazole and N-ethyl-3-vinylcarbazole

The polymerization of N-ethyl-2-vinylcarbazole and N-ethyl-3-vinylcarbazole by an anionic mechanism has been demonstrated. Polymerization reactions were monitored by ultraviolet/visible spectroscopy and λ_max and ε values for the propagating carbanions determined. The 2-vinyl monomer exhibits all the features of a standard “living” polymer; the carbanion is stable at ambient temperatures and high molecular weight, M?_n ? 10⁶, narrow distribution polymers and block copolymers with styrene have been prepared. The carbanion from the 3-vinyl monomer is much less stable and a clean polymerization can only be conducted at temperatures below -60°C. A comparison of the anionic polymerization characteristics of the N-, 2-, and 3-vinyl carbazole monomer series is presented.     

Effect of single-walled carbon nanotubes with imide cycles on the synthesis and properties of polycaproamide

The anionic polymerization of ε-caprolactam in the presence of single-walled carbon nanotubes with grafted acyllactam groups or polyimide macromolecules is performed. It is shown that the polymerization of ε-caprolactam slows down with an increase in the filler concentration. The introduction of 0.01 wt % nanotubes with polyimide fragments into polycaproamide leads to a 25% increase in the compressive modulus. In this case, the Izod impact strength is 10 kJ/m², that is, 150% higher than that for an unfilled polycaproamide or polycaproamide containing other types of nanotubes.     

Low-temperature polymerization of lactams by using as catalyst the salt derived from NaAlEt4 and monomer and with several compounds as initiator

Low-temperature polymerization of α-pyrrolidone, α-piperidone, and ?-caprolactam was examined by using the salts derived from NaAlEt₄ and monomer, sodium lactamates, or the salt derived from AlEt₃ and monomer as catalyst and with N-acetyl lactams, ethyl acetate, or lactones as initiator. Sodium lactamate catalyst gave unsatisfactory results in the cases of ethyl acetate or lactones initiators, and gave the following order for the relative efficiency of initiators: N-acetyl lactam > ?-caprolactone ≥ ethyl acetate > β-propiolactone. The polymerization results obtained by the salt from NaAlEt₄ catalyst–ethyl acetate initiator system were nearly the same as those with N-acetyl lactam. The increases in the degree of polymerization and in the yield of polymer were observed in case of the salt from NaAlEt₄ catalyst-lactone initiator system, particularly in the cases of α-piperidone and ?-caprolactam. Also an incorporation of initiator into polymer chain was observed.     

Block copolymerization. V. Block anionic polymerization of lactams

Bischloroformates of hydroxy-terminated poly(tetramethylene glycol) (PTG) and polystyrene (PSt) were prepared and used as the initiators for the anionic polymerization of α-pyrrolidone and ε-caprolactam in bulk at 30°C and 80°C, respectively. Initiation efficiency was sufficiently high to give well-defined nylon–PTG(or PSt)–nylon block copolymers. Both the yield and the viscosity of the block copolymer increased with polymerization time up to 50% conversion of the lactam.     

Al(Cap)3 as initiator in the anionic polymerization of ε-caprolactam at high temperature

Mechanism for polymerization of ε-caprolactam in the presence of both sodium and aluminum caprolactamate was investigated at 171°C. The role of Al(Cap)₃ as an initiator was revealed. The apparent rate constant of propagation reaction decreased with the increase in the concentration of Al(Cap)₃, as the two different metal salts interact even at 171°C. The activation energy of the overall polymerization reaction with this catalyst system was estimated to be 41.18 kcal/mole.     

Preparation of monodisperse hydrophilic polyamide by anionic polymerization of bicyclic oxalactam

The preparation of a monodisperse hydrophilic polyamide was achieved in the anionic polymerization of a bicyclic oxalactam, 8-oxa-6-azabicyclo[3.2.1]octan-7-one (abbreviated BOL) with the use of N-benzoyl BOL and potassium pyrrolidonate (2 and 0.5 mol % to BOL, respectively) in dimethyl sulfoxide at 25°C. The number-average molecular weight of the polyamide increased in direct proportion to the monomer conversion, and was consistent with the value calculated from the amounts of the consumed monomer and activator. The molecular weight distribution (MWD) of the polyamide obtained until the middle stage of polymerization (polymerization time, < 10 min; monomer conversion, < 60%) was found to be narrow (M_w/M_n = 1.1). The MWD was gradually broadened in the later stage of the polymerization, which may result from the redistribution of molecular weight of the resulting polyamide not only by the polymerization–depolymerization equilibrium, but also by transamidation between polymer chains.     

