Radical‐initiated polymerization of β‐methyl‐α‐methylene‐γ‐butyrolactone

β‐Methyl‐α‐methylene‐γ‐butyrolactone (MMBL) was synthesized and then was polymerized in an N,N‐dimethylformamide (DMF) solution with 2,2‐azobisisobutyronitrile (AIBN) initiation. The homopolymer of MMBL was soluble in DMF and acetonitrile. MMBL was homopolymerized without competing depolymerization from 50 to 70 °C. The rate of polymerization (R_p) for MMBL followed the kinetic expression R_p = [AIBN]^0.54[MMBL]^1.04. The overall activation energy was calculated to be 86.9 kJ/mol, k_p/k_t^1/2 was equal to 0.050 (where k_p is the rate constant for propagation and k_t is the rate constant for termination), and the rate of initiation was 2.17 × 10^?8 mol L^?1 s^?1. The free energy of activation, the activation enthalpy, and the activation entropy were 106.0, 84.1, and 0.0658 kJ mol^?1, respectively, for homopolymerization. The initiation efficiency was approximately 1. Styrene and MMBL were copolymerized in DMF solutions at 60 °C with AIBN as the initiator. The reactivity ratios (r₁ = 0.22 and r₂ = 0.73) for this copolymerization were calculated with the Kelen–Tudos method. The general reactivity parameter Q and the polarity parameter e for MMBL were calculated to be 1.54 and 0.55, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1759–1777, 2003     

Kinetic study of the radical polymerization behavior of N‐(1‐phenylethylaminocarbonyl)methacrylamide

Polymerization of N‐(1‐phenylethylaminocarbonyl)methacrylamide (PEACMA) with dimethyl 2,2′‐azobisisobutyrate (MAIB) was kinetically studied in dimethyl sulfoxide (DMSO). The overall activation energy of the polymerization was estimated to be 84 kJ/mol. The initial polymerization rate (R_p) is given by R_p = k[MAIB]^0.6[PEACMA]^0.9 at 60 °C, being similar to that of the conventional radical polymerization. The polymerization system involved electron spin resonance (ESR) spectroscopically observable propagating poly(PEACMA) radical under the actual polymerization conditions. ESR‐determined rate constants of propagation and termination were 140 L/mol s and 3.4 × 10⁴ L/mol s at 60 °C, respectively. The addition of LiCl accelerated the polymerization in N,N‐dimethylformamide but did not in DMSO. The copolymerization of PEACMA(M₁) and styrene(M₂) with MAIB in DMSO at 60 °C gave the following copolymerization parameters; r₁ = 0.20, r₂ = 0.51, Q₁ = 0.59, and e₁ = +0.70. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2013–2020, 2005     

Radical homo- and copolymerizations of methyl α-trifluoroacetoxyacrylate

Radical homo- and copolymerizations of methyl α-trifluoroacetoxyacrylate (MTFAA) are studied by using azo initiators at 40 and 60°C. The rate of the homopolymerization of MTFAA was lower than that of methyl α-acetoxyacrylate. Monomer reactivity ratios (r), and Q and e values were estimated to be r₁ = 0.03, r₂ = 0.27, Q₁ = 0.65, and e₁ = 1.38 from the copolymerization of MTFAA (M₁) and styrene (M₂) at 60°C. Preferential crosspropagation was observed in particular in the copolymerization of MTFAA and α-methylstyrene. The influence of replacing the hydrogens of the acetoxy moiety of the acyloxyacrylate with the fluorines upon the copolymerization reactivity is discussed on the basis of the ¹³C-NMR chemical shift of various acyloxyacrylates. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3537–3541, 1997     

A New Route to N‐Aryl 2‐Alkenamides,N‐Allyl N‐Aryl 2‐Alkenamides,and N‐Aryl α,β‐Unsaturated γ‐Lactams from N‐Aryl 3‐(Phenylsulfonyl)propanamides

A series of N‐aryl 2‐alkenamides were produced efficiently by treating N‐aryl 3‐(phenylsulfonyl)‐propanamides with potassium tert‐butoxide in THF at 0°C. With out isolation, it was further treated with an additional equivalent of potassium tert‐butoxide and allyl bromide to give N‐allyl N‐aryl 2‐alkenamides in one pot in good yields. Followed by a ring‐closing metathesis reaction, these N‐allyl N‐aryl 2‐alkenamides were respectively converted into corresponding N‐aryl α,β‐unsaturated γ‐lactams in moderate yields.     