Propene polymerization with rac-Me2Si(2-Me-Benz[e]Ind)2ZrX2 [X = Cl,Me] using different cation-generating reagents

Propene was polymerized with methylaluminoxane (MAO) and cationic activated rac-dimethylsilylene-2-methylbenz[e]indenylzirconocene [ MBI-Cl ₂] and [ MBI-Me ₂]. For cationic activation of the MBI-Me ₂ system tris(pentafluorophenyl)borane [I], N,N-dimethylanilinium tetra(pentafluorophenyl)borate [III] were used. The MAO-activated dimethyl complex showed higher activity with respect to the dichloride system using high catalyst concentrations and [Al]/[Zr] ratios. Most effective cationic activator for MBI-Me ₂ was N,N-dimethylanilinium tetra(pentafluorophenyl)borate [II] in combination with Al(i-Bu₃). Using tris(pentafluorophenyl)borane [I] at different polymerization conditions or N,N-dimethylanilinium tetra(pentafluorophenyl)borate [II] in combination with Al(Et)₃ no propene polymerization was observed due to the occurrence of reduction of the catalytically active site.     

Synthesis of well‐defined polyacrylonitrile by ICAR ATRP with low concentrations of catalyst

Acrylonitrile (AN) was polymerized by initiators for continuous activator regeneration (ICAR) atom transfer radical polymerization (ATRP). The effect of the ligand, tris(2‐pyridylmethyl)amine (TPMA) and N,N,N',N'‐tetrakis(2‐pyridylmethyl)ethylenediamine (TPEN), in the Cu‐based catalyst, the amount of catalyst, several alkyl halide initiators, targeted degree of polymerization, and amount of azobisisobutyronitrile (AIBN) added were studied. It was determined that the best conditions utilized 50 ppm of CuBr₂/TPMA as the catalyst and 2‐bromopropionitrile (BPN) as the initiator. This combination resulted in 46% conversion in 10 h and polyacrylonitrile (PAN) with the narrowest molecular weight distribution (M_w/M_n = 1.11–1.21). Excellent control was maintained after lowering the catalyst loading to 10 ppm, with 56% conversion in 10 h, experimental molecular weight closely matching the theoretical value, and low dispersity (M_w/M_n < 1.30). Catalyst loadings as low as 1 ppm still provided well‐controlled polymerizations of AN by ICAR ATRP, with 65% conversion in 10 h and PAN with relatively low dispersity (M_w/M_n = 1.41). High chain end functionality (CEF) was confirmed via ¹H NMR analysis, for short PAN chains, and via clean chain extensions with n‐butyl acrylate (BA). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1961–1968     

Atom transfer radical polymerization of sodium2‐acrylamido‐2‐methylpropanesulfonate

The first example of well‐controlled atom transfer radical polymerization (ATRP) of a permanently charged anionic acrylamide monomer is reported. ATRP of sodium 2‐acrylamido‐2‐methylpropanesulfonate (NaAMPS) was achieved with ethyl 2‐chloropropionate (ECP) as an initiator and the CuCl/CuCl₂/tris(2‐dimethylaminoethyl)amine (Me₆TREN) catalytic system. The polymerizations were carried out in 50:50 (v/v) N,N‐dimethylformamide (DMF)/water mixtures at 20 °C. Linear first‐order kinetic plots up to a 92% conversion for a target degree of polymerization of 50 were obtained with [ECP]/[CuCl]/[CuCl₂]/[Me₆TREN] = 1:1:1:2 and [AMPS] = 1 M. The molecular weight increased linearly with the conversion in good agreement with the theoretical values, and the polydispersities decreased with increasing conversion, reaching a lower limit of 1.11. The living character of the polymerization was confirmed by chain‐extension experiments. Block copolymers with N,N‐dimethylacrylamide and N‐isopropylacrylamide were also prepared. The use of a DMF/water mixed solvent should make possible the synthesis of new amphiphilic ionic block copolymers without the use of protecting group chemistry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4446–4454, 2005     

Anionic polymerization of ϵ-caprolactam activated with phosphadiazines

Phenylphosphonyl-N,N′-biscaprolactam (I) and phenylphosphonyl-N,N′-bis(3,5-dimethylpyrazole) (II) were synthesized and found to be very efficient activators for the anionic polymerization of caprolactam when used in combination with strong bases such as sodium caprolactam. Polymers obtained in the presence of I and II had generally higher molecular weights and were less sensitive to thermal degradation upon molding than those whose preparation entailed the use of N-acetyl-caprolactam (III) as an activator. Thermal behavior and tensile properties indicated that the structure of these polyamides differs from that encountered in nylon 6 prepared with conventional anionic catalyst systems.     