Asymmetric cyclopolymerization of N‐tert‐butyl‐N‐allylacrylamide in the presence of β‐cyclodextrin

The radical polymerization of N‐tert‐butyl‐N‐allylacrylamide (t‐BAA) was carried out in a dimethyl sulfoxide/H₂O mixture in the presence of β‐cyclodextrin (β‐CD). The polymerization proceeded with the complete cyclization of the t‐BAA unit and yielded optically active poly(t‐BAA). The IR spectrum of the obtained polymer showed that the cyclic structure in the polymer was a five‐membered ring. The optical activity of poly(t‐BAA) increased with an increasing molar ratio of β‐CD to the t‐BAA monomer. The interaction of β‐CD with t‐BAA was confirmed by ¹H NMR and ¹³C NMR analyses of the polymerization system. It is suggested that interaction of the t‐BAA monomer with the hydrophobic cavity of β‐CD plays an important role in the asymmetric cyclopolymerization of t‐BAA. The radical copolymerization of t‐BAA with styrene (St), methyl methacrylate, ethyl methacrylate, or benzyl methacrylate (BMA) also produced optically active copolymers with a cyclic structure from the t‐BAA unit. St and BMA carrying a phenyl group were predicted to compete with t‐BAA for interaction with β‐CD in the copolymerization system. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2098–2105, 2000     

A convenient synthesis of α,α′‐ homo‐ and α,α′‐hetero‐bifunctionalized poly(ε‐caprolactone)s by ring opening polymerization: The potentially valuable precursors for miktoarm star copolymers

Two new ring opening polymerization (ROP) initiators, namely, (3‐allyl‐2‐(allyloxy)phenyl)methanol and (3‐allyl‐2‐(prop‐2‐yn‐1‐yloxy)phenyl)methanol each containing two reactive functionalities viz. allyl, allyloxy and allyl, propargyloxy, respectively, were synthesized from 3‐allylsalicyaldehyde as a starting material. Well defined α‐allyl, α′‐allyloxy and α‐allyl, α′‐propargyloxy bifunctionalized poly(ε‐caprolactone)s with molecular weights in the range 4200–9500 and 3600–10,900 g/mol and molecular weight distributions in the range 1.16–1.18 and 1.15–1.16, respectively, were synthesized by ROP of ε‐caprolactone employing these initiators. The presence of α‐allyl, α′‐allyloxy and α‐allyl, α′‐propargyloxy functionalities on poly(ε‐caprolactone)s was confirmed by FT‐IR, ¹H, ¹³C NMR spectroscopy, and MALDI‐TOF analysis. The kinetic study of ROP of ε‐caprolactone with both the initiators revealed the pseudo first order kinetics with respect to ε‐caprolactone consumption and controlled behavior of polymerization reactions. The usefulness of α‐allyl, α′‐allyloxy functionalities on poly(ε‐caprolactone) was demonstrated by performing the thiol‐ene reaction with poly(ethylene glycol) thiol to obtain (mPEG)₂‐PCL miktoarm star copolymer. α‐Allyl, α′‐propargyloxy functionalities on poly(ε‐caprolactone) were utilized in orthogonal reactions i.e copper catalyzed alkyne‐azide click (CuAAC) with azido functionalized poly(N‐isopropylacrylamide) followed by thiol‐ene reaction with poly(ethylene glycol) thiol to synthesize PCL‐PNIPAAm‐mPEG miktoarm star terpolymer. The preliminary characterization of A₂B and ABC miktoarm star copolymers was carried out by ¹H NMR spectroscopy and gel permeation chromatography (GPC). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 844–860     

Studies on the Mass Spectra of N‐Aryl α,β‐Unsaturated γ‐Lactams

The mass spectra of a series of N‐aryl α,β‐unsaturated γ‐lactams were studied. Besides the molecular ion, the three characteristic fragments such as [M⁺‐29], [M⁺‐55], and [M⁺‐82] were commonly found in a series of N‐Aryl α,β‐unsaturated γ‐lactams in EI/MS. Further more the mechanism for the interpretation of these fragments is also de scribed.     

Stereospecific polymerization of benzyl α-(alkoxymethyl) acrylates

α-(Alkoxymethyl) acrylates, such as methyl α-(phenoxymethyl) acrylate, benzyl α-(methoxymethyl)acrylate (BMMA), benzyl α-(benzyloxymethyl)acrylate, and benzyl α-(tert-butoxymethyl)acrylate, were synthesized, and their polymerizability and the stereoregularity of the polymers obtained by radical and anionic methods were investigated. The radically obtained polymers were found to be atactic by ¹³C- and ¹H-NMR analyses, but the polymers obtained with lithium reagents in toluene at −78°C were highly isotactic. Further, it is noteworthy that isotactic polymers were also produced with lithium reagents even in tetrahydrofuran. Effects of polymerization temperature and counter cation on stereoregularity were clearly observed in the polymerization of BMMA, and a potassium reagent afforded an almost atactic polymer. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 721–726, 1997     

Electron spin resonance study on chemical‐crosslinking reaction mechanisms of polyethylene using a chemical agent. VI. Effect of α‐methyl styrene dimer

The effect of α‐methyl styrene dimer (AMSD), which is used as a scorch retarder, on the reaction mechanisms of the chemical crosslinking of polyethylene (PE) with dicumyl peroxide (DCP) at high temperatures was investigated using electron spin resonance. When AMSD was added to PE containing DCP, the AMSD radical was observed; however, the PE alkyl radical or allyl radical presence was not detected. At 145 °C, crosslinking was obstructed as a result of the reaction between AMSD and alkyl radicals. As the temperature increased, AMSD fragmented to form 2‐phenyl‐2‐propyl and double bonds in PE. This generation of double bonds, however, accelerated crosslinking at 180 °C and was more effective than when AMSD was not present. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2151–2156, 2001     

Poly(α‐methyleneglutarimide)s from radical polymerization of α‐methyleneglutarimides

α‐Methyleneglutaric acid, a metabolite of niacin (nicotinic acid), can be easily converted to its cyclic anhydride. We report here the first conversion of α‐methyleneglutaric anhydride to (a series of) α‐methyleneglutarimides. These monomers can be radically polymerized to the title polymers. These have relatively high glass transition properties compared to the lower homologs derived from itaconimides (α‐methylenesuccinimides). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1020–1026     

Radical copolymerization of maleimide with ethyl α‐ethylacrylate and α‐ethylacrylic acid via RAFT

The copolymerization of maleimide (MI) with α‐ethylacrylic acid (EAA) and with ethyl α‐ethylacrylate (EEA) in the presence of 2‐phenylprop‐2‐yl dithiobenzoate (PPDB) was investigated. The copolymerization of MI and EAA was difficult to conduct with the reversible addition–fragmentation chain transfer (RAFT) mechanism because reinitiation of expelled radicals by fragmentation chain transfer was inhibited by the association of EAA in polar solvent and the strong interaction of the imino of MI with the carboxyl of EAA between the propagation chains. When the carboxylic group of EAA was esterified, then the copolymerization went well via RAFT, and alternating copolymers with controlled molecular weight were obtained. Combining by electron spin resonance showed a different result. It was found that before 30% of the comonomer conversion had occurred, the copolymer poly(EEA‐co‐MI) showed increasing molecular weight with the conversion and a rather narrow molecular weight distribution; then the molecular weight of the copolymer began to retard. This phenomenon of retardation was aggravated at high temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3828–3835, 2004     

The reduction of Ag(I) by α‐silylamines R2NCH2SiX3

The introduction of the organosilicon substituent into the α‐position of an amino group results in cardinal change of the amine reactivity irrespective of the coordination state of silicon. Amines R₂NCH₂SiX₃ [R = Me, Et, PhCH₂, CH₂SiX₃; SiX₃ = SiMe₃, Si(OEt)₃, Si(OCH₂CH₂)₃N] easily react with AgNO₃, to give the corresponding ammonium salts (R₂NH⁺ CH₂SiX₃)·NO₃^?. At the same time, Ag(I) is reduced to Ag(0). The interaction of N‐methyl‐N,N‐bis(silatranylmethyl)amine with AgNO₃ has been investigated by EPR spectroscopy. It was proven that the reaction involved a single electron transfer stage with the formation of cation radical of this amine. A mechanism of the reaction is proposed. Copyright © 2006 John Wiley & Sons, Ltd.     