Synthesis of poly(methyl methacrylate) via ARGET ATRP and study of the effect of solvents and temperatures on its polymerization kinetics

This investigation reports the synthesis of poly(methyl methacrylate) via activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) and studies the effect of solvents and temperature on its polymerization kinetics. ARGET ATRP of methyl methacrylate (MMA) was carried out in different solvents and at different temperatures using CuBr₂ as catalyst in combination with N,N,N′,N″,N″‐pentamethyldiethylenetriamine as a ligand. Methyl 2‐chloro propionate was used as ATRP initiator and ascorbic acid was used as a reducing agent in the ARGET ATRP of MMA. The conversion was measured gravimetrically. The semilogarithmic plot of monomer conversion versus time was found to be linear, indicating that the polymerization follows first‐order kinetics. The linear polymerization kinetic plot also indicates the controlled nature of the polymerization. N,N‐Dimethylformamide (DMF), tetrahydrofuran (THF), toluene, and methyl ethyl ketone were used as solvents to study the effect on the polymerization kinetics. The effect of temperature on the kinetics of the polymerization was also studied at various temperatures. It has been observed that polymerization followed first‐order kinetics in every case. The rate of polymerization was found to be highest (k_app = 6.94 × 10⁻³ min⁻¹) at a fixed temperature when DMF was used as solvent. Activation energies for ARGET ATRP of MMA were also calculated using the Arrhenius equation.     

Anionically prepared poly(ε-caprolactam-co-ε-caprolactone) and poly(ε-caprolactam-co-δ-valerolactone) copolymers: Thermal and mechanical properties

Thermal and representative physico-mechanical properties of newly prepared poly[(ε-caprolactam)-co-(ε-caprolactone)] and poly[(ε-caprolactam)-co-(δ-valerolactone)] copolymers were studied. The copolymers were synthesized by anionic polymerization of ε-caprolactam activated by isocyanate end-capped oligomeric aliphatic polyesters designated as the macroactivators (MAs). Type, concentration and molecular weight of the MAs were varied, which resulted in copolymers with different structure and properties. The impact of the new MAs used in this study on the glass transition temperature and the melting temperature of poly-ε-caprolactam was investigated by DSC. DMTA was used to analyze the effect of copolymerization on the storage modulus (E^′) and tan δ of poly-ε-caprolactam. Conventional and high-resolution TGA data revealed that all the synthesized polyesteramides possess good thermal stability. Mechanical properties were studied by notched impact and tensile testing. According to the experimental data the impact toughness increase with the MA content, being six time higher compared to the poly(ε-caprolactam) in the best situation. Water absorption was also considered in relation to the composition of the copolymers.     

Anionic polymerization of N,N‐dialkylacrylamides containing alkoxysilyl groups in the presence of Lewis acids

With Ph₂CHK as an initiator, the anionic polymerization of N‐propyl‐N‐(3‐triisopropoxysilylpropyl)acrylamide ( 4 ) and N‐propyl‐N‐(3‐triethoxysilylpropyl)acryl‐amide generated polymers with predicted molecular weights and narrow molecular weight distributions (MWDs) in the presence of Et₂Zn or Et₃B; however, the resulting polymers obtained in the absence of such Lewis acids had very broad MWDs. The results were ascribed to the coordination of the propagating anionic end to a relatively weak Lewis acid, in which the activity of the end anion was appropriately controlled for moderate polymerization without side reactions. A well‐defined diblock copolymer of 4 and N,N‐diethylacrylamide was also prepared with the binary initiating system of Ph₂CHK and Et₂Zn, whereas no such block copolymer was prepared by polymerization initiated with 1,1‐diphenyl‐3‐methylpentyllithium, as the propagating anion together with the lithium ion reacted with alkoxysilyl side groups on the poly( 4 ) backbone to produce grafted polymers with high molecular weights. The hydrolysis of the alkoxysilyl side groups of poly( 4 ) in acidic water yielded an insoluble gel. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2754‐2764, 2005     