Cyclic polypeptides by thermal polymerization of α‐amino acid N‐carboxyanhydrides

The NCAs of the following five amino acids were polymerized in bulk at 120 °C without addition of a catalyst or initiator: sarcosine (Sar), L ‐alanine (L ‐Ala), D ,L ‐phenylalanine (D ,L ‐Phe), D ,L ‐leucine (D ,L ‐Leu) and D ,L ‐valine (D,L ‐Val). The virgin reaction products were characterized by viscosity measurements ¹³C NMR spectroscopy and MALDI‐TOF mass spectrometry. In addition to numerous low molar mass byproducts cyclic polypeptides were formed as the main reaction products in the mass range above 800 Da. Two types of cyclic oligo‐ and polypeptides were detected in all cases with exception of sarcosine NCA, which only yielded one class of cyclic polypeptides. The efficient formation of cyclic oligo‐ and polypeptides explains why high molar mass polymers cannot be obtained by thermal polymerizations of α‐amino acid NCAs. Various polymerization mechanisms were discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4012–4020, 2008     

Kinetic and ESR studies on radical polymerization behavior of N‐(2‐phenylethoxycarbonyl)methacrylamide

Polymerization of N‐(2‐phenylethoxycarbonyl)methacrylamide (PECMA) with dimethyl 2,2′‐azobisisobutyrate (MAIB) was investigated in tetrahydrofuran (THF) kinetically and by means of electron spin resonance (ESR). The overall activation energy of the polymerization was calculated to be 58 kJ/mol. The initial polymerization rate (R_p) is expressed by R_p = k[MAIB]^0.3[PECMA]^2.3 at 60 °C. Such unusual kinetics may be ascribable to primary radical termination and to acceleration of propagation due to monomer association. Propagating poly(PECMA) radical was observed as a 13‐line spectrum by ESR under practical polymerization conditions. ESR‐determined rate constants of propagation (k_p, 4.7–10.5 L/mol s) and termination (k_t, 4.6 × 10⁴ L/ml s) at 60 °C are much lower than those of methacrylamide and methacrylate esters. The Arrhenius plots of k_p and k_t gave activation energies of propagation (24 kJ/mol) and termination (25 kJ/mol). The copolymerizations of PECMA with styrene (St) and acrylonitrile were examined at 60 °C in THF. Copolymerization parameters obtained for the PECMA (M₁) − St(M₂) system are as follows: r₁ = 0.58, r₂ = 0.60, Q₁ = 0.73, and e₁ = +0.22. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4264–4271, 2000     

Control of stereospecificity in the radical polymerization of N‐methyl‐N‐(2‐pyridyl)acrylamide by conformational switching of the monomer with protonation

Radical polymerization of N‐methyl‐N‐(2‐pyridyl)acrylamide (MPyAAm) was carried out in dichloromethane at low temperatures in the presence of trifluoroacetic acid (TFA). The m dyad contents of the polymers obtained at 0 °C increased linearly from 37 to 60% with an increase in the [TFA]₀/[MPyAAm]₀ ratio from 1 to 5. Nuclear magnetic resonance (NMR) analysis of MPyAAm–TFA mixtures in dichloromethane‐d₂ revealed that the favorable conformation in terms of the pyridyl group to the carbonyl group in MPyAAm switched from s‐trans to s‐cis by protonation. The results suggest that controlling the conformation of MPyAAm resulted in control of the stereospecificity in radical polymerization of the monomer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Amphiphilic conetworks. II. Novel two‐step synthesis of poly[2‐(dimethylamino)ethyl methacrylate]–polyisobutylene,poly(N‐isopropylacrylamide)–polyisobutylene,and poly(N,N‐dimethylacrylamide)–polyisobutylene hydrogels

Amphiphilic polymer conetworks consisting of hydrophilic poly[2‐(dimethylamino)ethyl methacrylate], poly(N‐isopropylacrylamide), or poly(N,N‐dimethylacrylamide) and hydrophobic polyisobutylene chains were synthesized with a novel two‐step procedure. In the first step, a methacrylate‐multifunctional polyisobutylene crosslinker was prepared by the cationic copolymerization of isobutylene with 3‐isopropenyl‐α,α‐dimethylbenzyl isocyanate. In the second step, the methacrylate‐multifunctional polyisobutylene crosslinker, with a number‐average molecular weight of 8200 and an average functionality of approximately 4 per chain, was copolymerized radically with 2‐(dimethylamino)ethyl methacrylate, N‐isopropylacrylamide, or N,N‐dimethylacrylamide into transparent amphiphilic conetworks containing 42–47 mol % hydrophilic monomer. The synthesized conetworks were characterized with solid‐state ¹³C NMR spectroscopy and differential scanning calorimetry. The amphiphilic nature of the conetworks was proved by swelling in both water and n‐heptane. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6378–6384, 2006