Air‐stable and recoverable catalyst for copper‐catalyzed controlled/living radical polymerization of styrene; In situ generation of Cu(I) species via electron transfer reaction

Copper‐catalyzed controlled/living radical polymerization (LRP) of styrene (St) was conducted using the silica gel‐supported CuCl₂/N,N,N′,N′,N″‐pentamethyldiethylenetriamine (SG‐CuCl₂/PMDETA) complex as catalyst at 110 °C in the presence of a definite amount of air. This novel approach is based on in situ generation and regeneration of Cu(I) via electron transfer reaction between phenols and Cu(II). Sodium phenoxide or p‐methoxyphenol was used as a reducing agent of Cu(II) complexes in LRP. The number–average molecular weight, M_n,GPC, increases linearly with monomer conversion and agrees well with the theoretical values up to 85% conversion The molecular weight distribution, M_w/M_n, decreases as the conversion increases and reaches values below 1.2. The catalyst was recovered in aerobic condition and reused in copper‐catalyzed LRP of St. For the second run, the number–average molecular weights increased with monomer conversion and the polydispersities decreased as the polymerization proceeded and reached to the value <1.3 at 81% conversion. The recycled catalyst retained 90% of its original activity in the subsequent polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 77–87, 2006     

Ring-Opening polymerization of ε-caprolactone by rare earth coordination catalysts. I. Characteristics,kinetics, and mechanism of ε-caprolactone polymerization with nd(acac)3.3H2O-ALET3 system

Ring-opening polymerization of ε-caprolactone has been carried out by using rare earth coordination catalysts for the first time. The rare earth compounds, RE(acac)₃.3H₂O, Nd(P₂₀₄)₃, Nd(P₅₀₇)₃, Nd(naph)₃, Nd(BA)₃.2H₂O, etc. (where RE = La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Lu, Y; acac = acetylacetone; BA = benzoylacetone), combined with trialkyl aluminum, greatly increased the degree of conversion and the molecular weight of poly(ε-caprolactone) (PCL). The influence of reaction conditions on the polymerization of ε-caprolactone catalyzed by the Nd (acac)₃.3H₂O-AlEt₃ system has been examined in detail. The kinetics indicates that the polymerization rate has the first-order in monomer and a half-order in catalyst. The overall activation energy of the ring-opening polymerization amounts to 59.4 kJ/mol. By IR and UV-Vis spectra, ¹H- and ¹³C-NMR data, it is assumed that the ring-opening polymerization of ε-caprolactone catalyzed by the Nd(acac)₃.3H₂O-AlEt₃ system proceeds via complexation of monomer to catalyst, acyl-oxygen cleavage insertion propagation mechanism. © 1994 John Wiley & Sons, Inc.     

Atom transfer radical copolymerization of acrylonitrile and ethyl methacrylate at ambient temperature

Copolymerization of acrylonitrile (AN) and ethyl methacrylate (EMA) using copper‐based atom transfer radical polymerization (ATRP) at ambient temperature (30 °C) using various initiators has been investigated with the aim of achieving control over molecular weight distribution. The effect of variation of concentration of the initiator, ligand, catalyst, and temperature on the molecular weight distribution and kinetics were investigated. No polymerization at ambient temperature was observed with N,N,N′,N′,N″‐pentamethyldiethylenetriamine (PMDETA) ligand. The rate of polymerization exhibited 0.86 order dependence with respect to 2‐bromopropionitrile (BPN) initiator. The first‐order kinetics was observed using BPN as initiator, while curvature in first‐order kinetic plot was obtained for ethyl 2‐bromoisobutyrate (EBiB) and methyl 2‐bromopropionate (MBP), indicating that termination was taking place. Successful polymerization was also achieved with catalyst concentrations of 25 and 10% relative to initiator without loss of control over polymerization. The optimum [bpy]₀/[CuBr]₀ molar ratio for the copolymerization of AN and EMA through ATRP was found to be 3/1. For three different in‐feed ratios, the variation of copolymer composition (F_AN) with conversion indicated toward the synthesis of copolymers having slight changes in composition with conversion. The high chain‐end functionality of the synthesized AN‐EMA copolymers was verified by further chain extension with methyl acrylate and styrene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1975–1984, 2006